JPH0156094B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, an undercoat with good adhesion to the polycarbonate resin is coated and cured on the surface of a polycarbonate resin base material, and a hydrophilic epoxy topcoat containing an organic silane compound is coated and cured on top of the undercoat to improve wear resistance. The present invention relates to a coated polycarbonate resin molded article that also has antifogging properties. In general, polycarbonate resins have the drawbacks of being poor in impact resistance, transparency, abrasion resistance, and solvent resistance, easily scratching the surface, and being easily attacked by organic solvents. Furthermore, if the surface temperature falls below the dew point of the environment, it may become cloudy and lose its transparency, causing great inconvenience. Coating methods in which various coating films are formed on the surface are being researched as a way to improve these drawbacks, but it is difficult to find a coating method that has both abrasion resistance and antifogging properties, and has good adhesion. The current situation is that this is not the case. The object of the present invention is to eliminate such conventional drawbacks and provide a polycarbonate resin molded article that has wear resistance, antifogging properties, and adhesion properties. The present inventor applied a paint consisting of an organic silane compound having an epoxy group, a polyhydric alcohol having an ethylene oxide chain, a vinyl polymer having an epoxy group, and a curing catalyst to the base material of a polycarbonate resin molded article, and baked the coating. provides wear resistance and anti-fog properties at the same time.
Further, an undercoat treatment is performed in advance between the hydrophilic epoxy resin coating layer containing the organic silane compound and the base material of the polycarbonate resin molded article, and the hydrophilic epoxy resin coating layer containing the organic silane compound is applied to the base material. Improves the adhesion of polycarbonate resin molded articles to provide wear resistance and anti-fog properties.
We succeeded in imparting adhesive properties. That is, the present invention provides (A) general formula (1)

[Formula] (In the formula, R ¹ is an organic group having an epoxy group,
R ² is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms,
R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, a
is 1 to 3, b is 0 to 2, and a+b≦3) and/or its partial hydrolyzate 10 to 30
Part by weight (However,

Calculate as [Formula]. ) (B) 30 to 50 parts by weight of polyhydric alcohol having an ethylene oxide chain and (C) General formula (2)

[Formula] (In the formula, R ⁴ represents a hydrogen atom, R ⁵ represents a hydrogen atom or a lower alkyl group, and X represents a side chain having an epoxy group.)
Polymers or copolymers containing at least 20% by weight of repeating structural units of 30
An antifogging coating composition consisting of ~50 parts by weight of the above (A), (B), and (C) in total of 100 parts by weight as main components and a curing catalyst is coated and cured to form an overcoat layer, general Formula (3)

[Formula] (In the formula, R ⁶ is a hydrogen atom, R ⁷ is an atom or an alkyl group having 1 to 5 carbon atoms, and Y is a side chain having a carboxyl group or an amino group.) Polymer () or general formula

[Formula] (in the formula, R ⁸ represents a hydrogen atom, R ⁹ represents a hydrogen atom or a lower alkyl group, and Z represents a hydroxyl group-containing side chain) and general formula (5) General formula (5 )

[Formula] (In the formula, R ¹⁰ is a hydrogen atom, R ¹¹ is a hydrogen atom or a lower alkyl group, and W
is a side chain having a carboxyl group, an alkoxycarbonyl group, an amino group, a substituted amino group, an epoxy group or a tetrahydrofuryl group. This is a coated polycarbonate resin molded article having both abrasion resistance and antifogging properties, which is made by coating and curing a composition containing a polymer () having each of the repeating structural units shown in () as an undercoat layer. First, the top coat layer of the present invention will be explained. General formula (1) is included in the top coat layer (A) component used in the present invention.

[Formula] (However, in the formula, R ¹ is an organic group having an epoxy group, R ² is hydrogen or has 1 carbon number.
~6 hydrocarbon group, R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or 1 to 4 carbon atoms
acyl group, a is 1 to 3, b is 0 to 2, and a
+b≦3. ) Examples of the epoxy group-containing organic silane compounds include the following. Specific examples of silane compounds having one glycidoxy group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltri(methoxyethoxy)silane, γ-glycidoxypropyltriacetoxysilane, δ-glycidoxybutyltri Methoxysilane, δ-glycidoxybutyltriethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyl(methyl)dimethoxysilane, glycidoxymethyl(ethyl)dimethoxysilane, glycidoxymethyl(phenyl)dimethoxysilane, Glycidoxymethyl (vinyl) dimethoxysilane, glycidoxymethyl (dimethyl) methoxysilane, β-glycidoxyethyl (methyl) dimethoxysilane, β-glycidoxyethyl (ethyl) dimethoxysilane, β-glycidoxyethyl (dimethyl)methoxysilane, γ-glycidoxypropyl(methyl)dimethoxysilane, γ-glycidoxypropyl(ethyl)dimethoxysilane, γ-glycidoxypropyl(dimethyl)methoxysilane, δ-glycidoxybutyl(methyl) ) dimethoxysilane, δ-glycidoxybutyl(ethyl)dimethoxysilane, δ-glycidoxybutyl(dimethyl)methoxysilane, Specific examples of silane compounds having two or three glycidoxy groups include bis(glycidoxy) methyl)dimethoxysilane, bis(glycidoxymethyl)diethoxysilane, bis(glycidoxyethyl)dimethoxysilane, bis(glycidoxyethyl)diethoxysilane, bis(glycidoxypropyl)dimethoxysilane, bis(glycidoxypropyl)dimethoxysilane, tris(glycidoxypropyl)diethoxysilane, tris(glycidoxymethyl)methoxysilane, tris(glycidoxymethyl)ethoxysilane, tris(glycidoxyethyl)methoxysilane, tris(glycidoxyethyl)ethoxysilane, tris(glycidoxyethyl)ethoxysilane, Specific examples of silane compounds having a glycidyl group include glycidylmethyltrimethoxysilane, glycidylmethyltriethoxysilane, β-glycidylethyltrimethoxysilane, tris(glycidoxypropyl)methoxysilane, and tris(glycidoxypropyl)ethoxysilane. β-glycidyl ethyltriethoxysilane, γ-glycidylpropyltrimethoxysilane, γ-glycidylpropyltriethoxysilane, γ-glycidylpropyltri(methoxyethoxy)silane, γ-glycidylpropyltriacetoxysilane, having an alicyclic epoxy group Specific examples of silane compounds include 3,4-epoxycyclohexylmethyltrimethoxysilane, 3,4-epoxycyclohexylmethyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylpropyltrimethoxy Examples include silane, 3,4-epoxycyclohexylbutyltrimethoxysilane. The partial hydrolyzate of the epoxy group-containing organic silane compound in component (A) used in the top coat layer of the present invention refers to the alkoxy group, alkoxy It includes those in which part or all of an alkoxy group or acyloxy group is substituted with a hydroxyl group, and those in which the substituted hydroxyl groups are partially naturally condensed with each other. These epoxy-containing organic silane hydrolysates can be obtained, as is known, by hydrolyzing an epoxy group-containing organic silane in a mixed solvent such as water and alcohol in the presence of an acid. The polyhydric alcohol having an ethylene oxide chain used as the overcoat layer (B) component of the present invention is a polyhydric alcohol having at least one chain --(CH ₂ CH ₂ O-) in the molecule. If the molecular weight of the polyhydric alcohol having an ethylene oxide chain is too large, the reactivity of the hydroxyl group will decrease, making curing difficult and insufficient film forming properties will be obtained. The molecular weight of the polyhydric alcohol having an ethylene oxide chain is preferably in the range of 100 to 3,000, particularly preferably 200 to 2,000, since sufficient antifogging properties cannot be obtained if the amount is too small. Typical examples of polyhydric alcohols having an ethylene oxide chain that can be applied to the present invention include diethylene glycol, triethylene glycol, and those having a molecular weight of 100 to 3000.
polyethylene glycol, preferably with a molecular weight of 200 to 2000, a diol with the general formula HOCnH2nOH (n = 3 to 10) with 1 to 10, preferably 1 to 7 ethylene oxide chains added to both ends, glycerin, trimethylol Polyhydric alcohols such as propane, diglycerin, pentaerythritol, adonitol, sorbitol, inositol, etc. in which an ethylene oxide chain is added to at least one hydroxyl group, and mixtures thereof can be used. In particular, the following formula (In the formula, n ₁ to n _n are each independently an integer of 0 to 7, and at least two of them are integers of 1 or more, and m is an integer of 3 to 9.) Ethylene represented by A polyhydric alcohol having an oxide chain, especially in the above formula, n ₁ to n _n is 1 to 5
Compounds are preferred. General formula (2) used as the top coat layer (C) component of the present invention

[Formula] (In the formula, R ⁴ represents a hydrogen atom, R ⁵ represents a hydrogen atom or a lower alkyl group, and
represents a side chain having an epoxy group. ) Polymers (including oligomers) or copolymers (including cooligomers) containing repeating structural units represented by the following are polymers or copolymers containing at least one epoxy group in the molecule, such as Obtained by polymerization. Specific examples of vinyl monomers having epoxy groups include:
Glycidyl methacrylate and acrylate, β
-glycidoxyethyl methacrylate and acrylate, allyl glycidyl ether, 3,4-epoxybutyl methacrylate and acrylate,
Examples include 4,5-epoxypentyl methacrylate and acrylate. Component (c) may be not only a homopolymer or copolymer of a vinyl monomer having an epoxy group, but also a copolymer of a vinyl monomer having an epoxy group and another monomer copolymerizable with it. . That is, other vinyl monomers such as methacrylic acid and acrylic esters such as methyl methacrylate and acrylate, ethyl methacrylate and acrylate, butyl methacrylate and acrylate, hydroxyethyl methacrylate and acrylate, diethylene glycol monomethacrylate and acrylate, methacrylic acid and acrylic General polymerizable vinyl monomers such as acid, styrene, and vinyl acetate can be used as the other monomer. However, if the proportion of the repeating structural unit represented by the general formula (2) contained in component (c) is too small, the abrasion resistance of the coating will decrease. , more preferably 40% by weight or more. In addition, considering component (c) from the viewpoint of its production, if you try to polymerize only the vinyl monomer having an epoxy group, it will tend to gel due to self-crosslinking. It is preferable to copolymerize it with other copolymerizable monomers. In the present invention, the components (A), (B), and (C) are used in proportions of 5 to 50 parts by weight, 20 to 70 parts by weight, and 10 to 70 parts by weight, respectively (however, the total is 100 parts by weight). However, more preferably 10 to 30 parts by weight, and 30 to 30 parts by weight, respectively.
The amount is preferably 50 parts by weight, and 30 to 50 parts by weight.
If component (A) exceeds 50 parts by weight, the antifogging performance will be significantly reduced, and if it is less than 5 parts by weight, the abrasion resistance will not be sufficient. When component (A) is used in an amount of 5 to 15 parts by weight, component (A) may be any of the above-mentioned epoxy group-containing organic silane compounds and partially hydrolyzed products thereof. However, if component (A) is used in an amount exceeding 15 parts by weight, a partial hydrolyzate of an epoxy group-containing organosilane compound is used, or a mixture of an epoxy group-containing organosilane compound and an organosilane compound partial hydrolyzate is used. In particular, it is preferable to use a mixture having a partial hydrolyzate content of 70% by weight or more. The reason for this is that if the epoxy group-containing organic silane compound is present in a large amount without being hydrolyzed, the abrasion resistance and hot water resistance will deteriorate as well. If component (B) exceeds 70 parts by weight, the abrasion resistance will not be sufficient, and at the same time the hot water resistance will deteriorate, resulting in surface roughness and decreased hardness during long-term use, and if it is less than 20 parts by weight, the antifogging performance will decrease. If component (C) exceeds 70 parts by weight, the antifogging performance will deteriorate and at the same time a transparent and smooth film will not be obtained. If it is less than 10 parts by weight, the hot water resistance will be poor and the hardness will be reduced. If the content of the repeating structural unit in the polymer or copolymer that is component (C) is 20% to 40% by weight, component (C) should be 30 parts by weight or more to prevent a decrease in the abrasion resistance of the coating film. It is preferable that Furthermore, the curing catalyst used in the top coat layer of the present invention includes catalysts capable of initiating ring-opening polymerization, such as perchloric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid,
Para-toluenesulfonic acid, boron trifluoride and its complex with an electron donor. _SnCl4 , _ZnCl2 , _FeCl3 ,
Lewis acids such as AlCl ₃ , SbCl ₅ , TiCl ₄ and their complexes. Organic acid metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, and tin octylate. Boufurated metal salts such as zinc borofluoride and tin borofluoride. Boric acid organic esters such as ethyl borate and methyl borate. Alkali such as sodium hydroxide and potassium hydroxide. Titanate esters such as tetrabutoxytitanium and tetraisoproboxytitanium. Metal acetylacetonates such as chromium acetylacetonate, titanyl acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, and nickel acetylacetonate. Amines such as n-butylamine, di-n-butylamine, tri-n-butylamine, guanidine, biguanide, and imidazole. Examples include ammonium perchlorate. Among these catalysts, ammonium perchlorate can be particularly preferably used. That is, when ammonium perchlorate is used, the pot life of the paint is long, the curing conditions such as baking curing temperature and time are practical, and the paint film has excellent water resistance and adhesion. If the amount of curing catalyst added is too small, the time required for curing will be long, and if it is too large, it will tend to worsen the water resistance or cause the paint film to become discolored. ) and (C) from 0.05 to 100 parts by weight
It is desirable to add more preferably 0.1 to 10 parts by weight than 20 parts by weight. It is also possible to improve the wettability by adding a surfactant to the top coat composed of the three components (A), (B), and (C) above and a curing catalyst. The surfactant is not particularly limited and conventionally known surfactants can be used, but polyoxyethylene type nonionic surfactants are particularly preferably used. Specifically, polyoxyethylene alkyl ether type R—O—(
CH ₂ CH ₂ O―) _o H, polyoxyethylene alkylaryl ether type

[Formula] Polyoxyethylene alkylamine type R-NH (CH ₂ CH ₂ -) _o
H and

[Formula] Polyoxyethylene alkylamide type R-CONH
(CH ₂ CH ₂ O) - _o H and

[Formula] Polyoxyethylene polyol ester type (However, n ₁ to _{n 3} are each independently an integer from 1 to 7,
R ¹ to ^{R 3} are each independently hydrogen or carbon number 6
~16 acyl group m is 0 or an integer from 1 to 9), polyoxyethylene sorbitan ester type Examples include nonionic surfactants such as. When used, the top coat of the present invention is diluted to a concentration suitable for the coating operation. Examples of the solvent used for this dilution include alcohols, ketones, esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, etc., and these may be used alone or in combination. It may also be used as a mixed solvent of the above. Among these, lower alcohols (e.g. methanol, ethanol, propanol, butanol), cellosolves (e.g. methyl cellosolve, ethyl cellosolve, butyl cellosolve), lower alkyl carboxylic acids (e.g. formic acid, acetic acid, propionic acid), aromatic compounds (e.g. toluene, xylene) )
and esters (for example, ethyl acetate, butyl acetate), etc. are preferably used alone or as a mixed solvent. If necessary, a flow control agent may be added to the top coating of the present invention to obtain a smooth coating film.A small amount of flow control agent is sufficient, and the amount of flow control agent added is sufficient relative to the solid content of the composition. The objective can be achieved with a content of 5% by weight or less. The top coat of the present invention is coated by a commonly used coating method such as dipping, spraying, roller coating, or flow coating, and then coated at a temperature below the deformation temperature of the base material for 15 minutes to 5 minutes. By curing by baking for a time, a coating film with good antifogging properties, abrasion resistance, hot water resistance, and weather resistance can be obtained. The preferred thickness of the topcoat layer after baking hardening is 1 to 40 microns, more preferably 3 to 30 microns. If it is less than 1 micron, antifogging properties and abrasion resistance will not be sufficient, and if it is more than 40 microns, hot water resistance and adhesion will be poor. Next, the undercoat layer for increasing the adhesion between the top coat and polycarbonate will be explained. As an undercoat paint particularly suitable for polycarbonate resin base materials, general formula (3) (In the formula, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Y is a side chain having a carboxyl group or an amino group.) Polymer () or general formula (4) (In the formula, R ⁸ represents a hydrogen atom, R ⁹ represents a hydrogen atom or a lower alkyl group, and Z represents a hydroxyl group-containing side chain.) and general formula (5) (In the formula, R ¹⁰ represents a hydrogen atom, R ¹¹ represents a hydrogen atom or a lower alkyl group, and W represents a side chain having a carboxyl group, an alkoxycarbonyl group, an amino group, a substituted amino group, an epoxy group, or a tetrahydrofuryl group. It is a paint whose main component is a polymer () having each of the repeating structural units shown in (). The above polymer () contains at least 5 mol%, more preferably 20 to 100 mol%, of the repeating structural unit represented by the general formula (3), and the polymer () contains the repeating structural unit represented by the general formula (4) and ( It is preferable to contain at least 2.5 mol% of each of the repeating structural units shown in 5), and more preferably 5 to 90 mol% of each. Suitable polymers () can be easily produced by copolymerizing the following vinyl monomers alone or with other copolymerizable monomers. That is, examples of the above-mentioned vinyl monomers include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, maleic acid, itaconic acid, aminomethyl (meth)acrylate, (meth)acrylamide, and crotonamide. It may be used or two or more types may be used in combination. As other monomers that can be copolymerized with the above vinyl monomer and the vinyl monomers () and () described below, any compound can be used as long as it has at least one ethylenically unsaturated bond in the molecule. For example, olefins such as ethylene, diolefins such as butadiene,
Vinyl chloride, vinylidene chloride, vinyl compounds such as acrylonitrile, esters of acrylic acid or methacrylic acid such as methyl (meth)acrylate, etc., and these monomers may be used alone or in combination of two or more types. Can be done. Also, preferred as the above polymer () are:
It can be produced by copolymerizing the following vinyl monomers () and vinyl monomers () together with other monomers copolymerizable with these vinyl monomers, if necessary. Furthermore, it is also possible to use a blend of two or more types of the above-mentioned vinyl monomers () and polymers () obtained by copolymerizing the vinyl monomers () with other monomers that can be copolymerized with these vinyl monomers as necessary. . Examples of the vinyl monomer () include allyl alcohol: N-hydroxymethyl (meth)acrylamide, N-(2-
hydroxyethyl)(meth)acrylamide, N,
N-dihydroxymethyl (meth)acrylamide, N,N-di(2-hydroxyethyl) (meth)
Acrylamide: 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth)
Acrylate, 14-butylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, hydroxyallyl methacrylate,
Polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate: Hydroxymethylaminomethyl(meth)acrylate, 2-hydroxyethylaminomethyl(meth)acrylate, 2-(2-hydroxyethylamino)ethyl(meth)acrylate , N,N-di(hydroxymethyl)aminomethyl(meth)acrylate, N,N-di(2-hydroxyethyl)aminomethyl(meth)acrylate, etc., and each of these vinyl monomers () can be used alone. Alternatively, two or more types may be used in combination. Examples of the vinyl monomer () include acrylic acid, methacrylic acid, crotonic acid,
Vinyl acetic acid, maleic acid, itaconic acid: methyl (meth)acrylate, ethyl (meth)acrylate: (meth)acrylamide, crotonamide: N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth) ) acrylamide, N-butyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide,
N,N-dipropyl (meth)acrylamide,
N,N-dibutyl(meth)acrylamide, N-
Butoxymethyl (meth)acrylamide, N-
iso-butoxymethyl(meth)acrylamide,
2-(N-methylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)
Acrylate, 2-(N,N-dimethylamino)
Ethyl (meth)acrylate, 2-(N,N-diethylaminoethyl)(meth)acrylate, 2
-(N,N-dibutylamino)ethyl (meth)acrylate, 3-(N,N-diethylamino)propyl (meth)acrylate, 2-(N,N-dibutylamino)propyl (meth)acrylate,
3-(N,N-dibutylamino)propyl (meth)acrylate: allyl glycidyl ether,
Examples include glycidyl (meth)acrylate, glycidyl crotonate: tetrahydrofurfuryl (meth)acrylate, and these vinyl monomers () can be used alone or in combination of two or more. Particularly preferred among the above-mentioned undercoat paints is a paint whose main component is a polymer () having each of the repeating structural units represented by general formulas (3) and (4). In addition, the above polymer ()
Of the vinyl monomers () constituting, particularly preferred are N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N,N-dihydroxymethyl(meth)acrylamide, and N,N-dihydroxymethyl(meth)acrylamide. (2-hydroxyethyl) (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1.4-butylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono Examples include (meth)acrylate. Also, vinyl monomer ()
Among these, particularly preferred are methyl (meth)acrylate, ethyl (meth)acrylate, and 2-(N-
methylamino)ethyl(meth)acrylate, 2
-(ethylamino)ethyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2-(N,N-diethylamino)ethyl (meth)acrylate, 2-(N,N
-dibutylamino)ethyl (meth)acrylate, 3-(N,N-diethylamino)propyl (meth)acrylate, 2-(N,N-dibutylamino)propyl (meth)acrylate, 3-
Examples include (N,N-dibutylamino)propyl (meth)acrylate, allyl glycidyl ether, glycidyl (meth)acrylate, glycidyl crotonate, and tetrahydrofurfuryl (meth)acrylate. It is not necessarily necessary for the above-mentioned undercoat paint to contain a crosslinking agent. However, when the top coat is applied, the organic solvent in the top coat may erode the base coat, resulting in a decrease in the adhesion of the top coat. In order to prevent this, it is preferable to include a crosslinking agent in the undercoat. Examples of crosslinking agents that can be used include polyhydric alcohols such as 1.4-butanediol, glycerin, and polyethylene glycol. Melamines such as methylolmelamine and alkyl etherified methylolmelamine. Included are polyfunctional epoxy compounds such as ethylene glycol diglycidyl ether and glycerol polyglycidyl ether, and organoalkoxysilanes such as epoxysilane and aminosilane. These crosslinking agents may be used alone,
Alternatively, two or more types may be used in combination. The amount used is generally from 0.05 to 0.7 equivalents per equivalent of the polymer () or a functional group (carboxyl group, amino group, substituted amino group, hydroxyl group, epoxy group, or tetrahydrofuryl group) in the polymer (). It is preferably used in an amount of 0.1 to 0.4 equivalent. Examples of crosslinking catalysts used with this crosslinking agent include hydrochloric acid, ammonium chloride, ammonium nitrate, ammonium thiocyanate, ammonium perchlorate, triethylamine, N,N-dimethylaminopropylamine, tin octylate, etc. Generally, it is appropriate to use the amount in the range of 0.05 to 0.8 gram equivalent per 1 gram equivalent of the crosslinking agent. Moreover, this crosslinking catalyst may be used without a crosslinking agent. In this case, the appropriate amount to be used is 0.01 to 1.0 parts by weight per 100 parts by weight of the polymer () or (). Before use, the primer paint is diluted to a concentration suitable for the application job. Examples of diluents that can be used include methanol and other alcohols, methyl cellosolve and other ethers, methyl ethyl ketone and other ketones, and methyl acetate and other esters, which may be used alone or as a mixed solvent. It may also be used in the form of The degree of dilution is 0.1 to 25% by weight of the polymer () or polymer (), more preferably 0.5 to 15% by weight.
It is preferable to adjust the amount to % by weight. The undercoat may also contain small amounts of conventional paint additives, such as flow control agents, if necessary. A paint containing the above polymer () or polymer () as a main component, and optionally a crosslinking agent, a crosslinking catalyst, a diluent, and a flow control agent is applied to the surface of a polycarbonate resin molded article. The resulting coating film is dried and, if necessary, baked at a temperature lower than the heat deformation temperature of the resin molded article to obtain a coating film with an undercoat. The preferred thickness of this undercoat film is 0.1 to 3 microns. Examples of polycarbonate resins to which the present invention can be applied include bisphenol type polycarbonates such as 4,4'-isopropylidene diphenol polycarbonate, as well as U.S. Patent No. 3305520
and other polycarbonates, diethylene glycol bisallyl carbonate, etc., described in "Polycarbonates", pp. 161-176 (published in 1962) by Christopher and Foxx. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited by these Examples. Note that parts and % in the examples indicate parts by weight and % by weight, respectively. Furthermore, the performance of the coating film was evaluated using the following method. In other words, the antifogging property is measured by taking a sample kept at -10°C into an atmosphere of 22°C and 60% RH, and observing whether or not fogging occurs at that time. Abrasion resistance was evaluated by rubbing with a brass wire brush (Yoji type 4 line type) and examining the resistance to scratches as follows. A: No scratches even with strong friction B: Slight scratches with strong abrasion C: Scratches even with weak friction The adhesion is determined by the cross-cut tape test, i.e., by using a knife on the surface of the paint film to make 11 strips vertically and horizontally at 1 mm intervals. After cross-cutting 100 squares with parallel lines of , and pasting cellophane adhesive tape on them, peel off the tape and find the number of squares that will not peel off among the 100 squares. to be displayed. Hot water resistance was determined by immersing the sample in boiling water for 30 minutes and then examining the state of the coating film. Examples 1 to 9 Comparative Examples 1 to 3 A Undercoat (1) 36 parts by weight of 2-hydroxyethyl methacrylate)-dimethylaminoethyl methacrylate (14 parts by weight)-methyl methacrylate (50 parts by weight) copolymer solution (U-1) Adjustment: 320 g of ethyl cellosolve, 36 g of 2-hydroxyethyl methacrylate, 14 g of dimethylaminoethyl methacrylate, methyl methacrylate
50 g and 0.4 g of azobisisobutyronitrile were added, and the mixture was heated and stirred at 90° C. for 4 hours in a nitrogen atmosphere to copolymerize. The resulting solution turned into a pale yellow liquid with a molecular weight of about 22,000, and a copolymer of 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, and methyl methacrylate was formed. (2) Preparation of other copolymers, homopolymers, and homopolymers (U-2 to U-6) U-2 to U- shown in Table 1 using the same method as in (1).
Each copolymer or homopolymer of 6 was synthesized. (3) Preparation of paint The above copolymers or homopolymers are shown in Table 2.
Mix at the ratio of

[Table] A small amount of troll agent was added and diluted with ethyl cellosolve so that the solid content was 1.0 to 10.0% by weight. (4) Painting The above undercoat was applied by dipping onto a 1mm thick polycarbonate board that had been cleaned in advance.
It was heated and cured at 130°C for 20 minutes. B Top coating (5) Preparation of γ-glycidoxypropyltrimethoxysilane partial hydrolyzate solution (A-1) Dissolve 100.0 parts of γ-glycidoxypropyltrimethoxysilane in 68.4 parts of ethyl cellosolve,
Further, 34.2 parts of a 0.1N aqueous hydrochloric acid solution was gradually added, and the mixture was stirred at room temperature for hydrolysis, and then aged at room temperature for 20 hours or more. The resulting solution was clear and colorless. It contained 35% by weight of γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as . (6) Preparation of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane partial hydrolyzate solution (A-2) Dissolve 100.0 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in 73.2 parts of ethyl cellosolve. Then, 32.8 parts of a 0.01N aqueous hydrochloric acid solution was gradually added and the mixture was stirred at room temperature to effect hydrolysis, and then aged at room temperature for more than 20 hours.
The resulting solution is colorless and transparent.

It contained 35% by weight of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane hydrolyzate calculated as [Formula]. (7) Polyhydric alcohols having ethylene oxide chains (B-1 to B-4). Those shown in Table 4 were used.

[Table] (8) Preparation of glycidyl methacrylate (60 parts by weight) - hydroxyethyl methacrylate (40 parts by weight) copolymer solution (C-1) 140 g of ethyl cellosolve, 36 g of glycidyl methacrylate, 24 g of hydroxyethyl methacrylate and azobisisobutyronitrile Add 0.3g (AIBN) and heat while stirring gently.
Raise to 90℃. The process continues for about 4 hours while constantly blowing nitrogen. The obtained solution is
Pale yellow viscosity approximately 90CPS (molecular weight approximately 20,000,
It became a liquid with a resin solid content of 30% by weight, and was a copolymer of glycidyl methacrylate and hydroxyethyl methacrylate. (9) Preparation of glycidyl methacrylate (25 parts by weight)-ethyl methacrylate (50 parts by weight)-hydroxyethyl methacrylate (25 parts by weight) copolymer solution (C-2). 140 parts of ethyl cellosolve, 15 parts of glycidyl methacrylate, 30 parts of ethyl methacrylate, 15 parts of hydroxyethyl methacrylate,
Add 0.3 parts of AIBN and lower the temperature while stirring gently.
Raise to 90℃. The process continues for about 4 hours while constantly blowing nitrogen. The resulting solution turned into a pale yellow liquid with a viscosity of about 80 cps (molecular weight about 18,000), and a copolymer of glycidyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate, which had the same composition as the raw material monomer, was formed. (10) Curing catalyst. Ammonium perchlorate (D-1),
Aluminum acetylacetonate (D-2)
It was used. (11) Surfactant. Among nonionic active agents, polyoxyethylene alkylaryl type active agent (Liponox NCN manufactured by Lion Oil Co., Ltd.) (E-1),
Polyoxyethylene sorbitan ester type activator (manufactured by NOF Corporation, Nitsusan Nonion LT)
221) (E-2) was used. (12) Preparation of paint The above-mentioned epoxy group-containing organic silane compounds and/or their partial hydrolysates (A-1 to A-
2) Polyhydric alcohols having ethylene oxide chains (B-1 to B-4) and vinyl polymers or copolymers having epoxy groups (C-1 to B-4)
C-2) in the proportions shown in Table 2, add a curing catalyst, if necessary, a surfactant in the proportions shown in Table 2, and then add a small amount of flow control agent until the solid content is 20%.
Diluted with ethyl cellosolve to ~50% by weight. (13) Painting The above topcoat was applied by dipping to a 1mm thick polycarbonate board that had been given a basecoat.
It was heated and cured at ℃ for 1 hour. The performance results of the coating film are summarized in Table 3.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 (A) General formula (1) [Formula] (wherein R ¹ is an organic group having an epoxy group,
R ² is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms,
R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, a
is 1 to 3, b is 0 to 2, and a+b≦3. ) Epoxy group-containing organic silane compounds and/or partial hydrolysates thereof10~
30 parts by weight (calculated as [formula]) (B) 30 to 50 parts by weight of polyhydric alcohol having an ethylene oxide chain and (C) general formula (2) [formula] (in the formula, R ⁴ is a hydrogen atom , R ⁵ represents a hydrogen atom or a lower alkyl group, and X represents a side chain having an epoxy group.)
Polymers or copolymers containing at least 20% by weight of repeating structural units of 30
An antifogging coating composition consisting of ~50 parts by weight of the above (A), (B), and (C) in total of 100 parts by weight as main components and a curing catalyst is coated and cured to form an overcoat layer, general Formula (3) [Formula] (In the formula, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Y is a side chain having a carboxyl group or an amino group.) A polymer having a repeating structural unit () or general formula (4) [formula] (in the formula, R ⁸ represents a hydrogen atom, R ⁹ represents a hydrogen atom or a lower alkyl group, and Z represents a hydroxyl group-containing side chain). The repeating structural unit shown and general formula (5) [formula] (in the formula, R ¹⁰ is a hydrogen atom, R ¹¹ is a hydrogen atom or a lower alkyl group, and W
is a side chain having a carboxyl group, an alkoxycarbonyl group, an amino group, a substituted amino group, an epoxy group or a tetrahydrofuryl group. 1. A coated polycarbonate resin molded article having both abrasion resistance and antifogging properties and having an undercoat layer formed by coating and curing a composition containing a polymer () having each of the repeating structural units shown in (). 2. The coated polycarbonate resin molded article according to claim 1, wherein the epoxy group-containing organic silane compound is a glycidoxyalkyltrialkoxysilane. 3 The polyhydric alcohol having an ethylene oxide chain has the general formula (6) (In the formula, n ₁ to n _n are each independently an integer of 0 to 7, and at least two of them are integers of 1 or more, and m is an integer of 3 to 9.) A coated polycarbonate resin molded article according to claim 1 or 2. 4. The coated polycarbonate according to claims 1 to 3, wherein the curing catalyst is ammonium perchlorate, and the amount is 0.05 to 20 parts by weight per 100 parts by weight of (A), (B), and (C). resin molded articles.