TEPZZ 7Z5ZZ5B_T

(19)

(11) EP 2 705 005 B1

(12) EUROPEAN PATENT SPECIFICATION

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

of the grant of the patent: C03C 8/04 (2006.01) C03C 3/068 (2006.01)
06.03.2019 Bulletin 2019/10 C03C 3/093 (2006.01) C03C 3/095 (2006.01)
C03C 3/118 (2006.01) C03C 8/06 (2006.01)
(21) Application number: 12779499.8 C03C 8/14 (2006.01) C03C 8/18 (2006.01)
C03C 8/20 (2006.01) C03C 17/04 (2006.01)
(22) Date of filing: 02.05.2012
(86) International application number:
PCT/US2012/036037

(87) International publication number:

WO 2012/151228 (08.11.2012 Gazette 2012/45)

(54) GLASS FRIT COMPOSITIONS FOR ENAMELS

GLASFRITTENZUSAMMENSETZUNGEN FÜR EMAILLEN
COMPOSITIONS DE FRITTE DE VERRE POUR ÉMAUX

(84) Designated Contracting States: • KLIMAS, David, A.

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Pittsburgh
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PA 15241 (US)
PL PT RO RS SE SI SK SM TR
(74) Representative: Gille Hrabal
(30) Priority: 04.05.2011 US 201113100399 Brucknerstrasse 20
40593 Düsseldorf (DE)
(43) Date of publication of application:
12.03.2014 Bulletin 2014/11 (56) References cited:
WO-A1-98/35917 WO-A1-2007/032977
(73) Proprietor: FERRO CORPORATION GB-A- 2 034 300 JP-A- 56 125 241
Mayfield Heights, OH 44124 (US) US-A1- 2008 090 034 US-A1- 2010 009 836

(72) Inventors: Remarks:

• SINGH, Sandeep, K. The file contains technical information submitted after
Strongsville the application was filed and not included in this
Ohio 44149 (US) specification
• SAKOSKE, George, E.
Independence
OH 44131 (US)
EP 2 705 005 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 2 705 005 B1

Description

TECHNICAL FIELD

5 [0001] This invention relates to glass and enamel compositions, methods of forming enamel compositions, and methods
of forming an enamel on a substrate.

BACKGROUND

10 [0002] Lead-free and cadmium-free glass compositions are generally used to form glass frits which are, in turn, used
to formulate glass enamel compositions. These glass/glass ceramic enamel compositions are useful for forming deco-
rative coatings for glassware, chinaware, architectural glass and the like. They are especially useful in forming colored
borders around glass sheets used for automotive windshields, sidelights, and backlights. These colored borders enhance
the appearance as well as prevent UV degradation of underlying adhesives.
15 [0003] In general, these enamel compositions contain a glass frits, a colorant and an organic vehicle. They are applied
to a desired substrate and subsequently fired to burn off the organic vehicle and fuse the frit, thus bonding the enamel
coating to the substrate.
[0004] For example, automotive designs employ a black glass-ceramic enamel obscuration band around the periphery
of glass windshields to hide unevenness and protect the underlying adhesive from ultraviolet degradation. Architectural,
20 appliance, and container/dishware glass applications often include glass ceramic materials for decorative purposes.
[0005] With glass frit development there is usually a compromise involved with the final properties of the frit. In general,
glass frits that have low melting ranges have average chemical durability and relatively high thermal expansions, while
frits with high melting ranges have above average/excellent durability and relatively low thermal expansion. Therefore,
a need exits to formulate a glass and glass enamel compositions having low firing, low expansion, and good chemical
25 durability. Such glasses and glass enamels have been developed, which have low firing, acceptable chemical durability
and reasonable expansion, but they typically require the toxic lead oxide.
[0006] The document US 2010/009836 relates to low-firing, high durability glass and enamel compositions. The com-
positions disclosed therein are similar, but deviate from the ones disclosed in the current invention.

30 SUMMARY

[0007] The following presents a simplified summary of the invention disclosed herein in order to provide a basic
understanding of some aspects of the invention. This summary is not an extensive overview of the invention. It is intended
to neither identify key or critical elements of the invention nor delineate the scope of the invention. Its sole purpose is to
35 present some concepts of the invention in a simplified form as a prelude to the more detailed description that is presented
later.
[0008] In accordance with one aspect, an enamel composition is provided. More particularly, in accordance with this
aspect, the enamel composition includes a solid portion including a frit portion. The frit portion includes, prior to firing:
30 to 50 wt% of SiO 2; 4.5 to 20.2 wt% of Cs2O; 6.1 to 11.5 wt% of Na2O; 6.5 to 20.2 wt% of B2O3; 8 to 25 wt% of ZnO;
40 3.4 to 12.3 wt% of TiO 2; 0 to 40 wt% of Bi2O3; and 0 to 7 wt% of F.
[0009] In accordance with another aspect, a method for forming an enamel composition is provided. More particularly,
in accordance with this aspect, the method involves combining 30 to 50 wt% of SiO2; 4.5 to 20.2 wt% of Cs2O; 6.1 to
11.5 wt% of Na2O; 6.5 to 20.2 wt% of B2O3; 8 to 25 wt% of ZnO; 3.4 to 12.3 wt% of TiO2; 0 to 40 wt% of Bi2O3; and 0
to 7 wt% of F.
45 [0010] In accordance with yet another aspect, a method of forming an enamel on a substrate. More particularly, in
accordance with this aspect, the method involves providing an enamel composition on the substrate, the enamel com-
position containing a solid portion, the solid portion containing a frit portion, the frit portion containing, prior to firing: 30
to 50 wt% of SiO 2; 4.5 to 20.2 wt% of Cs2O; 6.1 to 11.5 wt% of Na2O; 6.5 to 20.2 wt% of B2O3; 8 to 25 wt% of ZnO; 3.4
to 12.3 wt% of TiO2; 0 to 40 wt% of Bi2O3; and 0 to 7 wt% of F; and firing the enamel composition and the substrate at
50 a temperature sufficient to adhere the enamel composition to the substrate.
[0011] To the accomplishment of the foregoing and related ends, the invention, then, involves the features hereinafter
fully described and particularly pointed out in the claims. The following description set forth in detail certain illustrative
embodiments of the invention. These embodiments are indicative, however, of but a few of the various ways in which
the principles of the invention may be employed. Other objects, advantages and novel features of the invention will
55 become apparent from the following detailed description of the invention.

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 EP 2 705 005 B1

DETAILED DESCRIPTION OF THE INVENTION

[0012] Glass sheets for automotive use are generally coated with the ceramic enamel composition and then subjected
to a forming process at elevated temperatures. During this treatment the enamel melts and fuses to the glass substrate
5 and the glass is formed into a desired final shape. However, conventional coatings exhibit a tendency to adhere to the
material covering the forming die, such as a fiberglass or metal fiber covered die, because these conventional enamels
have a low viscosity after melting and stick to other materials at high temperature. Accordingly, these materials are not
suitable for use in glass forming processes in which the heated glass coated with enamel contacts a material-covered
forming die.
10 [0013] Various approaches have been suggested in order to facilitate the forming of glass sheets with a ceramic
enamel coated thereon, withstanding of the elevated bending or forming temperatures, and repeated contact of the glass
sheet and the covered forming die without the enamel adhering to the forming die. For example, bismuth oxide-containing
formulations have been proposed.
[0014] However, certain of the bismuth containing systems produce a weak glass, such as when lithium is present,
15 and have poor silver bleed-through properties, as well as inadequate anti-stick properties. As a further problem, a number
of conventional ceramic enamel systems employ a lead-containing glass frit. For environmental considerations it is
desirable to avoid the use of any lead-containing system. Currently, many of the lead-free glass frits suitable for automotive
enamel use lithium ions. If not carefully controlled, however, the use of lithium can cause undesirable stresses and
substrate breakage.
20 [0015] Also, while some of the conventional enamel systems may perform fairly well in conventional glass forming
processes, some are not satisfactory for use in newly-developed "deep bend" processes for forming automotive glass.
It is essential that the enamel compositions also possess adequate resistance to certain chemical agents, which they
may contact, and many of the prior art compositions fail in this respect.
[0016] Conventional enamel compositions suffer from one or more of the deficiencies noted above, making it desirable
25 to provide a composition which avoids these shortcomings. The present invention provides such ceramic enamel com-
positions, a method for employing the compositions, and substrates coated therewith.
[0017] The present invention provides a glass composition and glass frit produced therefrom which can be used in
producing enamels. In particular, the invention relates to glass frit compositions, and glasses, ceramics, and enamels
made therefrom, which include SiO2, Cs2O, Na2O, B2O3, ZnO, and TiO2, and optionally Bi2O3 and F. The glass frits can
30 have one or more of the following advantages: improved chemical durability (e.g., good acid resistance); low thermal
expansion coefficient (TEC) (e.g., < 8.5 ppm/°C); and relatively low firing temperatures (e.g., < 593°C).
[0018] Enamel compositions of the invention include a glass frit portion, which in turn includes a combination of the
oxides of silicon, cesium, sodium, boron, zinc, and titanium, and optionally bismuth oxides and fluoride ion.
[0019] The components of the inventive compositions, articles and methods are detailed herein below. Compositional
35 percentages are by weight. All compositional percentages are by weight and are given for a blend prior to firing. Details
on each ingredient follow.

Frit (Glass) Component

40 [0020] The glass frit portions of the glass include SiO2, Cs2O, Na2O, B2O3, ZnO, and TiO2. The frit portions can
optionally include Bi2O3 and F. The frit portions herein include SiO2: 30-50 wt%, preferably 32-48 wt% and more preferably
34-38 wt%; Cs2O: 4.5-20.2 wt%; preferably 5.5-18.5 wt% and more preferably 6.5-16.5 wt%; Na2O: 6.1-11.5 wt%;
preferably 7.5-11.3 wt% and more preferably 8.5-11.1 wt%; B2O3; 6.5-20.2 wt%; preferably 7.5-18.5 wt% and more
preferably 8-16.5 wt%; ZnO: 8-25 wt%; preferably 9-23 wt% and more preferably 10-20 wt%; TiO2: 3.4-12.3 wt%;
45 preferably 4.3-11.3 wt% and more preferably 5.5-10.3 wt%; Bi2O3: 0-40 wt%; preferably 5-35 wt% and more preferably
10-20 wt%; and F: 0-7 wt%; preferably 1.5-6.5 wt% and more preferably 2.5-5.5 wt%.
[0021] In one embodiment, the frit portions include, prior to firing, 30 to 50 wt% of SiO2; 4.5 to 20.2 wt% of Cs2O; 6.1
to 11.5 wt% of Na2O; 6.5 to 20.2 wt% of B2O 3; 8 to 25 wt% of ZnO; 3.4 to 12.3 wt% of TiO2; 0 to 40 wt% of Bi2O3; and
0 to 7 wt% of F. In another embodiment, the frit portions include, prior to firing, 32 to 48 wt% of SiO 2; 5.5 to 18.5 wt%
50 of Cs2O; 7.5 to 11.3 wt% of Na2O; 7.5 to 18.5 wt% of B2O3; 9 to 23 wt% of ZnO; 4.3 to 11.3 wt% of TiO2; 5 to 35 wt%
of Bi2O3; and 1.5 to 6.5 wt% of F. In yet another embodiment, the frit portions include, prior to firing, 34 to 38 wt% of
SiO 2; 6.5 to 16.5 wt% of Cs2O; 8.5 to 11.1 wt% of Na2O; 8 to 16.5 wt% of B2O3; 10 to 20 wt% of ZnO; 5.5 to 10.3 wt%
of TiO2; 10 to 20 wt% of Bi2O3; and 2.5 to 5.5 wt% of F.
[0022] Other embodiments are possible, using, for example, a combination of ranges of oxides indicated hereinabove
55 as "broad," "preferred," and "more preferred" in various combinations, so long as such combinations of ranges can add
up to 100 wt%. For example, the glass frit compositions include, prior to firing, 30 to 50 wt% of SiO2; 5.5 to 18.5 wt% of
Cs2O; 8.5 to 11.1 wt% of Na2O; 6.5 to 20.2 wt% of B2O3; 9 to 23 wt% of ZnO; 5.5 to 10.3 wt% of TiO2; 0 to 40 wt% of
Bi2O3; and 1.5 to 6.5 wt% of F. In another embodiment, the glass frit compositions include, prior to firing, 32 to 48 wt%

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 EP 2 705 005 B1

of SiO2; 6.5 to 16.5 wt% of Cs2O; 6.1 to 11.5 wt% of Na2O; 7.5 to 18.5 wt% of B2O3; 10 to 20 wt% of ZnO; 3.4 to 12.3
wt% of TiO 2; 5 to 35 wt% of Bi2O3; and 2.5 to 5.5 wt% of F. In yet another embodiment, the glass frit compositions
include, prior to firing, 34 to 38 wt% of SiO2; 4.5 to 20.2 wt% of Cs2O; 7.5 to 11.3 wt% of Na2O; 8 to 16.5 wt% of B2O3;
8 to 25 wt% of ZnO; 4.3 to 11.3 wt% of TiO2; 10 to 20 wt% of Bi2O3; and 0 to 7 wt% of F.
5 [0023] Secondary, optional oxides can be added to frits according to the formulations in the preceding two paragraphs.
In one embodiment, at least one oxide selected from the group consisting of La2O3: 0.1-1 wt%, preferably 0.3-1 wt%,
more preferably 0.5-1 wt%; Nb2O5: 0.1-1 wt%, preferably 0.3-1 wt%, more preferably 0.5-1 wt%; MnO 2: 0.1-1 wt%,
preferably 0.3-1 wt%, more preferably 0.5-1 wt%; CeO2: 0.1-1 wt%, preferably 0.3-1 wt%, more preferably 0.5-1 wt%;
MoO3: 0.1-1 wt%, preferably 0.3-1 wt%, more preferably 0.5-1 wt%; and WO3: 0.1-1 wt%, preferably 0.3-1 wt%, more
10 preferably 0.5-1 wt% is added to the frit portions. In one embodiment, the total amount of the secondary oxides is 0.1
to 5 wt% of the frit portion. Combinations of ranges of secondary oxides indicated hereinabove as "broad," "preferred,"
and "more preferred" in various combinations are possible, so long as such combinations of ranges can add up to 5 wt%
of the frit portion. Addition of these oxides can improve melt ability and/or adhesion of the enamel composition.
[0024] Additional oxides can be added to any previously described embodiment to improve chemical resistance of the
15 enamel composition. In one embodiment, at least one selected the group consisting of Al2O3: 0.1-4 wt%, preferably
0.5-4 wt%, more preferably 1-4 wt%; and BaO: 0.1-3 wt%, preferably 0.5-3 wt%, more preferably 1-3 wt% is added to
the frit portions.
[0025] As can be seen above, the composition of the glass frits useful in this invention can be adapted over a broad
range of oxide compositions. Glasses can be formulated according to the principal glass and enamel compositions
20 above, together with, optionally one or more secondary and/or additional oxides. The frit compositions can be used to
form glass enamel compositions.
[0026] The glass frits can be formed by any suitable techniques. In one embodiment, the glass frits are formed by
blending the starting materials (e.g., oxides and optionally fluoride) and melting together at a temperature of 2000 to
2400 °F for 45 to 75 minutes to form a molten glass having the desired composition. The molten glass formed can then
25 be suddenly cooled by any suitable technique including water quenching to form a frit. The frit can then be ground using,
for example, milling techniques to a fine particle size, from 1 to 8 microns, preferably 2 to 6 microns, and more preferably
3 to 5 microns.
[0027] In one embodiment, the frit portions are substantially free of at least one of the elements selected from the
group consisting of lead, cadmium, and bismuth. In another embodiment, the subject frit portions are substantially free
30 of lead and cadmium, but the frit portions include bismuth. As used herein, "substantially free of an element" means that
the frit portions do not include the element in any form, or the element or any compounds that contain the element are
not intentionally added to the frit portions. For example, in some embodiments, all the materials used in forming the frit
portions are substantially free of at least one of the elements selected from the group consisting of lead, cadmium, and
bismuth. In another embodiment, a method of making the frit portions does not involve combining at least one of the
35 elements selected from the group consisting of lead, cadmium, and bismuth with the frit portions and/or precursor
materials of the frit portions.
[0028] The frit portions can have advantageously a low thermal expansion coefficient (TEC) from 25°C to 300°C. The
method of determining the TEC is described in detail below. In one embodiment, the frit portions have 8.5 x 10-6 0C-1 or
less of TEC. In another embodiment, the frit portions have 8.3 x 10-6 0C-1 or less of TEC. In yet another embodiment,
40 the frit portions have 8.0 x 10-6 0C-1 or less of TEC. In still yet another embodiment, the frit portions have 7.8 x 10-6 0C-1
or less of TEC. In another embodiment, the frit portions have 7.6 x 10-6 0C-1 or less of TEC. In one embodiment, the frit
portions have 5 x 10-6 0C-1 or more.
[0029] The frit portions can have advantageously a low firing temperature. The firing temperature is the temperature
where the glass frit has sufficient time to flow and fuse within a 15 minute fire and yield a glossy smooth surface. In one
45 embodiment, the frit portions have 593°C or less of firing temperature. In another embodiment, the frit portions have
582°C or less of firing temperature. In yet another embodiment, the frit portions have 571°C or less of firing temperature.

Enamel composition

50 [0030] The enamel compositions can include the glass frit compositions and vehicle with the optional presence of a
pigment such as a metal oxide pigment, as described in detail below. In one embodiment, the enamel compositions
further include crystallization materials, reducing agents, and conductive metals. The solid portion of the enamel com-
position is considered to be the glass frit portion, the pigment, the crystallization material, the reducing agents, and the
metals, taken together.
55 [0031] The enamel compositions can include any suitable amount of the frit portion. In one embodiment, the enamel
compositions include 60 to 85 wt% of the frit portion. In another embodiment, the enamel compositions include 65 to 83
wt% of the frit portion. In yet another embodiment, the enamel compositions include 70 to 80 wt% of the frit portion.
[0032] In one embodiment, the glass enamel compositions are formulated with conductive metals such as silver (e.g.,

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 EP 2 705 005 B1

silver particles) in order to provide conductive coatings for use, for example, as defrost circuits for automotive blacklites
and windshield. In such areas of utility, color maintenance, bond strength, solderability, absence of silver migration and
abrasion resistance are required performance characteristics. It is to be noted that the compositions containing the
subject glass frits are applicable for use in conjunction with such conductive coatings for the above noted areas of utility.
5 When the conductive coatings are applied in overlapping relationship with the enamels containing the glass frits, per-
formance improvements as observed after heat treatment can include good resistance to silver migration into the enamel,
substantial reduction of undesirable blue haze of the buss bar and performance of solder connections.
[0033] In one embodiment, when the enamel compositions include silver metal, the enamel compositions include 10
to 60 wt% of the silver metal. In another embodiment, the enamel compositions include 15 to 55 wt% of the silver metal.
10 In yet another embodiment, the enamel compositions include 20 to 50 wt% of the silver metal.

Organic Vehicle

[0034] The glass frits and enamel compositions can be combined with a vehicle. The glass frits can be combined with
15 the vehicle to form a printable enamel paste (e.g., printable enamel paste). The vehicle to be employed in the paste can
be selected on the basis of its end use application. In one embodiment, the vehicle adequately suspends the particulates
and burn off completely upon firing of the paste on the substrate. Vehicles are typically organic. Examples of organic
vehicles include compositions based on pine oils, vegetable oils, mineral oils, low molecular weight petroleum fractions,
tridecyl alcohols, synthetic and natural resins, and the like. In another embodiment, surfactants and/or other film forming
20 modifiers can also be included.
[0035] The specific vehicle and amounts employed are selected based upon the specific components of the paste
and the desired viscosity. The enamel paste in general can contain from 60 to 85 wt% solids as above described, more
preferably 65 to 83 wt% and 15 to 40 wt% of the suitable organic vehicle, more preferably 17 to 35 wt%.
[0036] The viscosity of the paste can be adjusted depending on application techniques on a substrate such as screen
25 printing, roll coating or spraying. The vehicles can be modified by viscous resins such as vinyl resins, solvents, film
formers such as cellulosic materials, and the like. For purposes of screen-printing, viscosities ranging from 10,000 to
80,000 and preferably 35,000 to 65,000 centipoises at 20° C, as determined on a Brookfield Viscometer, #7 spindle at
20 rpm, are appropriate.

30 Pigment

[0037] In certain embodiments, the glass frit can be combined with a pigment, such as a mixed metal oxide pigment.
When used, such pigments generally constitute no greater than 30 wt%, preferably 0.1-30 wt%, more preferably 1-25
wt%, still more preferably 2-20 wt%, of the glass enamel compositions herein, depending upon the range of color, gloss,
35 and opacity (e.g., transmittance) desired.
[0038] Keeping in mind the general preference for completely lead-free and cadmium-free compositions for some
applications such as food and beverages, useful pigments may come from several of the major classifications of complex
inorganic pigments, including corundum-hematite, olivine, priderite, pyrochlore, rutile, spinel, and spinel. Other categories
such as baddeleyite, borate, garnet, periclase, phenacite, phosphate, sphene and zircon may be suitable in certain
40 applications.
[0039] The glass frit (e.g., finely ground glass frit) can be combined with pigments such as a mixed metal oxide pigment,
any other type of metal powder, metal resonate, or other material of choice. Typical complex metal oxide pigments used
to produce black colors in the automotive industry would include oxides of copper, chrome, iron, cobalt, nickel, manga-
nese, and the like. Although these black spinel pigments are preferred for use in the automotive industry, other metal
45 oxide pigments to produce other various colors can be combined with the glass frit compositions in this invention.
Examples of other end uses include architectural, appliance, and beverage industries.
[0040] Examples of commercially available pigments include CuCr2O4, (Co,Fe)(Fe,Cr)2O4, (NiMnCrFe), and the like.
Specific examples available from Ferro Corporation, Washington, Pennsylvania include pigments having the following
Ferro Corporation product numbers: 2980 which is a cobalt chromium iron black pigment and V792 pigment which is a
50 nickel manganese iron chromium black pigment.

Crystalline Material

[0041] The enamel compositions can contain solids of crystalline seed materials along with the frit compositions herein
55 to promote crystallization. Examples of crystalline seed materials include zinc silicates, aluminum silicate, zinc borates,
zinc titanates, bismuth silicate and combinations thereof. Specific examples of crystalline seed materials include Zn2SiO4,
2ZnO·3TiO2, ZnTiO3, ZnO·B2O3, 3ZnO·B2O3, and 5ZnO·2B2O3. Further information on crystalline materials can be
found in, for example, U.S. Pat. No. 5,153,150 and U.S. Pat. No. 5,714,420 patents, which are hereby incorporated by

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 EP 2 705 005 B1

reference. In one embodiment, the enamel compositions include zinc silicate (such as Zn2SiO4) or bismuth silicate (such
as Bi2SiO4). In another embodiment, the enamel compositions include product number 2099, which is a zinc silicate
seed material or product number 2077, which is a bismuth silicate seed material and commercially available at Ferro
Corporation, Washington, Pennsylvania.
5 [0042] The enamel compositions can include any suitable amount of the solids of crystalline seed materials. In one
embodiment, the enamel compositions include 0.1 to 20 wt%, preferably 0.5 to 10 wt%, and more preferably 1 to 5 wt%
of at least one crystalline material. The crystalline seed material can yield anti-stick properties advantageous in press-
bend forming operations such as those used in the automotive glass industry.

10 Reducing agent

[0043] In certain embodiments, the enamel compositions include a reducing agent. For example, the enamel compo-
sitions include metals such as silicon, added separately from any oxide, in an amount of 0.1 to 5 wt%, preferably 0.5 to
4.5 wt% more preferably 1 to 4 wt%. Silicon metal is a reducing agent which prevents or minimizes the extent of oxidation,
15 especially of silver metal in conductive traces. Sulfides also can act as reducing agents. Such reducing agents have the
desired effect of preventing or minimizing the extent of silver migration into a glass substrate or coating. Other metals
that enhance the desired properties of the glass enamels herein or at a minimum, do not degrade such desired properties,
are also envisioned herein. For example, metals from which the oxides used in the frits or pigments herein may be used,
keeping in mind the preferences for low or essentially zero levels of heavy metals such as lead and cadmium.
20 [0044] In one embodiment, the solid portions include 30 to 95 wt% of the frit portion; 0.1 to 30 wt% pigment; 0.1 to 15
wt% crystalline material; 10 to 60 wt% silver; and optionally 0.1 to 5 wt% reducing agent.

Dispersing Surfactant

25 [0045] In certain embodiments, the enamel compositions include a dispersing surfactant. The dispersing surfactant
assists in pigment wetting, when an insoluble particulate inorganic pigment is used. A dispersing surfactant typically
contains a block copolymer with pigment affinic groups. Examples of surfactants include surfactants sold under the
Disperbyk® and Byk® trademarks by Byk Chemie of Wesel, Germany, such as Disperbyk 162 and 163, which are
solutions of high molecular weight block copolymers with pigment affinic groups, and a blend of solvents (xylene, buty-
30 lacetate and methoxypropylacetate). Disperbyk 162 has these solvents in a 3/1/1 ratio, while the ratio in Disperbyk 163
is 4/2/5. Disperbyk 140 is a solution of alkyl-ammonium salt of an acidic polymer in a methoxypropylacetate solvent.

Rheological Modifier

35 [0046] In certain embodiments, the enamel compositions include a rheological modifier. The rheological modifier can
be used to adjust the viscosity of the enamel composition. A variety of rheological modifiers can be used. Examples of
rheological modifiers include those sold under the Byk®, Disperplast®, and Viscobyk® trademarks, available from Byk
Chemie. They include, for example, BYK 400 series, such as BYK 411 and BYK 420, (modified urea solutions); BYK
W-900 series, (pigment wetting and dispersing additives); Disperplast series, (pigment wetting and dispersing additives
40 for plastisols and organosols); and Viscobyk series, (viscosity depressants for plastisols and organosols).

Flow aid

[0047] In certain embodiments, the enamel compositions include a flow aid. The flow aid is an additive used to control
45 the viscosity and rheology of enamel compositions, which affects the flow properties of liquid systems in a controlled
and predictable way. Rheology modifiers are generally considered as being either pseudoplastic or thixotropic in nature.
Examples of flow aids include those sold commercially under the Additol®, Multiflow®, and Modaflow® trademarks by
UCB Surface Specialties of Smyrna, Georgia. Specific examples include Additol VXW 6388, Additol VXW 6360, Additol
VXL 4930, Additol XL 425, Additol XW 395, Modaflow AQ 3000, Modaflow AQ 3025, Modaflow Resin, and Multiflow Resin.
50
Adhesion promoter

[0048] In certain embodiments, the enamel compositions include an adhesion promoter. Adhesion promoting polymers
can be used to improve the compatibility between a substrate and enamel. Examples of adhesion promoters include
55 those sold by GE Silicones of Wilton, Connecticut under the Silquest®, CoatOSil®, NXT®, XL-Pearl™ and Silcat®
trademarks, including the following product numbers, sold under the Silquest® trademark: A1101, A1102, A1126, A1128,
A1130, A1230, A1310, A162, A174, A178, A187, A2120. For example, Silquest® A-187 is (3-glycidoxypropyl) trimeth-
oxysilane, which is an epoxysilane adhesion promoter.

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 EP 2 705 005 B1

Stabilizers

[0049] In certain embodiments, the enamel compositions include light or UV stabilizers. Light or UV stabilizers are
classified according to their mode of action: UV blockers - that act by shielding the substrate from ultraviolet light; or
5 hindered amine light stabilizers (HALS) - that act by scavenging the radical intermediates formed in a photo-oxidation
process. In one embodiment, the compositions of the invention include 0.1 to 2 wt% of a light stabilizer, preferably 0.5
to 1.5%, and further include 0.1 to 4 wt% of a UV blocker, preferably 1 to 3 wt%.
[0050] Examples of Light stabilizers and UV blockers include those sold under the Irgafos®, Irganox®, Irgastab®,
Uvitex®, and Tinuvin® trademarks by from Ciba Specialty Chemicals, Tarrytown, NY, including product numbers 292
10 HP, 384-2, 400, 405, 411L, 5050, 5055, 5060, 5011, all using the Tinuvin trademark. Suitable UV blocking agents include
Norbloc 7966 (2-(2’ hydroxy-5’ methacryloxyethylphenyl)-2H-benzotriazole); Tinuvin 123 (bis- (2,2,6,6-tetramethyl-1-(oc-
tyloxy)-4-piperidinyl) ester); Tinuvin 99 (3- (2H-benzotriazole-2-yl) 5-(1,1-dimethyl ethyl) -4-hydroxybenzenepropanoic
acid, C7-9-branched alkyl esters) Tinuvin 171 (2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol). Products sold under
the Norbloc® trademark are available from Janssen Pharmaceutica of Beerse, Belgium. Suitable hindered amine light
15 stabilizers (HALS) are sold by the Clariant Corporation, Charlotte, NC, under the Hostavin® trademark, including Hostavin
845, Hostavin N20, Hostavin N24, Hostavin N30, Hostavin N391, Hostavin PR31, Hostavin ARO8, and Hostavin PR25.

Substrate

20 [0051] The invention can provide a substrate having fired thereon an enamel compositions (e.g., enamel paste) of the
invention. Any suitable substrate can be used in the subject invention. Examples of substrates include glass, ceramic
or other non-porous substrates. Specific examples of substrates include an automotive glass substrate, architectural
glass, appliances, LED’s (light emitting diodes), solar substrates, electronic sensor devices, and beverage containers.

25 Method of forming enamel on substrate

[0052] To prepare the enamel compositions of the invention, the necessary frit or frits are ground to a fine powder
using conventional techniques including milling. The frit component is then combined with the other solids components.
The solids are then mixed with the necessary vehicle to form the enamel paste. The viscosity is adjusted as desired.
30 [0053] Once the enamel paste is prepared, it can be applied to the substrate by any suitable technique. The enamel
paste can be applied by screen printing, decal application, spraying, brushing, roller coating or the like. Screen printing
can be preferred when the paste is applied to a glass substrate.
[0054] After application of the paste to a substrate in a desired pattern, the applied coating is then fired to adhere the
enamel to the substrate. The firing temperature is generally determined by the frit maturing temperature, and preferably
35 is in a broad temperature range. Typically, the firing range is in the range of 538°C to 677°C, more preferably in the
range of 549°C to 649°C, and most preferably 560°C to 621°C.
[0055] A glass substrate can be colored and/or decorated by applying any enamel composition described herein to
at least a portion of a substrate, for example, a glass substrate such as a glass sheet, or automotive glass, (e.g.,
windshield). An enamel composition can be applied in the form of a paste as disclosed herein. Glass, ceramic or other
40 non-porous substrates can also be sealed hermetically together using enamel compositions described herein.
[0056] In one embodiment, the method of forming an enamel composition involves combining: 30 to 50 wt% of SiO2;
4.5 to 20.2 wt% of Cs2O; 6.1 to 11.5 wt% of Na2O; 6.5 to 20.2 wt% of B2O 3; 8 to 25 wt% of ZnO; 3.4 to 12.3 wt% of
TiO2; 0 to 40 wt% of Bi2O3; and 0 to 7 wt% of F. In another embodiment, the method of forming an enamel on a substrate
involves providing an enamel composition on the substrate, the enamel composition containing a solid portion, the solid
45 portion containing a frit portion, the frit portion containing, prior to firing: 30 to 50 wt% of SiO2; 4.5 to 20.2 wt% of Cs2O;
6.1 to 11.5 wt% of Na2O; 6.5 to 20.2 wt% of B2O3; 8 to 25 wt% of ZnO; 3.4 to 12.3 wt% of TiO2; 0 to 40 wt% of Bi2O3;
and 0 to 7 wt% of F; and firing the enamel composition and the substrate at a temperature sufficient to adhere the enamel
composition to the substrate. In some applications, preferably, the frit portion and thus the enamel composition is free
of bismuth or oxides thereof. Specifically, in applications where the enamel composition is intended for processing in a
50 reducing atmosphere, it may be best if the composition is free of bismuth oxide for the presence of bismuth oxide may
lead to the formation of metallic bismuth, which is generally an undesirable result.
[0057] The enamel composition can be applied to the entire surface of a substrate, or to only a portion thereof, for
example the periphery. The method can involve forming a glass whereby the glass substrate is heated to an elevated
temperature and subjected to a forming pressure to bend the glass substrate. In particular, bending the glass substrate
55 can involve heating the glass substrate to an elevated temperature of, for example, at least 570°C, at least 600°C, at
least 625°C, or at least 650°C. Upon heating, the glass is subjected to a forming pressure, e.g., gravity sag or press
bending in the range of 690 to 34474 Pa, or 6900 to 27579 Pa, or typically 13790 to 20684 Pa, with a forming die.

7
 EP 2 705 005 B1

Examples

[0058] The following compositions represent exemplary embodiments of the invention. They are presented to explain
the invention in more detail, and do not limit the invention. Glass frit compositions and enamel compositions according
5 to the present invention are given in Tables 1-6, Frits 1-27, and Enamels 1-21. The results of the following investigations
are shown in Tables 1-6.
[0059] The glass frit compositions are produced by mixing together raw materials as shown in Tables 1,2 and 3. The
mixed raw batch compositions are melted at 2300° F for 45 minutes, followed by sudden cooling, using water quenching.
The glass compositions are then ground to a fine particle size, preferably between 2 to 6 microns using a ball mill. The
10 finely ground powder frits are then used to form glass enamel compositions.
[0060] The enamel compositions are produced by using some of the glass frit compositions and other compositions
such as pigments as shown in Tables 4,5 and 6. The finely ground glass frits are combined with a mixed metal oxide
pigment to form enamel compositions. V792 pigment is a nickel manganese iron chrome pigment, 2099 is a zinc silicate
seed material and 2077 is a bismuth silicate seed material. Both materials are commercially available at Ferro Corporation,
15 Washington, Pennsylvania. Further, the solids of the enamel compositions are dispersed and suspended in a vehicle
selected for the end use application to form the enamel paste. Although not shown, the glass frit composition of the
present investigation can be employed in producing enamel formulations in the same manner as the frits of Enamels 1-20.
[0061] Testing is performed by combining 4.0 grams of the glass frit or enamel composition with a pine oil based
vehicle and screen printing the resulting dispersion onto a microscope slide or automotive glass substrate at a wet
20 thickness of 2 mils. The slides or automotive glass substrate are then fired at various temperatures to determine the
"firing temperature," FT, or "minimum firing temperature," MF. The FT is the temperature where the glass has sufficient
time to flow and fuse within a 15 minute fire and yield a glossy smooth surface. The MF is the temperature where the
enamel has sufficient time to flow and fuse in a 3 minute fire and yield an enamel without interconnected porosity. Preheat
time is 10 and 3 minutes at 427°C for FT and MF, respectively.
25 [0062] A thermal expansion coefficient (TEC) is determined from 25°C to 300°C using an Orton model 1000R dilatom-
eter. The TEC is reported in the temperature range of 25° C to 325° C and has units of 10-6 0C-1. Glass transition
temperatures (Tg) and dilatometric softening temperatures (Td) are measured using the dilatometer.
[0063] Residual stress in transparent glass that results from enamel coatings is measured by utilizing ASTM C-978-87.
The technique uses polarized light and a quartz wedge attachment with an integral polarizer. A cross section of enamel
30 coated glass with 0.25 inches wide section having mutually perpendicular sides is prepared. These samples are annealed
at 1020° F for 15 minutes and used for stress measurements.
[0064] Gloss measurement of fired glass enamels are recorded at an angle of incident 45° using Gardco Novogloss
instrument. All trials are fired at test temperatures for 3 minutes with no preheat and gloss values are recorded.
[0065] Room temperature chemical durability is determined for 10 wt% citric acid, 10 wt% hydrochloric acid, and 4
35 wt% acetic acid solutions. The acid resistance is evaluated by utilizing ASTM C724-91. Fired trials are exposed to the
10 wt% citric acid solution for 15 minutes at room temperature, 10 wt% hydrochloric acid solution for 10 minutes at room
temperature, and 4 wt% acetic acid solution for 1 minute at room temperature. They are graded according to the following
scale:

40 Grade 1-No apparent attack

Grade 2-Appearance of iridescence or visible stain on the exposed surface when viewed at an angle of 45°, but not
apparent when viewed at angles less than 30°.
Grade 3-A definite stain which does not blur reflected images and is visible at angles less than 30°.
Grade 4-Definite stain with a gross color change or strongly iridescent surface visible at angles less than 30° and
45 which may blur reflected images.
Grade 5-Surface dull or matte with chalking possible.
Grade 6-Significant removal of enamel with pinholing evident.
Grade 7-Complete removal of enamel in exposed area.

50
Table 1. Glass frit formulations in wt%, firing temperatures, and properties
Oxides (wt.%) 1 2 3 4 5 6
SiO 2 36.6 36.6 34.5 35.5 36.6 36.6
55 Na2O 11.2 9.6 10.5 11 11.2 11.2
Cs2O 9.8 10.5 12.5 5.6 9.3 8.5
Al2O3 1 2.5 2 3.4 1.5 3.5

8
 EP 2 705 005 B1

(continued)

Oxides (wt.%) 1 2 3 4 5 6
B2O3 12.8 14.3 14.5 18 14.1 13.9
5 ZnO 14.3 16.5 14.8 16 12 11
TiO 2 9.3 7.4 7.4 5.4 10.3 10.3
F 5 2.6 3.8 5.1 5 5
TEC (25-325°)C 8.38 8.12 8.53 8 8.33 8.2
10
Tg (°C) 461 470 453 444 454 447
Td(°C) 504 511 504 493 509 496
Firing Temperature (F) 1080 1080 1060 1070 1080 1090
10 % citric Acid 3 2-3 5 3-4 2-3 3-4
10 % hydrochloric acid 3-4 3 5 3-4 3 3-4
15 4 % acetic acid 1-2 1-2 2-3 2-3 1-2 1-2
Stress (psi) 33 121 67 236 32 32

Table 2. Glass frit formulations in wt%, firing temperatures, and properties

20
Oxides (wt.%) 7 8 9 10 11 12 13 14 15 16 17 18
SiO2 40.5 37 38.5 37.5 32 34 36.6 36.6 36.6 35.6 35.7 36.6
Na2O 8.5 8.5 8.5 8.5 8.5 8.5 9 10 9.6 11.1 9.8 11.2
Cs2O 6.5 8.5 10.5 12.5 13.5 16.5 5.4 7.8 6.5 3.5 7.8 9.3
25
BaO 2 2 2 2 2 2 0 0 0 0 0 0
Al2O3 3.6 3.6 3.6 3.6 3.6 3.6 1 1 2.5 1.5 3.4 2.5
B2O3 8 8 8 8 8 8 19.4 16 16.3 19 20 12.6
ZnO 20.5 22 18.5 17.5 22 22 14.3 14.3 18.5 14.3 17 12.5
30 TiO2 5.4 5.4 5.4 5.4 5.4 5.4 9.3 9.3 7.4 9.3 0 10.3
F 0 0 0 0 0 0 5 5 2.6 5.7 6.3 5
CeO2 0.5 0.5 0.5 0.5 0.5 0 0 0 0 0 0 0
MnO2 0.5 0.5 0.5 0.5 0.5 0 0 0 0 0 0 0
La2O3 1 1 1 1 1 0 0 0 0 0 0 0
35
MoO3 1 1 1 1 1 0 0 0 0 0 0 0
Nb2O5 1 1 1 1 1 0 0 0 0 0 0 0
TEC (25-325°)C 7.46 8.14 7.71 8.66 9.39 9.04 8.32 8.16 7.5 8.37 8.11 8.47
Tg(°C) 515 510 508 507 499 498 442 447 474 439 426 444
40 Td(°C) 568 556 562 558 544 543 505 497 522 501 485 500
Firing Temperature (F) 1160 1140 1140 1140 1130 1120 1120 1100 1100 1100 1090 1090
10 % citric Acid 1 1 1 1-2 4-5 4-5 2-3 2-3 3-4 3-4 5 3-4
10 % hydrochloric acid 1 3 2-3 3 4-5 5 2-3 3-4 3-4 3-4 5 3-4
4 % acetic acid 1 1 1 1 2-3 2-3 1-2 1-2 1-2 2-3 2 1-2
45

Table 3. Glass frit formulations in wt%, firing temperatures, and properties

Oxides (wt.%) 19 20 21 22 23 24 25 26 27
50
SiO2 36.7 36.6 32.9 36.9 37.9 28.8 39.7 37.5 36.0
Na2O 9.0 4.5 2.5 3.5 5.5 2 7 7 7
Cs2O 8.5 9.3 9.3 9.3 7.3 7.3 10.85 9.05 6.05
Li2O 1.5 1 1 1 1 1 1.2 1.2 1.2
55 K2O 0 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Bi2O3 0 15 25 20 10 30 4 8 12
Al2O3 3 1.5 1.5 1.5 1.5 1.5 1.75 1.75 1.75

9
 EP 2 705 005 B1

(continued)

Oxides (wt.%) 19 20 21 22 23 24 25 26 27
B 2 O3 13 14 12 10 16 12 14 14 14
5 ZnO 13 4 2 2 6 4 10 10 10
TiO2 10.3 8.3 7.3 9.3 8.3 10.3 4.3 4.3 4.3
F 5 5 5 5 5 3.8 5 5 5
ZrO2 0 0 0 0 0 0 0.7 0.7 0.7
10
Y 2 O3 0 0 0 0 0 0 0 0 0.5

TEC (25-325°)C 9.34 8.93 8.74 9.13 8.78 7.7 9.45 9.54 9.26
Tg (°C) 434 434 431 434 433 428 435 425 425
Td(°C) 472 471 493 500 478 504 466 468 470
15 Firing Temperature (F) 1020 1020 1020 1030 1030 1100 1020 990 990
10 % Citric Acid 3 3-4 2-3 2-3 3-4 1 4 5 5
10 % hydrochloric acid 3-4 4-5 3-4 2 4-5 1 4-5 5-6 5
4 % acetic acid 1-2 1-2 2-3 1-2 2-3 1 2-3 3 2-3
20

Table 4. Black enamel formulations in wt%, firing data, and acid resistance performance data for pastes made with
selected frits from Table 1.
Enamel- Enamel- Enamel- Enamel- Enamel- Enamel- Enamel- Enamel-
25 Oxides (wt.%) 1 2 3 4 5 6 7 8
Frit-1 75 0 0 0 0 0 0 0
Frit-2 0 75 0 0 0 0 0 0
Frit-3 0 0 75 0 0 0 0 0
30 Frit-4 0 0 0 75 0 0 0 0
Frit-5 0 0 0 0 75 0 70.75 0
Frit-6 0 0 0 0 0 75 0 70.75
*V-792 25 25 25 25 25 25 23.58 23.58
*2099 0 0 0 0 0 0 5.66 5.66
35
Minimum
Firing
Temperature
(F) 1160 1160 1140 1140 1160 1150 1200 1180
10% citric acid 3 2-3 5 3-4 2-3 3-4 4 4
40
10%
hydrochloric 3-4 3 5 3-4 3 3-4 4 4
4% acetic acid 1-2 1-2 2-3 2-3 1-2 1-2 2 2

45

Table 5. Black enamel formulations in wt%, firing data, and acid resistance performance data for pastes made with
selected frits from Table 3.
Oxides (wt.%) Enamel-9 Enamel-10 Enamel-11 Enamel-12 Enamel-13 Enamel-14 Enamel-15
50 Frit-20 75 0 0 0 0 73 0
Frit-21 0 75 0 0 0 0 0
Frit-23 0 0 75 0 37.5 0 74
Frit-24 0 0 0 75 37.5 0 0
*V-792 25 25 25 25 25 21 20
55
*2077 0 0 0 0 0 4 4
Si-metal 0 0 0 0 0 2 2

10
 EP 2 705 005 B1

(continued)

Oxides (wt.%) Enamel-9 Enamel-10 Enamel-11 Enamel-12 Enamel-13 Enamel-14 Enamel-15

Minimum
5 Firing
Temperature
(F) 1090 1060 1110 1190 1160 1140 1130
10% citric acid 3-4 2-3 3-4 2 2-3 3 3
10%
10
hydrochloric 4-5 2 4-5 2-3 3 3-4 4
4% acetic acid 1-2 1-2 1-2 1 1-2 1-2 1-2

15 Table 6. Black enamel formulations in wt% and gloss at 45° with selected frits from Table 1 and Table 3.
Oxides (wt.%) Enamel-16 Enamel-17 Enamel-18 Enamel-19 Enamel-20 Enamel-21
Frit-5 70.75 0 73.5 0 0 0
Frit-6 0 70.75 0 73.5 0 0
20 Frit-20 0 0 0 0 76 76
Frit-23 0 0 0 0 0 0
V-792 23.58 23.58 24.5 24.5 20 20
2099 5.66 5.66 1.96 1.96 0 0
2077 0 0 0 0 4 4
25 Gloss at 1250° F 25.2 27.6 26.7 29.7 76.5 72.2
Gloss at 1275° F 28.8 33.8 45.3 33.2 80.2 84.2
Gloss at 1300° F 40.0 37.1 49.1 43.6 73.1 85.1
Gloss at 1325° F 49.0 40.4 50.8 43.5 71.7 80.2
30

[0066] These results demonstrate the excellent performance characteristics of the glass frits and enamel compositions
of the present invention, and particularly the low firing temperature, good chemical durability and thermal expansion
characteristics.

35

Claims

1. An enamel composition comprising a solid portion comprising a frit portion, the frit portion comprising, prior to firing:

40 30 to 50 wt% of SiO2;
4.5 to 20.2 wt% of Cs2O;
6.1 to 11.5 wt% of Na2O;
6.5 to 20.2 wt% of B2O3;
8 to 25 wt% of ZnO;
45 3.4 to 12.3 wt% of TiO2;
0 to 40 wt% of Bi2O3; and
0 to 7 wt% of F.

2. The enamel composition of claim 1, wherein the frit portion further comprises at least one selected from the group
50 consisting of:

0.1 to 1 wt% of La2O3;

0.1 to 1 wt% of Nb2O5;
0.1 to 1 wt% of MnO2;
55 0.1 to 1 wt% of CeO2;
0.1 to 1 wt% of MoO3; and
0.1 to 1 wt% of WO3, and

11
 EP 2 705 005 B1

a total amount of the oxides is 0.1 to 5 wt% of the frit portion.

3. The enamel composition of claim 1, wherein the frit portion further comprises at least one selected from the group
consisting of:
5
0.1 to 4 wt% of Al2O 3; and
0.1 to 3 wt% of BaO.

4. The enamel composition of claim 1, further comprising at least one crystalline seed material selected from the group
10 consisting of zinc borates, zinc silicates, zinc titanates, bismuth silicates and combinations thereof.

5. The enamel composition of claim 1 further comprising pigments.

6. The enamel composition of claim 1, wherein the frit portion has a firing temperature of 593 °C or less.
15
7. The enamel composition of claim 1, wherein the solid portion comprises:

60 to 85 wt% of the frit portion;

0.1 to 30 wt% of pigments;
20 0.1 to 15 wt% of crystalline materials;
10 to 60 wt% of silver; and optionally
0.1 to 5 wt% of reducing agents.

8. A method of forming an enamel composition, comprising:

25
combining:

30 to 50 wt% of SiO 2;
4.5 to 20.2 wt% of Cs2O;
30 6.1 to 11.5 wt% of Na2O;
6.5 to 20.2 wt% of B2O3;
8 to 25 wt% of ZnO;
3.4 to 12.3 wt% of TiO2;
0 to 40 wt% of Bi2O3; and
35 0 to 7 wt% of F.

9. The method of claim 8, further comprising:

combining at least one selected from the group consisting of:

40
0.1 to 1 wt% of La2O3;
0.1 to 1 wt% of Nb2O5;
0.1 to 1 wt% of MnO2;
0.1 to 1 wt% of CeO2;
45 0.1 to 1 wt% of MoO3; and
0.1 to 1 wt% of WO3.

10. The method of claim 8, further comprising:

50 combining at least one selected from the group consisting of:

0.1 to 4 wt% of Al2O3; and

0.1 to 3 wt% of BaO.

55 11. The method of claim 8, further comprising:

combining pigments; crystalline materials; optionally silver; and optionally reducing agents.

12
 EP 2 705 005 B1

12. A method of forming an enamel on a substrate, comprising:

providing an enamel composition on the substrate, the enamel composition comprising a solid portion, the solid
portion comprising a frit portion, the frit portion comprising, prior to firing:
5
30 to 50 wt% of SiO 2;
4.5 to 20.2 wt% of Cs2O;
6.1 to 11.5 wt% of Na2O;
6.5 to 20.2 wt% of B2O3;
10 8 to 25 wt% of ZnO;
3.4 to 12.3 wt% of TiO2;
0 to 40 wt% of Bi2O3; and
0 to 7 wt% of F; and

15 firing the enamel composition and the substrate at a temperature sufficient to adhere the enamel composition
to the substrate.

13. The method of claim 12, wherein the frit portion further comprises at least one selected from the group consisting of:

20 0.1 to 1 wt% of La2O3;

0.1 to 1 wt% of Nb2O5;
0.1 to 1 wt% of MnO2;
0.1 to 1 wt% of CeO2;
0.1 to 1 wt% of MoO3; and
25 0.1 to 1 wt% of WO3, and

a total amount of the oxides is 0.5 to 5 wt% of the frit portion.

14. The method of claim 12, wherein the frit portion further comprising at least one selected from the group consisting of:
30
0.1 to 4 wt% of Al2O 3; and
0.1 to 3 wt% of BaO.

15. The method of claim 12 wherein said enamel composition is bismuth-free.

35

Patentansprüche

1. Emailzusammensetzung mit einem festen Anteil, der einen Frittenanteil aufweist, wobei der Frittenanteil vor dem
40 Brennen aufweist: 30 bis 50 Gew.-% SiO2;

4,5 bis 20,2 Gew.-% Cs2O;

6,1 bis 11,5 Gew.-% Na2O;
6,5 bis 20,2 Gew.-% B2O3;
45 8 bis 25 Gew.-% ZnO;
3,4 bis 12,3 Gew.-% TiO2;
0 bis 40 Gew.-% Bi2O 3; und
0 bis 7 Gew.-% F.

50 2. Emailzusammensetzung gemäß Anspruch 1, wobei der Frittenanteil ferner zumindest eine Substanz aufweist, die
ausgewählt ist aus der Gruppe, die besteht aus:

0,1 bis 1 Gew.-% La2O3;

0,1 bis 1 Gew.-% Nb2O 5;
55 0,1 bis 1 Gew,-% MnO 2;
0,1 bis 1 Gew.-% CeO2;
0,1 bis 1 Gew.-% MoO 3; und
0,1 bis 1 Gew.-% WO3, und

13
 EP 2 705 005 B1

einer Gesamtmenge an Oxiden, die 0,1 bis 5 Gew.-% des Frittenanteils beträgt.

3. Emailzusammensetzung gemäß Anspruch 1, wobei der Frittenanteil ferner zumindest eine Substanz aufweist, die
ausgewählt ist aus der Gruppe, die besteht aus:
5
0,1 bis 4 Gew.-% Al2O3; und
0,1 bis 3 Gew.-% BaO.

4. Emailzusammensetzung gemäß Anspruch 1, ferner aufweisend zumindest ein kristallines Impfmaterial, das aus-
10 gewählt ist aus der Gruppe, die aus Zinkboraten, Zinksilikaten, Zinktitanaten, Wismutsilikaten und Kombinationen
daraus besteht.

5. Emailzusammensetzung gemäß Anspruch 1, die ferner Pigmente aufweist.

15 6. Emailzusammensetzung gemäß Anspruch 1, wobei der Frittenanteil eine Brenntemperatur von 593°C oder weniger
aufweist.

7. Emailzusammensetzung gemäß Anspruch 1, wobei der feste Anteil aufweist:

20 60 bis 85 Gew.-% des Frittenanteils;

0,1 bis 30 Gew.-% Pigmente;
0,1 bis 15 Gew.-% kristalline Materialien;
10 bis 60 Gew.-% Silber; und wahlweise
0,1 bis 5 Gew.-% Reduktionsmittel.
25
8. Verfahren zur Bildung einer Emailzusammensetzung, welches den Schritt des Kombinierens aufweist von:

30 bis 50 Gew.-% SiO2;

4,5 bis 20,2 Gew.-% Cs2O;
30 6,1 bis 11,5 Gew.-% Na2O;
6,5 bis 20,2 Gew,-% B2O3;
8 bis 25 Gew.-% ZnO;
3,4 bis 12,3 Gew.-% TiO2;
0 bis 40 Gew.-% Bi2O 3; und
35 0 bis 7 Gew.-% F.

9. Verfahren gemäß Anspruch 8, ferner aufweisend:

das Kombinieren zumindest einer Substanz, die ausgewählt ist aus der Gruppe, die besteht aus:
40
0,1 bis 1 Gew.-% La2O3;
0,1 bis 1 Gew.-% Nb2O5;
0,1 bis 1 Gew,-% MnO2;
0,1 bis 1 Gew.-% CeO2;
45 0,1 bis 1 Gew.-% MoO3; und
0,1 bis 1 Gew.-% WO3.

10. Verfahren gemäß Anspruch 8, ferner aufweisend:

50 das Kombinieren zumindest einer Substanz, die ausgewählt ist aus der Gruppe, die besteht aus:

0,1 bis 4 Gew.-% Al2O3; und

0,1 bis 3 Gew.-% BaO.

55 11. Verfahren gemäß Anspruch 8, ferner aufweisend:

das Kombinieren von Pigmenten; kristallinen Materialien; wahlweise Silber; und wahlweise Reduktionsmittel.

14
 EP 2 705 005 B1

12. Verfahren zur Bildung eines Emails auf einem Substrat, mit den Schritten:

Bereitstellen einer Emailzusammensetzung auf dem Substrat, wobei die Emailzusammensetzung einen festen
Anteil aufweist, wobei der feste Anteil einen Frittenanteil aufweist, wobei der Frittenanteil vor dem Brennen
5 aufweist:

30 bis 50 Gew.-% SiO2;

4,5 bis 20,2 Gew.-% Cs2O;
6,1 bis 11,5 Gew.-% Na2O;
10 6,5 bis 20,2 Gew,-% B2O 3;
8 bis 25 Gew.-% ZnO;
3,4 bis 12,3 Gew.-% TiO 2;
0 bis 40 Gew.-% Bi2O3; und
0 bis 7 Gew.-% F; und
15
Brennen der Emailzusammensetzung und des Substrats bei einer Temperatur, die ausreicht, um die Emailzu-
sammensetzung an dem Substrat anhaften zu lassen.

13. Verfahren gemäß Anspruch 12, wobei der Frittenanteil ferner zumindest eine Substanz aufweist, die ausgewählt
20 ist aus der Gruppe, die besteht aus:

0,1 bis 1 Gew.-% La2O3;

0,1 bis 1 Gew.-% Nb2O 5;
0,1 bis 1 Gew,-% MnO 2;
25 0,1 bis 1 Gew.-% CeO2;
0,1 bis 1 Gew.-% MoO 3; und
0,1 bis 1 Gew.-% WO3, und

einer Gesamtmenge an Oxiden, die 0,5 bis 5 Gew.-% des Frittenanteils beträgt.
30
14. Verfahren gemäß Anspruch 12, wobei der Frittenanteil ferner zumindest eine Substanz aufweist, die ausgewählt
ist aus der Gruppe, die besteht aus:

0,1 bis 4 Gew.-% Al2O3; und

35 0,1 bis 3 Gew.-% BaO.

15. Verfahren gemäß Anspruch 12, wobei die Emailzusammensetzung frei von Wismut ist.

40 Revendications

1. Composition d’émail comprenant une partie solide comprenant une partie de fritte, la partie de fritte comprenant,
avant la cuisson :

45 30 à 50 % en poids de SiO2;
4,5 à 20,2 % en poids de Cs2O;
6,1 à 11,5 % en poids de Na2O;
6,5 à 20,2 % en poids de B 2O3;
8 à 25 % en poids de ZnO;
50 3,4 à 12,3 % en poids deTiO2;
0 à 40 % en poids de Bi2O3; et
0 à 7 % en poids de F.

2. Composition d’émail selon la revendication 1, dans laquelle la partie de fritte comprend en outre au moins une
55 substance sélectionnée dans le groupe composé de :

0,1 à 1 % en poids de La2O3;

0,1 à 1 % en poids de Nb2O5;

15
 EP 2 705 005 B1

0,1 à 1 % en poids de MnO 2;

0,1 à 1 % en poids de CeO2;
0,1 à 1 % en poids de MoO 3; et
0,1 à 1 % en poids de WO3, et
5
une quantité totale des oxydes étant comprise entre 0,1 et 5 % en poids de la partie de fritte.

3. Composition d’émail selon la revendication 1, dans laquelle la partie de fritte comprend en outre au moins une
substance sélectionnée dans le groupe composé de :
10
0,1 à 4 % en poids de Al2O3 ; et
0,1 à 3 % en poids de BaO.

4. Composition d’émail selon la revendication 1, comprenant en outre au moins un matériau d’ensemencement cristallin
15 sélectionné dans le groupe composé de borates de zinc, de silicates de zinc, de titanates de zinc, de silicates de
bismuth et de combinaisons de ceux-ci.

5. Composition d’émail selon la revendication 1, comprenant en outre des pigments.

20 6. Composition d’émail selon la revendication 1, dans laquelle la partie de fritte comprend une température de cuisson
de 593°C ou moins.

7. Composition d’émail selon la revendication 1, dans laquelle la partie solide comprend :

25 60 à 85 % en poids de la partie de fritte ;

0,1 à 30 % en poids de pigments ;
0,1 à 15 % en poids de matériaux cristallins ;
10 à 60 % en poids d’argent ; et facultativement
0,1 à 5 % en poids d’agents de réduction.
30
8. Procédé de formation d’une composition d’émail, comprenant l’étape de combiner :

30 à 50 % en poids de SiO2;
4,5 à 20,2 % en poids de Cs2O;
35 6,1 à 11,5 % en poids de Na2O;
6,5 à 20,2 % en poids de B 2O3;
8 à 25 % en poids de ZnO;
3,4 à 12,3 % en poids deTiO2;
0 à 40 % en poids de Bi2O3; et
40 0 à 7 % en poids de F.

9. Procédé selon la revendication 8, comprenant en outre l’étape de combiner au moins une substance sélectionnée
dans le groupe composé de :

45 0,1 à 1 % en poids de La2O3;

0,1 à 1 % en poids de Nb2O5;
0,1 à 1 % en poids de MnO 2;
0,1 à 1 % en poids de CeO2;
0,1 à 1 % en poids de MoO 3; et
50 0,1 à 1 % en poids de WO3.

10. Procédé selon la revendication 8, comprenant en outre l’étape de combiner au moins une substance sélectionnée
dans le groupe composé de :

55 0,1 à 4 % en poids de Al2O3 ; et

0,1 à 3 % en poids de BaO.

11. Procédé selon la revendication 8, comprenant en outre l’étape de combiner des pigments ; des matériaux cristallins ;

16
 EP 2 705 005 B1

facultativement de l’argent ; et facultativement des agents de réduction.

12. Procédé de formation d’un émail sur un substrat, comprenant les étapes de :

5 appliquer une composition d’émail sur le substrat, la composition d’émail comprenant une partie solide, la partie
solide comprenant une partie de fritte,
la partie de fritte comprenant, avant la cuisson :

30 à 50 % en poids de SiO2;
10 4,5 à 20,2 % en poids de Cs2O;
6,1 à 11,5 % en poids de Na2O;
6,5 à 20,2 % en poids de B2O3;
8 à 25 % en poids de ZnO;
3,4 à 12,3 % en poids de TiO2;
15 0 à 40 % en poids de Bi2O 3; et
0 à 7 % en poids de F ; et

cuire la composition d’émail et le substrat à une température suffisante pour faire adhérer la composition d’émail
au substrat.
20
13. Procédé selon la revendication 12, dans lequel la partie de fritte comprend en outre au moins une substance
sélectionnée dans le groupe composé de :

0,1 à 1 % en poids de La2O3;

25 0,1 à 1 % en poids de Nb2O5;
0,1 à 1 % en poids de MnO 2;
0,1 à 1 % en poids de CeO2;
0,1 à 1 % en poids de MoO 3; et
0,1 à 1 % en poids de WO3, et
30
une quantité totale des oxydes étant comprise entre 0,1 et 5 % en poids de la partie de fritte.

14. Procédé selon la revendication 12, dans lequel la partie de fritte comprend en outre au moins une substance
sélectionnée dans le groupe composé de :
35
0,1 à 4 % en poids de Al2O3 ; et
0,1 à 3 % en poids de BaO.

15. Procédé selon la revendication 12, dans lequel ladite composition d’émail est dépourvue de bismuth.
40

45

50

55

17
 EP 2 705 005 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 2010009836 A [0006] • US 5714420 A [0041]

• US 5153150 A [0041]

18