TEPZZ 57865ZA_T

(19)

(11) EP 2 578 650 A1

(12) EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43) Date of publication: (51) Int Cl.:

10.04.2013 Bulletin 2013/15 C09J 4/00 (2006.01) B32B 27/00 (2006.01)
B32B 27/30 (2006.01) C09D 4/00 (2006.01)
(21) Application number: 11789807.2 C09D 113/00 (2006.01) C09D 115/00 (2006.01)
C09D 163/00 (2006.01) C09D 167/08 (2006.01)
(22) Date of filing: 31.05.2011 C09J 113/00 (2006.01) C09J 115/00 (2006.01)
C09J 163/00 (2006.01) C09J 167/08 (2006.01)

(86) International application number:

PCT/JP2011/062499

(87) International publication number:

WO 2011/152404 (08.12.2011 Gazette 2011/49)

(84) Designated Contracting States: (72) Inventors:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • TASAKA, Michihisa
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Kawasaki-city
PL PT RO RS SE SI SK SM TR Kanagawa 215-0001 (JP)
• KANNO, Hiroyasu
(30) Priority: 01.06.2010 PCT/JP2010/059253 Tokyo 175-0094 (JP)
01.06.2010 PCT/JP2010/059252
(74) Representative: Wilson, Justin Scott et al
(71) Applicants: Withers & Rogers LLP
• Riken Technos Corp. 4 More London Riverside
Chuo-ku London SE1 2AU (GB)
Tokyo 103-8438 (JP)
• BASF SE
67056 Ludwigshafen (DE)

(54) COMPOSITION FOR USE AS COATING MATERIAL AND ADHESIVE, METHOD FOR ADHESIVE
BONDING, AND LAMINATED PRODUCTS

(57) A paint and an adhesive composition of the vided that the total of the components (a), (b) and (c) is
present invention containing (a) a vinyl ester resin or un- 100 mass%) and (d) an initiator by 0.1 to 15 parts by
saturated polyester resin by 20 to 40 mass%, (b) a mod- mass to a total of 100 parts by mass of the components
ifying agent by 0.1 to 50 mass%, (c) a vinyl monomer (a), (b) and (c).
and/or (meth)acrylate monomer by 30 to 70 mass% (pro-
EP 2 578 650 A1

Printed by Jouve, 75001 PARIS (FR)

 EP 2 578 650 A1

Description

Technical Field

5 [0001] The present invention relates to an adhesive composition, a bonding method and a laminate. More particularly,
the present invention relates to a paint and an adhesive composition that show an excellent adhesion property relative
to a layer of soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; concrete; wood
panel; stone; artificial marble; polyolefin resin or copolymer of polyolefin resin modified by a polar group-containing
compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer;
10 polyester-based resin; polyurethane-based resin; epoxy-based resin or acryl-based resin.
Furthermore, the present invention relates to a paint and an adhesive composition that is highly transparent and capable
of forming a coating film having an antifouling property of hardly allowing foreign objects such as fingerprints and airborne
dusts to adhere to it.
The present invention also relates to a bonding method for such an adhesive composition and a layer of any of the
15 above-described materials.
The present invention also relates to a laminate of such an adhesive composition and a layer of any of the above-
described materials.
The present invention also relates to a paint for flooring materials, an adhesive composition and a flooring material, and
more particularly, it relates to a paint for flooring materials and an adhesive composition that have an excellent adhesion
20 property relative to concrete floors, resin-coated concrete floors, wooden floors and resin-coated flooring base materials
that are made of wood and is capable of providing excellent water resistance, abrasive resistance, transparency, surface
smoothness, flexibility, shock resistance (and if necessary antistatic properties) but does not degrade the working en-
vironment and also to a flooring material having such properties.

25 Background Art

[0002] Adhesive agents, paints and adhesive compositions made of vinyl ester-based resin (urethane (meth)acrylate),
epoxy (meth)acrylate, polyester (meth)acrylate), a reactive diluent and a curing agent have been and are widely utilized
in various fields including packaging materials, display materials such as label materials, electronic parts, precision
30 equipments and building materials. In recent years, thermosetting type compositions under consideration have been
employed with an aim of increasing the manufacturing speed and productivity improvement of manufacturing processes.
More recently, however, they have been replaced to a large extent by liquid curable adhesive agents, paints and adhesive
compositions of active energy-line curable types such as UV rays and electron beam curable types. Thus, the field of
utilization expands and the demand for higher performance products is intensified. In other words, the demand for higher
35 performance liquid curable adhesive agents, paints and adhesive compositions of active energy-line curable types have
been and being intensified.
[0003] Patent Document 1 listed below discloses an adhesive agent comprising a specific epoxy compound, urethane
(meth)acrylate, a reactive diluent, a specific long-chain alkyl (meth)acrylate and a photopolymerization initiator but it is
not satisfactory in terms of adhesion property relative to a layer of soft or hard vinyl chloride resin; polystyrene; polycar-
40 bonate; glass; aluminum; steel plate; polyolefin resin modified by a polar group-containing compound or copolymer of
olefin and a polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based
resin; or acryl-based resin and also in terms of well-balanced properties of transparency, surface smoothness, flexibility
and shock resistance.
[0004] Patent Document 2 listed below discloses a UV curable type functional paint and an adhesive composition that
45 are realized by using hydroxy methacrylate as monomer for epoxy acrylate-based oligomer and excellent in terms of
thick film forming when compounded with silica. However such a paint and an adhesive composition do not provide a
satisfactory adhesion relative to a layer of glass, polycarbonate, acryl-based resin, polyester-based resin, hard vinyl
chloride resin, soft vinyl chloride resin or styrene-based resin. When such a paint and an adhesive composition is
compounded with one or more functional materials such as an IR absorbing material, a UV absorbing material, an
50 antistatic material and/or an electromagnetic shielding material, the cured paint and the cured adhesive composition are
far from satisfactory in terms of showing the expected functionality. Additionally, they also are not satisfactory in terms
of well-balanced properties of water resistance, abrasive resistance, transparency, surface smoothness, flexibility and
shock resistance.
[0005] Dirt such as sweat or fingerprints of the user and airborne foreign objects can easily adhere to the surface of
55 the image display unit such as a mobile phone. Particularly, dirt such as fingerprints gives rise to not only a filthy feeling
but also a problem of reducing the contrast of the image being displayed on the display screen of the unit.
[0006] Techniques of bonding a film to the display screen of an image display apparatus by means of an adhesive
agent are known (see, for example, Patent Document 3 listed below). With such a technique, if the film on the display

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 EP 2 578 650 A1

screen of the image display unit of a mobile phone becomes dirty, the mobile phone may remain usable simply by
replacing the film with a new one, although the use of such a film is practically unfeasible because the used film becomes
a waste and the film in use can be separated from the display screen along the periphery and reduce the contrast of the
image being displayed on the display screen of the unit. Techniques of arranging a cover on a mobile phone main body
5 to protect the display screen are also known (see, for example, Patent Document 4). With this techniques, while the
image display section of the mobile phone does not become dirty so long as the mobile phone is not used, dirt such as
fingerprints of the user can adhere to it once the mobile phone is operated and additionally, there is a problem that the
mobile phone is subjected to restrictions in terms of design and appearance.
[0007] Techniques of arranging an antifouling layer on the image display screen are also known. Vacuum deposition
10 that is a sort of physical vacuum deposition (PVD) is employed to form such an antifouling layer. With a vacuum deposition
process, the solid or granular target filled in the target container arranged in vacuum of not higher than about 10-4Pa in
a vacuum deposition apparatus is heated to evaporate and the generated vapor is made to deposit on the surface of a
substrate arranged opposite to the target and held to a predetermined temperature level to form a thin film on it. With a
vacuum deposition process, a highly-pure thin film can be formed at a high film forming rate in a high degree of vacuum
15 without changing the structure of the polymer that becomes a thin film at the time of deposition. Heating techniques are
being popularly employed to evaporate the target and the heating techniques that can be used for vacuum deposition
include resistance heating, electron beam method and laser method (laser ablation). A technique of forming a coat film
of a fluorine compound on an inorganic or organic substrate to be used for a display screen such as a liquid crystal
display screen by means of a vapor deposition process (see Patent Document 5 listed below) and a technique of treating
20 a liquid crystal display screen with a fluorinated silazane compound by means of a vapor deposition process or the like
(see Patent Document 6) have been disclosed.
[0008] However, because known fluorine-containing thin films do not have a satisfactory antifouling property and the
formed film has a disadvantage that dirt can easily adhere to it and that it has a poor light permeability, there can arise
a problem that the image being displayed on the relatively small display screen of a mobile phone is not clear as well
25 as a problem that the fluorine-containing thin film formed by means of a vacuum deposition process is poorly durable
and liable to be peeled off with time.
[0009] To date, paints and adhesive compositions including those that are epoxy-based, urethane-based, polyes-
ter-based and acryl-based have been popularly employed as paints and adhesive compositions for floor base materials
of concrete, wood panel, stone and so on. They can provide floor base materials with design, solvent resistance, chemical
30 resistance and a good appearance. For example, Patent Document 7 listed below discloses a floor finishing technique
of directly applying a paint and an adhesive composition containing acryllic silicon resin, a curing agent or a curing
catalyst, a pigment and a solvent and having a specific steam permeability on concrete. Patent Document 8 listed below
discloses a floor paint and an adhesive composition curing composition comprising a copolymer component having a
main chain that is substantially formed by a vinyl-based polymer and containing a hydrolyzable silicon group and an
35 amino group in a molecule, and a curing catalyst component.
However, currently known floor paints and adhesive compositions including the known paints and the adhesive compo-
sitions described in Patent Documents 7 and 8 are poorly adhesive relative to floor base members including floors made
of concrete, resin-coated concrete floors, wooden floors and resin-coated wooden floors and not fully satisfactory in
terms of well-balanced properties of water resistance, abrasion resistance, transparency, surface smoothness, flexibility
40 and shock resistance. Additionally, known floor paints and adhesive compositions require the use of a xylene- or toluene-
based solvent and are accompanied by a problem of degrading the working environment.

[Prior Art Documents]

45 [Patent Documents]

[0010]

[Patent Document 1] Japanese Patent Application Laid-Open Publication No. 02-296879

50 [Patent Document 2] Japanese Patent Application Laid-Open Publication No. 58-49702
[Patent Document 3] Japanese Patent Application Laid-Open Publication No. 2003-15531
[Patent Document 4] Japanese Patent Application Laid-Open Publication No. 08-331631
[Patent Document 5] Japanese Patent Application Laid-Open Publication No. 09-111223
[Patent Document 6] Japanese Patent Application Laid-Open Publication No. 08-201746
55 [Patent Document 7] Japanese Patent Application Laid-Open Publication No. 2000-256612
[Patent Document 8] Japanese Patent Application Laid-Open Publication No. 2002-363485

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 EP 2 578 650 A1

Disclosure of the Invention

Problem to be Solved by the Invention

5 [0011] Thus, in view of the above-identified problems, an object of the present invention is to provide a paint, an
adhesive composition, a bonding method and a laminate that can furnish soft or hard vinyl chloride resins; polystyrene;
polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone; artificial marble; a polyolefin resin or copoly-
mers of polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing compound;
magnesium; acrylonitrile-butadiene-styrene copolymers; polyester-based resins; polyurethane-based resins; epoxy-
10 based resins; and acryl-based resins with adhesiveness, hardness, water resistance, abrasion resistance, transparency,
surface smoothness, flexibility, shock resistance and an antifouling property in a well-balanced manner, and exhibit a
desired functionality to an unexpected extent when the paint and the adhesive composition are compounded with one
or more functional materials selected from antifouling-property imparting materials, scratch resistance enhancing ma-
terials, shock resistance enhancing materials, IR absorbing materials, UV absorbing materials, electromagnetic shielding
15 materials, electroconductive revealing materials, antistatic materials and flame retardancy imparting materials.

Means for Solving the Problem

[0012] As a result of intensive research efforts, the inventor of the present invention came to find that a paint and an
20 adhesive composition containing the below-listed components (a), (b), (c) and (d) with a specific quantitative relationship
can solve the above-identified problems and thus completed the present invention.
[0013] Thus, the present invention is defined as follows:

1.
25 A paint and an adhesive composition characterized by containing:

(a) a vinyl ester resin or unsaturated polyester resin by 20 to 40 mass%;

(b) a modifying agent by 0.1 to 50 mass%;
(c) a vinyl monomer and/or (meth) acrylate monomer by 30 to 70 mass% (provided that the total of the components
30 (a), (b) and (c) is 100mass%); and
(d) an initiator by 0.1 to 15 parts by parts by mass to a total of 100 parts by mass of the components (a), (b) and (c).

2. The paint and an adhesive composition as defined in 1 above, characterized in that the component (a) is at least
one item selected from a group of urethane (meth)acrylate, polyester (meth)acrylate and epoxy (meth)acrylate.
35 3. The paint and an adhesive composition as defined in 1 or 2 above, characterized in that the component (b) is at
least one item selected from a group of (b-1) polyols having an hydroxyl value of 40 to 330 mgKOH/g; (b-2) polyols
having an hydroxyl value of 40 to 330 mgKOH/g and an acid value of 2 to 20 mgKOH/g; (b-3) modified rubber; (b-
4) compounds having an epoxy equivalent of 150 to 700 g/mol; and (b-5) fluorine-based resin having a hydroxyl
value of 40 to 330 mgKOH/g.
40 4. The paint and an adhesive composition as defined in 3 above, characterized in that the component (b-1) is at
least one item selected from a group of (b-1-1) castor oil-based polyols having a hydroxyl value of 40 to 330 mgKOH/g;
(b-1-2) polybutadiene-based polyols having a hydroxyl value of 40 to 330 mgKOH/g; and (b-1-3) polyisoprene-based
polyols having a hydroxyl value of 40 to 330 mgKOH/g.
5. The paint and an adhesive composition as defined in 4 above, characterized in that the component (b-1) is an
45 aromatic castor oil-based polyol (b-1-1-1) having a hydroxyl value of 40 to 330 mgKOH/g.
6. The paint and an adhesive composition as defined in 3 above, characterized in that the component (b-2) is a
castor oil-based polyol (b-2-1) having a hydroxyl value of 40 to 330 mgKOH/g and an acid value of 2 to 20 mgKOH/g.
7. The paint and an adhesive composition as defined in 3 above, characterized in that the component (b-3) is an
acid-modified polybutadiene or an acid-modified polyisoprene.
50 8. The paint and an adhesive composition as defined in 3 above, characterized in that the component (b-4) is a
polyepoxy compound (b-4-1) having an epoxy equivalent of 150 to 250 g/mol.
9. The paint and an adhesive composition as defined in 3 above, characterized in that the component (b-4) is a
polymer (b-4-2) having an epoxy equivalent of 500 to 700 g/mol and a saturated skeleton.
10. The paint and an adhesive composition as defined in 3 above, characterized in that the component (b-5) is a
55 fluorine-based resin (b-5-1) having a hydroxyl value of 40 to 330 mgKOH/g.
11. The paint and an adhesive composition as defined in 1 or 2 above, characterized in that the component (c) is
a monomer having an N-vinyl group.
12. The paint and an adhesive composition as defined in any of 1 through 11 above, characterized in that the

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component (c) is at least a monomer selected from (c-1) compounds having a ring structure and an ethylenically
unsaturated group and (c-2) compounds having no ring structure and an ethylenically unsaturated group.
13. The paint and an adhesive composition as defined in any of 1 through 12 above, characterized in that the
adherend of the adhesive composition is soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; alumi-
5 num; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer of polyolefin resin
modified by a polar group-containing compound or olefin and a polar group-containing compound; magnesium;
acrylonitrile-butadiene-styrene copolymer; polyester-based resin; polyurethane-based resin; epoxy-based resin; or
acryl-based resin.
14. The paint and an adhesive composition as defined in any of 1 through 13 above, characterized by further
10 comprising a functional material.
15. The paint and an adhesive composition as defined in 14 above, characterized in that the functional material is
at least one item selected from a group of antifouling-property imparting materials, scratch resistance enhancing
materials, shock resistance enhancing materials, IR absorbing materials, UV absorbing materials, electromagnetic
shielding materials, electroconductive revealing materials, antistatic materials and flame retardancy imparting ma-
15 terials.
16. The paint and an adhesive composition as defined in 15 above, characterized in that the antifouling-property
imparting materials are silicone compounds.
17. The paint and an adhesive composition as defined in 16 above, characterized in that they are used for antifoul-
ing-property protective walls (glass substitutes, protective walls for highways, sports arenas, bridges and so on)
20 and display coatings of television sets, mobile phones and game machines.
18. The paint and an adhesive composition as defined in 15 above, characterized in that the scratch resistance
enhancing materials are organosilica compounds.
19. The paint and an adhesive composition as defined in 15 above, characterized in that the scratch resistance
enhancing materials are alumina ceramic compounds.
25 20. The paint and an adhesive composition as defined in 18 or 19 above, characterized in that they are used for
glass substitutes, protective walls for highways, sports arenas and bridges and display hard coatings of television
sets, mobile phones and game machines.
21. The paint and an adhesive composition as defined in 15 above, characterized in that the shock resistance
enhancing materials are core-shell polymer particles.
30 22. The paint and an adhesive composition as defined in 21 above, characterized in that they are used for car interior
and exterior decorating members, floors, walls, protective walls for highways, sports arenas and bridges and display
coatings of television sets, mobile phones and game machines.
23. The paint and an adhesive composition as defined in 15 above, characterized in that the IR absorbing materials
are metal oxides such as ATO (antimony tin complex oxide and antimony doped tin oxide), ITO (indium tin complex
35 oxide).
24. The paint and an adhesive composition as defined in 21 above, characterized in that they are used for car interior
and exterior decorating members, floors, walls, protective walls for highways, sports arenas and bridges and heat
shield coatings of television sets, mobile phones and game machine housing.
25. The paint and an adhesive composition as defined in 15 above, characterized in that the UV absorbing materials
40 are at least one item selected from a group of salicylate-based, benzophenone-based, benzotriazole-based, sub-
stituted acrylonitrile-based, and triazine-based organic compounds and inorganic compounds such as hybrid inor-
ganic particles obtained by way of a complexing process of treating any of carbon nanotubes, zinc oxide, aluminum
doped zinc oxide, gallium doped zinc oxide, titanium dioxide, cerium oxide and titanium dioxide microparticles with
iron oxide, and hybrid inorganic particles obtained by coating the surfaces of cerium oxide microparticles with
45 amorphous silica.
26. The paint and an adhesive composition as defined in 25 above, characterized in that they are used for anti-yel-
lowing coatings and UV degradation preventive coatings of car interior and exterior decorating members, floors,
walls, boats and canoes.
27. The paint and an adhesive composition as defined in 15 above, characterized in that the IR absorbing materials
50 are organic pigment components that are at least one item selected from a group of basic lead carbonate, basic
lead sulfate, basic lead silicate, zinc oxide (specific gravity: 5.47 to 5.61), zinc sulfide (specific gravity: 4.1) lithopone,
antimony trioxide (specific gravity: 4.2), titanium dioxide (specific gravity: 4.2) and graphite (specific gravity: 3.3).
28. The paint and an adhesive composition as defined in 25 above, characterized in that the IR absorbing materials
are for solar cell backsheets, walls and roof coatings.
55 29. The paint and an adhesive composition as defined in 15 above, characterized in that the electromagnetic shielding
materials are electroconductive particles of at least one item selected from a group of (1) carbon particles and/or
powder, (2) particles and/or powder of any of metals of nickel, indium, chromium, gold, vanadium, tin, cadmium,
silver, platinum, aluminum, copper, titanium, cobalt, lead and so on, alloys of any of them and their electroconductive

5
 EP 2 578 650 A1

oxides and (3) particles of plastic materials such as polyethylene having a coating layer of any of electroconductive
materials of (1) or (2) above formed on the surfaces thereof.
30. The paint and an adhesive composition as defined in 25 above, characterized in that they are used for car interior
and exterior decorating members, floors, walls and roof coatings.
5 31. The paint and an adhesive composition as defined in 15 above, characterized in that the electroconductive
revealing materials are electroconductive particles of at least one item selected from a group of electroconductive
carbon black and carbon nanotubes.
32. The paint and an adhesive composition as defined in 31 above, characterized in that they are used for car interior
and exterior decorating members, floors and electrode coatings.
10 33. The paint and an adhesive composition as defined in 15 above, characterized in that the antistatic materials are
at least one item selected from a group of metal oxides, metal salts, surface active agents and ionic liquids.
34. The paint and an adhesive composition as defined in 33 above, characterized in that the metal oxides and the
metal salts are at least one item selected from a group of zinc oxide, aluminum doped zinc oxide, gallium doped
zinc oxide, ATO, ITO, tin oxide, antimony pentoxide, zirconium oxide, titanium oxide and aluminum oxide.
15 35. The paint and an adhesive composition as defined in 33 above, characterized in that the surface active agents
are at least one item selected from a group of anionic, nonionic, cationic and amphoteric surface-active agents.
36. The paint and an adhesive composition as defined in 33 above, characterized in that the ionic liquids contain
cations of at least one item selected from a group of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium
and sulfonium.
20 37. The paint and an adhesive composition as defined in 33 above, characterized in that the ionic liquids contain
anions of at least one item selected from a group of halogen, carboxylates, sulfates, sulfonates, thiocyanates,
aluminates, borates, phosphates, phosphinates, amides, antimonates, imides and methides.
38. The paint and an adhesive composition as defined in any of 33 through 35 above, characterized in that they are
used for floors, walls, electric appliance housings and display coatings of TV mobile phones and game machines.
25 39. The paint and an adhesive composition as defined in 15 above, characterized in that the flame retardancy
imparting materials contain a flame retardant agent of at least one item selected from a group of phosphor-based
flame retardant agents, bromide-based flame retardant agents, chlorine-based flame retardant agents, aluminum
hydroxide and zinc borate.
40. The paint and an adhesive composition as defined in 39 above, characterized in that they are used for walls,
30 floors, electric appliance housings, connectors and electric wire coatings. 41.

[0014] A bonding method characterized by executing:

Step I:
35
mixing

(a) a vinyl ester resin or unsaturated polyester resin by 20 to 40 mass%;

(b) a modifying agent by 0.1 to 50 mass%;
40 (c) a vinyl monomer and/or (meth) acrylate monomer by 30 to 70 mass% (provided that the total of the
components (a), (b) and (c) is 100 mass%); and
(d) an initiator by 0.1 to 15 parts by mass to a total of 100 parts by mass of the components (a), (b) and (c)
in an arbitrary order to prepare an adhesive composition;

45 Step II:

forming a layer (A) of the adhesive composition by laminating the adhesive composition obtained in the step I
on the surface of a layer (B1) of a soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum;
steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or a copolymer of polyolefin resin
50 modified by a polar group-containing compound or olefin and a polar group-containing compound; magnesium;
an acrylonitrile-butadiene-styrene copolymer; a polyester-based resin; a polyurethane-based resin; an epoxy-
based resin; or an acryl-based resin;

Step III:
55
additionally laminating a layer (B2) of a soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass;
aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or a copolymer of polyolefin
resin modified by a polar group-containing compound or olefin and a polar group-containing compound; mag-

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 EP 2 578 650 A1

nesium; an acrylonitrile-butadiene-styrene copolymer; a polyester-based resin; a polyurethane-based resin; an

epoxy-based resin; or an acryl-based resin on the layer (A) of the adhesive composition of the laminate obtained
in the step II in the order of Step I, Step II and Step III.

5 42. A laminate characterized by being formed by laying a layer (A) of an adhesive composition containing:

(a) a vinyl ester resin or unsaturated polyester resin by 20 to 40 mass%;

(b) a modifying agent by 0.1 to 50 mass%;
(c) a vinyl monomer and/or (meth) acrylate monomer by 30 to 70 mass% (provided that the total of the components
10 (a), (b) and (c) is 100 mass%); and
(d) an initiator by 0.1 to 15 parts by mass to a total of 100 parts by mass of the components (a), (b) and (c)
(provided that the total of the components (a), (b), (c) and (d) is 100 mass%); and

a layer (B1) of a soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; concrete;
15 wood panel; stone; artificial marble; polyolefin resin or a copolymer of polyolefin resin modified by a polar group-
containing compound or olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-
styrene copolymer; a polyester-based resin; a polyurethane-based resin; an epoxy-based resin; or an acryl-based
resin so as to make the layer (A) and the layer (B1) contact each other.
43. The laminate as defined in 42 above, characterized in that the thickness of the layer (A) of the paint and the
20 adhesive composition is between 1 and 200 mm.
44.
The paint and an adhesive composition as defined in 1 above, characterized in that they are used for electroacoustic
transducers.
45.
25 The paint and an adhesive composition as defined in 1 above, characterized in that they are used for coating of
steel structures.

Advantages of the Invention

30 [0015] Because a paint according to the present invention contains specific components (a) through (d) at a specific
compounding ratio, it shows a satisfactory adhesion property relative to a layer of a soft or hard vinyl chloride resin;
polystyrene; polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin
or copolymer of polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing
compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin (e.g., polyethylene terephtha-
35 late: PET); polyurethane-based resin; epoxy-based resin; or acryl-based resin (e.g., polymethyl methacrylate: PMMA)
and can provide a paint layer that exhibits a desired functionality when compounded with one or more functional materials
such as an IR absorbing material, a UV absorbing material, an antistatic material and/or an electromagnetic shielding
material and in which hardness, water resistance, abrasion resistance, transparency, surface smoothness, flexibility and
shock resistance are highly well-balanced. Additionally, because a paint according to the present invention has a viscosity
40 appropriate for application, it does not need to be diluted with an organic solvent and hence can provide an excellent
working environment.
Because a laminate according to the present invention is formed by laminating a layer (A) of an adhesive composition
according to the present invention as defined above and a layer (B) of soft or hard vinyl chloride resin; polystyrene;
polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer
45 of polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing compound;
magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin (e.g., polyethylene terephthalate PET);
polyurethane-based resin; epoxy-based resin; or acryl-based resin (e.g., polymethyl methacrylate PMMA) so as to make
the layer (A) and the layer (B) contact each other, the two layers show an excellent adhesion property (and can be used
for direct coating without requiring the layer (B) to be treated with a primer) and the laminate shows water resistance,
50 abrasion resistance, transparency, surface smoothness, flexibility and shock resistance in a highly well-balanced manner.
[0016] A paint according to the present invention shows a viscosity that is advantageous for painting operations without
being diluted with an organic solvent. For example, a paint according to the present invention typically has a viscosity
at 25°C of between 5 and 5, 000 mPa · s, preferably between 10 and 2, 000 mPa · s (as observed by means of a B-type
viscometer). Note, however, a paint according to the present invention may be diluted with an organic solvent if necessary.
55 [0017] Because an adhesive composition according to the present invention contains the components (a), (b), (c) and
(d) with a specific quantitative relationship, it has an excellent adhesion property to a layer of polar resin, ceramic, metal
or the like, more specifically to a layer of soft or hard vinyl chloride resins; polystyrene; polycarbonate; glass; aluminum;
steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer of polyolefin resin modified by

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 EP 2 578 650 A1

a polar group-containing compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-butadi-
ene-styrene copolymer; polyester-based resin; polyurethane-based resin; epoxy-based resin; or acryl-based resin and
also properties of transparency, surface smoothness, flexibility and shock resistance in a highly well-balanced manner.
Because a bonding method according to the present invention is a method of laminating a layer (A) of an adhesive
5 composition containing the components (a) through (d) with a specific quantitative relationship and layers (B1) and (B2)
of soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone;
artificial marble; polyolefin resin or copolymer of polyolefin resin modified by a polar group-containing compound or olefin
and a polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin;
polyurethane-based resin; epoxy-based resin; or acryl-based resin by way of steps that are to be executed in a specific
10 order, the three layers are firmly bonded together.
A laminate according to one aspect of the present invention is a laminate (A) of an adhesive composition containing the
components (a) through (d) with a specific quantitative relationship and a layer (B1) of soft or hard vinyl chloride resin;
polystyrene; polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin
or copolymer of polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing
15 compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin; polyurethane-based resin;
epoxy-based resin; or acryl-based resin. Because the layer (A) of an adhesive composition has properties of transparency,
surface smoothness, flexibility and shock resistance in a highly well-balanced manner, it operates advantageously as
primer layer for the layer (B1).
Because a laminate according to another aspect of the present invention is a laminate (A) of an adhesive composition
20 containing the components (a) through (d) with a specific quantitative relationship and layers (B1) and (B2) of soft or
hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone; artificial
marble; polyolefin resin or copolymer of polyolefin resin modified by a polar group-containing compound or olefin and a
polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin; poly-
urethane-based resin; epoxy-based resin; or acryl-based resin, it shows an excellent adhesive effect of firmly bonding
25 the layers (A), (B1) and (B2) together. Additionally, it has properties of transparency, surface smoothness, flexibility and
shock resistance in a highly well-balanced manner.

Best Mode for Carrying Out the Invention

30 [0018] Now, the present invention will be described in greater detail below.

(a) Vinyl ester resin or unsaturated polyester resin

[0019] The component (a) of an adhesive composition according to the present invention is either vinyl ester resin or
35 unsaturated polyester resin. More specifically, the vinyl ester resin is selected from urethane (meth)acrylate) resin, epoxy
(meth)acrylate resin, polyester (meth)acrylate resin, of which urethane (meth)acrylate resin is preferable because it is
particularly advantageous in terms of flexibility, shock resistance and adhesiveness relative to different materials. Note
that the expression of (meth)acrylate as used herein refers to acrylate or methacryate.
[0020] Preferably, such urethane (meth)acrylate resins are those that can be obtained by way of a reaction of polyol,
40 polyisocyanate and (meth) acrylate having one or more hydroxyl groups in a molecule and has two or more (meth)acryloyl
groups in a molecule.
[0021] Preferably, polyols that can be used for a urethane (meth)acrylate resin have a number-average molecular
weight preferably between 200 and 3,000, more preferably between 400 and 2,000. Examples of such polyols typically
include polyether polyols, polyester polyols, polycarbonate polyols and polybutadiene polyols. A polyol selected from
45 the above listed ones may be used. Alternatively, two or more of such polyols can be used in combinations.
[0022] For the purpose of the present invention, polyether polyols may include polyols obtained by adding alkylene
oxide to bisphenol A and bisphenol F besides polyalkylene oxides such as polyethylene glycol, polypropylene glycol
and polytetramethylene glycol.
[0023] The expression of polyester polyols as used herein refers to condensate polymers of dibasic acids and polyhydric
50 alcohols or ring-opened polymers of cyclic ester compounds such as polycaprolactone. Examples of the dibasic acids
that can be used for the present invention include phthalic acid, phthalic anhydride, halogenated phthalic anhydride,
isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hex-
ahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric
acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenecar-
55 boxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4’-bisphenyldicarboxylic
acid and dialkyl esters thereof. Examples of polyhydric alcohols that can be used for the present invention include
ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene
glycol, polypropylene glycol, 2-methyl-1,3-propane diol, 1, 3-butane diol, neopentyl glycol, hydrogenated bisphenol A,

8
 EP 2 578 650 A1

1,4-butane diol, 1,6-hexane diol, bisphenol A - propylene oxide or ethylene oxide adduct, 1,2,3,4-tetrahydroxybutane,
glycerin, trimethylolpropane, 1,3-propane diol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol,
1,4-cyclohexane dimethanol, para-xylene glycol, bicyclohexyl-4,4’-diol, 2,6-decalin glycol and 2,7-decalin glycol.
[0024] Examples of polyisocyanates that can be used for the urethane (meth) acrylate resins include 2,4-TDI, isomers
5 thereof and mixtures of isomers thereof, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate,
toridine diisocyanate, naphthalene diisocyanate and triphenylmethane triisocyanate. Any one of these polyisocyantes
can be used alone and also any two or more of them can be used in combination.
[0025] Examples of (meth)acrylates (hydroxyl group-containing (meth)acrylate) having one or more hydroxyl groups
in a molecule to be used for the urethane (meth)acrylate resins include mono(meth)acrylates such as 2-hydroxyethyl
10 (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydoxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate
and polypropylene glycol mono(meth)acrylate and polyhydric (meth)acrylates such as tris(hydroxyethyl) isocyanurate
di(meth)acrylate and pentaerythritol tri(meth)acrylate.
[0026] Exemplar methods of manufacturing the urethane (meth) acrylate resins include (1) a method of firstly causing
a polyisocyanate and a polyol to react with each other preferably at a ratio of NCO/OH = 1.3 to 2 to produce a terminal
15 isocyanate compound and then causing the compound to react with a hydroxyl group-containing (meth) acrylate so that
the isocyanate group and the hydroxyl group are substantially equal to quantity and (2) a method of causing a polyiso-
cyanate compound and a hydroxyl group-containing (meth)acrylate to react at a ratio of NCO/OH = not less than 2 to
produce a one-terminal isocyanate compound and then adding a polyol for reaction.
[0027] Epoxy (meth)acrylate resins that can be used as vinyl ester resins refer to ones preferably containing two or
20 more (meth) acryloyl groups in a molecule that can be obtained by way of a reaction of such a resin and an unsaturated
monobasic acid in the presence of an esterification catalyst.
[0028] Examples of the epoxy resin as used herein include a bisphenol type or novolac-type epoxy resin used alone
and mixtures of bisphenol type and novolac type epoxy resins whose average epoxy equivalent is preferably within the
range between 150 and 450.
25 [0029] Typical examples of the bisphenol-type epoxy resin include glycidyl ether type epoxy resins substantially having
two or more epoxy groups in a molecule that can be obtained by way of a reaction of epichlorohydrin and bisphenol A
or bisphenol F, methylglycidyl ether type epoxy resins that can be obtained by way of a reaction of methylepichlorohydrin
and bisphenol A or bisphenol F, and epoxy resins that can be obtained from alkylene oxide adduct of bisphenol A and
epichlorohydrin or methyl epichlorohydrin. Typical examples of the novolac-type epoxy resins include those that can be
30 obtained by way of a reaction of phenol novolac or cresol novolac and epichlorohydrin or methyl epichlorohydrin.
[0030] Typical examples of the unsaturated monobasic acid to be used for the epoxy (meth) acrylate resin include
acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, mono(2-ethyl-
hexyl) maleate and sorbic acid. Any of these unsaturated monobasic acids can be used alone or as a mixture of two or
more of any of them. The reaction of an epoxy resin and an unsaturated monobasic acid is conducted at temperature
35 preferably betweens 60 and 140°C, more preferably between 80 and 120°C, in the presence of an esterification catalyst.
[0031] Examples of the esterification catalysts may be known catalysts and include tertiary amines such as triethyl
amine, N,N-dimethylbenzylamine, N,N-dimethylaniline and diazabicyclooctane, triphenylphosphine and diethylamine
hydrochloride.
[0032] Polyester (meth)acrylate resins to be used as vinyl ester resins are saturated or unsaturated polyesters having
40 two or more (meth)acryloyl groups in a molecule, whose terminals are caused to react with a (meth) acryl compound.
The number-average molecular weight of such resins is preferably between 500 and 5,000.
[0033] Saturated polyesters that can be used for the present invention are those obtained by way of a condensation
reaction of a saturated dibasic acid and a polyhydric alcohol. Unsaturated polyesters that can be used for the present
invention are those obtained by way of a condensation reaction of a dibasic acid selected from a group of dibasic acids
45 including α, β-unsaturated dibasic acids and a polyhydric alcohol. Note that, for the present invention, resins obtained
by causing a terminal of an unsaturated polyester to react with a (meth)acryl compound are included in vinyl ester resins
and should be discriminated from the unsaturated polyester resins that are described below.
[0034] Saturated dibasic acids as used herein include the compounds listed in the paragraph describing polyester
polyols. Examples of α, β-unsaturated dibasic acids include maleic acid, maleic acid anhydride, fumaric acid, itaconic
50 acid and itaconic acid anhydride. Polyhydric alcohols that can be used for the invention include the applicable compounds
listed in the paragraph describing polyester polyols.
[0035] (Meth) acrylate compounds for polyester (meth) acrylate resins that can be used as vinyl ester resins include
unsaturated glycidyl compounds, unsaturated monobasic acids such as acrylic acid and methacrylic acid and glycidyl
esters thereof. The use of glycidyl (meth)acrylates is preferable.
55 [0036] Unsaturated polyester resins are obtained by way of condensation polymerization of an acid component and
an alcohol component, using a known method. Any unsaturated polyester resins can be used without limitations so long
as such resins are known as thermosetting resins. Examples of candidate acid components include unsaturated dibasic
acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid. If necessary, saturated dibasic acids such

9
 EP 2 578 650 A1

as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid and sebacic acid and
acids other than dibasic acids such as benzoic acid and trimellitic acid can be used. Examples of alcohol components
include the polyhydric alcohols listed in the paragraph describing polyester polyols.

5 (b) Modifying agent

[0037] The component (d) to be used for the present invention is a modifying agent.
The (d) modifying agent may be at least one item selected from a group of polyols (b-1) having a hydroxyl value of 40
to 330 mgKOH/g, polyols (b-2) having a hydroxyl value of 40 to 330 mgKOH/g and an acid value of 2 to 20 mgKOH/g,
10 modified rubbers (b-3), compounds (b-4) having an epoxy equivalent of 150 to 700 g/mol and fluorine-based resins (b-
5) having a hydroxyl value of 40 to 330 mgKOH/g.
[0038] (i) Polyols (b-1) having a hydroxyl value of 40 to 330 mgKOH/g will be described below.
[0039] The hydroxyl value of the component (b) contributes to improvement of selective adhesiveness relative to the
adherend (soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate (e.g., SPCC) ;
15 copolymer of polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing
compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin; or acryl-based resin) that
characterizes the present invention.
[0040] Examples of (i) polyols (b-1) having a hydroxyl value of 40 to 330 mgKOH/g include aromatic-based, aliphat-
ic-based, polybutadiene-based, castor oil-based and polyisoprene-based polyols. Polyols of any of the above types
20 provide an excellent selective adhesive force relative to the adherend (soft or hard vinyl chloride resin; polystyrene;
polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer
of polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing compound;
magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin; polyurethane-based resin; epoxy-based
resin; or acryl-based resin).
25 (i) Thus, the hydroxyl value is preferably 40 to 330 mgKOH/g, more preferably 150 to 300 mgKOH/g, from the viewpoint
of adhesiveness.
[0041] (i) Polyols (b-1) that can more preferably be used for the present invention in terms selective adhesive force
relative to the adherend (soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate;
concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer of polyolefin resin modified by a polar
30 group-containing compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-butadiene-sty-
rene copolymer; polyester-based resin; polyurethane-based resin; epoxy-based resin; or acryl-based resin) include:

(i) castor oil-based polyols (b-1-1) having a hydroxyl value of 40 to 330 mgKOH/g,
(i) polybutadiene-based polyols (b-1-2) having a hydroxyl value of 40 to 330 mgKOH/g,
35 (i) polyisoprene based polyols and hydrogenated additives thereof (b-1-3) having a hydroxyl value of 40 to 330
mgKOH/g or
(i) epoxy polyol resins (b-1-4) having a hydroxyl value of 40 to 330 mgKOH/g.

[0042] If necessary, two or more of polyols of component (b) can be used as mixture for the present invention.
40 [0043] (i) castor oil-based polyols (b-1-1) having a hydroxyl value of 40 to 330 mgKOH/g will be described below.
[0044] The "castor oil" is a kind of oil that contains triester compounds of ricinoleic acid and glycerin. Ordinarily, it is
natural oil or processed natural oil but synthesized oil may be used for the present invention provided that it contains
such compounds. The ricinoleic acid employed to form the triester compounds contained in castor oil is preferably not
less than 90 mol% of the fatty acids contained to produce the entire triester compounds. The castor oil to be used for
45 the present invention may be a processed product such as a hydrogenated additive (obtained by hydrogenation relative
to the carbon-carbon unsaturated bonds in the ricinoleic acid skeleton). Normally, castor oil contains the triester com-
pounds (hydrogenated additive of trimester compounds if appropriate) equivalent to not less than 90 mol% (and up to
100 mol%) of the entire oil.
[0045] The "castor oil-based polyols" are ester compounds of ricinoleic acid and/or hydrogenated ricinoleic acid and
50 polyhydric alcohol. For the purpose of the present invention, both polyols obtained by using castor oil as starting material
and polyols obtained by using a starting material other than castor oil may be used so long as they have such a
composition. The polyhydric alcohols that can be used for the present invention are not subjected to any particular
limitations.
[0046] Examples of castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying
55 castor oil.
[0047] Polyols derived from castor oil are fatty acid ester based polyols originating from castor oil and include polyols
obtained by substituting part of the ricinoleic acid of the glycerin ester by oleic acid, those obtained by esterification of
ricinoleic acid that is obtained by saponifying castor oil with a short molecule polyol such as trimethylol propane or the

10
 EP 2 578 650 A1

like and mixtures of any of such polyol(s) and castor oil.

[0048] Examples of polyols obtained by modifying castor oil include vegetable oil-modified polyols, modified polyols
having an aromatic skeleton (e.g., bisphenol A, etc.). Vegetable oil-modified polyols can be obtained by substituting part
of ricinoleic acid of a glycerin ester with a higher fatty acid obtained from other plants such as linoleic acid, linolenic acid,
5 oleic acid or the like obtained from soy beans oil, rapeseed oil, olive oil or the like.
[0049] Out of castor oil-based polyols as described above, (i) castor oil-based polyols (b-1-1) having a hydroxyl value
of 40 to 330 mgKOH/g are preferable from the viewpoint of the advantages of the present invention. Furthermore, from
the viewpoint improving of toughness (shock resistance), flexibility and adhesives to different materials of a bonding
layer, (i) aromatic castor oil-based polyols (b-1-1-1) preferably having a hydroxyl value of 40 to 330 mgKOH/g, more
10 preferably having a hydroxyl value of 150 to 240 mgKOH/g.
[0050] The component (b-1-1-1) is any of modified polyols derived from castor oil having an aromatic skeleton (e.g.,
bisphenol A, etc.). The component (b-1-1-1) is commercially available. Examples of commercially available component
(b-1-1-1) include "URIC AC Series" (Itoh Oil Chemicals Co., Ltd.) and the like. Of such polyols, adducts obtained by
adding polyalkylene glycol and bisphenol A to ricinoleic acid are preferable in terms of adhesiveness to soft or hard vinyl
15 chloride resins; polystyrenes; polycarbonates; glass; aluminum; steel plate; copolymers of polyolefin resin modified by
a polar group-containing compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-butadi-
ene-styrene copolymers; polyester-based resins; or acryl-based resins and can be expressed by formula (4) shown below.
[0051]

20

25

30

[0052] in formula (4), where m represents an average number between 2 and 5 and n represents an average number
between 2 and 5.
35 [0053] Examples of modified polyols derived from castor oil expressed by the above formula (4) include those com-
mercially available from Itoh Oil Chemicals Co., Ltd. under the trade names of URIC AC-005 (hydroxyl value:
194~214mgKOH/mg, viscosity: 700 to 1,500 mPa·s/25°C), AC-006 (hydroxyl value: 168 to 187 mgKOH/mg, viscosity:
3,000 to 5,000 mPa · s/25°C), AC-008 (hydroxyl value: 180 mgKOH/mg, viscosity: 1,600 mPa · s/25°C) and AC-009
(hydroxyl value: 225 mgKOH/mg, viscosity: 1,500 mPa · s/25°C),
40 [0054] (i) polybutadiene-based polyols (b-1-2) having a hydroxyl value of 40 to 330 mgKOH/g will be described below.
[0055] Examples of polybutadiene-based polyols that can be used for the present invention include homopolymers
such as 1,2-polybutadiene polyols and 1,4-polybutadiene polyols; copolymers such as poly(pentadiene · butadiene)
polyols, poly(butadiene · styrene) polyols and poly(butadiene · acrylonitrile) polyols; and hydrogenated polybutadiene-
based polyols obtained by adding hydrogen atoms to any of them. Polybutadiene based polyols are commercially
45 available and include "Poly bd R-15HT (hydroxyl value: 102.7 mgKOH/mg, Mw: 1,200)" and "Poly bd R-45HT (hydroxyl
value: 46.6 mgKOH/mg, Mw: 2,800)" manufactured by Idemitsu Co., Ltd.
From the viewpoint of the advantages of the present invention, the hydroxyl value of (b-1-2) polybutadiene-based polyols
is preferably 40 to 330 mgKOH/g, more preferably 40 to 110 mgKOH/g.
The weight average molecular weight (GPC method) of (b-1-2) polybutadiene-based polyols is preferably between 50
50 and 3, 000, more preferably between 800 and 1,500.
[0056] (i) polyisoprene-based polyols and hydrogenated additives thereof (b-1-3) having a hydroxyl value of 40 to 330
mgKOH/g will be described below.
[0057] Examples of component (b-1-3) include "Poly ip (trade name)" (liquid polyisoprene having hydroxyl groups at
its terminals) available from Idemitsu Co., Ltd. Poly ip (trade name) (hydroxyl value: 46.6 mgKOH/mg, Mn: 2,500) is a
55 polyisoprene type liquid polymer having highly reactive hydroxyl groups at molecular terminals. Hydrogenated additives
of such polyols include "Epol (trade name)" ((liquid polyolefin having hydroxyl groups at its terminals). "Epol (tradename)"
(hydroxy value: 50.5 mgKOH/mg, Mn: 2,500) is a liquid polyolefin obtained by hydrogenating "Poly ip (trade name)." It
scarcely has double bonds remaining in the molecule.

11
 EP 2 578 650 A1

[0058] (i) epoxy polyol resins (b-1-4) having a hydroxyl value of 40 to 330 mgKOH/g
[0059] (i) epoxy polyol resins (b-1-4) having a hydroxyl value of 40 to 330 mgKOH/g that can be used for the present
invention are obtained by causing active hydrogen compounds to react with epoxy resins.
[0060] Examples of epoxy resins that can be used for the present invention include polyglycidyl ether compounds of
5 mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol and phloroglucinol; polygly-
cidyl ether compounds of polynuclear polyhydric phenol compounds such as dihydroxynaphthalene, biphenol, methylene
bisphenol (bisphenol F), methylene bis(orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), iso-
propylidene bis(orthocresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylben-
zene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2,-tetra(4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybi-
10 sphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin
novolac, bisphenol A novolac, bisphenol F novolac and terpene diphenol; polyglycidyl ether compounds of ethylene
oxides and/or propylene oxides adducts of mononuclear polyhydric phenol compounds or polynuclear polyhydric phenol
compounds as described above; polyglycidyl ether compounds of hydrogenated additives of mononuclear polyhydric
phenol compounds as described above; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene
15 glycol, butylene glycol, hexane diol, polyglycol, thiodiglycol, glycerin, trimethylol propane, pentaerythritol, sorbitol and
bisphenol A-ethylene oxide adduct; monopolymers and copolymers of glycidyl esters of fatty, aromatic and aliphatic
polybasic acids and glycidyl methacrylate such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid,
suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic
acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylene
20 tetrahydrophthalic acid; epoxy compounds having glycidyl amino groups such as N,N-diglycidyl aniline and bis(4-(N-
methyl-N-glycidylamino)phenyl) methane; epoxy compounds of cyclic olefin compounds such as vinylcyclohexene die-
poxide, dicyclopentadiene epoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-meth-
ylcyclohexylmethyl-6-methylcyclohexane carboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxy-
dized conjugated diene polymers such as epoxydized polybutadiene and epoxydized styrene-butadiene copolymers
25 and heterocyclic compounds such as triglycidyl isocyanurate. Epoxy resins as listed above may be internally cross-
linked by terminal isocyanate prepolymers.
[0061] Of the above-listed epoxy resins, the use of bisphenol-type epoxy resins such as polyglycidyl ether compounds
including bisphenol, methylene bisphenol (bisphenol F), methylene bis(orthocresol), ethylidene bisphenol (bisphenol
AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis(orthocresol), tetrabromobisphenol A, 1,3-bis(4-hydrox-
30 ycumylbenzen) and 1,4-bis(4-hydroxycumylbenzen) is preferable to obtain paint film that is excellent in terms of adhe-
siveness and decorativeness.
[0062] (i) Epoxy polyol resins (b-1-4) having a hydroxyl value of 40 to 330 mgKOH/g can be obtained by way of a
reaction of the epoxy groups of any of the above-listed epoxy resins and an active hydrogen compound such as a
carboxylic acid compound, a polyol or an amino compound.
35 [0063] Examples of the carboxylic acid compounds include fatty, aromatic and alicyclic ring monocarboxylic acids
such as acetic acid, propionic acid, 2,2-dimethylol propionic acid, 1,2-hydroxy stearic acid, lactic acid, butyric acid, octylic
acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenylacetic acid as well as cyclohexane
carboxylic acid; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid,
isophthalic acid, terephthalic acid, hexahydric acid and hydroxypolycarboxylic acid.
40 [0064] Examples of polyols as described above include low-molecular polyols such as ethylene glycol, diethylene
glycol, 1,2-propylene glycol, 1,3-popylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-
butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-
hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecan-
ediol, glycerin, trimethylolpropane and pentaerythritol.
45 [0065] Examples of amino compounds as described above include dialkyl amine compounds such as dibutyl amine
and dioctyl amine; alkanol amine compounds such as methylethanol amine, butylethanol amine, diethanol amine, di-
isopropanol amine and dimethylaminopropylethanol amine; and heterocyclic amine compounds such as morpholine,
piperidine and 4-methylpiperidine.
[0066] Among the above-listed active hydrogen compounds, alkanol amine compounds such as dimethanol amine
50 are preferable.
[0067] Additionally, epoxy resin chains can be extended by means of a compound having two or more active hydrogen
groups such as monoethanol amine and monoisopropanol amine.
[0068] When causing epoxy resin to react with an active hydrogen compound, known ordinary methods of adding an
active hydrogen compound to the epoxy resin can be adopted. For example, a method of causing them to react with
55 each other by heating to 60 to 200°C for 3 to 10 hours in the presence of a known catalyst such as a tertiary amine
compound or a phosphonium salt can be employed.
[0069] (i) Epoxy polyol resins (b-1-4) having a hydroxyl value of 40 to 330 mgKOH/g, preferably have a hydroxyl value
between 100 and 140 mgKOH/g from the viewpoint of the advantages of the present invention.

12
 EP 2 578 650 A1

[0070] Examples of (i) epoxy polyol resins (b-1-4) having a hydroxyl value of 40 to 330 mgKOH/g include EPICLON
U-125-60BT (hydroxyl value: 100 to 140 mgKOH/g) available from DIC Co., Ltd.
[0071] Polyols (b-2) having (i) a hydroxyl value of 40 to 330 mgKOH/g and (ii) an acid value of 2 to 20 mgKOH/g will
be described below.
5 [0072] As polyols (b-2) having (i) a hydroxyl value of 40 to 330 mgKOH/g and (ii) an acid value of 2 to 20 mgKOH/g,
aromatic based, aliphatic based and castor oil-based polyols show an improved selective adhesive force (an improved
adhesive force between different materials in particular) relative to the adherend (soft or hard vinyl chloride resin; poly-
styrene; polycarbonate; glass; aluminum; steel plate; copolymer of polyolefin resin modified by a polar group-containing
compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer;
10 polyester-based resin; or acryl-based resin) is characterized of the present invention, if they satisfy both the hydroxyl
value requirement of (i) and the acid value requirement of (ii). The hydroxyl value of (i) is more preferably 230 to 300
mgKOH/g. The acid value of (ii) is more preferably 4 to 15 mgKOH/g.
[0073] If both the requirement of (i) and that of (ii) are satisfied, examples of polyols (b-2) having (i) a hydroxyl value
of 40 to 330 mgKOH/g and (ii) an acid value of 2 to 20 mgKOH/g include: castor oil based polyols (b-2-1) having (i) a
15 hydroxyl value of 40 to 330 mgKOH/g and (ii) an acid value of 2 to 20 mgKOH/g.
[0074] Castor oil-based polyols (b-2-1) having (i) a hydroxyl value of 40 to 330 mgKOH/g and (ii) an acid value of 2
to 20 mgKOH/g are polyols derived from castor oil. For example, a polyol composition containing a castor oil-based
polyol derived from ricinoleic acid, an acid phosphate ester compound having a total number of carbon atoms of not
less than 12 and, if necessary, a terpene phenol as disclosed in Japanese Patent Application Laid-Open Publication
20 No. 2005-89712 can be used. Such compositions are available from Itoh Oil Chemicals Co., Ltd. under the trade names
of URIC H-1262, H2151U.
[0075] The above-cited URIC H-1262 that is available from Itoh Oil Chemicals Co., Ltd. is a polyol (viscosity: 3,500
to 8,500 mPa · s/25°C, hydroxyl value: 240 to 290 (unit mgKOH/g), acid value: 4 to 15 (unit mgKOH/g)) containing a
castor oil-based polyol and an acid phosphate ester compound having a total number of carbon atoms of not less than
25 12. It shows an excellent adhesiveness relative to the layer of soft or hard vinyl chloride resin; polystyrene; polycarbonate;
glass; aluminum; steel plate; copolymer of polyolefin resin modified by a polar group-containing compound or olefin and
a polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin; or
acryl-based resin; particularly in terms of adhesiveness to metals and hydrolysis resistance. The above-cited URIC H-
2151U that is also available from Itoh Oil Chemicals Co., Ltd. is a polyol (viscosity: 3,500 to 8,500 mPa · s/25°C, hydroxyl
30 value: 240 to 290 (unit mgKOH/g), acid value: 4 to 15 (unit mgKOH/g)) containing a castor oil-based polyol, an acid
phosphate ester compound having a total number of carbon atoms of not less than 12 and a terpene phenol. It shows
an excellent adhesiveness relative to the layer of soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass;
aluminum; steel plate; copolymer of polyolefin resin modified by a polar group-containing compound or olefin and a polar
group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin; or acryl-
35 based resin, particularly in terms of adhesiveness to metals and hydrolysis resistance.
[0076] Now, modified rubbers (b-3) will be described below.
Examples of modified rubbers (b-3) that can be used for the present invention include (b-3-1) liquid carboxylated polyiso-
prene and (b-3-2) carboxylated polybutadiene.

40 (b-3-1) carboxylated polyisoprene

[0077] Carboxylated polyisoprene (b-3-1) that can be used for the present invention has a functional feature of boosting
the wettability of the surface of the substrate and improving the adhesiveness when an adhesive composition according
to the present invention is bonded to a metal substrate or a glass substrate.
45 Examples of component (b-3-1) include as maleated polyisoprene available from Kuraray under the trade name of LIR-
420.

(b-3-2) carboxylated polybutadiene

50 [0078] Carboxylated polybutadiene (b) that can be used for the present invention has a functional feature of boosting
the wettability of the surface of the substrate and improving the adhesiveness when an adhesive composition according
to the present invention is bonded to a metal substrate or a glass substrate.
Component (b-3-2) is a polymer that is transparent liquid at room temperature and has a micro structure consisting of
vinyl 1,2-bond type, trans 1,4-bond type and cis 1,4-bond type in the main chain of polybutadiene. The vinyl 1,2-bond
55 is preferably not more than 30 wt%. The achieved storage stability of the adhesive component is degraded and hence
not preferable when the vinyl 1,2-bond exceeds 30 wt%. The cis 1,4-bonds are preferably not less than 40 wt%. The
achieved adhesiveness falls and is not preferable when the cis 1,4-bonds are less than 40 wt%.
[0079] Component (b-3-2) of carboxylated polybutadiene can be obtained by causing liquid polybutadiene to react

13
 EP 2 578 650 A1

with a carboxyl group-introduced compound and the ratio of 1, 3-butadiene from which the liquid polybutadiene is formed
and that of the carboxyl group-introduced compound is preferably such that 1,3-butadiene takes and the carboxyl group-
introduced compound respectively take 80 to 98 wt% and 2 to 20 wt%.
[0080] Liquid polybutadiene to be used for the reaction has a number-average molecular weight of preferably 500 to
5 10,000, more preferably 1,000 to 7,000 and desirably shows a broad molecular weight distribution. Preferably, such
liquid polybutadiene has an iodine value of iodine 30 to 500 g/substance 100 g as observed by a method conforming to
DIN 53241. In addition, such liquid polybutadiene preferably has a molecular structure where cis-double bonds take 70
to 90%, trans-double bonds take 10 to 30% and vinyl double bonds take 0 to 3%.
[0081] Examples of carboxyl group-introduced compounds that can be used for the present invention include ethyl-
10 ene-based unsaturated carboxyl compounds such as ethylene-based unsaturated dicarboxylic acid and anhydrides and
monoesters thereof. Specific examples include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid,
itaconic anhydride, 1,2-dimethyl maleic anhydride, maleic monomethyl ester and maleic monoethyl ester, of which maleic
anhydride is preferable from the viewpoint of safety, economy and reactivity. (Maleated polybutadiene is preferable).
[0082] Polybutadiene/maleic anhydride-adducts formed from polybutadiene and maleic anhydride can be manufac-
15 tured by means of any known method.
[0083] The acid value of maleated liquid polybutadiene is preferably between 50 and 120 (mgKOH/g), more preferably
between 70 and 90 (mgKOH/g) as observed by a method conforming to DIN ISO 3682. The adhesiveness of the adhesive
compound falls when the acid value is less than 50 (mgKOH/g), whereas the viscosity thereof rises to damage the
working property thereof when the acid value exceeds 120 (mgKOH/g).
20 [0084] In view of the trade off between the percentage of maleation and the viscosity of maleated liquid polybutadiene,
the percentage is preferably between 6 and 20%, more preferably between 6 and 15%, most preferably between 7 and
10%.
[0085] The viscosity (20°C) of maleated liquid polybutadiene is preferably between 3 and 16 Pa · s, more preferably
between 5 and 13 Pa · s, most preferably between 6 and 9 Pa · s, as observed by a method conforming to DIN 53214.
25 [0086] Maleated liquid polybutadiene of which the vinyl-double bonds are not more than 30% and the cis double bonds
are within the above cited range shows a higher flexibility and a high percentage of maleation (acid value) as described
above if compared with liquid polybutadiene whose cis-double bonds fall below the above-described lower limit. Thus,
adhesive compound obtained from such maleated liquid polybutadiene show a high adhesiveness and well polar is
provided. The adhesive composition according to the present invention, that is excellent in terms of flexible, flexibility
30 and decorativeness.
The viscosity of liquid polybutadiene whose cis-double bonds fall below the above-described lower limit suddenly rises
as the percentage of maleation rises, whereas the viscosity of liquid polybutadiene whose cis-double bonds are found
within the above range does not show such a sudden rise. Because the viscosity of such liquid polybutadiene is found
within the above range and hence low, it can provide a high reactivity and an improved working property. Additionally,
35 adhesive composition obtained from such liquid polybutadiene are excellent in terms of decorativeness.
[0087] Examples of commercially available maleated liquid polybutadiene include POLYVEST OC 800S and 1200S
(trade names) available from Evonik Degussa Corporation.
[0088] Now, compounds (b-4) having an epoxy equivalent of 150 to 700 g/mol will be described below.
[0089] Compounds (b-4) having an epoxy equivalent of 150 to 700 g/mol that can be used for the present invention
40 include polyepoxy compounds (b-4-1) having an epoxy equivalent of 150 to 250 g/mol.
[0090] With the composition according to the present invention, examples of polyepoxy compounds (d-4-1) having an
epoxy equivalent of 150 to 250 g/mol include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds
such as hydroquinone, resorcin, pyrocatechol and phloroglucinol; polyglycidyl ether compounds of polynuclear polyhydric
phenol compounds such as dihydroxy naphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(ortho-
45 cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(orthocresol), tetrabromo bi-
sphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane,
1,1,2,2,-tetra(4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novol-
ac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpene phenol; polyglycidyl
ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexane diol, polyglycol, thiod-
50 iglycol, glycerin, trimethylol propane, pentaerythritol, sorbitol and bisphenol A-ethylene oxide adduct; monopolymers
and copolymers of glycidyl esters of fatty, aromatic and aliphatic polybasic acids and glycidyl methacrylate such as
maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid,
dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid,
tetrahydrophthalic acid, hexahydrophthalic acid and endomethylene tetrahydrophthalic acid; epoxy compounds having
55 glycidyl amino groups such as N,N-diglycidyl aniline and bis(4-(N-methyl-N-glycidylamino)phenyl) methane and diglycidyl
orthotoluidine; epoxy compounds of cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentadiene
diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-
methylcyclohexane carboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxydized conjugated diene

14
 EP 2 578 650 A1

polymers such as epoxydized polybutadiene and epoxydized styrene-butadiene copolymers; and heterocyclic com-
pounds such as triglycidyl isocyanurate.
[0091] Examples of epoxy compounds having an epoxy equivalent of 150 to 250 g/mol (b-4-1) to be used for the
present invention, the use bisphenol-type epoxy resins such as polyglycidyl ethers of bisphenol compounds include
5 biphenol, methylene bisphenol (bisphenol F), methylene bis(orthocresol), ethylidene bisphenol, isopropylidene bisphenol
(bisphenol A), isopropylidene bis(orthocresol), tetrabromo bisphenol A, 1,3-bis(4-hydroxycumylbenzen), 1,9-bis(4-hy-
droxycumylbenzen), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2,-tetra(4-hydroxyphenyl) ethane, thiobisphenol, sulfobi-
sphenol, oxybisphenol and terpene diphenol is preferable to obtain paint film that is more preferable in terms of metal
adhesiveness.
10 [0092] Examples of commercially available products of polyglycidyl ethers of bisphenol compounds having an epoxy
equivalent of 150 to 250 g/mol include Adeka Resin EP-4100E (available from ASAHI DENKA KOGYO KK, bisphenol
A diglycidyl ether, epoxy equivalent: 190).
[0093] Compounds (b-4) having an epoxy equivalent of 150 to 700 g/mol that can be used for the present invention
also include polyolefin-based polymers (b-4-2) having an epoxy equivalent of 500 to 700 g/mol. Of such polyolefin-based
15 polymers, those that have a hydroxyl group at one terminal and into which epoxy groups are introduced are preferable.
Of such preferable polymers those that are liquid are more preferable.
[0094] Examples of commercially available polymers (b-4) having an epoxy equivalent of 150 to 700 g/mol that can
be used for the present invention include L-207 (KRATON LIQUID (trade name) also named as L-207 POLYMER)
available from Kuraray. L-207 is a polymer having an epoxy equivalent of 590 g/mol, a hydroxyl equivalent of 7,000
20 g/mol and a glass transition temperature of -53°C with a completely saturated skeleton (epoxidized ethylene · propylene-
ethylene · butylene-OH structure). The use of this polymer is preferable in terms of adhesiveness to metal.
[0095] Now, fluorine-based resins (b-5) will be described below.
Fluorine-based resins (b-5) that can be used for the present invention are above all fluorine-based resins having an
hydroxyl value between 40 and 330 mgKOH/g.
25 Such a fluorine-based resin can appropriately be selected from polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF),
polychloro trifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), polytetrafluoroethylene (PTFE),
tetrafluoroethylene perfluoroalkyl vinylether copolymer (PFA), tetrafluoroethylene hexafluoropropylene copolymer (FEP),
chlorotrifluoroethylene · ethylene copolymer (ECTFE), fluoroolefin · vinyl ether copolymer or acrylic modified products
of any of them.
30 [0096] In particular, examples of solvent-soluble type fluorine resins include copolymers of fluoroolefins and hydro-
carbon-based monomers such as vinyl ethers and vinyl esters. Thus, fluorine-containing polymers having a reactive
group such as a hydroxyl group, a carboxylic group, a hydrolytic silyl group or an epoxy group can be employed. Examples
of fluorine-containing polymers include copolymers of chlorotrifluoroethylene, cyclohexyl vinyl ether, alkyl vinyl ether
and hydroxyalkyl vinyl ether; copolymers of chlorotrifluoroethylene, alkylvinyl ether and aryl alcohol and copolymers of
35 chlorotrifluoroethylene, aliphatic carboxylic acid vinyl ester, hydroxylalkyl vinyl ester. Such copolymers are commercially
available typically under the trade names of Lumiflon (Asahi Glass Co., Ltd.) and Cefral Coat (Central Glass Co. , Ltd.).
Examples of such products include Lumiflon LF-550, LF-552, LF-554, LF-600, LF-601, LF-602, LF-100, LF-200, LF-
302, LF-400, LF-700, LF-916 and LF-936.
[0097] Of the above-listed copolymers, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVC), chlorotrifluoroethylene
40 · ethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE) and fluoroolefin · vinyl ether copolymer are preferable
and polyvinylidene fluoride (PVDF) and fluoroolefin · vinyl ether copolymer are more preferable from the viewpoint of
solvent solubility and adhesiveness relative to various substrates including substrates of glass, polycarbonate based
resins, polyester based resins, cellulose based resins, liquid crystal polymers and ethylene-vinyl acetate copolymers (to
be also referred to specific substrates hereinafter)and particularly EVA adhesiveness.
45 [0098] (b-5) fluorine-based resins can provide compositions with various properties such as heat resistance, cold
resistance, chemical resistance, flame retardancy, electric characteristics, low friction, non-viscosity, weather resistance,
UV protection and low refractivity.

Component (c) a vinyl monomer and/or a (meth)acrylate monomer

50
[0099] The component (c) of a paint and an adhesive composition according to the present invention is a vinyl monomer
and/or a (meth) acrylate monomer. Specific examples of such monomers include trimethylolpropane tri(meth)acrylate,
pentaerythritol tri(meth)acrylate, ethyleneglycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene gly-
col di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentylglycol di(meth)acrylate,
55 trimethylolpropane trioxyethyl (meth)acrylate, tris(2-hydroxyethyl) isocyanulate tri(meth)acrylate, tris(2-hydroxyethyl) iso-
cyanulate di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate.
[0100] Other examples include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl
(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)

15
 EP 2 578 650 A1

acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acr-
ylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acr-
ylate, nolyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate,
lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acr-
5 ylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethylene glycol mono(meth)
acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethoxy ethyl (meth)
acrylate, methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, dicyclopentadiene
(meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl
(meth)acrylate, bornyl (meth)acrylate, diacetone (meth)acrylate, isobutoxymethyl (meth)acrylamide, N-vinyl pyrrolidone,
10 N-vinyl caprolactam, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dimethylamino ethyl (meth)acrylate, di-
ethylamino ethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl (meth)acrylamide, N,N-dimeth-
ylaminopropyl (meth)acrylamide, (meth)acryloyl morphorine and vinyl ethers such as hydroxylbutyl vinyl ether, laurylvinyl
ether, cetylvinyl ether and 2-ethyl hexylvinyl ether.
[0101] The component (c) vinyl that is a vinyl monomer and/or a (meth)acrylate monomer of a paint and an adhesive
15 composition according to the present invention is preferably at least one item selected from compounds (c-1) having a
ring structure and an ethylenically unsaturated group and compounds (c-2) having no ring structure and having an
ethylenically unsaturated group, more preferably the compound (c-1) and the compound (c-2) in combination from the
viewpoint of high hardness revealing property, quick dryability, adhesiveness, non-yellowing property and low-viscosity
revealing property.
20 [0102] (c-1) The component (c-1) having a ring structure and an ethylenically unsaturated group that is to be used for
the present invention is a compound having a ring structure and an ethyelenically unsaturated group. Examples of
component compounds (c-1) include alicyclic structure-containing (meth)acrylates such as isobornyl (meth)acrylate,
bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate and dicyclopentanyl (meth)acrylate; benzyl (meth)acrylate, 4-butyl
cyclohexyl (meth)acrylate, acryloyl morpholine, vinyl imidazole and vinyl pyridine. Further more they include compounds
25 expressed by any of formulas (1) through (3) shown below.
[0103]

30

35

40

45

[0104] (where R2 represents a hydrogen atom or a methyl group and R3 represents an alkylene group with a carbon
number between 2 and 8, preferably between 2 and 5, while R4 represents a hydrogen atom or a methyl group and p
50 preferably represents a number between 1 and 4.)
[0105]

55

16
 EP 2 578 650 A1

10

[0106] (where R5, R6, R7 and R8 are independent from each other and H or CH3 and q is an integer between 1 and 5.)
15 [0107] When (c-1) and (c-2) are used in combination, the compounding ratio thereof is 80 to 20 parts by mass, preferably
75 to 25 parts by mass, for (c-1) and 20 to 80 parts by mass, preferably 25 to 75 parts by mass, for (c-2), provided that
(c-1) + (c-2) = 100 parts by mass. When the component (c-1) and (c-2) are used in combination with the above parts,
a pant and an adhesive composition according to the present invention excellently show scratch resistance, flexibility
and pencil hardness and hence can also be used for surface of hard coat layers. They are excellent in terms of pencil
20 hardness, flexibility and abrasion resistance and hence can be used for hard coats depending on applications when
urethane (meth) acrylate is used as component (a) in combination with components (c-1) and (c-2) with the above ratios.
[0108] When a cycloalkene or an alicyclic vinyl compound is used as component (c) in a paint and an adhesive
composition according to the present invention, the layer (A) of the paint or the adhesive composition becomes a hard
coat. Therefore, the paint or the adhesive composition preferably contains such a compound if it is for an application
25 where it desirably becomes a hard coat, whereas it preferably does not contain such a compound if it is for an application
where it desirably does not become a hard coat. Examples of cycloalkenes that can be used for the present invention
include cyclobutene, cyclopentene, cycloheptene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene,
1,5-cyclooctadiene and cyclooctene. The carbon number of such cycloalkenes is typically between 4 and 20. Cyclopen-
tadiene-based monomers can also be used for component (c). Cyclopentadiene-based monomers include cyclopenta-
30 diene and substitution derivatives thereof. Such substitution derivatives include alkyl substituted derivatives, alkylidene-
substituted derivatives and derivatives obtained by aromatic substitution. Such substitution derivatives may contain a
polar group such as a halogen, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an
imide group or a silyl group. The carbon number of cyclopentadiene monomers that can be used for the present invention
is typically between 4 and 20. Specific examples of such cyclopentadiene include dicyclopentadiene, 2-methyl dicy-
35 clopentadiene, 2-ethyl dicyclopentadiene, 5-methyl dicyclopentadiene, 5,5-dimethyl dicyclopentadiene and 2,3-dihydro
dicyclopentadiene. Examples of alicyclic vinyl compounds include cycloalkene vinyl compounds and cycloalkane viny
compounds. Cycloalkene vinyl compounds that can be used for the present invention typically have an aliphatic ring
having a double bond with a carbon member between 5 and 8 and also include a polymerizable vinyl group. The aliphatic
ring may have an alkyl group with a carbon number between 1 and 4 or a halogen atom as substituent group. Examples
40 of cycloalkene vinyl compounds include cyclopentene vinyl compounds such as 2-vinyl cyclopentene, 2-methyl-4-vi-
nylpentene, 3-vinylcyclopentene, 3-t-butyl-4-vinyl pentene; cyclohexene vinyl compounds such as 4-vinyl cyclohexene,
4-isopropenylvinyl cyclohexene, 1-methyl-4-vinyl cyclohexene, 1-methyl-4-isopropenylvinyl cyclohexene, 2-methyl-4-
vinyl cyclohexene, 2-methyl-4-isopropenyl vinyl cyclohexene; and cycloheptene vinyl compounds such as 2-vinyl cy-
cloheptene, 3-vinyl cycloheptene, 4-vinyl cycloheptene, 3-methyl-6-vinyl cycloheptene, 4-ethyl-6-vinyl cycloheptene and
45 3-t-butyl-5-vinyl cycloheptene; and cyclooctene vinyl compounds such as 2-vinyl cyclooctene, 3-vinyl cyclooctene, 4-
vinyl cyclooctene, 2-methyl-5-vinyl cyclooctene, 4-ethyl-6-vinyl cyclooctene and 3-t-butyl-7-vinyl cyclooctene. The cy-
cloalkene vinyl compounds having a (meth)acryloyl group for a vinyl bond can be used for the present invention. Cyclo-
alkane vinyl compounds having a saturated aliphatic ring with a carbon number between 5 and 8 and a polymerizable
vinyl group can be used for the present invention. Such aliphatic rings can have an alkyl group with a carbon number
50 between 1 and 4 or a halogen atom as substituent group. Examples of cycloalkane vinyl compounds include cyclopentane
vinyl compounds such as 2-vinyl cyclopentane, 2-methyl-4-vinyl pentane, 3-vinyl cyclopentane and 3-t-butyl-4-vinyl
pentane; cyclohexane vinyl compounds such as 4-vinyl cyclohexane, 4-isopropenyl vinyl cyclohexane, 1-methyl-4-vinyl
cyclohexane, 1-methyl-4-isopropenyl vinyl cyclohexane, 2-methyl-4-vinyl cyclohexane, 2-methyl-4-isopropenyl vinyl cy-
clohexane; cycloheptane vinyl compounds such as 2-vinyl cycloheptane, 3-vinyl cycloheptane, 4-vinyl cycloheptane, 3-
55 methyl-6-vinyl cycloheptane, 4-ethyl-6-vinyl cycloheptane and 3-t-butyl-5-vinyl cycloheptane; cyclooctane vinyl com-
pounds typically having a saturated aliphatic ring with a carbon number between 5 and 8 such as 2-vinyl cyclooctane,
3-vinyl cyclooctane, 4-vinyl cyclooctane, 2-methyl-5-vinyl cyclooctane, 4-ethyl-6-vinyl cyclooctane and 3-t-butyl-7-vinyl
cyclooctane and cycloalkane vinyl ether compounds such as 1,4-cyclohexane dimethanol divinyl ether, cyclopentane

17
 EP 2 578 650 A1

vinyl ether, cyclohexane vinyl ether, cycloheptane vinyl ether, cyclooxane vinyl ether, 4-methyl cyclohexyl vinyl ether
and cyclohexyl methyl vinyl ether. The cycloalkene vinyl compounds having a (meth)acryloyl group for a vinyl bond can
be used for the present invention.

5 (d) Initiator

[0109] A paint and an adhesive composition according to the present invention require (d) an initiator as indispensable
component.
[0110] Since the oligomer component (e.g., a vinyl ester resin or unsaturated polyester resin (a)) of a paint and an
10 adhesive composition according to the present invention has a double bond such as (meth) acryloyl group, they can be
cured with ease in a short period of time by heating, adding a thermal polymerization initiator, or by UV radiation or
electron beam radiation using an UV fluorescent lamp or a high-pressure mercury lamp, adding a photopolymerization
initiator. The use of UV radiation is preferable if heating an adherend and an adhesive composition is desirably to be
avoided.
15 [0111] When a paint and an adhesive composition according to the present invention are cured by heating, they can
be cured by heating them at temperature between room temperature and about 90°C. Examples of thermal polymerization
initiators that can be used for the present invention include benzoyl peroxide, lauryoyl peroxide, succinic peroxide,
methylethylketone peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and cyclohexanone peroxide. If the half life
temperatures (1 min.) of peroxides are between 100°C and 180°C, a satisfactory degree of hardness can be achieved
20 by 80°C x 10 minutes to 160°C 3 5 minutes.
[0112] Examples of photopolymerization initiators that can be used for the present invention include benzophenone,
2,4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, acetophenone, benzoin, benzoinethyl ether, ben-
zoin-n-propyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzyl-1-(4-isopropylphenyl)-
2-hydroxy-2-methylpropane-1-on, 2-hydroxy-2-methyl 1-phenylpropane-1-on, benzyl sulfide, thioxanthone, bis(2,4,6-
25 trimethylbenzoyl)-phenylphosphine oxide and 2-chloro thioxanthone.

(Compounding ratio of paint and that of adhesive composition)

[0113] In a paint and an adhesive composition according to the present invention, the component (a) is compounded
30 by 20 to 40 mass% with the other components from the viewpoint of adhesiveness, flexibility and shock resistance. More
preferably, the component (a) is compounded by 25 to 35 mass% from the viewpoint of easily workable viscosity. The
adhesiveness of a paint and an adhesive composition according to the present invention is degraded and the workability
thereof falls due to an increased viscosity when the compounding ratio of the component (a) exceeds 40 mass%. On
the other hand, when the compounding ratio of the component (a) is not more than 20 mass%, is degraded the adhe-
35 siveness, flexibility and shock resistance thereof relative to a layer of soft or hard vinyl chloride resin; polystyrene;
polycarbonate; glass; aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer
of polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing compound;
magnesium; acrylonitrile-butadiene-styrene copolymer; polyester-based resin; polyurethane-based resin; epoxy-based
resin or acryl-based resin.
40 [0114] In a paint and an adhesive composition according to the present invention, the component (b) is compounded
by 0.1 to 50 mass% with the other components from the viewpoint of adhesiveness and flexibility. The component (b)
is compounded more preferably by 10 to 30 mass% and most preferably by 10 to 25 mass% from the viewpoint of
adhesiveness, toughness (shock resistance) and bleed resistance. The bleed resistance of a paint and an adhesive
composition according to the present invention is degraded to by turn reduce the toughness (shock resistance) and the
45 adhesive force thereof when the compounding ratio of the component (b) exceeds 50 mass%. On the other hand, the
adhesiveness, the flexibility and the shock resistance falls when the compounding ratio thereof is less than 0.1 mass%.
[0115] In a paint and an adhesive composition according to the present invention, the component (c) is compounded
by 30 to 70 mass% with the other components from the viewpoint of adhesiveness, flexibility and shock resistance. The
component (c) is compounded more preferably by 40 to 65 mass% from the viewpoint of workable viscosity. The adhe-
50 siveness, the flexibility and the shock resistance of a paint and an adhesive composition according to the present invention
falls when the compounding ratio of the component (c) exceeds 70 mass%. On the other hand, the adhesiveness, the
flexibility and the shock resistance thereof are degraded and the workability thereof falls due to an increased viscosity
when the compounding ratio of the component (c) is less than 30 mass%.
[0116] In a paint and an adhesive composition according to the present invention, the component (d) is compounded
55 by 0.1 to 15 parts by mass with a total of 100 parts by mass of the components (a) through (c) from the viewpoint of
practical photocuring time (not longer than 10 seconds with a radiation intensity of 500 mJ/cm2). The component (d) is
compounded more preferably by 1 to 10 parts by mass, most preferably by 2 to 5 parts by mass, from the viewpoint of
practical photocuring time (not longer than 3 seconds with a radiation intensity of 500 mJ/cm2).

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The flexibility, the adhesiveness and the shock resistance of a paint and an adhesive composition according to the
present invention falls when the compounding ratio of the component (d) exceeds 15 parts by mass. On the other hand,
the adhesiveness thereof is unsatisfactory because of an insufficient degree of photocuring when the compounding ratio
of the component (d) is less than 0.1 parts by mass. When the photopolymerization initiator is used, the amount thereof
5 to be compounded with may be the same as described above.
[0117] If necessary, a functional filler or the like as filler that is popularly being used can be added and compounded
to a paint and an adhesive composition according to the present invention to such an extent that it does not adversely
affect achieving the object of the present invention.
[0118] Examples of materials that can be used for the purpose of imparting rigidity include talc and mica, which may
10 be used alone or in combination.
[0119] Examples of materials that can be used for the purpose of imparting thermal conductivity include barium sulfide
and magnesium oxide, any one of which may be used alone or any two or more of which may be used in combination.
[0120] Examples of materials that can be used for the purpose of imparting thermal expandability include thermally
expandable microcapsules. Examples of materials that can be used for the purpose of imparting a leveling effect include
15 silicone-based leveling agents.
[0121] The recommended viscosity at 25°C of a paint and an adhesive composition according to the present invention
is not more than 3, 000 mPa·s, more preferably between 100 and 2,000 mPa·s, although the viscosity is by no means
limited by such values. No component separation will take place with time and a reliable storage stability and a surface
smoothness that is practically free from air bubbles can be obtained when the viscosity is found within the above range.
20 The viscosity can be observed by means of a B-type viscometer.
[0122] At least one item selected from a group of metal oxides, metal salts, surface active agents and ionic liquids
can be compounded as antistatic material with a paint according to the present invention. Examples of metal oxides and
metal salts that can be used for this purpose include at least one item selected from a group of zinc oxide, aluminum
doped zinc oxide, gallium doped zinc oxide, ATO, ITO, tin oxide, antimony pentoxide, zirconium oxide, titanium oxide
25 and aluminum oxide.
An ionic liquid (e) is a salt in the liquid state that contains cations and anions. Examples of ionic liquids (e) that can be
used for the present invention include at least one item containing of cation and selected from a group of imidazolium,
pyridinium, pyrrolidinium, phosphonium, ammonium and sulfonium. Examples of cations are listed below.
[0123]
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[0129] Ionic liquids (e) that can be used for the present invention preferably contain anions selected from a group of
halogens, carboxylates, sulfates, sulfonates, thiocyanates, aluminates, borates, phosphates, phosphinates, amides,
antimonates, imides and methides. Examples of anions are listed below.
[0130]
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[0136] The ionic liquids that can be used for the present invention are preferably water soluble.
20 Examples of preferable ionic liquids that can be used for the purpose of the present invention include those having an
ion pair selected from (1-1) and (10-1), (1-1) and (10-4), (1-1) and (11-1), (1-2) and (8-3), (1-2) and (10-1), (1-2) and
(10-2), (1-2) and (10-4), (1-2) and (11-1), (1-6) and (7-11), (1-6) and (8-3), (1-6) and (8-5), (1-6) and (8-6), (1-6) and
(9-1), (1-6) and (9-2), (1-6) and (9-3), (1-6) and (10-1), (1-6) and (10-4), (1-6) and (10-7), (1-6) and (11-1), (1-6) and
(12-5), (1-6) and (12-6), (1-8) and (8-2), (1-8) and (8-5), (1-8) and (8-6), (1-8) and (9-1), (1-8) and (10-4), (1-12) and
25 (10-4), (1-13) and (10-4), (1-17) and (10-4), (2-1) and (9-1), (2-1) and (9-2), (3-1) and (8-2), (3-1) and (8-3), (3-1) and
(11-1), (3-5) and (8-3), (3-6) and (10-4), (3-8) and (9-2), (5-8) and (12-5) and (5-9) and (10-4) as combination of cation
and anion, of which ionic liquids having an ion pair selected from (1-2) and (8-3), (1-2) and (10-1) and (1-2) and (10-2)
are more preferable from the viewpoint of the advantage of the present invention (of providing both a strong adhesiveness
and an excellent antistatic effect relative to a substrate (B)). Particularly, an ionic liquid having an ion pair of (1-2) and
30 (8-3) is preferable in terms of strong adhesiveness and excellent antistatic effect relative to a substrate (B).
[0137] Any types of surface active agents including anionic, nonionic, cationic and amphoteric surface-active agents
can non-limitatively be used for the present invention. Typical examples of anionic surface active agents include alkylaryl
sulfonates, soaps such as sodium salts, potassium salts and triethanolamine salts of various fatty acids, salts and esters
of sulfuric acid such as alkyl sulfate salts and alkylpolyoxyalkyleneether sulfate salts, phosphate such as alkyl phosphate,
35 alkylaryl phosphate, alkylarylpolyoxyalkyleneether phosphate and alkylarylpolyoxyalkyleneether phosphate and polys-
oaps such as polystyrene sulfonate salts and sodium polyacrylate, any one of which may be used alone or any two or
more of which may be used in combination.
[0138] Typical examples of nonionic surface active agents include fatty acid esters such as sorbitan-fatty acid esters,
polyoxy ethylene sorbitan-fatty acid esters, glycerin-fatty acid esters, diglycerin-fatty acid esters, triglycerin-fatty acid
40 esters, tetraglycerin-fatty acid esters, pentaglycerin-fatty acid esters, hexaglycerin-fatty acid esters, ethylene glycol-fatty
acid esters, polyoxy ethylene glycol-fatty acid esters, sucrose-fatty acid esters and di(glycerin) borate-fatty acid esters,
polyethers such as alkyl polyoxy alkylene ether, alkyl aryl polyoxy alkylene ether, polyoxy ethylene glycol·polyoxy pro-
pylene glycol block copolymers, tertiarization amines such as N,N-di(polyoxyalkylene) alkyl amines, N, N, N’, N’ -tetra
(polyoxyalkylene) ethylene diamines and amides such as fatty acid monoalkylol amides and fatty acid dialkylol amides,
45 any one of which may be used alone or any two or more of which may be used in combination.
[0139] Typical examples of cationic surface active agents include quaternary ammonium salts such as tetraalkyl
ammonium salts, trialkyl (β-hydroxyalkyl) ammonium salts and dialkyl di(polyoxyalkylene) ammonium salts, any one of
which may be used alone or any two or more of which may be used in combination. Typically examples of amphoteric
surface-active agents include betaines such as trialkyl betaines and alkylimidazoline betaines and phospholipids such
50 as lecithin, any one of which may be used alone or any two or more of which may be used in combination.
[0140] One or more desired functionalities can be imparted to a paint and an adhesive composition according to the
present invention by compounding one or more functional materials with the remaining components. In such an instance,
a paint and an adhesive composition according to the present invention operate as binder or vehicle for making the
functional materials exert the intended effects. Examples of functional materials that can be used for the present invention
55 include IR absorbing materials, UV absorbing materials, antistatic materials and electromagnetic shielding materials.
Examples of IR absorbing materials include carbon nanotubes, zinc oxide, aluminum doped zinc oxide, gallium doped
zinc oxide, cesium-containing tungsten oxide, ATO (antimony tin complex oxide or antimony doped tin oxide) and ITO
(indium tin complex oxide). The compounding ratio of an IR absorbing material can be determined by referring to the

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desired IR absorbability but may typically be within a range between 0.1 and 30 mass% of a paint and an adhesive
composition according to the present invention. Examples of UV absorbing materials include salicylate-based, benzo-
phenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based organic compounds and inor-
ganic compounds such as hybrid inorganic particles obtained by way of a complexing process of treating any of carbon
5 nanotubes, zinc oxide, aluminum doped zinc oxide, gallium doped zinc oxide, titanium dioxide, cerium oxde and titanium
dioxide microparticles with iron oxide, and hybrid inorganic particles obtained by coating the surfaces of cerium oxide
microparticles with amorphous silica. The compounding ratio of an UV absorbing material can be determined by referring
to the desired UV absorbability but may typically be within a range between 0.1 and 30 mass% of a paint and an adhesive
composition according to the present invention.
10 Antistatic materials that can be used for the present invention include metal oxides and metal salts. Examples of metal
oxides include zinc oxide, aluminum doped zinc oxide, gallium doped zinc oxide, ATO, ITO, tin oxide, antimony pentoxide,
zirconium oxide, titanium oxide, aluminum oxide, which are listed earlier. Carbon nanotubes, which are also described
earlier, can also be utilized as antistatic material. While the compounding ratio of the antistatic material may be determined
appropriately from the viewpoint of the desired antistatic effect, it is typically between 0.1 and 30 mass% in a paint and
15 in an adhesive composition according to the present invention.
Electromagnetic shielding materials that can be used for the present invention include electroconductive particles. Ex-
amples of electro-conductive particles include (1) carbon particles and carbon powder, (2) particles and powders of
metals or alloys, such as nickel, indium, chromium, gold, vanadium, tin, cadmium, silver, platinum, aluminum, copper,
titanium, cobalt and lead, alloys of any of them and electroconductive oxides of any of them, (3) surface of plastic particles
20 such as polystyrene and polyethylene that are coated on the surfaces thereof selected from the electroconductive
materials listed in (1) and (2) above. While the compounding ratio of the electromagnetic shielding material may be
determined appropriately from the viewpoint of the desired electromagnetic shielding, it is typically between 60 and 90
mass% in a paint and an adhesive composition according to the present invention.

25 (f) White coloring agents

[0141] A composition according to the present invention may contain (f) a white coloring agent.
Examples of component (f) that can be used for the present invention include lead basic carbonate, lead basic sulfate,
lead basic silicate, zinc oxide (specific gravity: 5.47 to 5.61), zinc sulfide (specific gravity: 4.1), lithopone, antimony
30 trioxide (specific gravity: 5.5 to 5.6), titanium dioxide (specific gravity: 4.2) and graphite (specific gravity: 3.3), any one
of which may be used alone or any two or more of which may be used in combination.
The component (f) contains preferably titanium oxide or zinc sulfide, more preferably titanium oxide, as main ingredient.
Crystals of titanium oxide can be classified into two types, the tetragonal type and the orthorhombic type, due to the
difference of crystal lattice. The anatase type (low temperature type) and the rutile type (high temperature type) are
35 known for the tetragonal type while the Brookite type is known for the orthorhombic type. For the purpose of the present
invention, titanium dioxide of the rutile type that is inactivated by the effect of a photocatalyst is preferably used.
As for the shape of the component (f), it may be that of a spheroidal structure, although it may alternatively be that of
an elliptical structure, a needle-shaped structure, a polygonal structure or an amorphous structure.
The particle size of the component (f) is not subjected to any particular limitations so long as it is smaller than the
40 thickness of the applied paint when the paint is cured. However, the adhesiveness of a paint according to the present
invention relative to an adherend can be maintained in an excellent state by making the particle size of the paint between
about 0.01 and 3.0 mm when the thickness of the applied paint is between about 10 and 30 mm.
[0142] If necessary, any of various additives can be compounded with the other components of a composition according
to the present invention. Above all, a flame retardant agent is a preferable voluntary component.
45 Examples of flame retardant agents that can be used for the present invention include phosphor-based flame retardant
agents, boron-based flame retardant agents and chlorine-based flame retardant agents as well as aluminum hydroxide
and zinc borate.
When a flame retardant agent is employed, the ratio to which it is added is 50 to 160 parts by mass, preferably 80 to
140 parts by mass, relative to the total of 100 parts by mass of the components (a) through (c).
50 [0143] Preferable examples of silicone compounds that operate as antifouling-property imparting materials include
polyether modified silicone compound, polyester modified silicone compound, polyether modified and/or polyester mod-
ified silicone compounds such as polyether modified and polyester modified silicone compounds.
[0144] Examples of polyether modified and/or polyester modified silicone compounds include compounds obtained
by introducing one or more polyether chains and/or one or more polyester chains to all or some of the terminal and/or
55 side chains of polysiloxanes, although co-modified silicone compounds obtained by introducing one or more organic
groups such as epoxy groups and/or amino groups in addition to polyether chains and/or polyester chains may also be
used for the present invention. Additionally, compounds of the above-identified types preferably have one or more (meth)
acryloyl groups in a molecule because a satisfactory cross-linking density can be achieved after curing by irradiation of

27
 EP 2 578 650 A1

active energy lines with such groups.

[0145] Examples of polyether modified silicone compounds include KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-
615A, KF-945, KF-618, KF-6011, KF-6015, KF-6004, X-22-4272, X-22-4952, X-22-6266, X-22-3667, X-22-4741, X-
22-3939A, X-22-3908A (trade names, available from Shin Etsu Chemical Co., Ltd.), BYK-300, BYK-302, BYK-306, BYK-
5 310, BYK-320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-375, BYK-377, BYK-UV3510, BYK-
301, BYK-307, BYK-325, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348 (trade names, available from BYK Chemie
Gmbh), SILWET L-77, SILWET L-720, SILWET L-7001, SILWET L-7002, SILWET Y-7604, SILWET Y-7006, SILWET
FZ-2101, SILWET-FZ-2104, FZ-2105, SILWET FZ-2110, SILWET FZ-2118, SILWET FZ-2120, SILWET FZ-2122, SIL-
WET FZ-2123, SILWET FZ-2130, SILWET FZ-2154, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2163, SILWET
10 FZ-2164, SILWET FZ-2166, SILWET FZ-2191, SILWET FZ-2203, SILWET FZ-2207, SILWET FZ-2208, SILWET FZ-
3736, SILWET Y-7499, SILWET FZ-3789, SF8472, BY16-004, SF8428, SH3771, SH3746, BY16-036, SH3749, SH3748,
SH8400 and SF8410 (trade names, available from Toray-Dow Corning Silicone, Co., Ltd.), L032, L051, L066 (trade
names, available from WACKER ASAHIKASEI SILICONE, CO., LTD.). In particular, examples of polyether modified
silicone compounds include polydimethyl siloxane compounds, more specifically polydimethyl siloxane compounds hav-
15 ing one or more (meth)acryloyl groups in a molecule such as BYK-UV3500, BYK-UV3570 and BYK-UV3530 (trade
names, available from BYK-Chemie Gmbh).
[0146] Examples of the polyester modified silicone compounds include BYK-310, BYK-315 and BYK-370. In particular,
examples of polyester modified silicone compounds having one or more (meth) acryloyl groups in a molecule include
BYK-UV3500 (trade name, available from BYK-Chemie Gmbh). Any of the above-listed polyether modified and polyester
20 modified silicone compounds (S) may be used alone or any two or more of them may be used in combination.
[0147] Examples of the scratch resistance enhancing materials include microparticles of inorganic oxides, more spe-
cifically, organosilica compounds and alumina ceramic compounds.
Microparticles of inorganic oxides that can be used for the present invention may have a spheroidal, hollow, porous,
rod-like, fibrous or tabular shape or amorphous, of which a spheroidal shape is preferable. The primary particle size of
25 metal oxides is preferably between 1 and 100 nm. The mechanical characteristics can hardly be enhanced when the
primary particle size is less than 1 nm, whereas secondary agglomeration can easily take place to lose transparency
and other characteristics when the primary particle size is more than 100 nm.
Microparticles of the inorganic oxides as listed above are available in a state of dry powder or in a state of being dissolved
or dispersed in water or in an organic solvent. For realizing an excellently dispersed condition, the use of a sol obtained
30 by dissolving or dispersing any of the above-listed compounds in water or in an organic solvent is preferable. To be
more specific, the use of an aqueous organosilica sol or an organosilica sol obtained by dissolving or dispersing inorganic
microparticles in an organic solvent having an OH group or in a polar solvent having a ketone group as main ingredient
is most preferable. Typical examples of aqueous silica sols that can be used for the present invention include ST-20
(trade name, basic aqueous silica sol, available from Nissan Chemical Industries, Ltd.), ST-O (trade name, acidic aqueous
35 silica sol, available from Nissan Chemical Industries, Ltd.), ST-AK (trade name, weakly acidic aqueous silica sol, available
from Nissan Chemical Industries, Ltd.) and lithium silicate (basic silica·lithium oxide sol, available from Nissan Chemical
Industries, Ltd.). Typical examples of organosilica sols that can be used for the present invention include IPA-ST (trade
name, organosilica sol dispersed in isopropanol (IPA), available from Nissan Chemical Industries, Ltd.), MEK-ST (trade
name, organosilica sol dispersed in methyl ethyl ketone (MEK), available from Nissan Chemical Industries, Ltd.) and
40 sols obtained by solvent substitution by means of an organic solvent having an OH group, using either of them as starting
material (e.g., organosilica sols dispersed in PGM).
The solid content ratio in the dispersion liquid is typically between 5 and 50 wt%, preferably between 10 and 40 wt%,
because sols showing such a solid content ratio provide easy handling and are easily available.
[0148] For the purpose of the present invention such inorganic microparticles are added in the form of dispersion
45 where inorganic particles are uniformly dispersed in a diluent. One of the advantages of adding inorganic microparticles
in the form of dispersion liquid is that, as a result, secondary agglomeration of inorganic microparticles can be suppressed
and inorganic microparticles can be uniformly dispersed in a resin composition. Diluents such as organic solvents and
photopolymerizable monomers can non-limitatively be used for the present invention so long as they can uniformly
disperse silica and alumina. Specific examples of organic solvents and photopolymerizable monomers include trimethylol
50 propane tri(meth)acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di
(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butane diol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
trimethylol propane trioxyethyl (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dipropylene glycol diacrylate
(PDGDA), PO modified neopentyl glycol diacrylate and modified bisphenol A diacrylate in addition to PMA, TPGDA and
HDDA, which will be described below.
55 [0149] Known dispersions of the above-described category can be used for the present invention. Examples include
NANOBYK-3650 (trade name) available from BYK Chemie Gmbh that contains silica microparticles dispersed in methoxy
propyl acetate (PMA), tripropylene diacrylate (TPGDA), hexane diol diacrylate (HDDA), or NANOBYK—3601, 3602,
3610 (trade names) that contain alumina microparticles dispersed in PMA and NANOCRYL C145, C146, C350, C140,

28
 EP 2 578 650 A1

C150 (trade names) available from Hanse-Chemie Gmbh that contain silica microparticles dispersed in a photopolym-
erizable monomer. Any one of the above-listed may be used alone or any two or more of them can be used in combination.
Of the above-listed, NANOBYK-3650 and NANOBYK-3610 prepared by dispersing microparticles that are surface-
treated with silicone or a derivative thereof are preferably employed.
5 [0150] Any core-shell polymer particles can be employed as shock resistance enhancing material so long as they are
provided as graft copolymer. Specific examples include Kane Ace B-564 (trade name) available from KANEKA COR-
PORATION and Paraloid BPM-500 and Paraloid 20784 (trade names) available from Rohm and Haas Company.
Of core-shell-type graft copolymers, the core particle size is preferably between 0.05 and 0.8 mm, more preferably
between 0.1 and 0.6 mm, most preferably between 0.1 and 0.5 mm in terms of weight average particle size. Excellent
10 shock resistance can be achieved when the core particle size is within a range between 0.05 and 0.8 mm. The graft
copolymer to be used for a shock resistance enhancing material preferably contains the rubber component by not less
than 40%, more preferably not less than 60%.
[0151] Materials that can be used as rubber component for the present invention include butadiene rubber, butadi-
ene-acryl composite rubber, acryl rubber, acryl-silicone composite rubber, isobutylene-silicone composite rubber, iso-
15 prene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acryl
rubber, silicone rubber, epichlorohydorin rubber, fluorine rubber and rubbers obtained by adding hydrogen to any of the
unsaturated bonds of such robbers, although the use of a rubber component that does not contain any halogen atom is
preferable in terms of environmental load because the use of a rubber component containing an halogen atom gives
rise to an apprehension of generating toxic substances when incinerated. The glass transition temperature of the rubber
20 component is preferably not higher than -10°C, more preferably not higher than -30°C. Of the candidate rubber compo-
nents, the use of butadiene rubber, butadiene-acryl composite rubber, acryl rubber or acryl-silicone composite rubber
is preferable. Composite rubber refers to copolymerized rubber of two rubber components or rubber obtained by polym-
erization so as to show an IPN structure where two rubber components inter-penetrate (are inter-tangled).
[0152] Examples of aromatic vinyl compounds that can be used for copolymerization into a rubber component for the
25 purpose of the present invention include styrene, α-methyl styrene, p-methyl styrene, alkoxy styrene and halogenated
styrene, of which styrene is preferable in particular. Examples of acrylic esters that can be used for copolymerization
include methyl acrylate, butyl acrylate, cyclohexyl acrylate and octyl acrylate. Examples of methacrylic esters that can
be used for copolymerization include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacr-
ylate and octyl methacrylate, of which methyl methacrylate is preferable. Particularly, the rubber components that can
30 be used for the present invention preferably contain a methacrylic acid ester such as methyl methacrylate as indispensable
ingredient. More specifically, a methacrylic ester is contained in 100 wt% of the graft component (100 wt% of the shell
in the case of a core-shell type polymer) preferably by not less than 10 wt%, more preferably by not less than 15 wt%.
[0153] Any graft copolymers containing a rubber component having a glass transition temperature not higher than
10°C that is to be used for the present invention may be manufactured by way of a polymerization process selected
35 from block polymerization, solution polymerization, suspension polymerization and emulsion polymerization. The copo-
lymerization system to be used for the present invention may be that of one-step grafting or that of multi-step graft. A
mixture of only the graft component that is produced as by product through the manufacturing process and the copolymer
may be used. Processes that can be used for polymerization include soap free polymerization designed to use potassium
persulfate as initiator, seed polymerization and two-step swelling polymerization in addition to popular emulsion polym-
40 erization. When suspension polymerization is employed, a method of holding the aqueous phase and the monomer
phase separately, accurately supplying them into a continuous-type disperser and controlling the particle size by way
of the number of revolutions of the disperser may be used for it. When such a continuous manufacturing process is
employed, the particle size can be controlled by a method of supplying the monomer phase into an aqueous liquid having
a dispersion power by way of an orifice of a diameter between several and several tens mm or a porous filter. In the
45 case of core-shell-type graft polymerization, the reaction may be of one-step or of multi-step for both cores and shells.
[0154] A paint and an adhesive composition according to the present invention show a particularly excellent adhesion
property relative to a layer of soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate;
concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer of polyolefin resin modified by a polar
group-containing compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-butadiene-sty-
50 rene copolymer; polyester-based resin; polyurethane-based resin; epoxy-based resin; or acryl-based resin (to be referred
to as specific adherend layer (B1) or specific adherend layer (B2) hereinafter). The conventional art does not disclose
any adhesive composition showing an excellent adhesion property to such adherends. Additionally, an adhesive com-
position according to the present invention shows an extremely excellent adhesion property (between dissimilar materials)
when dissimilar materials are employed for adherend B1 and adherend B2. Specific examples of "between dissimilar
55 materials" include between hard vinyl chloride resin and glass, between soft vinyl chloride resin and glass, between
polystyrene-based resin and aluminum, between polycarbonate resin and aluminum, between polystyrene-based resin
and glass, between polycarbonate resin and glass, between acrylonitrile-butadiene-styrene copolymer (ABS) and glass,
between glass and aluminum, between magnesium and polycarbonate resin, between a steel plate and acrylic resin

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(e.g., polymethyl methacrylate (PMMA)), between polyester (e.g., polyethylene terephtharate) and acrylonitrile-butadi-
ene-styrene copolymer (ABS) and between acrylic resin (e.g., polymethyl methacrylate (PMMA) and acrylonitrile-buta-
diene-styrene copolymer (ABS)). Polyolefin resins modified by a polar group containing compound are olefins into which
a polar group such as -OH, -NO2, -CO, -NH 2, -NH, -OCH3, -SO3 or the like. Examples of such olefins include polyolefin
5 resins that are grafted with at least either maleic anhydride or glycidyl methacrylate. Specific examples include polyeth-
ylene and polypropylene that are grafted with maleic anhydride and polyethylene and polypropylene that are grafted
with glycidyl methacrylate. Examples of copolymers of olefin and a polar group containing compound include a copolymer
(EVA) of ethylene and vinyl acetate, copolymers (EAA, EMA, etc.,) of ethylene and (meth)acrylic acid and a copolymer
(EEA) of ethylene and a (meth)acrylic ester.
10 [0155] A paint according to the present invention can be applied onto a substrate and cured. Application techniques
that can be used for a paint according to the present invention include spin coating, (doctor), knife coating, micro gravure
coating, direct gravure coating, offset gravure coating, reverse gravure coating, reverse roll coating, (Mayer) bar coating,
dye coating, spray coating and dip coating (examples of apparatus for spin coating include ASS-301 Type (trade name)
Manual Spinner, available from ABLE JAPAN Co., Ltd.). When a UV reaction initiator or an electron beam reaction
15 initiator is employed for the component (d), the paint can be cured by irradiating UV rays or an electron beam. For
irradiation conditions, an irradiation intensity between 150 and 1,000 mJ/cm2 and an irradiation time between 1 and 60
seconds may be adopted when UV rays are used. When an organic peroxide is employed for the component (d), the
paint can be cured by heating it at 100 to 150°C.
[0156] The recommended thickness of a layer formed by applying a paint according to the present invention is between
20 2 and 200 mm, preferably between 5 and 150 mm, more preferably between 10 and 100 mm from the viewpoint of cost
and performance.
[0157] A layer (A) of a paint according to the present invention can be formed and cured on a substrate (B) with
excellent adhesiveness relative to the latter and without using any primer, if the substrate is selected from various
substrates, to which any ordinary paint has hitherto been unable to adhere and become cured without using a special
25 primer, including, for example, those of soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum;
steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer of polyolefin resin modified by
a polar group-containing compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-butadi-
ene-styrene copolymer; polyester-based resin (e.g., polyethylene terephthalate PET); polyurethane-based resin; epoxy-
based resin; or acryl-based resin (e.g., polymethyl methacrylate PMMA). (If allowable from the viewpoint of cost and
30 other factors, even stronger adhesiveness can be obtained by using a primer on the substrate.)

(Bonding method according to the present invention)

[0158] A bonding method according to the present invention comprises Step I of mixing the components (a) through
35 (d) and, if necessary one or more filling materials in an voluntary order act the above-defined compounding ratio to
prepare a paint and an adhesive composition according to the present invention, Step II of laminating the adhesive
composition on a layer (B1) of a specific adherend to form a layer (A) of the adhesive composition and Step III of further
laminating the layer (A) of the adhesive composition and another layer (B2) of a specific adherend. With the bonding
method according to the present invention the three layers (B1)-(A)-(B2) will be firmly bonded.
40 The thickness of the layer (A) of an adhesive composition (cured coating film) is non-limitatively between 2 mm and 50
mm, preferably between 5 mm and 30 mm, more preferably between 8 mm and 20 mm. (When a paint and an adhesive
composition according to the present invention are prepared by solventless (volatile), the thickness of the applied paint
or composition and the thickness of the cured paint or composition, do not show a significant difference because the
applied paint or composition does not contract significantly in the curing process.) The coating film shows an excellent
45 degree of transparency while the curving, if any, of the formed resin body due to curing and contraction can be alleviated
and the degradation of the surface hardness due to the uncured binder resin component can be prevented from taking
place by adjusting the thickness of the coating film. Application techniques that can be applied to a paint and an adhesive
composition according to the present invention include spin coating, (doctor) knife coating, micro gravure coating, direct
gravure coating, offset gravure coating, reverse gravure coating, reverse roll coating, (Mayer) bar coating, dye coating,
50 spray coating and dip coating. Examples of apparatus for spin coating include ASS-301 Type (trade name) Manual
Spinner, available from ABLE JAPAN Co., Ltd.
With a method of preparing an adhesive composition according to the present invention, the component (b) and the
component (c) are added respectively as reactive diluent and as modifier to the component (a) in a vessel equipped
with an agitator. Thereafter, the component (d) is added and agitated sufficiently until no unmolten residue is left. When
55 one or more components are to be added, they are added finally and agitated thoroughly. The adhesive composition
that is obtained by agitation needs to be quickly worked or stored in a cold and dark storage facility.

30
 EP 2 578 650 A1

(Laminate according to the present invention)

[0159] A laminate according to the present invention comprises (B1)-(A) and is obtained by preparing a paint and an
adhesive composition according to the present invention in a manner as described above and applying the adhesive
5 composition to a layer (B1) of a specific adherend to form a layer (A) of the adhesive composition. In a different mode
of carrying out the invention, a laminate according to the present invention comprises (B1)-(A)-(B2) and is obtained by
laminating the adhesive composition onto a layer (B1) of a specific adherend to form a layer (A) of the adhesive composition
and additionally laminating a layer (B2) of a specific adherend on the layer (A).
A laminate according to the present invention provides excellent adhesiveness between the layers (B1) and (B2) of the
10 specific adherends and the layer (A) of the adhesive composition and shows transparency, surface smoothness, flexibility
and shock resistance in a well-balanced manner.
In a laminate according to the present invention and comprising (B1)-(A), the layer (A) of the adhesive composition
operates advantageously as primer layer for (B1). Such a primer layer can typically take a role of enhancing the adhe-
siveness relative to the paint and the adhesive composition applied onto it depending on the application of the laminate.
15 Note, however, that a layer of the specific adherend and a layer of the adhesive composition can be laminated alternately
for a plural times and the product of such an operation is also within the scope of a laminate according to the present
invention.

(Applications)
20
[0160] Exemplar applications of a paint and an adhesive composition according to the present invention are listed below.

1. Antifouling-property imparting materials:

25 antifouling protective walls (glass substituting members and protective walls for highways, sports arenas, bridges
and so on) and display coatings for television sets, mobile phones and game machines

2. Scratch resistance enhancing materials:

30 glass substituting members, protective walls for highways, sports arenas and bridges and display hard coatings
for television sets, mobile phones and game machines

3. Shock resistance enhancing materials:

35 automobile interior and exterior decorating members, floors, walls, protective walls for highways, sports arenas
and bridges and display coatings for television sets, mobile phones and game machines

4. IR absorbing materials:

40 automobile interior and exterior decorating members, floors, walls, roofs, protective walls for highways and
bridges and heat shield coatings for television sets, mobile phones and game machines

5. UV absorbing materials:

45 automobile interior and exterior decorating members, floors, walls, anti-yellowing coatings for boats and canoes
and UV degradation prevention coatings

6. IR reflecting materials (white light reflecting materials) titanium oxide:

50 solar cell backsheets and coatings for walls and roofs

7. Electromagnetic shielding materials:

automobile interior and exterior decorating members and coatings for floors, walls and roofs
55
8. Electroconductive revealing materials:

automobile interior and exterior decorating members, walls, electrode coatings

31
 EP 2 578 650 A1

9. Antistatic materials:

floors, walls, electric appliance housings, display coatings for television sets, mobile phones and game machines

5 10. Flame retardancy imparting materials:

walls, floors, electric appliance housings, connectors, electric wire coatings.

11. For electroacoustic transducers

10 12. For coatings steel structures

[Examples]

[0161] Now, the present invention will be described further by way of examples and comparative examples, although
15 the present invention is by no means limited by the examples that are described below.
[0162] The materials used in Examples and Comparative Examples are listed below.

Component (a-1) vinyl ester resin

20 (i) urethane acrylate

[0163] CN963B80: urethane acrylate (HDDA blend), type = polyester, 60°C viscosity = 1, 100, number of functional
groups = 2, available from Sartomer Company

25 (ii) polyester acrylate

[0164] CN292: polyester acrylate, type = aliphatic polyester, 25°C viscosity = 630, number of functional groups = 4,
available from Sartomer Company

30 (iii) epoxy acrylate

[0165] CNUVE151: epoxy acrylate, type = polyester, 25°C viscosity = 150, 000, number of functional groups = 2,
available from Sartomer Company

35 (iv) aliphatic urethane acrylate

[0166] CN966J75: aliphatic urethane acrylate (IBOA blend), type = polyester, 60°C viscosity = 4, 240, 20°C viscosity
= 105, 000, number of functional groups = 2, available from Sartomer Company

40 Component (a-2) unsaturated polyester resin

[0167] RIGOLAC21E-A-2 (trade name) : available from Showa Highpolymer Co., Ltd.

Component (a-3) vinyl ester resin

45
[0168] RIPOXY VR-77 (trade name): available from Showa Highpolymer Co., Ltd.
viscosity: 1,000 (dPa·s/25°C)
molecular weight: 510

50 Component (c) compound having a ring structure and an ethylenically unsaturated group

[0169]

(i) N-vinyl pyrrolidone: available from Nippon Shokubai Co., Ltd.

55 molecular weight: 111.14
boiling point: 219°C
vapor pressure (24°C): 0.10 mm Hg
flash point: 98°C

32
 EP 2 578 650 A1

viscosity (25°C): 2 cps

melting point: 13°C
(ii) N-vinyl caprolactam: available from BASF
boiling point: 117°C (10 mm, Hg)
5 vapor pressure < 0.1 mm Hg (20°C)
flash point: 110°C
melting point: 35°C
viscosity (40°C): 3.5 cps

10 [0170] Dipropylene glycol diacrylate DPGDA: available from Shin-Nakamura Chemical Co., Ltd.
specific gravity: 1.05 (25°C)
viscosity: 8 (mPa·s/25°C)
refractive index: 1.449)
[0171] Tripropylene glycol diacrylate TPGDA: available from Shin-Nakamura Chemical Co., Ltd.
15 specific gravity: 1.039 (25°C)
viscosity: 12 (mPa·s/25°C)
refractive index: 1.449
Dipentaerythritol polyacrylate A-9550: available from Shin-Nakamura Chemical Co., Ltd.
specific gravity: 1.89 (25°C)
20 viscosity: 6500 (mPa·s/25°C)
refractive index: 1.489
Acryloyl morphorine (ACMO) : available from KOHJIN Film and Chemicals Co., Ltd.
molecular weight: 141.17
specific gravity: 1.122
25
Component (b) modifier

(b-1-2) polybutadiene-based polyol

30 [0172] Poly bd R-15HT: available from Idemitsu Co., Ltd.,

viscosity: 1.5 Pa·s/30°C
hydroxyl value: 102.7 mgKOH/g

(b-1-1-1) aromatic castor oil-based polyol

35
[0173] URIC (trade name) AC-006, (polyol derived from castor oil and expressed by the formula (4) above): available
from Itoh Oil Chemicals Co., Ltd.
viscosity: 0.7 to 1.5 Pa·s/25°C
hydroxyl value: 194 to 214 mgKOH/g
40
(b-1-3) polyisoprene-based polyol

[0174] Poly ip (trade name), polyisoprene-type liquid polymer having highly reactive hydroxyl groups at molecular
terminals: available from Idemitsu Co., Ltd.
45 hydroxyl value: 46.6 mgKOH/mg
number average molecular weight Mn: 2,500

(b-2-1) castor oil-based polyol

50 [0175] URIC H-1262: available from Itoh Oil Chemicals Co., Ltd. polyol containing a castor oil based polyol and an
alkyl acid phosphate having a total number of carbon atoms of not less than 12, viscosity: 3, 500 to 8, 500 Pa·s/25°C,
acid value: 4 to 15 mgKOH/g, hydroxyl value: 240 to 290 (unit: mgKOH/g)

(b-2-1) castor oil based polyol

55
[0176] URIC H-2151U, available from Itoh Oil Chemicals Co., Ltd. polyol containing a castor oil-based polyol, a phos-
phoric acid ester compound having a total number of carbon atoms of not less than 12
viscosity: 3,500 to 8,500 mPa·s/25°C

33
 EP 2 578 650 A1

acid value: 4 to 15 (unit: mgKOH/g)

hydroxyl value: 240 to 290 (unit: mgKOH/g)

(b-1-3) hydrogen adduct of polyisoprene-based polyol

5
[0177] EPOL (trade name): available from Idemitsu Co., Ltd., liquid polyolefin with hydroxyl terminal groups
viscosity: 75 Pa·s/30°C
hydroxyl value: 50.5 mgKOH/g
number average molecular weight: 2,500
10
(b-3-1) maleated polyisoprene

[0178] LIR-420 (trade name): available from Kuraray acid value: 40 mgKOH/g
(b-3-2) maleic acid modified polybutadiene
15 Ricon 130MA8: available from Sartomer Company
Viscosity: 6.5 Pa·s/30°C
acid value: 46 mgKOH/mg
number average molecular weight: 2,700

20 (b-3-2) maleic acid modified polybutadiene

[0179] POLYVEST (trade name) OC 800S: available from Evonik Degussa Corporation
(in polybutadiene, 1,4-cis double bonds: 75%, 1,4-trans double bonds: 24%, vinyl bonds: 1%, maleation ratio: 7.5%,
number average molecular weight: 3,300 (GPC), weight average molecular weight: 13,600 (GPC), viscosity (20°C): 6
25 to 9 Pa·s (as measured according to DIN 53214), acid value: 70 to 90 mgKOH/g, iodine value; 380 to 420 g/100 g,
(polymerized with Ziegler Natta catalyst)

(b-1-4) epoxy polyol resin

30 [0180] EPICLON (trade name) U-125-60BT: available from DIC Co., Ltd.
Viscosity: 70 Pa·s/30°C
hydroxyl value: 120 mgKOH/g

(b-4-1) polyepoxy compound having epoxy equivalent of 150 to 250 g/mol

35
[0181] Adeka Resin EP-4100E (available from ASAHI DENKA KOGYO KK, bisphenol A diglycidyl ether, epoxy equiv-
alent: 190).

(b-4-2) polymer having saturated skeleton having epoxy equivalent of 500 to 700 g/mol
40
[0182] L-207 (KRATON LIQUID (trade name) also named as L-207 POLYMER), available from Kuraray (polymer
having an epoxy equivalent of 590 g/mol, a hydroxyl equivalent of 7,000 g/mol, a glass transition temperature of -53°C
with a completely saturated skeleton (epoxidized ethylene·propylene-ethylene·butylene-OH structure))

45 (b-5-1)

[0183] Lumiflon LF-200, trade name,(Asahi Glass Co., Ltd., fluoroolefin·vinylether copolymer, hydroxyl value: 52 mg-
KOH/g, glass transition temperature: 35°C, melting point: 148°C, xylene: 40%, effective components: 40%)
[0184] Since this material contains solvent, an amount obtained by reducing the effective components to 100% was
50 used.

(b-5-2)

[0185] Lumiflon LF-302, trade name, (Asahi Glass Co., Ltd., fluoroolefin·vinylether copolymer, hydroxyl value: 47
55 mgKOH/g, xylene: 50%, effective components: 50%)
Since this material contains solvent, an amount obtained by reducing the effective components to 100% was used.
[0186] The characteristics of each polyol were observed in the following manner.

34
 EP 2 578 650 A1

· Viscosity measurement method

[0187] A single cylinder-type rotational viscometer (B type TVC-5) was employed as viscometer according to JIS
K7117-1.
5
1. A 500 ml beaker (standard) was used as measuring instrument.
2. As standard rotors, two rotors were selected from M1 to M4 rotors for low to medium viscosities and H1 to H7
rotors for medium to high viscosities.

10 · Hydroxyl value measurement method

[0188] The hydroxyl value is the milligrams of potassium hydroxide required for acetylation of the OH groups contained
in 1 g of a sample. The OH groups in each sample were acetylated by means of acetic anhydride according to JIS K
1557-1 and the unconsumed acetic acid was titrated by means of potassium hydroxide solution.
15 [0189]

20

[0190]
25
A: the quantity of 0.5 mol/< potassium hydroxide ethanol solution (m<) consumed in a blank test
B: the quantity of 0.5 mol/< potassium hydroxide ethanol solution (m<) consumed for titration
f: factor

30 · Acid value measurement method

[0191] The acid value is the milligrams of potassium hydroxide required to neutralization of the acidic components
contained in 1 g of a sample. According to JIS K 1557-5,

35 (1) Measurement of end point pH

10 mL of buffer storage solution B was taken into a 200 mL beaker, to which 100 mL of a titration solvent was
added, and electrodes were dipped into it. The pH that changed within 0.1 pH in 30 seconds was determined
as buffer end point.
40
(2) Measurement of acid value

1. 20 g of a sample was accurately measured and taken into a 200 mL beaker.

2. 125 mL of toluene·2-propanol·purewater mixture solvent was added and titrated with titration solution of 0.1
45 mol/L potassium hydroxide.

As a result of (1), 11.72 pH was selected as end point and the acid value was determined by means of the formula
shown below. The same procedures were followed for a blank.

50

D: titration value (mL)

B: blank (0.085 mL)
55 K: KOH molecular weight (56.1)
F: factor of titration solution (1.000)
M: molar concentration of titration solution (0.1 mol/L)

35
 EP 2 578 650 A1

S: quantity of extracted sample (g)

[0192] Component (e) initiator

(i) photopolymerization initiator

5 IRGACURE (trade name) 819: available from CIBA Corporation bis(2,4,6-trimethyl benzoyl)-phenylphosphine oxide
(ii) thermal polymerization initiator
PERHEXA 25B: available from NOF Corporation (1 minute half life temperature: 179°C), 2,5-dimethyl-2,5-di(tert-
butylperoxy) hexane

10 [Description of functional materials]

[0193] Antifouling-property imparting material: (polydimethyl siloxane compounds having one or more polyether mod-
ified acryloyl groups) BYK-UV3500 (trade name), available from BYK-Chemie Gmbh. Scratch resistance enhancing
material: (organosilica sol MEK-ST (trade name)), available from Nissan Chemical Industries, Ltd. Scratch resistance
15 enhancing material: (alumina ceramic NANOBYK-3602), available from BYK-Chemie Gmbh, alumina 30%/tripropylene
glycol diacrylate, alumina particle size = 40 nm. Shock resistance enhancing material: (PARALOID BPM-500) (available
from Dow Chemical Company) : acryl-based shock resistance improving material, specific gravity = 1.10
IR absorbing material: (SUNCOLLOID IR-40K) available from Nissan Chemical Industries, Ltd., 33% antimony double
oxide / 4% amorphous silica / 1% tin oxide / 58% methyl ethyl ketone / 3% propyl alcohol / 1% additive
20 UV absorbing material: (UV absorbing agent TINUVIN 326) available from BASF
2-tert-butyl-6-(5-chlorobenzotriazol-2-yl)-4-methylphenol IR reflecting material (white light reflecting material) (titanium
oxide, available from ISHIHARA SANGYO KAISHA Ltd., CR-90 (trade name))
Electromagnetic shielding material: zinc oxide 23-K (trade name), electroconductive zinc oxide - available from Haku-
suitech Ltd., primary particle size 120 to 150 mm
25 Electroconductive revealing material: carbon nanotubes VGCF-S, available from SHOWA DENKO K. K. , fiber diameter
80 nm, fiber length 10 mm
Antistatic material: (CELNAX CX-Z603M-F2) 60% antimony double oxide / 40% methyl alcohol, available from Nissan
Chemical Industries, Ltd.
Antistatic material: (ionic liquid, available from Signa Aldrich Co., Ltd.) BASIONIC LQ 01: 1-ethyl-3-methylimidazolium
30 ethyl sulfate, specific gravity = 1.239
Antistatic material: (available from LION AKZO Co., Ltd., TMAC-100 (tetramethyl ammonium chloride (ionic liquid having
ion pair of (5-10) and (7-2))
[Organic solvents]
N-methyl pyrroridone (NMP)
35 ethylene carbonate (EC)
propylene carbonate (PC)
dimethyl carbonate (DMC)
methyl ethyl ketone (MEK)
methyl isobutyl ketone (MIBK)
40 propylene glycol monomethyl ether (PGM)
cyclohexane (anon)

Examples 1 to 38, Comparative Examples 1 to 8

45 [0194] Using the compounding ratios (parts by mass) listed in Table 1 through 8 shown below, the component (a) was
put into a vessel equipped with an agitator and then the component (c) was added thereto and agitated sufficiently at
ambient temperature. Thereafter, the component (b) was added and agitated. When the liquid temperature got to the
ambient temperature, the component (d) was added and agitated sufficiently until no unmolten residue was found to
obtain an adhesive composition. The viscosity (mPa·s) at 25°C of the obtained adhesive composition was observed.
50 The viscosity at 25°C was observed by means of a handy-type digital viscometer, TVC-7 type Viscometer (available
from TOKI SANGYO Co., Ltd.) and a rotor (Type 0 to Type 5) that matches the different the viscosity. Tables 1 through
8 also show the obtained results.
[0195] Then, the adhesive composition was applied onto each of the specific adherends (B1) (dimensions: 150 mm
3 25 mm 3 thickness 1 mm) shown in Tables 1 through 8 by spin coating (the thickness of the applied adhesive
55 composition: 15 to 20 mm) and cured in air by irradiating UV rays at an energy level of 500 mJ/cm 2 to prepare a laminate.
When the adhesive composition is made to contain an organic solvent for application, the applied adhesive composition
was dried in an oven having a dark room in the inside at 100°C for 5 minutes and subsequently cured by irradiating UV
rays in a manner as described above to prepare a laminate.

36
 EP 2 578 650 A1

When a thermal polymerization initiator was used and if necessary, 6% naphthene cobalt was added to the composition
by 0 to 0.5 parts by mass and heat treated at 100°C for 30 minutes to cure the composition and prepare a laminate.
[0196] Example 24 is an instance that differs from Example 2 only in that (ii) thermal polymerization initiator was
employed as component (d).
5 The adhesive composition was applied onto each of the specific adherends (B1) (dimensions: 150 mm 3 25 mm 3
thickness 1 mm) shown in Tables 1 through 8 by spin coating (the thickness of the applied adhesive composition: 15 to
20 mm) and cured by means of a heat treatment conducted at 100°C for 10 minutes to prepare a laminate.
[0197] The used specific adherends (B1) are listed below.

10 · hard vinyl chloride resin PVC (available from RIKEN TECHNOS CORP, Riken PVC Compound RE-3844 (trade
name))
· soft vinyl chloride resin PVC (available from RIKEN TECHNOS CORP, Leony BZL6060N (trade name))
· polystyrene PS (available from TOYO STYRENE Co., Ltd., TOYO STYROL GP G100C (trade name))
· polycarbonate PC (available from TEIJIN CHEMICALS Ltd., PANLIGHT L-1225L (trade name))
15 · acrylonitrile-butadiene-styrene copolymer ABS (available from UMG ABS Ltd., UMG ABS EX114 (trade name))
· glass (microscope slide glass for prepared specimen)
· aluminum (H5052, Al-Mg based)
· magnesium (available from Osaka Fuji Kogyo Co., Ltd., AZ31B, Mg content not less than 91%)
· steel plate (SPCC: cold stretched steel plate)
20 · PET: available from UNITIKA Ltd., UNITIKA polyester resin MA-2103
· PMMA: available from Mitsubishi Rayon Co., Ltd., Acrypet VH

[Description of substrates]

25 [0198] Concrete: commercially available ordinary concrete (mixture of cement, aggregate, water and (chemical) ad-
mixture) Wood panel: commercially available solid wood (black pine, red pine, Japanese larch, Yezo spruce, hinoki
cypress, etc.)
Stone: commercially available stone (natural granite, natural marble (limestone), natural sandstone, etc.)
Artificial marble: commercially available artificial marble (polyester based, acryl based, etc.)
30 PP: NOVATEC BC8, MFR = 1.8 g/10 min, available from Japan Polypropylene Corporation
HDPE: NOVATEC HJ360, MFR = 5.5 g/10 min, available from Japan Polyethylene Corporation
Maleic modified PE: AMPLIFY GR209, available from Dow Chemical Company, specific gravity = 0.8985, hardness =
96A Thermoplastic polyurethane elastomer (T-1180, DIC Bayer Polymer Ltd.), ester type (adipate), hardness 80A
2-part liquid polyurethane resin: FLONE 22 A liquid (main agent) and B liquid (curing agent) were mixed at ratio of 1:1
35 and subsequently the mixture was applied onto a 130 mm 3 130 mm 3 1 mm polycarbonate plate to a thickness of
about 2 mm by means of a roller. The applied mixture was left uncared for not less than 7 days for curing (available from
Higashi Nippon Paint Co., Ltd.). A liquid: viscosity 4,500 mPa·s, B liquid: viscosity 18,000 mPa·s, viscosity immediately
after mixing A and B 5,200 mPa·s.
2-part liquid epoxy resin: FLONE EPOROLER A liquid (main agent) and B liquid (curing agent) were mixed at ratio of
40 6:1 and subsequently the mixture was applied onto a 130 mm 3 130 mm 3 1 mm polycarbonate plate to a thickness
of about 2 mm by means of a roller. The applied mixture was left uncared for not less than 7 days for curing (available
from Higashi Nippon Paint Co., Ltd.). A liquid: viscosity 2,800 mPa·s, B liquid: viscosity 800 mPa·s, viscosity immediately
after mixing A and B 1,200 mPa·s.
[0199] Each of the obtained laminates was subjected to the following tests.
45
[Test methods]

(Adhesion test: cross-cut tape test)

50 [0200] An adhesion test was conducted to observe the adhesion relative to each substrate by means of a test conforming
to the cross cut tape test method defined in JIS K 5400.
[0201] Cross-cut tape test (application thickness 15 to 20 mm (spin coating)): 1 3 1 mm square scars were formed by
cross cutting using a box cutter on the test surface (layer (A) side of composition). A box cutter guide was employed.
The number of square cross cuts was longitudinal 10 3 transversal 10 = 100. A cellophane tape was pressed hard
55 against and made adhering to the areas of square cross cuts and the tape was pulled off rapidly at the end at an angle
of 45° to observe the condition of each of the square cross cuts (and find out the number of square cross cuts that were
left unpeeled).

37
 EP 2 578 650 A1

(Water resistance test)

[0202] Each sample on the corresponding laminate was immersed in boiled water (pure water) for an hour and dried
naturally. The dried sample was visually observed for deterioration of appearance of the hard coat layer.
5 o: Neither paint peeling nor paint cracking was observed (after 1 hour immersion).
3: Paint peeling and paint cracking were observed (after 1 hour immersion).

· Test on adhesiveness relative to dissimilar materials

10 [0203] For each sample, a test on adhesiveness relative to dissimilar materials was conducted by way of a shear
adhesion measurement as shown below. Tables 1 through 8 show the obtained results.
The above adhesive composition was applied onto each of the specific adherends (B1) having dimensions of 150 mm
3 1 mm thickness 3 25 mm width by spin coating (to an application thickness of 15 to 20 mm) to form a layer (A) of the
adhesive composition and one the specific adherend (B2) having dimensions same as those of the specific adherends
15 (B1) shown in Tables 1 to 8 was bonded to it under pressure. Then, the adhesive composition was cured by irradiating
UV rays (wavelength; 325 nm, integrated radiation intensity: 50 mJ/cm2) from the side of the transparent layer for UV
curing to prepare a laminate. Subsequently, the specific adherend (B2) was pulled in a direction parallel to the bonding
surface of the layer (A) of the adhesive composition to observe the tensile strength at break (MPa/25 mm). Tables 1
through 8 show the obtained results. Note that, in Tables 1 through 8, each laminate comprising the (B1)-(A)-(B2) was
20 expressed as (B1) vs (B2). If, for example, (B1) is hard PVC and (B2) is glass, an expression of "hard PVC vs glass"
was used.

(Weather resistance test)

25 [0204] Each laminate was exposed to cycles of 12-minute rain fall and after exposure 48-minute drying for 500 and
1, 000 hours at black panel temperature of 63°C by means of a sunshine weather meter and the appearance was observed.

o: no appearance change observed

3: bleaching, yellowing, peeling observed
30
(Flame retardancy test)

[0205] A combustion test was conducted according to the Safety Standard UL94 (o: combustion time not more than
10 seconds, Δ: combustion time not less than 10 seconds, x: entirely combusted) of UNDERWRITERS LABORATORIES
35 INC.

(Surface resistance test)

[0206] As for the surface resistance of each of the examples and the comparative examples, an adhesive composition
40 according to the present invention was applied onto a glass substrate (dimensions: 150 mm 3 25 mm 3 thickness 1
mm) by spin coating (the thickness of the applied adhesive composition: 10 mm) and the surface resistivity (Ω/sq.) was
observed by means of a HIRESTER UP (MCP-HT450), a high resisitvity meter available from Mitsubishi Chemical
Corporation, applying a voltage of 500 V according to ASTMD257. The average value (n = 5) of the resistivities of five
samples was used as the resistivity of the example or comparative example.
45
(Various transmittance tests)

[0207] As for the visible light transmittance of each of the examples and the comparative examples, the spectral
transmittance curve was obtained by means of a U-4000 type automatic recording spectrophotometer (available from
50 Hitachi Ltd.) according to JIS R-3106 and the average transmittance in the wavelength range between 380 and 780 nm
was determined for a D light source.
[0208] As for the UV transmittance of each of the examples and the comparative examples, the average transmittance
in the wavelength range between 300 and 380 nm was determined by using a similar means according to ISO/DIS 13837.
As for the IR transmittance of each of the examples and the comparative examples, the average transmittance in the
55 wavelength range between 780 and 2,000 nm was determined by using a similar means according to ISO/DIS 13837B.

38
 EP 2 578 650 A1

Shock resistance test

[0209] test method: An adhesive composition was applied onto a 25 mm-wide and 1 mm-thick steel plate to a thickness
of 15 to 20 mm by spin coatings and, after curing, a spherical weight of 1 kgw was dropped from a height of 1 meter onto
5 the sample. The shock resistance of the sample was evaluated according to the rating system shown below. o: no peeling
Δ: partly peeled and cracked
3: totally peeled and cracked

Flexibility
10
[0210] test method: An adhesive composition was applied onto a 25 mm-wide and 1 mm-thick substrate to a thickness
of 15 to 20 mm by spin coatings and, after curing, a 90° bending test was conducted by applying the sample to an iron
rod having a diameter of 10 mm. The flexibility of the sample was evaluated according to the rating system shown below.
o: no peeling
15 Δ: partly peeled and cracked
x: totally peeled and cracked

Transparency test

20 [0211] To evaluate the transparency of each sample, the haze of the molded body (glass substrate) of each of the
examples and the comparative examples based on JIS-K 7136: 2000 was observed by means of a haze meter (NDH2000:
available from NIPPON DENSHOKU INDUSTRIES Co., Ltd.). The samples that showed a measurement value of less
than 1.0% were rated as "D", the samples that showed a measurement value of not less than 1.0% and less than 2.0%
were rated as "o" and the samples that showed a measurement value of not less than 2.0% were rated as "3". The
25 measurement surface were conducted at the film coated surface of each sample.

Slip resistance coefficient (when used for a floor)

[0212] test method: An adhesive composition according to the present invention was applied onto a 25 mm-wide and
30 1 mm-thick PC substrate to a thickness of 15 to 20 mm by spin coatings and, after curing, the coefficient of slip resistance
(C. S. R) of the sample was observed according to JIS A 1509-2008 and evaluated according to the rating system shown
below. When the sample piece was small, a plurality of samples were laid on a floor for the test. not more than 0.4: 3
slippery and hazardous 0.4 to 0.5: Δ hardly slippery on a flat floor and hence safe not less than 0.5: o hardly slippery on
an inclined floor and hence safe
35
(Measurement of haze value and total light transmittance)

[0213] Each of the coated glass substrate samples was observed for haze value and total light transmittance by means
of an instrument ("COH-300A": trade name) available from NIPPON DENSHOKU INDUSTRIES Co., Ltd.
40
(Measurement of pencil hardness)

[0214] Each of the coated glass substrate samples was observed for pencil hardness according to the pencil hardness
test method described in JIS K 5400.
45 [0215] Each sample was judged for the presence or absence of scratches by means of the naked eyes of the observer
described in JIS K 5400. However, if the scratches were delicate, the depth of each of the scratches (recessed parts)
was measured by commercially available stylus type surface roughness tester and, "an occurrence of scratches" was
determined when the average depth of the five different scratches was not less than 0.2 mm.

50 (Measurement of Taber abrasion)

[0216] Each of the coated PC (polycarbonate) substrate samples was subjected to a Taber abrasion test (CS-10
abrasion paper, 500 g, 20 times) and subsequently the sample was evaluated for Taber abrasion by seeing of the
difference (ΔH) of the haze value of the film coat before and after the abrasion as determined by means of the formula
55 shown below.

39
 EP 2 578 650 A1

5 Speaker durability evaluation

[0217] A coating was applied to each sample cone paper-made ø16mm circular dome type vibration plate having a
tangential edge to a film thickness of about 10 mm. Then, a micro speaker unit comprising a voice coil, a magnet, a
frame and a damper was prepared by using the vibration plate. The obtained micro speaker was connected to the
10 terminal of a durability tester (ST-2000B: trade name, available from SIGMA Electronics Co., Ltd.) and subjected to load
level shifts, using three levels 0.3 W (1.55 V), 0.7 W (2.34 V) and 1.0 W (2.83 V), of white noise per EIA mode and the
condition of the vibration plate was evaluated according to the rating system shown below (number of samples for
evaluation: 5 sets).
(o) : The vibration plate showed neither cracks not breakdown in not less than 4 sets after a continuous input of 100 hours.
15 (Δ): The vibration plate showed neither cracks not breakdown in not less than 2 sets after an input is not less than 10
hours and is less than 100 hours.
(x): The vibration plate showed both cracks and breakdown in not less than 1 sets after an input is less than 10 hours.

Antirust effect
20
[0218] An adhesive composition according to the present invention was applied onto sample SUS substrates to a film
thickness of 10 mm.
A composite cycle test lasting a total of 8 hours was conducted on each of the samples. In a cycle, salts spray test
(CASS) was conducted at 35°C for 4 hours, subsequently the film coat was dried in a hot and humid condition at 60°C
25 and 50% RH for 2 hours and then an humidity durability test was conducted at 50°C and 95% RH.
The salts spray test (CASS) was conducted by means of the salt spray test method conforming to JIS Z 2371 but the
test liquid was changed from salt water to CASS test solution. CASS test solution is an aqueous solution containing
sodium chloride by 40 g/L and copper (II) chloride by 0.205 g/L and whose pH value was adjusted to 3.0 by means of
acetic acid.
30 A composite cycle test was repeated for 200 times on each sample and the sample was evaluated according to the
rating system shown below (number of evaluated samples: 2 sets).

(o): Neither rust nor swells were observed in 2 sets.

(Δ) : Rust and swells were observed in 1 set.
35 (3): Rust and swells were observed in 2 sets.

[0219]

[Table 1-1]
40
Table 1 Exam. Exam. Exam. Exam. Exam.
Component 1 2 3 4 5
CN975 urethane acrylate available from
(a-1) (i) 30
Sartomer Co. 20 to 40
45
CN292 polyester acrylate available from
(a-1) (ii)
Sartomer Co. 20 to 40
CNUVE151 epoxy acrylate available from
(a-1) (iii) 30 30 30 30
Sartomer Co. 20 to 40
50
CN963B80 urethane acrylate available from
(a-1) (iv)
Sartomer Co. 20 to 40
LIGOLAC21 E-A-2 available from Showa
(a-2)
Highpolymer Co. 20 to 40
55
(b-1-2) polybutadiene polyol Poly bd R-15HT 50

40
 EP 2 578 650 A1

(continued)
Table 1 Exam. Exam. Exam. Exam. Exam.
Component 1 2 3 4 5
5
aromatic castor oil-based polyol URIC AC-
(b-1-1-1) 10 10 10 10 10
006 50
(b-1-3) polyisoprene-based polyol Poly ip 50
(b-2-1) castor oil-based polyol URIC H-1262 50
10
(b-2-1) castor oil-based polyol URIC H-2151 U 50
(b-1-3) hydroxy-terminated liquid polyolefin Epol 50
(b-3-1) maleated polyisoprene LIR-420 50
15 (b-3-2) Ricon130MA8 50
maleic acid modified poly-butadiene
(b-3-2)
POLYVEST OC 800 S 0.1 to 50
(b-1-4) epoxy polyol EPICLON U-125-60BT 50
20
polyepoxy compound ADEKA RESIN
(b-4-1)
EP-4100E 50
(b-4-2) L-207 50
(b-5-1) Lumiflon LF-200 50
25
(b-5-2) Lumiflon LF-302 50
(c-1) (i) N-vinyl caprolactam 30 to 70 60 40 40 20 60
(c-2) (i) dipropylene glycol diacrylate (DPGDA) 30 to 70 20 40
30 (c-2) (ii) tripropylene glycol diacrylate (TPGDA) 30 to 70 20
(c-2) (iii) dipentaerythritol polyacrylate 30 to 70
(c-1) (ii) acryloil morphorine(ACMO) 30 to 70
(d) (i) IRGACURE 819 15 5 5 5 5 5
35
(d) (ii) PERHEXA 25B 15
Total (parts by mass) 105 105 105 105 105
antifouling-property imparting material
40 (BYK-UV3500)
ST)
scratch resistance enhancing material
(NANOBYK- 3602)
45 shock resistance enhancing material
(PARALOID BPM-500)

[0220]

50
[Table 1-2]
IR absorbing material(IR-40K)
UV absorbing material
(TINUVIN326)
55
IR reflecting material (Ti02
CR-90)

41
 EP 2 578 650 A1

(continued)
electromagnetic shielding
material (23-K)
5 S)
antistatic material (CX-Z603M-
F2)
antistatic material (LQ-01)
10
antistatic material (TMAC-100)
flame retardant imparting
material (P type flame
retardant PX-200)
15 Evaluation result viscosity mPa.s(25°C) 1300 1600 1600 1000 1050
haze value % (glass coat) 1.2 1 1.3 0.9 1.3
total light transmittance %
85 84 85 86 86
(glass coat)
20
pencil hardness (glass coat) HB HB HB HB HB
taber abrasion (ΔH) % (PC
7.9 7.5 8.7 6.7 9.1
coat)
weather resistance
25 3 3 3 3 3
test(1000hr)
weather resistance test
s s s s s
(500hr)
surface resistance test( Ω /sq.) 1015 1015 1015 1015 1015
30
IR transmittance(%) at
80 to 85 80 to 85 80 to 85 80 to 85 80 to 85
780nm~2000nm
UV transmittance(%) at
50 to 55 50 to 55 50 to 55 50 to 55 50 to 55
300~380nm
35
visible light transmittance(%)
90 to 95 90 to 95 90 to 95 90 to 95 90 to 95
at 380~780nm
flame retardancy 3 3 3 3 3
skid resistance coefficient Δ Δ Δ Δ Δ
40
adhesion test
hard vinyl chloride resin 100 100 100 100 100
soft vinyl chloride resin 100 100 100 100 100
45
PS 100 100 100 100 100
PC 100 100 100 100 100
glass 100 100 100 100 100

50
aluminum 100 100 100 100 100
steel plate 100 100 100 100 100
concrete 100 100 100 100 100
wood 100 100 100 100 100
55
stone 100 100 100 100 100

42
 EP 2 578 650 A1

(continued)
artificial marble 100 100 100 100 100
PP 0 0 0 0 0
5
HDPE 0 0 0 0 0
MAH-PE 100 100 100 100 100
magnesium 85 80 80 80 85

10 ABS 100 100 100 100 100

PET 100 100 100 100 100
thermoplastic polyurethane
100 100 100 100 100
elastomer
15 2-part liquid polyurethane 100 100 100 100 100
2-part liquid epoxy 100 100 100 100 100
PMMA 100 100 100 100 100
Water resistance test
20
hard vinyl chloride resin s s s s s
soft vinyl chloride resin s s s s s
PS s s s s s
25 PC s s s s s
glass s s s s s

[0221]
30
[Table 1-3]
aluminum s s s s s
steel plate s s s s s
35 concrete s s s s s
wood s s s s s
stone s s s s s
artificial marble s s s s s
40
PP - - - - -
HDPE - - - - -
MAH-PE s s s s s
45
magnesium s s s s s
ABS s s s s s
PET s s s s s

50
thermoplastic polyurethane elastomer s s s s s
2-part liquid polyurethane s s s s s
2-part liquid epoxy s s s s s
PMMA s s s s s
55
Shock resistance test
hard vinyl chloride resin s s s s s

43
 EP 2 578 650 A1

(continued)
soft vinyl chloride resin s s s s s
PS s s s s s
5
PC s s s s s
glass s s s s s
aluminum s s s s s

10 steel plate s s s s s
concrete s s s s s
wood s s s s s
stone s s s s s
15
artificial marble s s s s s
PP - - - - -
HDPE - - - - -

20 MAH-PE s s s s s
magnesium s s s s s
ABS s s s s s
PET s s s s s
25
thermoplastic polyurethane elastomer s s s s s
2-part liquid polyurethane s s s s s
2-part liquid epoxy s s s s s
30 PMMA s s s s s
flexibility test
hard vinyl chloride resin s s s s s
soft vinyl chloride resin s s s s s
35
PS s s s s s
PC s s s s s
glass Δ Δ Δ Δ Δ
40 aluminum s s s s s
steel plate s s s s s
concrete s s s s s
wood s s s s s
45
stone s s s s s
artificial marble Δ Δ Δ Δ Δ
PP - - - - -
50 HDPE - - - - -
MAH-PE s s s s s
magnesium s s s s s
ABS s s s s s
55
PET s s s s s
thermoplastic polyurethane elastomer s s s s s

44
 EP 2 578 650 A1

(continued)
2-part liquid polyurethane s s s s s

5 [0222]

[Table 1-4]
2-part liquid epoxy s s s s s

10 PMMA Δ Δ Δ Δ Δ
test on adhesiveness relative to dissimilar
materials(B1)-(A)-(B2) MPa
hard PVC vs glass 7.3 7.2 7.7 7.5 8
15 soft PVC vs glass 7.7 7.9 7.6 7.8 7.8
PS vs aluminum 8.9 8.2 8.7 8.2 8.3
PC vs aluminum 8.1 8 8.5 8.9 8.6
PS vs glass 7.6 7.5 7.7 7.2 7.7
20
PC vs glass 7.8 7.5 7 7.8 7.2
ABSvs glass 7.1 7.3 7.5 7.6 7.9
glass vs alminum 8 8.7 8.2 8.4 8.6
25 magnesium vs PC 7.5 7.8 7 7.6 7.4
steel plate vs PMMA 8.9 8.8 8.1 8.7 8
PET vs ABS 8.5 8.9 8.3 8.8 8.6
PMMA vs ABS 8.1 8 8.8 8.6 8.9
30
speaker durability evaluation s s s s s
antirust effect s s s s s

35 [0223]

[Table 2-1]
Table 2 Exam. Exam. Exam. Exam.

40
Component 6 7 8 9
(a-1) (i) Co. 20 to 40
(a-1) (ii) Co. 20 to 40
(a-1) (iii) Co. 20 to 40
45
CN963B80 urethane acrylate available from Sartomer
(a-1) (iv) 20 to 40 30 30 30 30
Co.
(a-2) Co. 20 to 40
(b-1-2) polybutadiene polyol Poly bd R-15HT 50
50
(b-1-1-1) aromatic castor oil-based polyol URIC AC-006 50 10 10 10 10
(b-1-3) polyisoprene-based polyol Poly ip 50
(b-2-1) castor oil-based polyol URIC H-1262 50
55 (b-2-1) castor oil-based polyol URIC H-2151 U 50
(b-1-3) hydroxy-terminated liquid polyolefin Epol 50

45
 EP 2 578 650 A1

(continued)
Table 2 Exam. Exam. Exam. Exam.
Component 6 7 8 9
5
(b-3-1) maleated polyisoprene LIR-420 50
(b-3-2) maleic acid modified poly-butadiene Ricon130MA8 50
maleic acid modified poly-butadiene POLYVEST OC
(b-3-2) 0.1 to 50
800 S
10
(b-1-4) epoxy polyol EPICLON U-125-60BT 50
(b-4-1) polyepoxy compound ADEKA RESIN EP-4100E 50
(b-4-2) L-207 50
15 (b-5-1) Lumiflon LF-200 50
(b-5-2) Lumiflon LF-302 50
(c-1) (i) N-vinyl caprolactam 30 to 70 30 30 30 30
(c-2) (i) dipropylene glycol diacrylate (DPGDA) 30 to 70 30
20
(c-2) (ii) tripropylene glycol diacrylate (TPGDA) 30 to 70 30
(c-2) (iii) dipentaerythritol polyacrylate 30 to 70 30
(c-1) (ii) acryloil morphorine(ACMO) 30 to 70 30
25 (d) (i) IRGACURE 819 0.1 to 15 5 5 5 5
(d) (ii) PERHEXA 25B 0.1 to 15
Total (parts by mass) 105 105 105 105
UV3500)
30
scratch resistance enhancing material (MEK-ST)
scratch resistance enhancing material(NANOBYK-
3602)

35 shock resistance enhancing material (PARALOID

BPM-500)
IR absorbing material(IR-40K)
UV absorbing material (TINUVIN326)
40 IR reflecting material (TiO2 CR-90)
electromagnetic shielding material (23-K)

[0224]
45
[Table 2-2]
electroconductive expressing material
(VGCF-S)

50 antistatic material (CX-Z603M-F2)

antistatic material (LQ-01)
antistatic material (TMAC-100)
flame retardant imparting material (P type
55 flame retardant PX-200)
Evaluation result viscosity mPa.s(25°C) 1000 1000 1000 1000

46
 EP 2 578 650 A1

(continued)
haze value % (glass coat) 1 1 1 1
total light transmittance % (glass coat) 88 88 88 88
5
pencil hardness (glass coat) F F H H
taber abrasion (ΔH) % (PC coat) 6.1 6.1 5.4 5.4
weather resistance test(1000hr) 3 3 3 3

10 weather resistance test (500hr) s s s s

surface resistance test (Ω /sq.) 1015 1015 1015 1015
IR transmittance(%) at 780nm~2000nm 80 to 85 80 to 85 80 to 85 80 to 85
UV transmittance(%) at 300~380nm 50 to 55 50 to 55 50 to 55 50 to 55
15
visible light transmittance(%) at
90 to 95 90 to 95 90 to 95 90 to 95
380~780nm
flame retardancy 3 3 3 3
skid resistance coefficient Δ Δ Δ Δ
20
adhesion test
hard vinyl chloride resin 100 100 100 100
soft vinyl chloride resin 100 100 100 100
25 PS 100 100 100 100
PC 100 100 100 100
glass 100 100 100 100
aluminum 100 100 100 100
30
steel plate 100 100 100 100
concrete 100 100 100 100
wood 100 100 100 100
35
stone 100 100 100 100
artificial marble 100 100 100 100
PP 0 0 0 0

40
HDPE 0 0 0 0
MAH-PE 100 100 100 100
magnesium 80 80 70 70
ABS 100 100 100 100
45
PET 100 100 100 100
thermoplastic polyurethane elastomer 100 100 100 100

[0225]
50
[Table 2-3]
2-part liquid polyurethane 100 100 100 100
2-part liquid epoxy 100 100 100 100
55
PMMA 100 100 100 100
Water resistance test

47
 EP 2 578 650 A1

(continued)
hard vinyl chloride resin s s s s
soft vinyl chloride resin s s s s
5
PS s s s s
PC s s s s
glass s s s s

10 aluminum s s s s
steel plate s s s s
concrete s s s s
wood s s s s
15
stone s s s s
artificial marble s s s s
PP - - - -

20 HDPE - - - -
MAH-PE s s s s
magnesium s s s s
ABS s s s s
25
PET s s s s
thermoplastic polyurethane elastomer s s s s
2-part liquid polyurethane s s s s
30 2-part liquid epoxy s s s s
PMMA s s s s
Shock resistance test
hard vinyl chloride resin s s s s
35
soft vinyl chloride resin s s s s
PS s s s s
PC s s s s
40 glass s s s s
aluminum s s s s
steel plate s s s s
concrete s s s s
45
wood s s s s
stone s s s s
artificial marble s s s s
50
[0226]

[Table 2-4]
PP - - - -
55
HDPE - - - -
MAH-PE O O O O

48
 EP 2 578 650 A1

(continued)
magnesium O O O O
ABS O O O O
5
PET O O O O
thermoplastic polyurethane elastomer O O O O
2-part liquid polyurethane O O O O

10 2-part liquid epoxy O O O O

PMMA O O O O
flexibility test
hard vinyl chloride resin O O O O
15
soft vinyl chloride resin O O O O
PS O O O O
PC O O O O

20 glass Δ Δ Δ O
aluminum O O O O
steel plate O O O O
concrete O O O O
25
wood O O O O
stone O O O O
artificial marble Δ Δ Δ O
30 PP - - - -
HDPE - - - -
MAH-PE O O O O
magnesium O O O O
35
ABS O O O O
PET O O O O
thermoplastic polyurethane elastomer O O O O
40 2-part liquid polyurethane O O O O
2-part liquid epoxy O O O O
PMMA Δ Δ Δ O
test on adhesiveness relative to dissimilar
45
materials(B1)-(A)-(B2) MPa
hard PVC vs glass 9 8.6 8.7 13.9
soft PVC vs glass 8.8 8.9 8.6 12.1

50 PS vs aluminum 8.5 8.7 8.4 8.9

PC vs alminum 8 8.2 8.4 8.2
PS vs glass 8.7 8.3 8.1 12.3
PC vs glass 8.8 8.2 8.3 12
55
ABSvs glass 8.7 8.6 8.6 13.4
glass vs alminum 8.6 8.6 8.9 8

49
 EP 2 578 650 A1

(continued)
magnesium vs PC 7.6 7 7.6 7.7
steel plate vs PMMA 8.4 8 8.1 8
5
PET vs ABS 8.6 8.3 8.1 8.2
PMMA vs ABS 8.1 8.4 8.8 8.2
speaker durability evaluation O O O O

10 antirust effect O O O O

[0227]

[Table 3-1]
15
Table 3 Exam. Exam. Exam. Exam. Exam.
Component 10 11 12 13 14
CN975 urethane acrylate available from
(a-1) (i) 20 to 40
Sartomer Co.
20
CN292 polyester acrylate available from
(a-1) (ii) 20 to 40 30
Sartomer Co.
CNUVE151 epoxy acrylate available from
(a-1) (iii) 20 to 40 30 30 30
Sartomer Co.
25
CN963B80 urethane acrylate available from
(a-1) (iv) 20 to 40 30
Sartomer Co.
LIGOLAC21 E-A-2 available from Showa
(a-2) 20 to 40
Highpolymer Co.
30
(b-1-2) polybutadiene polyol Poly bd R-15HT 50
aromatic castor oil-based polyol URIC AC-
(b-1-1-1) 50 10 10
006
(b-1-3) polyisoprene-based polyol Poly ip 50 10
35
(b-2-1) castor oil-based polyol URIC H-1262 50 10
(b-2-1) castor oil-based polyol URIC H-2151U 50 10
(b-1-3) hydroxy-terminated liquid polyolefin Epol 50
40 (b-3-1) maleated polylsoprene LIR-420 50
(b-3-2) Ricon130MA8 50
(b-3-2) POLYVEST OC 800 S 50
(b-1-4) epoxy polyol EPICLON U-125-60BT 50
45
polyepoxy compound ADEKA RESIN
(b-4-1) 50
EP-4100E
(b-4-2) L-207 50

50 (b-5-1) Lumiflon LF-200 50

(b-5-2) Lumiflon LF-302 50
(c-1) (i) N-vinyl caprolactam 30 to 70 60 60 60 60 60
(c-2) (i) dipropylene glycol diacrylate (DPGDA) 30 to 70
55
(c-2) (ii) tripropylene glycol diacrylate (TPGDA) 30 to 70
(c-2) (iii) dipentaerythritol polyacrylate 30 to 70

50
 EP 2 578 650 A1

(continued)
Table 3 Exam. Exam. Exam. Exam. Exam.
Component 10 11 12 13 14
5
(c-1) (ii) acryloil morphorine(ACMO) 30 to 70
(d) (i) IRGACURE 819 0.1 to 15 5 5 5 5 5
(d) (ii) PERHEXA 25B 0.1 to 15

10 Total (parts by mass) 105 105 105 105 105

antifouling-property imparting material
(BYK-UV3500)
scratch resistance enhancing material
15 (MEK-ST)
scratch resistance enhancing material
(NANOBYK- 3602)
shock resistance enhancing material
(PARALOID BPM-500)
20
IR absorbing material (IR-40K)
UV absorbing material (TINUVIN326)
IR reflecting material (TiO2 CR-90)
25
electromagnetic shielding material (23-K)

[0228]

30
[Table 3-2]
S)
antistatic material (CX-Z603M-
F2)

35 antistatic material (LQ-01)

antistatic material (TMAC-100)
flame retardant imparting
material (P type flame
40 retardant PX-200)
Evaluation result viscosity mPa.s(25°C) 340 1350 1350 1400 1380
haze value % (glass coat) 1.2 1.2 1 1.1 0.9
total light transmittance %
85 86 87 87 86
45 (glass coat)
pencil hardness (glass coat) HB HB HB HB HB
taber abrasion (ΔH) % (PC
8.1 8.9 7.9 8.4 6.6
coat)
50
weather resistance
3 3 3 3 3
test(1000hr)
weather resistance test
O O O O O
(500hr)
55
surface resistance test(Ω/sq.) 1015 1015 1015 1015 1015

51
 EP 2 578 650 A1

(continued)
IR transmittance(%) at
80 to 85 80 to 85 80 to 85 80 to 85 80 to 85
780nm∼2000nm
5 UV transmittance(%) at
50 to 55 50 to 55 50 to 55 50 to 55 50 to 55
300∼380nm
visible light transmittance(%)
90 to 95 90 to 95 90 to 95 90 to 95 90 to 95
at 380∼780nm
10 flame retardancy 3 3 3 3 3
skid resistance coefficient Δ Δ Δ Δ Δ
adhesion test
hard vinyl chloride resin 100 100 100 100 100
15
soft vinyl chloride resin 100 100 100 100 100
PS 100 100 100 100 100
PC 100 100 100 100 100
20 glass 100 100 100 100 100
aluminum 100 100 100 100 100
steel plate 100 100 100 100 100
concrete 100 100 100 100 100
25
wood 100 100 100 100 100
stone 100 100 100 100 100
artificial marble 100 100 100 100 100
30 PP 60 60 60 60 60
HDPE 0 0 0 0 0
MAH-PE 100 100 100 100 100
magnesium 90 90 90 90 90
35
ABS 100 100 100 100 100
PET 100 100 100 100 100
thermoplastic polyurethane
100 100 100 100 100
40 elastomer
2-part liquid polyurethane 100 100 100 100 100
2-part liquid epoxy 100 100 100 100 100
PMMA 100 100 100 100 100
45

[0229]

[Table 3-3]

50 Water resistance test

hard vinyl chloride resin O O O O O
soft vinyl chloride resin O O O O O
PS O O O O O
55
PC O O O O O
glass O O O O O

52
 EP 2 578 650 A1

(continued)
aluminum O O O O O
steel plate O O O O O
5
concrete O O O O O
wood O O O O O
stone O O O O O

10 artificial marble O O O O O
PP 3 3 3 3 3
HDPE - - - - -
MAH-PE O O O O O
15
magnesium O O O O O
ABS O O O O O
PET O O O O O

20 thermoplastic polyurethane elastomer O O O O O

2-part liquid polyurethane O O O O O
2-part liquid epoxy O O O O O
PMMA O O O O O
25
Shock resistance test
hard vinyl chloride resin O O O O O
soft vinyl chloride resin O O O O O
30 PS O O O O O
PC O O O O O
glass Δ Δ Δ Δ Δ
aluminum O O O O O
35
steel plate O O O O O
concrete O O O O O
wood O O O O O
40 stone O O O O O
artificial marble Δ Δ Δ Δ Δ
PP 3 3 3 3 3
HDPE - - - - -
45
MAH-PE O O O O O
magnesium O O O O O
ABS O O O O O
50 PET O O O O O
thermoplastic polyurethane elastomer O O O O O
2-part liquid polyurethane O O O O O
2-part liquid epoxy O O O O O
55

[0230]

53
 EP 2 578 650 A1

[Table 3-4]
PMMA Δ Δ Δ Δ Δ
flexibility test
5
hard vinyl chloride resin O O O O O
soft vinyl chloride resin O O O O O
PS O O O O O

10 PC O O O O O
glass O O O O O
aluminum O O O O O
steel plate O O O O O
15
concrete O O O O O
wood O O O O O
stone O O O O O

20 artificial marble O O O O O
PP O O O O O
HDPE O O O O O
MAH-PE O O O O O
25
magnesium O O O O O
ABS O O O O O
PET O O O O O
30 thermoplastic polyurethane elastomer O O O O O
2-part liquid polyurethane O O O O O
2-part liquid epoxy O O O O O
PMMA O O O O O
35
test on adhesiveness relative to dissimilar
materials(B1)-(A)-(82) MPa
hard PVC vs glass 8.5 8.8 8.1 8.3 8

40
soft PVC vs glass 8.1 8.6 8.8 9 8.7
PS vs aluminum 8.2 8.9 8.5 8.2 8.5
PC vs alminum 8.6 8.1 9 8.5 8.1
PS vs glass 8.2 8.7 8 8.5 8.3
45
PC vs glass 8.2 8.4 8.4 8.9 8.3
ABSvs glass 8.2 8.6 8.5 8.6 8
glass vs alminum 8.7 9 8.4 8.1 8.7

50 magnesium vs PC 7.8 7.8 7.5 7.5 7.6

steel plate vs PMMA 8.9 8.9 8.4 8.9 8.4
PET vs ABS 8.6 8.6 8.1 8.5 8.9
PMMA vs ABS 8.2 8 9 8.5 8.6
55
speaker durability evaluation O O O O O
antirust effect O O O O O

54
 EP 2 578 650 A1

[0231]

[Table 4-1]
Table 4 Exam. Exam. Exam. Exam. Exam.
5
Component 15 16 17 18 19
CN975 urethane acrylate available from
(a-1) (i) 20 to 40
Sartomer Co.

10 CN292 polyester acrylate available from

(a-1) (ii) 20 to 40
Sartomer Co.
CNUVE151 epoxy acrylate available from
(a-1) (iii) 20 to 40 30 30 30 30 30
Sartomer Co.
CN963B80 urethane acrylate available from
15 (a-1) (iv) 20 to 40
Sartomer Co.
LIGOLAC21E-A-2 available from Showa
(a-2) 20 to 40
Highpolymer Co.
(b-1-2) polybutadiene polyol Poly bd R-15HT 50
20
aromatic castor oil-based polyol URIC AC-
(b-1-1-1) 50
006
(b-1-3) polyisoprene-based polyol Poly ip 50

25 (b-2-1) castor oil-based polyol URIC H-1262 50

(b-2-1) castor oil-based polyol URIC H-2151 U 50
(b-1-3) hydroxy-terminated liquid polyolefin Epol 50 10
(b-3-1) maleated polyisoprene LIR-420 50 10
30
(b-3-2) Ricon130MA8 50 10
maleic acid modified poly-butadiene
(b-3-2) 0.1 to 50 10
POLYVEST OC 800 S
(b-1-4) epoxy polyol EPICLON U-125-60BT 50 10
35
polyepoxy compound ADEKA RESIN
(b-4-1) 50
EP-4100E
(b-4-2) L-207 50

40 (b-5-1) Lumiflon LF-200 50

(b-5-2) Lumiflon LF-302 50
(c-1) (i) N-vinyl caprolactam 30 to 70 60 60 60 60 60
(c-2) (i) dipropylene glycol diacrylate (DPGDA) 30 to 70
45
(c-2) (ii) tripropylene glycol diacrylate (TPGDA) 30 to 70
(c-2) (iii) dipentaerythritol polyacrylate 30 to 70
(c-1) (ii) acryloil morphorine(ACMO) 30 to 70

50 (d) (i) IRGACURE 819 0.1 to 15 5 5 5 5 5

(d) (ii) PERHEXA 25B 0.1 to 15
Total (parts by mass) 105 105 105 105 105
antifouling-property imparting material
55 (BYK-UV3500)
ST)

55
 EP 2 578 650 A1

(continued)
Table 4 Exam. Exam. Exam. Exam. Exam.
Component 15 16 17 18 19
5
scratch resistance enhancing material
(NANOBYK- 3602)
shock resistance enhancing material
(PARALOID BPM-500)
10
IR absorbing material (IR-40K)
UV absorbing material (TINUVIN326)
IR reflecting material (Ti02 CR-90)

15 electromagnetic shielding material (23-K)

S)

[0232]
20
[Table 4-2]
antistatic material (CX-Z603M-
F2)
antistatic material (LQ-01)
25
antistatic material (TMAC-100)
flame retardant imparting
material (P type flame
retardant PX-200)
30
Evaluation result viscosity mPa.s(25°C) 1350 1350 1400 1350 1350
haze value % (glass coat) 1.2 0.9 1 1.2 1
total light transmittance %
85 86 86 85 86
(glass coat)
35
pencil hardness (glass coat) HB HB HB HB HB
taber abrasion (ΔH) % (PC
8.1 6.6 7.1 8.1 7.1
coat)

40 weather resistance test

3 3 3 3 3
(1000hr)
weather resistance test
s s s s s
(500hr)

45
surface resistance test (Ω / sq.) 1015 1015 1015 1015 1015
IR transmittance(%) at
80 to 85 80 to 85 80 to 85 80 to 85 80 to 85
780nm~2000nm
UV transmittance(%) at
50 to 55 50 to 55 50 to 55 50 to 55 50 to 55
300~380nm.
50
visible light transmittance(%)
90 to 95 90 to 95 90 to 95 90 to 95 90 to 95
at 380~780nm
flame retardancy 3 3 3 3 3

55 skid resistance coefficient Δ Δ Δ Δ Δ

56
 EP 2 578 650 A1

(continued)
adhesion test
hard vinyl chloride resin 100 100 100 100 100
5
soft vinyl chloride resin 100 100 100 100 100
PS 100 100 100 100 100
PC 100 100 100 100 100

10 glass 100 100 100 100 100

aluminum 100 100 100 100 100
steel plate 100 100 100 100 100
concrete 100 100 100 100 100
15
wood 100 100 100 100 100
stone 100 100 100 100 100
artificial marble 100 100 100 100 100

20 PP 100 60 90 90 60
HDPE 100 0 80 80 0
MAH-PE 100 100 100 100 100
magnesium 90 90 90 100 90
25
ABS 100 100 100 100 100
PET 100 100 100 100 100
thermoplastic polyurethane
100 100 100 100 100
elastomer
30
2-part liquid polyurethane 100 100 100 100 100
2-part liquid epoxy 100 100 100 100 100
PMMA 100 100 100 100 100
35
Water resistance test

[0233]

40
[Table 4-3]
hard vinyl chloride resin s s s s s
soft vinyl chloride resin s s s s s
PS s s s s s
45
PC s s s s s
glass Δ Δ Δ Δ Δ
aluminum s s s s s

50
steel plate s s s s s
concrete s s s s s
wood s s s s s
stone s s s s s
55
artificial marble Δ Δ Δ Δ Δ
PP s 3 s s 3

57
 EP 2 578 650 A1

(continued)
HDPE s - s s -
MAH-PE s s s s s
5
magnesium s s s s s
ABS s s s s s
PET s s s s s

10 thermoplastic polyurethane elastomer s s s s s

2-part liquid polyurethane s s s s s
2-part liquid epoxy s s s s s
PMMA Δ Δ Δ Δ Δ
15
Shock resistance test
hard vinyl chloride resin s s s s s
soft vinyl chloride resin s s s s s

20 PS s s s s s
PC s s s s s
glass s s s s s
aluminum s s s s s
25
steel plate s s s s s
concrete s s s s s
wood s s s s s
30 stone s s s s s
artificial marble s s s s s
PP s 3 s s 3
HDPE s s s s s
35
MAH-PE s s s s s
magnesium s s s s s
ABS s s s s s
40 PET s s s s s
thermoplastic polyurethane elastomer s s s s s
2-part liquid polyurethane s s s s s
2-part liquid epoxy s s s s s
45
PMMA s s s s s

[0234]

50 [Table 4-4]
flexibility test
hard vinyl chloride resin s s s s s
soft vinyl chloride resin s s s s s
55
PS s s s s s
PC s s s s s

58
 EP 2 578 650 A1

(continued)
glass s s s s s
aluminum s s s s s
5
steel plate s s s s s
concrete s s s s s
wood s s s s s

10 stone s s s s s
artificial marble s s s s s
PP s 3 s s 3
HDPE s - s s -
15
MAH-PE s s s s s
magnesium s s s s s
ABS s s s s s

20 PET s s s s s
thermoplastic polyurethane elastomer s s s s s
2-part liquid polyurethane s s s s s
2-part liquid epoxy s s s s s
25
PMMA s s s s s
test on adhesiveness relative to dissimilar
materials(B1)-(A)-(B2) MPa
hard PVC vs glass 8 8.3 8.4 8.8 8.2
30
soft PVC vs glass 8 8.9 8.1 8.4 8.8
PS vs aluminum 8.4 8 8.7 8.1 8.9
PC vs alminum 8.6 8.1 8.7 8.3 8.2
35
PS vs glass 8.1 8.5 8.9 8.2 8.8
PC vs glass 8.6 8 8.1 9 9
ABSvs glass 8 8.8 8.5 9 8.4

40
glass vs alminum 8.9 8.9 8 8.2 8.1
magnesium vs PC 7.8 7.5 7.9 7.1 7.1
steel plate vs PMMA 8.5 8.8 8.9 8.6 8
PET vs ABS 8.8 8.7 8.8 8.2 8
45
PMMA vs ABS 8.5 8.7 8.4 8.6 8.4
speaker durability evaluation s s s s s
antirust effect Δ Δ Δ Δ s

50
[0235]

55

59
 EP 2 578 650 A1

[Table 5-1]
Table 5 Exam. Exam. Exam. Exam. Exam. Exam.
Component 20 21 22 23 24 25
5
CN975 urethane
20 to
(a-1) (i) acrylate available from
40
Sartomer Co.
CN292 polyester
20 to
10 (a-1) (ii) acrylate available from
40
Sartomer Co.
CNUVE151 epoxy
20 to
(a-1) (iii) acrylate available from 30 30 30 30 30
40
Sartomer Co.
15
CN963B80 urethane
20 to
(a-1) (iv) acrylate available from
40
Sartomer Co.
LIGOLAC21 E-A-2
20 20 to
(a-2) available from Showa 30
40
Highpolymer Co.
polybutadiene polyol
(b-1-2) 50
Poly bd R-15HT
25 aromatic castor
(b-1-1-1) oil-based polyol URIC 50 10 10
AC-006
polyisoprene-based
(b-1-3) 50
polyol Poly ip
30
castor oil-based polyol
(b-2-1) 50
URIC H-1262
castor oil-based polyol
(b-2-1) 50
URIC H-2151U
35
hydroxy-terminated
(b-1-3) 50
liquid polyolefin Epol
maleated polyisoprene
(b-3-1) 50
LIR-420
40
(b-3-2) Ricon130MA8 50
maleic acid modified
0.1 to
(b-3-2) poly-butadiene
50
POLYVEST OC 800 S
45
epoxy polyol EPICLON
(b-1-4) 50
U-125-60BT
polyepoxy compound
(b-4-1) ADEKA RESIN 50 10
50 EP-4100E
(b-4-2) L-207 50 10
(b-5-1) 10) 50 16.7
(b-5-2) 10) 50 20
55

60
 EP 2 578 650 A1

(continued)
Table 5 Exam. Exam. Exam. Exam. Exam. Exam.
Component 20 21 22 23 24 25
5
30 to
(c-1) (i) N-vinyl caprolactam 60 60 60 60 60 60
70
dipropylene glycol 30 to
(c-2) (i)
diacrylate (DPGDA) 70
10
tripropylene glycol 30 to
(c-2) (ii)
diacrylate (TPGDA) 70
dipentaerythritol 30 to
(c-2) (iii)
polyacrylate 70
15 acryloil 30 to
(c-1) (ii)
morphorine(ACMO) 70
0.1 to
(d) (i) IRGACURE 819 5 5 5 5 5
15
20 0.1 to
(d) (ii) PERHEXA 25B 0.3
15
Total (parts by mass) 105 105 111.7 115 100.3 105
antifouling-property
25 imparting material
(BYK-UV3500)
ST)
scratch resistance
30 enhancing material
(NANOBYK- 3602)
shock resistance
enhancing material
(PARALOID BPM-500)
35
IR absorbing material
(IR-40K)
UV absorbing material
(TINUVIN326)
40

[0236]

[Table 5-2]
45 IR reflecting material
(Ti02 CR-90)
electromagnetic
shielding material
(23-K)
50
S)
antistatic material
(CX-Z603M-F2)

55
antistatic material
(LQ-01)

61
 EP 2 578 650 A1

(continued)
antistatic material
(TMAC-100)
5 flame retardant
imparting material (P
type flame retardant
PX-200)
Evaluation viscosity
10 1300 1400 900 810 1250 1580
result mPa.s(25°C)
haze value % (glass
1 0.9 0.9 0.9 1.1 1.2
coat)
total light
15
transmittance % 86 86 86 86 86 84
(glass coat)
pencil hardness
HB HB HB HB HB HB
(glass coat)
20 taber abrasion (ΔH)
7.1 6.6 7.5 9.6 7.6 8.1
% (PC coat)
weather resistance
3 3 s s 3 3
test(1000hr)
25 weather resistance
s s s s s s
test (500hr)
surface resistance
1015 1015 1015 1015 1015 1015
test( Ω/sq.)
30 IR transmittance(%)
80 to 85 80 to 85 80 to 85 80 to 85 80 to 85 80 to 85
at 780nm~2000nm
UV transmittance(%)
50 to 55 50 to 55 50 to 55 50 to 55 50 to 55 50 to 55
at 300~380nm

35 visible light
transmittance(%) at 90 to 95 90 to 95 90 to 95 90 to 95 90 to 95 90 to 95
380~780nm
flame retardancy 3 3 3 3 3 3

40 skid resistance
Δ Δ Δ Δ Δ Δ
coefficient
adhesion test
hard vinyl chloride
100 100 100 100 100 100
45
resin
soft vinyl chloride
100 100 100 100 100 100
resin
PS 100 100 100 100 100 100
50 PC 100 100 100 100 100 100
glass 100 100 100 100 100 100
aluminum 100 100 100 100 100 100
steel plate 100 100 100 100 100 100
55
concrete 100 100 100 100 100 100

62
 EP 2 578 650 A1

(continued)
wood 100 100 100 100 100 100
stone 100 100 100 100 100 100
5
artificial marble 100 100 100 100 100 100
PP 60 60 60 60 60 60
HDPE 10 10 10 10 0 0

10 MAH-PE 100 100 100 100 100 100

magnesium 100 100 100 100 100 100
ABS 100 100 100 100 100 100
PET 100 100 100 100 100 100
15
thermoplastic
polyurethane 100 100 100 100 100 100
elastomer
2-part liquid
100 100 100 100 100 100
20 polyurethane

[0237]

[Table 5-3]
25
2-part liquid epoxy 100 100 100 100 100 100
PMMA 100 100 100 100 100 100
Water resistance test
30 hard vinyl chloride resin s s s s s s
soft vinyl chloride resin s s s s s s
PS s s s s s s
PC s s s s s s
35
glass s s s s s s
aluminum s s s s s s
steel plate s s s s s s
40 concrete s s s s s s
wood s s s s s s
stone s s s s s s
artificial marble s s s s s s
45
PP s s s s 3 3
HDPE 3 3 3 3 - -
MAH-PE s s s s s s
50 magnesium s s s s s s
ABS s s s s s s
PET s s s s s s
thermoplastic polyurethane
55 s s s s s s
elastomer
2-part liquid polyurethane s s s s s s

63
 EP 2 578 650 A1

(continued)
2-part liquid epoxy s s s s s s
PMMA s s s s s s
5
Shock resistance test
hard vinyl chloride resin s s s s s s
soft vinyl chloride resin s s s s s s

10 PS s s s s s s
PC s s s s s s
glass s s s s s s
aluminum s s s s s s
15
steel plate s s s s s s
concrete s s s s s s
wood s s s s s s

20 stone s s s s s s
artificial marble s s s s s s
PP s s s s 3 3
HDPE 3 3 3 3 - -
25
MAH-PE s s s s s s
magnesium s s s s s s
ABS s s s s s s
30 PET s s s s s s
thermoplastic polyurethane
s s s s s s
elastomer

35 [0238]

[Table 5-4]
2-part liquid polyurethane O O O O O O
2-part liquid epoxy O O O O O O
40
PMMA O O O O O O
flexibility test
hard vinyl chloride resin O O O O O O
45
soft vinyl chloride resin O O O O O O
PS O O O O O O
PC O O O O O O

50
glass Δ Δ O O Δ Δ
aluminum O O O O O O
steel plate O O O O O O
concrete O O O O O O
55
wood O O O O O O
stone O O O O O O

64
 EP 2 578 650 A1

(continued)
artificial marble Δ Δ O O Δ Δ
PP O O O O 3 3
5
HDPE 3 3 3 3 - -
MAH-PE O O O O O O
magnesium O O O O O O

10 ABS O O O O O O
PET O O O O O O
thermoplastic polyurethane
O O O O O O
elastomer
15 2-part liquid polyurethane O O O O O O
2-part liquid epoxy O O O O O O
PMMA Δ Δ O O Δ Δ
test on adhesiveness relative to
20
dissimilar materials
(B1)-(A)-(B2) MPa
hard PVC vs glass 8.3 9 8.7 8.7 8.2 8.8
soft PVC vs glass 8.8 9 8.3 8.3 8.7 8
25
PS vs aluminum 8.8 9 8.5 8.5 8.6 8.4
PC vs alminum 8.1 8.6 8.7 8.7 9 9
PS vs glass 8.5 8.6 8.1 8.1 8.8 8.9
30 PC vs glass 9 8.9 8.3 8.3 8.3 8
ABSvs glass 8.9 8.8 8.1 8.1 8.6 8.5
glass vs alminum 8.1 8.3 8.5 8.5 8.5 8.5
magnesium vs PC 7.9 7 7.6 7.6 7.5 7.8
35
steel plate vs PMMA 8.3 8.7 8.2 8.2 9 8.8
PET vs ABS 8.1 8.7 8.3 8.3 8 8.4
PMMA vs ABS 8.8 8.5 8.3 8.3 8.1 8
40
speaker durability evaluation O O O O O O
antirust effect O O O O O O

[0239]
45
[Table 6-1]
Comp . Comp . Comp . Comp . Comp . Comp .
Table 6
Ex. Ex. Ex. Ex. Ex. Ex.

50 Component 1 2 3 4 5 6
GN975 urethane
20 to
(a-1) (i) acrylate available from
40
Sartomer Co.

55 CN292 polyester
20 to
(a-1) (ii) acrylate available from
40
Sartomer Co.

65
 EP 2 578 650 A1

(continued)
Comp . Comp . Comp . Comp . Comp . Comp .
Table 6
Ex. Ex. Ex. Ex. Ex. Ex.
5 Component 1 2 3 4 5 6
CNUVE151 epoxy
20 to
(a-1) (iii) acrylate available from 15 45 65 20 35 25
40
Sartomer Co.
10 CNH63b80 urethane
20 to
(a-1) (iv) acrylate available from
40
Sartomer Co.
LIGULAC2TE-A-2
20 to
(a-2) available from Showa
15 40
Highpolymer Co.
polybutadiene polyol
(b-1-2) 50
Poly bd R-15HT
aromatic castor
20 (b-1-1-1) oil-based polyol URIC 50 20 10 10 5 55
AC-006
polyisoprene-based
(b-1-3) 50
polyol Poly ip
25 castor oil-based polyol
(b-2-1) 50
URIC H-1262
castor oil-based polyol
(b-2-1) 50
URIC H-2151U
30 hydroxy-terminated
(b-1-3) 50
liquid polyolefin Epol
maleated polyisoprene
(b-3-1) 50
LIR-420

35 (b-3-2) Ricon130MA8 50
(b-3-2) POLYVEST OC 800 S 50
epoxy polyol EPICLON
(b-1-4) 50
U-125-60BT
40 polyepoxy compound
(b-4-1) ADEKA RESIN 50
EP-4100E
(b-4-2) L-207 50
45 (b-5-1) Lumiflon LF-200 50
(b-5-2) Lumiflon LF-302 50
30 to
(c-1) (i) N-vinyl caprolactam 65 45 25 75 65 40
70
50
dipropylene glycol 30 to
(c-2) (i)
diacrylate (DPGDA) 70

55

66
 EP 2 578 650 A1

(continued)
Comp . Comp . Comp . Comp . Comp . Comp .
Table 6
Ex. Ex. Ex. Ex. Ex. Ex.
5 Component 1 2 3 4 5 6
tripropylene glycol 30 to
(c-2) (ii)
diacrylate (TPGDA) 70
dipentaerythritol 30 to
(c-2) (iii)
10 polyacrylate 70
acryloil 30 to
(c-1) (ii)
morphorine(ACMO) 70
0.1 to
(d) (i) IRGACURE 819 5 5 5 5 5 5
15 15
0.1 to
(d) (ii) PERHEXA 25B
15
Total (parts by mass) 105 105 105 105 105 125
20 UV3500)
ST)
scratch resistance
enhancing material
25 (NANOBYK-3602)
shock resistance
BPM-500) enhancing material
(PARALOID BPM-500)

30 IR absorbing material
(IR-40K)
UV absorbing material
(TINUVIN326)

35 IR reflecting material
(TiO2 CR-90)
electromagnetic
shielding material
(23-K)
40
S)
antistatic material
(CX-Z603M-F2)
antistatic material
45
(LQ-01 )
antistatic material
(TMAC-100)

50

55

67
 EP 2 578 650 A1

(continued)
Comp . Comp . Comp . Comp . Comp . Comp .
Table 6
Ex. Ex. Ex. Ex. Ex. Ex.
5 Component 1 2 3 4 5 6
flame retardant
imparting material (P
type flame retardant
PX-200)
10

[0240]

[Table 6-2]
15 Evaluation viscosity
600 1500 600 1500 1050 1120
result mPa.s(25°C)
haze value % (glass
1.1 0.8 1.1 0.8 0.8 1.1
coat)
20 total light
transmittance % 86 87 86 87 87 80
(glass coat)
pencil hardness
HB HB HB HB HB 2B
(glass coat)
25
taber abrasion (ΔH)
17.8 9.3 17.8 9.3 9.2 7.6
% (PC coat)
weather resistance
3 3 3 3 3 3
test(1000hr)
30
weather resistance
O O O O O O
test (500hr)
surface resistance
1015 1010 1015 1015 1015 1015
test(Ω/sq.)
35
IR transmittance(%)
80 to 85 80 to 85 80 to 85 80 to 85 80 to 85 80 to 85
at 780nm∼2000nm
UV transmittance(%)
50 to 55 50 to 55 50 to 55 50 to 55 50 to 55 50 to 55
at 300∼380nm
40
visible light
transmittance(%) at 90 to 95 90 to 95 90 to 95 90 to 95 90 to 95 90 to 95
380∼780nm
flame retardancy 3 3 3 3 3 3
45
skid resistance
Δ 3 3 3 3 O
coefficient
adhesion test
hard vinyl chloride
50 56 56 56 56 56 56
resin
soft vinyl chloride
56 56 56 56 56 56
resin
PS 44 56 44 56 50 47
55
PC 56 56 56 56 56 56

68
 EP 2 578 650 A1

(continued)
glass 33 56 33 56 44 44
aluminum 43 45 43 45 42 40
5
steel plate 45 49 45 49 52 57
concrete 46 58 46 58 45 59
wood 66 71 66 71 66 65

10 stone 37 35 37 35 34 38
artificial marble 32 40 32 40 30 30
PP 0 0 0 0 0 0
HDPE 0 0 0 0 0 0
15
MAH-PE 75 65 75 65 70 73
magnesium 0 0 0 0 0 0
ABS 56 56 56 56 39 56

20 PET 56 56 56 56 56 56
thermoplastic
polyurethane 65 70 65 70 70 73
elastomer

25 2-part liquid
69 66 69 66 69 67
polyurethane
2-part liquid epoxy 71 65 71 65 68 70
PMMA 39 56 39 56 33 50
30 Water resistance test
hard vinyl chloride
3 Δ 3 Δ Δ 3
resin
soft vinyl chloride
3 Δ 3 Δ Δ 3
35 resin
PS 3 Δ 3 Δ Δ 3
PC 3 Δ 3 Δ Δ 3
glass 3 Δ 3 Δ Δ 3
40
aluminum 3 Δ 3 Δ Δ 3
steel plate 3 Δ 3 Δ Δ 3
concrete 3 Δ 3 Δ Δ 3
45 wood 3 Δ 3 Δ Δ 3
stone 3 Δ 3 Δ Δ 3
artificial marble 3 Δ 3 Δ Δ 3
pp - - - - - -
50

[0241]

[Table 6-3]
55 HDPE - - - - - -
MAH-PE 3 Δ 3 Δ Δ 3

69
 EP 2 578 650 A1

(continued)
magnesium - - - - - -
ABS 3 Δ 3 Δ Δ 3
5
PET Δ Δ 3 Δ Δ 3
thermoplastic polyurethane
3 Δ 3 Δ Δ 3
elastomer
2-part liquid polyurethane 3 Δ 3 Δ Δ 3
10
2-part liquid epoxy 3 Δ 3 Δ Δ 3
PMMA 3 Δ 3 Δ Δ 3
Shock resistance test
15 hard vinyl chloride resin 3 Δ 3 Δ 3 O
soft vinyl chloride resin 3 Δ 3 Δ 3 O
PS 3 Δ 3 Δ 3 O
PC 3 Δ 3 Δ 3 O
20
glass 3 Δ 3 Δ 3 O
aluminum 3 Δ 3 Δ 3 O
steel plate 3 Δ 3 Δ 3 O
25 concrete 3 Δ 3 Δ 3 O
wood 3 Δ 3 Δ 3 O
stone 3 Δ 3 Δ 3 O
artificial marble 3 Δ 3 Δ 3 O
30
PP - - - - - -
HDPE - - - - - -
MAH-PE 3 Δ 3 Δ Δ 3
35
magnesium - - - - - -
ABS 3 Δ 3 Δ 3 O
PET 3 Δ 3 Δ 3 O
thermoplastic polyurethane
40 3 Δ 3 Δ 3 O
elastomer
2-part liquid polyurethane 3 Δ 3 Δ 3 O
2-part liquid epoxy 3 Δ 3 Δ 3 O
45 PMMA 3 Δ 3 Δ 3 O
flexibility test
hard vinyl chloride resin 3 Δ 3 Δ 3 O
soft vinyl chloride resin 3 Δ 3 Δ 3 O
50
PS 3 Δ 3 Δ 3 O
PC 3 Δ 3 Δ 3 O
glass 3 3 3 3 3 O
55 aluminum 3 Δ 3 Δ 3 O
steel plate 3 Δ 3 Δ 3 O

70
 EP 2 578 650 A1

(continued)
concrete 3 Δ 3 Δ 3 O
wood 3 Δ 3 Δ 3 O
5
stone 3 Δ 3 Δ 3 O
artificial marble 3 3 3 3 3 O
PP - - - - - -

10 HDPE - - - - - -
MAH-PE 3 Δ 3 Δ Δ 3
magnesium - - - - - -
ABS 3 Δ 3 Δ 3 O
15
PET 3 Δ 3 Δ 3 O
thermoplastic polyurethane
3 Δ 3 Δ 3 O
elastomer
2-part liquid polyurethane 3 Δ 3 Δ 3 O
20
2-part liquid epoxy 3 Δ 3 Δ 3 O

[0242]

25 [Table 6-4]
PMMA 3 3 3 3 3 O
test on adhesiveness relative to
dissimilar materials (B1)-(A)-(B2)
30 MPa
hard PVC vs glass 2.2 3.1 2.2 3.1 2.5 4.1
soft PVC vs glass 3 2.9 3 2.9 4.8 3.7
PS vs aluminum 2 2 2 2 3.6 2.4
35
PC vs alminum 3.2 4.1 3.2 4.1 4.6 3.3
PS vs glass 2.7 4 2.7 4 2.4 2.1
PC vs glass 3.9 3.8 3.9 3.8 5 4.3
40 ABSvs glass 4.9 4.6 4.9 4.6 3 3.3
glass vs alminum 2.2 3.4 2.2 3.4 2.9 2.5
magnesium vs PC 0 0 0 0 0 0
steel plate vs PMMA 5 2.7 5 2.7 2.6 2.4
45
PET vs ABS 2.6 2.8 2.6 2.8 2.2 3.2
PMMA vs ABS 2.9 2.6 2.9 2.6 4.7 4.6
speaker durability evaluation 3 3 3 Δ Δ 3
50 antirust effect 3 3 3 3 3 3

[0243]

55

71
 EP 2 578 650 A1

[Table 7-1]
Table 7 Comp. Ex. Comp. Ex.
Component 7 8
5
(a-1) (i) CN975 urethane acrylate available from Sartomer Co. 20 to 40
(a-1) (ii) CN292 polyester acrylate available from Sartomer Co. 20 to 40
(a-1) (iii) CNUVE151 epoxy acrylate available from Sartomer Co. 20 to 40 30 30

10 (a-1) (iv) CN963B80 urethane acrylate available from Sartomer Co. 20 to 40

(a-2) LIGOLAC21E-A-2 available from Showa Highpolymer Co. 20 to 40
(b-1-2) polybutadiene polyol Poly bd R-15HT 0.1 to 50
(b-1-1-1) aromatic castor oil-based polyol URIC AC-006 0.1 to 50 10 10
15
(b-1-3) polyisoprene-based polyol Poly ip 0.1 to 50
(b-2-1) castor oil-based polyol URIC H-1262 0.1 to 50
(b-2-1) castor oil-based polyol URIC H-2151 U 0.1 to 50

20 (b-1-3) hydroxy-terminated liquid polyolefin Epol 0.1 to 50

(b-3-1) maleated polyisoprene LIR-420 0.1 to 50
(b-3-2) maleic acid modified poly-butadiene Ricon130MA8 0.1 to 50
(b-3-2) maleic acid modified poly-butadiene POLYVEST OC 800 S 0.1 to 50
25
(b-1-4) epoxy polyol EPICLON U-125-60BT 0.1 to 50
(b-4-1) polyepoxy compound ADEKA RESIN EP-4100E 0.1 to 50
(b-4-2) L-207 0.1 to 50
30 (b-5-1) Lumiflon LF-200 0.1 to 50
(b-5-2) Lumiflon LF-302 0.1 to 50
(c-1) (i) N-vinyl caprolactam 30 to 70 60 60
(c-2) (i) dipropylene glycol diacrylate (DPGDA) 30 to 70
35
(c-2) (ii) tripropylene glycol diacrylate (TPGDA) 30 to 70
(c-2) (iii) dipentaerythritol polyacrylate 30 to 70
(c-1) (ii) acryloil morphorine(ACMO) 30 to 70
40 (d) (i) IRGACURE 819 0.1 to 15 0.05 20
(d) (ii) PERHEXA25B 0.1 to 15
Total (parts by mass) 100.05 120
antifouling-property imparting material (BYK-UV3500)
45
scratch resistance enhancing material (MEK-ST)
scratch resistance enhancing material (NANOBYK- 3602)
500)
50 IR absorbing material (IR-40K)
UV absorbing material (TINUVIN326)
IR reflecting material (Ti02 CR-90)
electromagnetic shielding material (23-K)
55
electroconductive expressing material (VGCF-S)
antistatic material (CX-Z603M-F2)

72
 EP 2 578 650 A1

(continued)
Table 7 Comp. Ex. Comp. Ex.
Component 7 8
5
antistatic material (LQ-01)

[0244]

10 [Table 7-2]
antistatic material (TMAC-100)
flame retardant imparting material (P type flame retardant PX-200)
Evaluation result viscosity mPa.s(25°C) 1050 1050
15
haze value % (glass coat) - 0.8
total light transmittance % (glass coat) - 89
pencil hardness (glass coat) - HB

20 taber abrasion (ΔH) % (PC coat) - 2.1

weather resistance test(1000hr) 3 3
weather resistance test (500hr) s s
surface resistance test(Ω/sq.) 1015 1015
25
IR transmittance(%) at 780nm~2000nm 80 to 85 80 to 85
UV transmittance(%) at 300~380nm 50 to 55 50 to 55
visible light transmittance(%) at 380~780nm 90 to 95 90 to 95

30 flame retardancy 3 3
skid resistance coefficient 3 3
adhesion test uncured
hard vinyl chloride resin - 56
35
soft vinyl chloride resin - 56
PS - 50
PC - 56
40 glass - 47
aluminum - 37
steel plate - 55
concrete - 54
45
wood - 75
stone - 41
artificial marble - 30
50 PP - 0
HDPE - 0
MAH-PE - 66
magnesium - 0
55
ABS - 56

73
 EP 2 578 650 A1

(continued)
PET - 56
thermoplastic polyurethane elastomer - 74
5
2-part liquid polyurethane - 70
2-part liquid epoxy - 75
PMMA - 47

10 Water resistance test

hard vinyl chloride resin - 3
soft vinyl chloride resin - 3

15 [0245]

[Table 7-3]
PS - 3

20 PC - 3
glass - 3
aluminum - 3
steel plate - 3
25
concrete - 3
wood - 3
stone - 3

30 artificial marble - 3
PP - 3
HDPE - 3
MAH-PE - 3
35
magnesium - 3
ABS - 3
PET - 3
40 thermoplastic polyurethane elastomer - 3
2-part liquid polyurethane - 3
2-part liquid epoxy - 3
PMMA - 3
45
Shock resistance test
hard vinyl chloride resin - 3
soft vinyl chloride resin - 3
50 PS - 3
PC - 3
glass - 3
aluminum - 3
55
steel plate - 3
concrete - 3

74
 EP 2 578 650 A1

(continued)
wood - 3
stone - 3
5
artificial marble - 3
PP - 3
HDPE - 3

10 MAH-PE - 3
magnesium - 3
ABS - 3
PET - 3
15
thermoplastic polyurethane elastomer - 3
2-part liquid polyurethane - 3
2-part liquid epoxy - 3

20
[0246]

[Table 7-4]
PMMA - 3
25
flexibility test
hard vinyl chloride resin - 3
soft vinyl chloride resin - 3

30 PS - 3
PC - 3
glass - 3
aluminum - 3
35
steel plate - 3
concrete - 3
wood - 3
40 stone - 3
artificial marble - 3
PP - 3
HDPE - 3
45
MAH-PE - 3
magnesium - 3
ABS - 3
50 PET - 3
thermoplastic polyurethane elastomer - 3
2-part liquid polyurethane - 3
2-part liquid epoxy - 3
55
PMMA - 3
test on adhesiveness relative to dissimilar materials (B1)-(A)-(B2) MPa

75
 EP 2 578 650 A1

(continued)
hard PVC vs glass - 4.9
soft PVC vs glass - 4.1
5
PS vs aluminum - 2.5
PC vs alminum - 3
PS vs glass - 3.8

10 PC vs glass - 2.2
ABSvs glass - 2.3
glass vs alminum - 3.8
magnesium vs PC - 0
15
steel plate vs PMMA - 3.2
PET vs ABS - 4.1
PMMA vs ABS - 4.7

20 speaker durability evaluation - 3

antirust effect - 3

[0247]
25

30

35

40

45

50

55

76
 5

55
50
45
40
35
30
25
20
15
10
[Table 8-1]
Table 8 Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam
Component 26 27 28 29 30 31 32 33 34 35 36 37 38
CN975 urethane acrylate
(a-1) (i) available from Sartomer 20 to 40 30 30 30 30 30 30 30 30 30 30 30 30 30
Co.
CN292 polyester acrylate
(a-1) (ii) available from Sartomer 20 to 40
Co.
CNUVE151 epoxy
(a-1) (iii) acrylate available from 20 to 40
Sartomer Co.
CNH63B80 urethane
(a-1) (iv) acrylate available from 20 to 40
Sartomer Co.
LIGOLAC21E-A-2

77
(a-2) available from Showa 20 to 40
Highpolymer Co.
EP 2 578 650 A1

polybutadiene polyol Poly

(b-1-2) 0.1 to 50
bd R-15HT
aromatic castor oil-based
(b-1-1-1) 0.1 to 50 10 10 10 10 10 10 10 10 10 10 10 10 10
polyol URIC AC-006
polyisoprene-based
(b-1-3) 0.1 to 50
polyol Poly ip
castor oil-based polyol
(b-2-1) 0.1 to 50
URIC H-1262
castor oil-based polyol
(b-2-1) 0.1 to 50
URIC H-2151U
 5

55
50
45
40
35
30
25
20
15
10
(continued)
Table 8 Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam
Component 26 27 28 29 30 31 32 33 34 35 36 37 38
hydroxy-terminated liquid
(b-1-3) 0.1 to 50
polyolefin Epol
(b-3-1) 420 50
maleic acid modified
(b-3-2) poly-butadiene 0.1 to 50
Ricon130MA8
maleic acid modified
(b-3-2) poly-butadiene 0.1 to 50
POLYVEST OC 800 S
epoxy polyol EPICLON
(b-1-4) 0.1 to 50
U-125-60BT
polyepoxy compound
(b-4-1) ADEKA RESIN 0.1 to 50

78
EP-4100E
(b-4-2) L-207 50
EP 2 578 650 A1

(b-5-1) Lumiflon LF-200 50

(b-5-2) Lumiflon LF-302 50
(c-1) (i) N-vinyl caprolactam 70 60 60 60 60 60 60 60 60 60 60 60 60 60
dipropylene glycol
(c-2) (i) 30 to 70
diacrylate (DPGDA)
tripropylene glycol
(c-2) (ii) 30 to 70
diacrylate (TPGDA)
dipentaerythritol
(c-2) (iii) 70
polyacrylate
 5

55
50
45
40
35
30
25
20
15
10
(continued)
Table 8 Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam Exam
Component 26 27 28 29 30 31 32 33 34 35 36 37 38
acryloil
(c-1) (ii) 70
morphorine(ACMO)
(d) (i) IRGACURE 819 0.1 to 5 5 5 5 5 5 5 5 5 5 5 5 5
(d) (ii) PERHEXA 25B 0.5 to 1.5
Total (parts by mass) 105 105 105 105 105 105 105 105 105 105 105 105 105
antifouling-property
1
imparting material (BYK-
scratch resistance
enhancing material 30
(MEK-ST)
scratch resistance
enhancing material 10
(NANOBYK- 3602)

79
shock resistance
enhancing
5
EP 2 578 650 A1

material(PARALOID
BPM-500)
40K) 15
UV absorbing material
5
(TINUVIN326)
 5

55
50
45
40
35
30
25
20
15
10
[0248]

[Table 8-2]
IR reflecting material
15
( TiO2 CR-90)
electromagnetic
shielding material 60
(23-K)
electroconductive
expressing material 5
(VGCF-S)
antistatic material
100
(CX-Z603M-F2)
antistatic material
5
(LQ-01)
antistatic material
5
(TMAC-100)

80
flame retardant
impartingmaterial (P
100
type flame retardant
EP 2 578 650 A1

PX-200)
Evaluation viscosity
950 350 580 1250 400 1050 2800 4500 2300 520 1100 1200 5300
result mPa.s(25°C)
haze value % (glass
1.3 1.3 1.3 1.5 1.6 1.3 48 28 55 1.5 1.3 2.1 1.3
coat)
total light
transmittance % 86 86 86 83 83 86 28 55 25 86 86 83 63
(glass coat)
pencil hardness
HB 2H H HB H HB HB H HB HB HB HB F
(glass coat)
taber abrasion (ΔH) %
8.6 3.2 5.1 8.5 8.7 9.1 21 25 13.5 9.1 9.5 10.2 24.5
(PC coat)
 5

55
50
45
40
35
30
25
20
15
10
(continued)
weather resistance
3 3 3 s 3 s s s s 3 3 3 3
test (1000hr)
weather resistance
s s s s s s s s s s s s s
test (500hr)
surface resistance
1015 1015 1015 1015 1015 1015 1015 108 102 108 108 1011 1013
test(Ω/ sq.)
IR transmittance(%)
80 to 85 80 to 85 80 to 85 80 to 85 30 to 35 80 to 85 <5 15 to 20 10 to 15 10 to 15 10 to 15 10 to 15 <5
at 780nm ~2000nm
UV transmittance(%)
50 to 55 50 to 55 50 to 55 50 to 55 <1 50 to 55 <1 <1 <1 <1 50 to 55 50 to 55 <1
at 300 ~380nm
visible light
transmittance(%) at 90 to 95 90 to 95 90 to 95 90 to 95 80 to 85 90 to 95 30 to 35 20 to 25 25 to 30 30 to 35 30 to 35 30 to 35 20 to 25
380~780nm
flame retardancy 3 3 3 3 3 3 3 Δ 3 3 3 3 s
skid resistance
3 3 3 s Δ Δ Δ 3 Δ Δ Δ Δ Δ
coefficient

81
adhesion test
hard vinyl chloride
EP 2 578 650 A1

100 100 100 100 100 100 100 100 100 100 100 100 100
resin
soft vinyl chloride
100 100 100 100 100 100 100 100 100 100 100 100 100
resin
PS 100 100 100 100 100 100 100 100 100 100 100 100 100
PC 100 100 100 100 100 100 100 100 100 100 100 100 100
glass 100 100 100 100 100 100 100 100 100 100 100 100 100
aluminum 100 100 100 100 100 100 100 100 100 100 100 100 100
steel plate 100 100 100 100 100 100 100 100 100 100 100 100 100
concrete 100 100 100 100 100 100 100 100 100 100 100 100 100
wood 100 100 100 100 100 100 100 100 100 100 100 100 100
 5

55
50
45
40
35
30
25
20
15
10
(continued)
stone 100 100 100 100 100 100 100 100 100 100 100 100 100
artificial marble 100 100 100 100 100 100 100 100 100 100 100 100 100
PP 0 0 0 0 0 0 0 0 0 0 0 0 0
HDPE 0 0 0 0 0 0 0 0 0 0 0 0 0
MAH-PE 100 100 100 100 100 100 100 100 100 100 100 100 100
magnesium 80 85 85 90 85 85 85 85 85 85 85 85 85
ABS 100 100 100 100 100 100 100 100 100 100 100 100 100
PET 100 100 100 100 100 100 100 100 100 100 100 100 100
thermoplastic
polyurethane 100 100 100 100 100 100 100 100 100 100 100 100 100
elastomer
2-part liquid
100 100 100 100 100 100 100 100 100 100 100 100 100
polyurethane
2-part liquid epoxy 100 100 100 100 100 100 100 100 100 100 100 100 100

82
EP 2 578 650 A1
 EP 2 578 650 A1

[0249]

[Table 8-3]
PMMA 100 100 100 100 100 100 100 100 100 100 100 100 100
5
Water
resistance
test
hard vinyl
10 chloride resin s s s s s s s s s s s s s
soft vinyl
chloride resin s s s s s s s s s s s s s
PS s s s s s s s s s s s s s
15
PC s s s s s s s s s s s s s
glass s s s s s s s s s s s s s
aluminum s s s s s s s s s s s s s

20 steel plate s s s s s s s s s s s s s
concrete s s s s s s s s s s s s s
wood s s s s s s s s s s s s s
stone s s s s s s s s s s s s s
25
artificial
marble s s s s s s s s s s s s s
PP - - - - - - - - - - - - -
HDPE - - - - - - - - - - - - -
30
MAH-PE s s s s s s s s s s s s s
magnesium s s s s s s s s s s s s s
ABS s s s s s s s s s s s s s
35
PET s s s s s s s s s s s s s
thermoplastic
polyurethane
elastomer s s s s s s s s s s s s s
40 2-part liquid
polyurethane s s s s s s s s s s s s s
2-part liquid
epoxy s s s s s s s s s s s s s
45 PMMA s s s s s s s s s s s s s
Shock
resistance
test
50 hard vinyl
chloride resin s s s s s s s s s s s s s
soft vinyl
chloride resin s s s s s s s s s s s s s

55 PS s s s s s s s s s s s s s
PC s s s s s s s s s s s s s
glass s s s s s s s s s s s s s

83
 EP 2 578 650 A1

(continued)
aluminum s s s s s s s s s s s s s
steel pilate s s s s s s s s s s s s s
5
concrete s s s s s s s s s s s s s
wood s s s s s s s s s s s s s
stone s s s s s s s s s s s s s

10 artificial
marble s s s s s s s s s s s s s
PP - - - - - - - - - - - - -
HDPE - - - - - - - - - - - - -
15 MAH-PE s s s s s s s s s s s s s
magnesium s s s s s s s s s s s s s
ABS s s s s s s s s s s s s s
PET s s s s s s s s s s s s s
20
thermoplastic
polyurethane
elastomer s s s s s s s s s s s s s
2-part liquid
25
polyurethane s s s s s s s s s s s s s
2-part liquid
epoxy s s s s s s s s s s s s s
PMMA s s s s s s s s s s s s s
30

[0250]

[Table 8-4]
35 flexibility test
hard vinyl
chloride resin O O O O O O O O O O O O O
soft vinyl
40 chloride resin O O O O O O O O O O O O O
PS O O O O O O O O O O O O O
PC O O O O O O O O O O O O O
glass Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ
45
aluminum O O O O O O O O O O O O O
steel plate O O O O O O O O O O O O O
concrete O O O O O O O O O O O O O

50 wood O O O O O O O O O O O O O
stone O O O O O O O O O O O O O
artificial
marble Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ
55 PP - - - - - - - - - - - - -
HDPE - - - - - - - - - - - - -

84
 EP 2 578 650 A1

(continued)
MAH-PE O O O O O O O O O O O O O
magnesium O O O O O O O O O O O O O
5
ABS O O O O O O O O O O O O O
PET O O O O O O O O O O O O O
elastomer O O o O o O O O O O O O O

10 2-part liquid
polyurethane O O O O O O O O O O O O O
2-part liquid
epoxy O O O O O O O O O O O O O

15 PMMA Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ
test on
adhesiveness
relative to
dissimilar
20 materials
(B1)-(A)-(82)
MPa
hard PVC vs
glass 7.9 8 7.6 7.9 7.3 7.8 7.4 8 7 7.4 7.4 7.5 7.8
25
soft PVC vs
glass 8.9 8.7 8.4 8.4 8.9 8 8.7 8.3 8.2 8.9 8.3 7.7 9
PS vs
aluminum 8.3 8 8.9 8.9 8.2 8.6 8.9 8.7 8.9 8 8.4 9.3 8.2
30
PC vs alminum 8.9 8.5 8.4 8.9 8.8 8 8.2 8.6 8.9 9 8.8 8.4 8.2
PS vs glass 8.3 8.3 8.4 8.4 8.1 8.9 9 8.7 8.4 8.6 8 8.9 8.2
PC vs glass 8.6 8.2 8.2 8 9 8.6 8.3 8.9 9 8.8 8.9 8.3 9
35 ABSvs glass 8.4 8.3 8.5 8.7 8.8 8.3 8 8.8 8.1 8.2 9 8.3 8.8
glass vs
alminum 8.6 8.4 8 8.3 8.6 8.2 8 8.7 8.5 8.8 8 8.4 8.5
magnesium vs
40 PC 7.6 7.6 6.7 7 7.9 7.2 7.8 7.7 7.7 7.5 7.4 7.3 7.4
steel plate vs
PMMA 8 8.6 8.7 8.8 8 8.2 8.6 8.3 8.9 8.9 9 9.6 8.7
PET vs ABS 9 8.5 8.2 8 9 8.3 8 8.8 8.6 8 8.3 8.2 8.1
45
PMMA vs ABS 8.3 8.1 8 8.6 8.2 8.7 8.6 8.8 8.6 8.3 8.7 8.8 8.3
speaker
durability
evaluation O O O O O O Δ Δ O O O O Δ
50
antirust effect O O O O O O O O O O O O O

[0251] As apparent from the Tables, in Examples 1 through 38 where an adhesive composition according to the present
invention was employed, the adhesive compositions used there showed an excellent adhesiveness to polar resin, ce-
55 ramic, metal and so on because it contained the components (a), (b), (c) and (d) with a specific quantitative relationship.
On the other hand, in Comparative Examples 1 through 4 and 6 through 8, the adhesive compositions used there could
not provide the advantages of the present invention because they did not satisfy the requirement of the range of com-
pounding ratio specified according to the present invention. Additionally, the adhesive composition used in Comparative

85
 EP 2 578 650 A1

Example 5 also could not provide the advantages of the present invention because it did not contain the component (b).

[Industrial Applicability]

5 [0252] A paint and an adhesive composition according to the present invention provide excellent adhesiveness to soft
or hard vinyl chloride resins; polystyrenes; polycarbonates; glass; aluminum; steel plate; concrete; wood panel; stone;
artificial marble; polyolefin resin or copolymers of polyolefin resin modified by a polar group-containing compound or
olefin and a polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymers; polyester-based
resins (e.g., polyethylene terephthalate PET); polyurethane-based resins; epoxy-based resins; or acryl-based resins
10 (e.g., polymethyl methacrylate PMMA) and also furnish them with transparency, surface smoothness, flexibility and
shock resistance in a well-balanced manner. Therefore, they are suitable for forming a transparent primer layer on the
surface of any of the above-listed specific adherends and bonding any two of the specific adherends (particularly between
dissimilar materials). Additionally, they are useful in the various fields of building materials, packaging materials, printing
materials, display materials, electric and electronic part materials, optical part materials, liquid crystal panels and so on.
15 Furthermore, since a paint and an adhesive composition according to the present invention excellently shows adhesive-
ness, hardness, water resistance, abrasion resistance, transparency, surface smoothness, flexibility, shock resistance
and an antifouling property, they can advantageously furnish electroacoustic transducers such as loudspeakers, receivers
and microphones with durability and steel frame building and steel frame bridges with antirust effect and durability.

20
Claims

1. A paint and an adhesive composition characterized by comprising:

25 (a) a vinyl ester resin or unsaturated polyester resin by 20 to 40 mass%;

(b) a modifying agent by 0.1 to 50 mass%;
(c) a vinyl monomer and/or (meth) acrylate monomer by 30 to 70 mass% (provided that the total of the components
(a), (b) and (c) is 100 mass%); and
(d) an initiator by 0.1 to 15 parts by mass to a total of 100 parts by mass of the components (a), (b) and (c).
30
2. The paint and an adhesive composition according to claim 1, characterized in that the component (a) is at least
one item selected from a group of urethane (meth)acrylate, polyester (meth)acrylate and epoxy (meth)acrylate.

3. The paint and an adhesive composition according to claim 1 or 2, characterized in that the component (b) is at
35 least one item selected from a group of (b-1) polyols having an hydroxyl value of 40 to 330 mgKOH/g; (b-2) polyols
having an hydroxyl value of 40 to 330 mgKOH/g and an acid value of 2 to 20 mgKOH/g; (b-3) modified rubber; (b-
4) compounds having an epoxy equivalent of 150 to 700 g/mol; and (b-5) fluorine-based resin having a hydroxyl
value of 40 to 330 mgKOH/g.

40 4. The paint and an adhesive composition according to claim 3, characterized in that the component (b-1) is at least
one item selected from a group of (b-1-1) castor oil-based polyols having a hydroxyl value of 40 to 330 mgKOH/g;
(b-1-2) polybutadiene-based polyols having a hydroxyl value of 40 to 330 mgKOH/g and (b-1-3) polyisoprene-based
polyols having a hydroxyl value of 40 to 330 mgKOH/g or hydrogen adduct thereof.

45 5. The paint and an adhesive composition according to claim 4, characterized in that the component (b-1) is an
aromatic castor oil-based polyol (b-1-1-1) having a hydroxyl value of 40 to 330 mgKOH/g.

6. The paint and an adhesive composition according to claim 3, characterized in that the component (b-2) is a castor
oil-based polyol (b-2-1) having a hydroxyl value of 40 to 330 mgKOH/g and an acid value of 2 to 20 mgKOH/g.
50
7. The paint and an adhesive composition according to claim 3, characterized in that the component (b-3) is an acid-
modified polybutadiene or an acid-modified polyisoprene.

8. The paint and an adhesive composition according to claim 3, characterized in that the component (b-4) is a
55 polyepoxy compound (b-4-1) having an epoxy equivalent of 150 to 250 g/mol.

9. The paint and an adhesive composition according to claim 3, characterized in that the component (b-4) is a polymer
(b-4-2) having an epoxy equivalent of 500 to 700 g/mol and a saturated skeleton.

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10. The paint and an adhesive composition according to claim 3, characterized in that the component (b-5) is a fluorine-
based resin (b-5-1) having a hydroxyl value of 40 to 330 mgKOH/g.

11. The paint and an adhesive composition according to claim 1 or 2, characterized in that the component (c) is a
5 monomer having an N-vinyl group.

12. The paint and an adhesive composition according to any of claims 1 through 11, characterized in that the component
(c) is at least a monomer selected from (c-1) compounds having a ring structure and an ethylenically unsaturated
group and (c-2) compounds having no ring structure and an ethylenically unsaturated group.
10
13. The paint and an adhesive composition according to any of claims 1 through 12, characterized in that the adherend
of the adhesive composition is soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel
plate; concrete; wood panel; stone; artificial marble; polyolefin resin or copolymer of polyolefin resin modified by a
polar group-containing compound or olefin and a polar group-containing compound; magnesium; acrylonitrile-buta-
15 diene-styrene copolymer; polyester-based resin; polyurethane-based resin; epoxy-based resin or acryl-based resin.

14. The paint and an adhesive composition according to any of claims 1 through 13, characterized by further comprising
a functional material.

20 15. The paint and an adhesive composition according to claim 14, characterized in that the functional material is at
least one item selected from a group of antifouling-property imparting materials, scratch resistance enhancing
materials, shock resistance enhancing materials, IR absorbing materials, UV absorbing materials, IR reflective
materials, electromagnetic shielding materials, electroconductive revealing materials, antistatic materials and flame
retardancy imparting materials.
25
16. The paint and an adhesive composition according to claim 15, characterized in that the antifouling-property im-
parting materials are silicone compounds.

17. The paint and an adhesive composition according to claim 16, characterized in that they are used for antifouling-
30 property protective walls (glass substitutes, protective walls for highways, sports arenas, bridges and so on) and
display coatings of television sets, mobile phones and game machines.

18. The paint and an adhesive composition according to claim 15, characterized in that the scratch resistance enhancing
materials are organosilica compounds.
35
19. The paint and an adhesive composition according to claim 15, characterized in that the scratch resistance enhancing
materials are alumina ceramic compounds.

20. The paint and an adhesive composition according to claim 18 or 19, characterized in that it is used for glass
40 substitutes, protective walls for highways, sports arenas and bridges and display hard coatings of television sets,
mobile phones and game machines.

21. The paint and an adhesive composition according to claim 15, characterized in that the shock resistance enhancing
materials are core-shell polymer particles.
45
22. The paint and an adhesive composition according to claim 21, characterized in that they are used for car interior
and exterior decorating members, floors, walls, protective walls for highways, sports arenas and bridges and display
coatings of television sets, mobile phones and game machines.

50 23. The paint and an adhesive composition according to claim 15, characterized in that the IR absorbing materials
are metal oxides such as ATO (antimony tin complex oxide or antimony doped tin oxide) and ITO (indium tin complex
oxide).

24. The paint and an adhesive composition according to claim 21, characterized in that they are used for car interior
55 and exterior decorating members, floors, walls, protective walls for highways, sports arenas and bridges and heat
shield coatings of television sets, mobile phones and game machine housing.

25. The paint and an adhesive composition according to claim 15, characterized in that the UV absorbing materials

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are at least one item selected from a group of salicylate-based, benzophenone-based, benzotriazole-based, sub-
stituted acrylonitrile-based, and triazine-based organic compounds and inorganic compounds such as hybrid inor-
ganic particles obtained by way of a complexing process of treating any of carbon nanotubes, zinc oxide, aluminum
doped zinc oxide, gallium doped zinc oxide, titanium dioxide, cerium oxide and titanium dioxide microparticles with
5 iron oxide, and hybrid inorganic particles obtained by coating the surfaces of cerium oxide microparticles with
amorphous silica.

26. The paint and an adhesive composition according to claim 25, characterized in that they are used for anti-yellowing
coatings and UV degradation preventive coatings of car interior and exterior decorating members, floors, walls,
10 boats and canoes.

27. The paint and an adhesive composition according to claim 15, characterized in that the IR reflective materials are
organic pigment components that are at least one item selected from a group of basic lead carbonate, basic lead
sulfate, basic lead silicate, zinc oxide (specific gravity: 5.47 to 5.61), zinc sulfide (specific gravity: 4.1), lithopone,
15 antimony trioxide (specific gravity: 5.5 to 5.6), titanium dioxide (specific gravity: 4.2) and graphite (specific gravity: 3.3).

28. The paint and an adhesive composition according to claim 25, characterized in that they are used for solar cell
backsheets, walls and roof coatings.

20 29. The paint and an adhesive composition according to claim 15, characterized in that the electromagnetic shielding
materials are electroconductive particles of at least one item selected from a group of (1) carbon particles and/or
powder; (2) particles and/or powder of any of metals of nickel, indium, chromium, gold, vanadium, tin, cadmium,
silver, platinum, aluminum, copper, titanium, cobalt, lead and so on, alloys of any of them and their electroconductive
oxides; and (3) particles of plastic materials such as polystyrene, polyethylene having a coating layer of any of
25 electroconductive materials of (1) or (2) above formed on the surfaces thereof.

30. The paint and an adhesive composition according to claim 25, characterized in that they are used for car interior
and exterior decorating members, floors, walls and roof coatings.

30 31. The paint and an adhesive composition according to claim 15, characterized in that the electroconductive revealing
materials are electroconductive particles of at least one item selected from a group of electroconductive carbon
black and carbon nanotubess.

32. The paint and an adhesive composition according to claim 31, characterized in that they are used for car interior
35 and exterior decorating members, floors and electrode coatings.

33. The paint and an adhesive composition according to claim 15, characterized in that the antistatic materials are at
least one item selected from a group of metal oxides, metal salts, surface active agents and ionic liquids.

40 34. The paint and an adhesive composition according to claim 33, characterized in that the metal oxides and the metal
salts are at least one item selected from a group of zinc oxide, aluminum doped zinc oxide, gallium doped zinc
oxide, ATO, ITO, tin oxide, antimony pentoxide, zirconium oxide, titanium oxide and aluminum oxide.

35. The paint and an adhesive composition according to claim 33, characterized in that the surface active agents are
45 at least one item selected from a group of anionic, nonionic, cationic and amphoteric surface-active agents.

36. The paint and an adhesive composition according to claim 33, characterized in that the ionic liquids contain cations
of at least one item selected from a group of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium and
sulfonium.
50
37. The paint and an adhesive composition according to claim 33, characterized in that the ionic liquids contain anions
of at least one item selected from a group of halogen, carboxylates, sulfates, sulfonates, thiocyanates, aluminates,
borates, phosphates, phosphinates, amides, antimonates, imides and methides.

55 38. The paint and an adhesive composition according to any of claims 33 through 35, characterized in that they are
used for floors, walls, electric appliance housings and display coatings of TV mobile phones or game machines.

39. The paint and an adhesive composition according to claim 15, characterized in that the flame retardancy imparting

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materials contain a flame retardant agent of at least one item selected from a group of phosphor-based flame
retardant agents, bromide-based flame retardant agents, chlorine-based flame retardant agents, aluminum hydrox-
ide and zinc borate.

5 40. The paint and an adhesive composition according to claim 39, characterized in that they are used for walls, floors,
electric appliance housings, connectors and electric wire coatings.

41. A bonding method characterized by executing:

10 Step I:

mixing

(a) a vinyl ester resin or unsaturated polyester resin by 20 to 40 mass%;

15 (b) a modifying agent by 0.1 to 50 mass%;
(c) a vinyl monomer and/or (meth) acrylate monomer by 30 to 70 mass % (provided that the total of
the components (a), (b) and (c) is 100 mass%); and
(d) an initiator by 0.1 to 15 parts by mass to a total of 100 parts by mass of the components (a), (b)
and (c) (provided that the total of the components (a), (b), (c) and (d) is 100 mass%) in an arbitrary
20 order to prepare an adhesive composition;

Step II:

forming a layer (A) of the adhesive composition by laminating the adhesive composition obtained in the
25 step I on the surface of a layer (B1) of a soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass;
aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or a copolymer of
polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing
compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester-based resin; a poly-
urethane-based resin; an epoxy-based resin; or an acryl-based resin;
30
Step III:

additionally laminating a layer (B2) of a soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass;
aluminum; steel plate; concrete; wood panel; stone; artificial marble; polyolefin resin or a copolymer of
35 polyolefin resin modified by a polar group-containing compound or olefin and a polar group-containing
compound; magnesium; an acrylonitrile-butadiene-styrene copolymer;
a polyester-based resin; a polyurethane-based resin; an epoxy-based resin; or an acryl-based resin on the
layer (A) of the adhesive composition of the laminate obtained in the step II, in the order of Step I, Step II
and Step III.
40
42. A laminate characterized by being formed by laminating a layer (A) of an adhesive composition containing:

(a) a vinyl ester resin or unsaturated polyester resin by 20 to 40 mass%;

(b) a modifying agent by 0.1 to 50 mass%;
45 (c) a vinyl monomer and/or (meth) acrylate monomer by 30 to 70 mass% % (provided that the total of the
components (a), (b) and (c) is 100 mass%); and
(d) an initiator by 0.1 to 15 parts by mass to a total of 100 parts by mass of the components (a), (b) and (c)
(provided that the total of the components (a), (b), (c) and (d) is 100 mass%); and
a layer (B1) of a soft or hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate;
50 concrete; wood panel; stone; artificial marble; polyolefin resin or a copolymer of polyolefin resin modified by a
polar group-containing compound or olefin and a polar group-containing compound; magnesium; an acrylonitrile-
butadiene-styrene copolymer; a polyester-based resin; a polyurethane-based resin; an epoxy-based resin; or
an acryl-based resin so as to make the layer (A) and the layer (B1) contact each other.

55 43. The laminate according to claim 42, characterized in that the thickness of the layer (A) of the paint and the adhesive
composition is between 1 and 200 mm.

44. The paint and an adhesive composition according to claim 1, characterized in that they are used for electroacoustic

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transducers.

45. The paint and an adhesive composition according to claim 1, characterized in that they are used for coating of
steel structures.
5

10

15

20

25

30

35

40

45

50

55

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• JP 2296879 A [0010] • JP 8201746 A [0010]

• JP 58049702 A [0010] • JP 2000256612 A [0010]
• JP 2003015531 A [0010] • JP 2002363485 A [0010]
• JP 8331631 A [0010] • JP 2005089712 A [0074]
• JP 9111223 A [0010]

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