JP2002036443A - Window made of resin protected on surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a window made of a resin and having good appearance, hot water resistance and adhesive properties and covered on a surface of a base capable of giving a wear resistance of a high level not in prior art. SOLUTION: The window made of the resin protected on its surface comprises a coating film resin of a first layer containing an acrylic resin of at least 50 wt.% of the film resin and the acrylic resin containing a repeating unit of a specific methacrylic acid derivative of 50 mol% or more and laminated on the surface of the base, and a coating film layer of a second layer obtained by laminating a coating film layer obtained by thermosetting an organosiloxane resin containing (A) a colloidal silica (component a), (B) a hydrolytic condensate of a trialkoxysilane (component b) and (C) a hydrolytic condensate of a tetraalkoxysilane (component c).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin window whose surface is protected. More specifically, the present invention relates to a resin window in which a layer mainly composed of an acrylic resin and a cured layer of an organosiloxane are sequentially laminated on a transparent resin substrate, so that abrasion resistance is significantly improved.

[0002]

2. Description of the Related Art Many windows are mounted on automobiles, various transportation means, and buildings. At present, inorganic glass is widely used for these windows. For example, windows mounted on cars and various types of transportation (hereinafter referred to as vehicles), houses,
Most of the windows attached to buildings such as buildings are composed of windows made of inorganic glass, and in some cases, a soft synthetic resin window frame is attached to the outer periphery of the window.

[0003] Since inorganic glass has the disadvantage of being heavy, for example, when inorganic glass is used for a window of a vehicle, the weight of the vehicle becomes heavy, which causes a reduction in fuel efficiency. There was a problem. Furthermore, since inorganic glass has poor impact resistance, when using inorganic glass for windows of buildings and private cars, there is a security problem that a mob can easily enter the building or private car by destroying the window. However, there have been safety problems such as injury due to sharp fragments generated when the inorganic glass is broken.

In order to improve security and security,
2. Description of the Related Art Resin windows mainly made of polycarbonate resin are used for windows of bank counters, windows of racetrack ticket offices, windows of vending machines, and the like.

[0005] A resin window is usually formed by cutting out a sheet obtained by injection molding or extrusion molding of a thermoplastic resin to form a window portion, and performing a surface treatment such as a hard coat treatment, or The hard-coated window is mounted in a window molding die, and a thermoplastic resin is injection-molded therein to form a hard-coated window. Next, a method of attaching the window frame portion created in a separate process to the outer peripheral portion of the window portion, or mounting the window portion in a window frame portion forming die, and then injection molding a soft thermoplastic resin. It is formed by a method of molding a window frame portion and integrating the window frame portion and the window portion.

[0006] If the surface of such a resin window is damaged and external visibility is deteriorated, it cannot be used comfortably. Therefore, resin windows are required to have as high abrasion resistance and abrasion resistance as possible as long as other performances are not impaired.

Many proposals have been made to improve the abrasion resistance of a plastic by coating the surface of the plastic with a siloxane-based cured film. For example, JP-A-51-
JP-A-2736 and JP-A-55-94971 describe a coating composition comprising a partial condensate of trihydroxysilane and colloidal silica. Also, JP-A-48-26822 and JP-A-51-2
No. 33128 describes a coating composition mainly containing a partial condensate of an alkyl trialkoxysilane and a tetraalkoxysilane. Further, JP-A-63-278979 and JP-A-1-30647
No. 6 discloses a coating composition in which colloidal silica is added to a condensate of an alkyl trialkoxysilane and a tetraalkoxysilane.

However, those obtained by laminating a cured film obtained from these coating compositions on a transparent plastic substrate have a certain level of excellent abrasion resistance and abrasion resistance, but have the same abrasion resistance as glass. Not that,
Further improvement in abrasion resistance is required.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin window whose surface is protected by a cured film capable of imparting an unprecedentedly high level of wear resistance. The present inventor has conducted intensive studies to achieve this object, and as a result, a first layer mainly composed of acrylic resin and colloidal silica, trialkoxysilane hydrolyzed condensate and The present inventors have found that a resin window in which a second layer formed by thermally curing an organosiloxane resin made of a tetraalkoxysilane hydrolyzed condensate is sequentially laminated from the first layer has an unprecedentedly high level of wear resistance. The invention has been reached.

[0010]

That is, according to the present invention, at least 50% by weight of the coating resin is an acrylic resin as a first layer on the surface of the base material of the resin window. The acrylic resin has the following formula (1)

[0011]

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(Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms.) A coating resin, which is an acrylic resin containing 50 mol% or more of a repeating unit represented by the formula: As a layer, (A) colloidal silica (a component),
(B) Hydrolysis condensate of trialkoxysilane represented by the following formula (2) (component b)

[0013]

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(Wherein R ² represents an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group,
1 carbon atom substituted with one or more groups selected from the group consisting of a glycidoxy group and a 3,4-epoxycyclohexyl group
And R ³ is an alkyl group having 1 to 4 carbon atoms. ) And (C) a hydrolysis condensate of a tetraalkoxysilane represented by the following formula (3) (component (c)):

[0015]

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(Wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms). A resin window having a protected surface provided with a coating layer obtained by thermosetting an organosiloxane resin comprising: You.

In the present invention, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight of the coating resin laminated on the substrate surface of the window part made of resin as the first layer. Is an acrylic resin. If the acrylic resin content is less than 50% by weight, the adhesion between the transparent resin substrate and the second layer of the organosiloxane resin thermosetting layer is poor, which is not preferable.

Further, the acrylic resin has the formula (1)
Is an acrylic resin containing 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more of the repeating unit represented by If the repeating unit represented by the formula (1) in the acrylic resin is less than 50 mol%, the adhesion to the transparent resin substrate and the second layer of the organosiloxane resin thermosetting layer is poor, which is not preferable.

The acrylic resin is a polymer obtained by polymerizing 50 mol% or more of an alkyl methacrylate monomer and 50 mol% or less of a vinyl monomer. Specific examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, and these can be used alone or in combination of two or more. Of these, methyl methacrylate and ethyl methacrylate are preferred.

The other vinyl monomers are copolymerizable with an alkyl methacrylate monomer, and in particular, acrylic acid, methacrylic acid or derivatives thereof are preferred in view of durability such as adhesiveness and weather resistance. used. Specifically, acrylic acid, methacrylic acid, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl methacrylate, N, N-diethylaminoethyl methacrylate, glycidyl methacrylate, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane,
Examples thereof include 3-methacryloxypropylmethyldimethoxysilane, and these can be used alone or as a mixture of two or more. Further, a mixture of two or more acrylic resins may be used.

The acrylic resin is preferably of a thermosetting type, and desirably contains 0.01 to 50 mol% of a vinyl monomer having a crosslinkable reactive group. Examples of the vinyl monomer having such a crosslinkable reactive group include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyl trimethoxy silane, and 3-methacryloxy propyl trimethoxy silane. , 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and the like.

The molecular weight of the acrylic resin is preferably 20,000 to 600,000 in terms of weight average molecular weight,
More preferably, it is used in the range of from 0.000 to 400,000. The acrylic resin having such a molecular weight range is preferable because performance such as adhesion and strength as the first layer is sufficiently exhibited.

As a preferred embodiment of the acrylic resin, the above formula (1) and the following formula (4)

[0024]

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(Where X is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 2 to ⁵ carbon atoms,
R ⁶ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 or 1. Is a copolymer comprising a repeating unit represented by the formula (1), and a molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (4) is 9
An acrylic resin having a range of 9.99: 0.01 to 50:50, preferably a range of 99: 1 to 60:40, and more preferably a range of 97: 3 to 70:30 is employed. . The acrylic resin copolymer has at least 5 coating film resins laminated on the surface of the transparent resin substrate as the first layer.
It is 0% by weight, preferably at least 70% by weight, more preferably at least 90% by weight, and typically it is desirable that the coating resin is substantially this acrylic resin copolymer.

Such an acrylic resin is a copolymer obtained by polymerizing an alkyl methacrylate monomer and an acrylate or methacrylate monomer having an alkoxysilyl group in the above-mentioned ratio. As the acrylate or methacrylate monomer having such an alkoxysilyl group, specifically, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and the like, and 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyl. Dimethoxysilane is preferred, and 3-methacryloxypropyltrimethoxysilane is particularly preferred.

By using an acrylic resin obtained by copolymerizing an acrylate or methacrylate monomer having an alkoxysilyl group with an alkyl methacrylate monomer, the adhesion to the second organosiloxane resin thermosetting layer is further improved. Further, the hot water resistance of the transparent resin molded article is further improved, and those copolymerized in the above ratio range are less likely to gel and have excellent storage stability. Since such a copolymer has an alkoxysilyl group, it is structurally similar to the second layer and has an affinity, so that it is estimated that the adhesion to the second layer is further enhanced.

A preferred embodiment of the coating resin of the first layer is represented by the following formula (5):

[0029]

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(Wherein R ⁷ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group,
1 carbon atom substituted with one or more groups selected from the group consisting of a glycidoxy group and a 3,4-epoxycyclohexyl group
R ⁸ is an alkyl group having 1 to 4 carbon atoms, and r is an integer of 0 to 2. Hydrolytic condensate 40 wt% of the compound represented by) _(R ⁷ _r -SiO
_{4-r / 2} ), the above formula (1) and the following formula (6)

[0031]

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(Wherein, Y is a hydrogen atom or a methyl group, and R ⁹ is an alkylene group having 2 to 5 carbon atoms). The molar ratio of the repeating unit represented by 1) to the repeating unit represented by the formula (6) is 99: 1 to 5
Mixtures or reactants with 99-60% by weight of an acrylic resin at 0:50 are preferably used.

Examples of the alkoxysilane represented by the formula (5) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, methyltrimethylsilane. Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ
-Aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and the like. Alkyl trialkoxysilanes are preferred, especially methyltrimethoxysilane and methyltriethoxysilane. These can be used alone or in combination.

The hydrolysis-condensation product of the alkoxysilane is generally 0.2 to 4 equivalents, preferably 0.5 to 2 equivalents, more preferably 1 to 1 equivalent to 1 equivalent of the alkoxy group of the alkoxysilane under acidic conditions. 20 using 5 equivalents of water
It is obtained by performing a hydrolytic condensation reaction at 〜40 ° C. for 1 hour to several days. Acids are used in the hydrolysis-condensation reaction. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid. And organic acids such as succinic acid, maleic acid, lactic acid and p-toluenesulfonic acid, and volatile acids such as acetic acid and hydrochloric acid are preferred. The acid is usually used at a concentration of 0.0001 to 2N, preferably 0.001 to 0.1N when an inorganic acid is used, and 100 parts by weight of trialkoxysilane when an organic acid is used. It is used in the range of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight.

The repeating unit represented by the formula (1) and the repeating unit represented by the formula (6) have a molar ratio of 9
9: 1 to 50:50, preferably 97: 3.
~ 55: 45, more preferably 95: 5-
An acrylic resin having a hydroxy group in the range of 60:40 is employed. Within this range, the hot water resistance of the resin window is sufficient, which is preferable.

Such an acrylic resin is a copolymer obtained by polymerizing an alkyl methacrylate monomer and an acrylate or methacrylate monomer having a hydroxy group in the above ratio. As the acrylate or methacrylate monomer having such a hydroxy group, specifically, 2-hydroxyethyl acrylate,
Examples thereof include 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. Among them, 2-hydroxyethyl methacrylate is preferably used.

The hydrolysis-condensation product of the alkoxysilane and
The mixing ratio of the acrylic resin having a hydroxy group is as described above.
Is 1 to 40% by weight, preferably 5 to 30% by weight (only
R ⁷ _r-SiO_{4-r / 2}Weight), and the latter is
99 to 60% by weight, preferably 95 to 70% by weight
You. By preparing such a composition, such acrylic
The resin layer is composed of a transparent resin substrate and the second layer of organo.
Can maintain good adhesion to the siloxane resin thermosetting layer
it can. Further, a hydrolysis-condensation product of the alkoxysilane
And the acrylic resin having a hydroxy group, the above ratio
The mixture mixed in the range of
Can be used.

It is also preferred to further mix a melamine resin with a mixture or a reaction product of the hydrolysis condensate of the alkoxysilane and the acrylic resin having a hydroxy group in order to improve physical properties such as adhesion. . The melamine resin to be used includes, for example, fully alkylated methylated melamine represented by hexamethoxymethyl melamine, a resin in which a part of the methoxymethyl group of hexamethoxymethyl melamine has become a methylol group, an imino group, or butoxy. Methyl groups, fully alkyl-type butylated melamine represented by hexabutoxymethylmelamine, and the like are mentioned, and fully alkyl-type methylated melamine represented by hexamethoxymethylmelamine is preferably used. These melamine resins can be used alone or as a mixture. When a melamine resin is used, an acid catalyst is preferably added to promote the curing of the melamine resin. Such acid catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid,
Inorganic acids such as sulfamic acid, maleic acid, formic acid, acetic acid,
Organic acids such as propionic acid, butyric acid, oxalic acid, succinic acid, lactic acid, benzenesulfonic acid, and paratoluenesulfonic acid are used, and preferably have sufficient acidity such as maleic acid, benzenesulfonic acid, and paratoluenesulfonic acid. A non-volatile acid is used. Such an acid catalyst is used in an amount of preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the melamine resin.

The preferred amount of the melamine resin is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of a mixture or a reaction product of a hydrolyzed condensate of an alkoxysilane and an acrylic resin having a hydroxy group. More preferred. By mixing in such a range, the coating resin layer can maintain good adhesion to the transparent resin base material and the thermosetting organosiloxane resin layer of the second layer.

As a method for forming the above-mentioned coating resin (first layer) used in the present invention, a coating resin component such as an acrylic resin and an additive component such as a light stabilizer and an ultraviolet absorber described later are added to a base material. The coating composition is dissolved in a volatile solvent that does not react with or dissolve the transparent resin, the coating composition is applied to the surface of the transparent resin substrate, and then the solvent is removed by heating or the like. Will be If necessary, after removing the solvent, it is also preferable to further heat to 40 to 140 ° C. to crosslink the crosslinkable group.

Examples of such a solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran, 1,4-dioxane and 1,2-dimethoxyethane, and esters such as ethyl acetate and ethoxyethyl acetate. , Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1
-Alcohols such as propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, n-hexane, n-heptane, isooctane,
Examples thereof include hydrocarbons such as benzene, toluene, xylene, gasoline, light oil, and kerosene, acetonitrile, nitromethane, and water, and these may be used alone or as a mixture of two or more. The concentration of the solid content of the coating resin in such a coating composition is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

The coating composition may contain a light stabilizer and an ultraviolet absorber for the purpose of improving the weather resistance of the resin substrate.

As the light stabilizer, for example, bis (2,
2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4
-Octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4
-Piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate, bis (2,2,6,6-tetra Hindered amines such as methyl-4-piperidyl) phenyl phosphite, nickel complexes such as nickel bis (octylphenyl sulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate) These agents may be used alone or in combination of two or more.
It is preferably used in an amount of 1 to 50 parts by weight, more preferably 1 to 10 parts by weight, based on 00 parts by weight.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2,2'-dihydroxy-
Benzophenones such as 4,4'-dimethoxybenzophenone, 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-
5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-
Benzotriazoles such as (hydroxyphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,
3-diphenyl acrylate, 2-ethylhexyl-2
Cyanoacrylates such as cyano-3,3-diphenylacrylate, salicylates such as phenyl salicylate and p-octylphenyl salicylate, diethyl-
benzylidene malonates such as p-methoxybenzylidene malonate and bis (2-ethylhexyl) benzylidene malonate; These agents may be used alone or in combination of two or more, and are preferably used in an amount of 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the coating resin.

The coating composition is applied to a resin substrate by a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, a roller coating method, or the like. Can be appropriately selected according to the conditions. The substrate coated with such a coating composition is usually dried at room temperature to a temperature not higher than the thermal deformation temperature of the substrate, and the solvent is dried and removed. Heating causes the crosslinkable groups to crosslink, and as a first layer, a transparent resin substrate obtained by laminating the above-mentioned coating resin is obtained.

The thickness of the first coating resin layer is determined by the thickness required to sufficiently adhere the transparent resin base material to the second layer and to maintain the required amount of the additive. And preferably 0.1 to 10 μm, more preferably 1 to 5 μm
It is.

By forming the first layer composed of the coating resin mainly composed of the acrylic resin, the adhesion between the second layer and the transparent resin substrate is improved, and the resin having excellent wear resistance and weather resistance is obtained. You can get windows.

In the present invention, the second layer to be laminated next on the first layer is composed of colloidal silica (a component) and a hydrolyzed condensate of trialkoxysilane represented by the above formula (2) (b component). And a coating layer formed by thermosetting an organosiloxane resin comprising a hydrolytic condensate (component (c)) of a tetraalkoxysilane represented by the formula (3).

The second layer is preferably used for coating comprising an organosiloxane resin solid comprising the above-mentioned hydrolyzed condensate of colloidal silica, trialkoxysilane and tetraalkoxysilane, an acid, a curing catalyst and a solvent. Formed using the composition.

The colloidal silica of the component a has a diameter of 5
Silica fine particles having a diameter of from 200 to 200 nm, preferably from 5 to 40 nm, are colloidally dispersed in water or an organic solvent. The colloidal silica can be used in either an aqueous dispersion type or an organic solvent dispersion type, but it is preferable to use an aqueous dispersion type. Specific examples of such colloidal silica include Snowtex O manufactured by Nissan Chemical Industries, Ltd. as a product dispersed in an acidic aqueous solution, and Snowtex 30 manufactured by Nissan Chemical Industries, Ltd. as a product dispersed in a basic aqueous solution. , Snowtex 40, Catalyst Kasei Kogyo Co., Ltd.'s Cataloid S30, Cataloid S40, Nissan Chemical Industries' MA-ST, IP
A-ST, NBA-ST, IBA-ST, EG-ST,
XBA-ST, NPC-ST, DMAC-ST and the like.

The hydrolysis-condensation product of trialkoxysilane, which is the component b, is obtained by subjecting the trialkoxysilane of the formula (2) to a hydrolysis-condensation reaction.

Examples of such trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane and the like can be used, and these can be used alone or in combination.

In order to obtain a coating composition for forming a coating layer having particularly excellent abrasion resistance, 70% by weight is required.
The above is preferably methyl trialkoxy silane, and more preferably substantially the entire amount is methyl trialkoxy silane. However, improved adhesion, hydrophilicity,
A small amount of the above trialkoxysilanes other than methyltrialkoxysilane may be added for the purpose of expressing functions such as water repellency.

The hydrolysis-condensation product of the tetraalkoxysilane as the component (c) is obtained by subjecting the tetraalkoxysilane of the formula (3) to a hydrolysis-condensation reaction. Examples of such tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and the like,
Preferred are tetramethoxysilane and tetraethoxysilane. These tetraalkoxysilanes can be used alone or in combination.

The component (b) and the component (c) are a mixture of a product obtained by partially or entirely hydrolyzing the alkoxysilane and a product obtained by subjecting a part or all of the hydrolyzate to a condensation reaction. It is obtained by doing.

The solid content of the organosiloxane resin comprising the components a to c can be prepared through a process comprising the following steps (1) and (2) to form a coat layer having no precipitate and having more excellent abrasion resistance. It can be obtained and is preferably adopted.

Process (1): The trialkoxysilane of the formula (2) is subjected to a hydrolysis-condensation reaction under acidic conditions in a colloidal silica dispersion.

Here, when a water-dispersed colloidal silica dispersion is used, the water required for the hydrolysis reaction of the trialkoxysilane is supplied from this dispersion, and water may be further added if necessary. Usually, 1 to 10 equivalents, preferably 1.5 to 7 equivalents, more preferably 3 to 5 equivalents of water is used per 1 equivalent of trialkoxysilane.

As described above, the hydrolysis-condensation reaction of trialkoxysilane must be performed under acidic conditions, and an acid is generally used as a hydrolyzing agent in order to perform hydrolysis under such conditions. Such an acid may be added in advance to the trialkoxysilane or colloidal silica dispersion, or may be added after mixing both. Further, the addition can be divided into one time or two or more times. Such acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, inorganic acids such as sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid,
Oxalic acid, succinic acid, maleic acid, lactic acid, organic acids such as paratoluenesulfonic acid, and the like, formic acid, acetic acid, propionic acid, butyric acid, from the viewpoint of easy control of pH,
Organic carboxylic acids such as oxalic acid, succinic acid and maleic acid are preferred, and acetic acid is particularly preferred.

When an inorganic acid is used as the acid, it is usually 0.0001 to 2N, preferably 0.001 to 0.
It is used at a concentration of 1N. When an organic acid is used, it is used in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of trialkoxysilane.

The conditions for the hydrolysis and condensation of the trialkoxysilane vary depending on the type of trialkoxysilane used and the type and amount of colloidal silica coexisting in the system. Is 20-4
0 ° C., reaction time is 1 hour to several days.

Process (2): (i) The tetraalkoxysilane of the above formula (3) is added to the reaction solution obtained by the reaction of the process (1) to cause a hydrolysis and condensation reaction, or (ii) the process (1) ) Is mixed with the reaction solution obtained by previously subjecting the tetraalkoxysilane of the formula (3) to a hydrolytic condensation reaction.

(I) When tetraalkoxysilane is added to the reaction solution obtained in the reaction of the process (1) to cause a hydrolysis and condensation reaction, the hydrolysis and condensation reaction is performed under acidic conditions. Since the reaction solution obtained by the reaction of the process (1) is usually acidic and contains water, the tetraalkoxysilane may be added as it is, or water and an acid may be further added if necessary. As the acid, those similar to the aforementioned acids are used, and volatile acids such as acetic acid and hydrochloric acid are preferable. The acid is usually 0.1 when an inorganic acid is used.
0001 to 2N, preferably used at a concentration of 0.001 to 0.1N, and when using an organic acid, 0.1 to 50 parts by weight with respect to 100 parts by weight of tetraalkoxysilane,
Preferably it is used in the range of 1 to 30 parts by weight.

The water required for the hydrolysis reaction is usually 1 to 100 equivalents, preferably 2 to 50 equivalents, more preferably 4 to 30 equivalents to 1 equivalent of tetraalkoxysilane.

The hydrolysis and condensation conditions of the tetraalkoxysilane are determined by the type of the tetraalkoxysilane used,
Since it varies depending on the type and amount of colloidal silica coexisting in the system, it cannot be said unconditionally.
４０40 ° C., and the reaction time is 10 minutes to several days.

On the other hand, when (ii) the reaction solution obtained by the reaction of the process (1) is mixed with the reaction solution in which the tetraalkoxysilane of the formula (3) has been subjected to a hydrolysis condensation reaction, First, it is necessary to hydrolyze and condense tetraalkoxysilane. This hydrolysis-condensation reaction is usually carried out under an acidic condition under the conditions of 1 to 1 equivalent of tetraalkoxysilane.
The reaction is carried out by reacting with 100 equivalents, preferably 2 to 50 equivalents, more preferably 4 to 20 equivalents of water at 20 to 40 ° C for 1 hour to several days. An acid is used in the hydrolysis-condensation reaction, and examples of the acid include the same acids as described above, and volatile acids such as acetic acid and hydrochloric acid are preferable. The acid is usually 0.000 when an inorganic acid is used.
It is used at a concentration of 1 to 2N, preferably 0.001 to 0.1N. When an organic acid is used, it is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of tetraalkoxysilane. Used in parts by weight.

The mixing ratio of each of the components a to c, which is the solid content of the organosiloxane resin, depends on the stability of the coating composition solution, the transparency of the obtained cured film, the abrasion resistance, the abrasion resistance, the adhesion, and the like. It is determined in view of the occurrence of cracks and the like. Preferably, component a is 5 to 45% by weight and component b is R
50 to 80% by weight in terms of ² SiO _3/2 , and the component c is Si
It is used in an amount of 2 to 30% by weight in terms of O ₂ , and more preferably, the component a is 15 to 35% by weight, and the component b is R ² S.
55 to 75% by weight in terms of iO _3/2 , and the c component is Si
In terms of O ₂ is 3 to 20 wt%.

The coating composition used for the second layer usually further contains a curing catalyst. Examples of such a catalyst include lithium salts of aliphatic carboxylic acids such as formic acid, propionic acid, butyric acid, lactic acid, tartaric acid, and succinic acid, alkali metal salts such as sodium salt and potassium salt, benzyltrimethylammonium salt, tetramethylammonium salt, and tetraethylammonium salt. Examples thereof include quaternary ammonium salts such as ammonium salts, and sodium acetate, potassium acetate and benzyltrimethylammonium acetate are preferably used. When a basic aqueous dispersion type colloidal silica is used as the colloidal silica and an aliphatic carboxylic acid is used as the acid during the hydrolysis of the alkoxysilane, the curing catalyst is already contained in the coating composition. Will be. The necessary content varies depending on the curing conditions, but the curing catalyst is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the solid content of the organosiloxane resin composed of the components a to c. -5 parts by weight.

The solvent used in the coating composition for the second layer is required to dissolve the solid content of the organosiloxane resin stably, for which purpose at least 20% by weight or more, preferably 50% by weight or more. Is preferably alcohol. Examples of such alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, Butoxyethanol and the like, and a low-boiling alcohol having 1 to 4 carbon atoms is preferable. From the viewpoint of solubility, stability and coatability, 2-butanol is preferred.
Propanol is particularly preferred. In the solvent, water that does not participate in the hydrolysis reaction with water in water-dispersed colloidal silica, lower alcohol generated by the hydrolysis of alkoxysilane, when organic solvent-dispersed colloidal silica is used, An organic solvent for the dispersion medium and an acid added for adjusting the pH of the coating composition are also included. pH
Acids used for regulation include hydrochloric acid, sulfuric acid, nitric acid,
Inorganic acids such as phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid; and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, and paratoluenesulfonic acid. Organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are preferred from the viewpoint of ease of control. Other solvents must be miscible with water / alcohol, for example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, tetrahydrofuran,
Examples thereof include ethers such as 1,4-dioxane and 1,2-dimethoxyethane, and esters such as ethyl acetate and ethoxyethyl acetate. The solvent is preferably used in an amount of 50 to 900 parts by weight, more preferably 150 to 700 parts by weight, based on 100 parts by weight of the solid content of the organosiloxane resin composed of the components a to c.

The pH of the coating composition for the second layer is adjusted to 3.0 to 3.0 by adjusting the contents of the acid and the curing catalyst.
It is desirably adjusted to 6.0, preferably 4.0 to 5.5. Thereby, gelation of the coating composition at normal temperature can be prevented, and storage stability can be increased. The coating composition usually becomes a stable composition by further aging for several hours to several days.

The coating composition for the second layer is coated on the first layer formed on the transparent resin substrate, and cured by heating to form the second layer. As the coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, and a roller coating method can be appropriately selected according to the shape of the substrate to be coated. The substrate coated with such a composition is usually heated and cured after drying and removing the solvent at a temperature from room temperature to a temperature not higher than the thermal deformation temperature of the substrate. It is preferable to perform such thermal curing at a high temperature within a range in which there is no problem with the heat resistance of the substrate because curing can be completed earlier. At room temperature, thermosetting does not proceed and a cured film cannot be obtained. This means that the solid content of the organosiloxane resin in the coating composition is partially condensed. In the course of the thermal curing, the remaining Si-OH causes a condensation reaction to form a Si-O-Si bond, and a coat layer having excellent wear resistance is obtained. Thermal curing is preferably 50
C. to 200 C., more preferably 80 C. to 160 C.
, More preferably in the range of 100 ° C to 140 ° C, preferably 10 minutes to 4 hours, more preferably 20 minutes.
The composition is cured by heating for from 3 minutes to 3 hours, preferably from 30 minutes to 2 hours.

The thickness of the second layer is usually 2 to 10 μm, preferably 3 to 8 μm. When the thickness of the coat layer is within the above range, cracks are generated in the coat layer due to stress generated during thermosetting, and the adhesion between the coat layer and the base material is not reduced, and the present invention The intended coat layer having sufficient wear resistance can be obtained.

Further, a known leveling agent can be blended with the coating composition of the first and second layers of the present invention for the purpose of improving coatability and smoothness of the obtained coating film. The compounding amount is 100 for the coating composition.
The range of 0.01 to 2 parts by weight with respect to parts by weight is preferred.
Dyes, pigments, fillers, and the like may be added as long as the object of the present invention is not impaired.

The resin base material for the resin window used in the present invention is a transparent resin base material having a haze value of 0.4% or less, and specifically, an acrylic resin such as polycarbonate resin, polymethyl methacrylate, or polyethylene. Terephthalate, polybutylene terephthalate, poly (ethylene-
Polyester resins such as 2,6-naphthalate), polystyrene, polypropylene, polyarylate, and polyethersulfone. Acrylic resins such as polycarbonate resins and polymethyl methacrylate are preferred, and polycarbonate resins are particularly preferred, because of their adhesiveness to the first layer and usefulness as a substrate having excellent wear resistance.

The resin-made automobile window of the present invention is formed by a resin-made automobile window or a window frame attached to the outer periphery of the window. The resin window whose surface is protected according to the present invention is obtained by heat-treating the first layer mainly composed of an acrylic resin layer and an organopolysiloxane resin composed of colloidal silica, a trialkoxysilane hydrolysis condensate and a tetraalkoxysilane hydrolysis condensate. The second hardened
By having the layer, a resin window having a high level of abrasion resistance, which has not been achieved in the past, can be obtained.

Further, the resin window obtained by the present invention is made of Cali
Using a brase CS-10F wear wheel, load 500g
Taber abrasion test at lower 1000 rotations (ASTM D10
44), and the change in the haze value before and after the test is 2% or less. This is based on the JIS standard that the change in the haze value before and after the Taber abrasion test under the same conditions as described above requires 2% or less in the outside of the front window glass of the automobile. Is used as a window glass for vehicles mounted on automobiles and various types of transportation, and has excellent durability as a window material for building materials mounted on buildings such as houses and buildings. Is shown.

[0077]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The obtained resin window was evaluated by the following method. Also,
Parts and% in the examples mean parts by weight and% by weight.

(1) Appearance evaluation: The presence or absence of cracks, blisters, wrinkles, and cloudiness of the resin window was visually observed.

(2) Visible light transmittance / haze value: Cut out from a flat portion of a resin window. 50 × 50 × 5m
m sample, Nippon Denshoku haze meter 1001D
It was measured using P.

(3) Adhesion: Nichiban adhesive tape (trade name “Cellotape”) was made on the coat layer by cutting with a cutter knife at 100 intervals of 1 mm, and strongly peeled off vertically onto the substrate. Evaluation was based on the number of remaining grids (J
(Based on IS K5400).

(4) Scratch resistance: After a test piece was rubbed with # 0000 steel wool, the state of scratches on the surface was visually evaluated on a five-point scale. 1: No damage at all when rubbed 10 times with a load of 500g 2: Slightly damaged when rubbed 10 times with a load of 500g 3: Slightly damaged when rubbed 10 times with a load of 500g 4: Damaged when rubbed 10 times with a load of 500g 5: 100g load Rub 10 times

(5) Abrasion resistance: Cut out from a flat portion of a resin window. Using a sample of 95 × 95 × 5 mm thickness, using a Calibrase CS-10F wear wheel, a 1000-rotation Taber abrasion test was performed under a load of 500 g, and the haze after the Taber abrasion test and the haze before the Taber abrasion test were measured. Was measured and evaluated (ASTM D1044).
Compliant). (Haze = Td / Tt × 100, Td: scattered light transmittance, Tt: total light transmittance)

(6) Hot water resistance: The test piece was immersed in boiling water for one hour, and the appearance change and adhesion of the coat layer were evaluated.

(Synthesis of Acrylic Resins (I) to (VIII)) Reference Example 1 95.1 parts of methyl methacrylate (hereinafter abbreviated as MMA) in a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 11. 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as MPTMS)
4 parts, 0.16 part of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 1,2-dimethoxyethane 20
0 parts were added, mixed and dissolved. Then, in a nitrogen stream 7
The reaction was carried out with stirring at 0 ° C. for 6 hours. The obtained reaction solution is n
-Reprecipitation purification by adding to hexane, MMA / MPTMS
86 parts of a copolymer (acrylic resin (I)) having a composition ratio of 95/5 (molar ratio) was obtained. The weight average molecular weight of the copolymer was measured by GPC (column; Shodex GPCA-
804, eluent: 12 from THF) in terms of polystyrene
0000.

[Reference Example 2] 90.1 parts of MMA, MPTM
MM in the same manner as in Reference Example 1 except that S24.8 was used.
95 parts of a copolymer (acrylic resin (II)) having a composition ratio of A / MPTMS of 90/10 (molar ratio) was obtained. The weight average molecular weight of the copolymer is 15,000 in terms of polystyrene.
It was 0.

Reference Example 3 In a flask similar to Reference Example 1, 90.1 parts of MMA, 13 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), and 0.1 parts of AIBN.
14 parts and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Then, the reaction was carried out in a nitrogen stream at 70 ° C. for 6 hours with stirring. The obtained reaction solution was added to n-hexane for reprecipitation purification, and the composition ratio of MMA / HEMA was 90/90.
10 (molar ratio) copolymer (acrylic resin (II
I)) 80 parts were obtained. The weight average molecular weight of the copolymer was 180000 in terms of polystyrene.

[Reference Example 4] 70 parts of MMA, HEMA39
And MMA / HEMA composition ratio 70/30 (molar ratio) in the same manner as in Reference Example 3 except that 0.18 part of AIBN was used.
90 parts of a copolymer (acrylic resin (IV)) was obtained.
The weight average molecular weight of the copolymer is 8 in terms of polystyrene.
0000.

Reference Example 5 In the same flask as in Reference Example 1, 100.1 parts of MMA, 0.12 parts of AIBN,
-200 parts of dimethoxyethane was added, mixed and dissolved. Then, the reaction was carried out in a nitrogen stream at 70 ° C. for 6 hours with stirring. The resulting reaction solution was added to n-hexane and purified by reprecipitation to obtain 92 parts of a polymethyl methacrylate resin (acrylic resin (V)). The weight average molecular weight of the polymer was 200000 in terms of polystyrene.

Reference Example 6 30 parts of MMA, MPTMS1
Reference Example 1 except that 73.6 parts and 0.2 parts of AIBN were used.
MMA / MPTMS composition ratio 30/70
(Molar ratio) copolymer (acrylic resin (VI)) 14
0 parts were obtained. The weight average molecular weight of the copolymer was 80,000 in terms of polystyrene.

Reference Example 7 Ethyl methacrylate (hereinafter abbreviated as EMA) 8 was placed in the same flask as in Reference Example 1.
9.3 parts, 49.6 parts of MPTMS, 0.16 parts of AIBN and 200 parts of 1,2-dimethoxyethane were added and mixed,
Dissolved. Then, the reaction was carried out in a nitrogen stream at 70 ° C. for 6 hours with stirring. The obtained reaction solution was added to n-hexane for reprecipitation purification, and the composition ratio of EMA / MPTMS was 80/20.
(Molar ratio) copolymer (acrylic resin (VII)) 1
05 parts were obtained. The weight average molecular weight of the copolymer was 150,000 in terms of polystyrene.

Reference Example 8 In the same flask as in Reference Example 1, 89.3 parts of EMA, 26 parts of HEMA, 0.1 parts of AIBN were added.
8 parts and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Then, the reaction was carried out in a nitrogen stream at 70 ° C. for 6 hours with stirring. The obtained reaction solution was added to n-hexane for reprecipitation purification, and the composition ratio of EMA / HEMA was 80/2.
0 (molar ratio) of the copolymer (acrylic resin (VII
I)) 90 parts are obtained. The weight average molecular weight of the copolymer was 60000 in terms of polystyrene.

(Preparation of Organosiloxane Resin Solution) Reference Example 9 142 parts of methyltrimethoxysilane, 72 parts of distilled water, and 20 parts of acetic acid were mixed under cooling with ice water. The mixture was stirred at 25 ° C. for 1 hour and isopropanol 116
The resulting mixture was diluted with 3 parts by weight to obtain 350 parts of a methyltrimethoxysilane hydrolyzed condensate solution (X).

Reference Example 10 Tetraethoxysilane 20
8 parts and 81 parts of 0.01N hydrochloric acid were mixed with cooling with ice water.
The mixture was stirred at 25 ° C. for 3 hours and diluted with 11 parts of isopropanol to obtain 300 parts of a tetraethoxysilane hydrolyzed condensate solution (Y).

(Preparation of First Layer Composition) Reference Example 11 10 parts of the acrylic resin (I) was dissolved in a mixed solvent consisting of 30 parts of methyl isobutyl ketone and 10 parts of 2-butanol. Dissolve 1 part of dihydroxybenzophenone to form a coating composition (i-
1) was prepared.

Reference Example 12 The acrylic resin (II)
10 parts were dissolved in a mixed solvent consisting of 60 parts of methyl isobutyl ketone, 20 parts of 2-butanol and 10 parts of 2-ethoxyethanol, and 1 part of 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole was dissolved. Thus, a coating composition (i-2) was prepared.

Reference Example 13 The acrylic resin (II)
I) 7.5 parts of 30 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone, 10 parts of isopropanol and 2 parts
-Ethanol dissolved in a mixed solvent consisting of 10 parts of ethoxyethanol, and further added with 10 parts of the methyltrimethoxysilane hydrolyzed condensate solution (X) obtained in Reference Example 9 and the tetraethoxysilane hydrolyzate obtained in Reference Example 10. 2.5 parts of the decomposition condensate solution (Y) was added and stirred at 25 ° C. for 5 minutes to give 2- (5′-methyl-2′-hydroxyphenyl)
The coating composition (i-3) was prepared by dissolving 2 parts of benzotriazole.

Reference Example 14 The acrylic resin (II)
I) 9 parts were dissolved in a mixed solvent consisting of 60 parts of methyl ethyl ketone, 12 parts of isopropanol and 14 parts of 2-ethoxyethanol, and the solution of the hydrolyzed condensate of methyltrimethoxysilane obtained in Reference Example 9 (X) was added to this solution.
5 parts were added and stirred at 25 ° C. for 5 minutes, and 1 part of 2- (5′-methyl-2′-hydroxyphenyl) benzotriazole was dissolved to prepare a coating composition (i-4).

Reference Example 15 The acrylic resin (IV)
8 parts was dissolved in a mixed solvent consisting of 30 parts of methyl ethyl ketone, 6.5 parts of isopropanol and 15 parts of 2-ethoxyethanol, and the solution of the hydrolyzed condensate of methyltrimethoxysilane obtained in Reference Example 9 (X) was added to this solution.
10 parts were added and stirred at 25 ° C. for 5 minutes to obtain 2- (5′-
Methyl-2'-hydroxyphenyl) benzotriazole (1 part) was dissolved to prepare a coating composition (i-5).

Reference Example 16 The acrylic resin (IV)
8 parts were methyl ethyl ketone 40 parts, methyl isobutyl ketone 20 parts, ethanol 5.2 parts, isopropanol 1
Dissolve in a mixed solvent consisting of 4 parts and 10 parts of 2-ethoxyethanol, and then add the methyltrimethoxysilane hydrolyzed condensate solution (X) 10 obtained in Reference Example 9 to this solution.
And stirred at 25 ° C. for 5 minutes. Then, a melamine resin (Cymel 30 manufactured by Mitsui Cytec Co., Ltd.) was added to the solution.
3) Add 1 part and stir at 25 ° C. for 5 minutes to give 2- (5 ′)
-Methyl-2'-hydroxyphenyl) benzotriazole (1 part) dissolved in coating composition (i-6)
Was prepared.

Reference Example 17 The acrylic resin (VI
I) 10 parts were dissolved in a mixed solvent consisting of 40 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and 20 parts of isopropanol, and 1 part of 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole was dissolved to form a coating. Composition (i-7) was prepared.

Reference Example 18 The acrylic resin (VII)
I) 7.5 parts of 30 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone, 10 parts of isopropanol and 2 parts
-Dissolve in a mixed solvent consisting of 10 parts of ethoxyethanol, further add 12.5 parts of the methyltrimethoxysilane hydrolyzed condensate solution (X) obtained in Reference Example 9 to this solution, and stir at 25 ° C for 5 minutes. 2- (5'-methyl-2 '
(Hydroxyphenyl) benzotriazole (1 part) was dissolved to prepare a coating composition (i-8).

Reference Example 19 The acrylic resin (V) 1
0 part is dissolved in a mixed solvent consisting of 40 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and 20 parts of isopropanol, and 1 part of 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole is dissolved to form a coating composition. (I-9) was prepared.

Reference Example 20 The acrylic resin (VI)
10 parts are dissolved in a mixed solvent consisting of 40 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and 20 parts of isopropanol, and 1 part of 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole is dissolved to form a coating composition. (I-10) was prepared.

(Preparation of Composition for Second Layer) Reference Example 21 Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30)
(Weight%), 100 parts of distilled water, 2 parts of acetic acid and 20 parts of acetic acid were added and stirred, and 130 parts of methyltrimethoxysilane was added to this dispersion under cooling with an ice water bath. This mixture was stirred at 25 ° C. for 1 hour, and 30 parts of the tetraethoxysilane hydrolyzed condensate solution (Y) obtained in Reference Example 10 and 2 parts of sodium acetate as a curing catalyst were cooled with ice water. The mixture was mixed under the following conditions, and diluted with 200 parts of isopropanol to obtain a coating composition (ii-1).

Reference Example 22 Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.)
20 parts of acetic acid was added to 100 parts of a solid content (30% by weight) and stirred, and 122 parts of methyltrimethoxysilane was added to this dispersion under cooling with an ice water bath. This mixture was stirred at 25 ° C. for 1 hour, and 50 parts of the tetraethoxysilane hydrolyzed condensate solution (Y) obtained in Reference Example 10 and 1 part of potassium acetate as a curing catalyst were cooled with ice water. The mixture was mixed under the following conditions, and diluted with 408 parts of isopropanol to obtain a coating composition (ii-2).

Reference Example 23 Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.)
(Solid content: 30% by weight) 60 parts of distilled water and 15 parts of acetic acid
0 parts was added and stirred, and 146 parts of methyltrimethoxysilane was added to this dispersion under cooling with an ice water bath. This mixture was stirred at 25 ° C. for 1 hour, and the resulting mixture was added with Reference Example 10
50 parts of the tetraethoxysilane hydrolyzed condensate solution (Y) obtained in (1) and sodium acetate 0.1 as a curing catalyst.
Two parts were mixed under cooling with ice water, and diluted with 9 parts of isopropanol to prepare a coating composition (ii-3).

[Reference Example 24] Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.)
(Solid content 30% by weight) 60 parts of distilled water 28 parts, acetic acid 2
0 parts was added and stirred, and 130 parts of methyltrimethoxysilane was added to the dispersion under cooling with an ice water bath. This mixture was stirred at 25 ° C. for 1 hour, and the resulting mixture was added with Reference Example 10
90 parts of the tetraethoxysilane hydrolyzed condensate solution (Y) obtained in the above was mixed with 4 parts of benzyltrimethylammonium acetate as a curing catalyst under cooling with ice water, and diluted with 172 parts of isopropanol to prepare a coating composition (i).
i-4) was prepared.

[Reference Example 25] Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.)
90 parts of distilled water and 90 parts of acetic acid
The mixture was stirred, and 136 parts of methyltrimethoxysilane was added to the dispersion under cooling with an ice water bath. This mixture is
The reaction solution obtained by stirring at 5 ° C. for 1 hour was mixed with 30 parts of the tetraethoxysilane hydrolyzed condensate solution (Y) obtained in Reference Example 10 and 2 parts of potassium acetate as a curing catalyst under cooling with ice water. And diluted with 170 parts of isopropanol to prepare a coating composition (ii-5).

[Reference Example 26] Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.)
12 parts of distilled water and 20 parts of acetic acid were added to 100 parts of a solid content concentration (30% by weight) and stirred, and 134 parts of methyltrimethoxysilane was added to this dispersion under cooling with an ice water bath. This mixture was stirred at 25 ° C. for 1 hour, and the resulting mixture was added to Reference Example 1
The coating composition (ii-6) was prepared by adding 20 parts of the tetraethoxysilane hydrolyzed condensate solution (Y) obtained in Step No. 0 and 1 part of sodium acetate as a curing catalyst and diluting with 200 parts of isopropanol.

[Reference Example 27] Isopropanol-dispersed colloidal silica dispersion (IPA manufactured by Nissan Chemical Industries, Ltd.)
-ST-S solid content concentration 25% by weight)
0 parts were added and stirred, and 72 parts of distilled water was added dropwise at room temperature for 20 minutes. 130 parts of methyltrimethoxysilane was added to the thus obtained dispersion under cooling in an ice water bath. This mixture was stirred at 25 ° C. for 1 hour, and 30 parts of the tetraethoxysilane hydrolyzed condensate solution (Y) obtained in Reference Example 10 and 2 parts of sodium acetate as a curing catalyst were cooled with ice water. Mix below, isopropanol 130
To prepare a coating composition (ii-7).

[Reference Example 28] Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.)
12 parts of distilled water and 20 parts of acetic acid were added to 100 parts of a solid content concentration (30% by weight) and the mixture was stirred, and 130 parts of methyltrimethoxysilane was added to this dispersion under cooling with an ice water bath. The mixture was stirred at 25 ° C. for 1 hour, and 15.2 parts of tetramethoxysilane was added to the reaction solution obtained. The mixture was stirred at 25 ° C. for 1 hour, 1 part of sodium acetate was added as a curing catalyst, and the mixture was diluted with 200 parts of isopropanol to prepare a coating composition (ii-8).

[Reference Example 29] Water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.)
2 parts of distilled water and 2 parts of acetic acid
0 parts was added and stirred, and 142 parts of methyltrimethoxysilane was added to this dispersion under cooling with an ice water bath. The mixture was stirred at 25 ° C. for 1 hour, 2 parts of sodium acetate was added, and the mixture was diluted with 236 parts of isopropanol to prepare a coating composition (ii-9).

[Reference Example 30] 146 parts of methyltrimethoxysilane, 90 parts of distilled water and 20 parts of acetic acid were mixed under cooling in an ice water bath, and the mixture was stirred at 25 ° C for 1 hour to obtain a reaction solution. 71 parts of tetramethoxysilane were added. The mixture was stirred at 25 ° C. for 1 hour, 2 parts of sodium acetate was added, and the mixture was diluted with 173 parts of isopropanol to prepare a coating composition (ii-10).

Example 1 A polycarbonate resin (L-1225 manufactured by Teijin Chemicals Ltd.) was used as a thermoplastic resin. In the cavity of the window molding die, a thermoplastic resin is placed at a resin temperature of 285 ° C., a die temperature of 60 ° C., and an injection pressure (gauge pressure) of 16.
Injection and injection were performed under the condition of 0 MPa to prepare a window portion of a house window having a size of 700 × 600 × 5 mm.

The coating composition (i-1) prepared in Reference Example 11 was applied to the window of the house by dip coating, allowed to stand at 25 ° C. for 20 minutes, and then left at 120 ° C. for 30 minutes.
Heat cured for minutes. Next, the coating composition (ii-1) prepared in Reference Example 21 was formed on the coating surface of the window.
Was applied by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then heat-cured at 120 ° C. for 1 hour to prepare a house window having a surface protected by attaching a window frame. Table 3 shows the evaluation results of the obtained windows for houses whose surfaces were protected.

Example 2 On one side of a transparent 0.2 mm thick polycarbonate resin (hereinafter abbreviated as PC resin) film, the first layer coating composition (i-2) was placed in a hot air drying oven having a length of 2 m. , 1m length from coat part to drying oven
Using a micro gravure coater, the temperature in the hot air drying furnace was 130 ° C, and the film winding speed (coating speed) was 2 m.
The coating was performed by a roll coating method under the conditions of / min and thermally cured. Next, the second layer coating composition (ii-2) is applied on the coating surface of the film under the same conditions and heat-cured, and the obtained film is heat-treated at 120 ° C. for 1 hour and further heat-cured to harden. A coated film was prepared.

The obtained film was mounted on a window molding die, and a thermoplastic resin was filled in the cavity with a resin temperature of 285.
° C, mold temperature 60 ° C, injection pressure (gauge pressure) 160MP
Injection and injection under condition a, vertical 700 × horizontal 600 × thickness 5m
A window part of a resin house window having an m-size surface protected was prepared, and a window frame part was attached to obtain a house window. Table 3 shows the evaluation results of the obtained windows for houses whose surfaces were protected.

[Example 3] A window for a house having a size of 700 x 600 x 5 mm was cut out from a 5 mm thick PC resin sheet, and the obtained window for a house was prepared in Reference Example 13 using the obtained window. The coating composition (i-3) thus prepared was applied by a dip coating method, allowed to stand at 25 ° C for 20 minutes, and thermally cured at 120 ° C for 30 minutes. Then, on the coating surface of the window,
The coating composition (ii-
3) was applied by dip coating, allowed to stand at 25 ° C. for 20 minutes, and then heat-cured at 120 ° C. for 1 hour to prepare a window for a house whose surface was protected by attaching a window frame. Table 3 shows the evaluation results of the obtained windows for houses whose surfaces were protected.

[Examples 4 to 10] A first layer coating shown in Table 1 was formed on a resin window prepared in the same manner as in Example 1 in the same manner as in Example 1, and then applied on the coating. The second layer shown in Table 2 was formed in the same manner as in Example 1 to form a resin window whose surface was protected. Table 3 shows the evaluation results of the obtained resin windows whose surfaces were protected.

Comparative Example 1 A first layer coating shown in Table 1 was formed on a resin window formed in the same manner as in Example 1 in the same manner as in Example 1, and then Example 1 was formed on the coating. The second layer shown in Table 2 was formed in the same manner as in Example 2 to form a resin window whose surface was protected. Table 3 shows the evaluation results of the obtained resin windows whose surfaces were protected. The abrasion resistance and the abrasion resistance could not be measured because part of the coat layer was peeled off during the test.

[Comparative Examples 2 and 3] The first layer coating shown in Table 1 was formed in the same manner as in Example 1 on a resin window formed in the same manner as in Example 1, and then applied to the coating. The second layer shown in Table 2 was formed in the same manner as in Example 1 to form a resin window whose surface was protected. Table 3 shows the evaluation results of the obtained resin windows whose surfaces were protected.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

In Tables 1 and 2, (1) MTMOS; methyltrimethoxysilane (2) TEOS: tetraethoxysilane (3) TMOS: tetramethoxysilane (4) S-30; water-dispersed colloidal silica Dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by weight, average particle size 20 nm) (5) IPA-ST-S; isopropanol-dispersed colloidal silica dispersion (Nissan Chemical Industries, Ltd. IPA) −
ST-S solid content concentration 25% by weight, average particle size 10n
m) (6) UV-1; 2,4-dihydroxybenzophenone (7) UV-2; represents 2- (5′-methyl-2′-hydroxyphenyl) benzotriazole, and the weight part of trialkoxysilane is RSiO _{3 / 2}
, And parts by weight of tetraalkoxysilane indicate values converted to SiO ₂ .

[0126]

The resin window of the present invention has an appearance, hot water resistance,
It has good adhesiveness, particularly excellent abrasion resistance, and can prevent abrasion of the surface of the base material at an unprecedentedly high level. Therefore, it is suitably used as a resin window, and its industrial effect is remarkable.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 133/10 C09D 133/10 143/04 143/04 161/28 161/28 183/02 183/02 183 / 04 183/04 (72) Inventor Yoshihiko Imanaka 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo F-term in Teijin Chemicals Limited (Reference) 4F006 AA36 AB24 BA02 CA04 4F100 AA20C AK01A AK25B AK45A AK52C AL01B AL08B BA03 BA10A BA10C CA23C EH46B GB07 GB32.

Claims (6)

[Claims] 1. A resin layer, wherein at least 50% by weight of a coating resin is an acrylic resin on a surface of a base material of a resin window portion, and the acrylic resin has the following formula (1): ] (Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms.) A coating resin, which is an acrylic resin containing 50 mol% or more of a repeating unit represented by the following formula, is laminated, and a second layer is formed thereon. (A) Colloidal silica (a component), (B) Hydrolysis condensate of trialkoxysilane represented by the following formula (2) (b component) (Wherein, R ² is substituted by one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. And R ³ is an alkyl group having 1 to 4 carbon atoms) and (C) a hydrolyzed condensate of a tetraalkoxysilane represented by the following formula (3) (component c): ) (Wherein, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms.) A resin window having a protected surface on which a coating layer formed by thermosetting an organosiloxane resin is laminated. 2. The method according to claim 1, wherein the acrylic resin in the first layer has the formula (1) and the following formula (4). (Where X is a hydrogen atom or a methyl group;
⁵ is an alkylene group having 2 to 5 carbon atoms, R ⁶ is C 1 -C
And n is an integer of 0 or 1. ), Wherein the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (4) is 99.99:
The surface-protected resin window according to claim 1, wherein the ratio is in the range of 0.01 to 50:50. 3. The coating resin of the first layer is represented by the following formula (5): (Wherein, R ⁷ is substituted by one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. R ⁸ is an alkyl group having 1 to 4 carbon atoms,
r is an integer of 0 to 2. Hydrolytic condensate 40 wt% of the compound represented by) (and weight) in terms of _{^{R 7 r -SiO 4-r /}} 2, the formula (1) and the following formula (6) embedded image (Where Y is a hydrogen atom or a methyl group;
⁹ is an alkylene group having 2 to 5 carbon atoms. Acrylics comprising a repeating unit represented by formula (1), wherein the molar ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (6) is 99: 1 to 50:50. 2. A resin having a protected surface according to claim 1, wherein the resin is a mixture or a reactant with 99 to 60% by weight of a resin, and a coating resin comprising 0 to 20 parts by weight of a melamine resin with respect to 100 parts by weight of the mixture or the reactant. Windows. 4. The method according to claim 1, wherein the second layer comprises (A) colloidal silica (a).
Component), (B) trialkoxy represented by the above formula (2)
Hydrolyzed condensate of silane (component (b)) and (C)
Hydrolysis of tetraalkoxysilane represented by formula (3)
An organosiloxane resin consisting of a decondensate (component c)
A component is 5 to 45% by weight, and b component is R ^TwoSiO_3/2
50 to 80% by weight in terms of_TwoConvert to
Heat the organosiloxane resin of 2 to 30% by weight
2. The protected surface according to claim 1, which is a cured coating layer.
Window made of resin. 5. A Taber abrasion test (ASTM D1044) of 1000 rotations under a load of 500 g using a Calibrase CS-10F abrasion wheel, wherein a change in haze value before and after the test is 2% or less. A resin window whose surface is protected as described. 6. The resin window having a protected surface according to claim 1, wherein the base material of the resin window portion is a polycarbonate resin.