JPH0132249B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has excellent abrasion resistance, which is obtained by coating and curing a polycarbonate resin base material with an undercoat that has good adhesion to the polycarbonate resin, and then coating and curing a topcoat containing silicone resin on top of that. The present invention relates to coated polycarbonate resin molded articles. Generally, polycarbonate resin has impact resistance,
Due to its excellent transparency, it is widely used as a transparent plastic material, but it has the drawbacks of poor abrasion resistance and solvent resistance, the surface is easily scratched, and it is easily attacked by organic solvents. Various methods of coating with thermosetting resin have been proposed as methods to improve these drawbacks, but at present none of them is fully satisfactory. For example, trialkoxysilanes such as methyltrialkoxysilane and phenyltrialkoxysilane, combinations of these with tetraalkoxysilanes such as ethylsilicate and butylsilicate, or mixtures with other resin paints are known. It has not been possible to obtain a coating that has good physical properties such as abrasion resistance, hot water resistance, heat resistance, adhesion, and paint pot life. In addition, the special public official 15743, Showa 53-15743,
53-35589, epoxy group-containing alkoxysilanes, Lewis acids such as _BF3 , _BF3 etherate, or complexes thereof, HCl, HBr, HI, _HNO3 , _HClO4 ,
Articles coated and cured with coating compositions containing curing catalysts such as metal salts of prensted acid, cobalt naphthenate, zinc naphthenate, and other organic acids such as H ₃ PO ₄ have been disclosed. The pot slice is too short or takes a long time to harden, making it impractical. Furthermore, the adhesion to polycarbonate base materials is poor. Japanese Patent Publication No. 52-39691 discloses a coating composition containing a hydrolyzate of colloidal silica and methyltrimethoxysilane as main components, and this cured coating film has sufficient hardness but is not flexible. Furthermore, it is extremely difficult to obtain good adhesion to plastic substrates.
JP-A-53-111336 describes one or more compounds selected from compounds containing epoxy groups and/or silanol and/or siloxane groups, silica fine particles of 1 to 100 millimicrons, and aluminum chelate compounds. However, these cured coatings have insufficient hardness, resulting in a decrease in hardness when immersed in boiling water, etc., and also have poor adhesion to bisphenol type polycarbonate. The present inventors have made extensive efforts to eliminate such drawbacks and provide a polycarbonate resin molded article with improved abrasion resistance, hot water resistance, heat resistance, weather resistance, and adhesion to substrates. As a result of research, wear resistance was improved by applying a top coat containing a hydrolyzate of an epoxy group-containing organosilane, a hydrolyzate of an organosilicon compound, colloidal silica, and a curing catalyst to a polycarbonate resin base material, and baking it. , further applying an undercoat treatment between the top coat layer and the polycarbonate resin base material,
Improves the adhesion of the top coat layer to the base material,
Therefore, it was effective in improving the abrasion resistance, adhesion, hot water resistance, heat resistance, weather resistance, etc. of polycarbonate resin molded articles. (1) The following (A), (B), (C) and (D) (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 a carbon number 1-4 acyl group, a is 1-4
3, b is 0 to 2, and a+b≦3. )
One or more hydrolysates selected from silicon compounds having an epoxy group represented by
100 parts by weight (calculated based on solid content,

【formula】 Calculate as. ) (B) General formula (2)

[Formula] (In the formula, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, or an organic group having fluorine or chlorine, and R ⁵ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an alkoxyalkyl group having 1 to 6 carbon atoms. 4 acyl group, C is 0~
It is 3. ) 56 to 550 parts by weight of a hydrolyzate of an organosilicon compound (calculated based on solid content) Calculate as. ] (C) 4 to 334 parts by weight of colloidal silica [calculated based on solid content and calculated as SiO ₂ ]
However, the total of (B) and (C) does not exceed 567 parts by weight, and (D) a coating composition containing a curing catalyst is coated and cured to form an overcoat layer according to 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 X is a side chain having a carboxyl group, an amino group, or an epoxy group.) Polymer having () 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 Y represents a hydroxyl group-containing side chain.) and general formula (5) (In the formula, R ¹⁰ is a hydrogen atom, R ¹¹ is a hydrogen atom or a lower alkyl group, Z is a carboxyl group,
It is a side chain having 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 improved abrasion resistance and having an undercoat layer formed by coating and curing a composition containing a polymer () having each of the repeating structural units shown in (). Component (A) represented by general formula (1) used in the present invention
Examples of the silicon compound having an epoxy group include the following. Specific examples of silicon compounds having one glycidoxy group include glycidoxymethyltrimethoxysilane glycidoxymethyltriethoxysilane β-glycidoxyethyltrimethoxysilane β-glycidoxyethyltriethoxysilane γ-glycid Xypropyltrimethoxysilane γ-Glycidoxypropyltriethoxysilane γ-Glycidoxypropyltri(methoxyethoxy)silane γ-Glycidoxypropyltriacetoxysilane δ-Glycidoxybutyltrimethoxysilane δ-Glycidoxybutyl Triethoxysilane 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 silicon compounds having two or three glycidoxy groups include: bis(glycidoxymethyl)dimethoxysilane bis(glycidoxymethyl)diethoxysilane bis(glycidoxyethyl)dimethoxysilane bis( Glycidoxyethyl)diethoxysilane Bis(glycidoxypropyl)dimethoxysilane Bis(glycidoxypropyl)diethoxysilane Tris(glycidoxymethyl)methoxysilane Tris(glycidoxymethyl)ethoxysilane Tris(glycidoxypropyl)diethoxysilane Ethyl)methoxysilane Tris(glycidoxyethyl)ethoxysilane Tris(glycidoxypropyl)methoxysilane Tris(glycidoxypropyl)ethoxysilane Specific examples of silicon compounds having glycidyl groups include: glycidylmethyltrimethoxysilane glycidylmethyl Triethoxysilane β-glycidylethyltrimethoxysilane β-glycidylethyltriethoxysilane γ-glycidylpropyltrimethoxysilane γ-glycidylpropyltriethoxysilane γ-glycidylpropyltri(methoxyethoxy)silane γ-glycidylpropyltriacetoxysilane Alicyclic Specific examples of silicon compounds having the formula epoxy group include: 3,4-epoxycyclohexylmethyltrimethoxysilane 3,4-epoxycyclohexylmethyltriethoxysilane 3,4-epoxycyclohexylethyltrimethoxysilane 3,4-epoxycyclohexylpropyl Trimethoxysilane 3,4-epoxycyclohexylbutyltrimethoxysilane can be mentioned. The above general formula (2) which is the component (B) used in the present invention
Examples of the organosilicon compound represented by include the following. Namely, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, vinyltriacetoxy Silane, γ
-methacryloxypropyltrimethoxysilane,
γ-Aminopropyltriethoxysilane, N-β
-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-bis(β-hydroxyethyl)-γ-aminopropyltriethoxysilane,
N-β-(aminoethyl)-γ-aminopropyl(methyl)dimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. . These may be used alone or in combination of two or more. Component (C) colloidal silica is a dispersion medium,
For example, it is a colloidal solution in which ultrafine particles of silicic anhydride, preferably having a particle size of 1 to 100 millimicrons, are dispersed in water or an alcoholic dispersion medium, and is produced by a well-known method and is commercially available. By using these components (B) and (C) in combination with component (A), the weather resistance of the coating film is improved, and the appearance and hardness after a weather resistance test are improved. In the present invention, one or more hydrolysates selected from the silicon compounds having an epoxy group represented by the general formula (1) used as the component (A) and the general formula ( The hydrolyzate of one or more selected from the organosilicon compounds shown in 2) is one in which a part or all of the alkoxy group, alkoxyalkoxy group, or acyloxy group in the silicon compound is substituted with a hydroxyl group. and some naturally condensed substituted hydroxyl groups. These hydrolysates can be obtained by hydrolysis in a mixed solvent such as water and alcohol in the presence of an acid, as is known in the art. When the silicon compounds represented by the general formulas (1) and (2) are used without being hydrolyzed, the cured coating film becomes white and the abrasion resistance is insufficient.
When using the silicon compounds represented by the general formulas (1) and (2) as a hydrolyzate, better results are often obtained by mixing them and simultaneously co-hydrolyzing them than by hydrolyzing them separately. In the present invention, the mixing amount of components (A), (B), and (C) is 100 parts by weight in total of component (A) (calculated based on solid content).

Calculate as [Formula]. ), a total of 56 to 550 parts by weight of component (B) (calculated on solid content,

Calculate as [Formula]. ] and component (C) 4 to 334 parts by weight of colloidal silica [calculated based on solid content, calculated as _SiO2 . ] component (B) and component (C)
The total amount is 60 to 567 parts by weight. More preferably,
For 100 parts by weight of component (A), component (B) is 105 to 430 parts by weight, component (C) is 16 to 200 parts by weight, and the total of component (B) and component (C) is 121 to 473 parts by weight. . If the total amount of component (B) and component (C) is less than 60 parts by weight, the effect of their combined use will be small, and if it exceeds 567 parts by weight, the flexibility of the cured coating will be significantly reduced, making it even better. It becomes extremely difficult to obtain adhesion. As the curing catalyst for component (D) in the coating composition for the top coat layer in the present invention, the following catalysts can be used. i.e. ammonium perchlorate, ammonium nitrate, ammonium chloride,
Ammonium thiocyanate, perchloric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, para-toluenesulfonic acid, boron trifluoride and its complexes with electron donors. _SnCl4 , _ZnCl3 , _FeCl3 , _AlCl3 , _SbCl5 ,
Lewis acids such as 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. n-butylamine, di-n
Examples include amines such as -butylamine, tri-n-butylamine, guanidine, biguanide, and imidazole. However, among these curing catalysts, ammonium perchlorate, which is a type of latent catalyst, is most suitable as a curing catalyst that provides good hardness and adhesion of the coating film and has a long pot life of the coating liquid. As the curing catalyst contained in the top coating composition of the present invention, one or more of the various curing catalysts described above may be used in combination. The amount of these curing catalysts added is 0.05 to 10 parts by weight based on the solid content of the top coating composition.
More preferably, it is 0.1 to 5% by weight. Solvents that may be included in the topcoat composition include:
Alcohol. Examples include ketones, esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, etc., and one or more of these can be used as a mixed solvent. In particular, lower alcohols such as methanol, ethanol, probanol, isoprobanol, butanol, cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; lower alkyl carboxylic acids such as formic acid, acetic acid, and propionic acid; aromatic compounds such as toluene and xylene; It is preferable to use esters such as ethyl acetate and butyl acetate alone or as a mixed solvent. Furthermore, in order to obtain a smooth coating film, if necessary, a flow control agent made of a block copolymer of alkylene oxide and dimethyl siloxane, such as NUC Silicone Y-7006 (trade name) manufactured by Nippon Unicar Co., Ltd.
etc. can be added. The amount of these flow control agents added is sufficient in a small amount, and is 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, based on the entire coating composition. Further, small amounts of antioxidants, ultraviolet absorbers, etc. can also be added. Coating with top coat paint is done by the commonly used dipping method, spraying method, roller coating method,
Or, after coating a polycarbonate base material that has been coated with the undercoat paint described below and baked using a coating method such as flow coating method,
By baking and curing at a temperature of 20 minutes to 5 hours at a temperature of 130° C. or above and below the deformation temperature of the substrate (for example 130° C.), a coating film with good wear resistance, adhesion, hot water resistance, and weather resistance can be obtained. The preferred thickness of this top coat is 1 to 30 microns, more preferably 3 to 15 microns. 1
If it is less than 30 microns, the wear resistance will not be sufficient, and if it is more than 30 microns, cracks will easily occur. Next, the undercoat layer for increasing the adhesion between the overcoat layer and the polycarbonate resin base material 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 X is a side chain having a carboxyl group, an amino group, or an epoxy group.) Polymer having () 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 Y represents a hydroxyl group-containing side chain.) and the general formula
(Five) (In the formula, R ¹⁰ is a hydrogen atom, and R ¹¹ is a hydrogen atom or a side chain having a lower alkyl 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 following. The above polymer () contains at least 5 mol%, more preferably 10 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 vinyl monomer include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, maleic acid, itaconic acid, aminomethyl (meth)acrylate, (meth)acrylamide, crotonamide, glycidyl (meth)acrylate, etc. Each of these vinyl monomers may be used alone,
Alternatively, 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,
Examples include vinyl compounds such as vinyl chloride, vinylidene chloride, and acrylonitrile, and esters of acrylic acid or methacrylic acid such as methyl (meth)acrylate. These monomers may be used alone or in combination of two or more types. be able to. One or more of the polymers () can be used in combination as an undercoat. In addition, suitable polymers () are as follows:
It can be produced by copolymerizing the following vinyl monomers () and vinyl monomers () together with other monomers copolymerizable with these vinyl monomers, if 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, 1,4
-Butylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, bidroxyallyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate: hydroxymethylaminomethyl(meth)acrylate, 2-hydroxyethyl Aminomethyl (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 these vinyl monomers () may be used alone, or 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: (meth)acrylic glycidyl ether, allyl glycidyl ether, glycidyl (meth)acrylate, glycidyl crotonate: tetrahydrofurfuryl (meth)acrylate, etc. These vinyl monomers ()
can be used alone or in combination of two or more. One or more of the polymers () can be used in combination as an undercoat. It is not always 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. It is preferable to include a crosslinking agent in the undercoat paint. 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, alkoxysilanes having epoxy groups, and hydrolysates thereof. These crosslinking agents may be used alone,
Alternatively, two or more types may be used in combination. In addition, examples of the crosslinking catalyst used with this crosslinking agent include hydrochloric acid, ammonium chloride, ammonium nitrate, ammonium thiocyanate, ammonium perchlorate, etc., and the amount used is generally 0.03 to 1.0 parts by weight based on the resin solid content. It is appropriate to use the ratio of 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 10% by weight of the polymer () or polymer (), more preferably 0.5 to 5% 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 coating containing the above-mentioned polymer () or polymer () as a main component, to which a crosslinking agent, a crosslinking catalyst, a diluent, and a flow control agent are added as necessary, is applied to the surface of a polycarbonate resin molded article. An undercoat film is obtained by drying the resulting coating film and, if necessary, baking it at a temperature lower than the heat deformation temperature of the resin molded article. The preferred thickness of this undercoat film is 0.1 to 1 micron. By providing this undercoat film, hydroxyl groups, carboxyl groups, amino groups, etc. in the paint film react with silicon components, etc. in the paint film, and therefore, the topcoat film is transferred to the polycarbonate resin through the undercoat film. This results in strong adhesion to the molded article. 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. These are used as various molded products, such as eyeglass lenses, ski goggles, doors, automobile windows, and partitions. The coated polycarbonate resin molded article according to the present invention can be colored by dyeing its coating layer, if necessary. The dyeing method is, for example, in a dye bath containing general disperse dyes, dispersants, PH adjustment liquid, etc.
This is done by immersion treatment under conditions of 1 minute. In this way, a dyed article with excellent abrasion resistance can be obtained. 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. The performance of the coating film was evaluated using the following method. That is, abrasion resistance: The resistance to scratching by rubbing with #0000 steel wool was examined and judged as follows. A: No scratches even if rubbed strongly. B: Slight damage occurs when rubbed strongly. C: Even weak friction causes scratches. Adhesion: In the so-called cross-cut tape test, cross-cut 100 squares by making 11 parallel lines vertically and horizontally at 1 mm intervals on the surface of the coating film using a knife.
After adhering cellophane adhesive tape thereon, the tape was peeled off and the number of squares that did not peel off among 100 squares was indicated. Hot water resistance: The state of the coating film was examined after being immersed in boiling water for 1 hour. Heat resistance: The state of the coating film was examined after being stored in a hot air drying oven at 120°C for 100 hours. Chemical resistance: The state of the coating film was examined after being immersed in the following chemicals at room temperature for 100 hours. 3% sulfuric acid, 1% sodium hydroxide, 95% ethanol, acetone, ethyl acetate carbon tetrachloride, toluene, n-heptane, 10% saline. Example 1 A top coat and an undercoat were prepared as follows. (1) Preparation of top coat; 80 parts of γ-glycidoxypropyltrimethoxysilane, 144 parts of methyltrimethoxysilane, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%)
Mix 71 parts and 170 parts of 0.1N hydrochloric acid aqueous solution,
Hydrolysis was carried out by refluxing at 80-85°C for 2 hours. The obtained solution is γ-glycidoxypropyltrimethoxysilane hydrolyzate 12.2%, calculated as
It contained 15.3% methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 and 3.1% colloidal silica calculated as SiO ₂ . The ternary cohydrolyzate solution obtained in this way
To 410 parts, 73 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of flow control agent were added to make a top coat. (2) Preparation of primer paint (a); Ethyl Cellosolve 230
30 parts of 2-hydroxyethyl methacrylate
70 parts of glycidyl methacrylate and 0.4 parts of azobisisobutyronitrile were dissolved, and the mixture was heated and stirred at 90° C. for 4 hours in a nitrogen atmosphere to copolymerize.
(Copolymer-i) Solution obtained in this way 100
0.1 part of triethylamine, 270 parts of ethyl cellosolve, and a small amount of flow control agent.
It was used as an undercoat paint (a). First, the undercoat paint prepared in (2) above was applied to a polycarbonate base material that had been washed in advance, and then heated and dried in a hot air drying oven at 130°C for 30 minutes. Next, the top coat prepared in (1) above was applied to the polycarbonate coated with the undercoat layer obtained in this manner, and the coat was dried by heating in a hot air drying oven at 130°C for 60 minutes to cure. The coated polycarbonate molded article thus obtained is transparent, has an abrasion resistance of A, and an adhesion of 100/10.
0, hot water resistance and heat resistance are good, and the abrasion resistance and adhesion after the hot water resistance test are A and 10, respectively.
It was good at 0/100. Furthermore, the appearance and hardness after 500 hours of sunshine weather meter testing were extremely good. Furthermore, the chemical resistance was good for all chemicals, and no abnormality was observed in the appearance after the test. Example 2 320 parts of ethyl cellosolve, 14 parts of 2-hydroxyethyl methacrylate, 55 parts of methyl methacrylate
90 parts of glycidyl methacrylate and 0.5 parts of azobisisobutyronitrile were dissolved under a nitrogen atmosphere.
The mixture was heated and stirred at ℃ for 4 hours to copolymerize (copolymer). To 100 parts of the solution thus obtained were added 0.1 part of triethylamine, 270 parts of ethyl cellosolve, and a small amount of a flow control agent to prepare an undercoat paint (b). onto a pre-cleaned polycarbonate base material.
First, the undercoat paint prepared above was applied and dried by heating at 130°C for 30 minutes in a hot air drying oven. Next, a top coat similar to that in Example 1 was applied to the polycarbonate coated with the undercoat layer obtained in this way,
It was heated and dried in a hot air drying oven at 130°C for 60 minutes to harden it. The coating film of the coated polycarbonate molded article obtained in this way had good adhesion and after a hot water test,
It was 0/100. Example 3 8 parts of glycidyl methacrylate, 72 parts of methyl methacrylate and 0.4 parts of azobisisobutyronitrile were dissolved in 320 parts of ethyl cellosolve and copolymerized by heating and stirring at 90°C for 4 hours in a nitrogen atmosphere. --). To 110 parts of the solution thus obtained were added 22 parts of toluene, 88 parts of butyl cellosolve, and a small amount of a flow control agent to prepare an undercoat paint (C).
First, apply an undercoat (C) to the pre-washed polycarbonate base material, and dry it in a hot air drying oven at 130℃ for 10 minutes.
It was dried by heating for a minute. Next, Example 1 was applied to the polycarbonate coated with the undercoat layer thus obtained.
Apply the same top coat as above and dry in a hot air drying oven at 130°C.
It was dried and cured by heating at ℃ for 60 minutes. The coated polycarbonate molded article thus obtained had good adhesion, with a rating of 100/100 after a hot water test. Example 4 A top coat and an undercoat were prepared as follows. (1) Preparation of undercoat; γ-glycidoxypropyltrimethoxysilane
60 parts, 173 parts of methyltrimethoxysilane, 71 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%), and 0.1N aqueous hydrochloric acid solution
190 parts were mixed and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as 8.6%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5
It contained 17.3% and 2.9% colloidal silica calculated as _SiO2 . The ternary cohydrolyzate solution obtained in this way
47 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of flow control agent were added to 436 parts to make an undercoat paint. (2) Preparation of undercoat (d): 320 parts of ethyl cellosolve, 76 parts of 2-hydroxyethyl methacrylate, 4 parts of dimethylaminoethyl methacrylate, and azobisisobutyronitrile.
0.4 part was dissolved and stirred under heating at 90° C. for 4 hours under a nitrogen atmosphere to copolymerize. (Copolymer) To 26 parts of the copolymer solution (iv) thus obtained, 41 parts of the copolymer solution (i) used in Example 1, and ethyl cellosolve.
258 parts and a small amount of flow control agent were added to prepare an undercoat (d). onto a pre-cleaned polycarbonate base material.
First, the undercoat paint prepared in (2) above was applied and dried by heating at 130°C for 10 minutes in a hot air drying oven. Next, the top coat prepared in (1) above was applied to the polycarbonate coated with the undercoat layer obtained in this manner, and was cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article thus obtained was transparent, had good hot water resistance and heat resistance, and had good abrasion resistance and adhesion of A and 100/100, respectively, after the hot water resistance test. Furthermore, the appearance and hardness after 500 hours of sunshine weather meter testing were extremely good. Example 5 A top coat and an undercoat were prepared as follows. (1) Preparation of top coat; γ-glycidoxypropyltrimethoxysilane
40 parts, 202 parts of methyltrimethoxysilane, 71 parts of colloidal silica (Snowtex-C, manufactured by Nissan Chemical Industries, Ltd., solid content 20%), and 0.1N aqueous hydrochloric acid solution.
211 parts were mixed and refluxed at 80-85°C for 1 hour to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate 5.4% calculated as [Formula], methyltrimethoxysilane hydrolyzate 19.0% calculated as CH ₃ SiO _1.5 and colloidal silica 2.7% calculated as SiO ₂
It contained. The ternary cohydrolyzate solution obtained in this way
To 463 parts, 20 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of flow control agent were added to form a top coat. (2) Preparation of undercoat (e) 320 parts of ethyl cellosolve, 32 parts of 2-hydroxyethyl methacrylate, 36 parts of methyl methacrylate
12 parts of dimethylaminoethyl methacrylate and 0.4 parts of azobisisobutyronitrile were dissolved and heated and stirred at 90° C. for 4 hours in a nitrogen atmosphere to copolymerize (copolymer). On the other hand, 324 parts of a 0.1N aqueous hydrochloric acid solution was added to 944 parts of γ-glycidoxypropyltrimethoxysilane, and the mixture was stirred at room temperature for 5 hours to carry out hydrolysis. To 23.5 parts of the hydrolyzate of γ-glycidoxypropyltrimethoxysilane thus obtained, 26.6 parts of the copolymer (v), 0.1 part of ammonium perchlorate,
A primer coating (e) was prepared by adding 170 parts of ethyl cellosolve and a small amount of a flow control agent. First, the undercoat paint prepared in (2) above was applied to a polycarbonate base material that had been washed in advance, and then heated and dried in a hot air drying oven at 130°C for 10 minutes. Next, the top coat prepared in (1) above is applied to the polycarbonate coated with the undercoat layer obtained in this way,
It was cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article thus obtained was transparent, had an abrasion resistance of A, and had a good adhesion of 100/100 after the hot water resistance test. In addition, the chemical resistance was good for all chemicals, and no abnormality was observed in the appearance after the test. Example 6 γ-glycidoxypropyltrimethoxysilane
60 parts, 144 parts of methyltrimethoxysilane, 142 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%), and 0.1N aqueous hydrochloric acid solution
98 parts were mixed and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 9.6%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 16.0%
and colloidal silica calculated as SiO ₂ 6.4
It contained %. The ternary cohydrolyzate solution obtained in this way
To 417 parts, 66 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of flow control agent were added to make a top coat. The above-mentioned top coat paint was applied to polycarbonate which had been subjected to the undercoat treatment in the same manner as in Example 4, and was cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article thus obtained is
Transparent, wear resistance is A, adhesion is 100/100, hot water resistance and heat resistance are good, no abnormalities were observed in appearance after each test, and adhesion was 100/100.
It was hot. Example 7 A top coat and an undercoat were prepared as follows. (1) Preparation of top coat 77 parts of isopropyl alcohol, 60 parts of γ-glycidoxypropyltrimethoxysilane, 115 parts of methyltrimethoxysilane, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20)
%) 213 parts and 5 parts of 1N hydrochloric acid, 80-85
Hydrolysis was carried out by refluxing at °C for 2 hours. The obtained solution is Contains 9.1% γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as CH 2 SiO _1.5 , methyltrimethoxysilane hydrolyzate 12.1% calculated as CH ₂ SiO 1.5 and colloidal silica 9.1% calculated as SiO ₂ there was. The ternary cohydrolyzate solution obtained in this way
To 417 parts, 66 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of flow control agent were added to make a top coat. (2) Preparation of undercoat (f) 100 parts of the solution of copolymer (iv) described in Example 4, 2.8 parts of hexa(methoxymethyl)melamine, 0.18 parts of ammonium perchlorate, 900 parts of ethyl cellosolve and flow control. Add a little paint and apply a primer coat.
(f). onto a pre-cleaned polycarbonate base material.
First, the undercoat paint prepared in (2) above was applied and dried by heating at 130°C for 20 minutes in a hot air drying oven. Next, the undercoat layer obtained in this way (film thickness 0.3 microns)
The top coat prepared in (1) above was applied to the polycarbonate coated with
It was heated and dried for 60 minutes to harden it. The thickness of the topcoat layer after curing was 5 microns. The thus obtained coated polycarbonate molded article is transparent and has an abrasion resistance of A, adhesion is 100/100 hot water resistance, and has good heat resistance, and after the hot water resistance test, abrasion resistance and adhesion are A, respectively. , which was good at 100/100. In addition, the chemical resistance was good for all chemicals, and no abnormality was observed in the appearance after the test. Example 8 γ-glycidoxypropyltrimethoxysilane
39 parts, 3,3,3-trifluoropropyltrimethoxysilane 2.9 parts, methyltrimethoxysilane
110 parts, colloidal silica (manufactured by Nissan Chemical Industries, Ltd.)
Snowtex-C, solid content 20%) 75 parts and 0.1
100 parts of a normal aqueous hydrochloric acid solution was added, and the mixture was refluxed at 80 to 85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate 8.5% calculated as [Formula], 3,3,3-trifluoropropyltrimethoxysilane hydrolyzate 0.6 calculated as CF ₃ C ₂ H ₄ SiO _1.5 %, 16.7% methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 and 4.6% colloidal silica calculated as SiO ₂ . Quaternary cohydrolyzate solution obtained in this way
To 310 parts, 49 parts of ethyl cellosolve, 0.9 parts of ammonium perchlorate, and a small amount of flow control agent were added to make a top coat. The above-mentioned top coat paint was applied to polycarbonate which had been subjected to the undercoat treatment in the same manner as in Example 4, and was cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article thus obtained is
It was transparent, had abrasion resistance of A, adhesion of 100/100, good hot water resistance and heat resistance, and had good abrasion resistance and adhesion of A and 100/100, respectively, after the hot water resistance test. Furthermore, the appearance and hardness after 500 hours of sunshine weather meter testing were extremely good. Example 9 36 parts of 2-hydroxyethyl methacrylate, 14 parts of dimethylaminoethyl methacrylate, 50 parts of methyl methacrylate, and 0.4 parts of azobisisobutyronitrile were dissolved in 320 parts of ethyl cellosolve, and the mixture was heated and stirred at 90°C for 4 hours under a nitrogen atmosphere. and copolymerized. (Copolymer) Additionally, 20 parts of 2-hydroxyethyl methacrylate, 80 parts of methyl methacrylate and 0.4 parts of azobisisobutyronitrile were dissolved in 320 parts of ethyl cellosolve and copolymerized in the same manner. (Copolymer). 130 parts of ethyl cellosolve to the above copolymer ()
9 parts, 80 parts of copolymer (vii), and a small amount of a flow control agent were added to prepare an undercoat (g). First, apply the above primer paint to a pre-washed polycarbonate substrate, and dry it in a hot air drying oven at 130°C.
It was dried by heating at ℃ for 30 minutes. Next, the polycarbonate coated with the undercoat layer thus obtained was coated with the same topcoat paint as in Example 1, and cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article thus obtained was transparent, had an abrasion resistance of A, an adhesion of 100/100, and had a good adhesion of 100/100 after the hot water resistance test. Comparative Example 1 Colloidal silica (Nissan Chemical Co., Ltd.
341 parts of Snotex-C (Snowtex-C, solid content 20%) manufactured by Co., Ltd. were added, and the mixture was stirred for 2 hours under external ice cooling to perform hydrolysis. The resulting solution was methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 18.4
Colloidal Silica calculated as %, _TiO2
It contained 12.3%. A top coat was prepared by adding 98 parts of isopropyl alcohol, 1.5 parts of ammonium perchlorate, and a small amount of a flow control agent to 500 parts of the hydrolyzate solution thus obtained. The above-mentioned top coat paint was applied to polycarbonate which had been subjected to the undercoat treatment in the same manner as in Example 9, and was cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article thus obtained is
It was transparent and had good abrasion resistance, but adhesion was poor and was 0/100 after a hot water resistance test. Example 10 γ-glycidoxypropyltrimethoxysilane
150 parts, 72 parts of methyltrimethoxysilane, 179 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%), and 0.1N aqueous hydrochloric acid solution
52 parts were added and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 23.5%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 7.8
Colloidal silica calculated as % and _SiO2
It contained 7.9%. The ternary cohydrolyzate solution obtained in this way
To 319 parts, 164 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of flow control agent were added to make a top coat. The above-mentioned top coat paint was applied to polycarbonate which had been subjected to the undercoat treatment in the same manner as in Example 4, and was cured by heating and drying in a hot air drying oven at 120°C for 60 minutes. The coated polycarbonate molded article obtained in this way is transparent, has an abrasion resistance of A, an adhesion of 100/100, good hot water resistance and heat resistance, and has good abrasion resistance and adhesion after the hot water resistance test. Each A, 100/100
It was good. Further, no abnormality was observed in the appearance after the chemical resistance test. Example 11 γ-glycidoxypropyltrimethoxysilane
60 parts, methyltrimethoxysilane 58 parts, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex)
C, solid content 20%) 355 parts and 0.1N hydrochloric acid aqueous solution 21
1 part was added and refluxed at 80-85°C for 2 hours to effect hydrolysis. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate 8.6% calculated as [Formula], methyltrimethoxysilane hydrolyzate 5.7% calculated as CH ₃ SiO _1.5 and colloidal silica 14.4% calculated as SiO ₂
It contained. To 434 parts of the ternary cohydrolyzate solution thus obtained were added 49 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of a flow control agent to prepare a top coat. The above-mentioned top coat paint was applied to polycarbonate which had been subjected to the undercoat treatment in the same manner as in Example 4, and was cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article obtained in this way is transparent and has good abrasion resistance of A and adhesion of 100/100, and after hot water resistance test, abrasion resistance and adhesion of A and 100/100 respectively. It was hot. Example 12 γ-glycidoxypropyltrimethoxysilane
80 parts, methyltrimethoxysilane 86 parts, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex)
C, solid content 20%) 213 parts isopropyl alcohol
Add 90 parts and 35 parts of 0.1 N hydrochloric acid aqueous solution to 80-85
Hydrolysis was carried out by refluxing at °C for 2 hours. The obtained solution is

γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as [Formula] 11.3%, methyltrimethoxysilane hydrolyzate calculated as CH ₃ SiO _1.5 8.5
Colloidal silica calculated as % and _SiO2
It contained 8.5%. The ternary cohydrolyzate solution obtained in this way
To 417 parts, 66 parts of ethyl cellosolve, 1.0 part of ammonium perchlorate, and a small amount of flow control agent were added to form a top coat. The above-mentioned top coat paint was applied to polycarbonate which had been subjected to the undercoat treatment in the same manner as in Example 7, and was cured by heating and drying at 120°C for 60 minutes. The coated polycarbonate thus obtained was transparent and had good abrasion resistance and adhesion after a hot water resistance test of A and 100/100, respectively. Comparative Example 2 An undercoat (g) was prepared by adding 40 parts of ethylene glycol diacetate and 150 parts of butyl cellosolve to 22 parts of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. First, apply the above primer paint to a pre-washed polycarbonate substrate, and dry it in a hot air drying oven at 130°C.
It was dried by heating at ℃ for 10 minutes. Next, the polycarbonate coated with the undercoat layer thus obtained was coated with the same topcoat paint as in Example 1, and cured by heating and drying in a hot air drying oven at 130°C for 60 minutes. The coated polycarbonate molded article thus obtained is
After the hot water resistance test, the appearance turned white and the paint film naturally peeled off. Comparative Example 3 A top coat similar to that in Example 12 was applied to a pre-cleaned polycarbonate base material without any undercoat treatment, and the resultant was heated and dried in a hot air drying oven at 120°C for 60 minutes.
Although it was cured, the coating film was lifted from the polycarbonate substrate and appeared as an isolated coating film. Example 13 A copolymer or homopolymer was synthesized using comonomers or monomers, solvents, and initiators as shown in Table 1, and a crosslinking agent, curing catalyst, and solvent as shown in Table 2 were added thereto to prepare an undercoat paint. h
~P was prepared. Apply each of the prepared undercoat paints h to P to a polycarbonate base material that has been cleaned in advance,
It was cured by heating and drying in a hot air drying oven at 130°C for 20 minutes.

【table】

Claims (1)

[Claims] 1 The following (A), (B), (C) and (D) (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 4 carbon atoms;
3, b is 0 to 2, and a+b≦3. )
One or more hydrolysates selected from silicon compounds having an epoxy group represented by
100 parts by weight (calculated based on solid content, Calculate as. ) (B) General formula (2) [Formula] (In the formula, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, or an organic group having fluorine or chlorine, and R ⁵ is a hydrocarbon group having 1 to 5 carbon atoms. , an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, C is 0 to
It is 3. ) 56 to 550 parts by weight of the hydrolyzate of the organosilicon compound (calculated based on solid content and calculated as [Formula]). ] (C) 4 to 334 parts by weight of colloidal silica [calculated based on solid content and calculated as SiO ₂ ]
However, the total of (B) and (C) does not exceed 567 parts by weight,
and (D) a coating composition containing a curing catalyst is coated and cured to form an overcoat layer (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 X is a side chain having a carboxyl group, an amino group, or an epoxy group.) Polymer having () 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 Y represents a hydroxyl group-containing side chain.) and general formula (5) (In the formula, R ¹⁰ is a hydrogen atom, R ¹¹ is a hydrogen atom or a lower alkyl group, Z is a carboxyl group,
It is a side chain having an alkoxycarbonyl group, an amino group, a substituted amino group, an epoxy group, or a tetrahydrofuryl group. A coated polycarbonate resin molded article having improved abrasion resistance, which is formed by coating and curing a composition containing a polymer () having each of the repeating structural units shown in ) as an undercoat layer. 2 The content of the hydrolyzate (B) is 105 to 430 parts by weight, and the content of the colloidal silica (C) is 16 to 430 parts by weight.
200 parts by weight, and the total of (B) and (C) does not exceed 473 parts by weight. The coated polycarbonate resin molded article according to claim 1. 3. Claims in which the curing catalyst is a curing catalyst selected from perchlorates, hydrochlorides, sulfates, nitrates, carboxylates, highly fluorinated aliphatic sulfonates, and highly fluorinated aliphatic sulfonylates. The coated polycarbonate resin molded article according to item 1 or 2. 4. Claim 1 or 2, wherein the curing catalyst is ammonium perchlorate, ammonium chloride, ammonium sulfate or ammonium nitrate.
The coated polycarbonate resin molded article described in 2.