United States Patent (19) 11 Patent Number: 4,970,178
Klimas et al. 45 Date of Patent: Nov. 13, 1990
54 LEAD-FREE GLASS FRIT COMPOSITIONS 56 References Cited
(75) Inventors: David A. Klimas, Bridgeville; Boyd U.S. PATENT DOCUMENTS
R. Frazee, Washington, both of Pa. 2,799,590 7/1957 Armistead ............................. 106/53
4,312,951 1/1982 Eppler ......... ... 501/26
(73) Assignee: Ciba-Geigy Corporation, Ardsley, 4,316,963 2/1982 Hommel et al. ... 501/26
N.Y. 4,340,645 7/1982 O'Conor ............. ... 5O1/26
4,349,635 9/1982 Davis et al. ......... ... 50/26
(21) Appl. No.: 394,241 4,361,654 11/1982 Ohmura et al. ..... ... 501/26
4,417,913 11/1983 Davis et al. .......................... 65/59.1
22) Fied: Aug. 14, 1989
FOREIGN PATENT DOCUMENTS
Related U.S. Application Data 1013597 12/1965 United Kingdom .
63 Continuation of Ser. No. 330,985, Mar. 23, 1989, aban 2092.123 8/1982 United Kingdom.
doned, which is a continuation of Ser. No. 256,161, Primary Examiner-Mark L. Bell
Oct. 7, 1988, abandoned, which is a continuation of Attorney, Agent, or Firm-Harry Fallber
Ser. No. 180,003, Apr. 5, 1988, abandoned, which is a
continuation of Ser. No. 926,072, Nov. 3, 1986, aban 57 ABSTRACT
doned.
Lead-free glass frit compositions for use in vitreous
(51) Int. Cl. .......................... CO3C 8/04; CO3C 8/06; coatings consisting essentially of Na2O-ZnO-B-
CO3C 3/093; CO3C 3/089 2O3-SiO2 in appropriate concentrations including
52 U.S. C. ........................................ 501/26; 501/25; molar amounts of at most 17.5 mole percent of B2O3 and
501/58; 501/59; 501/65; 501/67 at least 40 mole percent of SiO2.
58) Field of Search ....................... 501/26, 25, 58, 59,
501/65, 67 4. Claims, No Drawings
4,970,178
1. 2
It is a further object to provide such frits which are
LEAD-FREE GLASS FRIT COMPOSITIONS low melting and are particularly resistant to acid attack.
Various other objects and advantages of this inven
This application is a continuation, of application Ser. tion will become apparent from the following descrip
No. 330,985, filed 3/23/89, now abandoned, which is a 5 tive material.
continuation of Ser. No. 256,161, filed 10/7/88, now It has now been surprisingly determined that the
abandoned, which is a continuation of Ser. No. 180,603 aforementioned objectives are met by preparing lead
filed 4/5/88 now abandoned, which in turn is a continu free glass frits which consist of Na2O, ZnO, B2O3 and
ation of Ser. No. 926,072 filed 11/3/86, now abandoned. SiO2 in appropriate concentration ranges. Such systems
Decorating compositions generally fall into two cate 10 meet the primary requirement of being operative in
gories; glazes and enamels. The glazes are usually vitreous coatings without the presence of lead and cad
thought of as clear glasses, while enamels are glazes mium components. In addition, these formulations ex
which contain a coloring material such as a pigment. In hibit a broad range of desirable properties including low
actual usage, the glazes and enamels are used in a finely melting points, sufficiently low thermal expansion to
divided form called a "frit', which is selectively applied 15 avoid crazing when applied over soda-line-silica glass
to the surfaces of the glassware, glass-ceramic ware, and low water solubility to facilitate their use in water
chinaware and ceramic ware in accordance with the based spray mediums. Of particular significance is the
intended decorative or ornamental pattern. Any of sev excellent resistance to acid attack, such as that encoun
eral decorating techniques known in the industry can be tered from various acid-containing liquids such as juice.
used to achieve this result. Typically, the frit is in the 20 As a result, these glass frit compositions are available
form of a paste which consists of the finely divided for a broad range of glazing, enameling and decorating
glaze or enamel composition plus a vehicle. After appli applications on a wide variety of glassware and china
cation to the ware by silkscreen or other technique, the ware. They can also be applied in a variety of printing
ware is heated or fired to fuse the frit, to volatilize the methods.
vehicle or medium and to firmly bond the decoration to 25 More specifically, the glass frit compositions of this
the surface of the ware. invention consist of
There are a variety of decorating compositions avail
able which are used in the decorating of glassware,
chinaware and the like, to produce selected patterns and Broad Range (nole %) Preferred Range (mole %)
ornamentation. These available compositions fre 30 Na2O 3.9-8.5 5.0-140
quently contain lead and/or cadmium oxides. Lead ZnO
B2O3
4.0-30.0
3.9-17.5
8.0-25.0
6.0-3.0
oxide was previously used in these compositions to SiO2 40.0-74.0 45.0-600
lower the melting point of the frit so that the frit could
be fused onto the surface of the ware at as low a temper
ature as possible to avoid thermal deformation of the 35 It is particularly to be noted that coatings which
ware. Cadmium oxide had been used in the past as a significantly exceed the 17.5 mole percent B2O3 concen
colorant in certain frits. However, adverse toxicologi tration do not exhibit the minimum level of acid resis
cal effects from these systems have resulted in various tance required for such products. In addition, coatings
prohibitions on the use of lead and cadmium in decora which contain less than the minimum 400 mole percent
tive glazes. It has, therefore, been necessary to formu 40 SiO2 content are likewise deficient in acid resistance.
late glass frit products with equivalent or improved In addition to the oxides listed above, the coatings
performance characteristics but with no lead or cad may contain one or more of the following without ad
mium components. versely effecting the performance characteristics:
A number of such lead-free products have been dis
closed. By way of illustration, U.S. Pat. No. 4,376,169 45 mole percent
discloses frits which require the presence of alkali oxide,
B2O3, Al2O3, SiO2, F, P2O5, ZnO and TiO2 and which K2O 0-8.0
Li2O 0-5.0
have critical compositional limits; U.S. Pat. No. CaO 0-8.0
4,446,241 discloses frits which require the presence of Sr0 0-8.0
Li2O, B2Oo3 and SiO2 among other oxides; U.S. Pat. No. 50 BaO
Bi2O3
0-9.0
0-10.0
4,537,862 discloses frits which require the presence of Al2O3 0-40
B2O3, SiO2, ZrO2 and rare earth oxides with the weight ZrO2 0-60
ratio of ZrO2 to rare earth oxides being critical; U.S Pat. TiO2 O-70
No. 4,554,258 discloses frits which require the presence MoO3 0-1.0
of BiO3, B2O3, SiO2 and alkali metal oxides where the 55 WO3 0-0
F. 0-40
alkali metal oxides are necessarily present in specified
concentrations and U.S. Pat. No. 4,590,171 discloses
frits which require the presence of Li2O, Na2O, Ba0, The K2O and Li2O will generally replace a portion of
Ba2O3, Al2O3, SiO2, ZrO2 and F. It is thus seen that the the Na2O content. The K2O will tend to increase the
formulations have varied the nature and concentration 60 firing temperature and thermal expansion, while the
of the oxide components in an attempt to provide ac Li2O will lower the firing temperature but may create
ceptable frit formulations. While such frits are alleged some thermal stresses. The CaO, SrC) and BaO can be
to exhibit a variety of desirable properties, they still added as partial replacement for the ZnO, such compo
exhibit deficiencies in one or more performance areas. nents increasing firing temperature and thermal expan
Accordingly, it is the primary object of this invention 65 sion. Additions of ZrO2 will improve alkali resistance,
to provide lead-free glass frit compositions which ex while the TiO2 will improve acid resistance.
hibit a broad range of improved performance character The glass frits can be prepared by mixing together the
istics. oxide producing materials, such materials being well
4,970,178 4.
3
known to those skilled in the art, charging the raw These results thus indicate the excellent performance
material mix into a glass melting furnace at tempera benefits of the instant systems, particularly in the area of
tures of 1000-1200° C. to produce the fused glass and acid resistance. In addition, the results of control For
then fritting the glass as by pouring into water or pass mulation A illustrate the adverse effects obtained by
ing through water-cooled rolls. If required, the frit can 5 utilizing B2O3 in excess of the prescribed amounts.
be ground into powder by conventional grinding tech A similar composition can be prepared using, on a
niques. The resulting products generally have melting mole percent basis, 13.1% Na2O, 19.7% ZnO, 8.2%
points in the range of 450 to 600 C. and coefficients of B2O3 and 59.0% SiO2, with the expectation of compara
thermal expansion in the range of 70 to 90x 10-7 per 10 ble performance characteristics.
C. - Summarizing, this invention is seen to provide lead
The frits of the present invention are particularly free glass frit compositions exhibiting excellent perfor
useful for vitrifiable glass decorating colors, but they mance characteristics particularly in the area of acid
may also be used in related applications such as coatings resistance. Variations may be made in procedures, pro
on ceramic substrates. For example, to use these materi portions and materials without departing from the
als as a glass decorating color, a slip made up of the frit 15 scope of the invention as defined by the following
claims.
of the present invention, titanium dioxide and an al What is claimed is:
cohol-water mixture is prepared. This slip is then ap 1. A lead-free glass grit composition consisting essen
plied to the exterior of a glassjar or a light bulb (e.g. by tially of the following components in the indicated
spraying) and the coated surface is then fired at 680 C. 20 molar percent amounts:
for three minutes. The result is a smooth vitreous coat
ing which will resist attack from a variety of acidic and
alkaline materials. It is also to be noted that colorants Na2O 5.0-140
ZnO 8.0-25.0
and pigments can be dissolved and/or suspended in the B2O3 6.0-3.0
frits to yield colored glazes and enamels. 25 SiO2 45.0-600
The following examples further illustrate the embodi K2O 0-8.0
ments of this invention. In these examples, known tech Li2O 0-5.0
CaO 0-8.0
niques are utilized to mix the appropriate raw batch SrO 0-8.0
glass compositions, to melt them at generally about BaO 0-9.0
1200 C. for about 45 minutes and then to frit the com 30 Bi2O3 0-0.0
positions. Al2O3 0-40
ZrO2 0-6.0
Testing is conducted by adding 4.0 grams of the glass TiO2 0-7.0
frit to 1.0 gram of a pine oil-based medium and screen WO3 0-1.0.
printing the resulting dispersion onto glass slides at a
wet thickness of 2 mills. The slides are fired at several 35 2. The composition of claim 1 consisting essentially of
temperatures to determine "Gloss Temperature', i.e. the following components in the indicated mole percent
the lowest temperature which enables the glass powder amounts:
to flow sufficiently to form a smooth transparent coat
ling.
Acid resistance is evaluated first by utilizing ASTM Na2O
ZnO
12.1
18.2
C724-81 and then by immersing the coated glass slides B2O3 12.2
in 4% acetic acid for a period of 24 hours. Coatings SiO2 54.5
rated 'A' in the first test and coatings which are not TiO2 3.0.
etched or only marginally etched in the second test are
deemed to be acid resistant. 45
3. The composition of claim 1 consisting essentially of
Typical frit formulations on this invention and one the following components in the indicated mole percent
control formulation and their attendant performance amounts:
characteristics are noted in the following table.
50 Na2O 11.4
- Formulation (mole %) - ZnO 17.2
Ingredient 1 2 3 4. 5 6 A B2O3 11.4
SiO2 514
Na2O 12.1 11.4 12.1 11.4 11.4 5.7 13.2 TiO2 2.9
ZnO 18.2 17.2 13.7 17.1 8.6 17.2 13.2 Bi2O3 5.7.
B2O3 12.2 11.4 12.1 17. 17.1 7. 21.0 55
SiO2 54.5 54 54.6 51.5 51.4 51.4 47.4
TiO2 3.0 2.9 3.0 2.9 2.9 2.9 3.9 4. The composition of claim 1 consisting essentially of
Li2O
K2O
---- m
m
4.5
-
DO ---
-
m
5.7
---
-
the following components in the indicated mole percent
Bi2O3 - 5.7 - m - -
anaOutS:
BaO - m - u 8.6 -
F2 --- m - 1.3 60
Gloss 650 607 621 650 677 650 621 Na2O 12.1
Temp (C.) ZnO 13.7
Acid A A. A. A A. A. C B2O3 12.1
Rating SiO2 54.6
4%. Acetic not not not sl. sl. sl. coating 65 TiO2 3.0
Acid etched etched etched etch etch etch remov Li2O 4.5.
ed
