JPS5978240A - Coated polycarbonate resin molding - Google Patents

Abstract

PURPOSE:To provide the titled resin molding having improved wear resistance, etc., by providing a topcoat layer contg. a colloidal silica-contg. organopolysiloxane on an undercoat layer contg. an alkoxysilyl group-contg. vinyl copolymer. CONSTITUTION:A copolymer of an alkoxysilyl group-contg. acrylic and/or vinyl monomer such as vinyltrimethoxysilane with other monomer (e.g. methyl acrylate) copolymerizable therewith is mixed with a curing catalyst such as zinc naphthenate. The resulting compsn. is applied to a polycarbonate resin substrate and cured to form an undercoat layer. A compsn. contg. a colloidal silica-contg. organopolysiloxane such as glycidoxymethyltrimethoxysilane is then applied to the undercoat layer and cured to form a topcoat layer, thus obtaining the desired coated polycarbonate resin molding.

Description

Detailed Description of the Invention The present invention is made by coating a polycarbonate resin base material with an undercoat paint that has good adhesion to the polycarbonate resin and curing it, and then coating and curing a topcoat paint containing a silicone resin thereon. This invention relates to coated polycarbonate resin molded articles with excellent abrasion resistance.

In general, polycarbonate resin is widely used as a transparent plastic material due to its excellent impact resistance and transparency, but it has poor abrasion resistance and solvent resistance, and its surface is easily scratched and is easily attacked by organic solvents. There is a drawback. As a method to improve these drawbacks, a method of adding thermosetting resin to the resin has been proposed, 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. Abrasion resistance, hot water resistance,
A material with good physical properties such as heat resistance, adhesion, and paint pot life has not been obtained. Saida Tokuko Showa 58 157
4B, 5B-85589 contains an epoxy group-containing alkoxysilane containing a Lewis acid such as BF2 or BF8 etherate or a complex thereof, 11Ct, )lBr,
ilI, I-INCJ! , HCz04.1llIP
04 etc. knob 17 stedic acid, cobalt naphthenate,
Articles coated and cured with a 41 composition containing a curing catalyst such as a metal salt of an organic acid such as zinc naphthenate are disclosed, but these paints have a short bot life or take a long time to cure. expensive and impractical. Furthermore, polycarbonate
1. Adhesion to the base material is poor. Special Public Service 1989-1989
No. 691 discloses a coating composition mainly composed of colloidal silica, methyl trimetoya, and a hydrolyzate of disilane, and the cured coating film has sufficient hardness but poor adhesion. Furthermore, it is extremely difficult to obtain good U adhesion to Plusdec substrates. Japanese Unexamined Patent Publication 1983
111886 contains one or more compounds selected from compounds containing an epoxy group and/or a silanol and/or siloxane group;
002 Limicron silica particles and aluminum Uno
Coating compositions containing chelate compounds have been disclosed, but the hardness of these cured coatings is insufficient, and hardness decreases when immersed in boiling water, etc., and adhesion to bisphenol-type polycarbonate is poor. It is.

In addition, special table 55-500856, 55-50085
No. 8 discloses a polycarbonate article having a thermoplastic acrylic polymer as an undercoat layer and a thermoset colloidal silica-filled organopolysiloxane as an overcoat layer -C.
However, its adhesion, hot water resistance, weather resistance, etc. are not fully satisfactory.

The present inventors, with the aim of eliminating such drawbacks and providing polycarbonate-based resin molded articles with improved abrasion resistance, solvent resistance, chemical resistance, and weather resistance, have conducted extensive research and found that polycarbonate・A F coating layer is applied to the polycarbonate resin base material by applying an undercoat containing an acrylic or vinyl copolymer having an alkoxysilyl group in the side chain and a curing catalyst and baking it, and then applying the F coating layer to the polycarbonate resin base material.
In order to avoid improving the adhesion of the topcoat layer, a topcoat containing an organopolysiloxane containing colloidal silica is applied on the undercoat layer and baked to improve the abrasion resistance of the polycarbonate resin molded article. It has been found that the wear resistance, solvent resistance, chemical resistance, weather resistance, etc. of

However, the present invention provides (a) a copolymer of an acrylic or/and vinyl monomer having an alkoxysilyl group and another monomer copolymerizable with these monomers, and (+))
Coating and curing a composition containing a curing catalyst to form an undercoat layer;
The object of the present invention is to provide a coated polycarbonate resin molded article having improved abrasion resistance and having an overcoat layer formed by coating and curing a composition containing an organopolysiloxane containing colloidal silica.

In the present invention, a composition containing a colloidal silica-containing organopolysiloxane used as a top coat means at least one member selected from the group consisting of (5) and (2) below.
seeds, stores] and (1)), Kano (formula 11, υ is an organic group having an epoxy group, k2 is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, R8 is a hydrocarbon group having 1 to 5 carbon atoms, Alkoxyalkyl group or acyl group having 1 to 4 carbon atoms, a is 1 to B, b is θ to 2, and a+b≦8
It is. ) Hydrolyzate (JS) of one or two types of silicon compounds having an epoxy group represented by (JS) - General formula (2) R-5i - (OR) 4
-c (2) (in the formula, a hydrocarbon group having 1 to 6 carbon atoms,
methacryloxy group, i) group, mercapto group, fluorine or chlorine-containing organic group R5 has 1 to 5 carbon atoms, alkoxyalkyl group or 1 carbon number
-4 acyl group, C is 0-8. ) A composition containing a hydrolyzate of an organosilicon compound represented by (C) colloidal silica (I)) a curing catalyst, preferably a silicon compound having an epoxy group represented by (A/) general formula (1) One or more hydrolysates selected from lO゛0 parts by weight (calculated based on solid content b, calculated as Ra-5iO x i') (
n) 56 to 550 parts by weight of a hydrolyzate of the organosilicon compound represented by the general formula (2) (however, the total solid content is n)
i -4) 4':'', calculated as C.) (C)
Colloidal silica 4 to 334 parts by weight (However, the total solid content is calculated as if, 1., SiO2), l! : The total of (C) does not exceed 567 parts by weight, preferably 60 to 567 parts by weight, and (
1)) A composition containing a curing catalyst.

More preferred 17 is component (A) 1. 12 for the OO choir section, component Q is I OF1-480 choir section and component 0
is 16 to 200 parts by weight (component σ%) and the chorus of six components is 121 to 47 parts by weight. If the chorus of the component (equal seven formations) ←] is less than 60 i, Ill jft part, it can be used in combination'? The effect of 1-I decreases, and when the amount exceeds 567 parts by weight, the i'4J flexibility of the hardened 1-I film decreases;
and it becomes extremely difficult to obtain even better adhesion.

Examples of the silicon compound having an epoxy group represented by the general formula (1) used in the present invention include the following. Specific examples of silicon compounds having one glycidoxy group include glycidoxymethyltrimethoxysilane glycidoxymethyltriethoxysilane β-glycidoxyethyltrimethoxysilane β-glycidoxyethyltriethoxysilane r-glyside Xyprobyltrimethoxysilane γ-glycid 4-dipropyltriethoxysilane r-glycidoxyprobyltri(methoxyethoxy)silane r-glycidoxypropyltriacetoxysilane 2-glycidoxybutyltrimethoxysilane δ-glyside xybutyltriethoxysilaneglycidoxymethyldimethoxysilaneglyside dimethyl(methyl)dimethoxysilaneglycidoxymethyl(ethyl)dimethoxysilaneglycidoxymethyl(phenyl)dimethoxysilanglyS nodoxymethyl(vinyl)dime 1, xysilaneglyside Yodimethyl (dimethyl) methoxysilano β-glycidoxyethyl (methyl) dimethoxysilane β-glycidoxyethyl (ethyl) dimethoxysilane β-glycidoxyethyl (dimethyl) methoxysilane r-glycidoxypropyl (methyl) dimethoxy Silane r-glycidoxypropyl (ethyl) dimethoxysilane γ-glycidoxypropyl (dimethyl) methoxysilane δ-glycidoxybutyl (methyl) dimethoxysilane δ-gridoxybutyl (ethyl) dimethoxysilane δ-glycidoxy Specific examples of silicon compounds having 2 or 8 butyl(dimethyl)methoxysilane glycidoxy groups include bis(crisitoxymethyl)dimethoxysilane bis(glycidoxymethyl)jethoxysilane bis(glycidoxyethyl) dimethoxysilane bis(glycidoxyethyl)jethoxysilane bis(glycidoxypropyl)dimethoxysilane bis(glycidoxypropyl)jethoxysilane tris(glycidoxymethyl)methoxysilane tris(
(glycidoxymethyl) ethoxysilantris (glycidoxyethyl)methoxysilantris (glycidoxyethyl)
Methoxysilantris (crisitoxyprovir)
Specific examples of silicon compounds having a quinsilane glycidyl group include glycidylmethyltrimethoxysilane glycidylmethyltriethoxysilane β-glycidylethyltrimethoxysilane β-glycidylethyltriethoxysilane γ-glycidylprobyltrimethoxysilane r-glycidylpropylene Biltriethoxysilane γ-glycidylpropyltri(methoxyethoxy)solan r-glycidylpropyltriacetoxysilane Specific examples of silicon compounds having an alicyclic epoxy group include: 8.4-epoxycyclohexylmedyltrimethoxysilane 3.4-EpoxycyclohexylmethyltriethoxyS
Nosilane 3.4-Epoxycyclohexylethyltrimethoxyζ
Furan 3.4-epoxycyclohexylpropyltrimethoxysilane 3.4-epoxycyclohexylbutyltrimethoxysilane may be mentioned.

The component (il) used in the present invention is the general formula (2)
) Examples of the organosilicon compound represented by the formula include the following. Namely, trimethylmethobase disilane, dimethyldimethobase disilane, methyltrimethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, vinyll-IJ ethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriale Toxysilane, r-methacryloxypropyltrimethoxysilane, r-aminopropyltriethoxysilano, N-(β-aminoethyl)4-aminopropyl) dimethoxysilano, N-bis(β-hydroxyethyl) −
r-Aminopropyltriethoxy/ran, N-(β-
(aminoethyl)-r-aminopropyl(methyl)dimethoxysilano, r-chloropropyll, dimethoxysilano N r-mercaptopropyltrimethoxysilane,
Examples include 8°8.8-trifluoropropyl 1-dimethoxysilano. These may be used alone or in combination of two or more.

Component C), colloidal silica, refers to a dispersion medium such as water or an alcohol dispersion medium containing silicic anhydride, preferably 1 to
This is a colloidal solution prepared by dispersing ultrafine particles with a particle size of 100 millimicrons, and is manufactured by a well-known method and is commercially available.

By using these components (31) and (a) together with component (5), the weather resistance of the coating film is improved, and the appearance and hardness after a weather resistance test are improved.

One or more hydrolysates selected from the silicon compounds having an epoxy group represented by the above general formula (1) used as component (he) in the present invention and component C
The hydrolyzate of one or more selected from the organosilicon compounds represented by the general formula (2) used as B) is a part of the alkoxy group, alkoxyalkoxy group, or acyloxy group in the silicon compound. Alternatively, it includes those completely substituted with hydroxyl groups and those in which substituted hydroxyl groups are partially naturally condensed.

These hydrolyzates can be obtained by hydrolysis in the presence of an acid in a mixed solution such as water and alcohol, as is well known. The above general formulas (1) and (2)
When the silicon compound represented by is used without being hydrolyzed, the cured coating film becomes white and the abrasion resistance is also insufficient.

When using the silicon compounds represented by general formulas (1) and (2) as a hydrolyzate, rather than hydrolyzing them separately,
In many cases, it is better to mix them and hydrolyze them at the same time.

As the curing catalyst on the component side in the coating composition for the top coat layer in the present invention, the following catalysts can be used. Namely ammonium perchlorate, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium thiocyanate, perchloric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, para-toluenesulfonic acid, boron trifluoride and its complex with an electron donor. .

5nCA4, Zn, C1B, FeCt8,
AtC68, 5bCt5.

Lewis acids such as TiC44 and their complexes.

Organic acid metal salts such as sodium acetate, zinc naphthenate, gobalt naphthenate, zinc octylate, tin octylate. Borofluoride metal salts such as borofluoride zinc oxide and borofluoride tin oxide. Ethyl boric acid? and boric acid organic esters such as methyl borate, and alecromers such as sodium hydroxide and potassium hydroxide.

Titanate esthetics such as tetrabutoxytitanium and tetraisoprosfoxytitanium. Metal acetylacetonate such as chromium acetylacetonate, titanyl acetifure acetonate, aluminum acetylacetonate, cobalt acetylacetonate, di-V Kerurea old tylacetonate, etc.
Rare acetonates. Amines such as n-butylamine, di-n-butyfuramine, trilobite, guanidine, biguanide, imidazole, ammonium trifluoromethylsulfonate, sodium trifluoromethylsulfonate, trifluoromethyl Highly fluorinated aliphatic salts such as potassium sulfonate,
N114 (CF 8 SO2) 2C, Rr 1K (
CFgSO2)2G(1Ba [(CF a 802
) 2cti ] 2 etc., high fluoride, solubilized aliphatic sulfur 1;
Examples include nil-based compounds.

Among these curing catalysts, the hardness, transparency, etc. of the coating film are good, and the paint liquid has a good hardness. Perchlorates, hydrochlorides, sulfates, carboxylates, highly fluorinated aliphatic sulfonates, and highly fluorinated aliphatic sulfonyl salts represented by ammonium methylsulfonate and bis(trifluoromethylsulfonyl)bromomethylammonium A suitable compound is -C.

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 1.0% based on the solid content of the top coating composition. 0.05-10 weight NLJ96,
More preferably, it is 0.1 to 5 parts by weight.

Examples of solvents that may be included in the top coating composition include alcohols. Ketones. Examples include esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, etc., and one or more of these can be used as a mixed solvent. Especially methanol,
Ethanol, propatool, ink "J Lower alcohols such as panol and butanol, methylcellosoalkyl carbon M [i: aromatic compounds such as toluene and xylene; esters such as ethyl acetate and butyl acetate; and acetone,
It is preferable to use ketones such as methyl edyl ketone and methyl isobutyl ketone alone or in a mixed solvent.

Furthermore, in order to obtain a smooth coating film, a flow control agent such as a fluorosurfactant or a block copolymer of alkylene oxide and dimethyl siloxy-none may be added, if necessary.

A small amount of these flow control agents is sufficient, and the amount of addition is 0. O1-5 is 96% by weight, more preferably 0.08-8% by weight. It is also possible to add small amounts of antioxidants, ultraviolet absorbers, etc.

Coating with the top coat is done by a commonly used coach ink method such as dipping, spraying, roller coating, or flow coating. After coating the material, it is baked for 20 minutes to 5 hours at a temperature of 70°C or higher and lower than the deformation temperature of the base material (for example, 130°C) to create a coating with good wear resistance, adhesion, hot water resistance, and weather resistance. A membrane is obtained.

The preferred thickness of the topcoat film is 1 to 8°ε chron,
More preferably, it is 3 to 15 microns. If it is less than 1 micron, the abrasion resistance will not be sufficient, and if it is less than 80 microns, scratches will easily occur.In accordance with the present invention, an acrylic or vinyl monomer having an alkoxysilyl group used as an undercoat, A copolymer with other monomers that can be copolymerized with it means that in its molecule,
・General formula (in the formula, R6 is hydrogen or a methyl group, R7 is a hydrocarbon group having 1 to 6 carbon atoms, 1 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, d is 061
Or 2. R8 may be the same group or a mixture of different groups. ) or/and general formula (in the formula, 9 is a hydrocarbon group having 1 to 6 carbon atoms, R10 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, e is 0 .1 or 2.k
may be the same group or a mixture of different groups. ) A copolymer having the structure shown in
Usually monomers represented by the general formula (3) % formula % (4) 6 7 8 9 10 (wherein R, R, R, R, R, d and e have the above meanings) and these It can be obtained by combining the above monomer with another copolymerizable monomer. If -1BIO is a mixture of different groups, a copolymer may be obtained by polymerizing monomers containing different groups, or a copolymer may be obtained by polymerizing monomers having the same groups. It can also be obtained by Kokichi, in which the compound is transesterified in the presence of an alcohol.

In the acrylic monomer having an alkoxysilyl group represented by the general formula (8), k in the general formula is, for example, an alkyl group such as methyl, ethyl, propyl, butyl; an aryl group such as phenyl; Alkenyl groups, etc.; 1 (8 includes, for example, alkyl groups such as methyl, ethyl, butylbutyl; alkoxyalkyl groups such as methoxyethoxy, ethoxyethoxy, butoxyethoxy; acyl groups such as acetyl;
Various compounds are used in the present invention depending on the types of t6, R7, R8 and the number of d, and specific examples include the following. r-(meth)acryloquinepropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, r-(meth)acryloxypropylmethyldimethoxysilane, r
(meth)acryloxypropyldimethylmethoxysilane, r(meth)acryloxypropyldimethylethoxysilane, and the like.

In the vinyl monomer having an alkoxysilyl group represented by the general formula (4), 9 in the general formula is the same as 7 above.
Examples of groups similar to B9 and RIO include the same groups as 8 above, and various compounds are used in the present invention depending on the type of B9 and RIO and the number of e, but specific examples include the following: Things can be mentioned. Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(
(β-methoxyethoxy)silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyljethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysolane, and the like.

Other monomers copolymerizable with the monomers represented by general formulas (8) and (4) include the following.

Methyl (meth)acrylate, Ethyl (meth)acrylate, Propyl (meth)acrylate, Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate , butylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycidyl(meth)acrylic 1 note, dimethylaminoethyl(meth)acrylate, diethylaminoethyl (
meth)acrylate, dibutylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate,
Dibutylaminopropyl (meth)acrylate, (meth)acrylamide, methylol (meth)acrylamide, butoxymethyl (meth)acrylamide, (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene, vinyltoluene, vinyl acetate, acrylonitrile , allyl alcohol, etc., but the general formula (8),
Any monomer may be used as long as it is copolymerizable with the monomer shown in (4).

The monomers represented by general formulas (8) and (4) are contained in the copolymer obtained in polymerization 17 in an amount of 1 to 70% by weight, preferably 2 to 40% by weight, and more preferably 2 to 80% by weight.
included. If the weight is less than 196, the adhesion between the undercoat and the topcoat containing colloidal silica-containing organopolysiloxane will decrease, and if it is more than 70, the adhesion of the undercoat to the polycarbonate resin substrate will decrease. The stability of the coating solution decreases by 1 degree as well.

The weight average molecular weight of the copolymer is from 10,000 to 800,000, preferably from 2 to 800,000.
・It is 200,000. If it is less than 10,000, the adhesion to the polycarbonate resin base material will deteriorate, and if it is more than 300,000, the appearance of the coating film will be impaired, which is not preferable.

The curing catalyst used in the undercoating paint Iζ of the present invention includes inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid. Formic acid, acetic acid, propionic acid, para-toluenesulfonic acid,
Organic acids such as oxalic acid.

Zinc naphthenate, cobalt naphthenate, lead naphthenate,
Organic acid metal salts such as zinc octylate and tin octylate.
-Amines such as butylamine, di-n-butylamine, jetanolamine, S-trimethoxysilylpropylamine, and imitazole. Boron trifluoride and its complex with an electron compound. Boric acid organic esters such as methyl borate and ethyl borate. Organic titanates such as tetra-n-butoxytitanium and its oligomers, tetraisopropoxyditane and its oligomers, diisopropoxybis(acetylacetonate)titanium, di-n-butoxybis(triethanolaminate)titanium. 5nCL4,Z
nCl2, FeCLs, AlCl2.5bcz5.
1'1C4411 Which Lewis acids and their complexes.

1.5-diazabicyclo(4,8,0)nonene 5s
1 * 8-Sabishifuo(5,4,0)undeshi-7 and other bicyclic ashibazines and their salts.

Organic soot compounds such as dibutyltin dilaurate and dibutyltin maleate. 4 such as tetramethylammonium chloride, triethylbenzylammonium bromide, etc.
grade ammonium salt.

Examples include metal acetylacetonates such as chromium acetylacetonate, titanyl acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, and nickel acetylacetonate. Among these curing catalysts, organic acids, amines, metal acetylacetonates, and organic titanates are used as catalysts that are particularly effective in forming coating films on polycarbonate resin paper stocks and have a long pot life. I can list several types.

The various curing catalysts mentioned above may be used alone or in combination of two or more. The amount of curing catalyst added is 0.01 to 10% by weight, preferably 0.01 to 10% by weight, based on the copolymer.
It is 1 to 5% smooth.

If it is less than 0.01 weight 4t96, no effect as a curing catalyst will be recognized, and if it is more than 10% by weight, the stability of the coating liquid will decrease.

In order to obtain an undercoat paint, in addition to the above-mentioned components, a solvent and various additives are added as desired.

Examples of solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and diaton alcohol; cellosolves such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, and butyl cellosolve; ethyl acetate, Δ'pe-butyl, and ethylene glycol. Examples include acetic acid compounds such as diacetate and ethyl cellosolve acetate; ketones such as acetic acid, methyl ethyl ketone, methyl isobutyl ketone, and diisopropyl ketone; and carboxylic acids such as formic acid, acetic acid, and propionic acid. These can be used in combination.

Examples of additives include flow control agents, ultraviolet stabilizers, ultraviolet stabilizers, and antioxidants.

Examples of the flow control agent include a fluorine-based surfactant manufactured by JFl, a block copolymer of alkylene oxide and dimethylsiloxane, etc., and the amount of the flow control agent in the undercoat composition is 0 to 5% by weight, more preferably 0 to 3% by weight. %.

As the ultraviolet absorber, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
．． Benzophenones 9 such as 2'-dihydroxy-4-methoxybenzophenone: 2-(2'-hydroquine-5'-methylphenyl)benzotriazole, 2-(
2'-Hydroxy-5'-(-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-octylphenyl)benzotriazole, 2-(2'-hydroxy-8',5'-di1- Benzotriazoles such as ethyl-2-cyano-3, ethyl-2-cyano-3,
Examples include cyanoacrylates such as 8'-diphenylacryl/-l-, in an amount of 1 to 200 parts per 100 parts by weight of the acrylic copolymer or vinyl copolymer in the undercoat composition.
Use the heavy V part.

An undercoat film is obtained by applying an undercoat composition comprising the above-mentioned components to the surface of a polycarbonate resin molded article and baking the coated film at a temperature 3 times lower than the heat distortion temperature of the resin molded article.

Baking is carried out at 70 to 130°C for 20 minutes to 5 hours. In this case, when the top coat is applied after the 11 undercoats have been completely cured by baking, the undercoat film will be completely cured. It is more preferable to select the baking conditions so that the curing is completed.The method of applying the undercoat of the present invention is the commonly used dipping method, spraying method, roller coating method, flow coating method, etc. It may be selected appropriately depending on conditions such as the shape of the resin base material.

The preferred thickness of the resulting undercoat film is 0.05 to 10j.
More preferably (1,5 to 5ε chrons.0)
If it is smaller than .05 microns, the adhesion will decrease, and if it is larger than 10 microns, the coating may become cloudy or cracks may occur. In order to obtain the desired thickness, the solid content of the coating composition is adjusted by using the above-mentioned solvent depending on the coating method and conditions, but the solid content of the coating composition is approximately 1 to 2.
0 contribution J'it%.

Polycarbonate resins to which the present invention can be applied include:
For example, in addition to bis7, : / - type polycarbonates such as 4.4'-.f sopropylidenodiphenol polycarbonate, U.S. Pat. (published in 1962), diethylene glycol bisallyl carbonate, and the like.

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, immersion treatment at a temperature of 85 = 95 degrees Celsius for 5 to 30 minutes in a dye bath in which general disperse dyes, dispersants, p IJi"J preparations, etc. are added to water. In this way, dyed articles 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 to these Examples.

In addition, part 96 in the example is the stop part and heavy swelling 19, respectively.
show the shadow

The performance of the coating film was evaluated using the following method. Abrasion resistance: The resistance to scratches was examined by rubbing with #0000 steel wool, and the following supplements were added.

A: Strong (no scratches even when rubbed.

B: Slight damage occurs when rubbed strongly.

C: Even weak friction causes scratches.

(= 1 adhesion property: In the so-called cross-cut tape test, 11 parallel lines are placed vertically and horizontally at 11 intervals on the surface of the coating film, and 100 squares are cross-cut, and cellophane adhesive tape is attached on top of the cross-cuts. After that, the tape was peeled off, and the number of squares that did not peel off among 100 squares was expressed.

Body pasting property: The state of the coating film after being immersed in boiling water for 1 hour was examined.

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 condition of the coating film was examined after immersion in the chemicals listed in F. for 100 hours at room temperature.

8% sulfuric acid, 196 sodium hydroxide, 95% ethanol, acetone, ethyl acetate carbon tetrachloride, toluene, n-hebutane, 10% saline.

Example 1 A top coat and an undercoat were prepared as follows.

(1) Preparation of top coating; 80 parts of r-glycidoxypropyltrimethoxysilane, 144 parts of methyltrimethoxysilane, 71 parts of colloidal silica (manufactured by Yasan Kagaku Kogyo Co., Ltd., Snowtex-C1 solid content 20%) and 0
, mixed 170 parts of 1N hydrochloric acid aqueous solution at 17.80-85°C.
Hydrolysis was carried out by running the solution at high speed for 2 hours.

r-glycidoxypropyltrimethoxysilane hydrolyzate 12.2% calculated as
It contained 15.3% methyltrimethoxysilane hydrolyzate calculated as 5i02 and 3.1% colloidal silica calculated as 5i02.

To 41 parts of the 8-element cohydrolyzate solution thus obtained, 78 parts of ethyl cellosolve, 1 l of ammonium perchlorate, 8
A small amount of flow control agent was added to make a top coat.

(2) Adjustment of undercoat paint; Ethyl Cellosolve 400
1 part of benzoyl peroxide, 190 parts of ethyl methacrylate, and 10 parts of γ-methacryloxypropyltrimethoxysilane was heated at 75°C under a gaseous atmosphere.
．． A solution of 0 part dissolved in 200 parts of ethyl-cellosolve (r
(-C) was added over a period of 2 hours, and the temperature was maintained for an additional 6 hours. Thereafter, 200 parts of ethyl cellosolve, 2 parts of aluminum acetylacetonate, and 20 parts of 2,4-dihydroxybenzophenone were added to prepare an undercoat.

This undercoat paint 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 180° C. for 80 minutes.

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 180°C for 60 minutes.

The coated polycarbonate molded article obtained in this manner was transparent and had an abrasion resistance of A, (-J adhesion of 100
/100, hot water resistance and heat resistance are good, and +ll
After the hydrothermal test, the abrasion and adhesion properties were A and 1, respectively.
It was good at 00/100.

Furthermore, the appearance, hardness, and adhesion after 1,500 hours were extremely good. In addition, chemical resistance was good for all chemicals, and no abnormalities were observed in the appearance after the test.

Comparative Example 1 Example 1 was carried out in the same manner as in Example 1, except that the undercoat paint was prepared without using aluminum acetylacetonate. The coated polycarbonate molded article thus obtained is transparent, has an abrasion resistance of A, and an adhesion of 100.
/1OO1 Hot water resistance and heat resistance were good, but Zareshine Weather-Ometer too.

Adhesion over time was Q/100.

Comparative Example 2 400 parts of ethyl cellosolve, 20 parts of ethyl methacrylate
1.0 parts of benzoyl peroxide was added to 200 parts of ethyl cellosolve while keeping the mixture at 75°C under nitrogen atmosphere.
The solution was added over a period of 2 hours and kept at the same temperature for an additional 6 hours. Then 1400 parts of ethyl cellosolve,
2. Add 20 parts of 4-dihydroxybenzophenone and
It was used as paint.

This undercoat paint was applied to a polycarbonate base material that had been washed in advance, and was heated and dried in a hot air drying oven at .taO.degree. C. for 80 minutes.

Next, the top coat used in Example 1 was applied to the polycarbonate coated with the coating layer obtained in this way.
It was cured by heating and drying at 80° C. for 60 minutes.

The coated polycarbonate molded article thus obtained was transparent and had an abrasion resistance of A and an adhesion of 100/100, but the adhesion after the hot water resistance test was 0/l 00.

Example 2 -1 Two-coat paint and one-double paint were adjusted as follows.

(1) Preparation of top coat; 60 parts of r-glycidoxypropyltrimethoxysilane, 178 parts of methyltrimethoxysilane, colloidal silica (Nippon Kagaku Kogyo Co., Ltd.)
71 parts of Snowtex-C1 (solid content: 2096) and 190 parts of a 0.1 N acetic acid aqueous solution were mixed, and 80-85
Hydrolysis was carried out by refluxing at °C for 2 hours.

r-glycidoxypropyltrimethoxysilane hydrolyzate 8.6% calculated as 11 as -o1.5, CH3
It contained 17.8% of methyltrimethoxysilane hydrolyzate calculated as 5i01.5 and 2.9% of colloidal silica calculated as 5i02.

The ternary cohydrolyzate (iN(fc
42 parts of ethyl cellosolve, 13 parts of Jmm element ammonium, and a small amount of flow control agent were added to 450 parts to prepare a top coat.

(2) Adjustment of undercoat paint; Butyl Cellosolve 300
160 parts of methyl methacrylate, 40 parts of r-methacryloxybrobyltrimethoxysilano, and 2.0 parts of penozoyl peroxide while maintaining the temperature of 100° C. in a nitrogen atmosphere.
0 parts of 9 compound was added over 3 hours + 7 u, and the temperature was maintained at the same temperature for 1 fU at 3 hours. Then butyl cellosolve 115
5 parts of ethylene glycol diacetate, 0.4 parts of para-toluenesulfonic acid, 80 parts of 2-hydroxy-4-methoxybenzophenone, and a small amount of a flow control agent were added to prepare an undercoat paint.

This undercoat paint was applied to a polycarbonate base material that had been washed in advance, and dried by heating at 180'C for 80 minutes in a hot air drying oven.

Next, the polycarbonate coated with the undercoat layer obtained in this way was coated with the topcoat paint prepared in the above (1), and dried by heating at 180'C for 60 minutes in a hot air drying oven. Let it harden.

The coated polycarbonate molded article obtained in this way is transparent, has an abrasion resistance of A, and an adhesion of 1 (to/100).The abrasion resistance and adhesion after the hot water resistance test are also A and 10, respectively.
It was good at 0/100. More sunshine weather
The appearance, hardness, and adhesion after 1,500 hours of meter testing were extremely good.

Example 3 Top coat and undercoat were adjusted as follows.

(1) Preparation of top coat 77 parts of isopropyl alcohol, 60 parts of γ-glycidoxypropyltrimethoxysilane, 115 parts of methyltrimethoxysilane, colloidal silica (Nichikagaku Kogyo Co., Ltd.)
Snowtex-C1 solid content 21) 96) 2
Add 18 parts and 5 parts of lN hydrochloric acid, and heat at 80 to 85°C for 2 hours.
Reflux for a period of time to dissolve the water.

The resulting solution is CH2-CO-CH2-0-C8116-5i 01.
γ-glycidoxypropyltrimethoxysilane hydrolyzate calculated as 5\1 9.1 C6, C1l B Si
It contained 12.19 g of methylcyto-11 methoxysilane hydrolyzate calculated as OH,5 and 9.196 g of colloidal silica calculated as 5i02.

To 417 parts of the 8-component cohydrolyzate solution thus obtained, 66 parts of ethyl cellosolve and 1.0 parts of ammonium perchlorate.
Part a: A small amount of flow control agent was added to make a top coat.

(2) Preparation of undercoat paint: A mixture of 884 parts of methyl methacrylate butyl ketone and 216 parts of methyl ethyl ketone was mixed with 1 part of methyl methacrylate while keeping it at 90°C in a nitrogen atmosphere.
A mixture of 80 parts of r-methacryloxypropylmethyldimethoxysilane, 20 parts of azobisisobutyronitrile was added over 2 hours, and the temperature was maintained for an additional 5 hours. Thereafter, 624 parts of methyl isobutyl ketone, 576 parts of isopropyl alcohol, and 1 liter of di-n-butylamine were added.
10 parts of θ% aqueous solution was added to prepare an undercoat.

This undercoat paint was applied to a polycarbonate base material that had been washed in advance, and was dried by heating at 120° C. for 30 minutes in a hot air drying oven.

Next, the top coat prepared in (1) above was applied to the polycarbonate sewn 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 thus obtained coated polycarbonate molded article is transparent and has an abrasion resistance of A and an adhesion of 100/100, and an abrasion resistance and an adhesion of A and 100 after a hot water resistance test, respectively.
/100, which was good. Further, the appearance, abrasion resistance, and adhesion after 1000 hours of Zanshine Weather-Ometer test were good, but the adhesion after 1500 hours of ffJI decreased to 80/100.

Example 4 The preparation of the undercoat paint in Example 8 was carried out in the same manner as in Example 82, except that vinyltrimethoxysilane was used instead of γ-methacryloxypropylmethyldimethoxysilane.

The colored polycarbonate molded article obtained was transparent and had abrasion resistance and adhesion of A and 100/1, respectively, after a hot water resistance test.
It was 100. Furthermore, after 1,500 hours of sunshine weather off-road testing, the appearance and abrasion resistance were excellent, and the neck thinness was 80/1 (10).

Example 5 Top coat and undercoat were adjusted as follows.

(1) Preparation of top coat: 80 parts of r-glycidoxypropyltrimethoxysilane, 86 parts of methyltrimethoxysilane, colloidal silica (manufactured by Nichikagaku Kogyo Co., Ltd.)
213 parts of Snowtex-C1 (solid content 20%), 90 parts of isopropyl alcohol, (1,I JIf), and 35 parts of a constant aqueous hydrochloric acid solution were added, and the mixture was refluxed at 80 to 85° C. for 2 hours to perform hydrolysis. Obtained solution IJ1 Limethotoshisilane hydrolyzate 11.3%, C118S
It contained 8.596% of methyltrimethoxysilanohydrolyzate, calculated as i(month, 5) and 8.5% of colloidal silica, calculated as 3i027 and d1°.

The ternary cohydrolyzate solution r(1417
66 parts of ethyl cellosolve, 1 part of ammonium perchlorate
．． A small amount of flow control agent was added to form a top coat.

(2) Adjustment of undercoat paint; 400 parts of ethyl cellosolve,
180 parts of methyl methacrylate, styrene 4061<,
A mixture of 20 parts of r-methacryloxypropyltrimethoxysilane was added over 2 hours to a solution of 1.0 part of benzoyl peroxynoid dissolved in 200 parts of ethyl cellosolve while maintaining the mixture at 75°C in an atmosphere of all 9 elements, followed by a further 8 hours. It was kept at the same temperature. After that, 1400 parts of ethyl cellosolve, 4 parts of tetraisopropoxy titanium, 2-(2'-hydroxy-
80 parts of 5'-octylphenyl)benzotriazole was added to prepare an undercoat.

This undercoat paint was applied to a polycarbonate paper stock 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 two-coat paint prepared in step (1) above was applied to the polycarbonate coated with the undercoat layer thus obtained, 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 and has abrasion resistance and adhesion of A after a hot water resistance test.
, which was good at 100/100. Furthermore, after 1500 hours of non-shine weather meter testing, the appearance, hardness, and adhesion were extremely good.

Claims (1)

[Scope of Claims] (1) (a) A copolymer of an acrylic or/and vinyl monomer having an alkoxysilyl group and another monomer copolymerizable with these monomers, and (IJ ) Coated polycarbonate 1-based resin with improved abrasion resistance, coated and cured with a composition containing a curing catalyst to form an undercoat layer, and coated and cured with a composition containing a colloidal silica-containing organopolysiloxane to form an overcoat layer. Molded articles. (2) The composition containing the colloidal silica-containing organopolysiloxane contains at least one selected from the group consisting of the following (5) and (Is), 0 and 0, (wherein R1 is an organic group having an epoxy group, Shao is water, a hydrocarbon group having 1 to 6 carbon atoms, k3 is a hydrocarbon group having 1 to 5 carbon atoms, Alfuxia 11/kyl group or acyl group having 1 to 4 carbon atoms, 3 is 1-8.1) is 0 to 2 and a 4-
b≦3. 1 or 2 silicon compounds having an epoxy S group represented by ) or 2) Hydrolyzate (B) General formula (2) R'-5i-(OR')4 -C
(2) (In the formula, R4 is a hydrocarbon group having 1 to 6 carbon atoms, a methacryloxy group, an amino group, a mercapto group, an organic group having chlorine, and R5 is a hydrocarbon group having 1 to 5 carbon atoms. A hydrolyzate of an organosilicon compound (C) colloidal silica and (I )) The coated polycarbonate resin composition article according to claim 1, which is a composition containing a curing catalyst. (3) The above-mentioned colloidal silica-containing organacuble I] The composition containing siloxane is
Parts by weight (calculated based on solid content, 1) 56 to 550 parts by weight of hydrolyzate (calculated based on solid content, ii: 1)
, R-Si -0-7- (calculated) 4 to 384 parts by weight of the above 0 colloidal silicon (however, the solid content is calculated as 1.5i02)
The coated polycarbonate resin molded article according to claim 2, wherein the total of Φ) and 0 does not exceed 567 parts by weight, and the composition contains the 0 curing catalyst. (4) The above (1υ hydrolyzate content is 105 to 430
The content of the 0 colloidal silica is 16 to 200 parts by weight, and the total of (B) and 0 is 473 parts by weight.
A curing catalyst selected from the coated polycarbonate resin salt, nitrate, carboxylate, highly fluorinated aliphatic sulfonate, and highly fluorinated aliphatic sulfonyl compound according to claim 3, not exceeding parts by weight. Claim 2
The coated polycarbonate resin molded article described in 2. (6) The coated polycarbonate resin molded article according to claim 1g1, wherein the curing catalyst (b) is a curing catalyst selected from organic acids, organic acid metal salts, amines, metal acetylacetonates, and organic titanates. .