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Patent US6497964 - Coating compositions and method for the surface protection of plastic substrate - Google Patents
A composition comprising (1) 0.1-50 parts by weight of the reaction product of a hydroxyl group-containing benzophenone compound with a silane and/or a hydrolyzate thereof and (2) 100 parts by weight of a silane compound and/or a hydrolyzate thereof is applied to a polycarbonate sheet to form a protective...http://www.google.com/patents/US6497964?utm_source=gb-gplus-sharePatent US6497964 - Coating compositions and method for the surface protection of plastic substrate
Publication number US6497964 B1
Application number US 09/621,627
Also published as DE60037705D1, DE60037705T2, DE60041841D1, EP1070750A2, EP1070750A3, EP1070750B1, EP1801176A1, EP1801176B1
Publication number 09621627, 621627, US 6497964 B1, US 6497964B1, US-B1-6497964, US6497964 B1, US6497964B1
Inventors Kazuyuki Matsumura, Masaaki Yamaya, Kazuharu Sato, Koichi Higuchi, Muneo Kudo
Original Assignee Shin-Etsu Chemical Co., Ltd., Kabushi Kaishi Toyoda Jidoshokki Seisakusho
Patent Citations (5), Referenced by (32), Classifications (23), Legal Events (5)
US 6497964 B1
A composition comprising (1) 0.1-50 parts by weight of the reaction product of a hydroxyl group-containing benzophenone compound with a silane and/or a hydrolyzate thereof and (2) 100 parts by weight of a silane compound and/or a hydrolyzate thereof is applied to a polycarbonate sheet to form a protective coating having mar and weather resistance. A composition comprising the reaction product of a hydroxyl group-containing benzophenone compound with a silane and/or a hydrolyzate thereof is useful for undercoating.
1. A protective coating composition having improved weather resistance, comprising
(1) 0.1 to 50 parts by weight of a reaction product obtained by reacting a hydroxyl group-containing benzophenone compound with a silane and/or a (partial) hydrolyzate thereof in the presence of a quaternary ammonium salt catalyst, and
(2) 100 parts by weight of a silane compound of the following general formula (C) and/or a (partial) hydrolyzate thereof:
wherein R4 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, m and n each are equal to 0, 1 or 2, and the sum of m and n is equal to 0, 1 or 2.
3. The protective coating composition of claim 1 wherein component (1) is a reaction product obtained by reacting a compound of the general formula (A):
wherein X, which may be the same or different, is hydrogen or a hydroxyl group, at least one X being a hydroxyl group, with an epoxy group-containing silane of the following general formula (B) and/or a (partial) hydrolyzate thereof:
R1 aSiR2 b(OR3)4-a-b (B)
wherein R1 is an epoxy group-containing organic group, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, a is equal to 1 or 2, b is equal to 0 or 1, and the sum of a and b is equal to 1 or 2, in the presence of said quaternary ammonium salt catalyst.
6. The protective coating composition of claim 1, wherein said hydroxyl-group containing benzophenone compound is reacted with said silane and/or said (partial) hydrolyzate thereof in the presence of said catalyst at a temperature of 50 to 150° C. for about 4 to 20 hours.
9. The protective coating composition of claim 7 wherein component (1) is a reaction product obtained by reacting a compound of the general formula (A):
12. The protective coating composition of claim 7, wherein said hydroxyl-group containing benzophenone compound is reacted with said silane and/or said (partial) hydrolyzate thereof in the presence of said catalyst at a temperature of 50 to 150° C. for about 4 to 20 hours.
23. The undercoating composition of claim 22 wherein the reaction product and/or the (partial) hydrolyzate thereof is a reaction product obtained by reacting a compound of the following general formula (A):
(i) applying an organic solvent solution of the undercoating composition of claim 16 onto a plastic substrate,
(iii) applying an organopolysiloxane composition onto the cured undercoating composition, said organopolysiloxane composition comprising colloidal silica and a hydrolyzate or co-hydrolyzate of a silane compound of the following general formula (C′):
R5 mSiR2 n(OR3)4-m-n (C′)
wherein R5 is selected from the class consisting of a C1-10 alkyl group, an aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group and an organic group having an epoxy, (meth)acryloxy, mercapto, amino or cyano group, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, m and n each are equal to 0, 1 or 2, and the sum of m and n is equal to 0, 1 or 2, and
28. The method of claim 27 wherein the plastic substrate is comprised of a polycarbonate resin.
(iii) applying a protective coating composition onto the cured undercoating composition, said protective coating composition comprising
(1) 0.1 to 50 parts by weight of a reaction product obtained by reacting a hydroxyl group-containing benzophenone compound with a silane and/or a (partial) hydrolyzate thereof in the presence of a catalyst, and
wherein R4 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, m and n each are equal to 0, 1 or 2, and the sum of m and n is equal to 0, 1 or 2, and
(iv) heating the coating of the protective coating composition for curing.
31. The method of claim 30 wherein the plastic substrate is comprised of a polycarbonate resin.
(iii) applying a protective coating composition onto the cured undercoating composition, said protective coating composition comprising a co-hydrolyzate resulting from co-hydrolysis of:
34. The method of claim 33 wherein the plastic substrate is comprised of a polycarbonate resin.
38. The undercoating composition of claim 22, wherein said hydroxyl-group containing benzophenone compound is reacted with said silane and/or said (partial) hydrolyzate thereof in the presence of said catalyst at a temperature of 50 to 150° C. for about 4 to 20 hours.
An object of the invention is to provide a coating composition having improved long-term weather resistance and surface protection performance on a plastic substrate, and suited as an outermost coating on such a substrate. Another object is to provide an article having a coating of the coating composition on a substrate.
We have found that significant improvements are made when a protective coating composition comprising (1) the reaction product of a hydroxyl group-containing benzophenone compound with a silane and/or a (partial) hydrolyzate thereof, preferably the reaction product obtained by reacting a compound of the following general formula (A) with an epoxy group-containing silane of the following general formula (B) in the presence of a catalyst, and/or a (partial) hydrolyzate thereof, (2) a silane of the following general formula (C) and/or a (partial) hydrolyzate thereof, and optionally and preferably, (3) a microparticulate inorganic oxide containing titanium, cerium or zinc, and capable of absorbing light with a wavelength of up to 400 nm, or a protective coating composition comprising a co-hydrolyzate of components (1) and (2), and optionally and preferably, component (3) is applied and cured onto plastic substrates, typically polycarbonate resins. The benzophenone organic UV absorber does not bleed out because of silyl modification or detract from mar resistance because of good compatibility with component (2). The benzophenone organic UV absorber containing at least three OH groups in a molecule maintains a UV absorbing capability substantially unchanged despite silyl modification. The use of benzophenone organic UV absorber in combination with the microparticulate inorganic oxide capable of absorbing light with a wavelength of up to 400 nm achieves the synergistic effect of effectively absorbing light in a wide UV region for significantly improving the weather resistance of plastic substrates, typically polycarbonate resins.
In formula (A), X, which may be the same or different, is hydrogen or a hydroxyl group, and at least one X is a hydroxyl group.
In formula (B), R1 is an epoxy group-containing organic group, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, “a” is equal to 1 or 2, “b” is equal to 0 or 1, and the sum of a and b is equal to 1 or 2.
In formula (C), R4 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, m and n each are equal to 0, 1 or 2, and the sum of m and n is equal to 0, 1 or 2.
wherein R4 is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, m and n each are equal to 0, 1 or 2, and the sum of m and n is equal to 0, 1 or 2, and/or a (partial) hydrolyzate thereof.
wherein R4, R2, R3, m and n are as defined above and/or a (partial) hydrolyzate thereof.
wherein R5 is a C1-10 alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group or an organic group having an epoxy, (meth)acryloxy, mercapto, amino or cyano group, R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, R3 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms which may contain an oxygen atom, m and n each are equal to 0, 1 or 2, and the sum of m and n is equal to 0, 1 or 2, and colloidal silica, and
In the weather resistant protective coating composition according to the first aspect of the invention, a first component is the reaction product of a hydroxyl group-containing benzophenone compound with a silane and/or a (partial) hydrolyzate thereof. The silane is reacted with hydroxyl groups on the benzophenone compound. Any benzophenone compound having at least one hydroxyl group may be used although benzophenone compounds of the following general formula (A) are preferred. Any silane compound having a functional group capable of reacting with hydroxyl groups on the benzophenone compound may be used although epoxy group-containing silane compounds are preferred.
Accordingly, the preferred first component is the reaction product obtained by reacting a benzophenone compound of the following general formula (A) with an epoxy group-containing organoxysilane of the following general formula (B) in the presence of a catalyst, and/or a (partial) hydrolyzate thereof. Specifically the reaction product is obtained by reacting hydroxyl groups on the benzophenone UV absorber (A) with epoxy groups on the epoxy group-containing organoxysilane (B).
Examples of the benzophenone compound (A) which is one reactant from which component (1) is prepared are given below.
Of these, 2,2′, 4,4′-tetrahydroxybenzophenone is especially preferred because of its UV absorbing capability.
R1 aSiR2 b(OR3)4-a-b (B).
In formula (B), R2 is an alkyl group of 1 to 10 carbon atoms or aryl group, for example, methyl, ethyl, propyl, hexyl, decyl or phenyl.
The letter “a” is equal to 1 or 2, “b” is equal to 0 or 1, and a+b is equal to 1 or 2.
R1 is an epoxy group-containing organic group, examples of which are given below.
Illustrative examples of the epoxy group-containing silane (B) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane. From the standpoints of solubility in protective coating compositions and reactivity with benzophenone compounds, the preferred silane compounds are γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane.
The reaction is usually effected in the presence of the catalyst by heating compounds (A) and (B) at a temperature of 50 to 150° C. for about 4 to 20 hours. The reaction may be effected in a solventless system or in a solvent in which both compounds (A) and (B) are dissolved. The use of a solvent is rather preferable for ease of reaction control and handling. Suitable solvents include toluene, xylene, ethyl acetate and butyl acetate.
In the protective coating composition of the invention, colloidal silica is preferably blended as a fourth component. Colloidal silica is blended in an amount of 1 to 200 parts, especially 10 to 150 parts by weight of per 100 parts by weight of component (2). One exemplary blending procedure is by mixing 20 to 90 parts by weight of the silane compound and/or its (partial) hydrolyzate (2) with 10 to 80 parts by weight as solids of a colloidal silica containing silica fines having a particle size of 1 to 100 nm to a total amount of 100 parts by weight. The mixture is diluted with alcohol, water or water-miscible solvent to a nonvolatile concentration of 15 to 20% by weight. The dilution is ripened at room temperature for about 3 to 5 days or at 40 to 60° C. for about 10 to 15 hours. The term “colloidal silica” is a dispersion of silica fines in water or an alcohol such as methanol, ethanol, isobutanol or diacetone alcohol.
Heat curing conditions are not critical although heating at 100 to 130° C. for about one hour is preferred.
In this reaction, the amino group-containing alkoxysilane and the epoxy group-containing alkoxysilane are preferably used in such amounts that the molar ratio of epoxy groups to amino groups may range from 0.3/1 to 1.2/1. If the molar ratio of epoxy/amino is less than 0.3, only a less number of alkoxy groups per molecule participate in crosslinking, leading to short cure, and the entire molecule is not spread, leading to a weak surface bond. If the molar ratio of epoxy/amino is more than 1.2, amino (═N—H) groups which can be amidated during subsequent amidation step become few, exacerbating water-resistant bond.
The cured coating of the undercoating composition is obtained by heating the wet coating at 80 to 200° C.
wherein R5 is a C1-10 alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group or an organic group having an epoxy, (meth)acryloxy, mercapto, amino or cyano group, R2 and R3 are as defined above in formula (B), m and n each are equal to 0, 1 or 2, and m+n is equal to 0, 1 or 2. The colloidal silica is obtained by dispersing silica fines having a particle size of about 1 to 100 mμ in water or an alcohol such as methanol, ethanol, isobutanol or diacetone alcohol. To the hydrolyzate or co-hydrolyzate, 5 to 70% by weight of the colloidal silica is added.
The organopolysiloxane composition is applied onto the undercoat of the undercoating composition on a plastic substrate and cured by heating, typically at a temperature of 50 to 140° C. In this way, a top coat is formed on the plastic substrate to a high bond strength. The top coat of organopolysiloxane synergistically cooperates with the undercoat of the undercoating composition to accomplish high adhesion and abrasion resistance as well as excellent weather resistance and its stability due to tight fixation of the UV absorber in the undercoat. The top coat generally has a thickness of about 1 to 10 μm though not critical.
A 0.2-liter flask equipped with a stirrer, condenser and thermometer was charged with 50 g (0.20 mol) of 2,2′, 4,4′-tetrahydroxybenzophenone, 47.2 g (0.20 mol) of γ-glycidoxypropyltrimethoxysilane, 0.81 g (0.0036 mol) of benzyltriethylammonium chloride, and 100 g of butyl acetate, which were stirred and heated at 60° C. for dissolution. At this point, the solution was yellow and clear. The solution was heated to 120° C., at which temperature reaction was effected for 4 hours, obtaining a brown clear solution. By gas chromatography analysis, the disappearance of the reactant, γ-glycidoxypropyltrimethoxysilane was confirmed. The solid concentration was 50.1%. A dilution obtained by diluting the solution with ethanol to a solid concentration of 0.05 g/liter was analyzed for absorbance by spectrophotometry, finding an absorbance: λmax 349.9 nm and Abs 2.82, which was substantially identical with the absorbance of the reactant, 2,2′,4,4′-tetrahydroxybenzophenone as analyzed at the same concentration: λmax 351.7 nm and Abs 3.01, with the light absorption waveform of the former being also substantially identical with the latter.
A 0.2-liter flask equipped with a stirrer, condenser and thermometer was charged with 50 g (0.20 mol) of 2,2′,4,4′-tetrahydroxybenzophenone, 47.2 g (0.20 mol) of γ-glycidoxypropyltrimethoxysilane, 1 g (0.0092 mol) of tetramethylammonium chloride, and 100 g of butyl acetate, which were stirred and heated at 60° C. for dissolution. At this point, the solution was yellow and clear. The solution was heated to 120° C., at which temperature reaction was effected for 4 hours, obtaining a brown clear solution. By gas chromatography analysis, the disappearance of the reactant, γ-glycidoxypropyltrimethoxysilane was confirmed. The solid concentration was 49.9%. A dilution obtained by diluting the solution with ethanol to a solid concentration of 0.05 g/liter was analyzed for absorbance by spectrophotometry, finding an absorbance: λmax 349.8 nm and Abs 2.86, which was substantially identical with the absorbance of the reactant, 2,2′,4,4′-tetrahydroxybenzophenone as analyzed at the same concentration: λmax 351.7 nm and Abs 3.01, with the light absorption waveform of the former being also substantially identical with the latter.
A 0.2-liter flask equipped with a stirrer, condenser and thermometer was charged with 50 g (0.20 mol) of 2,2′,4,4′-tetrahydroxybenzophenone, 49.3 g (0.20 mol) of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 0.81 g (0.0036 mol) of benzyltriethylammonium chloride, and 100 g of butyl acetate, which were stirred and heated at 60° C. for dissolution. At this point, the solution was yellow and clear. The solution was heated to 120° C., at which temperature reaction was effected for 4 hours, obtaining a brown clear solution. By gas chromatography analysis, the disappearance of the reactant, γ-glycidoxypropyltrimethoxysilane was confirmed. The solid concentration was 51.0%. A dilution obtained by diluting the solution with ethanol to a solid concentration of 0.05 g/liter was analyzed for absorbance by spectrophotometry, finding an absorbance: λmax 350.9 nm and Abs 2.88, which was substantially identical with the absorbance of the reactant, 2,2′,4,4′-tetrahydroxybenzophenone as analyzed at the same concentration: λmax 351.7 nm and Abs 3.01, with the light absorption waveform of the former being also substantially identical with the latter.
A 0.2-liter flask equipped with a stirrer, condenser and thermometer was charged with 50 g (0.20 mol) of 2,2′,4,4′-tetrahydroxybenzophenone, 94.4 g (0.40 mol) of γ-glycidoxypropyltrimethoxysilane, 1.62 g (0.0072 mol) of benzyltriethylammonium chloride, and 150 g of butyl acetate, which were stirred and heated at 60° C. for dissolution. At this point, the solution was yellow and clear. The solution was heated to 120° C., at which temperature reaction was effected for 4 hours, obtaining a brown clear solution. By gas chromatography analysis, the disappearance of the reactant, γ-glycidoxypropyltrimethoxysilane was confirmed. The solid concentration was 50.3%. A dilution obtained by diluting the solution with ethanol to a solid concentration of 0.05 g/liter was analyzed for absorbance by spectrophotometry, finding an absorbance: λmax 348.9 nm and Abs 2.79, which was substantially identical with the absorbance of the reactant, 2,2′,4,4′-tetrahydroxy-benzophenone as analyzed at the same concentration: λmax 351.7 nm and Abs 3.01, with the light absorption waveform of the former being also substantially identical with the latter.
A 0.2-liter flask equipped with a stirrer, condenser and thermometer was charged with 50 g (0.20 mol) of 2,2′,4,4′-tetrahydroxybenzophenone, 49.6 g (0.20 mol) of γ-glycidoxypropylmethyldiethoxysilane, 0.81 g (0.0036 mol) of benzyltriethylammonium chloride, and 100 g of butyl acetate, which were stirred and heated at 60° C. for dissolution. At this point, the solution was yellow and clear. The solution was heated to 120° C., at which temperature reaction was effected for 4 hours, obtaining a brown clear solution. By gas chromatography analysis, the disappearance of the reactant, γ-glycidoxypropylmethyldiethoxysilane was confirmed. The solid concentration was 50.0%. A dilution obtained by diluting the solution with ethanol to a solid concentration of 0.05 g/liter was analyzed for absorbance by spectrophotometry, finding an absorbance: λmax 350.9 nm and Abs 2.88, which was substantially identical with the absorbance of the reactant, 2,2′,4 ,4′-tetrahydroxybenzophenone as analyzed at the same concentration: λmax 351.7 nm and Abs 3.01, with the light absorption waveform of the former being also substantially identical with the latter.
A 0.2-liter flask equipped with a stirrer, condenser and thermometer was charged with 42.4 g (0.20 mol) of 2,4-dihydroxybenzophenone, 47.2 g (0.20 mol) of γ-glycidoxypropyltrimethoxysilane, 0.81 g (0.0036 mol) of benzyltriethylammonium chloride, and 90 g of butyl acetate, which were stirred and heated at 60° C. for dissolution. At this point, the solution was yellow and clear. The solution was heated to 120° C., at which temperature reaction was effected for 4 hours, obtaining a yellowish brown clear solution. By gas chromatography analysis, the disappearance of the reactant, γ-glycidoxypropyltrimethoxysilane was confirmed. The solid concentration was 49.7%. A dilution obtained by diluting the solution with ethanol to a solid concentration of 0.05 g/liter was analyzed for absorbance by spectrophotometry, finding an absorbance: λmax 272.9 nm and Abs 1.52, which was slightly shifted to a shorter wavelength as compared with the absorbance of the reactant, 2,4-dihydroxybenzophenone as analyzed at the same concentration: λmax 289.1 nm and Abs 2.61, with the intensity being also lightly lowered.
Synthesis of Alkoxysilyl-containing Organic Copolymers Synthesis Example 7
A 0.5-liter flask equipped with a stirrer, condenser and thermometer was charged with 20 g of γ-methacryloxypropyltrimethoxysilane, 60 g of methyl methacrylate, 5 g of ethyl acrylate, 5 g of vinyl acetate, 10 g of glycidyl methacrylate, 0.2 g of ethylene glycol dimethacrylate, 0.5 g of azobisisobutyronitrile as a polymerization initiator, and 20 g of diacetone alcohol and 80 g of ethylene glycol monomethyl ether as solvents. The contents were stirred for 5 hours at 80 to 90° C. under a nitrogen stream. The resulting solution containing an organic copolymer having alkoxysilyl groups had a viscosity of 43,600 centistokes, and the copolymer contained 20% of γ-methacryloxypropyltrimethoxysilane.
The procedure of Synthesis Example 7 was repeated except that the amount of γ-methacryloxypropyltrimethoxysilane was changed to 10 g and the amount of methyl methacrylate was changed to 70 g, obtaining a solution containing an organic copolymer having alkoxysilyl groups. The organic copolymer solution had a viscosity of 40,600 centistokes, and the copolymer contained 10% of γ-methacryloxypropyltrimethoxysilane.
The procedure of Synthesis Example 7 was repeated except that 20 of γ-methacryloxypropyltrimethoxysilane was replaced by 20 g of vinyltrimethoxysilane, obtaining a solution containing an organic copolymer having alkoxysilyl groups. The organic copolymer solution had a viscosity of 39,700 centistokes, and the copolymer contained 20% of vinyltrimethoxysilane.
Synthesis of Colloidal Silica-containing Organopolysiloxane Composition Synthesis Example 11
A 1.0-liter flask equipped with a stirrer, condenser and thermometer was charged with 164 g of methyltriethoxysilane and 46 g of isobutanol, which were maintained below 5° C. under ice cooling with stirring. To this was added 138 g of colloidal silica (containing 20% of SiO2) below 5° C. The mixture was stirred for 2 hours under ice cooling and for a further 8 hours at 20 to 25° C. Thereafter, 45 g of diacetone alcohol and 50 g of isobutanol were added, 1.5 g of a 10% aqueous solution of sodium propionate was then added, and the resulting mixture was adjusted to pH 6 to 7 with acetic acid. This was adjusted with isobutanol to a nonvolatile content of 17% as measured by JIS K-6833 and ripened for 5 days at room temperature. The resulting colloidal silica-containing organopolysiloxane composition had a viscosity of about 5 centistokes and the nonvolatile component had a number average molecular weight of about 1,000.
The procedure of Synthesis Example 11 was repeated except that 3.0 g of a 10% aqueous solution of tetramethylammonium benzoate was used instead of the sodium propionate aqueous solution, obtaining a colloidal silica-containing organopolysiloxane composition.
The procedure of Synthesis Example 11 was repeated except that there was further added 1.8 g of 2,2′,4 ,4′-tetrahydroxybenzophenone (corresponding to 2 parts per 100 parts of the solids of the colloidal silica-containing organopolysiloxane composition), obtaining a colloidal silica-containing organopolysiloxane composition.
A 0.3-liter flask equipped with a stirrer, condenser and thermometer was charged with 100 g (0.5 mol) of 2,2,6,6-tetramethyl-4-allyl-piperidine and 0.13 g of a butanol solution of chloroplatinic acid (2% solution of H2PtCl6. 6H2O). To the flask at room temperature, 80.6 g (0.66 mol) of trimethoxysilane was added dropwise over one hour, and reaction effected at 90° C. for 5 hours.
At the end of reaction, distillation was effected under vacuum, collecting 126 g of a fraction at 151-154° C. at 7 mmHg. By gas chromatography, 2,2,6,6-tetramethyl-piperidino-4-propyltrimethoxysilane was collected at a purity of 97%. Its structure was confirmed by IR spectrometry and proton-NMR analysis.
An accelerated weathering test was carried out by a sunshine carbon arc weatherometer according to JIS K-5400. After 5,000 hours, a yellowing factor and adhesion were examined. Those samples having a yellowing factor of up to 7 and good adhesion were rated “Passed.”
A 0.5-liter flask equipped with a stirrer, condenser and thermometer was charged with 20 g of γ-methacryloxy-propyltrimethoxysilane, 60 g of methyl methacrylate, 5 g of ethyl acrylate, 5 g of vinyl acetate, 10 g of glycidyl methacrylate, 0.2 g of ethylene glycol dimethacrylate, 0.5 g of azobisisobutyronitrile as a polymerization initiator, and 20 g of diacetone alcohol and 80 g of ethylene glycol monomethyl ether as solvents. The contents were stirred for 5 hours at 80 to 90° C. under a nitrogen stream. The resulting solution of thermosetting acrylic resin had a viscosity of 43,600 centistokes, and the copolymer contained 40% of alkoxyl group. The resin solution was diluted with a 20/80 mixture of diacetone alcohol and ethylene glycol monomethyl ether so as to give a nonvolatile concentration of 10% as measured according to JIS K-6833. The thus prepared primer had a viscosity of 20 to 40 centistokes. UVA-7 was added to the primer in an amount of 6 parts per 100 parts of solids in the primer and fully dissolved therein, completing the primer.
A 1.0-liter flask equipped with a stirrer, condenser and thermometer was charged with 164 g of methyltriethoxysilane and 46 g of isobutanol, which were maintained below 5° C. under ice cooling while stirring. To the flask, 138 g of water-dispersed colloidal silica (containing 20% of SiO2) below 5° C. was added. The contents were stirred for 2 hours under ice cooling and for 8 hours at 20 to 25° C., following which 45 g of diacetone alcohol and 50 g of isobutanol were added. Thereafter, 1.5 g of a 10% aqueous solution of sodium propionate was added to the reaction solution, which was adjusted to pH 6 to 7 with acetic acid. This was diluted with isobutanol so as to give a nonvolatile concentration of 17% as measured according to JIS K-6833. Ripening for 5 days at room temperature yielded a silane hydrolyzate solution having a viscosity of about 5 centistokes and the nonvolatile matter had a number average molecular weight of about 1,000. The UV absorbers UVA-1 and UV-1 were added to the silane hydrolyzate solution in amounts of 10 parts as solids of UVA-1 and 20 parts as solids of UV-1 per 100 parts of solids in the solution and fully dissolved therein, obtaining a protective coating composition.
The primer was applied onto a polycarbonate resin sheet of 0.5 mm thick by the flow coating method and cured at about 120° C. for about 30 minutes, obtaining a cured primer coating of 2 to 5 μm thick. The protective coating composition was applied onto the primer coating by the flow coating method and cured at about 120° C. for about one hour, obtaining a cured protective coating of 2 to 5 μm. The thus surface-coated sheet was examined for physical properties, with the results shown in Table 3.
(a) Preparation of Primer A Primer was Prepared as in Example 1.
A 1.0-liter flask equipped with a stirrer, condenser and thermometer was charged with 164 g of methyltriethoxysilane, 19.7 g of UVA-1 and 46 g of isobutanol, which were maintained below 5° C. under ice cooling while stirring. To the flask, 138 g of water-dispersed colloidal silica (containing 20% of SiO2) below 5° C. was added. The contents were stirred for 2 hours under ice cooling and for 8 hours at 20 to 25° C., following which 45 g of diacetone alcohol and 50 g of isobutanol were added. Thereafter, 1.5 g of a 10% aqueous solution of sodium propionate was added to the reaction solution, which was adjusted to pH 6 to 7 with acetic acid. This was diluted with isobutanol so as to give a nonvolatile concentration of 19% as measured according to JIS K-6833. Ripening for 5 days at room temperature yielded a silane hydrolyzate solution having a viscosity of about 5 centistokes and the nonvolatile matter had a number average molecular weight of about 1,000. The UV absorber UV-1 was added to the silane hydrolyzate solution in amounts of 20 parts as solids of UV-1 per 100 parts of solids in the solution and fully dissolved therein, obtaining a protective coating composition.
A 1.0-liter flask equipped with a stirrer, condenser and thermometer was charged with 164 g of methyltriethoxysilane, 19.7 g of UVA-3 and 46 g of isobutanol, which were maintained below 5° C. under ice cooling while stirring. To the flask, 138 g of water-dispersed colloidal silica (containing 20% of SiO2) below 5° C. was added. The contents were stirred for 2 hours under ice cooling and for 8 hours at 20 to 25° C., following which 45 g of diacetone alcohol and 50 g of isobutanol were added. Thereafter, 1.5 g of a 10% aqueous solution of sodium propionate was added to the reaction solution, which was adjusted to pH 6 to 7 with acetic acid. This was diluted with isobutanol so as to give a nonvolatile concentration of 19% as measured according to JIS K-6833. Ripening for 5 days at room temperature yielded a silane hydrolyzate solution having a viscosity of about 5 centistokes and the nonvolatile matter had a number average molecular weight of about 1,000. The UV absorber UV-1 was added to the silane hydrolyzate solution in amounts of 20 parts as solids of UV-1 per 100 parts of solids in the solution and fully dissolved therein, obtaining a protective coating composition.
A 1.0-liter flask equipped with a stirrer, condenser and thermometer was charged with 164 g of methyltriethoxysilane, 19.7 g of UV-5 and 46 g of isobutanol, which were maintained below 5° C. under ice cooling while stirring. To the flask, 138 g of water-dispersed colloidal silica (containing 20% of SiO2) below 5° C. was added. The contents were stirred for 2 hours under ice cooling and for 8 hours at 20 to 25° C., following which 45 g of diacetone alcohol and 50 g of isobutanol were added. Thereafter, 1.5 g of a 10% aqueous solution of sodium propionate was added to the reaction solution, which was adjusted to pH 6 to 7 with acetic acid. This was diluted with isobutanol so as to give a nonvolatile concentration of 19% as measured according to JIS K-6833. Ripening for 5 days at room temperature yielded a silane hydrolyzate solution having a viscosity of about 5 centistokes and the nonvolatile matter had a number average molecular weight of about 1,000. The UV absorber UV-1 was added to the silane hydrolyzate solution in amounts of 20 parts as solids of UV-1 per 100 parts of solids in the solution and fully dissolved therein, obtaining a protective coating composition.
A 1.0-liter flask equipped with a stirrer, condenser and thermometer was charged with 164 g of methyltriethoxysilane, 19.7 g of UVA-6 and 46 g of isobutanol, which were maintained below 50° C. under ice cooling while stirring. To the flask, 138 g of water-dispersed colloidal silica (containing 20% of SiO2) below 5° C. was added. The contents were stirred for 2 hours under ice cooling and for 8 hours at 20 to 25° C., following which 45 g of diacetone alcohol and 50 g of isobutanol were added. Thereafter, 1.5 g of a 10% aqueous solution of sodium propionate was added to the reaction solution, which was adjusted to pH 6 to 7 with acetic acid. This was diluted with isobutanol so as to give a nonvolatile concentration of 19% as measured according to JIS K-6833. Ripening for 5 days at room temperature yielded a silane hydrolyzate solution having a viscosity of about 5 centistokes and the nonvolatile matter had a number average molecular weight of about 1,000. The UV absorber UV-1 was added to the silane hydrolyzate solution in amounts of 20 parts as solids of UV-1 per 100 parts of solids in the solution and fully dissolved therein, obtaining a protective coating composition.
Examples 7-39 and Comparative Examples 1-8
Primers and protective coating compositions were prepared according to the composition shown in Tables 1 and 2 by the same procedure as in Example 1
composition (parts) Primer (parts)
UVA UV UVA HALS
Example 1  UVA-1 (10) UV-1 (20) UVA-7 (6) —
Example 2  UVA-1 (10) UV-1 (20) UVA-7 (6) —
Example 3  (incorporated in UV-1 (20) UVA-7 (6) —
Example 4  (incorporated in UV-1 (20) UVA-7 (6) —
Example 5  (incorporated in UV-1 (20) UVA-7 (6) —
Example 6  (incorporated in UV-1 (20) UVA-7 (6) —
Example 7  UVA-2 (10) UV-1 (20) UVA-7 (6) —
Example 8  UVA-3 (10) UV-1 (20) UVA-7 (6) —
Example 9  UVA-4 (10) UV-1 (20) UVA-7 (6) —
Example 10 UVA-5 (10) UV-1 (20) UVA-7 (6) —
Example 11 UVA-6 (10) UV-1 (20) UVA-7 (6) —
Example 12 UVA-1 (20) UV-1 (20) UVA-7 (6) —
Example 13 UVA-1 (10) UV-1 (30) UVA-7 (6) —
Example 14 UVA-1 (30) UV-1 (20) UVA-7 (6) —
Example 15 UVA-1 (10) UV-1 (50) UVA-7 (6) —
Example 16 UVA-1 (6)  UV-1 (20) UVA-7 (6) —
Example 17 UVA-1 (5)  UV-1 (20) UVA-7 (6) —
UVA-3 (5)
Example 18 UVA-1 (5)  UV-1 (20) UVA-7 (6) —
UVA-4 (5)
Example 19 UVA-1 (5)  UV-1 (20) UVA-7 (6) —
UVA-5 (5)
Example 20 UVA-1 (8)  UV-1 (20) UVA-7 (6) —
UVA-6 (2)
Example 21 UVA-1 (10) UV-1 (20) UVA-7 (6) HALS-1 (0.05)
Example 22 UVA-1 (10) UV-2 (20) UVA-7 (6) HALS-1 (0.05)
Example 23 UVA-1 (10) UV-3 (20) UVA-7 (6) HALS-1 (0.05)
Example 24 UVA-1 (10) UV-4 (20) UVA-7 (6) HALS-1 (0.05)
Example 25 UVA-1 (10) UV-5 (20) UVA-7 (6) HALS-1 (0.05)
Example 26 UVA-1 (10) UV-2 (20) UVA-1 (6) HALS-1 (0.05)
Example 27 UVA-1 (10) UV-2 (20) UVA-1 (1.5) HALS-1 (0.05)
Example 28 UVA-1 (10) UV-2 (20) UVA-1 (3) HALS-1 (0.05)
Example 29 UVA-1 (10) UV-2 (20) UVA-7 (6) HALS-2 (0.05)
Example 30 UVA-1 (10) UV-1 (20) UVA-8 (8) —
Example 31 UVA-1 (10) UV-1 (20) UVA-9 (8) —
Example 32 UVA-1 (10) UV-1 (20) UVA-10 (8) —
Example 33 UVA-1 (10) UV-1 (20) UVA-11 (8) —
Example 34 UVA-1 (10) UV-1 (20) UVA-12 (8) —
Example 35 UVA-1 (30) — UVA-1 (6) HALS-1 (0.05)
Example 36 UVA-3 (30) — UVA-1 (6) HALS-2 (0.05)
Example 37 UVA-5 (30) — UVA-1 (6) —
Example 38 UVA-1 (10) — UVA-1 (6) HALS-3 (0.1)
Example 39 UVA-1 (10) UV-1 (20) UVA-1 (6) HALS-3 (0.1)
Comparative UVA-7 (10) — UVA-7 (6) —
Comparative UVA-7 (4)  — UVA-7 (8) —
Comparative UVA-7 (20) — UVA-7 (6) —
Comparative UVA-8 (20) — UVA-7 (6) —
Comparative — UV-1 (2.0) UVA-7 (6) —
Comparative UVA-7 (10) UV-1 (2.0) UVA-7 (6) —
Comparative — — UVA-7 (6) —
Comparative UVA-7 (10) — UVA-7 (6) HALS-1 (0.5)
Taber Yellowing
Yellowing factor abrasion factor Adhesion
Example 1 1.2 8 2.0 100/100
Example 2 1.2 8 2.5 100/100
Example 3 1.0 7 1.5 100/100
Example 4 1.0 7 2.0 100/100
Example 5 0.9 7 2.0 100/100
Example 6 1.4 9 4.0 100/100
Example 7 1.2 8 1.5 100/100
Example 8 1.2 7 1.5 100/100
Example 9 0.9 9 1.5 100/100
Example 10 0.9 9 4.5 100/100
Example 11 1.0 7 1.5 100/100
Example 12 1.0 8 1.5 100/100
Example 13 1.0 7 1.5 100/100
Example 14 1.5 9 2.0 100/100
Example 15 1.0 7 1.5 100/100
Example 16 1.0 7 1.5 100/100
Example 17 1.0 7 1.5 100/100
Example 18 1.0 7 1.5 100/100
Example 19 1.0 7 1.5 100/100
Example 20 1.2 8 2.5 100/100
Example 21 1.0 7 1.5 100/100
Example 22 1.0 7 1.5 100/100
Example 23 1.0 7 1.5 100/100
Example 24 0.8 8 1.5 100/100
Example 25 0.8 8 2.0 100/100
Example 26 0.9 7 2.0 100/100
Example 27 1.2 7 1.5 100/100
Example 28 1.2 7 1.5 100/100
Example 29 1.2 8 1.5 100/100
Example 30 1.0 9 2.5 100/100
Example 31 1.2 8 2.0 100/100
Example 32 1.2 8 2.0 100/100
Example 33 1.0 8 2.0 100/100
Example 34 1.0 8 2.0 100/100
Example 35 1.0 7 2.0 100/100
Example 36 1.0 8 2.0 100/100
Example 37 1.0 8 2.0 100/100
Example 38 1.0 8 1.5 100/100
Example 39 1.0 7 1.5 100/100
Example 1 3.1 10 15 0/100
Example 2 7.0 15 30 0/100
Example 3 4.0 15 8.0 0/100
Example 4 1.0 20 35 0/100
Example 5 2.5 15 20 0/100
Example 6 2.0 8 9.0 0/100
Example 7 0.9 15 20 0/100
Example 8 1.2 9 10 0/100
Examples 40-56 and Comparative Examples 9-17
The organic copolymers prepared in Synthesis Examples 7 to 9 (Pol-1 to 3), polymethyl methacrylate having an average molecular weight of 150,000, the compounds containing nitrogen and alkoxysilyl groups in a molecule (NSi-1 and NSi-2), the silyl-modified ultraviolet absorbers (UVA-1 to 6), the ultraviolet absorbers (UVA-7 to 12), and the light stabilizers (HALS-1 to 3) were mixed in the amounts shown in Tables 5 to 7. The mixtures were diluted with a 20/80 mixture of diacetone alcohol and ethylene glycol monomethyl ether so as to give a concentration of 10% as solids of the organic copolymer. In this way, undercoating compositions A to Z were prepared as shown in Tables 5 to 7.
Each of the undercoating compositions was applied onto a polycarbonate resin sheet of 0.5 mm thick, which had been surface cleaned, by the flow coating method and cured at about 120° C. for about 30 minutes, obtaining a cured undercoat of 2 to 5 μm thick. Each of the colloidal silica-containing organopolysiloxane compositions of Synthesis Examples 11 to 13 was applied onto the undercoat by the flow coating method and cured at about 120° C. for about one hour, obtaining a cured top coat of 2 to 5 μm. The thus surface-coated sheet was examined for physical properties, with the results shown in Table 8.
Undercoating A B C D E F G H I
UVA UVA-1 UVA-1 UVA-1 UVA-2 UVA-3 UVA-4 UVA-5 UVA-6 UVA-1
20 30 40 30 30 30 30 30 30
parts parts parts parts parts parts parts parts parts
Organic Pol-1 Pol-1 Pol-1 Pol-2 Pol-3 Pol-1 Pol-1 Pol-1 Pol-1
copolymer 100 100 100 100 100 100 100 100 100
Polymethyl — — — — — — — — —
NSi — — — — — — — — —
HALS — — — — — — — — —
Colloidal HC-1 HC-1 HC-1 HC-1 HC-1 HC-2 HC-2 HC-2 HC-3
Undercoating J K L M N O P Q
UVA UVA-1 UVA-1 UVA-1 UVA-1 UVA-1 UVA-1 UVA-1 UVA-1
30 parts 30 parts 30 parts 27 27 27 27 27
parts + parts + parts + parts + parts +
UVA-7 UVA-9 UVA-10 UVA-11 UVA-12
3 parts 3 parts 3 parts 3 parts 3 parts
Organic Pol-1 Pol-1 Pol-2 Pol-1 Pol-1 Pol-1 Pol-1 Pol-1
copolymer 100 100 100 100 100 100 100 100
Polymethyl 20 20 20 — — — 20 —
methacrylate parts parts parts parts
NSi Nsi-1 Nsi-2 Nsi-2 Nsi-2 Nsi-2 Nsi-2 Nsi-2 Nsi-2
5 parts 20 parts 30 parts 20 parts 20 parts 20 parts 20 parts 20 parts
HALS HALS-1 HALS-2 HALS-3 HALS-1 HALS-3 HALS-3 HALS-1 HALS-1
10 parts 10 parts 6 parts 3 parts 10 parts 6 parts 2 parts 2 parts
Colloidal HC-1 HC-1 HC-3 HC-3 HC-3 HC-3 HC-3 HC-3
Undercoating R S T U V W X Y Z
UVA UVA-7 UVA-7 UVA-7 UVA-8 UVA-9 UVA-10 UVA-11 UVA-12 UVA-7
10 20 10 20 20 20 20 20 20
Organic Pol-1 Pol-1 Pol-1 Pol-2 Pol-3 Pol-1 Pol-1 Pol-2 Pol-1
Polymethyl — — — — — — — — 20
NSi — — — — — — — — Nsi-2
HALS — HALS-2 — — — HALS-3 — — HALS-2
Colloidal HC-1 HC-1 HC-3 HC-3 HC-1 HC-2 HC-2 HC-2 HC-1
Example 40 1.0 8 1.5 100/100
Example 41 1.5 8 1.5 100/100
Example 42 1.5 7 2.0 100/100
Example 43 1.0 8 1.5 100/100
Example 44 0.9 8 1.5 100/100
Example 45 1.0 9 1.5 100/100
Example 46 1.0 9 2.0 100/100
Example 47 1.2 7 2.0 100/100
Example 48 1.0 8 1.5 100/100
Example 49 1.0 9 2.5 100/100
Example 50 1.0 8 2.0 100/100
Example 51 1.0 8 1.0 100/100
Example 52 1.5 7 2.5 100/100
Example 53 1.5 9 2.0 100/100
Example 54 1.0 8 1.5 100/100
Example 55 1.0 8 1.5 100/100
Example 56 1.0 7 1.5 100/100
Example 9 4.0 15 15 0/100
Example 10 8.0 20 30 0/100
Example 11 4.0 15 8.0 0/100
Example 12 1.5 20 35 0/100
Example 13 1.0 8 15 100/100
Example 14 3.0 11 20 100/100
Example 15 2.0 10 15 100/100
Example 16 2.0 10 15 100/100
Example 17 4.0 11 20 50/100
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U.S. Classification 428/447, 427/204, 524/858, 427/164, 524/859, 528/21, 106/287.1, 528/29, 524/588, 528/12, 427/387, 428/412
International Classification C09D183/06, C09D143/04, C09D4/00
Cooperative Classification Y10T428/31507, Y10T428/31663, C09D143/04, C09D183/06, C09D4/00
European Classification C09D4/00, C09D143/04, C09D183/06
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MATSUMURA, KAZUYUKI;YAMAYA, MASAAKI;SATO, KAZUHARU;AND OTHERS;REEL/FRAME:010961/0800