WO2001007528A1 - Pigmented coatings for ceramic substrates - Google Patents
Pigmented coatings for ceramic substrates Download PDFInfo
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- WO2001007528A1 WO2001007528A1 PCT/US2000/019958 US0019958W WO0107528A1 WO 2001007528 A1 WO2001007528 A1 WO 2001007528A1 US 0019958 W US0019958 W US 0019958W WO 0107528 A1 WO0107528 A1 WO 0107528A1
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- Prior art keywords
- functional
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- blocked
- glycidyloxy
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces
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- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
Definitions
- Ceramic substrates especially those of glass, are often coated, either locally or completely, with one or more coating compositions.
- Local application is usually practiced to apply lettering, designs, or other indicia to the ceramic substrates; when used in this manner the coating compositions are generally referred to as " inks" .
- inks Application of indicia to glass bottles is a commercially important example.
- the coatings applied to bottles must be tough and resistant to marring by abrasion or impact and they should be resistant to degredation by caustic solutions commonly employed for cleaning bottles .
- one embodiment of the invention is a crosslinking composition comprising: (a) amino-functional curing agent; (b) blocked polyisocyanate; and, optionally,
- organo- functional siloxane comprising a member selected from the group consisting of epoxy-functional siloxane, amino- functional siloxane, (blocked isocyanato) -functional siloxane, and a mixture of two or more thereof.
- compositions which may be used for coating, said composition comprising: (a) reactive organic resin which is polyhydroxy- functional, polyepoxy- functional , or both epoxy-functional and hydroxy- functional; (b) color- imparting pigment; (c) reactive wax; and
- crosslinking composition comprising: (1) amino- functional curing agent; (2) blocked polyisocyanate; and, optionally,
- organo-functional siloxane comprising a member selected frorr. the group consisting of epoxy-functional siloxane, amino- functional siloxane, (blocked isocyanato) -functional siloxane, and a mixture of two or more thereof.
- Yet another embodiment is an article comprising a ceramic substrate having thereon at least one coating of the above composition which has been crosslinked.
- inks are considered to be coating compositions.
- the amino- functional curing agents are themselves kn ⁇ *-m curing agents for epoxy resins. Such amino- functional curing agents are reasonably shelf stable at ambient room temperatures, and sufficiently stable at application temperatures so that it does not unduly shorten the pot life of the coating composition in which the crosslinking composition is employed. " Pot life" is the length of time the coating will remain fluid enough to apply to substrates at application temperatures.
- Illustrative amino- functional curing agents which may be used include melamine, 2 , 4 , 6-tris (alkoxycarbonylamino) - 1, 3 , 5-triazine (also known as " TACT" ) where each alkoxy independently contains from 1 to 4 carbon atoms, and compounds represented by the formula:
- R 1( R 2 , R 3 each independently represents hydrogen, alkyl containing from 1 to 3 carbon atoms, or hydroxyalkyl containing from 1 to 3 carbon atoms
- R 4 represents hydrogen, phenyl , cyano, acetyl, or
- R 5 represents O, S, or NH
- R 6 and R 7 each independently represents hydrogen, alkyl containing from 1 to 3 carbon atoms, hydroxyalkyl containing from 1 to 3 carbon atoms, or phenyl .
- R 1# R 2 , R 3 , R 6 , and R 7 is alkyl containing from 1 to 3 carbon atoms, it is independently methyl, ethyl, propyl, or isopropyl.
- the alkyl groups may be the same or some may be different from the others.
- the preferred alkyl group is methyl.
- R lr R 2 , R 3 , R 6 , and R 7 When any of R lr R 2 , R 3 , R 6 , and R 7 is hydroxyalkyl containing from 1 to 3 carbon atoms, it usually is independently hydroxymethyl , hydroxyethyl , or hydroxypropyl .
- the hydroxyalkyl groups may be the same or some may be different from the others.
- the preferred hydroxyalkyl group is hydroxymethyl.
- all of R 1 R 2 , R 3 , R 6 , and R 7 are hydrogen .
- Suitable amino- functional curing agents include melamine [CAS 108-78-1], 2,4,6- tris (methoxycarbonylamino) -1, 3, 5-triazine [CAS 150986-36-0], 2, 4, 6-tris (butoxycarbonylamino) -1,3, 5-triazine [CAS 150986-45-1] , dicyandiamide [CAS 461-58-5] , 1, 3-diphenylguanidine [CAS 102-06-7], urea [CAS 57-13-6], thiourea [CAS 62-56-6] , acetylurea [CAS 591-07-1] , biguanide [CAS 56-03-1] , heptamethylbiguanide [CAS ..1446-22-9] , 2-ethyl- 4-methylimidazole [CAS 931-36-2] , and diaminodiphenyl sulfone [CAS 80-08-0] .
- the amino-functional curing agent may comprise one amino-functional curing agent or it may comprise a mixture of two or more amino- functional curing agents.
- Organic isocyanates react with organic compounds containing at least one "active hydrogen" , i.e., a hydrogen atom replaceable by sodium. Substantially all organic compounds containing a hydrogen atom attr -hed to oxygen or nitrogen will react with isocyanates under the proper conditions.
- An organic compound containing active hydrogen is suitable as a blocking agent if the product of its reaction with an isocyanate is unreactive with hydroxyl, amino, amido, ureylene, carbamyl, carbamyloxy, or other groups containing active hydrogen at room temperature, but reacts, by intermediate unblocking or otherwise, with one or more such groups of other compounds at an elevated temperature, usually in the range of from 90°C to 325°C, to form desired products.
- the reaction product of a blocking agent and an isocyanate is known as a " blocked isocyanate" .
- the reaction to form the blocked isocyanate is reversed at the elevated temperature to regenerate isocyanato-functionality which then reacts with other compounds containing active hydrogen to form the desired products.
- the blocking agent contains active hydrogen attached to an oxygen atom or a nitrogen atom.
- Any suitable aliphatic, cycloaliphatic, aromatic- alkyl monoalcohol or phenolic compound may be used as a blocking agent in accordance with the present invention.
- suitable aliphatic, cycloaliphatic, aromatic- alkyl monoalcohol or phenolic compound may be used as a blocking agent in accordance with the present invention.
- suitable aliphatic, cycloaliphatic, aromatic- alkyl monoalcohol or phenolic compound may be used as a blocking agent in accordance with the present invention. Examples include but are by no means limited to methyl alcohol, ethyl alcohol, chloroethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol,
- 5-di-tert-butyl-4-hydroxytoluene tertiary hydroxylamines such as diethylethanolamine
- oximes such as methyl ethyl ketone oximes, acetone oxime, 2-butanone oxime and cyclohexanone oxime .
- Any suitable compound containing amine, amide, urea, urethane, or other groups having an active hydrogen attached to a nitrogen atom may be used.
- examples of such compounds include, but are not limited to, dibutylamine, morpholine, 3-aminoproyl morpholine, diisopropylamine, 2-phenylimidazoline, benzotriazole, benzyl methacrylohydroxamate , 2-pyrolidone and ⁇ -caprolactam.
- Polyfunctional blocking agents may be used when desired.
- Examples include, but are not limited to ethylene glycol, propropylene glycol, poly (ethylene glycol), poly (propylene glycol) , Pluronic type polypropylene, poly (tetrahydrofuran) , trimethylolpropane, ethoxylated trimethylolpropane, and poly (vinyl alcohol) .
- Blocking is often accomplished by reacting the isocyanato groups of the isocyanato-functional compound with blocking agent at temperatures in the range of from 25 °C to 120°C, although other temperatures may often be used.
- the organic blocked isocyanate is formed by reacting a sufficient quantity of blocking agent with the organic polyisocyanate to insure that substantially no unreacted isocyanato groups are present in the product .
- blocked isocyanato functionality does not contain the isocyanato group; rather it contains a group which is the reaction product of the isocyanato group and the blocking agent.
- an isocyanato group blocked with an alcohol contains a urethane group
- an isocyanato group blocked with a primary or secondary amine contains a urea group.
- any suitable organic polyisocyanate may be used.
- classes of organic polyisocyanates include, but are not limited to, the aliphatic polyisocyanates, the cycloaliphatic polyisocyanates, the aliphatic-cycloaliphatic polyisocyanates, the aromatic polyisocyanates, the aliphatic- aromatic polyisocyanates, the uretedione polyisocyanates, and the biuret polyisocyanates .
- the polyisocyanates may be diisocyanates, triisocyanates, tetraisocyanstes or higher order isocyanates.
- polyisocyanates Only one polyisocyanate or a mixture of two -or more polyisocyanates may be used. When mixtures are used, the constituent polyisocyanates may be from the same class or from different classes. Representative examples of suitable polyisocyanates which may be blocked include, but are not limited to:
- N,N' " -tris (6-isocyanatohexyl) biuret , 2, 3 -bis (8-isocyanatooctyl) -4-octyl-5-hexylcyclohexene, polymeric polyisocyanates such as dimers and trimers, and prepolymers which are derived from a polyol, including a hydrocarbon polyol, a polyether polyol, and a polyest .- polyol.
- An example is an adduct (approximately 3:1, molar) of l-isocyanatomethyl-5-isocyanato-l, 3 , 3-trimethylcyclohexane [CAS 4098-71-9] and 1, 1 , 1-trimethylolpropane [CAS 77-99-6] .
- the optional organo- functional siloxane which may be employed in the crosslinking composition comprises a member selected from the group consisting of epoxy-functional siloxane, amino- functional siloxane, (blocked isocyanato) -functional siloxane, and a mixture of two or more thereof.
- the presence of the organo-functional siloxane in the crosslinking composition improves the adhesion of the coating composition to the substrate.
- the epoxy-functional siloxane comprises a member selected from the group consisting of: ( ⁇ - (glycidyloxy) alkyl) trialkoxysilane,
- Only one epoxy-functional siloxane or a mixture of two or more epoxy-functional siloxanes may be used when desired.
- the amino-functional siloxane comprises a member selected from the group consisting of:
- Suitable amino-functional silanes include : (2-aminoethyl)dimethoxymethylsilane [CAS 115599-33-2],
- Isocyanato groups of isocyanato-functional siloxanes may be reacted with blocking agents to form (blocked isocyanato) -functional siloxanes.
- the principles, blocking agents, and blocking procedures are substantially the same as those described above in respect of the formation of blocked polyisocyanates .
- the (blocked isocyanato) -functional siloxane comprise a member selected from the group consisting of: ( (blocked isocyanato) alkyl ) trialkoxysilane , ((blocked isocyanato) alkyl) dialkoxyalkylsilane, ( (blocked isocyanato) alkyl) alkoxydialkylsilane, and a mixture of two or more thereof .
- the (blocked isocyanato) -functional siloxane comprises a member selected from the group consisting of :
- the (blocked isocyanato) -functional siloxanes corresponding to these exemplary isocyanato-functional siloxanes are: (3- (blocked isocyanato) propyl) trimethoxysilane, (3- (blocked isocyanato) propyl) diethoxyethylsilane, and (3- (blocked isocyanato) propyl) triethoxysilane . Only one (blocked isocyanato) -functional siloxane or a mixture of two or more (blocked isocyanato) -functional siloxanes may be used when desired.
- the crosslinking composition may be formed by admixing the components at temperatures below those which would cause significant reaction.
- the relative proportions of the components of the crosslinking composition may be widely varied.
- the amino-functional curing agent usually constitutes from 10 to 70 percent by weight of the crosslinking composition. Often the amino-functional curing agent constitutes from 20 to 50 percent by weight of the crosslinking composition. From 25 to 35 percent by weight of the crosslinking composition is preferred.
- the blocked polyisocyanate ordinarily constitutes from 2 to 80 percent by weight of the crosslinking composition. Frequently the blocked polyisocyanate constitutes from 5 to 75 percent by weight of the crosslinking composition. From 10 to 65 percent by weight of the crosslinking composition is preferred.
- the organo- functional siloxane may constitute from 0 to 70 percent by weight and usually constitutes from 5 to 70 percent by weight of the crosslinking composition. In many instances the organo- functional siloxane constitutes from 8 to 65 percent by weight of the crosslinking composition. From 10 to 60 percent by weight of the crosslinking composition is preferred when the siloxane is present.
- the reactive organic resin which is polyhydroxy- functional and which may be used in the coating composition of the invention may be widely varied.
- a class of polyhydroxy- functional reactive organic resin which is frequently employed comprises the polyhydroxy- functional polyester resins.
- polyhydroxy- functional means that on a number average molecular weight basis, the polyester contains on average, more than one hydroxyl group per molecule . Preferably the polyester contains, on average, at least two hydroxyl groups per molecule.
- polyhydroxy- functional polyester resins which can be used in the present invention are numerous and widely varied. Such polyhydroxy- functional polyesters are preferably polyhydroxy-functional substantially saturated polyester resins, as that term is customarily understood in the industry. As used herein and in the claims, the term " saturated polyester” is intended to include polyesters containing aromatic unsaturation since aromatic unsaturation is generally unreactive in polyesters. Nevertheless, some ethylenic unsaturation may be present when circumstances warrant. Ethylenic unsaturation, when present, is often introduced by employing a small amount of ethylenically unsaturated acid such as maleic acid or fumaric acid, during preparation of the polyester.
- saturated polyester is intended to include polyesters containing aromatic unsaturation since aromatic unsaturation is generally unreactive in polyesters. Nevertheless, some ethylenic unsaturation may be present when circumstances warrant. Ethylenic unsaturation, when present, is often introduced by employing a small amount of ethylenically unsaturated acid such as maleic acid
- the acids used to prepare the hydroxy- functional polyesters employed in the present invention are ethylenically unsaturated acids .
- ethylenically unsaturated acids are ethylenically unsaturated acids.
- the ethylenically unsaturated acids are substantially absent.
- the polyhydroxy-functional polyesters may be produced from one or more polyol ⁇ and one or more pol carboxylic acids using well-known polycondensation procedures employing an excess of polyol to obtain a polymer having the desired proportion of hydroxyl groups.
- polycondensation procedures include, but are not limited to, direct esterification of polycarboxylic acid (or its anhydride if such anhydride exists) with polyol, transesteresterification, and reaction between polycarboxylic acid halide and the polyol.
- direct esterification of polycarboxylic acid or its anhydride if such anhydride exists
- the polyols which can be used are numerous and widely varied. They are often aliphatic alicyclic, aromatic, aliphatic-alicyclic, aliphatic-aromatic, alicyclic-aromatic, or aliphatic-alicyclic-aromatic in nature. Usually the polyols contain from 2 to 20 carbon atoms. Frequently the polyols contain from 2 to 12 carbon atoms. The polyols are usually predominately diols. In most instances diols constitute at least 90 mole percent of the polyols. Often diols constitute at least 95 mole percent of the polyols. At least 98 mole percent is preferred. Frequently diols constitute all of the polyols.
- diols examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1, 3-propanediol , dipropylene glycol, trimethylene glycol, 2 , 4-dimethyl-2-ethylhexane-l, 3-diol, 2 , 2-dimethylpropane-l, 3-diol, 2-ethyl-2-butylpropane-l, 3-diol, 2 -ethyl -2 -isobutylpropane-1, 3-diol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, thiodiethanol , 1, 2-cyclohexanediol , 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedim
- a minor amount, that is, up to 10 mole percent of the polyol may be triol, tetrol, or higher functional polyol.
- Examples include, but are not limited to, glycerol, 1, 1, 1-trimethylolethane, 1, 1, 1- rimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, ⁇ -methylglucoside, and sorbitan.
- the polycarboxylic acids which can be used are also numerous and widely varied. They are often aliphatic, alicyclic, aromatic, aliphatic-alicyclic, aliphatic -aromatic, alicyclic-aromatic, or aliphatic-alic :lic-aromatic in nature. Usually they contain from 4 to 20 carbon atoms.
- the polycarboxylic acids are usually predominately dicarboxylic acids. In most instances dicarboxylic acids constitute at least 90 mole percent of the polycarboxylic acids. Often dicarboxylic acids constitute at least 95 mole percent of the polycarboxylic acids. At least 98 mole percent is preferred. Frequently dicarboxylic acids constitute all of the polycarboxylic acids.
- dicarboxylic acids examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 3-cyclohexanedicarboxylic acid, and 1, 4-cyclohexanedicarboxylic acid.
- a minor amount, that is, up to 10 mole percent of the polycarboxylic acid may be tricarboxylic acid or higher functional polycarboxylic acid. Examples include, but are not limited to, trimellitic acid and 1, 2 , 3-propanetrioic acid.
- the hydroxy-functionality of the polyhydroxy- functional polyester resins which are used in the present invention is conveniently characterized by the hydroxyl number, which is well known and may be determined according to the procedure of ASTM E 222-94, the entire disclosure of which is incorporated herein by reference.
- the polyhydroxy- functional polyester resins have a hydroxyl number of at least 5. In many instances the hydroxyl number is in the range of from 5 to 200.
- the number average molecular weight of the polyhydroxy-functional polyester resin is usually in the range of from 500 to 10,000, although lower or higher number average molecular weights may be used when desired. As used herein, number average molecular weights are determined by gel permeation c ⁇ romatography using polystyrene standards.
- the inherent viscosity (logarithmic-viscosity number) of the polyhydroxy-functional polyester resin is often in the range of from 0.1 to 0.5 deciliters/gram, as described in Chemical Engineers Handbook, 5th Edition, 1973. Lower or higher inherent viscosities can be used when desired.
- the polyhydroxy- functional polyester resin used in the present invention is semi-crystalline, that is, the polyester has a discernible crystallization or melting point by differential scanning calorimetry (DSC) .
- the polyhydroxy- functional polyester resin used in the present invention may be amorphous, that is the polyester exhibits no, or only a trace of, crystallization or melting point as determined by differential scanning calorimetry.
- the polyepoxy- functional reactive organic resin which may be used in the coating composition of the invention may also be widely varied. As used herein and in the claims, the term " polyepoxy- functional" means that on a number average molecular weight basis, the resin contains on average, more than one epoxy group per molecule.
- the resin contains, on average, at least two hydroxyl groups per molecule.
- polyglycidyl ethers of polyhydric alcohols are the polyglycidyl ethers of polyhydric alcohols.
- Useful polyglycidyl ethers of polyhydric alcohols can be formed by reacting epihalohydrins, such as epichlorohydrin [CAS 106-89-8] , with polyhydric alcohols, especially dihydric alcohols, in the presence of an alkali condensation and dehydrohalogenation catalyst such as sodium hydroxide or potassium hydroxide.
- phenolic hydroxyls react with epichlorohydrin in much the same way as aliphatic alcoholic hydroxyls
- compounds having at least two phenolic hydroxyls are, for purposes of the present discussion, regarded as polyhydric alcohols.
- Suitable polyhydric alcohols can be aromatic, aliphatic or cycloaliphatic .
- Suitable aliphatic polyhydric alcohols include, but are not limited to, aliphatic dihydric alcohols such as : ethylene glycol [CAS 107-21-1] , neopentyl glycol [CAS 126-30-7] , diethylene glycol [CAS 111-46-6] , triethylene glycol [CAS 112-27-6] , tetraethylene glycol [CAS 112-60-7] , dipropylene glycol [CAS 110-98-5] ,
- Suitable aliphatic polyhydric alcohols having more than two alcoholic hydroxyl groups include, but are not limited to: sorbitol [CAS 50-70-4] , mannitol [CAS 69-65-8] , glycerol [CAS 56-81-5] ,
- aromatic polyhydric alcohols examples include : pyrocatechol [CAS 120-80-9] , resorcinol [CAS 108-46-3] , hydroquinone [CAS 123-31-9] , 4 , 4 ' - (1-methylethylidene) bis [phenol] [bisphenol A;
- ethylene oxide or propylene oxide extended aromatic polyhydric alcohols are known and may be used when desired.
- Suitable cycloaliphatic polyhydric alcohols include, Hut are not limited to: 1, 2-cyclohexanediol [CAS 931-17-9], 1,3-cyclohexanediol [CAS 504-01-8], 1,4-cyclohexanediol [CAS 556-48-9], 1,2-cyclohexanedimethanol [CAS 3971-29-7], 1,3 -cyclohexanedimethanol [CAS 3971-28-6], 1, 4-cyclohexanedimethanol [CAS 105-08-8],
- polyepoxy-functional resins containing at least two epoxy groups per molecule are those containing, on average, at least one epoxycycloaliphatic group per molecule. These resins may be made by epoxidation of the cycloalkene group using a peracid such as peracetic acid.
- a resin that contains one epoxycycloalkyl group and a pendent epoxy group is 1- (epoxyethyl) -3 , 4-epoxycyclohexane [CAS 106-87-6].
- epoxy-functional resins containing two or more epoxycycloalkyl groups include, but are not limited to: bis (2,3-epoxycyclopentyl) ether [CAS 2386-90-5],
- Poly(primary amino) -functional and poly (secondary amino) -functional compounds may be used to chain-extend the polyepoxy-functional resins.
- Suitable polyepoxy-functional resins usually have an epoxide equivalent weight (i.e., molecular weight of resin per epoxide group) in the range of from 100 to 4000, as measured by titration with perchloric acid using methyl violet as an indicator. Often the polyepoxy- functional resins have an epoxide equivalent weight in the range of from 170 to 700. Preferably the epoxide equivalent weight is in the range of from 250 to 600.
- Other useful polyepoxides are disclosed in U.S. Patent No. 5,820,987 at column 4, line 52 through column 6, line 59. The disclosure of U.S. Patent
- polyepoxy-functional organic resins formed by reacting diols with epichlorohydrin also contain polyhydroxy-functionality.
- ideal reaction products having number average molecular weights of greater than 624 theoretically have, on average, two epoxy groups and more than one hydroxyl group per molecule.
- suitable commercially available polyepoxy-functional and polyhydroxy-functional resins are Epon® 828, 836, and 880 epoxy resins. If the number average molecular weight is 908 or greater, ideal reaction products of bisphenol A and epichlorohydrin theoetically have, on average, two epoxy groups and at least two hydroxyl group per molecule.
- Examples of such polyepoxy- functional and polyhydroxy- functional resins which are commercially available are Epon® 1001F, 1002, 1004, 1007, and 1009.
- the Epon® resins are available from Shell Chemicals Co., Houston, TX, USA.
- the polyepoxy-functional resin may be reacted with various terminating agents, as for example amino-functional siloxane, to convert some, or even all, of the terminal epoxy groups to terminal groups of other functionality. In most instances, the consumption of the epoxy groups during the termination reaction is accompanied by the generation of hydroxy groups on the resin.
- Color-imparting pigments used in formulating the coating compositions of the present invention are f._:ely divided solid powders, insoluble but wettable under the conditions of use. They confer substantial color (which includes white, black and grey) to the coating compositions of the invention and to coatings formed from such coating compositions. Finely divided solid powders which do not impart substantial color to the coating compositions and to coatings formed therefrom are, for purposes of the present invention, considered not to be pigments, but rather, they are considered to be substantially colorless fillers.
- the color-imparting pigments may be widely varied.
- color-imparting pigments may be organic or inorganic. It is preferred to use color-imparting pigments which do not contain heavy metals although some heavy metals such as copper which are not very toxic in the concentrations employed, may be present. In general it is preferred to use titanium dioxide as a white pigment and carbon in one of its forms as a black pigment, and to use organic pigments for imparting colors other than white, black, or grey. Examples of color-imparting pigments include, but are not limited to: Carbon Black Lampblack Furnace Black
- Pigment Yellow 13 [CAS 5102-83-0]
- Pigment Yellow 74 [CAS 6358-31-2]
- Pigment Yellow 110 [CAS 5590-18-1]
- Pigment Yellow 138 [CAS 56731-19-2]
- Pigment Yellow 110 [CAS 5590-18-1]
- Pigment Yellow 138 [CAS 56731-19-2]
- Pigment Yellow 191 [CAS 125423-54-7]
- Pigment Orange 5 [CAS 3468-63-1]
- Pigment Red 2 [CAS 6041-94-7]
- Pigment Red 3 [CAS 2425-85-6]
- Pigment Red 23 [CAS 6471-49-4] , Pigment Red 38 [CAS 6358-87-8] , Pigment Red 52 [CAS 17852-99-2] , Pigment Red 57 [CAS 5281-04-9] , Pigment Red 112 [CAS 6535-46-2] , Pigment Red 122 [CAS 980-26-7] , Pigment Red 123 [CAS 24108-89-2] , Pigment Red 144 [CAS 5280-78-4] , Pigment Red 170 [CAS 2786-76-7] , Pigment Red 177 [CAS 4051-63-2] , Pigment Red 179 [CAS 5521-31-3] , Pigment Red 202 [CAS 68859-50-7] , Pigment Red 254 [CAS 122390-98-1] , Pigment Violet 19 [CAS 1047-16-1] , and Pigment Violet 23 [CAS 6358-30-1] . Only one color- imparting pigment or a mixture of two or more color- imparting pigments may be used.
- Reactive waxes are long-chain aliphatic substances which have at least one reactive group having an active hydrogen, usually selected from hydroxyl, amido, ureylene, carbamyl, and carbamyloxy, and which have the physical characteristics commonly associated with waxes.
- the reactive waxes comprise many different classes of compounds. Examples of reactive waxes include normal primary alkanols having from 12 to 20 carbon atoms, normal primary amines having from 12 to 20 carbon atoms, normal saturated monocarboxylic acids having from 8 to 20 carbon atoms, and normal saturated monocarboxylic amides having from 8 to 20 carbon atoms. Although the normal (that is, straight chain) structures are preferred, some branching may be present, as for example isostearyl alcohol.
- reactive waxes include the poly (ethylene oxides) having normal molecular weights of at least 1000, the poly (propylene oxides) having normal molecular weights of at least 5000; these may terminated with two hydroxyl groups or with one hydroxyl group and one lower alkoxy group.
- Saturated long chain aliphatic diols or saturated long chain dicarboxylic acids having waxy characteristics may also be used. While saturated compounds are preferred, a small amount of unsaturation may be present, as for example oleic acid.
- more than one reactive group may be in the molecule, as for example 12-hydroxystearic acid and sebacic acid.
- the reactive waxes the normal primary alkanols having from 12 to 20 carbon atoms are preferred.
- Stearyl alcohol is especially preferred.
- the relative proportions of the components of the coating composition may be widely varied.
- the reactive organic resin which is polyhydroxy- functional, polyepoxy-functional, or both polyepoxy-functional and polyhydroxy- functional usually constitutes from 20 to
- the coating composition 80 percent by weight of the coating composition. Often such reactive organic resin constitutes from 30 to 70 percent by weight of the coating composition. From 40 to 60 percent by weight of the coating composition is preferred.
- the color- imparting pigment ordinarily constitutes from 1 to 45 percent by weight of the coating composition. Frequently the color- imparting pigment constitutes from 3 to 40 percent by weight of the coating composition. From 5 to 35 percent by weight of the coating composition is preferred.
- the reactive wax usually constitutes from 0.1 to
- the crosslinking composition usually constitutes from 1 to 20 percent by weight of the coating composition. In many instances the crosslinking composition constitutes from 2 to 18 percent by weight of the coating composition. From 3 to 16 percent by weight of the coating composition is preferred.
- Substantially colorless fillers are materials which may optionally be present in the coating composition. Such fillers are finely divided particulate solids which impart little or no color to the final coatings.
- the fillers usually have a maximum dimension of less than 500 nanometers. Often the fillers have a maximum dimension of less than 100 nanometers. Frequently the maximum dimension is less than 50 nanometers. In many instances the maximum dimension is less than 20 nanometers. Often the maximum dimension is in the range of from 5 to 20 nanometers.
- the fillers are hydrophobic. Examples of suitable hydrophobic fillers include Aerosil ® fumed silicas designated R972, R974, R812, R812S, R805 (Degussa Corporation, Ridgefield Park, NJ,USA) .
- antioxidants include antioxidants, degassing aids, flow modifiers, sag control agents, viscosity agents and Fluorescent Whitening Agents.
- these optional materials are usually present in the coating composition in their customary amounts for their customary purposes. In most instances the optional materials, when present, will constitute from 0.01 to 15 percent by weight of the coating composition. Often optional materialt , when present, will constitute from 0.01 to 10 percent by weight of the coating composition.
- the coating composition may be formed by admixing the ingredients at temperatures below those which would cause significant reaction.
- the coating compositions of the present invention can be applied directly to ceramic substrates and/or to one or more previously applied coatings of the same or similar coating compositions. Usually they are applied at elevate. " temperatures so that the chilling effect of the cooler substrate will quickly substantially solidify the coating. Such solidification is helpful in maintaining fine-line definition, in permitting application of multiple coatings without impairing the definition of any previously applied coating, and in permitting multiple coating while avoiding energy-inefficient crosslinking between coating applications.
- the application temperature of a subsequently applied coating is lower than the temperature at which a previously applied coating will liquefy or unduly soften. This will enhance preservation of the fine- line definition and resolution of the previously applied coating.
- ceramic substrate is used in its broadest sense, unless otherwise more restrictively qualified.
- ceramic substrates include, but are not limited to, unglazed pottery, glazed pottery, unglazed earthenware, glazed earthenware, unglazed porcelain, glazed porcelain, coffee cups, tea cups, wall tiles, Christmas tree ornaments, promotional ware, and glass substrates.
- glass substrates include, but are not limited to, window glass, automotiv glass, drinking glasses, glass bottles, glass jugs, glass jars, glass pitchers, and glass jewelry.
- Coating compositions which are applied at elevated temperatures because they are substantially solids at room temperature are usually applied using screen coating techniques.
- Coating compositions which are liquids at room temperature can be applied by spraying, curtain coating, roller application, printing, and brushing. These techniques are only exemplary; others may be used as desired.
- Curing of one or more of the applied coating compositions is accomplished at temperatures higher than those at which the polyisocyanates were blocked. In most instances the curing temperature is at least 150°C. The curing temperature should not be so high as to cause unwanted coloration or other thermal degredation of the coatings. Usually the curing temperature is in the range of from 150°C to 200°C. Unfortunately some crosslinking does occur at application temperatures and such crosslinking eventually causes the coating composition to thicken to the point it cannot be applied. A major problem with the prior coatings has been short pot life. Frequently the pot lives of the coating compositions of the present invention are longer than many of the coating compositions of the prior art.
- Ethyl acrylate-co-2-ethylhexyl Acrylate polymer [CAS 26376-86-3] Monsanto Company, St. Louis, MO, USA.
- Epon 836 bisphenol A diglycidyl ether was warmed in an oven at 100°C.
- the materials shown in Table 2 were charged to a mixer and mixed at 100°C to give a clear liquid:
- Warmed Epon ' 836 bisphenol A diglycidyl ether (7) 200.0
- Vestagon ® EP B 1400 believed to be an adduct of isophorone diisocyanate [CAS 4098-71-9] ,
- a red coating composition was formed by adding 105.0 parts of the first mixture to the container containing 22.6 parts of the second mixture and admixing the materials well at 100°C.
- EXAMPLE 3 A portion of the white coating composition prepared in Example 1 was printed on a glass bottle using a standard pattern on a Strutz GP-4 Semi-Automatic General Purpose
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00950542A EP1214382A1 (en) | 1999-07-22 | 2000-07-21 | Pigmented coatings for ceramic substrates |
MXPA02000776A MXPA02000776A (en) | 1999-07-22 | 2000-07-21 | Pigmented coatings for ceramic substrates. |
AU63637/00A AU6363700A (en) | 1999-07-22 | 2000-07-21 | Pigmented coatings for ceramic substrates |
CA002380086A CA2380086A1 (en) | 1999-07-22 | 2000-07-21 | Pigmented coatings for ceramic substrates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US35947399A | 1999-07-22 | 1999-07-22 | |
US09/359,473 | 1999-07-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001007528A1 true WO2001007528A1 (en) | 2001-02-01 |
Family
ID=23413944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/019958 WO2001007528A1 (en) | 1999-07-22 | 2000-07-21 | Pigmented coatings for ceramic substrates |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1214382A1 (en) |
AU (1) | AU6363700A (en) |
WO (1) | WO2001007528A1 (en) |
ZA (1) | ZA200200744B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004014815A1 (en) * | 2002-07-12 | 2004-02-19 | Andreas Schultze-Kraft | Solvent-free method for hydrophobic color coating of glass granulates, product therefrom and use thereof |
WO2005058999A1 (en) | 2003-12-16 | 2005-06-30 | E.I. Dupont De Nemours And Company | Processes for preparing printable and printed articles |
WO2011038722A3 (en) * | 2009-10-01 | 2011-05-26 | Andreas Schultze-Kraft | Coated glass granulate as concrete aggregate |
US8193293B2 (en) | 2008-03-17 | 2012-06-05 | Ppg Industries Ohio, Inc. | Low temperature curable coating compositions and related methods |
WO2014202313A1 (en) * | 2013-06-21 | 2014-12-24 | Basf Coatings Gmbh | Pigmented coating agent and method for producing a multilayer coating using the pigmented coating agent for producing a pane adhesion |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0343676A2 (en) * | 1988-05-27 | 1989-11-29 | Teroson Gmbh | Reactive hot melt structural adhesive |
EP0551727A1 (en) * | 1992-01-10 | 1993-07-21 | Morton International, Inc. | Coating composition and metal coil coating process employing same |
EP0712909A2 (en) * | 1994-11-10 | 1996-05-22 | Nippon Paint Co., Ltd. | Soft segment-containing modified epoxy resin and cathodic electrodeposition paints containing same |
DE19755031A1 (en) * | 1997-12-11 | 1999-06-17 | Rainer Dipl Chem Dr Gras | Room temperature-curable epoxy resin mixtures for coatings on various substrates, adhesives, sealing materials and molded parts |
-
2000
- 2000-07-21 EP EP00950542A patent/EP1214382A1/en not_active Withdrawn
- 2000-07-21 WO PCT/US2000/019958 patent/WO2001007528A1/en not_active Application Discontinuation
- 2000-07-21 AU AU63637/00A patent/AU6363700A/en not_active Abandoned
-
2002
- 2002-01-28 ZA ZA200200744A patent/ZA200200744B/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0343676A2 (en) * | 1988-05-27 | 1989-11-29 | Teroson Gmbh | Reactive hot melt structural adhesive |
EP0551727A1 (en) * | 1992-01-10 | 1993-07-21 | Morton International, Inc. | Coating composition and metal coil coating process employing same |
EP0712909A2 (en) * | 1994-11-10 | 1996-05-22 | Nippon Paint Co., Ltd. | Soft segment-containing modified epoxy resin and cathodic electrodeposition paints containing same |
DE19755031A1 (en) * | 1997-12-11 | 1999-06-17 | Rainer Dipl Chem Dr Gras | Room temperature-curable epoxy resin mixtures for coatings on various substrates, adhesives, sealing materials and molded parts |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004014815A1 (en) * | 2002-07-12 | 2004-02-19 | Andreas Schultze-Kraft | Solvent-free method for hydrophobic color coating of glass granulates, product therefrom and use thereof |
WO2005058999A1 (en) | 2003-12-16 | 2005-06-30 | E.I. Dupont De Nemours And Company | Processes for preparing printable and printed articles |
US8193293B2 (en) | 2008-03-17 | 2012-06-05 | Ppg Industries Ohio, Inc. | Low temperature curable coating compositions and related methods |
WO2011038722A3 (en) * | 2009-10-01 | 2011-05-26 | Andreas Schultze-Kraft | Coated glass granulate as concrete aggregate |
WO2014202313A1 (en) * | 2013-06-21 | 2014-12-24 | Basf Coatings Gmbh | Pigmented coating agent and method for producing a multilayer coating using the pigmented coating agent for producing a pane adhesion |
US9528025B2 (en) | 2013-06-21 | 2016-12-27 | Basf Coatings Gmbh | Pigmented coating agent and method for producing a multilayer coating using the pigmented coating agent for producing a pane adhesion |
Also Published As
Publication number | Publication date |
---|---|
AU6363700A (en) | 2001-02-13 |
EP1214382A1 (en) | 2002-06-19 |
ZA200200744B (en) | 2003-04-29 |
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