CA1333621C - Glass enamel coating compositions - Google Patents
Glass enamel coating compositionsInfo
- Publication number
- CA1333621C CA1333621C CA000589297A CA589297A CA1333621C CA 1333621 C CA1333621 C CA 1333621C CA 000589297 A CA000589297 A CA 000589297A CA 589297 A CA589297 A CA 589297A CA 1333621 C CA1333621 C CA 1333621C
- Authority
- CA
- Canada
- Prior art keywords
- glass
- enamel
- frit
- vehicle
- glass sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000002320 enamel (paints) Substances 0.000 title abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000049 pigment Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 230000006872 improvement Effects 0.000 claims abstract description 6
- 210000003298 dental enamel Anatomy 0.000 claims description 56
- 239000011133 lead Substances 0.000 claims description 7
- 239000002657 fibrous material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 6
- 239000011029 spinel Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000010665 pine oil Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- -1 moybdenum Chemical compound 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 239000003039 volatile agent Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 239000005388 borosilicate glass Substances 0.000 claims 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000012423 maintenance Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000022972 amelogenesis Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000006105 batch ingredient Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000016768 molybdenum Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
In glass enamel coating compositions containing a glass frit system, a metal oxide pigment and a vehicle therefor, the improvement comprising the presence therein of iron metal powder to provide anti-stick, color mainten-ance and glass adhesion properties; the resulting coatings being particularly effective for application to glass sheets which are subsequently subjected to high temperature forming procedures.
Description
1333~21 P-16887/+/CGC 1328 GLASS ENAMEL COATING COMPOSITIONS
Glass enamel paint compositions are well known to those skilled in the art. These materials can be utilized for a variety of applications but are of particular use in decorating glass sheets. For example, the coatings may be used to form borders around the edge of glass sheets which are converted into windshields, sidelites or backlites in motor vehicles.
It has been noted, however, that when glass sheets having the glass enamel coated thereon are subjected to a forming process at elevated temperatures, the prior art coatings exhibit a tendency to adhere to the materials covering the forming die. Accordingly, such prior art materials are unavailable for use in glass forming processes in which a heated glass sheet coated with the glass enamel is engaged by a material-covered forming die, generally a fiberglass-covered forming die.
Various aproaches have been suggested in order to facilitate the forming of glass sheets with a glass enamel coated thereon and to withstand the elevated bending or forming temperatures and the repeated contact of the glass sheet and the covered forming die without having the enamel adhere to the forming die. For example, U.S. 4,596,590 discloses the addition of metal oxide powder, including ferrous oxide, to the paint composition to provide the desired non-stick barrier between the coating and the fiberglass-covered forming die. U.S. 4,684,388 and U.S.
4,684,389 disclose similar approaches, the former patent adding a mixture of finely divided zinc metal powder and finely divided stannous oxide powder as the anti-stick barrier and the latter patent adding finely divided zinc metal powder for the similar effect. Although each of ;~e.
13~3621 these systems has been effective in reducing the indicated problem, greater reduction of adhesion and further improvement of surface appearance are still desired.
This invention seeks to provide an improved glass enamel coating composition.
The invention also provides such coatings which are readily available for application to glass sheets and which exhibit anti-stick properties during glass formation.
Various advantages of this invention will become apparent from the following description thereof.
The invention provides in the method for forming a glass enamel coated glass sheet, the glass enamel composition comprising a glass frit, a metal oxide pigment and a vehicle for the glass enamel wherein the glass enamel composition is coated onto the glass sheet, the coated glass sheet is then heated to soften the sheet, to remove the volatiles in said enamel and to bond the remainder of the enamel to the sheet, the softened coated glass sheet is then contacted with a fibrous material covered forming die, the forming die is then removed and the glass sheet cooled;
the improvement comprising prior to coating the frit onto the glass sheet incorporating into the enamel composition from about 2-75%, by weight, of iron metal powder whereby said enamel composition exhibits virtually no adhesion to the fibrous material during the period which it contacts said fibrous material of said forming die in the glass sheet contacting step.
It has now been surprisingly discovered that by introducing iron powder into glass enamel compositions, the difficulties encountered with prior art formulations are - 2a - 21489-7616 substantially overcome. Thus, the resulting compositions can be readily applied to glass sheets and facilitate the formation of a smooth continuous coating which does not adhere to the fiberglass die coating when the heated coated glass is contacted with such materials. Accordingly, the bending or forming operations are not hindered by the above described sticking phenomenon. In addition, such enamel compositions exhibit increased opacity and increased glass adhesion. In particular, the presence of iron powder in UV
curable coatings substantially eliminates the potential for release of the enamel from the glass substrate.
The invention thus relates to the improved glass enamel composition and to the glass forming method utilizing such enamels. More specifically, the glass enamel compositions contain, as the primary ingredients, iron powder, glass frit, metal oxide pigment and vehicle.
Any conventional soft glass frit or frit mixture can be utilized in the instant formulation. The frit will generally be ground to pass through 325 mesh screen (U.S.
Standard Sieve size). The primary purpose of the frit is to bond the pigmentary product to the glass surface. The frit may comprise any appropriate combination of metal oxides. Typical oxides may be selected from the oxides of zinc, lead, silicon, titanium, zirconium, sodium, boron, lithium, potassium, calcium, aluminum, tin, vanadium, moly-bdenum, magnesium, iron, manganese and the like.
Correspondingly, various fluorides may appear in the frit.
The batch composition which will provide the above noted oxides and fluorides may contain various salts, such as oxides, carbonates, sulfates, nitrates, fluorides and the like, of the above noted metals. The batch ingredients are selected in order to achieve predetermined frit properties. Lead, zinc alkali and bismuth alkali borosilicate frits are preferred for purposes of this invention.
The frit is prepared by melting the batch ingredients at temperatures of from about 900 to 1600C.
and then quenching the molten glass either with the use of water or by pouring the melt between two cooled metal rolls rotating in opposite direction. Melting generally is conducted in a ceramic or platinum crucible or in an appropriately lined furnace. The resulting chips, chunks or flakes of frit are then ground into fine particles.
Metal oxide pigments are well known to those skilled in the art. Applicable oxides include, for example, 4 133~621 chrome, cobalt, iron, nic~el, copper, manganese, and the like. Although the latter metal oxides form preferred black spinel pigments, other variations to produce dark gray and other colors are likewise-contemplated.
The vehicle is selected on the basis of the end use application. It is essential that the vehicle adequately suspend the particulates and burn off completely upon firing of the composition. Vehicles are typically organic and include compositions based on pine oils, vegetable oils, mineral oils, low molecular weight petroleum fractions, tridecyl alcohol, and the like. The vehicles may be modified by viscous resins such as vinyl resins, solvents, film formers such as cellulosic materials, and the like.
Correspondingly, UV-base vehicles are equally applicable for use in the instant invention. Such UV-base vehicles are well known to those skilled in the art and will generally be composed of polymerizable monomers and/or oligomers containing, for example, acrylate or methacrylate functional groups, together with photoinitiators and polymerization inhibitors. Representative systems are disclosed in U.S. 4,306,012 and U.S. 4,649,062. As is recognized, such systems are cured with ultraviolet radiation after application to the glass substrate.
The modified glass enamels contain from about 2-75%
of iron powder, preferably 5-35% and most preferably 20-30%;
from about lO to 85% glass frit/pigment combination and pre-ferably 30 to 65%; and from about lO to 45% vehicle and pre-ferably 14 to 30%. The percentages are based on the weight of the formulated glass enamel paste. The pigment component will generally comprise from 10 to 40%, by weight, of the indicated combined oxide system. The resulting compositions wiIl be viscous in nature, the viscosity depending on application method and end use. For purposes of screen printing, viscosities ranging from 10,000-80,000, and preferably 20,000-65,000, centipoises at 20C. as determined on a Brookfield Viscometer, ~7 spindle at 20 rpm are appropriate.
A wide variety of optional ingredients may be included in these formulations. These may be added to modify viscosity and to enhance properties such as bond strength and abrasion resistance. Various bismuth and bismuth-containing compounds for bond strength; certain refractory materials such as zirconium oxide to increase abrasion resistance; suspending agents such as iso-stearic acid; and fumed silica and other silica products to modify viscosity; may be included for the indicated benefits.
The compositions are prepared by blending the solid materials, adding the liquid ingredients thereto and then thoroughly mixing or kneading the two in order to form a smooth, thick paste. The paste is then further dispersed by means of a conventional machine such as a three-roll mill or dispersator such as a Cowles or Morehouse mill.
Methods for applying the enamel coatings are well known to those skilled in the art. The dispersed compositions may be applied by techniques such as screen printing, decal application, spraying, brushing, roller coating, and the like. Screen printing is preferred for purposes of applying the composition to glass substrates.
After the enamel has been applied to the glass sheet, the glass sheet is heated to a temperature which softens the glass sufficiently so that the glass sheet can be formed. Generally, this temperature is in a range of about 600-760CC. Compositions which are formulated to be responsive to UV radiation may be exposed to such radiation prior to heating to bond the enamel to the glass sheet.
After heating, the glass sheet and the enamel thereon are engaged by the fiberglass covered forming die to place the heated glass sheet into a desired shape. The heating operation, of course, burns off the organic materials contained in the enamel and bonds the remaining portion of the enamel to the glass sheet. The iron powder addition to the enamel serves to prevent sticking of any of the enamel to the forming die and also provides a smooth continuous surface to the resulting enamelled surface.
After the forming die has been removed from engagement with the glass sheet and the enamel without any sticking of the enamel thereto, the glass sheet may be cooled to obtain a formed glass sheet with enamel thereon.
The glass sheet may be rapidly cooled in a glass tempering operation to achieve a tempered glass product having the enamel thereon or annealed when utilized for windshield applications. The resulting glass sheet is then readily available for use in a variety of applications, particularly the automotive applications noted hereinabove.
Glass enamel paint compositions are also formulated with silver metal in order to provide conductive coatings for use, for example, as defrost circuits for automotive backlites and windshield. In such areas of utility, color maintenance, bond strength, solderability, absence of _ 7 _ 13336~1 silver migration and abrasion resistance are required performance characteristics. It is to be noted that the instant iron powder-containing systems are particularly applicable for use in conjunction with such conductive coatings for the above noted areas of utility. When the conductive coatings are applied in overlapping relationship with the iron-containing systems, performance improvements as observed after heat treatment include good resistance to silver migration into the enamel, substantial reduction of undesirable blue haze of the buss bar (bar connecting ends of individual horizontal conductive elements of defrost circuit) and permanence of solder connections.
The following examples further illustrate the embodiments of this invention. In these examples, all parts are given by weight unless otherwise specified.
Example 1 This example illustrates the preparation and application of typical enamels of this invention.
The following formulations are prepared:
%, by weight _ 2 3 4 5 6 A B C_ _ _ _ _ _ Lead boro-silicate/black spinel pigment blend (glass enamel powder)* 61.5 61.559.8 59.870.4 70.4 8181 81 Pine Oil-Based Vehicle 15.4 - 17.1 - 17.6 - 19 - -UV-base vehicle(l) - 15.4 - _ _ 17.6 - 19 UV-base vehicle(2) - - - 17.1 - - - - 19 Iron powder ( 325 mesh) 23.1 23.1 23.1 23.1 12.0 12.0 (1) 1708 from Drakenfeld Colors (2) 1718 from Drakenfeld Colors * 58 parts lead borosilicate frit and 42 parts black spinel pigment The enamels are prepared by blending the liquid and solid ingredients and then dispersing the paste in an appropriate mill.
The performance characteristics of the enamels are determined in a laboratory screening procedure by applying the enamels to 10.2cm x 10.2cm x 4 mm glass plates, heating the slide to 705C for 3 minutes, impressing a slightly curved, ceramic cloth covered press bar at a estimated pressure of 25-50 pounds onto the softened glass for a period of five seconds with a rolling motion, removing the press bar and visually identifying the degree of adhesion between the enamel and the ceramic cloth.
Each of formulations 1-6 exhibited virtually no adhesion as evidenced by the almost complete absence of ceramic cloth on the plate. In contrast, formulations A, B
and C exhibited noticeable amounts of ceramic cloth on the plate indicative of undesirable adhesion.
Example 2 Formulation B is utilized as the base composition for each of the following test procedures, incorporating iron as indicated.
In each instance, the iron-containing glass enamel is screen printed onto the glass and cured at a rate of 1067 cm./minute under a mercury vapor lamp (ID/lHg).
Thereafter, a conductive coating of 70% silver metal, 3%
glass frit and 27% tridecyl alcohol-based vehicle (alI
percentages by weight) is scréen printed over the cured iron-containing glass enamel so as to provide areas of overlap and then dried. The dual coated glass panel is them fired in a vertical position at the indicated temperatures and firing times. Observations are then made as to opacity and anti-stick characteristics for the individual glass enamel coating. In addition, the degree of "release" is determined, this being the condition where the cured enamel begins to lose its adhesion to the glass - lo- 1333621 substrate as identified by the appearance of silvery or white dots indicative of release onset when looking through the glass to the underside of the enamel. In addition, the overlapping areas are evaluated for enamel development (surface hardness) and resistance to silver migration into the iron-containing glass enamel.
Test condition 1 = 705C fire temperature for 2.25 minutes Test condition 2 = 705C fire temperature for 2.75 minutes Test condition 3 = 730C fire temperature for 3 minutes TC Fe(%, by wt.) ED SB OP R A-S
F G G E
G E E E
Glass enamel paint compositions are well known to those skilled in the art. These materials can be utilized for a variety of applications but are of particular use in decorating glass sheets. For example, the coatings may be used to form borders around the edge of glass sheets which are converted into windshields, sidelites or backlites in motor vehicles.
It has been noted, however, that when glass sheets having the glass enamel coated thereon are subjected to a forming process at elevated temperatures, the prior art coatings exhibit a tendency to adhere to the materials covering the forming die. Accordingly, such prior art materials are unavailable for use in glass forming processes in which a heated glass sheet coated with the glass enamel is engaged by a material-covered forming die, generally a fiberglass-covered forming die.
Various aproaches have been suggested in order to facilitate the forming of glass sheets with a glass enamel coated thereon and to withstand the elevated bending or forming temperatures and the repeated contact of the glass sheet and the covered forming die without having the enamel adhere to the forming die. For example, U.S. 4,596,590 discloses the addition of metal oxide powder, including ferrous oxide, to the paint composition to provide the desired non-stick barrier between the coating and the fiberglass-covered forming die. U.S. 4,684,388 and U.S.
4,684,389 disclose similar approaches, the former patent adding a mixture of finely divided zinc metal powder and finely divided stannous oxide powder as the anti-stick barrier and the latter patent adding finely divided zinc metal powder for the similar effect. Although each of ;~e.
13~3621 these systems has been effective in reducing the indicated problem, greater reduction of adhesion and further improvement of surface appearance are still desired.
This invention seeks to provide an improved glass enamel coating composition.
The invention also provides such coatings which are readily available for application to glass sheets and which exhibit anti-stick properties during glass formation.
Various advantages of this invention will become apparent from the following description thereof.
The invention provides in the method for forming a glass enamel coated glass sheet, the glass enamel composition comprising a glass frit, a metal oxide pigment and a vehicle for the glass enamel wherein the glass enamel composition is coated onto the glass sheet, the coated glass sheet is then heated to soften the sheet, to remove the volatiles in said enamel and to bond the remainder of the enamel to the sheet, the softened coated glass sheet is then contacted with a fibrous material covered forming die, the forming die is then removed and the glass sheet cooled;
the improvement comprising prior to coating the frit onto the glass sheet incorporating into the enamel composition from about 2-75%, by weight, of iron metal powder whereby said enamel composition exhibits virtually no adhesion to the fibrous material during the period which it contacts said fibrous material of said forming die in the glass sheet contacting step.
It has now been surprisingly discovered that by introducing iron powder into glass enamel compositions, the difficulties encountered with prior art formulations are - 2a - 21489-7616 substantially overcome. Thus, the resulting compositions can be readily applied to glass sheets and facilitate the formation of a smooth continuous coating which does not adhere to the fiberglass die coating when the heated coated glass is contacted with such materials. Accordingly, the bending or forming operations are not hindered by the above described sticking phenomenon. In addition, such enamel compositions exhibit increased opacity and increased glass adhesion. In particular, the presence of iron powder in UV
curable coatings substantially eliminates the potential for release of the enamel from the glass substrate.
The invention thus relates to the improved glass enamel composition and to the glass forming method utilizing such enamels. More specifically, the glass enamel compositions contain, as the primary ingredients, iron powder, glass frit, metal oxide pigment and vehicle.
Any conventional soft glass frit or frit mixture can be utilized in the instant formulation. The frit will generally be ground to pass through 325 mesh screen (U.S.
Standard Sieve size). The primary purpose of the frit is to bond the pigmentary product to the glass surface. The frit may comprise any appropriate combination of metal oxides. Typical oxides may be selected from the oxides of zinc, lead, silicon, titanium, zirconium, sodium, boron, lithium, potassium, calcium, aluminum, tin, vanadium, moly-bdenum, magnesium, iron, manganese and the like.
Correspondingly, various fluorides may appear in the frit.
The batch composition which will provide the above noted oxides and fluorides may contain various salts, such as oxides, carbonates, sulfates, nitrates, fluorides and the like, of the above noted metals. The batch ingredients are selected in order to achieve predetermined frit properties. Lead, zinc alkali and bismuth alkali borosilicate frits are preferred for purposes of this invention.
The frit is prepared by melting the batch ingredients at temperatures of from about 900 to 1600C.
and then quenching the molten glass either with the use of water or by pouring the melt between two cooled metal rolls rotating in opposite direction. Melting generally is conducted in a ceramic or platinum crucible or in an appropriately lined furnace. The resulting chips, chunks or flakes of frit are then ground into fine particles.
Metal oxide pigments are well known to those skilled in the art. Applicable oxides include, for example, 4 133~621 chrome, cobalt, iron, nic~el, copper, manganese, and the like. Although the latter metal oxides form preferred black spinel pigments, other variations to produce dark gray and other colors are likewise-contemplated.
The vehicle is selected on the basis of the end use application. It is essential that the vehicle adequately suspend the particulates and burn off completely upon firing of the composition. Vehicles are typically organic and include compositions based on pine oils, vegetable oils, mineral oils, low molecular weight petroleum fractions, tridecyl alcohol, and the like. The vehicles may be modified by viscous resins such as vinyl resins, solvents, film formers such as cellulosic materials, and the like.
Correspondingly, UV-base vehicles are equally applicable for use in the instant invention. Such UV-base vehicles are well known to those skilled in the art and will generally be composed of polymerizable monomers and/or oligomers containing, for example, acrylate or methacrylate functional groups, together with photoinitiators and polymerization inhibitors. Representative systems are disclosed in U.S. 4,306,012 and U.S. 4,649,062. As is recognized, such systems are cured with ultraviolet radiation after application to the glass substrate.
The modified glass enamels contain from about 2-75%
of iron powder, preferably 5-35% and most preferably 20-30%;
from about lO to 85% glass frit/pigment combination and pre-ferably 30 to 65%; and from about lO to 45% vehicle and pre-ferably 14 to 30%. The percentages are based on the weight of the formulated glass enamel paste. The pigment component will generally comprise from 10 to 40%, by weight, of the indicated combined oxide system. The resulting compositions wiIl be viscous in nature, the viscosity depending on application method and end use. For purposes of screen printing, viscosities ranging from 10,000-80,000, and preferably 20,000-65,000, centipoises at 20C. as determined on a Brookfield Viscometer, ~7 spindle at 20 rpm are appropriate.
A wide variety of optional ingredients may be included in these formulations. These may be added to modify viscosity and to enhance properties such as bond strength and abrasion resistance. Various bismuth and bismuth-containing compounds for bond strength; certain refractory materials such as zirconium oxide to increase abrasion resistance; suspending agents such as iso-stearic acid; and fumed silica and other silica products to modify viscosity; may be included for the indicated benefits.
The compositions are prepared by blending the solid materials, adding the liquid ingredients thereto and then thoroughly mixing or kneading the two in order to form a smooth, thick paste. The paste is then further dispersed by means of a conventional machine such as a three-roll mill or dispersator such as a Cowles or Morehouse mill.
Methods for applying the enamel coatings are well known to those skilled in the art. The dispersed compositions may be applied by techniques such as screen printing, decal application, spraying, brushing, roller coating, and the like. Screen printing is preferred for purposes of applying the composition to glass substrates.
After the enamel has been applied to the glass sheet, the glass sheet is heated to a temperature which softens the glass sufficiently so that the glass sheet can be formed. Generally, this temperature is in a range of about 600-760CC. Compositions which are formulated to be responsive to UV radiation may be exposed to such radiation prior to heating to bond the enamel to the glass sheet.
After heating, the glass sheet and the enamel thereon are engaged by the fiberglass covered forming die to place the heated glass sheet into a desired shape. The heating operation, of course, burns off the organic materials contained in the enamel and bonds the remaining portion of the enamel to the glass sheet. The iron powder addition to the enamel serves to prevent sticking of any of the enamel to the forming die and also provides a smooth continuous surface to the resulting enamelled surface.
After the forming die has been removed from engagement with the glass sheet and the enamel without any sticking of the enamel thereto, the glass sheet may be cooled to obtain a formed glass sheet with enamel thereon.
The glass sheet may be rapidly cooled in a glass tempering operation to achieve a tempered glass product having the enamel thereon or annealed when utilized for windshield applications. The resulting glass sheet is then readily available for use in a variety of applications, particularly the automotive applications noted hereinabove.
Glass enamel paint compositions are also formulated with silver metal in order to provide conductive coatings for use, for example, as defrost circuits for automotive backlites and windshield. In such areas of utility, color maintenance, bond strength, solderability, absence of _ 7 _ 13336~1 silver migration and abrasion resistance are required performance characteristics. It is to be noted that the instant iron powder-containing systems are particularly applicable for use in conjunction with such conductive coatings for the above noted areas of utility. When the conductive coatings are applied in overlapping relationship with the iron-containing systems, performance improvements as observed after heat treatment include good resistance to silver migration into the enamel, substantial reduction of undesirable blue haze of the buss bar (bar connecting ends of individual horizontal conductive elements of defrost circuit) and permanence of solder connections.
The following examples further illustrate the embodiments of this invention. In these examples, all parts are given by weight unless otherwise specified.
Example 1 This example illustrates the preparation and application of typical enamels of this invention.
The following formulations are prepared:
%, by weight _ 2 3 4 5 6 A B C_ _ _ _ _ _ Lead boro-silicate/black spinel pigment blend (glass enamel powder)* 61.5 61.559.8 59.870.4 70.4 8181 81 Pine Oil-Based Vehicle 15.4 - 17.1 - 17.6 - 19 - -UV-base vehicle(l) - 15.4 - _ _ 17.6 - 19 UV-base vehicle(2) - - - 17.1 - - - - 19 Iron powder ( 325 mesh) 23.1 23.1 23.1 23.1 12.0 12.0 (1) 1708 from Drakenfeld Colors (2) 1718 from Drakenfeld Colors * 58 parts lead borosilicate frit and 42 parts black spinel pigment The enamels are prepared by blending the liquid and solid ingredients and then dispersing the paste in an appropriate mill.
The performance characteristics of the enamels are determined in a laboratory screening procedure by applying the enamels to 10.2cm x 10.2cm x 4 mm glass plates, heating the slide to 705C for 3 minutes, impressing a slightly curved, ceramic cloth covered press bar at a estimated pressure of 25-50 pounds onto the softened glass for a period of five seconds with a rolling motion, removing the press bar and visually identifying the degree of adhesion between the enamel and the ceramic cloth.
Each of formulations 1-6 exhibited virtually no adhesion as evidenced by the almost complete absence of ceramic cloth on the plate. In contrast, formulations A, B
and C exhibited noticeable amounts of ceramic cloth on the plate indicative of undesirable adhesion.
Example 2 Formulation B is utilized as the base composition for each of the following test procedures, incorporating iron as indicated.
In each instance, the iron-containing glass enamel is screen printed onto the glass and cured at a rate of 1067 cm./minute under a mercury vapor lamp (ID/lHg).
Thereafter, a conductive coating of 70% silver metal, 3%
glass frit and 27% tridecyl alcohol-based vehicle (alI
percentages by weight) is scréen printed over the cured iron-containing glass enamel so as to provide areas of overlap and then dried. The dual coated glass panel is them fired in a vertical position at the indicated temperatures and firing times. Observations are then made as to opacity and anti-stick characteristics for the individual glass enamel coating. In addition, the degree of "release" is determined, this being the condition where the cured enamel begins to lose its adhesion to the glass - lo- 1333621 substrate as identified by the appearance of silvery or white dots indicative of release onset when looking through the glass to the underside of the enamel. In addition, the overlapping areas are evaluated for enamel development (surface hardness) and resistance to silver migration into the iron-containing glass enamel.
Test condition 1 = 705C fire temperature for 2.25 minutes Test condition 2 = 705C fire temperature for 2.75 minutes Test condition 3 = 730C fire temperature for 3 minutes TC Fe(%, by wt.) ED SB OP R A-S
F G G E
G E E E
TC = test condition ED = enamel development SB = resistance to silver migration OP = opacity-R = absence of release A-S = anti-stick F = fair performance G = good performance E = excellent performance When control B is subjected to these tests, silver migration and reduced anti-stick properties are in evidence.
Example 3 The general preparative procedure of Example 2 is repeated. Thereafter, solderability characteristics are determined by slightly abrading the bus bar, lightly soldering a tin-plated copper braid thereto using 1.27 cm Bi/As/Sn solder at a solder temperature of 400C, allowing the soldered section to cool to ambient temperature and utilizing an Instron ~odel 1000 tensile tester to measure the force necessary to remove the braid. The results are as follows:
TCFe(%, by wt.) Solder Pull (lbs.) 1 5 18.2 1 - 16.4 2 5 9.1 2 - 0.0 1 10 18.3 1 - 13.1 2 10 10.3 2 - 0.0 1 20 14.2 1 - 11.4 2 20 12.9 2 - 0.0 These data thus illustrate a further performance benefit of the glass enamels of this invention.
Summarizing, this invention provides glass enamel compositions exhibiting a wide variety of performance improvements as a result of the presence of iron powder therein. Variations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
Example 3 The general preparative procedure of Example 2 is repeated. Thereafter, solderability characteristics are determined by slightly abrading the bus bar, lightly soldering a tin-plated copper braid thereto using 1.27 cm Bi/As/Sn solder at a solder temperature of 400C, allowing the soldered section to cool to ambient temperature and utilizing an Instron ~odel 1000 tensile tester to measure the force necessary to remove the braid. The results are as follows:
TCFe(%, by wt.) Solder Pull (lbs.) 1 5 18.2 1 - 16.4 2 5 9.1 2 - 0.0 1 10 18.3 1 - 13.1 2 10 10.3 2 - 0.0 1 20 14.2 1 - 11.4 2 20 12.9 2 - 0.0 These data thus illustrate a further performance benefit of the glass enamels of this invention.
Summarizing, this invention provides glass enamel compositions exhibiting a wide variety of performance improvements as a result of the presence of iron powder therein. Variations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
Claims (11)
1. In the method for forming a glass enamel coated glass sheet, the glass enamel composi-tion comprising a glass frit, a metal oxide pigment and a vehicle for the glass enamel, wherein the glass enamel composition is coated onto the glass sheet, the coated glass sheet is then heated to soften the sheet, to remove the volatiles in said enamel and to bond the remainder of the enamel to the sheet, the softened coated glass sheet is then contacted with a fibrous material covered forming die, the forming die is then removed and the glass sheet cooled; the improvement comprising prior to coating the frit onto the glass sheet incorporating into the enamel composition from about 2-75 %, by weight, of iron metal powder whereby said enamel composition exhibits virtually no adhesion to the fibrous material during the period which it contacts said fibrous material of said forming die in the glass sheet contacting step.
2. The method of claim 1, wherein said vehicle is a UV curable vehicle and wherein the coated glass sheet is cured with ultraviolet radiation prior to the heating step.
3. The method of claim 2, wherein said enamel composition comprises a lead borosilicate frit, a black spinel pigment, iron metal powder and a UV curable vehicle for the glass enamel.
4. The method of claim 1, wherein said glass frit comprises a mixture of metal oxides.
5. The method of claim 4, wherein said oxides are selected from the group consisting of zinc, lead, silicon, titanium, zirconium, sodium, boron, lithium, potassium, calcium, aluminium, tin, vanadium, moybdenum, magnesium, iron and manganese oxides.
6. The method of claim 5, wherein said frit is a lead borosilicate glass frit.
7. The method of claim 1, wherein an organic vehicle is present.
8. The method of claim 7, wherein said vehicle contains pine oil, vegetable oils, mineral oils, low molecular weight petroleum fractions or tridecyl alcohol.
9. The method of claim 8, wherein said vehicle contains pine oil.
10. The method of claim 1, wherein said pigment is a black spinel pigment.
11. The method of claim 1, wherein said enamel composition comprises a lead-borosilicate frit, a black spinel pigment, iron powder and a pine oil-based vehicle therefor.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15026188A | 1988-01-29 | 1988-01-29 | |
US150,261 | 1988-01-29 |
Publications (1)
Publication Number | Publication Date |
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CA1333621C true CA1333621C (en) | 1994-12-20 |
Family
ID=22533742
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000589297A Expired - Fee Related CA1333621C (en) | 1988-01-29 | 1989-01-27 | Glass enamel coating compositions |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0326519B1 (en) |
JP (1) | JP2659426B2 (en) |
KR (1) | KR960008655B1 (en) |
CA (1) | CA1333621C (en) |
DE (1) | DE58902785D1 (en) |
ES (1) | ES2035636T3 (en) |
MX (1) | MX169491B (en) |
ZA (1) | ZA89660B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2047706T3 (en) * | 1988-09-28 | 1994-03-01 | Ciba Geigy Ag | ENAMEL COMPOSITIONS FOR COATINGS. |
FR2703043B1 (en) * | 1993-03-26 | 1995-10-20 | Saint Gobain Vitrage Int | Composition for glazing glass substrates, application to laminated glazing and products obtained. |
WO1994022779A2 (en) * | 1993-03-26 | 1994-10-13 | Saint-Gobain Vitrage International | Method for fabricating laminated enamelled glazing, and enamelled composition used therefor |
FR2724377B1 (en) | 1994-09-09 | 1996-10-31 | Saint Gobain Vitrage | EMAIL COMPOSITION FOR GLASS SUBSTRATE |
FR2728558A1 (en) | 1994-12-23 | 1996-06-28 | Saint Gobain Vitrage | METHOD FOR ENAMELLING GLASS SUBSTRATES AND COMPOSITION USED THEREFOR |
WO2000037362A1 (en) * | 1998-12-18 | 2000-06-29 | Dmc?2¿ Degussa Metals Catalysts Cerdec Ag | Bismuth manganese oxide pigments |
DE102010047033B3 (en) * | 2010-09-30 | 2012-03-08 | Benteler Automobiltechnik Gmbh | Molded component useful for a motor vehicle, comprises a base body, which is made of a metal sheet and is provided with a smaller, locally arranged reinforcement plate |
JP2016513065A (en) * | 2013-02-21 | 2016-05-12 | コーニング インコーポレイテッド | Method for forming tempered sintered glass structure |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2112115B1 (en) * | 1970-11-05 | 1976-04-16 | Boussois Souchon Neuvesel Sa | |
JPS5915099B2 (en) * | 1980-03-17 | 1984-04-07 | セントラル硝子株式会社 | Method for forming colored parts on plate glass |
JPS57123844A (en) * | 1981-01-20 | 1982-08-02 | Central Glass Co Ltd | Formation of colored layer or electrically-conductive layer on plate glass |
-
1989
- 1989-01-23 ES ES198989810053T patent/ES2035636T3/en not_active Expired - Lifetime
- 1989-01-23 EP EP89810053A patent/EP0326519B1/en not_active Expired - Lifetime
- 1989-01-23 DE DE8989810053T patent/DE58902785D1/en not_active Expired - Fee Related
- 1989-01-24 KR KR89000706A patent/KR960008655B1/en not_active IP Right Cessation
- 1989-01-27 CA CA000589297A patent/CA1333621C/en not_active Expired - Fee Related
- 1989-01-27 ZA ZA89660A patent/ZA89660B/en unknown
- 1989-01-27 JP JP1016528A patent/JP2659426B2/en not_active Expired - Lifetime
- 1989-01-27 MX MX014677A patent/MX169491B/en unknown
Also Published As
Publication number | Publication date |
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JP2659426B2 (en) | 1997-09-30 |
ZA89660B (en) | 1989-09-27 |
EP0326519A1 (en) | 1989-08-02 |
KR960008655B1 (en) | 1996-06-28 |
ES2035636T3 (en) | 1993-04-16 |
KR890011800A (en) | 1989-08-22 |
DE58902785D1 (en) | 1993-01-07 |
MX169491B (en) | 1993-07-07 |
JPH023469A (en) | 1990-01-09 |
EP0326519B1 (en) | 1992-11-25 |
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