TEPZZ ¥68859B_T

(19)

(11) EP 2 368 859 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C03C 8/02 (2006.01) C03C 8/14 (2006.01)
18.01.2017 Bulletin 2017/03 C03C 3/062 (2006.01) C03C 8/22 (2006.01)
C03C 8/04 (2006.01) C03C 10/00 (2006.01)
(21) Application number: 11003051.7 C03C 17/04 (2006.01) C03C 8/20 (2006.01)
C03C 3/064 (2006.01)
(22) Date of filing: 12.05.2003

(54) Durable glass enamel composition

Dauerhafte Glas-Emaillezusammensetzung
Composition d’émail à verre durable

(84) Designated Contracting States: • Blonski, Robert P.

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR North Royalton, OH 44133 (US)
HU IE IT LI LU MC NL PT RO SE SI SK TR • Joyce, Ivan H.
Hudson, OH 44236 (US)
(30) Priority: 15.05.2002 US 146488 • Korn, George C.
07.04.2003 US 408737 Corapolis, PA 15108 (US)
• Anquetil, Jérôme
(43) Date of publication of application: 55000 Bar-le-Duc (FR)
28.09.2011 Bulletin 2011/39
(74) Representative: Reinhardt, Markus
(62) Document number(s) of the earlier application(s) in Patentanwaltskanzlei Reinhardt
accordance with Art. 76 EPC: Postfach 11 65
03733995.9 / 1 503 964 83225 Aschau (DE)

(73) Proprietor: FERRO CORPORATION (56) References cited:

Cleveland, OH 44114 (US) EP-A- 0 987 227 EP-A- 1 452 498
WO-A-02/00563 US-A- 5 203 902
(72) Inventors: US-A- 5 578 533
• Sridharan, Srinivasan
Strongsville, OH 44136 (US)
EP 2 368 859 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 2 368 859 B1

Description

FIELD OF INVENTION

5 [0001] The present invention provides a glass enamel composition that partially crystallizes bismuth titanate and
optionally zinc titanate crystals upon firing.

BACKGROUND OF THE INVENTION

10 [0002] Partially crystallizing glass enamel compositions that fuse at relatively low temperatures are used, for example,
to form opaque dark-colored enamel bands on the outer edges of sections of automotive glass such as windshields and
side and rear windows. These opaque dark-colored enamel bands, which typically vary in width from about 1.5 cm to
about 15.0 cm, greatly enhance the aesthetic appearance of the sections of glass upon which they are applied and also
block the transmission of sunlight through the glass to protect underlying adhesives from degradation by ultraviolet
15 radiation. Moreover, these opaque colored enamel bands preferably have the ability to conceal silver-containing buss
bars and wiring connections of rear glass defrosting systems from view from the outside of the vehicle.
[0003] As noted in Gettys et al., U.S. Pat. No. 4,882,301, glass sections for automotive applications are often produced
with varying degrees of curvature as opposed to flat, planar surfaces. If a curvature is desired in a given section of glass,
the glass is heated to a temperature in the vicinity of about 700°C and then subjected to a bending or curving stress
20 employing any number of suitable molding or pressing techniques. At or near that temperature, the section of glass can
be bent as desired, and the surface of the section of glass will maintain sufficient stiffness to resist marking or defects
caused by contact with the press head of the equipment employed to bend or curve the glass or the vacuum head utilized
to pick up and transport the section of glass during the bending operation.
[0004] It was discovered several years ago that specially formulated glass enamel compositions could be applied to
25 planar sections of glass and fired to form opaque dark-colored enamel bands at the same time as the bending or forming
operations were performed on the section of glass. As set forth in U.S. Pat. No. 4,882,301, these glass enamel compo-
sitions had to have the ability to fuse and partially crystallize at the temperature at which a section of glass would be
preheated preparatory to a bending or forming operation. It is believed that the partial crystallization of the enamel forms
a dense, hard, protective layer that prevents the enamel from sticking to the press or vacuum head during the glass
30 bending and transporting operations.
[0005] Generally speaking, prior art glass enamel systems suitable for use in such automotive applications fit within
one of five broad categories or types. The first category relates to lead and/or cadmium based enamel systems that
partially crystallize upon firing. Glass enamel systems such as disclosed in U.S. Pat. No. 4,882,301 are representative
of this type.
35 [0006] The second category relates to lead-free and cadmium-free enamel systems that include crystalline seed
materials that promote partial crystallization of the enamel upon firing. Glass enamel systems such as disclosed in
Ruderer et al., U.S. Pat. No. 5,153,150, Ruderer et al., U.S. Pat. No. 5,208,191, Sakoske, U.S. Pat. No. 5,677,251,
Sakoske et al., U.S. Pat. No. 5,714,420, Sakoske, U.S. Pat. No. 5,753,685, and Sakoske, U.S, Pat. No. 5,783,507, are
representative of this type.
40 [0007] The third category relates to partially crystallizing lead-free and cadmium-free enamel systems that include
substantial amounts of Bi2O3, but little if any ZnO. Glass enamel systems such as disclosed in Murkens, U.S. Pat. No.
5,203,902, and Manabe et al., U.S. Pat. No. 5,578,533, and Sridharan et al., U.S. Pat. No. 6,105,394, are representative
of this type.
[0008] The fourth category relates to partially crystallizing lead-free and cadmium-free enamel systems that include
45 substantial amounts of ZnO, but little Bi2O3. Glass enamel systems such as disclosed in Ruderer et al., U.S. Pat. No.
5,306,674, Anquetil et al., U.S. Pat. No. 5,350,718, Emlemdi et al., U.S. Pat. 5,504,045, Heitmann et al., U.S. Pat. No.
5,707,909, and Harada et al., U.S. Pat. No. 5,817,586, are representative of this type.
[0009] The fifth category relates to partially crystallizing lead-free and cadmium-free enamel systems that include both
Bi2O3 and ZnO as essential components. Glass enamel systems such as disclosed in Roberts, U.S, Pat. No. 5,252,521,
50 Ryan, U.S. Pat. No. 5,616,417, and Punchak, U.S. Pat. No. 5,629,247, are representative of this type. Further glass
enamel compositions are disclosed in the documents EP-1 452 498 A, WO 02/00563 A and EP-0 987 227 A.
[0010] Although improvements have been made in recent years, the chemical durability of known lead-free and cad-
mium-free glass enamel systems used in automotive glass applications has been less than desired. Therefore, a need
exists for lead-free and cadmium-free enamel compositions that exhibit excellent chemical durability to acids, water,
55 and alkalis. Such enamel compositions must be able to fuse and preferably, partially crystallize at temperatures at which
sections of glass are preheated preparatory to forming operations so as not to stick to press or vacuum heads. Moreover,
such enamel compositions should be effective in blocking ultraviolet radiation and in retarding the migration of silver
and subsequent showing from overprinted buss bars and wiring connections of rear glass defrosting systems.

2
 EP 2 368 859 B1

SUMMARY OF INVENTION

[0011] The present invention provides a glass enamel composition as set out in claim 1 that partially crystallizes and
fuses at relatively low firing temperatures. Conceptually, the glass enamel composition according to the present invention
5 comprises an entirely new category of glass enamels in that it forms crystals predominantly of bismuth titanate and
optionally of zinc titanate upon firing. Enamel layers formed using a composition according to the present invention
exhibit excellent resistance to acids and other chemical agents, far surpassing the acid resistance provided by enamel
layers formed using known partially crystallizing lead-free and cadmium-free glass enamel systems.
[0012] A glass enamel composition according to the invention comprises a solids portion comprising a glass component,
10 which comprises a mixture of glass frits. In an embodiment of the invention, the glass component comprises by weight
from 11 % to 52% SiO2, from 3.4% to 40% TiO2, from 5% to 75% Bi2O3 up to 8% B2O3, up to 14% BaO + SrO, up to
45% by weight ZnO, and from 0.1% to 30% of any one or a combination of coloring oxides selected from the group
consisting of Cr2O 3, Fe2O3, MnO2, NiO, CO 2O3, and CeO2, provided that the sum of the amount of Bi2O3 and ZnO in
said glass component comprises 30% to 85% of the glass component by weight. Even though the SiO2 content of the
15 glass component is relatively low, non-silicate bismuth titanate and optional zinc titanate type crystals form and grow
during firing, leaving most of the SiO2 concentrated in the residual glass. This is believed to be the reason why the
enamel exhibits such an excellent acid resistance.
[0013] The foregoing and other features of the invention are hereinafter more fully described and particularly pointed
out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these
20 being indicative, however, of but a few of the various ways in which the principles of the present invention may be
employed.

BRIEF DESCRIPTION OF THE DRAWING

25 [0014] Fig. 1 is a graph showing the percent weight loss of various partially crystallizing glass enamel compositions
as a function of soaking time in a 0.1 N H2SO4 solution heated to 86°C.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

30 [0015] The present invention provides partially crystallizing lead-free and cadmium-free glass enamel compositions
that form residual glass and non-silicate crystals upon firing. As used throughout the instant specification in the appended
claims, the phrase "lead-free and cadmium-free" means that no lead, or PbO, cadmium, or CdO, has been intentionally
added to the composition, and that the composition comprises less than about 0.5% by weight PbO or CdO upon firing.
A predominant portion of the non-silicate crystals are titanate crystals, preferably bismuth titanate and optionally zinc
35 titanate. Throughout the instant specification and in the appended claims, the term "predominant portion" means more
than 50% by weight of all crystals in the fired enamel. Crystal weights can be determined by conventional x-ray diffraction
methods, which are known.
[0016] A glass enamel composition according to the invention preferably comprises a solids portion comprising a glass
component. As used in the instant specification and the appended claims, the term "solids portion" means that portion
40 of the glass enamel composition that remains after firing.
[0017] In an embodiment of the invention, the glass component comprises by weight from 11% to 52% SiO2, from
3.4% to 40% TiO2, from 5% to 75% Bi2O3, up to 8% B2O3, up to 14% BaO + SrO, up to 45% by weight ZnO, and from
0.1% to 30% of any one or a combination of coloring oxides selected from the group consisting of Cr2O3, Fe2O 3, MnO2,
NiO, Co2O3, and CeO2, provided that the sum of the amount of Bi2O3 and ZnO in said glass component comprises 30%
45 to 85% of the glass component by weight. More preferably, the glass component according to the embodiment of the
invention comprises by weight from 14% to 35% SiO2. from 5% to 35% TiO2, from 8% to 74% Bi2O3, up to 35% ZnO,
up to 6% B2O3, up to 10% BaO + SrO, and from 0.5% to 25% of said coloring oxides, provided that the sum of the
amount of Bi2O3 and ZnO in said glass component comprises 33% to 74% of the glass component by weight. The use
of coloring oxides in the glass component according to the embodiment of the invention, in addition to adjusting the color
50 of the enamel, helps to modify the expansion of the glass and improve the durability of the fired enamel.
[0018] The glass component can further comprise a total of up to 35% by weight, and more preferably from 0.1% to
30% by weight, of other optional oxides to adjust the color and other characteristics of the bismuth titanate and optional
zinc titanate crystals and the residual glass upon firing. Preferably, such other optional oxides comprise the following:
up to 25%, and more preferably up to 13%, alkali metal oxides (e.g., Li2O, Na2O, and K2O), up to 15%, and more
55 preferably up to 13%, Al2O3; a total of up to 25%, and more preferably a total of up to 20%, alkaline-earth metal oxides
(e.g., BaO, SrO, CaO, and MgO), provided that the sum of BaO + SrO does not exceed 14% by weight, and more
preferably 10% by weight of the glass component; up to 25%, and more preferably up to 10%, V2O5; up to 15%, and
more preferably up to 8%, Sb2O3; a total of up to 25%, and more preferably a total of up to 20%, of any one or a

3
 EP 2 368 859 B1

combination of La2O3, Y2O3, Nb2O5, and ZrO2; and a total of up to 20%, and more preferably a total of up to 15%. of
any one or a combination of SnO, In2O3, and MoO3. In the embodiment of the invention, the sum of coloring oxides and
all other optional oxides in the glass component will preferably not exceed 35%, and more preferably 30%, of the glass
component by weight.
5 [0019] It will be appreciated that the glass component of the glass enamel composition according to the invention
comprise a mixture of several glass frits, including non-crystallizing glass frits, so as to obtain a glass component providing
the overall oxide composition as previously described. A embodiment comprises a glass component containing a com-
bination of at least two glass frits, wherein the glass component comprises by weight from 50% to 90% of one or more
first glass frits that upon firing form titanate crystals, and from 10% to 50% of one or more second glass frits that upon
10 firing do not form titanate crystals, wherein the sum of the components of all glass frits present in the glass component
comprises by weight from 11% to 52% SiO2, from 3.4% to 40% TiO2, from 5% to 75% Bi2O3, up to 45% ZnO, up to 8%
B2O3, up to 14% BaO + SrO, provided that the sum of the amount of Bi2O3 and ZnO in the glass frits comprises from
30% to 85% of the glass component by weight. More preferably, the sum of the components of the first and second
glass frits comprises by weight from 14% to 35% SiO2 from 5% to 35% TiO2, from 8% to 74% Bi2O3 up to 6% B2O3, up
15 to 10% BaO + SrO, and up to 35% by weight ZnO, provided that the sum of the amount of Bi2O3 and ZnO in the glass
frits comprises from 33% to 74% of the glass component by weight. Furthermore, the solids portion of the glass enamel
component by weight. Furthermore, the solids portion of the glass enamel composition can further comprise one or more
inorganic pigments such as, for example, copper chrome black, iron cobalt chrome black, iron nickel manganese chrome
black, bismuth manganate, that can interact with the glass component to precipitate titanate crystals and/or impart
20 coloration. These inorganic pigments are not part of the glass, but are added as inorganic pigments.
[0020] A glass enamel composition according to the present invention can be fired at a temperature of from 485°C to
780°C, and more preferably from 520°C to 725°C, typically in about five minutes. It will be appreciated that firing times
are not per se critical, and that a range of firing schedules can be employed depending upon the substrate and thickness
of the enamel layer being formed. When used in automotive glass bending applications, firing is typically conducted at
25 685°C for about five minutes.
[0021] Upon firing, a glass enamel composition according to the invention will form crystals that predominantly comprise
bismuth titanates, and optionally zinc titanates. It will be appreciated that the proportional amount of bismuth titanates
and/or zinc titanates in the fired enamel will depend, in large part, upon the amount of Bi2O3 and/or ZnO present in the
glass component at the time of firing. In addition to the predominant bismuth titanate and optional zinc titanate crystals,
30 lesser amounts of other crystal forms (e.g., transition metal titanates, bismuth silicate, zinc silicate, bismuth borate, zinc
borate) may also be formed upon firing, if the conditions are suitable.
[0022] Depending upon the composition of the glass component, various different types of titanate crystals can be
formed upon firing. For example, when the glass component comprises appropriate amounts of Bi2O3, TiO2, and V2O5,
orthorhombic bismuth-vanadium titanate crystals (6.5Bi2O3 · 2.5V205 TiO2) may be formed upon firing. In the absence
35 of V2O 5, cubic bismuth titanate crystals (Bi2O3 · 2TiO 2), orthorhombic bismuth titanate crystals (2Bi2O3 · 3TiO2), or a
combination of both cubic and orthorhombic bismuth titanate crystals may be formed. Moreover, when the glass com-
ponent contains appropriate amounts of ZnO, hexagonal zinc titanate (ZnO · Ti02) and/or cubic zinc titanate crystals
(2ZnO · 3TiO2) may be formed in addition to bismuth titanate crystals. It will be appreciated that the solids portion of the
glass enamel composition according to the invention can further comprise seed materials (e.g., bismuth titanates etc.)
40 to promote the rapid formation of titanate crystals upon firing.
[0023] An enamel layer formed using a glass enamel composition according to the present invention far surpasses
the acid resistance of enamel layers formed using known partially crystallizing lead-free and cadmium-free glass enamels.
Without being bound to a particular theory, applicants speculate that as the predominant titanate crystals form and grow
during firing, TiO2 and Bi2O 3 and/or ZnO are depleted from the residual glass, but SiO2 is not. As the titanate crystals
45 grow, the relative concentration of SiO2 in the residual glass surrounding the crystals increases over the SiO2 content
of the original glass. Generally speaking, a residual glass that is rich in SiO 2 is substantially more resistant to chemical
attack than a residual glass that has been depleted of SiO 2 due to the formation of silicate crystals, such as is the case
with known partially crystallizing lead-free and cadmium-free glass enamel systems.
[0024] In addition to the glass component, the solids portion of a glass enamel composition according to the present
50 invention may further comprise one or more inorganic pigments. As noted above, inorganic pigments can be used if the
glass component does not include sufficient coloring oxides (e.g.,Co3O4, Cr2O3, Fe2O 3, MnO2, NiO, CuO) to provide
the desired coloration in the final enamel layer and/or to provide materials that can interact with the glass component to
promote the formation of titanate crystals. Examples of suitable inorganic pigments include copper chrome black sold
under the trade designation K-393, iron nickel manganese chrome black sold under the trade designation V792, and
55 iron cobalt chrome black sold under the trade designation F-6340, all sold by the Ferro Corporation of Cleveland, Ohio.
When used, inorganic pigments generally account for less than about 40%, or more preferably less than about 30%, by
weight of the solids portion of the enamel composition.
[0025] The solids portion of the glass enamel composition according to the invention can further comprise one or more

4
 EP 2 368 859 B1

fillers. Examples of suitable fillers include alumina (Al2O3), buss bar hiding control agents such as fine silicon powders
(up to about 3% by weight), zircon, cordierite (2MgO · 2Al2O3 · 5SiO2), willemite (2ZnO - SiO2), beta-eucryptite (LiAlSiO4),
transition metal oxides such as FeO and silicon dioxide (SiO2). Fillers generally comprise less than about 30%, and
more preferably less than 20%, by weight of the solids portion of the enamel composition.
5 [0026] A glass enamel composition according to the present invention may also further comprise a suitable vehicle
or carrier that facilitates application of the glass enamel composition to a section of glass or other suitable substrate.
Depending upon the particular application, a glass enamel composition according to the invention can be applied as a
slurry, a paste, inkjet printable ink or as a thermoplastic pellet.
[0027] When used to form an opaque, dark band on a section of automobile glass, a glass enamel composition
10 according to the invention is preferably formed by dispersing the solids portion in a suitable vehicle or carrier, which
preferably comprises a solvent and a resin. Examples of potential suitable solvents include terpenes such as alpha- or
beta-terpineol or mixtures thereof with other solvents such as kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol
acetate, hexylene glycol and high-boiling alcohols and alcohol esters. Various combinations of these and other solvents
may be formulated to obtain the desired viscosity and volatility requirements for each application. Examples of potential
15 suitable resins include ethyl cellulose, ethyl hydroxy ethyl cellulose, wood rosin, mixtures of ethyl cellulose and phenolic
resins, polymethacrylates of lower alcohols and monobutyl ether of ethylene glycol monoacetate.
[0028] Optionally, the vehicle or carrier may also comprise a thixotrope and a wetting agent in order to facilitate the
application of the enamel composition to the section of glass. Examples of potential suitable thixotropic agents include
organic based thixotropics such as, for example, hydrogenated castor oil and derivatives thereof and ethyl cellulose.
20 Examples of potential suitable wetting agents include fatty acid esters, for example, N-tallow-1, 3-diaminopropane di-
oleate, N-tallow trimethylene diamine diacetate, N-coco trimethylene diamine, beta diamines, N-oleyl trimethylene di-
amine, N-tallow trimethylene diamine, and/or N-tallow trimethylene diamine di-oleate.
[0029] The glass component preferably comprises at least about 30% by weight of the solids portion. More preferably,
the glass component comprises at least about 60% by weight of the solids portion. Most preferably, the glass component
25 comprises from about 70% to about 100% by weight of the solids portion.
[0030] The glass enamel composition according to the invention is preferably applied to a section of glass by screen
printing or other conventional application technique. The section of glass is then preferably heated to a temperature of
from 485°C to 780°C, and most preferably to 520°C to 725°C, and then formed to a desired shape. Generally, the step
of firing the enamel and forming or shaping the section of glass is carried out simultaneously or at substantially the same
30 time. Such forming may be carried out utilizing a press device that may include a head covered with a material such as
FIBERFRAX refractory fiber. FIBERFRAX is a registered trademark for refractory fiber owned by the Stemcor Corporation
of Cleveland, Ohio.
[0031] During the forming operation, the refractory fiber contacts the applied layer of the glass enamel composition,
but does not stick. Applicants believe that the crystallization of bismuth titanate, and optionally zinc titanate, that occurs
35 during heating helps to prevent the refractory fiber from sticking to the enamel and/or causing the surface of the resultant
enamel finish produced by the enamel composition from becoming disrupted or disturbed. Similarly, the vacuum head
utilized to transport the glass is covered with a refractory fiber such as FIBERFRAX refractory fiber and applicants believe
that the crystallization that occurs during heating helps to prevent the refractory fiber from sticking to the enamel com-
position and/or causing the surface of the resultant enamel finish from becoming disrupted or disturbed.
40 [0032] The following examples are intended only to illustrate the invention and should not be construed as imposing
limitations upon the claims.

Example 1

45 [0033] Glasses A through M were prepared using conventional glass making techniques such that they had the
composition by weight percent shown in Table 1 below. Glasses A, B, and C do not precipitate predominantly titanate
crystals and thus, when viewed alone, do not provide a glass component within the scope of the present invention, Glass
L, when viewed alone, do provide a glass component that is within the scope of the present invention.

50 Table 1
Constituent (Weight Percent)
Glass
SiO2 TiO2 Bi2O3 ZnO Li2O K2O B2O3 Other Oxides
A 21.3 -- 70.3 2.4 0.5 1.0 -- Nb2O5 - 3.1
55
BaO - 1.4
Nb2O5 - 2.8
B 19.0 -- 54.1 2.1 1.8 -- -- BaO - 2.2

5
 EP 2 368 859 B1

(continued)

Constituent (Weight Percent)

Glass
SiO2 TiO2 Bi2O3 ZnO Li2O K2O B2O3 Other Oxides
5
MnO 2 - 13.5
Cr2O3 - 4.5
C 21.5 2.4 70.8 2.4 0.5 1.0 -- BaO - 1.4
D 21.0 4.6 69.2 2.3 0.5 1.0 -- BaO - 1.4
10
E 28.2 12.1 48.4 -- 1.6 4.9 4.8 --
F 20.2 20.1 48.4 -- 1.6 4.9 4.8 --
G 15.9 8.4 62.8 5.1 1.1 3.4 3.3 --
15
H 16.8 8.9 66.5 -- 0.6 3.6 3.6 --
J 32.1 23.3 8.8 24.2 1.4 4.4 5.8 --
K 28.3 19.8 23.1 18.2 1.2 4.2 5.2 --

20
L 14.6 7.7 57.5 -- 0.6 3.1 3.0 Cr2O3 -13.5
M 16.0 8.5 63.3 -- 0.6 3.4 3.4 CuO - 4.8

Example 2

25
[0034] Glasses A through M from Example 1 were each milled to an average particle size of from about 2 to about 6
microns and then dispersed in C31 medium (available from Ferro Corporation of Cleveland, Ohio) and mixed in a high
shear mixer for about 10 minutes. The weight ratio of the solids to medium was about 7.5. The resulting pastes were
each screen printed onto 5 cm by 10 cm by 3 mm thick automobile windshield coupons (on the tin side) using a 160
mesh screen to a wet print thickness of about 1 to about 1.5 mils. The glass coatings were dried in a forced air oven at
30
about 185°F (85°C) for about 30 minutes and then heat treated in an oven held at about 1250°F (677°C) for about 5
minutes. After cooling to room temperature (about 25°C), X-ray diffraction patterns of the fired glass coating were taken
using Cu K-alpha radiation to determine the type of crystalline materials, if any, precipitated in the glass coating during
the 1250°F (677°C) heat treatment.
[0035] The results are reported in Table 2 below, where "BS" means cubic bismuth silicate (Bi2O3 · SiO2) crystals;
35
"BT2" means cubic bismuth titanate (Bi2O3 · 2TiO2) crystals; "B2T3" means orthorhombic bismuth titanate (2Bi2O3 ·
3TiO2) crystals; and "Z2T3" means cubic zinc titanate (2ZnO · 3TiO2) crystals. The fused glass coatings were also tested
for chemical resistance in various solutions as reported in Table 2 as weight loss in mg per 27 cm2 for the given length
of time (1 to 144 hr) as noted.
Figure 1 graphically illustrates the comparative durability of glasses A through M in 0.1 N H2SO4 (1.43 pH, 86°C) in
40
terms of percent weight loss as a function of time.

Table 2
Percent Weight Loss In
45 Glass Crystal H2O @ H2SO4 0.1 HNO3 HCl Citric Acid H2SO4 0.1 N
Type(s) 80°C 100 N 25°C 2 10%(wt) 10%(wt) 10%(wt) 25°C 86°C 144
Hrs. Hrs. 25°C 1 Hr. 25°C 1 1 Hr. Hrs.
Hr.

50
A BS 3.5 0.8 1.5 20 2.7 100
B No Crystals 3.8 3.5 3.3 8.6 3.5 100
Formed
C BS 2.0 1.7 1.8 26.9 1.7 96
55 D BT2+BS 3.1 2.5 7.4 3 2.5 82
E BT2 +B2T3 0.1 0.3 0.6 0.2 0.5 <1
F BT2+ B2T3 0.1 0.1 0.4 0.3 0.4 <1

6
 EP 2 368 859 B1

(continued)

Percent Weight Loss In

Glass Crystal H2O @ H2SO4 0.1 HNO3 HCl Citric Acid H2SO4 0.1 N
5
Type(s) 80°C 100 N 25°C 2 10%(wt) 10%(wt) 10%(wt) 25°C 86°C 144
Hrs. Hrs. 25°C 1 Hr. 25°C 1 1 Hr. Hrs.
Hr.
G B2T3 +BT2 0.3 0.5 13.2 5 0.1 25.9
10
H B2T3 +BT2 0.1 0.3 0.3 0.7 0 32.7
I Z2T3 1.1 6.3 2.4 4.9 1 9.8
K Z2T3 1.2 0.4 0.2 0.1 0,2 27.2

15
L BT2 + B2T3 + 0.2 0.1 0.1 0.3 0 9.0
Cr titanates
M B2T3 0.1 0.3 0 1.1 0 50.9

Example 3
20

[0036] Glass Enamel Compositions 1 through 5 were each formed by combining the constituents in the parts by weight
shown in Table 3 below. Glasses B, H, K, L, and M were from Example 1. O-1749B Pigment is a copper manganese
iron inorganic pigment, K751 Pigment is a copper chrome manganese inorganic pigment, and V792 Pigment is a nickel
chrome manganese iron inorganic pigment, and C31 is an auto glass enamel medium, each of which is available from
25
the Ferro Corporation of Cleveland, Ohio. Enamels 2 and 3 are within the scope of the invention.

Table 3
Constituent Enamel 1 Enamel 2 Enamel 3 Enamel 4 Enamel 5
30 0-1749B Pigment 17.5 -- -- -- 17.5
K751 Pigment -- 5 5 5 --
V792 Pigment -- 12.5 12.5 12.5 --
Glass B 40 40 10 40 --
35
Glass H -- -- -- -- 80
Glass K 40 -- -- -- --
Glass L -- 40 70 -- --
40 Glass M -- -- -- 40 --
C31 Medium 17.4 17.4 17.4 17.4 17.4

Example 4
45

[0037] Glass Enamels 1 through 5 from Example 3 were each separately applied by screen printing onto 5 cm by 10
cm by 3 mm thick automobile windshield coupons (on the tin side) using a 160 mesh screen to a wet print thickness of
about 1 to about 1.5 mils. These glass enamels were dried in a forced air oven at about 185°F (85°C) for about 30
minutes and then heat treated in an oven held at about 1250°F (677°C) for about 2 to 8 minutes. After the enameled
50
coupons were cooled to room temperature (about 25°C), the enameled coupons were subjected to the same chemical
resistance testing as outlined in Example 2. The results of such testing are reported in Table 4 below.

55

7
 EP 2 368 859 B1

Table 4
Percent Weight Loss In
Enamel H2O @ 80°C H2SO4 0.1 HNO3 10% (wt) HCl 10% (wt) Citric Acid H2SO4 0.1 N
5 100 Hrs. N 25°C 2 25°C 1 Hr. 25°C 1 Hr. 10% (wt) 25°C 86°C 144 Hrs.
Hrs. 1 Hr.
1 18.3 14.1 3.6 3.1 9.1 34,8
2 7.2 3.7 1.9 1.4 1.1 68.0
10
3 7.0 3.8 3,5 1.7 3.1 21.9
4 2.2 0.5 1.8 5.5 0.3 100
5 1.9 2.9 6.0 0.7 1.4 37.1

15

Claims

1. A lead-free and cadmium-free glass enamel composition, that partially crystallizes bismuth titanate and optionally
zinc titanate crystals upon firing, comprising a solids portion, the solids portion comprising:
20

a glass component, the glass component comprising a mixture of glass frits, including a non-crystallizing glass
frit, so as to provide a glass component providing an overall oxide composition comprising:

from 11% to 52% by weight SiO2;

25
from 3.4% to 40% by weight TiO 2;
from 30% to 85% by weight Bi2O3 + ZnO, provided the Bi2O3 comprises from 5% to 75% of the glass
component by weight and the ZnO comprises up to 45% of the glass component by weight;
up to 8% by weight B2O3;
up to 14% by weight BaO + SrO; and
30
from 0.1% to 30% of any one or a combination of coloring oxides selected from the group consisting of
Cr2O 3, Fe2O3, MnO 2, NiO, Co2O3, and CeO 2; wherein the composition upon firing at a temperature of from
485°C to 780°C forms an enamel layer comprising crystals dispersed in a residual glass, wherein a pre-
dominant portion of the crystals comprise bismuth titanate, and
wherein less than 70% by weight of the enamel layer is removed upon exposure to an 86°C 0.1 N H2SO4
35 solution for 144 hours.

2. The lead-free and cadmium-free glass enamel composition according to claim 1 wherein the glass component
comprises:

40
from 14% to 35% by weight SiO2;
from 5% to 35% by weight TiO 2;
from 33% to 74% by weight Bi2O 3 + ZnO, provided the Bi2O3 comprises from 8% to 74% of the glass component
by weight and the ZnO comprises up to 35% of the glass component by weight;
up to 6% by weight B2O3;
45
up to 10% by weight BaO + SrO; and
from about 0.5% to 25% of any one or a combination of coloring oxides selected from the group consisting of
Cr2O3, Fe2O3, MnO2, NiO, Co2O3, and CeO2.

3. The lead-free and cadmium-free glass enamel composition according to claim 1 wherein the glass component further
50
comprises up to a total of 35% by weight of one or more optional oxides selected from the group consisting of:

alkali metal oxides, provided the sum of all alkali metal oxides comprises less than 25% of the glass component
by weight;
alkaline-earth metal oxides, provided the sum of all alkaline-earth metal oxides comprises less than 25% of the
55
glass component by weight;
La2O3, Y2O3, Nb2O 5, and ZrO2, provided the sum of all La2O3, Y2O3, Nb2O5, and ZrO 2 comprises less than
25% of the glass component by weight;

8
 EP 2 368 859 B1

SnO, In2O3, and MoO3, provided the sum of all SnO, In2O3, and MoO3 comprises less than 20% of the glass
component by weight;
Al2O3, provided the Al2O 3 comprises less than 15% of the glass component by weight;
V2O5, provided the V2O5 comprises less than 25% of the glass component by weight; and
5 Sb2O3, provided the Sb2O 3 comprises less than 15% of the glass component by weight.

4. The lead-free and cadmium-free glass enamel composition according to claim 2 wherein the glass component further
comprises from 0.1% to 30% by weight of one or more optional oxides selected from the group consisting of:

10 alkali metal oxides, provided the sum of all alkali metal oxides comprises less than 13% of the glass component
by weight;
alkaline-earth metal oxides, provided the sum of all alkaline-earth metal oxides comprises less than 20% of the
glass component by weight;
La2O3, Y2O3, Nb2O 5, and ZrO2, provided the sum of all La2O3, Y2O3, Nb2O5, and ZrO 2 comprises less than
15 20% of the glass component by weight;
SnO, In2O3, and MoO3, provided the sum of all SnO, In2O3, and MoO3 comprises less than 15% of the glass
component by weight;
Al2O3, provided the Al2O 3 comprises less than 15% of the glass component by weight;
V2O5, provided the V2O5 comprises less than 25% of the glass component by weight; and
20 Sb2O3, provided the Sb2O 3 comprises less than 15% of the glass component by weight.

5. The lead-free and cadmium-free glass enamel composition according to claim 1 wherein the solids portion further
comprises one or more selected from the group consisting of inorganic pigments, fillers, and seeds for titanate
crystals.
25
6. A section of glass having a lead-free and cadmium-free glass enamel composition according to claim 1 fused thereon
at a temperature of from 485°C to 780°C to form an enamel layer, the enamel layer comprising bismuth titanate
crystals and optionally zinc titanate crystals dispersed in a residual glass comprising SiO2, wherein less than 70%
by weight of the glass enamel coating layer is removed upon exposure to an 86°C 0.1 N H2SO 4 solution for 144 hours.
30

Patentansprüche

1. Blei-freie und Cadmium-freie Glasemailzusammensetzung, die teilweise Bismuttitanat- und gegebenenfalls Zinkti-
35 tanatkristalle beim Brennen kristallisiert, umfassend einen Feststoffanteil, wobei der Feststoffanteil umfasst:

eine Glaskomponente, wobei die Glaskomponente eine Mischung aus Glasfritten umfasst, umfassend eine
nicht-kristallisierende Glasfritte, um eine Glaskomponente bereitzustellen, die eine Gesamtoxidzusammenset-
zung bereitstellt, umfassend:
40
von etwa 11 Gew.-% bis etwa 52 Gew.-% SiO2;
von 3,4 Gew.-% bis etwa 40 Gew.-% TiO2;
von etwa 30 Gew.-% bis etwa 85 Gew.-% Bi2O3 + ZnO, mit der Maßgabe, dass Bi2O3 von etwa 5 Gew.-
% bis etwa 75 Gew.-% der Glaskomponente umfasst und ZnO bis zu etwa 45 Gew.-% der Glaskomponente
45 umfasst;
bis zu etwa 8 Gew.-% B2O 3;
bis zu etwa 14 Gew.-% BaO + SrO und
von etwa 0,1 Gew.-% bis etwa 30 Gew.-% irgendeiner oder einer Kombination aus färbenden Oxiden,
ausgewählt aus der Gruppe, bestehend aus Cr2O3, Fe2O3, MnO 2, NiO, Co2O3 und CeO 2;
50 wobei die Zusammensetzung beim Brennen bei einer Temperatur von etwa 485°C bis 780° eine Email-
schicht bildet, die Kristalle, dispergiert in einem Restglas, umfasst, wobei ein überwiegender Anteil der
Kristalle Bismuttitanat umfasst, und
wobei weniger als etwa 70 Gew.-% der Emailschicht beim Aussetzen an eine 86°C 0,1 N H2SO4-Lösung
für 144 Stunden entfernt wird.
55
2. Blei-freie und Cadmium-freie Glasemailzusammensetzung nach Anspruch 1, wobei die Glaskomponente umfasst:

von 14 Gew.-% bis 35 Gew.-% SiO 2;

9
 EP 2 368 859 B1

von 5 Gew.-% bis 35 Gew.-% TiO 2;

von 33 Gew.-% bis 74 Gew.-% Bi2O3 + ZnO, mit der Maßgabe, dass Bi2O 3 von 8 Gew.-% bis 74 Gew.-% der
Glaskomponente umfasst und ZnO bis zu 35 Gew.-% der Glaskomponente umfasst;
bis zu 6 Gew.-% B2O3;
5 bis zu 10 Gew.-% BaO + SrO; und
von etwa 0,5 % bis 25 % von irgendeiner oder einer Kombination an färbenden Oxiden, ausgewählt aus der
Gruppe, die aus Cr2O 3, Fe2O 3, MnO2, NiO, Co2O3 und CeO2 besteht.

3. Blei-freie und Cadmium-freie Glasemailzusammensetzung nach Anspruch 1, wobei die Glaskomponente ferner bis
10 zu einer Gesamtmenge von 35 Gew.-% ein oder mehrere optionale Oxide umfasst, ausgewählt aus der Gruppe,
die besteht aus:

Alkalimetalloxiden, mit der Maßgabe, dass die Summe aller Alkalimetalloxide weniger als 25 Gew.-% der Glas-
komponente umfasst;
15 Erdalkalimetalloxide, mit der Maßgabe, dass die Summe aller Erdalkalimetalloxide weniger als 25 Gew.-% der
Glaskomponente umfasst;
La2O3, Y2O3, Nb2O5 und ZrO2, mit der Maßgabe, dass die Summe aller La2O3, Y2O3, Nb2O5 und ZrO 2 weniger
als 25 Gew.-% der Glaskomponente umfasst;
SnO, In2O3 und MoO3, mit der Maßgabe, dass die Summe aller SnO, In2O3 und MoO3 weniger als 20 Gew.-
20 % der Glaskomponente umfasst;
Al2O3, mit der Maßgabe, dass Al2O3 weniger als 15 Gew.-% der Glaskomponente umfasst;
V2O5, mit der Maßgabe, dass V2O5 weniger als 25 Gew.-% der Glaskomponente umfasst; und
Sb2O3, mit der Maßgabe, dass Sb2O3 weniger als 15 Gew.-% der Glaskomponente umfasst.

25 4. Blei-freie und Cadmium-freie Glasemailzusammensetzung nach Anspruch 2, wobei die Glaskomponente ferner von
0,1 Gew.-% bis 30 Gew.-% ein oder mehrerer optionaler Oxide umfasst, ausgewählt aus der Gruppe, die besteht aus:

Alkalimetalloxiden, mit der Maßgabe, dass die Summe aller Alkalimetalloxide weniger als 13 Gew.-% der Glas-
komponente umfasst;
30 Erdalkalimetalloxide, mit der Maßgabe, dass die Summe aller Erdalkalimetalloxide weniger als 20 Gew.-% der
Glaskomponente umfasst; La2O3, Y2O3, Nb2O 5 und ZrO2, mit der Maßgabe, dass die Summe aller La2O3,
Y2O3, Nb2O5 und ZrO2 weniger als 20 Gew.-% der Glaskomponente umfasst;
SnO, In2O3 und MoO3, mit der Maßgabe, dass die Summe aller SnO, In2O3 und MoO3 weniger als 15 Gew.-
% der Glaskomponente umfasst;
35 Al2O3, mit der Maßgabe, dass Al2O3 weniger als 15 Gew.-% der Glaskomponente umfasst;
V2O5, mit der Maßgabe, dass V2O5 weniger als 25 Gew.-% der Glaskomponente umfasst; und
Sb2O3, mit der Maßgabe, dass Sb2O3 weniger als 15 Gew.-% der Glaskomponente umfasst.

5. Blei-freie und Cadmium-freie Glasemailzusammensetzung nach Anspruch 1, wobei der Feststoffanteil ferner ein
40 oder mehrere, ausgewählt aus der Gruppe, die aus anorganischen Pigmenten, Füllstoffen und Impfkristallen für
Titanatkristalle besteht, umfasst.

6. Glasabschnitt mit einer Blei-freien und Cadmium-freien Glasemailzusammensetzung nach Anspruch 1, darauf auf-
geschmolzen bei einer Temperatur von 485°C bis 780°C, um eine Emailschicht zu bilden, wobei die Emailschicht
45 Bismuttitanatkristalle umfasst und gegebenenfalls Zinktitanatkristalle, dispergiert in einem Restglas, umfassend
SiO2, wobei weniger als 70 Gew.-% der Glasemailbeschichtungsschicht beim Aussetzen an 86°C 0,1 N H2SO4-Lö-
sung für 144 Stunden entfernt wird.

50 Revendications

1. Composition d’émail à verre exempte de plomb et exempte de cadmium, qui cristallise partiellement des cristaux
de titanate de bismuth et facultativement de titanate de zinc lors de la cuisson, comprenant une partie de matières
solides, la partie de matières solides comprenant :
55
un composant verre, le composant verre comprenant un mélange de frittes de verre, comprenant une fritte de
verre ne cristallisant pas, de façon à fournir un composant verre fournissant une composition d’oxydes globale
comprenant :

10
 EP 2 368 859 B1

de 11 % à 52 % en poids de SiO2 ;
de 3,4 % à 40 % en poids de TiO2 ;
de 30 % à 85 % en poids de Bi2O3 + ZnO, à la condition que le Bi2O3 représente de 5 % à 75 % du
composant verre en poids et que le ZnO représente jusqu’à 45 % du composant verre en poids ;
5 jusqu’à 8 % en poids de B2O3 ;
jusqu’à 14 % en poids de BaO + SrO ; et
de 0,1 % à 30 % de l’un quelconque ou d’une combinaison d’oxydes colorants choisis dans le groupe
consistant en Cr2O 3, Fe2O 3, MnO2, NiO, Co2O3 et CeO 2 ;
la composition lors de la cuisson à une température de 485°C à 780°C formant une couche d’émail com-
10 prenant des cristaux dispersés dans un verre résiduel, une partie prédominante des cristaux comprenant
du titanate de bismuth, et
moins de 70 % en poids de la couche d’émail étant retirés lors de l’exposition à une solution de H2SO4 0,1
N à 86°C pendant 144 heures.

15 2. Composition d’émail à verre exempte de plomb et exempte de cadmium, selon la revendication 1, dans laquelle le
composant verre comprend :

de 14 % à 35 % en poids de SiO2 ;
de 5 % à 35 % en poids de TiO2 ;
20 de 33 % à 74 % en poids de Bi2O3 + ZnO, à la condition que le Bi2O3 représente de 8 % à 74 % du composant
verre en poids et que le ZnO représente jusqu’à 35 % du composant verre en poids ;
jusqu’à 6 % en poids de B2O3 ;
jusqu’à 10 % en poids de BaO + SrO ; et
d’environ 0,5 % à 25 % de l’un quelconque ou d’une combinaison d’oxydes colorants choisis dans le groupe
25 consistant en Cr2O3, Fe2O3, MnO2, NiO, Co2O3 et CeO 2.

3. Composition d’émail à verre exempte de plomb et exempte de cadmium, selon la revendication 1, dans laquelle le
composant verre comprend en outre jusqu’à un total de 35 % en poids d’un ou plusieurs oxydes facultatifs choisis
dans le groupe consistant en :
30
oxydes de métaux alcalins, à la condition que la somme de tous les oxydes de métaux alcalins représente
moins de 25 % du composant verre en poids ;
des oxydes de métaux alcalino-terreux, à la condition que la somme de tous les oxydes de métaux alcalino-
terreux représente moins de 25 % du composant verre en poids ;
35 La2O3, Y2O3, Nb2O5 et ZrO2, à la condition que la somme de tous les La2O3, Y2O3, Nb2O5 et ZrO2 représente
moins de 25 % du composant verre en poids ;
SnO, In2O3 et MoO3, à la condition que la somme de tous les SnO, In2O 3 et MoO3 représente moins de 20 %
du composant verre en poids ;
Al2O3, à la condition que l’Al2O 3 représente moins de 15 % du composant verre en poids ;
40 V2O5, à la condition que le V2O5 représente moins de 25 % du composant verre en poids ; et
Sb2O3, à la condition que le Sb2O 3 représente moins de 15 % du composant verre en poids.

4. Composition d’ émail à verre exempte de plomb et exempte de cadmium, selon la revendication 2, dans laquelle
le composant verre comprend en outre de 0,1 % à 30 % en poids d’un ou plusieurs oxydes facultatifs choisis dans
45 le groupe consistant en les oxydes de métaux alcalins, à la condition que la somme de tous les oxydes de métaux
alcalins représente moins de 13 % du composant verre en poids ;
les oxydes de métaux alcalino-terreux, à la condition que la somme de tous les oxydes de métaux alcalino-terreux
représente moins de 20 % du composant verre en poids ;
La2O3, Y2O3, Nb2O5 et ZrO2, à la condition que la somme de tous les La2O3, Y2O3, Nb2O5 et ZrO 2 représente
50 moins de 20 % du composant verre en poids ;
SnO, In2O3 et MoO 3, à la condition que la somme de tous les SnO, In2O3 et MoO3 représente moins de 15 % du
composant verre en poids ;
Al2O 3, à la condition que l’Al2O3 représente moins de 15 % du composant verre en poids ;
V2O5, à la condition que le V2O5 représente moins de 25 % du composant verre en poids ; et
55 Sb2O3, à la condition que le Sb2O3 représente moins de 15 % du composant verre en poids.

5. Composition d’émail à verre exempte de plomb et exempte de cadmium, selon la revendication 1, dans laquelle la
fraction de matières solides comprend en outre un ou plusieurs choisis dans le groupe consistant en les pigments

11
 EP 2 368 859 B1

inorganiques, les charges et les ensemencements pour les cristaux de titanate.

6. Section de verre ayant une composition d’émail à verre exempte de plomb et exempte de cadmium selon la reven-
dication 1 fusionnée sur celle-ci à une température de 485°C à 780°C pour former une couche d’émail, la couche
5 d’émail comprenant des cristaux de titanate de bismuth et facultativement des cristaux de titanate de zinc dispersés
dans un verre résiduel comprenant SiO2, où moins de 70 % en poids de la couche de revêtement d’émail à verre
sont retirés lors de l’exposition à une solution de H2SO4 0,1 N à 86°C pendant 144 heures.

10

15

20

25

30

35

40

45

50

55

12
EP 2 368 859 B1

13
 EP 2 368 859 B1

REFERENCES CITED IN THE DESCRIPTION

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

Patent documents cited in the description

• US 4882301 A, Gettys [0003] [0004] [0005] • US 5350718 A, Anquetil [0008]

• US 5153150 A, Ruderer [0006] • US 5504045 A, Emlemdi [0008]
• US 5208191 A, Ruderer [0006] • US 5707909 A, Heitmann [0008]
• US 5677251 A, Sakoske [0006] • US 5817586 A, Harada [0008]
• US 5714420 A, Sakoske [0006] • US 5252521 A, Roberts [0009]
• US 5753685 A, Sakoske [0006] • US 5616417 A, Ryan [0009]
• US 5783507 A, Sakoske [0006] • US 5629247 A, Punchak [0009]
• US 5203902 A, Murkens [0007] • EP 1452498 A [0009]
• US 5578533 A, Manabe [0007] • WO 0200563 A [0009]
• US 6105394 A, Sridharan [0007] • EP 0987227 A [0009]
• US 5306674 A, Ruderer [0008]

14