Patents

Aqueous emulsion, coating film, cured product, and laminate

Abstract
WO2015194611A1
The purpose of the present invention is to provide an aqueous emulsion with which it is possible to
WIPO (PCT)
bond to an adherend, or cause adherends to bond to each other, with sufficient strength. The present
invention is characterized by: an aqueous emulsion containing chlorinated rubber having a chlorine
atom content of 45 mass% or higher, and a compound having one or more polymerizable groups; a Download PDF
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coating film formed from this aqueous emulsion; and a cured product of this coating film.
Other languages: French, Japanese
Classifications Inventor: 史哲 松岡, 肥後　睦子

C09D5/022
Emulsions, e.g. oil in water
Worldwide applications
View 11 more classifications
2015

WO
CN
KR
JP
TW

Application PCT/JP2015/067537 events

2014-06-20 Priority to JP2014-126976

2014-06-20 Priority to JP2014126976

2015-06-18 Application filed by 住友化学株式会社

2015-12-23 Publication of WO2015194611A1

Info: Patent citations (15), Cited by (3), Legal events, Similar

documents, Priority and Related Applications

External links: Espacenet, Global Dossier, PatentScope, Discuss

Claims (22) Hide Dependent

1. An aqueous emulsion containing a chlorinated rubber having a chlorine atom content of 45% by mass or more, a compound having one or more polymerizable groups,
and water.

2. The aqueous emulsion according to claim 1, wherein the content of the compound having a polymerizable group is 50 to 10,000 parts by mass with respect to 100
parts by mass of the chlorinated rubber.

3. Containing water as a dispersion medium,

The aqueous emulsion according to claim 1 or 2, comprising a mixture of the chlorinated rubber and the compound having a polymerizable group as a dispersoid.

4. The aqueous emulsion according to any one of claims 1 to 3, wherein the dispersoid is liquid.

5. The aqueous emulsion according to any one of claims 1 to 4, wherein at least a part of the chlorinated rubber is dissolved in the dispersoid.

6. The aqueous emulsion according to any one of claims 1 to 5, comprising a solution in which at least a part of the chlorinated rubber is dissolved in the compound
having a polymerizable group as a dispersoid.

7. The aqueous emulsion according to any one of claims 1 to 6, wherein the compound having a polymerizable group is a liquid at 23 ° C under atmospheric
pressure.

8. The aqueous emulsion according to any one of claims 1 to 7, wherein the compound having a polymerizable group is a compound having an ethylenically
unsaturated double bond.

9. The aqueous emulsion according to any one of claims 1 to 8, further comprising a surfactant.

10. The aqueous emulsion according to any one of claims 1 to 9, further comprising a photopolymerization initiator.

11. The aqueous emulsion according to any one of claims 1 to 10, further comprising a light stabilizer.

12. The aqueous emulsion according to any one of claims 1 to 11, further comprising an ultraviolet curable oligomer.

13. The aqueous emulsion according to any one of claims 1 to 12, further comprising a fluorescent brightening agent.

14. The aqueous emulsion according to any one of claims 1 to 13, further comprising a leveling agent.

15. The aqueous emulsion according to any one of claims 3 to 14, wherein the dispersoid has a volume-based median diameter of 10 µm or less.

16. The aqueous emulsion according to any one of claims 1 to 15, wherein the chlorinated rubber does not have a carboxy group and a carboxylic anhydride structure.

17. The total amount of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group is 0. The aqueous emulsion
according to any one of claims 1 to 16, which is 1 to 70% by mass.

18. A coating film formed from the aqueous emulsion according to any one of claims 1 to 17.

19. A cured product of the coating film according to claim 18.

 20. A laminate in which the cured product according to claim 19, one or more adhesive layers, and a second substrate are laminated in this order on a first substrate
made of an olefin polymer. body.

21. The cured product according to claim 19, one or more adhesive layers, and a second substrate are laminated in this order on a first substrate made of an ethylene
/ vinyl acetate copolymer. Laminated body.

22. The laminate according to claim 20 or 21, wherein the adhesive layer and the second base material are laminated via the cured product according to claim 19.

Description

Aqueous emulsion and coating film, cured product and laminate

The present invention relates to an aqueous emulsion, a coating film, a cured product, and a laminate.

Patent Document 1 describes an aqueous emulsion containing an acid-modified chlorinated polyolefin that can be used as an adhesive. However, such an aqueous
emulsion could not adhere to adherends or adherends with sufficient strength.

JP 2007-31473 A

There is a need for an aqueous emulsion that can adhere to adherends or adherends with sufficient strength.

The present invention includes the following inventions.

[1] An aqueous emulsion containing a chlorinated rubber having a chlorine atom content of 45% by mass or more, a compound having one or more polymerizable groups,
and water.

[2] The aqueous emulsion according to [1], wherein the content of the compound having a polymerizable group is 50 to 10,000 parts by mass with respect to 100 parts by
mass of the chlorinated rubber.

[3] containing water as the dispersion medium,

The aqueous emulsion according to [1] or [2], comprising a mixture of the chlorinated rubber and the compound having a polymerizable group as a dispersoid.

[4] The aqueous emulsion according to any one of [1] to [3], wherein the dispersoid is liquid.

[5] The aqueous emulsion according to any one of [1] to [4], wherein at least a part of the chlorinated rubber is dissolved in the dispersoid.

[6] The aqueous emulsion according to any one of [1] to [5], containing as a dispersoid a solution in which at least a part of the chlorinated rubber is dissolved in the
compound having a polymerizable group.

[7] The aqueous emulsion according to any one of [1] to [6], wherein the compound having a polymerizable group is a liquid at 23 ° C. and atmospheric pressure.

[8] The aqueous emulsion according to any one of [1] to [7], wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated
double bond.

[9] The aqueous emulsion according to any one of [1] to [8], further comprising a surfactant.

[10] The aqueous emulsion according to any one of [1] to [9], further comprising a photopolymerization initiator.

[11] The aqueous emulsion according to any one of [1] to [10], further comprising a light stabilizer.

[12] The aqueous emulsion according to any one of [1] to [11], further comprising an ultraviolet curable oligomer.

[13] The aqueous emulsion according to any one of [1] to [12], further comprising an optical brightener.

[14] The aqueous emulsion according to any one of [1] to [13], further comprising a leveling agent.

[15] The aqueous emulsion according to any one of [3] to [14], wherein the volume-based median diameter of the dispersoid is 10 μm or less.

[16] The aqueous emulsion according to any one of [1] to [15], wherein the chlorinated rubber does not have a carboxy group and a carboxylic anhydride structure.

[17] The total amount of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group is based on the total amount of the
mass part of the chlorinated rubber, the compound having a polymerizable group, and water. The aqueous emulsion according to any one of [1] to [16], which is 0.1 to
70% by mass.

[18] A coating film formed from any of the aqueous emulsions described above.

[19] A cured product of the coating film according to [18].

[20] A cured product according to [19], one or more adhesive layers, and a second substrate are laminated in this order on the first substrate made of an olefin polymer.
Laminated body.

[21] On the first substrate made of an ethylene / vinyl acetate copolymer, the cured product according to [19], one or more adhesive layers thereon, and a second
substrate A laminated body laminated in this order.

[22] The laminate according to [20] or [21], wherein the adhesive layer and the second base material are laminated via the cured product according to [19].

According to the present invention, adherends or adherends can be bonded to each other with sufficient strength.

In one embodiment, the aqueous emulsion of the present invention mainly contains a chlorinated rubber and a compound having a polymerizable group. The aqueous
emulsion usually contains water as a dispersion medium. The aqueous emulsion of the present invention is useful as an aqueous adhesive.

<Chlorinated rubber>

Chlorinated rubber is a chlorinated rubber having a chlorine atom content of 45% by mass or more. One type of chlorinated rubber may be used, or two or more types may
be combined.

The chlorinated rubber may or may not have a melting point, but preferably has a melting point. Melting | fusing point becomes like this. Preferably it is 100 degreeC or
more, More preferably, it is 200 degreeC or more, More preferably, it is 240 degreeC or more. Moreover, it is preferably 350 ° C. or lower, more preferably 300 ° C. or lower.

The chlorine atom content of the chlorinated rubber is preferably 45 to 90% by mass, more preferably 55 to 90% by mass, and further preferably 60 to 80% by mass.

As the chlorinated rubber, one having no carboxy group and carboxylic anhydride structure can be used. When such a chlorinated rubber is used in the aqueous emulsion
of the present invention, particularly when the aqueous emulsion is used as an aqueous adhesive, the concern about a decrease in water resistance of the aqueous
adhesive is extremely small and effective. Specifically, it is preferable to use a carboxylic acid anhydride such as maleic anhydride which is not acid-modified.

The chlorinated rubber is not particularly limited as long as it is a chlorinated natural rubber or synthetic rubber, and specifically, chlorinated natural rubber, chlorinated
butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / halogen. Cyclic conjugated diene adduct, chlorinated butadiene styrene copolymer,
brominated poly (2,3-dichloro-1,3-butadiene) and α-haloacrylonitrile-co-2,3-dichloro-1,3-butadiene A copolymer etc. are mentioned. A copolymer or rubber containing a
hydrocarbon group having 4 or more carbon atoms as a raw material is preferable. More preferred are chlorinated natural rubber, chlorinated isoprene rubber and
chlorinated butadiene rubber.

As a method of chlorinating natural rubber or synthetic rubber, a conventionally known method can be adopted. For example, a method in which natural rubber or
synthetic rubber is dissolved in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene or an organic solvent such as toluene, and chlorine gas
is blown; the natural rubber or synthetic rubber is suspended or emulsified in water In which chlorine gas is blown in; a method in which natural rubber or synthetic rubber
is suspended or emulsified in water and chlorinated by introducing chlorine gas while irradiating with ultraviolet light; natural rubber or synthetic rubber and liquid under
low pressure For example, a method of directly chlorinating by contacting with chlorine. Further, the aggregated and solidified natural rubber or synthetic rubber may be
dissolved in an organic solvent and then chlorinated, or the aggregated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then
emulsified and dispersed to volatilize the solvent. It can also be chlorinated in a wet state. When natural rubber is chlorinated, it can be chlorinated by blowing chlorine
gas into latex natural rubber.

For example, polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid, or nitric acid are added to water and emulsified, and then uniformly
chlorinated polyisoprene can be obtained by blowing chlorine gas.

The chlorinated rubber has a polystyrene-equivalent weight average molecular weight of usually 1000 or more, preferably 3000 or more, more preferably 5000 or more,
and further preferably 10,000 or more. Moreover, it is 400000 or less normally, Preferably it is 200000 or less. The weight average molecular weight in terms of
polystyrene can be measured by gel permeation chromatography (GPC).

By setting it as such a range, when the aqueous emulsion of the present invention is used as an aqueous adhesive, sufficient adhesive strength can be secured, and an
excessive increase in viscosity can be suppressed to adhere to an adherend. Sufficient sex can be secured.

Examples of the chlorinated rubber include commercially available products and those manufactured according to any known method. Commercially available products
include Supercron (registered trademark) CR-10, CR-20 (Nippon Paper Industries Co., Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, Pergut S-90 Pergut S-130,
Pergut S-170 (Bayer MaterialScience), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK) and the like. As a well-known method, the method of
patent 2660478 is mentioned, for example.

<Compound having a polymerizable group>

The compound having a polymerizable group includes, for example, a vinyl group, an allyl group, a propenyl group, a vinylidene group, a vinylene group (meth) acryl group,
a (meth) acryloyl group, a vinyl ether group, a vinyl benzyl ether group as the polymerizable group. , (Meth) acryloxy group, (meth) allylamide group, styryloxy group,
styrylamide group, isocyanate group, thioisocyanate group, carboxyl group, alcoholic or phenolic hydroxyl group, silanol group, alicyclic epoxy group, epoxy group A ring-
opening polymerizable group such as a cyclic ether group such as glycidyl group and oxetane group. These groups may contain only 1 type, or 2 or more types, and may
contain only 1 type or 2 or more types.

Examples of the compound having a polymerizable group include a compound having an ethylenically unsaturated double bond, an epoxy compound, an oxetane
compound, and a glycidyl ether compound. These compounds may be used alone or in combination of two or more.

As the compound having a polymerizable group, a compound having at least one ethylenically unsaturated double bond is preferable.

The compound having an ethylenically unsaturated double bond preferably has 1 to 10 ethylenically unsaturated double bonds, more preferably 1 to 6, still more
preferably 1 to 3, and still more preferably 1 to Have two.

Compounds having one ethylenically unsaturated double bond include heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing
heterocycles such as N-methylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam). Compound: heterocyclic (meth) acrylate such as morpholine (meth) acrylate,
tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate ( For example, dimethylaminoethyl
(meth) acrylate, diethylaminoethyl (meth) acrylate), N, N′-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (for example, methoxyethylene (meth) acrylate,
Ethoxy-diethylene glycol (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), phenoxyalkyl (meth) acrylate (for example, 2-
phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, etc.) Alkylphenoxymethyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate), phenoxy (poly) alkylene
glycol (meth) acrylate (eg, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene) Glycol (meth) acrylate), alkylphenoxy (poly)
alkylene glycol (meth) acrylate (for example, Nylphenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, etc.), alkyl (meth) acrylate
(eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i -Propyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth)
acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, dodecyl (meth) acrylate, isomyristyl (meth) acrylate,
isostearyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meta Acrylate, behenyl (meth) acrylate, etc.), (meth) acrylates having an alicyclic skeleton (for example,
cyclohexyl (meth) acrylate, 4 (1,1-dimethylethyl) cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 3 , 3,5-trimethylcyclohexyl (meth) acrylate, norbornyl (meth)
acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate, menthyl (meth) acrylate, fenchyl (meth) acrylate, adamantyl
(meth) acrylate, dimethyl adamantyl (meth) acrylate, tricyclo [5.2.1.0 2,6] dec-8-yl = (meth) acrylate, tricyclo [ .2.1.0 2,6] dec-4-methyl = (meth) acrylate, cyclodecyl (meth)
acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, isobornyl (meth) acrylate, bornyl (meth ) Acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyalkyl
(meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, etc.), aralkyl (meth) acrylate ( For example, benzyl (meth) acrylate, o-
phenylphenol glycidyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, etc.), hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl) Chill (meth)
acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-o-phenylphenol Propyl (meth)
acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol
mono (Meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, polypropylene glycol (Meth)
acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol-propylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.), poly ε-
caprolactone mono (meth) acrylate, Mono [2- (meth) acryloyloxyethyl] acid phosphate, halogen-containing (meth) acrylate (eg, trifluoroethyl (meth) acrylate, 2,2,3,3-
tetrafluoropropyl (meth) acrylate, perfluorooctyl) Ethyl (meth) acrylate, N, N, N-trimethyl-N- (2-hydroxy-3methacryloyloxypropyl) -ammonium chloride, etc.), silicone-
containing (meth) acrylate (for example, (meth) T) Acrylic modified organopolysiloxane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane,
3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acrylic Oxypropylmethyldiethoxysilane, etc.), aromatic vinyl compounds (eg, styrene, α-methylstyrene, o-
vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p- Chlorostyrene, p-methoxystyrene, vinyl benzoate, etc.), unsaturated carboxylic acid
glycidyl ester-containing (meth) acrylates (for example, glycidyl (meth) acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, ( 3, -Epoxycyclohexyl) methyl
(meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc.), aliphatic vinyl compounds (eg, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl
ethyl ether, allyl glycidyl) Ethers), unsaturated amides or unsaturated imides (for example, acrylamide, methacrylamide, diacetone (meth) acrylamide, α-chloroacrylamide,
N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N -(2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and maleimide),
acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, In addition, a macromonomer having a monoacryloyl group or a monomethacryloyl group at the end of a polymer (for
example, polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, polysilicone, etc.) Can be mentioned.

Examples of the compound having two ethylenically unsaturated double bonds include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-
hydroxypropionate, (polyoxy) alkylene glycol Di (meth) acrylate (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate tetraethylene glycol di
(meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol -Propylene glycol di (meth) acrylate, polytetramethylene
glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate Rate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth)
acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, neopentyl glycol di (meth) acrylate , Propoxylated neopentyl glycol di (meth) acrylate, alkoxylated
neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Polyethylene glycol
di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, pentanediol di (meth) acrylate, 3-methyl-pentanediol di (meth) Acrylate, glycerin di (meth) acrylate,
trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, etc.), alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) adduct of bisphenol A di (meth)
Acrylate (eg, di (meth) acrylate of 2,2-bis (2-hydroxyethoxyphenyl) propane), di (meth) acrylate having a bridged cyclic hydrocarbon group (eg, cyclohexanedimethanol di
(meth)) Acrylate, di (meth) acrylate of tricyclodecane dimethylol (eg, tricyclodecane dimethanol di (meth) acrylate), dicyclopentadiene di (meth) acrylate), (meth) acrylate
of bifunctional epoxy resin Rylic acid adducts (for example, 2,2-bis (glycidyloxyphenyl) propane (meth) acrylic acid adducts, bisphenol A diglycidyl ether methacrylic acid
adducts, etc.), glycerin di (meth) acrylate, silicone-containing (meta ) Acrylate (for example, (meth) acryl-modified organopolysiloxane, etc.), diacetone acrylic amide and
the like.

Examples of the compound having three or more ethylenically unsaturated double bonds include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxytri
(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate,
ditrimethylolpropane tetraacrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tris (acryloyloxy) Isocyanurate, tris (2-
acryloyloxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri (meth) Examples include acrylate, tris (hydroxypropyl) isocyanurate tri (meth) acrylate, triallyl
trimellitic acid, triallyl isocyanurate, and silicone-containing (meth) acrylates (for example, (meth) acryl-modified organopolysiloxane). It is done.

Among them, the compound having one or more ethylenically unsaturated double bonds is preferably a compound having 5 to 25 carbon atoms, more preferably a
compound having 6 to 18 carbon atoms, and further preferably 8 to 16 carbon atoms. It is a compound of this.

Examples of the epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-
butylene oxide, 1,3-butadiene monooxide, 1,2 -Epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene
oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, bisphenol A diglycidyl ether, Neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether,
bisphenol S diglycidyl ether Tellurium, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy
novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S Diglycidyl ether, 3,4-epoxycyclohexylmethyl-
3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl- 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate,
methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, diethylene glycol ( , 4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate),
dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether,
trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide 1,2,7,8-
diepoxyoctane, 1,2,5,6-diepoxycyclooctane, and the like.

Especially, as an epoxy compound, an aromatic epoxide and an alicyclic epoxide are preferable and an alicyclic epoxide is more preferable from a viewpoint of being
excellent in a cure rate.

Examples of oxetane compounds include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-

butyloxetane, and 1,4-bis And [(3-ethyl-3-oxetanylmethoxy) methyl] benzene.

Examples of the glycidyl ether compound include 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane
polyglycidyl ether, glycerin polyglycidyl ether, diethylene glycol diglycidyl ether, and the like. .

The compound having a polymerizable group may be solid at 23 ° C., but is preferably a compound that is liquid at atmospheric pressure. Liquids include solutions,
emulsions, suspensions, colloids and the like. Due to these properties, a uniform aqueous emulsion can be obtained.

The compound having a polymerizable group contained in the aqueous emulsion of the present invention is usually 50 to 10,000 parts by weight, preferably 100 to 10,000
parts by weight, more preferably 200 to 10,000 parts by weight per 100 parts by weight of chlorinated rubber. The amount is 5000 parts by mass, and more preferably 400
to 5000 parts by mass.

The aqueous emulsion of the present invention may contain a polymerization inhibitor. Any polymerization inhibitor may be used as long as it delays or stops the radical
reaction. Polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monoester, N-nitrosodiphenylamine, phenothiazine, 4-t-butylcatechol, N-
phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol 2,5-di-t-butylhydroquinone, 1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl-p-
benzoquinone, Examples include 4-methoxyphenol, chloranil, pyrogallol, 2-oxydiphenylamine, phenothiazine and the like.

Commercially available polymerization inhibitors include Kinopower QS-10, Kinopower QS-20, Kinopower QS-30, Kinopower QS-40, Kinopower QS-W10 (manufactured by
Kawasaki Kasei Kogyo Co., Ltd.), Metoquinone Flakes, Nonflex Alba, MH, TBH, PBQ, tolquinone, TBQ (manufactured by Seiko Chemical Co., Ltd.) and the like can be
mentioned.

The polymerization inhibitor also has an aspect of maintaining a high storage stability of the composition and ensuring the curability. Therefore, in consideration of such
actions and the like, the addition amount of the polymerization inhibitor is preferably 0 with respect to 100 parts by mass of the total of parts by mass of the chlorinated
rubber and the compound having a polymerizable group. 0.005 to 0.4 parts by mass, more preferably 0.01 to 0.3 parts by mass, still more preferably 0.02 to 0.2 parts by
mass, and particularly preferably 0.035 to 0.2 parts by mass. The polymerization inhibitor is preferably dissolved in the compound having a polymerizable group.

<Water>

As water contained in the aqueous emulsion of the present invention, tap water or deionized water is usually used. The water contained in the aqueous emulsion is not
particularly limited as long as it is an amount that allows the chlorinated rubber and the compound having a polymerizable group to exist as a uniform dispersion
medium.

<Additives>

In the aqueous emulsion of the present invention, various additives can be added in addition to the chlorinated rubber and the compound having a polymerizable group.
Additives include surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent brighteners, leveling agents, basic compounds, organic
solvents, crosslinking agents, photosensitizers, other resins, Phenol stabilizer, phosphite stabilizer, amine stabilizer, amide stabilizer, anti-aging agent, weathering
stabilizer, antiseptic, anti-settling agent, antioxidant, thermal stabilizer, thixotropic agent, thickening Agent, antifoaming agent, viscosity modifier, weathering agent,
pigment dispersant, antistatic agent, lubricant, nucleating agent, flame retardant, oil agent, dye, curing agent; transition metal compounds such as titanium oxide (rutile
type) and zinc oxide Pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass
flakes, barium sulfate, clay, kaolin, finely divided silica, mica, silica Siumu, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, inorganic or
organic fillers as alumina and celite such like.

These additives and the like may constitute a dispersoid of the aqueous emulsion. In this case, at least a part of the chlorinated rubber may be dissolved in the
dispersoid. Here, that at least a part of the chlorinated rubber is dissolved in the dispersoid means that at least a part of the chlorinated rubber is dissolved in at least one
component among the components forming the dispersoid. To do. For example, when the aqueous emulsion of the present invention is filtered with a filter having a pore
size of 0.50 μm, it is sufficient that at least a part of the chlorinated rubber is contained in the filtrate. The chlorinated rubber contained in the filtrate is preferably 1% by
mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, relative to 100 parts by mass of the chlorinated rubber contained in the
aqueous emulsion before filtration. More preferably, it is 70 mass% or more.

Filtration with a filter is preferably performed after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group
contained in the aqueous emulsion.

When the chlorinated rubber contains other resins, it is preferable that at least a part of the chlorinated rubber is dissolved in a compound having a polymerizable group
or a dispersoid, but at least one of additives such as other resins. The part may be dissolved in a compound having a polymerizable group or a dispersoid.

Filtration with a filter is preferably performed after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group
contained in the aqueous emulsion.

In addition, when adding the said additive to the aqueous | water-based emulsion of this invention, all the additives may be mixed with the dispersoid in an aqueous |
water-based emulsion, and may be mixed with water. Being mixed may be dispersed or dissolved.

<Surfactant>

The surfactant preferably acts as an emulsifier. Examples of the surfactant include cationic, anionic, amphoteric and nonionic surfactants, and preferred are anionic and
nonionic surfactants. Surfactants may be used alone or in combination of two or more.
Anionic surfactants include fatty acid sodium such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, amino acid
condensate of higher fatty acid such as sodium lauroyl sarcosine, sodium N-lauroyl glutamate, Alkyl sulfonates, higher fatty acid ester sulfonates such as lauric acid
ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, higher fatty acid amide sulfonates such as oleic acid amide sulfonic acid, sodium
dodecylbenzene sulfonate Alkyl aryl sulfonates such as diisopropyl naphthalene sulfonate, formalin condensates of alkyl aryl sulfonates, pentadecane-2-sulfate, etc.
Secondary alcohol sulfate, polyoxyethylene alkyl phosphate such as dipolyoxyethylene dodecyl ether phosphate, lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl
ether ammonium sulfate, polyoxyethylene nonylpropenyl Ammonium phenyl ether sulfate, bis (polyoxyethylene polycyclic phenyl ether) bismethacrylate sulfate, alkyl allyl
succinate sulfonate sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2-sodium sulfoethyl methacrylate, alkoxy polyethylene glycol maleate , Higher alcohol
sulfates, higher carboxylates, alkylbenzene sulfonates, polyoxygens Lenalkyl sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt and vinyl sulfosuccinate, sodium
poly (meth) acrylate, ammonium poly (meth) acrylate, (meth) acrylic acid- (meth) acrylic acid ester copolymer Styrene-maleic acid copolymer, styrene-maleic acid
copolymer ammonium salt, styrene-maleic acid half ester copolymer ammonium salt, sodium carboxymethylcellulose and sodium naphthalene sulfonate formalin
condensate.

Cationic surfactants include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium
salts, alkylisoquinolinium salts, dialkylmorpholinium salts, benzethonium chloride, Alkylvinylpyridinium salts, alkylammonium salts such as dodecyltrimethylammonium
salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt,
dioxyalkylenedialkylammonium salt, allyltri Examples thereof include alkylammonium salts, diallyldialkylammonium salts, and polydiallyldimethylammonium chloride.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol
formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid. Ester, polyoxypropylene glycol monofatty acid ester,
polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester,
sucrose fatty acid ester, polyoxyethylene polyoxypropylene Block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxye Alkylene alkyl amines, and
polyoxyethylene alkanediol, alkoxy polyethylene glycol methacrylate, and the like. Polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene
fatty acid amide, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, polyvinyl pyrrolidone, dicyandiamide polyalkylene polyamine
condensate, polyethylene glycol, polyvinyl alcohol Etc.

Examples of amphoteric surfactants include N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-
dimethylaminoacetic acid, Examples thereof include 1- (2-carboxyethyl) pyrimidinium betaine, lecithin, lauryl betaine, and lauryl dimethylamine oxide.

Commercially available surfactants include EMAL 0, EMAL 10G, EMAL 2F paste, EMAL 20C, EMAL E-27C, EMAL 270J, EMAL E-27C, Neoperex GS, Neoperex G-15,
Neoperex G-25 , Neoperex G-65, Latemul PD-104, Perex OT-P, Perex TR, Perex SS-L, Perex SS-H, Demol N, Demol EP, Emulgen 102KG, Emulgen 104P, Emulgen 105,
Emulgen 106, Emulgen 108 Emulgen 404, Emulgen 130K, Emulgen 147, Emulgen LS-106, Emulgen LS-110, Emulgen A-60, Emulgen 109P, Emulgen 350, Latemul PD-420,
Rheodor 430V , Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Coatamine 24P, Amhitor 24B, Neoperex No. 6 powder, Latemul E-1000A, Perex OT-P, Emulgen LS-
114, Emulgen 210P, Emulgen 220, Emulgen 306P, Emulgen 320P, Emulgen 408, Emulgen 409PV, Emulgen 420, Amphital 86B and Amphital 20BS (manufactured by Kao)
Neugen EA-177, Neugen XL-40, Neugen TDS-30, Neugen TDX-80, Neugen LP-80, DKS NL-15, DKS NL-50, DKS NL-80, DKS NL-110, DKS NL-180, Neugen TDS-70, Neugen
TDS-100, Neugen ET-83, Neugen ET-160, Neugen YX-400, Haitenol NF-08, Haitenol 227L, Prisurf A212C, Plastic Surf A210D, Neocor P, Monogen Y-100, Katiogen TML,
Aqualon KH-10, Aqualon KH-1025, Aqualon HS-10, Aqualon RN-20, Aqualon RN-30, Pitzkor K-17L and Pitzkor V-7154 (Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.),
Adeka Pluronic F108, Adeka Pluronic L-61, Adeka Pluronic 17R-2 (manufactured by ADEKA), Eleminol JS-20, Eleminol RS-3000, Sanmorin OT-70, and Caribbon EN-200
(Sanyo) Manufactured by Kasei Kogyo Co., Ltd.), Kuraray Poval PVA-103, Kuraray Poval PVA-105, Kuraray Poval PVA-117, Kuraray Poval PVA-217, Kuraray Poval PVA-205,
Kuraray Poval PVA-203, Kura POVAL PVA-210, KURARAY POVAL PVA-235, KURARAY POVAL PVA-403, KURARAY POVAL PVA-405, KURARAY POVAL PVA-417, KURARAY
POVAL M-205, KURARAY POVAL MP-203, KURARAY POVAL KL-506 and KURARAY POVAL KL -318 (manufactured by Kuraray Co., Ltd.), Akumarim AKM-1511-60,
Akumalim AKM-053, Polystar OM and Pronon # 102 (manufactured by NOF Corporation).

The aqueous emulsion of the present invention preferably contains a surfactant. When a surfactant is included, the content of the surfactant is good to form an aqueous
emulsion, the adhesiveness of the aqueous emulsion is good, but it has a mass part of chlorinated rubber and a polymerizable group. Preferably, it is 30 parts by mass or
less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less with respect to 100 parts by mass of the total of the compounds. The
lower limit of the amount of surfactant is preferably at least 1 part by mass.

<Photopolymerization initiator>

A photopolymerization initiator is a compound that generates an active species by the action of light, a photo radical generator that generates an active radical by the
action of light, a photo acid generator that generates an acid by the action of light, and the action of light. Examples include photobase generators that generate bases.

Examples of the photo radical generator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine
compounds, sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), and carboxylic acid esters.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compounds include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-
methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-
morpholinophenyl) butane. -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl]
propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone and 2-hydroxy-2-methyl-1- [4- (1- And an oligomer of methylvinyl) phenyl] propan-1-
one.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-
bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-
yl) ethenyl] -1,3 , 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [ - (3,4-dimethoxyphenyl)
ethenyl] -1,3,5-triazine.

Examples include sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), carboxylic acid esters, and the like described later.

A commercially available thing can be used as a photoradical generator. Commercially available photoradical generators include Irgacure (registered trademark) 907, 184,
651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Seikol (registered trademark) BZ, Z And BEE (Seiko Chemical Co., Ltd.), Kayacure (registered trademark)
BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 and SP-170 (( ADEKA), TAZ-A and TAZ-PP (Nihon Shibel Hegner Co.,
Ltd.), TAZ-104 (Sanwa Chemical Co., Ltd.), Darocur (registered trademark) 1173 and MBF (BASF Japan Co., Ltd.) It is done.

These photo radical generators may be used alone or in combination.

Specific examples of the combination include Irgacure (registered trademark) 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%), Irgacure (registered
trademark) 1700 (bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one: 25/75%) and Irgacure® 1800 (bis (2,6-
dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%) (BASF Japan Ltd.).

Examples of the photoacid generator include sulfonic acid derivatives, onium salts, carboxylic acid esters, and the like.
Examples of the sulfonic acid derivatives include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidesulfonates such as
trifluoromethylsulfonate derivatives, benzoinsulfonates, 1-oxy-2-hydroxy-3 Mention may be made of sulfonates of propyl alcohol, pyrogallol trisulfonates, benzyl
sulfonates. Specifically, diphenyl disulfone, ditosyl disulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl)
diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) methane, benzoin tosylate 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-
methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosylate And lato, ortho-nitrophenyl
methyl tosylate, para-nitrophenyl tosylate and the like.

Examples of onium salts include tetrafluoroborate (BF 4− ), hexafluorophosphate (PF 6− ), hexafluoroantimonate (SbF 6− ), hexafluoroarsenate (AsF 6− ),
hexachloroantimonate (SbC 16). - ), Tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO 4− ),
trifluoromethanesulfonate ion (CF 3 SO 3− ), fluorosulfone acid ion (FSO 3-), toluenesulfonic acid ion, trinitrobenzene sulfonic acid anion, the use of sulfonium salts or
iodonium salts having an anion such as trinitrotoluene sulfonate anion Kill.

Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate,
triphenylsulfonium tetrakis (pentafluorobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium. Tetrakis (pentafluorobenzyl) borate,
dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium
hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenyls Honium hexahexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-
butoxyphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) Sulfonium
hexafluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium
tetrakis (pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) ) Sulfonium hexafluorophosphate, di (methoxysulfonyl) Nyl) methylsulfonium hexafluoroantimonate, di
(methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl)
methylsulfonium hexafluorophosphate, (4- Octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-
bis-trifluoromethylphenyl) borate, 4-acetamidophenyldiphenylsulfonium tetrafluoro Borate, 4-acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate,
dimethyl Naphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl)
borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxathinium hexafluorophosphate, 5-methyl Thianthrenium hexafluorophosphate, 10-phenyl-
9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xanthenium tetrafluoroborate, 10-phenyl-9-oxothioki Santenium tetrakis
(pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium teto Tetrafluoroborate, 5-methyl-10-oxo-thia Torre tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10-dioxo-
thia tray hexafluorophosphate, and the like.

Examples of the iodonium salt include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium
hexafluoroantimonate, [4- (2- Hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium
hexafluorophosphate, [4- (2-hydroxy-n-tetrade Siloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate,
bis (4-t-butylphenyl) iodonium hexafluoro Phosphate, bis (4-tert-butylphenyl) iodonium trifluorosulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis
(dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoro Borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis
(dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium triflate, diphenyliodonium bissulfate,
4,4'-dichlorodiphenyliodonium bisulphate, 4,4'-dibromodiphenyliodonium bisulphate , 3,3'-dinitrodiphenyliodonium bisulphate, 4,4'-dimethyldiphenyliodonium bisulphate,
4,4'-bissuccinimide diphenyliodonium bisulphate, 3-nitrodiphenyliodonium bisulphate, 4,4'-dimethoxy Examples thereof include diphenyliodonium bisulphate, bis
(dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate.

As other onium salts, aromatic diazonium salts can be used, for example, p-methoxybenzenediazonium, hexafluoroantimonate, and the like.

Commercially available onium salts include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110. SI-L147 (manufactured by Sanshin
Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide), Adekaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 (Asahi
Denka Kogyo Co., Ltd.), Irgacure 261, Irgacure 250 (Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2439 CI-2064 (Nippon Soda Co., Ltd.), CD-1010, CD-10 1, CD-
1012 (above, manufactured by Sartomer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI -105, NAI-106, SI-100, SI-101, SI-105,
SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured
by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (Sanwa Chemica CD1012
(manufactured by Sartomer), IBPF, IBCF (above, manufactured by Sanwa Chemical Co., Ltd.), BBI-101, BBI-102, BBI-103, BBI-109 (above, Midori Chemical Co., Ltd.) And
UVE1014 (manufactured by General Electronics), RHODORSIL-PI2074 (manufactured by Rhodia), WPI-113, WPI-116 (manufactured by Wako Pure Chemical Industries,
Ltd.) and the like.

J. Polymer Science: Part A: Polymer Chemistry, Vol. 31, 1473-1482 (1993), J.A. Polymer Science: Part A: polymer Chemistry, Vol. 31, 1483-1491 (1993) can also be used
diaryl iodonium salts that can be produced. These can be used alone or in combination of two or more.

As the carboxylic acid ester, 1,8-naphthalenedicarboxylic acid imidomethyl sulfonate, 1,8-naphthalenedicarboxylic acid imidotosyl sulfonate, 1,8-naphthalenedicarboxylic
acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imide camphor Sulfonate, succinimide phenyl sulfonate, succinimide tosyl sulfonate, succinimide
trifluoromethyl sulfonate, succinimide camphor sulfonate, phthalic imide trifluorosulfonate, cis-5-norbornene-endo-2,3-dicarboxylic imide Examples thereof include
trifluoromethyl sulfonate.

Examples of the photobase generator include acyclic acyloxyimino compounds, acyclic carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic
acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, Examples
include sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative
compounds, quaternary ammonium salt derivative compounds, α-lactone ring derivative compounds, amine imide compounds, and phthalimide derivative compounds.
These can be used alone or in combination of two or more.

When the aqueous emulsion of the present invention contains a photopolymerization initiator, the content thereof is stable with respect to 100 parts by mass of the total
of the parts by mass of the chlorinated rubber and the compound having a polymerizable group, From the viewpoint of reactivity and odor, it is preferably 40 parts by
mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

<Light stabilizer>

Examples of the light stabilizer include an ultraviolet absorber and a hindered amine light stabilizer. A light stabilizer may be used independently and may be used in
combination of 2 or more type.

Examples of the ultraviolet absorber include salicylic acids (eg, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), benzophenones (eg, oxalic acid
2,4-dihydroxybenzophenone, 2-hydroxy -4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-
methoxybenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, etc.), benzotriazoles (for example, 2- (2′-hydroxy-5′-
methylphenyl) benzotriazole, 2- (2′-hydroxy-5) '-Ter -Butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-
methylphenyl) ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di) tert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-
3 ′, 3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl} benzotriazole, etc.), triazines (For example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-
hydroxy Loxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-
propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2 -(2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6 -
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2, 4-dimethyl Ruphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-
octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine) and oxalic acid anilides (eg, N- (2-ethylphenyl) -N ′-(2-ethoxy-5-tert-butylphenyl) oxalic acid diamide,
N- (2-ethylphenyl)) -N '-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, oxalic acid diamides having an aryl group which may be substituted
on the nitrogen atom, etc.) Is mentioned.

Examples of hindered amine light stabilizers include ester group-containing piperidines (for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-
tetramethylpiperidine, 4 -Acryloyloxy-2,2,6,6-tetramethylpiperidine, etc.), ether group-containing piperidines (for example, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-
cyclohexyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc.), amide group-containing piperidines (for example, 4- (phenylcarbamoyloxy)
-2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-di As well as high molecular weight piperidine polycondensates (for example,
dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensates such as succinate, , 2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-
piperidinol and tridecyl alcohol, etc.).

When the aqueous emulsion of the present invention contains a light stabilizer, the content thereof is preferably 15 parts by mass or less with respect to 100 parts by
mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. More preferably, it is 10 mass parts or less, More
preferably, it is 5 mass parts or less.

<Ultraviolet curable oligomer>

Examples of the ultraviolet curable oligomer include urethane acrylate oligomer, epoxy acrylate oligomer, and polyester acrylate oligomer. The ultraviolet curable
oligomers may be used alone or in combination.

A commercially available urethane acrylate oligomer can be used. Examples of commercially available urethane acrylate oligomers include CN929, CN965, CN968,
CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (Sartomer), U-4HA and U-6HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) AH-
600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

A commercially available epoxy acrylate oligomer can be used. Examples of commercially available epoxy acrylate oligomers include CN116, CN120B60, CN120M50,
CN131B, CN132, CN137, CN152, and CN2102E (manufactured by Sartomer).

A commercially available polyester acrylate oligomer can be used. Examples of commercially available polyester acrylate oligomers include CN292, CN2259, CN2262,
CN2270, CN2271E, CN2272, CN2273, CN2276, CN2279, CN2285, CN2298, CN2300, CN2301, CN2302, CN2303, and CN2304. These polyester acrylate oligomers may be
used alone or in combination.

When the aqueous emulsion of the present invention contains an ultraviolet curable oligomer, the content is preferably 20 parts by mass with respect to 100 parts by
mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. Part or less, more preferably 15 parts by weight or less, still
more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.

<Fluorescent brightener>

Examples of fluorescent brighteners include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-

alkylimide, bisbenzoxazolylethylene, 1,4-bis (2-Benzoxazolyl) naphthalene, dialkylstilbene and the like. Commercially available optical brighteners include Kayahor 3BS
Liq. Kayahor TAC Liq. Kyaphor HBC Liq. , Kayalight B, Kyaphor AS 150, Kyaphor CR 200, Kyaphor JB Liq., Mikawhite ATN conc. (Manufactured by Nippon Kayaku Co., Ltd.),
TINOPAL OB, TINOPAL NFW Liqid (manufactured by BASF), Hakkol P, Hakkol PHD, Hakkol RF, Hakkol PSR, Hakkol PSR-B, Hakkol CYP-B, Hakkol PY-2000, Hakkol PY-2000
D, Hakkol BE conc, Hakkol SG conc 150, Hakkol TH-100, Hakkol S-100, Hakkol RX-1, Hakkol OW-11, Hakkol OW-10 extra, Hakkol KIP H / C, Hakol KIP H / C, Hakol Hakkol
PMS H / C (made by Showa Chemical Co., Ltd.), Nikkafluor SB conc, Nikkafluor KB, Nikkafluor OB Nikka bright CX H / C (manufactured by Nippon Chemical Industry Co.,
Ltd.) and the like. The optical brighteners may be used alone or in combination.

When the aqueous emulsion of the present invention contains a fluorescent brightening agent, the content thereof is preferably 5 with respect to 100 parts by mass of the
total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. It is no more than 3 parts by mass, more preferably no more than 3
parts by mass, and even more preferably no more than 1 part by mass.

<Leveling agent>

As a leveling agent, polyflow no. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), BYK300,
BYK306, BYK310, BYK320, BYK330, BYK346, BYK349, BYK-333, BYK-345, BYK-347, BYK-348, BYK-378 (manufactured by BYK Japan) KP-341, KP-358, KP-368, KF-96-50CS,
KF-50-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.), Footgent 222F, footage
251, FTX-218 (manufactured by Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (Mitsubishi Materials), MegaFuck F- 171 、 Me Fuck
F-177, Mega Fuck F-475, Mega Fuck F-556, Mega Fuck R-30 (manufactured by DIC), Adeka Coal W-193, Adeka Coal W-287, Adeka Coal W-288, Adeka Coal W-304 (ADEKA)
Manufactured), SN wet 366, Nopco 38-C, SN disperse sand 5468, SN disperse sand 5034, SN disper sand 5027, SN disperse sand 5040, SN disper sand 5020 (San
Nopco) fluoroalkylbenzene sulfonate, fluoroalkyl carboxylic acid Acid salt, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl
sulfonate, diglycerin tetrakis Reoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene
octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether , Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether,
polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palm Tate,
sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxye Ren sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate,
polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonates, or alkyl diphenylether disulfonic acid salts.

When the aqueous emulsion of the present invention contains a leveling agent, the content thereof is preferably 20 parts by mass or less with respect to 100 parts by
mass of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. More preferably, it is 10 mass parts or less, More
preferably, it is 5 mass parts or less.

<Base compound>

As a basic compound, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned, for example. Preferably, it is ammonia or an organic amine
compound.

Examples of organic amine compounds include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine,
iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3- Examples include diethylaminopropylamine, sec-butylamine, propylamine,
methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. N, N-dimethylethanolamine is preferable.

Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide and sodium hydroxide.

Basic compounds are readily available from the market.

When the aqueous emulsion of the present invention contains a basic compound, the content thereof is preferably 20 parts by mass with respect to 100 parts by mass of
the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. Part or less, more preferably 10 parts by weight or less, and still
more preferably 5 parts by weight or less.

<Organic solvent>

Examples of organic solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl
acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, and n-propanol. Alcohols such as isopropyl alcohol and n-butanol; glycol
solvents such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary
butyl ether) and butyl carbitol Cellosolve solvents; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-
methyl And glycol solvents such as xyl-3-methyl-1-butanol; and glycol ester solvents such as ethylene glycol monomethyl ether acetate, PMA (propylene glycol
monomethyl ether acetate), diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate. It is done. These may be used alone or in
combination.

When the aqueous emulsion of the present invention contains an organic solvent, the content thereof is 100 parts by mass with respect to 100 parts by mass of the mass
part of the chlorinated rubber and the compound having a polymerizable group, from the viewpoint of odor, Preferably it is 100 mass parts or less, More preferably, it is 50
mass parts or less, More preferably, it is 30 mass parts or less, More preferably, it is 10 mass parts or less.

<Crosslinking agent>

By including a crosslinking agent, there exists a tendency for adhesiveness, the water resistance of a contact bonding layer, and the solvent resistance of a contact
bonding layer to improve more.

Examples of the crosslinking agent include epoxy compounds, polyisocyanate compounds, oxazoline compounds, aziridine compounds, carbodiimide compounds, active
methylol compounds, active alkoxymethyl compounds, metal chelates, hydrazide compounds, and hydrazine compounds.

Preferred are aliphatic polyisocyanate compounds, carbodiimide compounds, oxazoline group-containing compounds, hydrazide compounds, and hydrazine compounds.
Of these, aqueous (water-soluble or water-dispersible) ones are more preferable. These crosslinking agents may be used alone or in combination.

Examples of the polyisocyanate compound include hexamethylene diisocyanate (HDI), 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and
oligomers or polymers thereof.

Specifically, Sumidur (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10, 44V20 made by Sumika Bayer
Urethane And E 21-1, Death Module (registered trademark) N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and DA-, manufactured by
Sumitomo Bayer Urethane Co., Ltd. L, E14 and E22, Bihijoule (registered trademark) 304 and XP2655 manufactured by Sumitomo Bayer Urethane Co., Ltd., BASONAT
(registered trademark) PLR8878 and HW-100 manufactured by BASF, Takenate (registered trademark) manufactured by Takeda Pharmaceutical Company Limited )
WD720, WD7 5 and WD730, Asahi Chemical Industry Co. Duranate (registered trademark) WB40-100, include WB40-80D and WX-1741 or the like.

Specific examples of carbodiimide-based crosslinking agents include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02), etc. Can be
mentioned.

Specific examples of hydrazide compound crosslinking agents include: Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH
(dodecanediohydrazide), IDH (isophthalic acid dihydrazide), SAH. (Salicylic acid hydrazide) and the like.

Specific examples of the hydrazine compound crosslinking agent include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine
monohydrobromide, hydrazine carbonate, and the like.

When the aqueous emulsion of the present invention contains a crosslinking agent, the content thereof is preferably 30 parts by mass with respect to 100 parts by mass
of the total of parts by mass of the chlorinated rubber and the compound having a polymerizable group. It is below, More preferably, it is 15 mass parts or less, More
preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less.

<Photosensitizer>

The photosensitizer can be appropriately selected according to the wavelength to be enhanced. The effective excitation wavelength range is usually 450 nm or less,
preferably in the range of 250 to 380 nm. Examples of the photosensitizer include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-
dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminoethylbenzoate, and isoacyl 4-dimethylaminobenzoate. .

When the aqueous emulsion of the present invention contains a photosensitizer, the content thereof is preferably 15 with respect to 100 parts by mass of the total of
parts by mass of the chlorinated rubber and the compound having a polymerizable group. It is not more than part by mass, more preferably not more than 10 parts by
mass, and still more preferably not more than 5 parts by mass.

<Other resins>

The aqueous emulsion of the present invention may contain other resins as long as the intended properties are not impaired.

Other resins include ethylene-vinyl ester resins, styrene-maleic acid resins, resins having structural units derived from α-olefins having 2 to 20 carbon atoms, chlorinated
products and modified products thereof, (meth) acrylic resins, polystyrene , Polyvinyl acetate, polyurethane, polyvinyl chloride, chlorinated polyvinyl chloride,
polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic ester copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, chloride
Vinylidene- (meth) acrylic acid ester copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, chlorinated resin having a structural unit derived from α-olefin
having 2 to 20 carbon atoms, ethylene-vinyl ester resin, polyurea, acrylonitrile Butadiene styrene resin, chloroprene Resin, acid-modified chloroprene resin, butyl rubber,
chlorinated butyl rubber, brominated butyl rubber, modified rubber, styrene- (meth) acrylic acid resin, synthetic rubber, natural rubber, styrene-butadiene resin, butadiene
resin, poly (meth) acrylonitrile resin (Meth) acrylamide resin, polyester resin, modified nylon resin, epoxy resin, styrenic block copolymer and oligomers thereof. Among
the above, the rubber containing a chlorine atom is preferably a rubber having a chlorine atom content of less than 45% by mass. These may be in the form of a solid (for
example, resin powder) or in the form of an emulsion.

The ethylene-vinyl ester resin is a copolymer containing a polymer composed of ethylene units and vinyl ester units. Examples of vinyl ester units include vinyl acetate,
vinyl propionate, vinyl pivalate, vinyl esters of tertiary carboxylic acids having 8 to 10 carbon atoms, and so-called vinyl versatates (for example, trade name: Veova
(registered trademark) manufactured by Shell Chemical Co., Ltd.). And alkyl acid vinyl esters such as 10). Of the vinyl ester units, vinyl acetate is preferred. When vinyl
acetate is used as the vinyl ester unit, the copolymer is an ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as “EVA”).

For example, ethylene-vinyl acetate copolymers have various vinyl acetate contents and shapes (films, blocks, fibers, foams), although the properties differ depending on
the vinyl acetate content and the like. The ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin. Preferred polyolefins include ethylene-octene
copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

In addition to ethylene units and vinyl ester units, the ethylene-vinyl ester resin may contain monomer units copolymerizable therewith. Examples of the monomer unit
include vinyl halides such as vinyl chloride, monomers having a small amount of a functional group such as an amide group, and (meth) acrylic acid esters.

Examples of the ethylene-vinyl ester resin copolymer include VINNOL E15 / 45, E15 / 45M, E15 / 48A, H15 / 42, H15 / 50, H11 / 59, H14 / 36, H40 / 50, H40 / 55, H40 / 60,
H30 / 48M (Wacker Chemie AG) and the like.

The ethylene-vinyl ester resin and the copolymer thereof may be in the form of an emulsion. Such an emulsion may be produced by emulsion polymerization of
monomers constituting the ethylene units and vinyl ester units, or commercially available ones may be used. Examples of the emulsion of the ethylene-vinyl ester resin
copolymer include Sumikaflex (registered trademark) 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ,
470HQ. 478HQ, 510HQ, 520HQ, 710, 752, 755, SDX-5100, 801HQ, 808HQ, 830, 850HQ, 900HL and 3950 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex
OM-4000 and OM-4200 (above Polysol (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa High) (Molecular Co., Ltd.)
Denka EVA-Tex (registered trademark) # 20, # 30, # 40M, # 60, # 81 and # 82 (manufactured by Denki Kagaku Kogyo Co., Ltd.).

Examples of the styrene-maleic acid resin include ARASTOR 700 and 703S (manufactured by Arakawa Chemical Industries, Ltd., SMA (registered trademark) 1000, SMA
(registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley's). Examples of the emulsion of styrene-maleic acid resin include VE-1122 (Starlight PMC Co.,
Ltd.).
Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-
undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and vinylcyclohexane.
Preferably, they are ethylene and propylene.

Examples of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium
density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density. Homopolymers such as polyethylene, ultra high molecular weight polyethylene and
polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene and atactic polypropylene, ethylene-propylene copolymer, propylene-1-butene
copolymer, ethylene Α-olefin copolymers such as a 1-butene copolymer, an ethylene-1-octene copolymer and an ethylene-1-hexene copolymer, and an α-olefin having 2 to
20 carbon atoms and the α-olefin Copolymers of monomers copolymerizable with olefins It is below. Further, the copolymer of an α-olefin having 2 to 20 carbon atoms
and a monomer copolymerizable with the α-olefin may contain one type of each monomer or two or more types. It may be a thing.

The resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms may be any of a homopolymer, a random copolymer, a block copolymer, and a
graft copolymer. Further, it may be reduced in molecular weight or high molecular weight by peroxide or the like.

As a modified product of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, the resin having a structural unit derived from an α-olefin
having a prime number of 2 to 20 is modified with an α, β-unsaturated carboxylic acid or the like. Modified products.

The modification rate of the modified product modified with α, β-unsaturated carboxylic acid or the like is usually 0.1 to 10% by mass, preferably 0.2 to 0.2% with respect
to 100% by mass of the copolymer before modification. 5% by mass, more preferably 0.2 to 4% by mass.

Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), α, β-unsaturated carboxylic acid
esters (methyl maleate, methyl itaconate) ), Α, β-unsaturated carboxylic anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). A modified product
obtained by combining these α, β-unsaturated carboxylic acids may also be used. These may be carboxylic anhydrides, carboxylic acids formed by hydrolysis, or a
mixture thereof.

Such a modified product includes a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms or a copolymer of an α-olefin having 2 to 20 carbon
atoms and a monomer copolymerizable with the α-olefin. A method of adding and modifying α, β-unsaturated carboxylic acids after melting, a method of modifying by
adding α, β-unsaturated carboxylic acids after dissolving in a solvent such as toluene and xylene, etc. It is produced by a known method.

The modification rate of the chlorinated resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is such that the chlorine atom content is
preferably 5 to 80 with respect to 100% by mass of the copolymer before modification. % By mass, more preferably 40 to 75% by mass. More preferably, it is 55 to 70% by
mass.

Chlorination of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is performed by dissolving or dispersing the resin having a structural
unit derived from an α-olefin having 2 to 20 carbon atoms in a solvent. It can be obtained by chlorinating a resin having a structural unit derived from an α-olefin having 2
to 20 carbon atoms by a method of blowing chlorine gas or the like.

Monomers copolymerizable with α-olefins having 2 to 20 carbon atoms include α, β-unsaturated carboxylic acids and anhydrides, metal salts of α, β-unsaturated
carboxylic acids, α, β-unsaturated carboxylic acids, and the like. Examples include acid esters, vinyl esters, vinyl ester saponified products, cyclic olefins, vinyl aromatic
compounds, polyene compounds (dienes and the like), (meth) acrylonitrile, vinyl halides, amides and vinylidene halides. These may be used alone or in combination for
copolymerization.

α, β-unsaturated carboxylic acid and its anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid,
crotonic acid, monomethyl maleate, monoethyl maleate, maleic Examples include acid half esters, maleic acid half amides, itaconic acid half esters, itaconic acid half
amides, and the like. Of these, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly
preferable.

Examples of the metal salt of α, β-unsaturated carboxylic acid include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals
such as magnesium, calcium and zinc. Specifically, the sodium salt and magnesium salt of (meth) acrylic acid are mentioned.

α, β-unsaturated carboxylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-
hydroxyethyl acrylate, maleic acid Examples include esterified products of dimethyl and methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth)
acrylate are preferred.

Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and vinyl versatate. Of these, vinyl acetate is preferred.

Examples of the vinyl ester saponified product include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.

Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2 -
Dihydrodicyclopentadiene, 5-chloronorbornene, cyclopentene, cyclohexene, cycloheptene, vinylcyclohexane and the like.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene,
dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene. Etc.

Examples of the polyene compound include linear or branched aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, aliphatic non-
conjugated polyene compounds, alicyclic non-conjugated polyene compounds, and aromatic non-conjugated polyene compounds. . These may have a substituent such
as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.

Aliphatic conjugated polyene compounds include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-methyl- Examples
include 1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene, and 2,3-dimethyl-1,3-decadiene.

Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro-1,
Examples include 3-butadiene, 2-chloro-1,3-pentadiene and 2-chloro-1,3-cyclohexadiene.

Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,9-decadiene, 3,3-dimethyl-1,4-hexadiene, 5-ethyl-1 , 4-
heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1 4, 4-decadiene, 6-methyl-1,6-undecadiene, 4-
ethylidene-12-methyl-1,11-pentadecadien, and the like.

Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl-3-
vinylcyclopentane, and methyltetrahydroindene.

Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

Examples of the copolymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include ethylene-unsaturated carboxylic acid copolymers such
as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer, and the ethylene -Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate
copolymer, ethylene / methyl methacrylate copolymer, wherein some or all of the carboxyl groups of the unsaturated carboxylic acid copolymer are neutralized with the
above metals. Polymer, ethylene-isobutyl acrylate copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-n-butyl acrylate copolymer, ethylene-
isobutyl acrylate-methacrylic acid copolymer, ethylene-acrylic Ethylene-unsaturated carboxylic acid esters such as n-butyl-methacrylic acid copolymer Ionomer in which
part or all of the sum carboxylic acid copolymer and a carboxyl group is neutralized with the metal, ethylene - ethylene such as vinyl acetate copolymer - vinyl ester
copolymer and the like.

Examples of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and modified products thereof include Mersen (registered trademark)
H H-6410M, H-6051, H-6960, H-6820, and H-6822X. (Tosoh Corporation), EVAL (registered trademark) L171B, F171B, H171B, E105B and G156B (Kuraray Co., Ltd.),
Soarnol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX , 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chemical
Industry Co., Ltd.), Soaredin (registered trademark) PG505 (Nippon Synthetic Chemical Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Soda Co., Ltd.),
Polytail (registered trademark) ) H (Mitsubishi Chemical Corporation), Epaul (Noboru) Trademarks) (Idemitsu Kosan Co., Ltd.), OREVAC (registered trademark) G 18211,
OE808 and OE825 (Arkema Corp.), LOTADAR MAH2210, 3200, P3 3200, 3210, 4210, 6200, 3410, 3430 and 4720 (Arkema ( Ltd.), BONDINE (registered trademark) LX4110,
HX8210, TX8030, HX8290, HX8410 and AX8390 (Arkema Corp.), OREVAC (registered trademark) T9314, T9318 and G18211 (Arkema Corp.), Umex (registered trademark)
2000 (Sanyo Chemical Industry Co., Ltd.), Auroren (registered trademark) 100S and 200T (Nippon Paper Chemical Co., Ltd.), and the like.

The resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof may be in the form of an emulsion. Such an
emulsion may be produced by emulsifying a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof, or a
commercially available product may be used. Examples of emulsions of resins having structural units derived from α-olefins having 2 to 20 carbon atoms and modified
products thereof include Arrow Base (registered trademark) SA-1200, SB-1200, SE-1200, SB-1010 (Unitika). ), Aptolock (registered trademark) BW-5550 (Mitsubishi
Chemical Corporation), Auroren (registered trademark) AE-202, AE-301 (Nippon Paper Industries Co., Ltd.), Aquatex (registered trademark) EC -1200, EC-1700, AC-3100,
MC-4400, HA-1100, 909 (Chuo Rika Kogyo Co., Ltd.).

Examples of the resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms include Eraslene (registered trademark) 401A and 303B
(Showa Denko KK), Harden (registered trademark) CY-9122P, CY- 9124P, HM-21P, M-28P, F-2P, F-6P, F-69, 13-LP, 13-LLP, 14-LWP, 14-WL-P, 15-LP, 15-LLP, 16- LP, DX-526P,
DX-530P and BS-40 (Toyobo Co., Ltd.), and Supercron (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE-510, HE- 515, HE-910, HE-915, HE-1070, HE-
1200, HP-205, HP-215 and HP-620 (Nippon Paper Chemical Co., Ltd. ), And the like.

The resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms may be in the form of an emulsion. Such an emulsion may be produced
by emulsifying a chlorinated resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, or a commercially available product may be used.
Examples of emulsions of resins having structural units derived from chlorinated α-olefins having 2 to 20 carbon atoms include, for example, HARDLEN® EW-5303, EH-
801, EW-5504, EZ-1000 and EZ- 2000 (Toyobo Co., Ltd.), Supercron (registered trademark) E-604, E-480T and E-415 (Nippon Paper Chemical Co., Ltd.).

Polyurethane is a polymer composed of urethane bonds, and is usually obtained by reaction of alcohol (—OH) and isocyanate (—NCO). In the polyurethane, the urethane
foam includes a polyurethane foamed by a volatile solvent such as carbon dioxide or freon produced by a reaction between an isocyanate and water.

A commercially available polyurethane can be used. Examples thereof include Nipponran (registered trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon
Polyurethane Industry Co., Ltd.). Examples of commercially available water-soluble urethanes include DISPAROL (registered trademark) U-42, U-53, U-54, U-56, KA-8484,
KA-8484, KA-8755, KA-8756, and KA-. 8766 (Sumitomo Bayer Urethane Co., Ltd.), Hydran (registered trademark) HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-
20, AP-60LM and AP-80 (DIC Corporation), Uprene (registered trademark) UXA-306, UXA-307, Permarine UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310
and Ucourt UWS-145 (Sanyo Chemical Industries, Ltd.) )), Superflex (registered trademark) 107M, 110, 126, 130, 150, 160, 210, 00, 361, 370, 410, 420, 460, 500M, 700,
750, 820 and 860 (Daiichi Kogyo Seiyaku Co., Ltd.), and Adekabon titer (registered trademark) HUX-401, HUX-420A, HUX-380 HUX-561, HUX-210, HUX-822, HUX-895, HUX-
830 (Adeka Co., Ltd.) and the like.

Polyvinyl chloride is obtained by a method such as suspension polymerization or bulk polymerization of vinyl chloride.

Examples of the polyvinyl chloride include hard polyvinyl chloride, semi-rigid polyvinyl chloride, and soft polyvinyl chloride. Preferably, it is soft polyvinyl chloride.

Examples of the polyvinyl chloride include Kanevinyl S-400, PSH-180, PSL-180 (Kaneka). Examples of the polyvinyl chloride emulsion include Vinibrand 701, 700, and 711
(Nisshin Chemical Industry Co., Ltd.).

Chlorinated polyvinyl chloride is obtained by chlorinating a polyvinyl chloride resin by a chlorination method such as a gas phase or a liquid phase. Examples of the
polyvinyl chloride resin include a vinyl chloride homopolymer and a vinyl chloride copolymer. Examples of the monomer constituting the vinyl chloride copolymer together
with vinyl chloride include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, maleic acid ester, and the like. Examples of the
chlorinated polyvinyl chloride include Sekisui PVC-HA (Sekisui Chemical Co., Ltd.).

Examples of the polyvinylidene chloride include Saran X05253-16 (manufactured by Dow Chemical Company), Saran Wrap (registered trademark) resin (manufactured by
Asahi Kasei Corporation), and the like. Examples of the polyvinylidene chloride emulsion include Diofan 193D, A736, A036, A050, A063, B204, A115 (manufactured by
Solvay).

Examples of the vinyl chloride-vinylidene chloride copolymer resin include IXAN SGA-1 (manufactured by Solvay).

Examples of the vinylidene chloride- (meth) acrylic acid ester copolymer resin include IXAN PVS-109, 801, 815, Diofan A586, A602, A610 (manufactured by Solvay).

The chloroprene-based resin is obtained by polymerizing chloroprene synthesized by dehydrochlorination of dichlorobutene obtained by chlorination of butadiene, or
copolymerizing with other monomers. Such other monomers include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid esters, methacrylic acid
esters, acrylic acid, methacrylic acid, itaconic acid and the like.

The acid-modified chloroprene resin is obtained by graft copolymerizing the above chloroprene resin with at least one selected from α, β-unsaturated carboxylic acids and
anhydrides thereof. Examples of α, β-unsaturated carboxylic acids and acid anhydrides thereof include those exemplified as modified products of resins having structural
units derived from α-olefins having 2 to 20 carbon atoms.

Examples of the chloroprene resin and acid-modified chloroprene resin include Skyprene (registered trademark) G-42, G-40S, G-55, G-40, S-1, G-40T, B-30S, and Y-31.
(Tosoh Corp.), Showprene (registered trademark) W, AF, WHV, WXJ, WB (Showa Denko), and Denkachloroprene (registered trademark) A-30, A-70, A-90, A- 91, M-130L,
DCR-11 (Electrochemical Industry Co., Ltd.) and the like. Examples of emulsions of chloroprene resin and acid-modified chloroprene resin include Skyprene (registered
trademark) GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390 and SL-590. (Tosoh Corporation), Shoprene (registered trademark) 115, 571, 572, 650, 671A, 750,
SD78 and SD77S (Showa Denko Co., Ltd.), and Denkachloroprene (registered trademark) LA-50 and LC-501 ( Electrochemical Industry Co., Ltd.)).

Examples of the chlorinated butyl rubber include Enjay Butyl® HT10-66 (manufactured by Enjay Chemical), JSR® CHLOROBUTYL® 1066 (manufactured by JSR), and
HT1066 (manufactured by ExxonMobil).

Examples of the brominated butyl rubber include JSR BROMOBUTYL５５2255, 2244 (manufactured by JSR), Exxon bromobutyl 2255 (ExxonMobil Chemical).

Examples of the modified rubber include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and a commercially
available product is Expro 50 (manufactured by Exxon).

Examples of the styrene block copolymer include a block copolymer composed of a diene block and a styrene block. Specifically, styrene-butadiene block copolymer
(SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-butylene-styrene copolymer. Examples thereof
include a polymer (SBBS) or a hydrogenated product of these block copolymers, a styrene / isobutylene-styrene triblock copolymer (SIBS), and a styrene-isobutylene
diblock copolymer (SIB). Such a hydrogenated product is a block copolymer in which all of the styrene block and the diene block are hydrogenated, or a block copolymer
in which only the diene block is hydrogenated or a part of the styrene block and the diene block. It may be a partially hydrogenated product such as a hydrogenated block
copolymer.
Other resins may include water-soluble resins such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose in order to further
improve the stability of the aqueous emulsion.

Further, as other resins, an adhesive resin or a resin having a function as a tackifier may be contained. Examples of such resins include rosins, terpene resins, petroleum
resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions
having 9 carbon atoms, and hydrogenated resins thereof. Examples thereof include resins, other petroleum resins, coumarone resins, and indene resins. Specifically,
rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester,
triethylene glycol ester, phenol modified product and ester thereof Rosins such as fluorides; terpene polymers, terpene phenols, β-pinene polymers, aromatic modified
terpene polymers, α-pinene polymers, terpene hydrogenated resins and other terpene resins; C 5 petroleum fractions A petroleum resin obtained by polymerizing a
petroleum fraction, a petroleum resin obtained by polymerizing a petroleum fraction having 9 carbon atoms and a hydrogenated resin thereof; a petroleum resin such as a
maleic acid-modified product and a fumaric acid-modified product, chlorinated paraffin, and the like.

Terpene resins include YS Resin PX, PXN, YS Polyster, Mighty Ace, YS Resin TO, TR and Clearon P, M, K (Yasuhara Chemical Co., Ltd.), Tamanol 803L, 901 (Arakawa
Chemical Industries, Ltd.) and And Teltac 80 (Nippon Terpene Chemical Co., Ltd.). Examples of the terpene resin emulsion include Tamanol E-200NT and E100 (Arakawa
Chemical Industries, Ltd.).

Examples of the chlorinated paraffin include Empara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265,
270, 150, A50 (Tosoh Corp.), and the like. It is done.

Other resin may be individual and may be contained in combination of 2 or more type.

Other resins can be easily obtained from the market.

The aqueous emulsion of the present invention may contain other resins as long as the properties thereof are not impaired, and the content thereof is a total of 100 parts
by mass of the chlorinated rubber and the compound having a polymerizable group. Preferably it is 100 mass parts or less with respect to a mass part, More preferably, it
is 50 mass parts or less, More preferably, it is 30 mass parts or less, More preferably, it is 20 mass parts or less. Other resins may be mixed with the aqueous emulsion of
the present invention in the form of an emulsion, or may be emulsified with a compound having a chlorinated rubber and a polymerizable group to form an aqueous
emulsion.

<Thickener>

Thickeners can be used to adjust the viscosity of the aqueous emulsion. As a thickener, Adecanol (registered trademark) UH-140S, UH-420, UH-438, UH-450VF, UH-462,
UH-472, UH-526, UH-530, UH-540, UH-541VF, UH-550, UH-752 and H-756VF (ADEKA), and SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A-818, 621N,
636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, and 4050 (San Nopco).

<Form of aqueous emulsion>

The aqueous emulsion of the present invention preferably contains a chlorinated rubber and a compound having a polymerizable group as a mixture. A mixture is a state
in which a chlorinated rubber and a compound having a polymerizable group are mixed, a state in which the chlorinated rubber is dispersed or swollen in a compound
having a polymerizable group, and at least a part of the chlorinated rubber is a polymerizable group. The state which melt | dissolves in the compound which has this is
included.

That at least a part of the chlorinated rubber is dissolved in the compound having a polymerizable group means that when the mixture of the chlorinated rubber and the
compound having a polymerizable group is filtered with a filter having a pore diameter of about 0.50 μm, the filtrate It is sufficient that at least a part of the chlorinated
rubber is contained therein. The chlorinated rubber contained in the filtrate is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably
30% by mass or more, relative to 100 parts by mass of the chlorinated rubber contained in the aqueous emulsion before filtration. More preferably, it is 70 mass% or
more.

Filtration with a filter is preferably performed after heating to a temperature equal to or higher than the melting point of the compound having a polymerizable group
contained in the aqueous emulsion.

Examples of a method of using a mixture of a chlorinated rubber and a compound having a polymerizable group include a method of mixing a chlorinated rubber and a
compound having a polymerizable group using a mixer. The mixing temperature is usually 25 to 100 ° C. The mixing time is preferably as short as possible. Examples of
the mixer include a Banbury mixer, a Henschel mixer, and a homomixer.

The mixture of the chlorinated rubber and the compound having a polymerizable group is preferably contained as a dispersoid. Here, dispersoid means particles
dispersed in water. In this case, the dispersoid may be a solid at 23 ° C. and atmospheric pressure, but is preferably a liquid.

The dispersoid is liquid as long as at least one of the components constituting the dispersoid has fluidity, and the dispersoid may contain a solid component or an
insoluble component.

When the dispersoid is a liquid and has fluidity, the fluidity may be high or low. This is because the stability of the aqueous emulsion tends to improve when the fluidity is
low, and the adhesiveness tends to improve when the fluidity is high.

The total content of the mass part of the chlorinated rubber and the mass part of the compound having a polymerizable group is preferably 0.1 relative to the total mass
of the chlorinated rubber, the compound having a polymerizable group and water. It is ˜70% by mass, more preferably 1 to 70% by mass, and further preferably 2% to 60%
by mass. Adhesiveness becomes favorable by setting it as the said range. In particular, when the content is 30% by mass or more, the stability of the aqueous emulsion
becomes good. Therefore, it is more preferably 30% by mass to 60% by mass, further preferably 40% by mass to 60% by mass, and still more preferably 45% by mass to
60% by mass.

The dispersoid in the aqueous emulsion has a volume-based median diameter of preferably 10 μm or less, more preferably 0.01 to 5 μm, still more preferably 0.01 to 2
μm, and even more preferably 0.01. ~ 1 μm. When it is within the above range, the stationary stability is good.

The volume-based median diameter is a particle diameter corresponding to a cumulative particle diameter distribution value of 50% on a volume basis, and means a
median diameter measured on a volume basis unless otherwise specified.

The average particle size of the dispersoid can be measured with a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA Corporation.

<Method for producing aqueous emulsion>

The aqueous emulsion of the present invention can be produced by a known method. For example, it can be produced by a post-emulsification method (for example,
forced emulsification method, self-emulsification method, phase inversion emulsification method, etc.) in which a chlorinated rubber and a compound having a
polymerizable group are dispersed in a dispersion medium such as water.

For example, a chlorinated rubber and a compound having a polymerizable group are added to a reactor (optional additives may be added), and after mixing, water and /
or a solvent are added, and optionally a surfactant. A method of emulsifying by adding an additive such as a photopolymerization initiator and then stirring while heating
can be mentioned.

Examples of the reactor include a container equipped with a heating device and a stirrer capable of applying a force such as a shearing force to the contents. A sealed
container or a pressure vessel is preferable. A common agitator can be used. Examples of such a reactor include a pressure-resistant autoclave with a stirrer. Stirring may
be performed at normal pressure or reduced pressure. The rotation speed of the stirrer is usually 50 to 20000 rpm.
The mixing temperature and the heating and stirring temperature are usually 10 to 90 ° C., preferably 15 to 80 ° C., more preferably 15 to 60 ° C., and usually 25 to 100 ° C.

Mixing and / or heating and stirring may be performed using a mixer such as a Banbury mixer, a Henschel mixer, and a homomixer in addition to the above-described
stirrer.

For example, additives such as a photopolymerization initiator, a crosslinking agent, an organic solvent, a basic compound, a thickener, and a leveling agent may be
added before adding water and / or a solvent, and water and / or a solvent may be added. You may add after adding, and may add after emulsification. In particular, the
light stabilizer, ultraviolet curable oligomer, fluorescent whitening agent, photosensitizer, and other resins are preferably added before adding water and / or solvent.

An aqueous emulsion having a large particle size may be obtained by pre-emulsifying in advance, and an aqueous emulsion having a small particle size may be obtained
by performing high-pressure shearing using an apparatus such as a high-pressure homogenizer or a high-pressure homojetter.

After emulsification, when the obtained aqueous emulsion contains an organic solvent, it is preferable to remove the organic solvent. The removal of the organic solvent
is usually performed by distilling off under reduced pressure.

In the production of the aqueous emulsion, when a surfactant is used, the surfactant may be separated and removed from the obtained aqueous emulsion. Separation
and removal of the surfactant can be performed by, for example, a centrifugal separator, a filtration filter having an average pore size smaller than the average particle
size of the aqueous emulsion, or an ultrafiltration membrane. However, the separation and removal of the surfactant may only reduce the amount of the surfactant.

Furthermore, it is preferable to cool the obtained aqueous emulsion. By cooling, an aqueous emulsion composed of a fine dispersoid can be obtained. It is preferable that
the cooling be performed slowly, for example, by leaving it at room temperature instead of rapid cooling. Thereby, a fine and homogeneous aqueous emulsion can be
obtained without aggregation of resin or the like during the cooling process.

<Use of aqueous emulsion>

As described above, the aqueous emulsion of the present invention is useful as a composition constituting an aqueous adhesive or the like. Moreover, you may use as a
composition for forming in a to-be-adhered body as a coating film or a coating film by an aqueous emulsion. A water-based adhesive, a coating film, a coating film, and
the like are usually used as a dried product or a cured product. In particular, the water-based adhesive effectively exhibits its function in the form of a coating film formed
from an aqueous emulsion or a cured product thereof.

Wood, plywood, medium density fiberboard (MDF), particle board, fiber board, etc. as adherends (including the first base material and the second base material) to be
coated, covered and adhered Cellulosic materials such as cotton cloth, cotton-containing fibers, linen and rayon; polyethylene (polyolefins mainly composed of structural
units derived from ethylene), polypropylene (polyolefins composed mainly of structural units derived from propylene), Polyolefins such as polystyrene (polyolefins mainly
composed of structural units derived from styrene), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether,
polyvinyl chloride, polyurethane , Urethane foam, ethylene-vinyl acetate copolymer (EV ), Plastic materials such as foamed EVA, nylon 6, nylon 66 and other polyamide-
based resins or foams thereof; polyurethane-based, polyamide-based and polyamino acid-based synthetic leather; ceramic materials such as glass and ceramics; and
iron, stainless steel, Examples thereof include metal materials such as copper and aluminum. These may be composite materials composed of a plurality of
components. Further, it may be a kneaded molded product of an inorganic filler such as talc, silica or activated carbon, carbon fiber and the like and a plastic material.

Among them, adhesives between cellulose materials and plastic materials, polyvinyl chloride, ethylene-vinyl acetate copolymers, cotton-containing fibers, nylon resins,
olefin polymers, polyurethanes, rubbers, styrene butadiene rubbers and other styrene block copolymers. It can be suitably used for adhesion of polymers and synthetic
leather. Examples of the shape of these materials include various types such as a film, a sheet, or a block, and preferably a film and a sheet.

The olefin polymer is a resin obtained by polymerizing an olefin, and examples thereof include homopolymers and copolymers having a structural unit derived from an α-
olefin having 2 to 20 carbon atoms. As an olefin polymer, what was illustrated by said other resin is mentioned.

Examples of the resin constituting the adherend include those exemplified above for the other resins.

The cotton-containing fibers may be 100% cotton fibers, or may be blended fibers of cotton and other natural fibers and / or chemical fibers. Other natural fibers include
wool, silk and hemp. Chemical fibers include synthetic fibers (for example, polyamide fibers such as polyester and nylon), semi-synthetic fibers (cellulose fibers such as
acetate, protein fibers such as promix), and regenerated fibers (rayon, cupra, polynosic, etc.) Cellulosic fibers) and inorganic fibers (carbon fibers, glass fibers) and the
like.

Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape.

Nylon resin is a so-called polyamide resin, which is a polymer composed of amide bonds. Specific examples include nylon 6, nylon 6,6, nylon 4,6, nylon 11, and nylon 12.
The nylon resin may have any shape such as a film, a block, a fiber, or a foam.

For example, natural rubber, thermoplastic rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene
rubber, butyl rubber and the like are mainly used as the rubber. In preparing the rubber composition, these diene rubbers may be used alone or in combination of two or
more. If necessary, reinforcing agents such as clay, carbon black or silica, silane coupling agents, anti-aging agents, softeners, zinc white, stearic acid, vulcanization
accelerators, vulcanizing agents, sulfur, etc. are appropriately blended. May be.

Synthetic leather includes both synthetic leather and artificial leather in the narrow sense. In other words, it may be a synthetic leather obtained by applying a synthetic
resin to a natural or synthetic fabric, or may be an artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as a
microfiber, such as a microfiber. Artificial leather obtained by impregnating a fabric (usually a nonwoven fabric) with a synthetic resin and further applying the synthetic
resin may be used. Examples of these synthetic resins include polyurethane resins, polyamide resins, and polyamino acid resins. A polyurethane resin is preferable.

The aqueous emulsion of the present invention is effective for bonding materials (hereinafter sometimes referred to as adherends) such as films, sheets, structural
materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes. Can be used for In particular, to bond
construction materials (adherents) such as underwear, insole, and outer sole in footwear such as men's shoes such as sports shoes, town shoes, and business shoes,
women's shoes, and industrial work shoes. It is suitable as an adhesive. The surface of these adherends may be smooth or may have irregularities. Moreover, you may
perform the primer process for improving adhesion | attachment, such as an adhesive agent, on the surface of a to-be-adhered body. Examples of the primer treatment
include blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation
treatment, plasma treatment, ion treatment, anchor layer formation, and the like.

As a method for adhering the adherend, a coating film, an adhesive layer, and an adherend (second substrate) obtained by drying the aqueous emulsion of the present
invention on an adherend (first substrate). The method of laminating | stacking in this order is mentioned.

First, an aqueous emulsion is applied to the surface of the first substrate, optionally the second substrate.

Any known coating method can be used for coating. For example, gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating,
curtain flow coating, spray coating, dip coating, brushing and spatula coating can be used.

After applying the aqueous emulsion to the first substrate, the obtained coating film may be dried or heat-treated, and then irradiated with electromagnetic waves.

When drying or heat treatment is performed, the coating film can be formed by drying or heat treatment to remove water or the solvent.

Examples of the heating temperature include about 30 to 150 ° C, preferably about 40 to 80 ° C.

The heating time is about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.

Before and after the heat drying treatment, the first substrate may be further treated by leaving (natural drying) or using a normal hot air circulation oven, an infrared
heater, electromagnetic waves such as ultraviolet rays, and the like. In this case, the heating temperature and time in the preliminary drying can be appropriately adjusted
according to the characteristics of the substrate, the composition of the aqueous emulsion to be used, and the like. For example, the same conditions as mentioned
above can be mentioned.

Application and drying of the aqueous emulsion may be performed only once or may be performed twice or more. As the coating method and the drying method, the
same method may be combined, or different methods may be combined.

In the case of electromagnetic wave treatment, examples of the light source include a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury
lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, and a laser. Preferably, a metal halide lamp, a high pressure mercury lamp, an ultra high pressure mercury
lamp, and a low pressure mercury lamp are mentioned. The irradiation amount is usually 5 mW / cm 2 to 2000 mW / cm 2 as a peak illuminance, preferably 10 mW / cm 2
to 2000 mW / cm 2, and the integrated irradiation amount is usually 20 to 3000 mJ / cm 2, preferably 100 to 2500 mJ / cm 2. is there.

Before applying the aqueous emulsion to the adherend, the surface of the first substrate may be subjected to a primer treatment. Examples of the primer treatment
include blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet
irradiation treatment, plasma treatment, ion treatment, and anchor layer formation treatment.

In the coating film after drying, it is preferable that 95% by mass or more of water contained in the aqueous emulsion is removed. Adhesiveness is securable by setting it
as this range.

The thickness of the coating film after drying is such that the thickness after drying is about 0.01 to 300 μm, preferably about 0.01 to 200 μm, more preferably about 0.01
to 50 μm. .

Next, an adhesive is applied to at least one of the first substrate and the second substrate to which the aqueous emulsion is applied, and is heat-dried. These coating and
heat drying treatments may be performed only once on at least one of the first base material and the second base material. However, one or more times of application
and heat drying of the adhesive may be performed on both. .

The adhesive application method, application thickness, heat treatment method, temperature, time, and other conditions can be changed as appropriate. The same
conditions as the application and drying of the aqueous emulsion described above may be selected, or different conditions may be selected.

When applying the adhesive to both the first substrate and the second substrate, the adhesive layer may not be the same adhesive for the first substrate and the second
substrate, Considering the adhesiveness of both, it is preferable to use the same adhesive. The water-based emulsion used above may be sufficient as an adhesive agent,
and a commercially available adhesive agent may be sufficient as it.

The thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive used, the material and form of the substrate, and the
like. For example, the thickness after drying is about 0.01 to 300 μm, preferably about 0.01 to 200 μm.

Before applying the aqueous emulsion to the adherend, the surface of the second substrate may be subjected to a primer treatment. The primer treatment can be
appropriately selected from the above.

As a method of bonding the surfaces of the first base material and the second base material to which the aqueous emulsion and / or adhesive is applied, either a
mechanical operation or a manual method may be used.

When bonding, heat, pressure or both may be applied. In the case of applying heat, it is necessary to set the temperature range in which the first base material, the
second base material, and the adhesive layer do not deteriorate, preferably about 120 ° C. or less, more preferably about 100 ° C. or less. It is. The heat load may be
performed using the above-described normal hot air circulation type oven, infrared heater, microwave oven, or the like. As a pressure in the case of applying a pressure,
about 100 g / cm < 2 > or more is mentioned, and less than the pressure which the shape of a 1st base material and a 2nd base material deform | transforms. In the case
of applying heat and / or pressure, the time is, for example, about 1 second to 10 days.

Examples of the first base material and the second base material are the same as the adherend described above. Among them, the first base material is preferably an
equipment made of an olefin polymer or an ethylene / vinyl acetate copolymer, and the second base material is polyvinyl chloride, synthetic leather, rubber, cotton-
containing fiber, and polyolefin base. A substrate selected from the group consisting of polymers is preferred.

The adhesive layer can be obtained, for example, by removing water, solvent, etc. from polyurethane, rubber adhesive, acrylic adhesive, epoxy adhesive, etc. by performing
heat drying, electromagnetic wave treatment, or the like.

Examples of the polyurethane include the same ones as described above.

Examples of rubber adhesives include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-
styrene block copolymer rubber (SIS), and styrene-butadiene-styrene block copolymer. Examples thereof include polymer rubber (SBS), butadiene-acrylonitrile copolymer
rubber (NBR), and butadiene rubber (BR). These may be used alone or in combination of two or more. In addition to these rubber components, an adhesion-imparting
resin such as a rosin resin, a terpene resin, or a petroleum resin may be mixed.

Preferred examples of the acrylic adhesive include a copolymer of an acrylic ester and / or a methacrylic ester as an adhesive component, a functional group monomer
component copolymerizable therewith, and an aggregating component. This copolymer may be crosslinked with an isocyanate crosslinking agent, a chelate crosslinking
agent, an epoxy crosslinking agent, or the like.

Examples of acrylic esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate,
2-ethylhexyl acrylate, Preferred examples include n-octyl acrylate and n-lauryl acrylate. Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, isopropyl
methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Preferred
examples include n-octyl methacrylate and n-lauryl methacrylate.

Examples of the functional group monomer component copolymerizable with acrylic acid ester and / or methacrylic acid ester include α, β-unsaturated carboxylic acids
such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; acrylic Acrylic acid or hydroxyalkyl ester of methacrylic acid such as
hydroxyethyl acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylolacrylamide, N-
methylolmethacrylamide, N-butoxy N-substituted or unsubstituted acrylamide such as methyl acrylamide and N-butoxy methacrylamide; glycidyl ester of acrylic acid or
methacrylic acid such as glycidyl methacrylate and glycidyl methacrylate; Preferable examples include acrylonitrile.

The epoxy adhesive is a compound having an average of one or more epoxy groups per molecule used as a component of a normal epoxy resin adhesive. Examples of
useful epoxy resins include epoxy resins obtained from bisphenol A and epichlorohydrin, polyglycidyl ethers obtained from bisphenol F and epichlorohydrin, hydrogenated
bisphenol A and epichlorohydrin, and the like. In addition, oxazolidone-modified epoxy resins, novolac type epoxy resins, polyfunctional phenol type epoxy resins, various
halogenated epoxy resins, glycidyl ester type epoxy resins, polyglycol type epoxy resins, cycloaliphatic epoxy resins, and the like can also be used. . These epoxy resins
can be used alone or in admixture of two or more.

Polyurethane, rubber adhesives, acrylic adhesives, and epoxy adhesives may be in the form of adhesives such as water-based, solvent-based, and hot melt.

The adhesive which comprises an adhesive bond layer may contain resin other than the adhesive agent mentioned above, and an additive.

Examples of the resin that may be contained in the adhesive layer include polyolefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl
acetate (PVAc), polytetrafluoroethylene (PTFE), Examples include various polymers and copolymers such as acrylonitrile butadiene styrene resin (ABS resin) and AS
resin, and modified polymers and modified products. These may be used alone or in combination of two or more.

Moreover, you may use resin which exhibits the function as an adhesive resin or a tackifier.

Examples of such resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins,
petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins,
coumarone resins, indene resins and polyurethane resins.

Additives that may be contained in the adhesive layer include surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent whitening
agents, leveling agents, basic compounds, organic solvents, crosslinking agents, Photosensitizer, other resins, phenol stabilizer, phosphite stabilizer, amine stabilizer,
amide stabilizer, anti-aging agent, weathering stabilizer, anti-settling agent, antioxidant, heat stabilizer, Antiseptic, thixotropic agent, thickener, antifoaming agent, viscosity
modifier, weathering agent, pigment dispersant, antistatic agent, lubricant, nucleating agent, flame retardant, oil agent, dye, curing agent; titanium oxide (rutile type) ) And
transition metal compounds such as zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate,
calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine End silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide,
magnesium oxide, inorganic or organic fillers such as alumina and Celite, and the like.

The coating film of the aqueous emulsion, the dried product of the coating film, and the cured product thereof preferably have a shear viscosity of less than 200 Pa · s. In
this range, the adhesiveness tends to improve. The shear viscosity was measured with a rotary rheometer using a cone plate (angle 2 °) with a shear rate of 1 s-1 and a
measurement temperature of 25 ° C. (when the melting point of the compound having a polymerizable group is higher than 25 ° C. Can be measured at a temperature 10
° C. higher than the melting point of the compound having a polymerizable group.

The dry product of the aqueous emulsion preferably excludes 95% by mass or more of the mass of water contained in the aqueous emulsion. Thereby, the influence of
water on the shear viscosity can be suppressed, and a desired shear viscosity can be obtained.

Examples of the aqueous emulsion of the present invention will be described in detail below. Unless otherwise indicated, the part and% in an example mean a mass
reference | standard.

The chlorine content of the chlorinated rubber and the polymer is a value measured by a flask combustion-ion chromatography method.

The component concentration of the aqueous emulsion is the mass of the total content of the mass part of the chlorinated rubber and the mass part of the compound
having a polymerizable group, with respect to the mass of the total mass of the chlorinated rubber, the compound having a polymerizable group, and water. It is a value
obtained by calculating the concentration (mass%).

The median diameter of the dispersoid is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA
Corporation. Unless otherwise specified, it is a median diameter value (unit: μm) measured on a volume basis.

The standing stability was evaluated by allowing the obtained aqueous emulsion to stand at room temperature for 1 week and observing the aqueous emulsion. When
phase separation was not visually confirmed in the aqueous emulsion, it was judged that the standing stability was good.

○: No change ×: Phase separation was confirmed visually

The chlorinated rubber, the compound having a polymerizable group, the photopolymerization initiator, the surfactant, the light stabilizer, the ultraviolet curable oligomer,
the fluorescent whitening agent, and the organic solvent in Production Examples and Evaluation Examples are as follows.

Chlorinated rubber 1: Pergut S20 (Bayer, chlorine content of 58.8% by mass or more)

Chlorinated rubber 2: Pergut S40 (Bayer, chlorine content of 65.5% by mass or more)

Chlorinated rubber 3: Pergut S10 (Bayer, chlorine content 64.1% by mass or more)

Chlorinated rubber 4: Pergut S5 (Bayer, chlorine content 61.2% by mass or more)

Polymer 1: Showrene W (Showa Denko KK, chloroprene rubber, chlorine content 37.8% by mass)

Polymer 2: Showrene AF (Showa Denko KK, chloroprene rubber, chlorine content 38.1% by mass)

Polymer 3: VINNOL E15 / 45 (Wacker Chemie AG, vinyl chloride / vinyl acetate copolymer resin)

Resin aqueous dispersion 1: Arrow Base SD (Unitika Ltd., modified polyolefin resin aqueous dispersion, solid content 25%)

Resin aqueous dispersion 2: Showrene SD77S (Showa Denko KK, chloroprene rubber, solid content 55%)

Resin aqueous dispersion 3: Aurolen AE-202 (Nippon Paper Industries, modified polyolefin resin aqueous dispersion, solid content 30%)

Resin aqueous dispersion 4: Aquatex HA-1100 (Chuo Rika Kogyo Co., Ltd., ethylene / vinyl acetate copolymer resin, solid content 45%)

Resin aqueous dispersion 5: Vinyblan 700 (Nissin Chemical Industry Co., Ltd., vinyl chloride resin aqueous dispersion, solid content 30%)

Resin aqueous dispersion 6: Diofan ™ A063 (Solvay Specialty Polymers Japan, vinylidene chloride resin aqueous dispersion, solid content 55%)

Compound having polymerizable group 1: dodecyl methacrylate (containing 970 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 2 having polymerizable group: 1,6-hexanediol dimethacrylate (containing 60 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 3 having a polymerizable group: stearyl methacrylate (containing 200 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 4 having a polymerizable group: 2-ethylhexyl methacrylate (containing 25 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 5 having a polymerizable group: cyclohexyl methacrylate (containing 50 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 6 having a polymerizable group: 2-ethylhexyl acrylate (containing 100 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 7 having a polymerizable group: diacetone acrylamide (containing 100 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 8 having a polymerizable group: Neopentyl glycol diglycidyl ether (Tokyo Chemical Industry Co., Ltd.)

Compound 9 having a polymerizable group: Blemmer VA (containing 200 ppm of 4-methoxyphenol, NOF Corporation)

Compound 10 having a polymerizable group: dodecyl acrylate (containing 100 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 11 having a polymerizable group: 1,6-hexanediol diacrylate (containing 100 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 12 having a polymerizable group: cyclohexyl acrylate (containing 100 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 13 having a polymerizable group: Polyethylene glycol dimethacrylate (containing 200 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)

Compound 14 having polymerizable group: SR489 (containing 170 ppm of 4-methoxyphenol, Arkema)

Compound 15 having a polymerizable group: SR340 (containing 200 ppm of 4-methoxyphenol and 200 ppm of 1,4-benzenediol, Arkema)

Compound 16 having a polymerizable group: CN131 (4-methoxyphenol 800 ppm, Arkema)

Compound 17 having a polymerizable group: NK ester DCP (containing 200 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)

Compound 18 having a polymerizable group: NK ester A-200 (containing 100 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)

Photopolymerization initiator 1: 2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)

Photopolymerization initiator 2: 1-hydroxycyclohexyl phenyl ketone (Tokyo Chemical Industry Co., Ltd.)

Photopolymerization initiator 3: 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine (Tokyo Chemical Industry Co., Ltd.)

Surfactant 1: Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)

Surfactant 2: LATEMUL E-1000A (30% aqueous solution, Kao Corporation)

Surfactant 3: Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.)

Surfactant 4: DKS NL-180 (Daiichi Kogyo Seiyaku Co., Ltd.)

Surfactant 5: Kuraray Poval 217 (Kuraray Co., Ltd.)

Surfactant 6: Kuraray Poval 205 (Kuraray Co., Ltd.)

Surfactant 7: Adeka Pluronic F108 (ADEKA)

Surfactant 8: Emulgen 102KG (Kao Corporation)

Surfactant 9: Emulgen 109P (Kao Corporation)

Surfactant 10: Emulgen 150 (Kao Corporation)

Basic compound 1: N, N-dimethylethanolamine (Tokyo Chemical Industry Co., Ltd.)

Light stabilizer 1: TINUVIN 1130 (BASF)

Light stabilizer 2: TINUVIN 123 (BASF)

UV curable oligomer 1: AH-600 (Kyoeisha Chemical Company)

UV curable oligomer 2: UA-306H (Kyoeisha Chemical Co., Ltd.)

Optical brightener 1: 1,4-bis (2-benzoxazolyl) naphthalene (Tokyo Chemical Industry Co., Ltd.)

Fluorescent whitening agent 2: Kyaphor SN (Nippon Kayaku Co., Ltd.)

Fluorescent whitening agent 3: Nikkafluor OB (Nippon Chemical Industry Co., Ltd.)

Organic solvent 1: Toluene (Wako Pure Chemical Industries, reagent special grade)

Organic solvent 2: 2-butanone (Wako Pure Chemical Industries, reagent special grade)

Organic solvent 3: 2-propanol (Wako Pure Chemical Industries, reagent special grade)

Leveling agent 1: BYK-349 (Big Chemie Japan)

Crosslinking agent: adipic acid dihydrazide (Tokyo Chemical Industry Co., Ltd.)

In each table, these components are expressed in parts by mass.

<Production Example 1>

In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)) and a compound
having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) ) 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical
Industry Co., Ltd.), 190 parts of tetrahydrofuran (Hayashi Junyaku Co., Ltd., reagent grade) were added and dissolved by stirring at 60 ° C. It cooled and prepared the
trahydrofuran solution of the chlorinated rubber 1 and the compound which has a polymeric group.

Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)) (3 parts) was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an
ion-exchange aqueous solution of Surfactant 1.

At room temperature, in a tetrahydrofuran solution of chlorinated rubber 1 and a compound having a polymerizable group, an ion exchange aqueous solution of
surfactant 1, 2 parts of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Were mixed with stirring. Next, TK Robotics (manufactured
by PRIMIX Co., Ltd.) equipped with a stirrer homomixer MARKII was prepared. The obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white
aqueous emulsion. The obtained aqueous emulsion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered through a 200
mesh nylon net to obtain an aqueous emulsion (E-1). The obtained aqueous emulsion (E-1) had a nonvolatile content concentration of 45%. Each added component is
listed in Table 1-1.

<Production Example 2>

An aqueous emulsion (E) was prepared in the same manner as in Production Example 1 except that 90 parts of dodecyl methacrylate was used instead of the compound
having a polymerizable group used in Production Example 1, and 5 parts of Aqualon KH-10 was used instead of the surfactant. -2) was obtained. The resulting aqueous
emulsion (E-2) had a non-volatile content of 47%. Each added component is listed in Table 1-1.

<Production Example 3>

In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), as a compound
having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 45 parts and 45 parts of 1,6-hexanediol dimethacrylate (Tokyo Kasei Kogyo Co.,
Ltd.) are added, and 190 parts of tetrahydrofuran (Hayashi Junyaku Co., Ltd., reagent grade) is added and dissolved by stirring at 60 ° C. and cooled to room temperature.
Then, a trahydrofuran solution of the chlorinated rubber 1 and the compound having a polymerizable group was prepared.

Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 5 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an
ion-exchange aqueous solution of Surfactant 1.

At room temperature, in a tetrahydrofuran solution of chlorinated rubber 1 and a compound having a polymerizable group, an ion exchange aqueous solution of
surfactant 1, 2 parts of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Was added and stirred to mix. Further, 5 parts of
photopolymerization initiator 1 (2-hydroxy-2-methylpropiophenone (Tokyo Kasei Kogyo Co., Ltd.)) was added and mixed by stirring. Next, TK Robotics (manufactured by
PRIMIX Co., Ltd.) equipped with a stirrer homomixer MARKII was prepared. The obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous
emulsion. The obtained aqueous emulsion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered through a 200 mesh nylon
net to obtain an aqueous emulsion (E-3). The resulting aqueous emulsion (E-3) had a nonvolatile content concentration of 43%. Each added component is listed in Table
1-1.

<Production Example 4>

In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), as a compound
having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry
Co., Ltd.) were charged, dissolved by stirring at 60 ° C., and cooled to room temperature.

Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 3 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an
ion-exchange aqueous solution of Surfactant 1.

At room temperature, in a mixture of chlorinated rubber 1 and a compound having a polymerizable group, an ion exchange aqueous solution of surfactant 1 and 2 parts
of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Was added and stirred to mix. Next, TK Robotics (manufactured by PRIMIX Co.,
Ltd.) equipped with a stirrer homomixer MARKII was prepared. The obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion.
Next, using a high pressure homogenizer (manufactured by SMT Co., Ltd.) LAB1000, the aqueous emulsion obtained by performing the treatment once at 800 bar was
filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-4). Each added component is listed in Table 1-2.
<Production Examples 5 to 14>

Using the chlorinated rubber, the compound having a polymerizable group, the surfactant, the basic compound 1 and ion-exchanged water in an amount of mass parts
shown in Table 1-2 and Table 1-3, Emulsions (E-5) to (E-14) were obtained.

<Production Example 15>

In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), as a compound
having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry
Co., Ltd.) were charged, dissolved by stirring at 60 ° C., and cooled to room temperature.

Surfactant 2 (Latemul (registered trademark) E-1000A (30% aqueous solution, Kao)) 5 parts is added to 100 parts of ion-exchanged water and dissolved by stirring at 60 °
C. Was prepared.

At room temperature, an ion exchange aqueous solution of surfactant 2 is added to a mixture of chlorinated rubber 1 and a compound having a polymerizable group, and
further 2 parts of N, N-dimethylethanolamine (Tokyo) as basic compound 1 Kasei Kogyo) was added and mixed by stirring. To this, 1 part of photopolymerization initiator
1 (2-hydroxy-2-methylpropiophenone (Tokyo Kasei Kogyo Co., Ltd.)) was added and mixed by stirring. Next, TK Robotics (manufactured by PRIMIX Co., Ltd.) equipped
with a stirrer homomixer MARKII was prepared. The obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion. Next, using a
high pressure homogenizer (manufactured by SMT Co., Ltd.) LAB1000, the aqueous emulsion obtained by performing the treatment once at 800 bar was filtered through
a 200 mesh nylon net to obtain an aqueous emulsion (E-15). Each added component is listed in Table 1-4.

<Production Examples 16 to 20>

Using the chlorinated rubber, the compound having a polymerizable group, the surfactant, the basic compound 1, the photopolymerization initiator, and the ion-exchanged
water shown in Table 1-4 in the same manner as in Production Example 15, Emulsions (E-16) to (E-20) were obtained.

<Production Examples 21 to 50>

Using the chlorinated rubber content, the compound having a polymerizable group, the surfactant, the basic compound 1 and ion-exchanged water in parts by mass
shown in Table 1-5 to Table 1-8 in the same manner as in Production Example 4, Aqueous emulsions (E-21) to (E-50) were obtained.
 

 
 

<Production Examples 51 to 60>

Mass parts of light stabilizer, ultraviolet curable oligomer or fluorescent brightening agent 1 shown in Table 1-9 and Table 1-10 were added simultaneously with
chlorinated rubber 1, and the masses shown in Table 1-9 and Table 1-10 were added. Aqueous emulsion (E-51) in the same manner as in Production Example 4 except
that the chlorinated rubber, the compound having a polymerizable group, the surfactant, the basic compound 1, the leveling agent 1 and the ion exchange water were
added. To (E60). Each added component is listed in Tables 1-9 and 1-10.
 

<Production Example 61>

In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), as a compound
having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 60 parts, 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Kasei Kogyo Co., Ltd.)
and 20 parts of organic solvent 1 (toluene (Wako Pure Chemical Industries, Ltd., reagent grade)) were charged and dissolved by stirring at 60 ° C. Cooled to room
temperature.

Surfactant 2 (Latemul (registered trademark) E-1000A (30% aqueous solution, Kao)) 5 parts is added to 100 parts of ion-exchanged water and dissolved by stirring at 60 °
C. Was prepared.

At room temperature, 2 parts of N, N-dimethylethanolamine (Tokyo Chemical Industry Co., Ltd.) as a basic compound 1 in an ion exchange aqueous solution of a
surfactant 2 in a mixture of chlorinated rubber 1, a compound having a polymerizable group and toluene. ) Was added and stirred to mix. To this was added 5 parts of
photopolymerization initiator 1 (2-hydroxy-2-methylpropiophenone (Tokyo Kasei Kogyo Co., Ltd.)), and the mixture was stirred and mixed. Next, TK Robotics
(manufactured by PRIMIX Co., Ltd.) equipped with a stirrer homomixer MARKII was prepared. The obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a
milky white aqueous emulsion. Subsequently, the aqueous emulsion obtained by performing the treatment once at 800 bar using a high-pressure homogenizer
(manufactured by SMT Co., Ltd.) LAB1000 was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-61). Each added component is listed in Table 1-
11.

<Production Examples 62 to 66>

Except not using the photopolymerization initiator 1 used in Production Example 61, in the same manner as in Production Example 61, parts by mass of chlorinated
rubber, compound having a polymerizable group, and surfactant shown in Table 1-11 Aqueous emulsions (E-61) to (E-66) were obtained using basic compound 1, an
organic solvent and ion-exchanged water.
<Production Example 67>

In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), as a compound
having a polymerizable group, dodecyl methacrylate (Tokyo Chemical Industry Co., Ltd.) 60 parts and 30 parts of 1,6-hexanediol dimethacrylate (Tokyo Chemical Industry
Co., Ltd.) were charged, dissolved by stirring at 60 ° C., and cooled to room temperature.

Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 3 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an
ion-exchange aqueous solution of Surfactant 1.

At room temperature, 2 parts of N, N-dimethylethanolamine (Tokyo Kasei Kogyo Co., Ltd.) as the basic compound 1 is added to the mixture of the chlorinated rubber 1
and the compound having a polymerizable group in an ion exchange aqueous solution of the surfactant 1. Added and mixed with stirring. Next, TK Robotics
(manufactured by PRIMIX Co., Ltd.) equipped with a stirrer homomixer MARKII was prepared. The obtained mixture was stirred at 5000 rpm for 2 minutes to obtain a
milky white aqueous emulsion. The obtained aqueous emulsion was filtered through a 200 mesh nylon mesh to obtain an aqueous emulsion (E-67). Each added
component is listed in Table 1-12.

<Production Examples 68 to 69>

An aqueous emulsion (E-68) was prepared in the same manner as in Production Example 67 using the chlorinated rubber, the compound having a polymerizable group,
the surfactant, the basic compound 1 and ion-exchanged water shown in Table 1-12. ) To (E-69) were obtained.

<Comparative Production Example 1>

An aqueous emulsion (S-1) was obtained in the same manner as in Production Example 11 except that Polymer 1 (Shoprene W (Showa Denko)) was used as the
chlorinated rubber 1 used in Production Example 11.

<Comparative Production Example 2>

An aqueous emulsion (S-2) was obtained in the same manner as in Production Example 11 except that the polymer 2 (Shoprene AF (Showa Denko)) was used for the
chlorinated rubber 1 used in Production Example 11.

<Comparative Production Example 3>

An aqueous emulsion (S-3) was obtained in the same manner as in Production Example 65, except that Polymer 1 (Shoprene W (Showa Denko)) was used for the
chlorinated rubber 1 used in Production Example 65.

<Production Examples 70 to 139>

Add 3 parts by weight of an aqueous emulsion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan), ion-exchanged water
as shown in Table 2-1 to Table 2-7. Stirring to obtain aqueous adhesives (F1) to (F70) containing the aqueous emulsion obtained in the production example.

In the following, as an embodiment of the aqueous emulsion of the present invention, a form further containing an additive more suitable as an adhesive is described as
“aqueous adhesive”.
<Production Examples 140 to 149>

Aqueous emulsion, photopolymerization initiator, compound having a polymerizable group, light stabilizer, leveling agent 1 (BYK (registered trademark) -349, Big Chemie
Japan), cross-linking agent, An organic solvent and ion-exchanged water were mixed and stirred with a three-one motor to obtain aqueous adhesives (F71) to (F80)
containing the aqueous emulsion obtained in the production example.

<Production Example 150>

In a separable flask reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10 parts of chlorinated rubber 1 (Pergut S20 (Bayer)), polymer 3
(VINNOL E15 / 45 (Wacker Chemie AG)) 1 As a compound having a polymerizable group, 60 parts of dodecyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.) and 30 parts of
1,6-hexanediol dimethacrylate (Tokyo Kasei Kogyo Co., Ltd.) are charged and dissolved by stirring at 60 ° C. Cooled to room temperature.

Surfactant 1 (Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.), 3 parts, was placed in 100 parts of ion-exchanged water and dissolved by stirring at 60 ° C. to prepare an
ion-exchange aqueous solution of Surfactant 1.

At room temperature, in a mixture of chlorinated rubber 1 and a compound having a polymerizable group, an ion exchange aqueous solution of surfactant 1 and 2 parts
of N, N-dimethylethanolamine as basic compound 1 (Tokyo Chemical Industry Co., Ltd.) Was added and stirred to mix. Next, TK Robotics (manufactured by PRIMIX Co.,
Ltd.) equipped with a stirrer homomixer MARKII was prepared. The obtained mixture was stirred at 16000 rpm for 2 minutes to obtain a milky white aqueous emulsion.
Subsequently, the aqueous emulsion obtained by performing the treatment once at 800 bar using a high-pressure homogenizer (manufactured by SMT Co., Ltd.)
LAB1000 was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-70). Each added component is listed in Table 2-9.
<Production Examples 151 to 157>

Three-one motor is mixed with water emulsion, resin aqueous dispersion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie
Japan Co., Ltd.) and ion-exchanged water in the parts by mass shown in Table 2-10. The aqueous adhesives (F81) to (F87) containing the aqueous emulsion obtained in
the production example were obtained.

<Production Examples 158 to 194>

The photopolymerization initiator or fluorescent brightening agent in parts by mass shown in Table 2-11 and Table 2-12 was added simultaneously with the chlorinated
rubber 1, and the chlorinated rubber in parts by mass shown in Table 2-11 and Table 2-12. Aqueous emulsions (E-71) to (E107) were obtained in the same manner as in
Production Example 4, except that a compound having a polymerizable group, a surfactant, basic compound 1 and ion-exchanged water were added.
<Production Examples 195 to 231>

Addition of water emulsion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.), ion-exchange water, and stirring
with a three-one motor as shown in Table 2-13, Production Example Water-based adhesives (F88) to (F124) containing the aqueous emulsion obtained in (1) were
obtained.
<Production Example 232>

Polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), Isocyanate (Desmodur (registered trademark) N3300, Sumika Bayer
Urethane Co., Ltd.), Leveling agent 1 (BYK (registered trademark)) ) -349, Big Chemie Japan Co., Ltd.) was mixed at a nonvolatile content ratio of 100 parts: 5 parts: 1 part
to obtain an aqueous emulsion (E200).

<Comparative Production Examples 4 to 6>

Aqueous emulsion, photopolymerization initiator, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.) and ion-exchanged water in parts by
mass shown in Table 2-14 are mixed, stirred with a three-one motor, Adhesives (H1) to (H3) were obtained.

<Evaluation Example 1>

The water-based adhesive (F1) is applied to M-EVA (ethylene-vinyl acetate copolymer foam), which is the first substrate, using a brush (coating amount: weight after
drying: about 3 g / m 2) And dried at 70 ° C. for 5 minutes, and M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye
Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m /
min, integrated light quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan) KK)

Subsequently, an aqueous emulsion (E200) was applied to soft polyvinyl chloride and M-EVA (A) using a brush (coating amount: weight about 50 g / m 2 after drying), and
oven-dried at 70 ° C. for 5 minutes. did. Thereafter, the coated surfaces of the obtained soft polyvinyl chloride and M-EVA (A) of the aqueous emulsion (E200) were
bonded to each other, pressed by hand, and further pressed by a press at 3 MPa for 20 seconds. As a result, a laminate (1) was obtained in which an adhesive layer made
of soft polyvinyl chloride and E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA as the first base material were laminated in this order.

The obtained laminate (1) was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), a
peeling speed of 50 mm / min, a peeling angle of 180 degrees, at room temperature, The adhesion between M-EVA and soft polyvinyl chloride in the laminate was
evaluated by measuring peel strength. The results are shown in Table 3-1.

○: Peel strength 55 N / inch or more.

X: Peel strength less than 55 N / inch.

<Evaluation Examples 2 to 79>

A laminate (2) in the same manner as in Evaluation Example 1 except that the water-based adhesive (F1) in Evaluation Example 1 was changed to any of water-based
adhesives (F1) to (F37) and (F39) to (F80). ) To (79) were obtained.

In the same manner as in Evaluation Example 1, the adhesion of the laminate was evaluated. The results are shown in Tables 3-1 to 3-8.
<Evaluation Example 80>

Similar to Evaluation Example 1 except that the aqueous adhesive (F1) in Evaluation Example 1 was changed to an aqueous adhesive (F38) and the amount of aqueous
adhesive applied to M-EVA was changed to about 1 g / m 2. Thus, a laminate (80) was obtained.

In the same manner as in Evaluation Example 1, the adhesion of the laminate was evaluated. The results are shown in Table 3-9.

<Evaluation Example 81>

The water-based adhesive (F1) in Evaluation Example 1 was changed to a water-based adhesive (F70) and irradiated once with ultraviolet rays (lamp: high-pressure
mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276m / min, integrated light quantity: 1100mJ / cm2 (UV integrated light quantity meter
UVICURE PLUS II, UV-A measurement value, FusionUV Systems

Japan K.K. K. After that, a laminate (81) was obtained in the same manner as in Evaluation Example 1 except that the ultraviolet rays under the same conditions were
further irradiated once.

In the same manner as in Evaluation Example 1, the adhesion of the laminate was evaluated. The results are shown in Table 3-10.

The laminates (1) to (81) generally exhibited a sufficiently high peel strength of 55 N / inch or more.

<Evaluation Example 82>

The water-based adhesive (F1) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 3 g / m 2 after drying), and 5
° C. at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye Grandage ECS-4011GX,
manufactured by Eye Graphics Co., Ltd.). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m / min, integrated light
quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan) KK)

Subsequently, an aqueous emulsion (E200) was applied to cotton canvas (Johoku Kogyo Co., Ltd.) using a brush (coating amount: weight about 50 g / m 2 after drying),
oven-dried at 70 ° C. for 5 minutes, and cotton canvas (A) was obtained. An aqueous emulsion (E200) was applied to the obtained cotton canvas (A) and M-EVA (A) using
a brush (coating amount: weight after drying of about 50 g / m 2 ), and the oven was kept at 70 ° C. for 5 minutes. Dried. Thereafter, the coated surfaces of the obtained
cotton canvas (A) and M-EVA (A) of the aqueous emulsion (E200) were bonded together, pressure bonded by hand, and further pressure bonded at 3 MPa for 20 seconds
by a press. As a result, a laminate (82) was obtained in which a cotton canvas, an adhesive layer made of E200, an adhesive layer irradiated with ultraviolet rays, and M-
EVA were laminated in this order.

<Evaluation Example 83>

The water-based adhesive (F1) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 3 g / m 2 after drying), and 5
° C. at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye Grandage ECS-4011GX,
manufactured by Eye Graphics Co., Ltd.). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m / min, integrated light
quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan) KK)

Subsequently, an acetone solution (2% by mass) of trichloroisocyanuric acid was applied to the rubber base material (Shinei Kako Co., Ltd.) with a brush (coating amount:
weight about 0.5 g / m 2 after drying), and 70 ° C. for 5 minutes Oven drying gave a rubber substrate (A). An aqueous emulsion (E200) was applied to the obtained rubber
base material (A) and M-EVA (A) using a brush (application amount: weight after drying of about 50 g / m 2 ), and at 70 ° C. for 5 minutes. Oven dried. Thereafter, the
coated surfaces of the obtained rubber base material (A) and M-EVA (A) of the aqueous emulsion (E200) were bonded together, pressure-bonded by hand, and further
pressure-bonded by pressing at 3 MPa for 20 seconds. As a result, a laminate (83) was obtained in which a rubber substrate (A), an adhesive layer made of E200, an
adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order.

<Evaluation Example 84>

The water-based adhesive (F1) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 3 g / m 2 after drying), and 5
° C. at 70 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye Grandage ECS-4011GX,
manufactured by Eye Graphics Co., Ltd.). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m / min, integrated light
quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan) KK)

Subsequently, an aqueous emulsion (E200) was applied to synthetic leather (Johoku Kogyo Co., Ltd.) and M-EVA (A) using a brush (coating amount: weight about 50 g /
m 2 after drying), and 5 at 70 ° C. Oven dried for minutes. Thereafter, the surfaces of the obtained synthetic leather (Johoku Kogyo Co., Ltd.) and M-EVA (A) coated with
an aqueous emulsion (E200) were bonded together and pressed by hand, and further pressed by a press at 3 MPa for 20 seconds. As a result, a laminate (84) was
obtained in which synthetic leather (Johoku Industrial Co., Ltd.), an adhesive layer made of E200, an adhesive layer irradiated with ultraviolet rays, and M-EVA were
laminated in this order.

The obtained laminates (82) to (84) were allowed to stand at room temperature for 24 hours, and thereafter, using a tensile tester (manufactured by Shimadzu Corp.,
Autograph), a peeling rate of 50 mm / min, a peeling angle of 180 degrees, At room temperature, the adhesion between M-EVA and cotton canvas, rubber substrate or
synthetic leather in the laminate was evaluated by measuring peel strength. The results are shown in Table 3-11.

○: Peel strength 55 N / inch or more.

X: Peel strength less than 55 N / inch.

<Evaluation Example 85>

1.01 g of the aqueous emulsion (E-4) obtained in Production Example 4 was diluted 10 times with ion-exchanged water and filtered using a membrane filter 1
(manufactured by ADVANTEC TOYO, nitrocellulose, pore size 0.45 μm). The filtrate was obtained. When methanol was added to the obtained filtrate, a precipitate was
formed. The precipitate was collected by filtration using a membrane filter 2 (manufactured by ADVANTEC TOYO, PTFE, pore size 0.50 μm), and further adhered to the
membrane filter 2 and the membrane filter 2 with methanol (Wako Pure Chemical Industries, reagent grade). The precipitate was washed. The membrane filter 2 and the
precipitate attached to the membrane filter 2 were dried under reduced pressure (10 hPa) for 24 hours at 22 ° C., and the precipitate attached to the membrane filter 2
was dissolved in THF. GPC measurement of the obtained THF solution and IR measurement of the substance obtained by drying the THF solution were performed. As a
result, chlorinated rubber 1 was detected. Of 100 parts by mass of the chlorinated rubber 1 contained in the aqueous emulsion obtained in Production Example 4, the
mass of the chlorinated rubber 1 contained in the aqueous emulsion after filtration was calculated from the GPC measurement result, and was 96 mass. %Met.

<Evaluation Example 86>

The shear viscosity of the composition obtained by drying the aqueous emulsion of Production Example 4 at 70 ° C. for 30 minutes was measured at 25 ° C. and a shear
rate of 1 s −1 with a rotary rheometer using a cone plate (angle 2 °). did. The shear viscosity was 23 Pa · s.

<Evaluation Example 87>

The shear viscosity of the composition obtained by drying the aqueous emulsion of Production Example 14 at 70 ° C. for 30 minutes was measured at 25 ° C. and a shear
rate of 1 s −1 with a rotary rheometer using a cone plate (angle 2 °). did. The shear viscosity was 46 Pa · s.

<Evaluation Example 88>

The shear viscosity of the composition obtained by drying the aqueous emulsion of Production Example 28 at 70 ° C. for 30 minutes was measured at 56 ° C. and a shear
rate of 1 s −1 with a rotary rheometer using a cone plate (angle 2 °). did. The shear viscosity was 12 Pa · s.

<Evaluation examples 89 to 91>

In Evaluation Example 1, “M-EVA (ethylene-vinyl acetate copolymer foam)” used as the first base material is shown in the “First base material” column of Table 3-12
below. Laminated bodies 89 to 91 were obtained in the same manner as in Evaluation Example 1, except that the difference was changed to.

The obtained laminate was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corp., Autograph), the peel
rate was 50 mm / min, the peel angle was 180 degrees, and the room temperature was The adhesion between the first substrate and soft polyvinyl chloride was
evaluated by measuring peel strength. The results are shown in Table 3-12.

○: Peel strength 55 N / inch or more.

X: Peel strength less than 55 N / inch.

PE / EVA = 60/40: Foam obtained by polymerizing polyethylene / ethylene-vinyl acetate copolymer at 60/40 (PE / EVA = 60/40) PE / SEBS = 50/50: Polyethylene / styrene-
ethylene- Foam obtained by polymerizing butylene-styrene block copolymer at 50/50 (PE / SEBS = 50/50) SBBS: Foam obtained by polymerizing with styrene-butadiene-
butylene-styrene block copolymer (SBBS)
<Evaluation examples 92 to 98>

Laminated bodies (92) to (98) were obtained in the same manner as in Evaluation Example 1 except that the aqueous adhesive (F1) in Evaluation Example 1 was
changed to any of the aqueous adhesives (F81) to (F87). .

In the same manner as in Evaluation Example 1, the adhesion of the laminate was evaluated. The results are shown in Table 3-13.

○: Peel strength 55 N / inch or more.

X: Peel strength less than 55 N / inch.

<Evaluation examples 99 to 135>

Laminates (99) to (135) were obtained in the same manner as in Evaluation Example 1 except that the aqueous adhesive (F1) in Evaluation Example 1 was changed to
any of the aqueous adhesives (F88) to (F124). .

In the same manner as in Evaluation Example 1, the adhesion of the laminate was evaluated. The results are shown in Table 3-14.

○: Peel strength 55 N / inch or more.

X: Peel strength less than 55 N / inch.

<Comparative Examples 1 to 3>

Comparative laminates (1) to (3) were obtained in the same manner as in Evaluation Example 1 except that the aqueous adhesive (F1) in Evaluation Example 1 was
changed to any of the aqueous adhesives (H1) to (H3). It was.

In the same manner as in Evaluation Example 1, the adhesion of the laminate was evaluated. The results are shown in Table 3-15.
Comparative laminates (1)-(3) generally exhibited low peel strengths of less than 55 N / inch.

The aqueous emulsion of the present invention can be usefully used as an adhesive or a coating film in order to adhere adherends to each other or with sufficient
strength.

Patent Citations (15)

Publication number Priority date Publication date Assignee Title

JPH03170564A
* 1989-11-29 1991-07-24 Toagosei Chem Ind Co Ltd Actinic radiation-curing water-dispersible gloss coating material

JPH04142322A
* 1990-10-02 1992-05-15 Toyo Kasei Kogyo Kk Synthetic resin composition

JPH05209006A
* 1991-03-27 1993-08-20 Toyo Kasei Kogyo Kk Production of resin composition emulsion

JPH06287521A
* 1993-03-30 1994-10-11 Toyo Kasei Kogyo Co Ltd Pollution-free bonding method by using aqueous emulsion resin
composition adhesive

JPH07300570A
* 1994-05-02 1995-11-14 Nippon Paint Co Ltd Water-based chlorinated polyolefin coating composition

JPH11254608A
* 1998-01-12 1999-09-21 Showa Denko Kk Resin laminate and its manufacture

JPH11263802A
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Concepts

machine-extracted Download Filter table

Name Image Sections Count Query match

emulsion title,claims,abstract,description 204 0.000

coating method title,claims,abstract,description 40 0.000

coating agent title,claims,abstract,description 38 0.000

compounds claims,abstract,description 147 0.000

elastomer claims,abstract,description 132 0.000

rubber claims,abstract,description 132 0.000

chlorine claims,abstract,description 14 0.000

chloro group claims,abstract,description 8 0.000

* Cl

adhesives claims,description 78 0.000

adhesive claims,description 74 0.000

water claims,description 66 0.000

surface-active agents claims,description 58 0.000

copolymers claims,description 48 0.000

mixtures claims,description 47 0.000

products claims,description 44 0.000

chemical substances by application claims,description 39 0.000

polymers claims,description 36 0.000

materials claims,description 31 0.000

substrates claims,description 30 0.000

layers claims,description 26 0.000

initiators claims,description 24 0.000

light stabilisers claims,description 16 0.000

liquids claims,description 10 0.000

carboxylic acid anhydrides claims,description 9 0.000

alkenes claims,description 8 0.000

carboxy group claims,description 6 0.000
O

* OH

dispersion media claims,description 5 0.000

brightening claims,description 4 0.000

2-acetyloxyethyl acetate claims,description 3 0.000
O
O
O
O

Show all concepts from the description section

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