JP2002060528A - Molded polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition molded article coated with hard coat(s) of good interfacial adhesion enough to have long durability even when bending. SOLUTION: This polycarbonate resin composition molded article is such that at least one side of the molded article of a polycarbonate resin composition (A component) <=50 ppm in total chlorine contents is coated to hard coating treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a molded article of a polycarbonate resin composition. More specifically, it is a resin molded article obtained by subjecting a polycarbonate resin composition having a specific chlorine content to a hard coat treatment, and particularly has a good adhesion to a hard coat layer even in bending. It is about the body.

[0002]

2. Description of the Related Art In recent years, in order to increase the value of a product in order to enhance the functionality and design of the product, to save resources and reduce environmental impact through recycling and painting-less products, etc., products having different functions assigned to each layer of the product. Design is desired. In particular, there is the highest demand for providing a specific function to the product surface to achieve high added value.

[0003] In response to such demands, conventionally, a hard coat is applied to the surface of a thermoplastic resin sheet, the sheet is inserted into a mold cavity surface or a core surface, and the thermoplastic resin is injection-molded into the mold cavity. A method has been proposed in which the sheet and the molded article are integrated by filling by a method, and value is added to the surface portion. In such a case, in order to strengthen the adhesiveness between the sheet portion and the thermoplastic resin, the thermoplastic resin forming the sheet is made of the same type as the thermoplastic resin injected and filled into the mold forming the molded article body. (Japanese Patent Application Laid-Open No. Sho 60
-92586, JP-A-60-195515, etc.).

[0004] By such a production method, for example, a laminate of a polycarbonate resin composition having a hard coat is produced, and a polycarbonate resin composition laminate having excellent transparency and strength and excellent surface hardness can be obtained.

[0005] However, when the laminate has a curved surface portion, it is necessary to bend the sheet on a plane to cope with it.
When a hard coat is applied, it is difficult to cope with such bending, and in areas where high bending stress is applied, peeling may occur at the interface between the hard coat agent and the polycarbonate substrate due to long-term properties such as wet heat resistance. Was.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molded article of a polycarbonate resin composition which has a higher resistance to bending and the like and has a hard coat having good interface adhesion. It is in.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, those obtained by subjecting a polycarbonate resin composition having a total chlorine content in terms of chlorine atoms of not more than a specific amount to a hard coat treatment, particularly The present inventors have found that they have a better resistance to bending work for a specific hard coat treatment, and have reached the present invention.

[0008]

According to the present invention, at least one surface of a molded article made of a polycarbonate resin composition (component A) having a total chlorine content of 50 ppm or less in terms of chlorine atoms is subjected to a hard coat treatment. The present invention relates to a molded article of a polycarbonate resin composition.

The polycarbonate polymer of the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or by polymerizing a carbonate prepolymer by a solid phase transesterification method. Or a polymer obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

Representative examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis {(4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) phenyl}
Propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis} (4-
(Hydroxy-3-phenyl) phenyl} propane, 2,
2-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxyphenyl) -3-methylbutane,
2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α′-bis (4- Hydroxyphenyl) -o-
Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α
α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester and the like. These may be used alone or in combination of two or more. Can be mixed and used.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

In producing the polycarbonate polymer by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol are required. An inhibitor or the like may be used. The polycarbonate polymer may be a branched polycarbonate polymer obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate polymers may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When a polyfunctional compound producing such a branched polycarbonate polymer is contained, such a ratio is preferably 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.005 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.
01 to 0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may be generated as a side reaction, and the amount of the branched structure is also 3, 0.001 to 1 mol%, preferably 0.1 to 1 mol%, based on the total amount of the aromatic polycarbonate.
005 to 0.5 mol%, particularly preferably 0.01 to 0.
Those having 3 mol% are preferred. The ratio can be calculated by ¹ H-NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amine compounds such as pyridine.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as tertiary amine such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, a quaternary ammonium compound, and a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (8) can be shown.

[0018]

Embedded image

(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
Wherein r is an integer of 1 to 5, preferably 1 to 3. ) Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Of these, phenols having a long-chain alkyl group represented by the following general formulas (9) and (10) as a substituent are preferably used.

[0021]

Embedded image

[0022]

Embedded image

(Wherein X is -RO-, -R-CO-O
-Or -RO-CO-, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

As the substituted phenols of the general formula (9), those having n of 10 to 30, especially 10 to 26, are preferred. Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (10), compounds wherein X is -R-CO-O- and R is a single bond are suitable, and n is 10-30, especially 10-2.
6 are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and tricontyl hydroxybenzoate. No. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such a polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × with ^respect to 1 mol of the starting dihydric phenol.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
Compounds such as bromophenyl phenyl carbonate, nitro phenyl phenyl carbonate, phenyl phenyl carbonate, methoxy carbonyl phenyl phenyl carbonate and ethoxy carbonyl phenyl phenyl carbonate can be added. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred,
Particularly, 2-methoxycarbonylphenylphenyl carbonate is preferably used.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonate, ethylbenzenebenzenesulfonate, butylbenzenesulfonate, octylbenzenesulfonate, phenylbenzenesulfonate, and p-toluenesulfone. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, dodecylbenzenesulfonate Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of the catalyst is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst, and 0.01 to 500 ppm relative to the polycarbonate polymer after polymerization.
It is more preferably used at a rate of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

Although the molecular weight of the polycarbonate polymer is not specified, if the molecular weight is less than 10,000, the strength becomes insufficient, and if it exceeds 40,000, the moldability deteriorates and it becomes difficult to reduce optical distortion. It is preferably from 10,000 to 40,000, more preferably from 13,000 to 35,000, and particularly preferably from 17,000 to 30,000 in terms of viscosity average molecular weight. Further, two or more polycarbonate polymers may be mixed. The viscosity average molecular weight referred to in the present invention is determined by inserting the specific viscosity (η _SP ) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate polymer in 100 ml of methylene chloride at 20 ° C. into the following equation. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The polycarbonate resin composition of the present invention comprises
Any of the above interfacial polycondensation method and melt transesterification method can be used, and for controlling the chlorine content, for example, acetone treatment of a polycarbonate resin composition,
Further, when pelletizing the polycarbonate resin composition powder, a method of forcibly injecting water in the middle of a vented extruder to perform a dechlorination compound, a method of non-solvent precipitation of a polycarbonate resin composition solution, and a further drying treatment It can be adjusted by various conventionally known methods such as strengthening.

Further, in a vessel containing a mixture of the polycarbonate resin composition powder and the warm water, the mixture is stirred,
A method for producing a polycarbonate resin composition powder from an organic solvent solution of a polycarbonate resin composition by continuously supplying an organic solvent solution of the polycarbonate resin composition and evaporating the solvent, wherein The temperature is maintained within the range of T1 (° C.) or T2 (° C.) shown in the following formula, the stirring speed is 60 to 100 rpm, and the stirring capacity is 5 to 10 kw / hr · m 3. The method can be preferably used because not only the reduction of residual chlorine compounds but also the production of a polycarbonate resin composition with less powder, good filterability, and excellent drying properties can be obtained. 0.0018 × M1 + 37 ≦ T1 (° C.) ≦ 0.0018
× M1 + 42 (M1: viscosity average molecular weight 10,000 to 20,000
0) 0.0007 × M2 + 59 ≦ T2 (° C.) ≦ 0.0007
× M2 + 64 (M2: viscosity average molecular weight 20,000 or more)

The polycarbonate resin composition used in the present invention, which is produced by the above method and whose total chlorine content converted into chlorine atoms is adjusted, has a total chlorine content of 50 ppm or less, preferably 30 ppm or less, more preferably Is 10p
pm or less. Total chlorine content is 50ppm
If it exceeds 300, the adhesion to the hard coat for bending cannot be sufficiently improved.

The chlorine content of the present invention is a value measured by a fluorescent X-ray analysis method using a PIX-2000 fully automatic fluorescent X-ray analyzer manufactured by RIKEN ELECTRIC INDUSTRY CO., LTD.

Although the cause of the chlorine content relating to the resistance to bending is unknown, it is believed that the chlorine compound remaining in the polycarbonate after molding of a sheet or the like remains to some extent. It is considered that microcracks tend to occur in the vicinity of the presence of the compound.

Further, in the present invention, the effect of the present invention can be further exhibited by containing a specific compound represented by the following formula (1) as a stabilizer. It is considered that this is because the generation of microcracks due to the presence of the chlorine compound can be suppressed, and the compound itself is hardly affected by the components of the hard coat agent.

[0039]

Embedded image

Wherein Ar ¹ , Ar ² and Ar ³ are dialkyl-substituted aromatic groups having 8 to 20 carbon atoms,
r ¹ , Ar ² and Ar ³ are all the same, two are the same,
Alternatively, any of the three different cases can be selected. )

Here, specific examples of such a compound include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, and tris (di-n-butylphenyl). Phosphite, tris (2,4-di-te
rt-butylphenyl) phosphite, tris (2,6
-Di-tert-butylphenyl) phosphite; tris (dialkyl-substituted phenyl) phosphite is preferred; tris (di-tert-butylphenyl) phosphite is more preferred; tris (2,4-di-tert) -Butylphenyl) phosphite is particularly preferred.

The ratio of the compound is 0.00% in 100% by weight of the polycarbonate resin composition of the component A.
It is preferably from 0.01 to 0.5% by weight, more preferably from 0.0 to 0.5% by weight.
005-0.1% by weight, more preferably 0.001-0.1%
0.07% by weight.

In the present invention, various hard coat agents can be used for the hard coat treatment. Examples of the hard coat agent used in the present invention include a silicon resin hard coat agent and an organic resin hard coat agent. . The silicone resin-based hard coat agent is a resin having a siloxane bond, and for example, hydrolyzes a mixture of trialkoxysilane and tetraalkoxysilane or a partial hydrolyzate of their alkylated product, methyltrialkoxysilane and phenyltrialkoxysilane. Decomposed products and partially hydrolyzed condensates of colloidal silica-filled organotrialkoxysilanes are exemplified. These include alcohols and the like generated during the condensation reaction, and may be further dissolved or dispersed in any organic solvent, water, or a mixture thereof, if necessary. Examples include fatty acid alcohols, polyhydric alcohols and their ethers and esters. In addition, various surfactants, for example, a siloxane-based or alkyl fluoride-based surfactant may be added to the hard coat layer in order to obtain a smooth surface state. Examples of the organic resin-based hard coating agent include a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, and a polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate. Among these hard coat agents, silicone resin hard coat agents which are excellent in long-term weather resistance and have relatively high surface hardness are preferable. In particular, after forming a primer layer composed of various resins, a silicon resin hard coat agent is formed thereon. It is preferable to form an adjusted cured layer from a coating agent.

Examples of the resin forming the primer layer include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, polyester acrylates, urethane acrylates, epoxy acrylates, which are composed of various blocked isocyanate components and polyol components. Examples include various polyfunctional acrylic resins such as phosphazene acrylate, melamine acrylate, and amino acrylate. These can be used alone or in combination of two or more. Among them, particularly preferred are those containing 50% by weight, more preferably 60% by weight or more of an acrylic resin and a polyfunctional acrylic resin, and those made of an acrylic resin are particularly preferred.

Further, the resin forming the primer layer of the silicone resin-based hard coat agent of the present invention includes a light stabilizer and an ultraviolet absorber described later, a catalyst for the silicone resin hard coat agent, a heat / photopolymerization initiator, Inhibitors, silicone defoamers,
It may contain a leveling agent, a thickener, an anti-settling agent, an anti-dripping agent, a flame retardant, various additives of organic / inorganic pigment / dye, and an auxiliary additive.

In the present invention, the acrylic resin forming the primer layer of the silicone resin-based hard coat agent may be prepared by applying (a) a primer composition mainly composed of a monomer component to the surface of a molded product and then heating or applying ultraviolet light. Curing by irradiation with an active energy ray such as an electron beam or radiation (hereinafter sometimes referred to as an acrylic resin (a)); and (b) a solution or melt of the polymer after polymerizing a polymer component in advance. Any of applying a liquid as a primer composition and curing by evaporating a solvent or the like (hereinafter, may be referred to as an acrylic resin (b)) can be used. In particular, the latter acrylic resin (b) is more preferable because unreacted residual monomer which is likely to cause deterioration is reduced as much as possible.

The acrylic resin has the following formula (2)
Is an acrylic resin containing at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol% of a repeating unit represented by the formula: When the content of the repeating unit represented by the following formula (2) in the acrylic resin is 50 mol% or more, the adhesion to the polycarbonate resin composition and the upper silicon hard coat layer becomes better, and the effect in the present invention is also large.

[0048]

Embedded image

(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms.) The acrylic resin can be copolymerized with 50 mol% or more of the alkyl methacrylate monomer and 50 mol% or less of the alkyl methacrylate monomer. It is a polymer obtained by polymerizing other monomers. Specific examples of the alkyl methacrylate monomer include methyl methacrylate,
Ethyl methacrylate, propyl methacrylate and butyl methacrylate are mentioned, and these can be used alone or in combination of two or more. Of these, methyl methacrylate and ethyl methacrylate are preferred.

As the other copolymerizable monomer, acrylic acid, methacrylic acid or a derivative thereof is preferably used, particularly in view of durability such as adhesion and weather resistance. Specifically, acrylic acid, methacrylic acid, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl (meth) acrylate,
-Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2
-Ethoxyethyl) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, trimethoxysilyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, glycidyl (meth) Acrylate, 3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropyltriethoxysilane, 3-
Examples thereof include (meth) acrylates such as methacryloxypropylmethyldimethoxysilane, N-vinylpyrrolidone, N-vinylcaprolactam, styrene, and acrylonitrile, and these can be used alone or as a mixture of two or more. Further, a mixture of two or more acrylic resins may be used.

Further, as such another copolymerizable monomer, a compound containing two or more polymerizable double bonds in the molecule can also be used. Specifically, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, Chain aliphatic polyvalent such as tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Esters of alcohol and (meth) acrylic acid, divinyl compounds such as divinylbenzene and diethylene glycol bisallyl carbonate, epoxy (meth) acrylate,
Urethane (meth) acrylate, polyester (meth)
Oligomer obtained by condensing acrylate, polyether (meth) acrylate, silicon (meth) acrylate, and the like, such as 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and pentaerythritol Esters of a chain aliphatic polyhydric alcohol such as tetraacrylate and (meth) acrylic acid are preferred. The amount of the compound containing two or more polymerizable double bonds in the molecule is 1 to 98% by weight in 100% by weight of the resin forming the primer layer in the case of the acrylic resin (a) in which the monomer is applied and cured. In the case of the acrylic resin (b) of a type to which a polymer is applied, the content is preferably 0.01 to 1% by weight.

In the present invention, the acrylic resin used as a primer of the silicone resin-based hard coat agent is 0.01 to 0.01%.
It is desirable to contain a monomer having a reactive group with mol% to 50 mol% of the alkoxysilane compound. Examples of the vinyl monomer having such a reactive group include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, Methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and the like can be mentioned.

In one preferred embodiment of the acrylic resin used as a primer of the silicone resin-based hard coating agent in the present invention, the repeating unit represented by the above formula (2) is 50 mol% or more and is represented by the following formula (3). Wherein the molar ratio of the repeating unit represented by the formula (2) and the following formula (3) is 99.99: 0.01 to 5
Acrylic resin of 0:50 can be mentioned. A more preferable range of the molar ratio is 99: 1 to 60: 4.
0, and a more preferable range is 97: 3 to 70:30.

[0054]

Embedded image

(Where X is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 to 5 carbon atoms,
R ³ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 or 1. )

The acrylic resin containing the repeating units of the formulas (2) and (3) accounts for at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight of the resin forming the primer layer; Typically, it is desirable that the resin forming the primer layer is substantially this acrylic resin.

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

In one preferred embodiment of the acrylic resin used as a primer of the silicone resin-based hard coating agent in the present invention, the repeating unit represented by the formula (2) is 50 mol% or more and the following formula (4) Acrylic resin containing a repeating unit represented by the formula (2) and having a molar ratio of the repeating unit represented by the formula (2) and the following formula (4) of from 99: 1 to 50:50 (hereinafter referred to as “hydroxy group-containing acrylic resin”)
99 to 60% by weight, and 1 to 40% by weight of a hydrolytic condensate of the compound represented by the following formula (5) (provided that R ⁵ _a R ⁶ _b SiO _{4- (a + b) / 2} Or a reaction product with the above).

[0059]

Embedded image

(Where Y is a hydrogen atom or a methyl group, and R ⁴ is an alkylene group having 2 to 5 carbon atoms)

[0061]

Embedded image

(Wherein R ⁵ and R ⁶ are the same or different from each other, and are an alkyl group, an alkenyl group, an aryl group having 10 or less carbon atoms, a halogen atom, an epoxy group, an amino group, a mercapto group, a methacryloxy group or A hydrocarbon group having a cyano group, R ⁷ is an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxyalkyl group, or an acyl group, and a and b are 0, 1 or 2, and a +
b is 0, 1 or 2. )

In the hydroxy group-containing acrylic resin, preferably, the molar ratio of the repeating unit represented by the formula (2) to the repeating unit represented by the formula (4) is 9
7: 3 to 55:45, more preferably 95: 5
60:40.

The units of the formulas (2) and (4) account for at least 50% by weight, preferably at least 70% by weight, more preferably 90% by weight in the resin forming the primer layer.
It is. Typically, there is a case where the resin forming the primer layer is substantially this acrylic resin copolymer.

Specific examples of the monomer corresponding to the above formula (4) include 2-hydroxyethyl acrylate,
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and the like. Among them, 2-hydroxyethyl methacrylate is preferably used.

On the other hand, specific examples of the alkoxysilane represented by the formula (5) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane and tetra-n-butoxysilane. Silanes such as isobutoxysilane and tetraacetosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrisilane Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ- Loropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxy Silane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β
-Glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane,
γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-
Glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ- Glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-
Glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-
Epoxycyclohexyl) methyltriethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β-
(3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3
4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-
Trialkoxy, triacyloxy or triphenoxysilanes such as (epoxycyclohexyl) butyltriethoxysilane or hydrolysates thereof, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloro Propylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethyldimethoxysilane, γ-mercapto Propyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, vinylmethyldimethoxy Silane, vinylmethyldiethoxysilane, glycidoxymethyldimethoxysilane,
Glycidoxymethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α -Glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypro Pilmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ- Examples thereof include alkoxysilanes or diacyloxysilanes such as glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, and γ-glycidoxypropylphenyldiethoxysilane, and hydrolysates thereof. These organic siloxanes can be used alone or in combination of two or more.

More preferably, in the above formula (5), R ⁵ and R ⁶ are an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group, a glycidoxy group, a 3,4
1 selected from the group consisting of epoxycyclohexyl groups
R ⁷ is an alkyl group having 1 to 4 carbon atoms substituted with the above group, and R ⁷ is an alkyl group having 1 to 4 carbon atoms. Specifically, for example, tetramethoxysilane, tetraethoxysilane, tetran -Propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetra isobutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, isobutyl trimethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane Γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , N-β- (A Aminoethyl)-.gamma.-aminopropyltrimethoxysilane, N-β- (aminoethyl) -
γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and the like. However, alkyltrialkoxysilanes are preferred, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferred. These can be used alone or in combination.

The hydrolysis condensate of the alkoxysilane is usually 0.2 to 4 equivalents, preferably 0.5 to 2 equivalents, more preferably 1 to 1 equivalent to 1 equivalent of the alkoxy group of the alkoxysilane under acidic conditions. 20 using 5 equivalents of water
It is obtained by carrying out a hydrolytic condensation reaction at ４０40 ° C. for 1 hour to several days. Acids are used in the hydrolysis-condensation reaction. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid. And organic acids such as succinic acid, maleic acid, lactic acid and p-toluenesulfonic acid, and volatile acids such as acetic acid and hydrochloric acid are preferred. When an inorganic acid is used, the acid is usually 0.0001 to 2 equivalents /
l, preferably at a concentration of 0.001 to 0.1 equivalent / l.
0.1 to 50 parts by weight, preferably 1 to 3 parts by weight
Used in the range of 0 parts by weight.

The mixing ratio of the hydrolyzed condensate of the alkoxysilane to the hydroxy group-containing acrylic resin is 1 to 40% by weight, preferably 5 to 30% by weight (provided that R ⁵ _a R ⁶ _b SiO _{4- (} weight converted to _{(a + b) / 2} ), with the latter being 99 to 60% by weight, preferably 95 to 70% by weight. By adjusting the resin to such a composition, the layer made of the acrylic resin has good adhesion to the polycarbonate resin composition and the upper silicon hard coat layer. In addition, the above-mentioned hydrolyzed condensate of alkoxysilane and the above-mentioned hydroxy-containing acrylic resin can be used as a mixture mixed in the above-mentioned ratio or a reaction product obtained by partially condensing.

Further, one preferred embodiment of an acrylic resin used as a primer of a silicone resin-based hard coat agent is
One example is a mixture or reaction product of the above-mentioned hydrolysis condensate of alkoxysilane and a hydroxy group-containing acrylic resin, further mixed with a melamine resin. The melamine resin to be used includes, for example, fully alkylated methylated melamine represented by hexamethoxymethylmelamine, a resin in which a part of the methoxymethyl group of hexamethoxymethylmelamine has become a methylol group, an imino group, or butoxy. Methyl groups, fully alkylated butylated melamines represented by hexabutoxymethylmelamine, and the like can be mentioned, and fully alkylated methylated melamines represented by hexamethoxymethylmelamine are preferably used. These melamine resins can be used alone or in combination.

The preferred mixing ratio of the melamine resin is 1 to 100 parts by weight of the mixture or the reaction product of the hydrolysis-condensation product of the alkoxysilane and the hydroxy group-containing acrylic resin.
It is preferably 20 to 20 parts by weight, more preferably 3 to 15 parts by weight. By mixing in such a range, the adhesion by the primer layer becomes better.

In the acrylic resin used as a primer of the silicone resin-based hard coat agent of the present invention,
In the case of the acrylic resin (b), the molecular weight of the acrylic resin is 20, 20 as a weight average molecular weight measured on the basis of a calibration curve calculated by GPC (gel permeation chromatography) using monodispersed standard polystyrene. 000 or more, more preferably 50,000 or more, and those having a weight average molecular weight of 10,000,000 or less are preferably used. The acrylic resin having such a molecular weight range is preferable because performance such as adhesion and strength as a primer layer is sufficiently exhibited.

In the method of forming a primer layer in the present invention, in the case of the acrylic resin (a), a monomer component and other various additives are reacted with the polycarbonate resin composition or volatilized without dissolving the polycarbonate resin composition. After preparing the primer composition by dissolving it in a solvent or homogenizing without using a solvent, applying the primer composition, then polymerizing the monomer component by ultraviolet light or heat, and removing the solvent. To form a primer layer.

On the other hand, in the case of the acrylic resin (b), the polymer component and other various additives are similarly dissolved in a volatile solvent which does not react and dissolve with the polycarbonate resin composition to prepare the primer composition. A primer layer is formed by coating and removing the solvent.

Further, if necessary, the above method is preferably followed by heating at 40 to 140 ° C. after removing the solvent to crosslink the crosslinkable group.

Further, it is possible to activate the surface by treating the primer layer with an alkali to increase the adhesion to the silicone resin-based hard coat layer. Such an alkali treatment includes, for example, immersing the primer layer in an alkaline solution as a 0.01 to 50% by weight aqueous solution of a strong base such as sodium hydroxide or potassium hydroxide.

The solvents used above include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran,
Ethers such as 1,4-dioxane and 1,2-dimethoxyethane, esters such as ethyl acetate and ethoxyethyl acetate, methanol, ethanol, 1-propanol, 2
-Propanol, 1-butanol, 2-butanol, 2
Alcohols such as -methyl-1-propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, gas oil, Hydrocarbons such as kerosene, acetonitrile,
Examples thereof include nitromethane and water, which may be used alone or as a mixture of two or more. The concentration of the solid content of the resin forming the primer layer in such a primer composition is preferably 1 to 50% by weight, and 3 to 30% by weight.
% Is more preferred.

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

As the light stabilizer, for example, bis (2,
2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4
-Octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4
-Piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate, bis (2,2,6,6-tetra Hindered amines such as methyl-4-piperidyl) phenyl phosphite; nickel bis (octylphenyl) sulfide; nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate; nickel dibutyldithiocarbamate; Complexes. These agents may be used alone or in combination of two or more, and preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the resin forming the primer layer. .

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2,2'-dihydroxy-
Benzophenones such as 4,4'-dimethoxybenzophenone, 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-
5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-
Benzotriazoles such as (hydroxyphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,
3-diphenyl acrylate, 2-ethylhexyl-2
Cyanoacrylates such as cyano-3,3-diphenylacrylate, salicylates such as phenyl salicylate and p-octylphenyl salicylate, diethyl-
benzylidene malonates such as p-methoxybenzylidene malonate and bis (2-ethylhexyl) benzylidene malonate; 2- (4,6-diphenyl-1,3,5
-Triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol And hydroxyphenol triazines. These agents may be used alone or in combination of two or more.
0.1 to 100 parts by weight, preferably 100 parts by weight,
More preferably, it is used in an amount of 0.5 to 50 parts by weight.

Further, the primer composition may contain a catalyst capable of curing the silicone resin-based hard coat agent, whereby the effect of various functional agents such as a resin and a stabilizer contained in the primer layer is obtained. Of the hard coat agent can be reduced. Examples of the catalyst capable of curing such a hard coat agent include metal salts and ammonium salts of acetylacetone, metal salts of ethyl acetoacetate, metal salts of acetylacetone and ethyl acetoacetate, alkali metal salts and ammonium salts of carboxylic acids, and choline. Amines such as acetate, primary to tertiary amine, diamide, imidazole and polyalkyleneamine; magnesium perchlorate, ammonium perchlorate; organic metal salts such as zinc naphthenate and tin octylate; SnCl ₄ ; Any compound or mixture selected from the group consisting of Lewis acids such as TiCl ₄ and ZnCl ₄ can be mentioned.

The above primer composition is applied to a molded article of the polycarbonate resin composition by a bar coating method, a doctor blade method, a dip coating method, a flow coating method (shower coater, curtain flow coater), a spray coating method, a spin coating method, A method such as a roller coating method (gravure roll coating method or transfer roll coating method) can be appropriately selected according to the shape of the substrate to be coated. The polycarbonate resin composition molded body coated with such a primer composition is usually dried at room temperature to a temperature equal to or lower than the thermal deformation temperature of the substrate, and the solvent is dried and removed.
Further, if necessary, after removing the solvent, the mixture is heated to 40 to 140 ° C. to crosslink the crosslinkable group, and a polycarbonate resin composition molded article obtained by laminating the resin forming the primer layer is obtained.

The thickness of the primer layer is set to a value necessary for sufficiently adhering the molded article of the polycarbonate resin composition and the silicon resin-based hard coat layer and maintaining the necessary amount of the additive. It is sufficient if it is dry, preferably 0.1 to 10 μm, more preferably 1 to 5 μm
It is.

The silicone resin-based hard coat agent of the present invention refers to a part or all of a hydrolyzed condensate of the alkoxysilane represented by the above formula (5), and specifically, the same ones as described above can be used. . More preferably, an organosiloxane resin comprising a hydrolysis condensate of a trialkoxysilane compound and a hydrolysis condensate of a tetraalkoxysilane compound can be exemplified.

The surface hardness of the hard coat layer, the dyeability,
From the viewpoint of adjusting the refractive index, the thickness of the coating film, and the like, it is preferable to include metal oxide fine particles dispersed in a colloidal state. Such metal components include Si, Ti, Ce, Fe, S
at least one metal oxide fine particle selected from n, Zr, Al, W, Sb, Ta, La, and In; a composite particle or solid solution composed of two or more metal oxides or a mixture thereof; The metal oxide fine particles are dispersed in water or another solvent to form a sol.

The particle size of the metal oxide fine particles is as follows.
It is 1 to 200 nm, preferably 1 to 100 nm, more preferably 5 to 40 nm. Fine particles of less than 1 nm are extremely difficult to produce themselves, which is disadvantageous in terms of production efficiency and economy, and exceeding 200 nm affects transparency. Colloidal silica is the most typical of such metal oxide fine particles, and is most preferably used in the present invention. More specifically, for example, as a product dispersed in an acidic aqueous solution, Snowtex O of Nissan Chemical Industries, Ltd., as a product dispersed in a basic aqueous solution, Snowtex 30, Nissan Chemical Industries, Ltd., Snowtex 4
0, Cataloid S30 and Cataloid S40 of Catalyst Chemical Industry Co., Ltd .; MA-ST, IPA-ST, NBA-ST of Nissan Chemical Industries, Ltd.
IBA-ST, EG-ST, XBA-ST, NPC-S
T, DMAC-ST and the like.

Further, as specific examples of other metal oxide fine particles, a metal oxide sol made of CeO ₂ may have a solid content of 15%, a water dispersion sol such as Needal U-15, Sb of Taki Chemical Co., Ltd. _{As a} metal oxide sol composed of ₂ O ₃ ,
Sun Colloid AMT-130 manufactured by Nissan Chemical Industries, Ltd., which is 30% solids and methanol dispersion sol, TiO ₂ —Fe ₂
As the composite metal oxide sol composed of O ₃ —SiO _2, Optolake 1130F-2 (A-8) manufactured by Catalyst Chemical Industry Co., Ltd.
As a composite metal oxide sol composed of O ₂ —CeO ₂ —SiO _2, Optolake 1130A-2 (A-
8) As the composite metal oxide sol composed of SnO ₂ -WO ₃ , a metal colloid sol composed of Nissan Chemical Co., Ltd.'s Sun Colloid HIS-30M, which is a sol dispersed in methanol, having a solid content of 30%, and Al ₂ O ₃ Examples thereof include alumina sol-200 manufactured by Nissan Chemical Co., Ltd., which is an aqueous dispersion sol having a solid content of 10%.

More preferred silicone resin-based hard coating agents of the present invention include colloidal silica (x component), a hydrolyzed condensate of a trialkoxysilane represented by the following formula (6) (y component), and the following formula (7) And an organosiloxane resin comprising a hydrolytic condensate (z component) of a tetraalkoxysilane represented by

[0089]

Embedded image

(Wherein R ⁸ represents an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group,
A carbon atom substituted with one or more groups selected from the group consisting of a glycidoxy group and a 3,4-epoxycyclohexyl group;
And R ⁹ is an alkyl group having 1 to 4 carbon atoms. )

[0091]

Embedded image

(Wherein, R ¹⁰ is an alkyl group having 1 to 4 carbon atoms.) As the colloidal silica of the x component, those mentioned above can be used.

The hydrolysis-condensation product of the trialkoxysilane as the y component is obtained by subjecting the trialkoxysilane of the formula (6) to a hydrolysis-condensation reaction. Examples of such trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ -Aminopropyltriethoxysilane and the like, which can be used alone or in combination.

In order to obtain a hard coat composition which forms a hard coat layer having particularly excellent abrasion resistance, it is preferable that 70% by weight or more is methyltrialkoxysilane, and substantially the entire amount is methyltrialkoxysilane. More preferably, it is silane. However, a small amount of the above-mentioned trialkoxysilanes other than methyltrialkoxysilane may be added for the purpose of improving the adhesiveness and expressing functions such as hydrophilicity and water repellency.

The hydrolysis-condensation product of the tetraalkoxysilane as the z component is obtained by subjecting the tetraalkoxysilane of the formula (7) to a hydrolysis-condensation reaction. Examples of such tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and the like,
Preferred are tetramethoxysilane and tetraethoxysilane. These tetraalkoxysilanes can be used alone or in combination.

The y component and the z component are a mixture of a product obtained by partially or entirely hydrolyzing the alkoxysilane and a condensate obtained by subjecting a part or all of the hydrolyzate to a condensation reaction. It is obtained by doing.

The solid content of the organosiloxane resin composed of the x component, the y component and the z component can be prepared through a process comprising the following processes (1) and (2). A coat layer having excellent properties can be obtained and is preferably employed.

Process (1): A trialkoxysilane of the formula (6) is subjected to a hydrolysis-condensation reaction under acidic conditions in a colloidal silica dispersion.

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

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

When an inorganic acid is used as the acid, it is usually 0.0001 to 2 equivalents / l, preferably 0.001 to 2 equivalents / l.
It is used at a concentration of 0.1 equivalent / l, and when an organic acid is used, 0.1 to 100 parts by weight of trialkoxysilane is used.
It is used in an amount of 50 parts by weight, preferably 1 to 30 parts by weight.

The conditions for the hydrolysis and condensation reaction of trialkoxysilane vary depending on the type of trialkoxysilane used, the type and amount of colloidal silica coexisting in the system, and therefore cannot be specified unconditionally. Is 20-4
0 ° C., reaction time is 1 hour to several days.

Process (2): (i) The tetraalkoxysilane of the formula (7) is added to the reaction solution obtained by the reaction of the process (1) to cause a hydrolysis and condensation reaction, or (ii) the process (1) ) Is mixed with the reaction solution obtained by previously subjecting the tetraalkoxysilane of the formula (7) to a hydrolysis-condensation reaction.

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

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

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

On the other hand, when (ii) the reaction solution obtained by the reaction of the process (1) is mixed with the reaction solution which has been subjected to the hydrolysis-condensation reaction of the tetraalkoxysilane of the above formula (7), First, it is necessary to hydrolyze and condense the tetraalkoxysilane. This hydrolysis-condensation reaction is usually carried out under acidic conditions with 1 to 1 equivalent of tetraalkoxysilane.
The reaction is carried out by using 100 equivalents, preferably 2 to 50 equivalents, more preferably 4 to 20 equivalents of water at 20 to 40 ° C for 1 hour to several days. An acid is used in the hydrolysis-condensation reaction, and examples of the acid include those similar to the above-mentioned acids, and volatile acids such as acetic acid and hydrochloric acid are preferable. The acid is usually 0.000 when an inorganic acid is used.
1-2 equivalent / l, preferably 0.001-0.1 equivalent /
When the organic acid is used, it is used in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the tetraalkoxysilane.

The mixing ratio of the components x, y, and z, which are the solid components of the organosiloxane resin, depends on the stability of the solution of the hard coat composition, the transparency of the obtained cured film, the abrasion resistance and the abrasion resistance. The x component is preferably 5 to 45% by weight, the y component is 50 to 80% by weight in terms of R ⁸ SiO _3/2 , and the z component is SiO _2. Used in an amount of 2 to 30% by weight, more preferably 15 to 35% by weight of the x component,
55 to 75% by weight of the y component in terms of R ⁸ SiO _3/2 ,
The z component is 3 to 20% by weight in terms of SiO _2.

The hard coat composition used in the above-mentioned silicone resin-based hard coat layer usually further contains a curing catalyst. Examples of such a catalyst include lithium salts of aliphatic carboxylic acids such as formic acid, propionic acid, butyric acid, lactic acid, tartaric acid, and succinic acid, alkali metal salts such as sodium salt and potassium salt, benzyltrimethylammonium salt, tetramethylammonium salt, and tetraethylammonium salt. Examples thereof include quaternary ammonium salts such as ammonium salts, and sodium acetate, potassium acetate and benzyltrimethylammonium acetate are preferably used. When using a basic water-dispersed colloidal silica as the colloidal silica, when using an aliphatic carboxylic acid as an acid during the hydrolysis of alkoxysilane,
This means that the hard coat composition already contains a curing catalyst. The necessary content varies depending on the curing conditions, but the curing catalyst is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the solid content of the organosiloxane resin composed of the x component, the y component and the z component. Is 0.1 to 5 parts by weight.

As the solvent used in the hard coat composition, it is necessary that the solid content of the organosiloxane resin is stably dissolved.
It is desirable that at least 50% by weight, preferably at least 50% by weight, is alcohol. Such alcohols include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol,
-Methyl-2-pentanol, 2-butoxyethanol, etc. are preferable, and a low-boiling alcohol having 1 to 4 carbon atoms is preferable, and 2-propanol is particularly preferable in terms of solubility, stability, and coating properties. In the solvent, water that does not participate in the hydrolysis reaction with water in water-dispersed colloidal silica, lower alcohol generated by the hydrolysis of alkoxysilane, when organic solvent-dispersed colloidal silica is used, Organic solvent of dispersion medium, pH of hard coat composition
Acids added for control are also included. Examples of acids used for pH adjustment include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid. Organic acids such as acid, lactic acid, and paratoluenesulfonic acid are exemplified, and organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are preferable from the viewpoint of easy control of pH. Other solvents must be miscible with water / alcohol, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and acetic acid. Esters such as ethyl and ethoxyethyl acetate are exemplified. The solvent is preferably used in an amount of 50 to 900 parts by weight, more preferably 150 to 70 parts by weight, based on 100 parts by weight of the solid content of the organosiloxane resin composed of the x, y and z components.
0 parts by weight.

The pH of the hard coat composition for forming the silicone resin-based hard coat layer is adjusted to 3.0 to 6.0, preferably 4.0 by adjusting the contents of the acid and the curing catalyst.
It is desirable to adjust to 0-5.5. Thereby, gelation of the hard coat composition at normal temperature can be prevented, and storage stability can be increased. The hard coat composition usually becomes a stable composition when further aged for several hours to several days.

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

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

Further, a known leveling agent can be blended with the above-mentioned composition of the primer layer and the hard coat layer of the present invention for the purpose of improving coatability and smoothness of the obtained coating film. The compounding amount is preferably in the range of 0.01 to 2 parts by weight based on 100 parts by weight of the primer composition or the hard coat composition. Dyes, pigments, fillers, and the like may be added as long as the object of the present invention is not impaired.

In the present invention, in addition to the hard coat,
It can be used after printing or other surface treatment.

As a printing method, a conventionally known printing method such as gravure printing, lithographic printing, flexographic printing, dry offset printing, pad printing, screen printing and the like can be used according to the product shape and printing use.

The composition of the printing ink used in printing can be a resin or oil as a main component. Examples of the resin include natural resins such as rosin, Gilsonite, shellac and copearl, and phenol. System and its derivatives, amino resin, butylated urea, melamine resin, polyester alkyd resin, styrene resin, acrylic resin, phenol resin, epoxy resin, polyamide resin, polycarbonate resin composition, saturated polyester resin, amorphous polyarylate Synthetic resins such as resin, amorphous polyolefin resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, butyral resin, methylcellulose resin, ethylcellulose resin, and urethane resin can be used. In particular, when printing is performed on the surface of the first layer or the second layer on the interface side with the third layer, an ink component having high heat resistance is required. A crystalline polyarylate resin is preferably used. In addition, a desired color can be adjusted by using a pigment or a dye in the printing ink.

On the other hand, as other surface treatments, various fluorine coats, water / oil repellent coats, and water immersion coats with a photocatalyst and the like can be used.

Although the molded article of the polycarbonate resin composition of the present invention can take various forms, particularly preferable in the present invention are those having the form of a sheet or a film. This is a case where insert molding is performed in a bent state or in a state where secondary processing having a curved surface is performed.

In such a case, the thickness of the sheet or the like is as follows.
Usually 50 to 2000 μm, preferably 100 to 1000
μm, more preferably 200 to 700 μm. Within such a range, the strength and flexibility of the sheet itself are well-balanced, so that it can be easily handled in various steps such as application of a hard coat, insertion into a mold, or bending before insertion.

The resin sheet or the like according to the present invention may have a three-dimensional pattern on the surface in addition to a mere flat surface at the interface contacting the resin by insert molding. When such a three-dimensional pattern is applied, if it has optical transparency, it becomes possible to obtain a molded article of the polycarbonate resin composition having high design properties and optical functions.

Here, the three-dimensional pattern refers to three-dimensional irregularities in which optical changes and non-uniformity can be visually recognized from the surface. Such a shape may be any of a character, a figure, a symbol, and a combination thereof. You may. Further, such a shape includes not only the design property but also an optically usable regular figure such as a lenticular lens and a set of dots that can be a diffusion starting point. In addition, such three-dimensional irregularities do not necessarily need to be visible to the naked eye, and due to the prism effect of the irregularities, optical effects (such as iridescent light) that cannot be obtained on a normal plane. What is necessary is just to have.

A mold release agent can be added to the polycarbonate resin composition of the component A of the present invention. As the release agent, a saturated fatty acid ester is generally used, for example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate,
Lower fatty acid esters such as stearic acid stearate, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the polycarbonate resin composition.

If necessary, a phosphorus-based heat stabilizer other than the phosphite compound represented by the above formula (1) can be added to the polycarbonate resin composition of the present invention. As the phosphorus-based heat stabilizer, a phosphite compound and a phosphate compound, and further preferably a phosphonite compound are used. Examples of the phosphite compound include distearylpentaerythritol diphosphite, bis (2,
4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol Diphosphite and the like, preferably distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter
(t-butyl-4-methylphenyl) pentaerythritol diphosphite and 4,4′-isopropylidene diphenol ditridecyl phosphite.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, Dioctyl phosphate,
Diisopropyl phosphate and the like,
Preferred are triphenyl phosphate and trimethyl phosphate.

As the phosphonite compound, tetrakis (2,4-di-iso-propylphenyl) -4,4 ′
-Biphenylenediphosphonite, tetrakis (2,4-
Di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di- tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,
3'-biphenylenediphosphonite, tetrakis (2,
6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 ′
-Biphenylenediphosphonite, bis (2,4-di-i
(so-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n-butylphenyl)
-3-phenyl-phenylphosphonite, bis (2,4
-Di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) ) -4-
Phenyl-phenylphosphonite, bis (2,6-di-
n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 3-phenyl-phenylphosphonite and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl)-
Phenyl-phenylphosphonite is preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-
(Butylphenyl) -phenyl-phenylphosphonite is more preferred. Such a phosphonite compound can be preferably used in combination with the above formula (1).

The resin of the present invention may contain an antioxidant generally known for the purpose of preventing oxidation. Examples thereof include phenolic antioxidants, and specifically, for example, vitamin E, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-ter
t-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-
6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert)
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-cyclohexylphenol), 2,2′-
Dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-
tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t
tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-
Hexanediol bis [3- (3,5-di-tert-
Butyl-4-hydroxyphenyl) propionate, bis [2-tert-butyl-4-methyl 6- (3-te
rt-butyl-5-methyl-2-hydroxybenzyl)
Phenyl] terephthalate, 3,9-bis {2- [3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4 -Thiobis (6-ter
t-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol),
2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6- Di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-ter
t-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-te
rt-butylanilino) -1,3,5-triazine,
N, N'-hexamethylenebis- (3,5-di-ter
t-butyl-4-hydroxyhydrocinnamide), N,
N'-bis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyl] hydrazine,
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-ter
t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-
Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate; tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane; The composition ratio of these antioxidants is 0.000 to 100 parts by weight of the polycarbonate resin composition.
1 to 0.5 part by weight is preferred.

Further, an ultraviolet absorber, a light stabilizer and the like may be blended for improving the weather resistance. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-
4-n-octoxybenzophenone, 2-hydroxy-
4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone,
2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,
Benzophenone ultraviolet absorbers represented by 4′-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like can be mentioned.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert)
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-amylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2- [2′-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-te)
rt-butylphenyl) -5-chlorobenzotriazole, 2,2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl -3- [3-ter
Benzotriazole ultraviolet absorbers represented by condensates with t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol can be mentioned.

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butylmalonate,
Condensate of 2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid with 1,2,2 Condensation product of 6,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethylpiperidyl) imino]}, poly {[6-morpholino-s-triazine-2,4-diyl] [(2,2,6
6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Methyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,
Condensation product with 4,8,10-tetraoxaspiro [5,5] undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -chloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ', β'-tetramethyl-3,9
-(2,4,8,10-tetraoxaspiro [5,5]
A condensate with undecane) diethanol and a hindered amine-based light stabilizer represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane can also be blended.

The amount of the ultraviolet absorber and the light stabilizer is based on 100 parts by weight of the polycarbonate resin composition.
0.0001 to 10 parts by weight, preferably 0.001 to 5 parts
In addition, a bluing agent can be added to the polycarbonate resin composition of the present invention, particularly when it has transparency, in order to cancel the yellow tint based on an ultraviolet absorber or the like. As the bluing agent, any one can be used without any particular difficulty as long as it is used in a polycarbonate resin composition. Generally, anthraquinone dyes are easily available and preferred. As a specific bluing agent, for example, a common name Solvent Violet 13
[CA. No (color index No) 60725;
Trade name "Macrolex Violet B" manufactured by Bayer, "Diaresin Blue G" manufactured by Mitsubishi Chemical Corporation, "Sumiplast Violet B" manufactured by Sumitomo Chemical Co., Ltd.], generic name Solvent Violet 31 [C
A. No. 68210; Trade name "Diaresin Violet D" manufactured by Mitsubishi Chemical Corporation], generic name Solvent
Violet 33 [CA. No. 60725; Trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name S
solvent Blue 94 [CA. No 61500;
Trade name: Mitsubishi Chemical Corporation "Diaresin Blue N"], Generic name: Solvent Violet 36 [C
A. No. 68210; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Solvent
Blue97 [trade name “Macrolex Blue RR” manufactured by Bayer AG] and generic name Solvent Blue
45 [CA. No. 61110; Trade name “Tetrazol Blue RLS” manufactured by Sando Co., Ltd.], Ciba Specialty
Examples include Macrolex Violet and Triazole Blue RLS from Chemicals, and particularly preferred are Macrolex Violet and Triazole Blue RLS.

The polycarbonate resin composition of the present invention may further contain other conventional additives such as reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon, milled fiber, Glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particles, ceramic fiber, aramid particle, aramid fiber ,
Polyarylate fiber, graphite, conductive carbon black, various whiskers, etc.), flame retardant (halogen,
Phosphate ester type, metal salt type, red phosphorus, silicon type, fluorine type, metal hydrate type, etc., heat resistant agent, colorant (pigment and dye such as carbon black and titanium oxide), light diffusing agent (acrylic crosslinking) Particles, silicon cross-linked particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents,
Inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers represented by graft rubbers, infrared absorbers, and photochromic agents can be blended.

In the present invention, a molded article of the polycarbonate resin composition having good adhesion to the hard coat layer is provided by subjecting the above-mentioned specific polycarbonate resin composition to a hard coat treatment. Maintaining good adhesion can increase the degree of freedom of design for various applications, especially in the field of transparency, where high optical properties such as glazing products for vehicles are required, and It is suitable for the field where the degree of freedom is required.

[0134]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention and its effects will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. In addition, evaluation was based on the following method.

(1) Wet heat acceleration test A test piece was mounted on a semicircular stainless steel bending jig having a radius of curvature of 25 mm shown in FIG. 1 so that the hard coat treated surface was on the front side (the thickness of the test piece was At 0.5mm
1% of maximum strain occurred). In such a state, it is put into a pressure cooker (TPC-411 manufactured by Espec Corporation) and subjected to a treatment at a temperature of 65 ° C., a pressure of 0.2 MPa and a humidity of 85% RH for 1,000 hours, and the haze before and after the treatment is measured. A reflection / transmittance meter manufactured by Murakami Color Research Laboratory (H
R-100) and measured according to JIS K7105, and showed a change in haze before and after the treatment. Haze change = (Haze after accelerated wet heat test) − (Initial haze)

(2) Adhesion After the above-mentioned wet heat acceleration treatment, 100 cross-cuts (1 mm ² ) were applied to the coating film, and a cellophane tape was adhered to the cross-section, and then the adhered cellophane tape was perpendicularly cut. And it peels off rapidly. At this time, the number of grids remaining without being peeled off was counted, and the following judgment was made based on how many pieces of the grid crossed 100. ◎ (best coating film adhesion): 100 remaining stitches (all remaining) ○ (good coating film adhesion): 99 to 96 remaining stitches (almost remaining) × (not adhered): Less than 95 remaining stitches (partially peeled or almost peeled)

[Examples 1 to 4, Comparative Example 1] The method of preparing a test piece is as follows. Each of the following polycarbonate resin compositions (PC-1 to PC-3) was 1330 Pa
Extruded at 280 ° C under reduced pressure by a T-die extruder having a gear pump and width 1000 mm, thickness 0.5 m
m of the polycarbonate resin composition sheet was obtained. After that, one of the surfaces is subjected to various silicon hard coat treatments (HC-1 to HC-3) shown below to obtain 110 mm × 50 mm.
Was prepared by punching out a test piece with a punching jig, and the above evaluation was performed. Table 1 shows combinations of the polycarbonate resin composition and the hard coat agent.

Polycarbonate Resin Composition (i) PC-1 Effective internal volume 500 L horizontal equipped with an organic solvent supply port, a hot water supply port, a steam introduction port, a vaporized organic solvent exhaust port and an overflow type discharge port of the polycarbonate resin composition. A stirrer having a ribbon shape as a stirring blade was attached to a biaxial container of a rotating shaft type mixer. 50 g of a polycarbonate resin composition powder having an average particle diameter of 7 mm and 250 g of water were charged into the container, and the temperature in the container was 77 ° C. while stirring at a stirring speed of 80 rpm, and the average molecular weight was 22,000. Was supplied at a rate of 10 kg / min, and hot water was supplied at a rate of 10 kg / min. During the supply, the amount of hot water in the container / the granular material of the polycarbonate resin composition (volume ratio) is maintained at about 5, and the temperature in the container is controlled by introducing steam using steam at a pressure of 2.7 kg / cm ^2. The temperature was maintained at 77 ° C. by heating the mouth and jacket. The stirring capacity was 6 kw / hr · m ³ . After the start of the supply, the level of the slurry in the container increased, and the generated polycarbonate resin composition powder and hot water were discharged from a discharge port provided in an upper portion of the container. On this occasion,
The residence time of the polycarbonate resin composition powder was 1 hour.

Next, samples were taken after the powders were discharged and the properties of the powders were stabilized. The polycarbonate resin composition powder and the hot water discharged from the discharge port were then centrifuged with a vertical centrifuge (manufactured by Kokusan) at a centrifugal force of 1,500 G, and the polycarbonate resin composition powder was separated by filtration. The separated polycarbonate resin composition powder was pulverized to an average particle size of 2 mm by a pulverizer, and dried at 140 ° C. for 4 hours by a hot air drier.

99.78 parts by weight of such a powder, Irg
afos168 (manufactured by Nippon Ciba Geigy) 0.02
Parts by weight and 0.2 parts by weight of pentaerythritol tetrastearate, and 1% by weight of ion-exchanged water with respect to the polycarbonate resin composition in a twin-screw extruder provided with a hydrogenation site and a vent port immediately after the hydrogenation site. While adding, suction was performed at a reduced pressure of 1330 Pa from the vent port to obtain a resin pelletized at 280 ° C. The pellet was extruded again to obtain a sheet. The viscosity average molecular weight of the polycarbonate resin composition obtained as a sheet was 22,000,
The chlorine content was 5 ppm.

(Ii) PC-2 Resin obtained by the same treatment as PC-1 except that 99.8 parts by weight of powder used in PC-1 and 0.2 part by weight of pentaerythritol tetrastearate were blended. .
The polycarbonate resin composition obtained as a sheet had a viscosity average molecular weight of 22,000 and a chlorine content of 5 pp.
m.

(Iii) PC-3 Production was carried out in the same manner as in the production method of PC-1, except that the temperature in the container was set to 50 ° C. The viscosity average molecular weight of the polycarbonate resin composition obtained as a sheet was 22,000, and the chlorine content was 370 ppm. Hard coat treatment method (hereinafter "parts" indicates parts by weight)

(I) HC-1 A methyl methacrylate (hereinafter abbreviated as MMA) 7 was provided in a flask equipped with a reflux condenser and a stirrer and purged with nitrogen.
0 parts, 2-hydroxyethyl methacrylate (hereinafter referred to as HE
39 parts of MA, 0.18 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Then, the reaction was carried out in a nitrogen stream at 70 ° C. for 6 hours with stirring.
The obtained reaction solution was added to n-hexane and purified by reprecipitation,
90 parts of a copolymer (acrylic resin (I)) having a composition ratio of MMA / HEMA of 70/30 (molar ratio) was obtained. The weight average molecular weight of the copolymer was measured by GPC (column; Sho).
dex GPCA-804; eluent; THF) was 80,000 in terms of polystyrene.

Further, methyltrimethoxysilane 142
Parts, 72 parts of distilled water and 20 parts of acetic acid were mixed under cooling with ice water,
The mixture was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol to obtain 350 parts of a solution (X) of a hydrolyzed condensate of methyltrimethoxysilane. On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01 equivalent / l hydrochloric acid were mixed under cooling with ice water, and the mixture was stirred at 25 ° C. for 3 hours.
It was diluted with 11 parts of isopropanol to obtain 300 parts of a tetraethoxysilane hydrolyzed condensate solution (Y).

Next, the first layer of the hard coat (primer layer)
As a composition for use, 8 parts of the acrylic resin (I) was added with 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone,
5.2 parts of ethanol, 14 parts of isopropanol and 2
Dissolved in a mixed solvent consisting of 10 parts of ethoxyethanol, 10 parts of a solution of the methyltrimethoxysilane hydrolyzed condensate (X) was added to this solution, and the mixture was stirred at 25 ° C. for 5 minutes. 1 part of Mitsui Cytec Co., Ltd. Cymel 303) was added and the mixture was added at 25 ° C for 5 minutes.
After stirring for minutes, a coating composition (i-1) was prepared.

Further, as a composition for the hard coat second layer (hard coat layer), 100 parts of a water-dispersed colloidal silica dispersion (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd., solid content concentration: 30% by weight) was added to distilled water 12 parts. And 20 parts of acetic acid, and the mixture was stirred, and 134 parts of methyltrimethoxysilane was added to the dispersion under cooling with an ice water bath. 25 of this mixture
To a reaction solution obtained by stirring at 1 ° C. for 1 hour, 20 parts of a tetraethoxysilane hydrolyzed condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added, and isopropanol 20 was added.
The mixture was diluted with 0 part to prepare a coating composition (ii-1).

The coating composition (i-1) was applied to one surface of a sheet made of the polycarbonate resin composition with a wire bar, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 30 minutes. The first layer had a dry thickness of 2.5 μm. Next, the coating composition (ii-1) was further applied to the coating surface of the sheet with a wire bar, allowed to stand at 25 ° C for 20 minutes, and thermally cured at 120 ° C for 2 hours. Second
The layer thickness was 5.0 μm dry.

(Ii) 90.1 parts of HC-2 MMA, 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as MPTMS) 24.8
And the composition ratio of MMA / MPTMS 90/10 in the same manner as in the case of HC-1 except that 0.16 part of AIBN and 0.16 part of AIBN are used.
(Molar ratio) 95 parts of a copolymer (acrylic resin (II)) were obtained. The weight average molecular weight of the copolymer was 150,000 in terms of polystyrene. 10 parts of the acrylic resin (II) was mixed with 60 parts of methyl isobutyl ketone,
Dissolved in a mixed solvent consisting of 20 parts of butanol and 10 parts of 2-ethoxyethanol, and prepared a coating composition (i
-2) was adjusted.

Further, 2 parts of distilled water and 20 parts of acetic acid were added to 100 parts of the same water-dispersible colloidal silica dispersion as HC-1, and the mixture was stirred, and 142 parts of methyltrimethoxysilane was added to the dispersion under cooling in an ice water bath. Was added. 25 of this mixture
The mixture was stirred at 1 ° C. for 1 hour, 2 parts of sodium acetate was added, and the mixture was diluted with 236 parts of isopropanol to prepare a coating composition (ii-2).

The coating composition (i-2) was applied to one surface of a sheet made of a polycarbonate resin composition with a wire bar, allowed to stand at 25 ° C. for 20 minutes, and then left at 120 ° C. for 30 minutes.
Heat cured for minutes. The thickness of the first layer is 2.5 μm dry
Met. Next, the coating composition (ii-2) was applied on the coating surface of the sheet with a wire bar,
For 20 minutes, and then heat-cured at 120 ° C. for 1 hour. The dry thickness of the second layer was 5.0 μm.

(Iii) HC-3 MMA 45 parts, MPTMS 136.4 parts, AIBN0.
MMA was performed in the same manner as in the case of HC-1 except that two parts were used.
Thus, 140 parts of a 45/55 (molar ratio) copolymer (acrylic resin (III)) having a composition ratio of / MPTMS was obtained. The weight average molecular weight of the copolymer was 88,00 in terms of polystyrene.
It was 0. 10 parts of such an acrylic resin (III) are mixed with 40 parts of methyl ethyl ketone and 30 parts of methyl isobutyl ketone 30
And a mixed solvent consisting of 20 parts of isopropanol to prepare a coating composition (i-3).

The coating composition (i-3) was applied to one surface of a polycarbonate resin composition sheet with a wire bar, allowed to stand at 25 ° C. for 20 minutes, and then left at 120 ° C. for 30 minutes.
Heat cured for minutes. The thickness of the first layer is 2.5 μm dry
Met. Next, the coating composition (ii-2) was applied on the coating surface of the sheet with a wire bar,
For 20 minutes, and then heat-cured at 120 ° C. for 1 hour. The dry thickness of the second layer was 5.0 μm.

As a result of the above evaluation, the total chlorine content in terms of chlorine atoms of the polycarbonate resin composition was 50%.
When less than ppm (PC-1, PC-2) was used, it was found that the change in haze after three-point bending wet heat treatment was small and the adhesion was not deteriorated, and it was good for bending work. The lower the total chlorine content, the better the effect was obtained. Further, when a specific compound was added as a stabilizer to the polycarbonate resin composition and a specific hard coat agent was coated, a more favorable effect was obtained. Table 1 shows the results.

[0154]

[Table 1]

[0155]

According to the present invention, it is possible to obtain a molded article of a polycarbonate resin composition having a higher resistance to bending and the like and having a hard coat with good interface adhesion. Since the use of a molded article obtained by applying a hard coat to a resin composition can be broadened more than ever, the industrial effect achieved is extremely large.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a state of a molded article during a wet heat acceleration test.

FIG. 2 is a schematic diagram showing a layer configuration of a molded product.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Strip-shaped molded article main body 2 Stainless steel bending jig 3 Fixing plate 4 Polycarbonate resin composition layer 5 Primer layer 6 Hard coat layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08G 64/02 C08G 64/02 4J038 77/04 77/04 4J100 C08J 5/00 C08J 5/00 C08K 5 / 524 C08K 5/524 C08L 69/00 C08L 69/00 C09D 5/00 C09D 5/00 D 133/10 133/10 183/02 183/02 183/04 183/04 F term (reference) 4F006 AA36 AA56 AB24 AB32 AB34 AB35 AB36 AB37 AB39 AB43 BA02 CA00 CA04 DA04 EA01 EA03 4F071 AA50 AC15 AE05 AF30 AH11 BA01 BC03 4J002 CG011 CG021 EW066 FA040 FD010 FD040 FD050 FD060 FD070 FD090 FD160 BB00 BB160 BB160 AD13 AB01 AD12 AB01 AD12 BD09A BD09B BD09C BE05A BE07 BF14A BG08X BH02 DB07 DB11 DB13 FA07 FC32 FC33 FC35 FC36 HA01 HC01 HC02 HC04A HC05A JA091 JB131 JB171 JC031 JC091 JC2 31 JC631 JC711 JC731 JC751 JF031 JF041 JF131 JF141 JF161 JF181 JF221 JF321 JF331 JF361 JF371 JF381 JF541 JF581 KA01 KD01 KE07 KE11 KH03 KH05 KH06 KH08 4J035 BA15 CA01K CA01U CA11K CA11U CA112 CA14K CA14U CA142 CA19K CA19U CA192 EA01 EB03 LB02 4J038 CG031 CG141 CH121 CH171 CH261 CJ131 DA001 DA161 DA162 DB001 DD001 DG301 DL021 DL031 GA03 GA06 GA09 LA03 MA06 NA11 NA12 PA19 PC08 4J100 AB02R AB16R AG64R AJ02R AL03P AL03R AL04R AL08Q AL08R AL09Q AL09R AL10R AL62R AL63R AL66R AM02R CA15R AM19RBA08 BC08

Claims (5)

[Claims] 1. The total chlorine content in terms of chlorine atoms is 50.
A molded article of a polycarbonate resin composition obtained by subjecting at least one surface of a molded article made of a polycarbonate resin composition (component A) to not more than 1 ppm to a hard coat treatment. 2. The polycarbonate resin composition is prepared by adding a compound represented by the following formula (1) to a component A in an amount of 0.00% by weight.
The molded article of the polycarbonate resin composition according to claim 1, comprising from 0.01 to 0.5% by weight. Embedded image (Wherein, Ar ¹ , Ar ² and Ar ^{3 each} have 8 to ² carbon atoms)
0 is a dialkyl-substituted aromatic group, wherein Ar ¹ , Ar ² and Ar ³ are all the same, two are the same, or all three are different. ) 3. The hard coat layer has a primer layer, and the primer layer contains at least 50 mol% of a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3): The molar ratio of the repeating units represented by the following formulas (2) and (3) is 99.99:
The molded article of the polycarbonate resin composition according to claim 1, wherein the molded article is an acrylic resin of 0.01 to 50:50. Embedded image (Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms.) (Where X is a hydrogen atom or a methyl group;
² is an alkylene group having 2 to 5 carbon atoms, R ³ is C 1 -C
And n is an integer of 0 or 1. ) 4. The hard coat layer has a primer layer, and the primer layer contains at least 50 mol% of a repeating unit represented by the above formula (2) and a repeating unit represented by the following formula (4): The molar ratio of the repeating unit represented by the above formula (2) and the following formula (4) is 99: 1 to 5
99 to 60% by weight of a 0:50 acrylic resin and 1 to 40% by weight of a hydrolytic condensate of a compound represented by the following formula (5) (provided that R ⁵ _a R ⁶ _b SiO _{4- (a + b) / 2} 3. The molded article of the polycarbonate resin composition according to claim 1, wherein the mixture is a mixture or a reaction product thereof. Embedded image (Where Y is a hydrogen atom or a methyl group;
⁴ is an alkylene group having 2 to 5 carbon atoms. ) (Wherein, R ⁵ and R ⁶ are the same or different from each other;
An alkyl group having 10 or less carbon atoms, an alkenyl group, an aryl group, or a hydrocarbon atom having a halogen atom, an epoxy group, an amino group, a mercapto group, a methacryloxy group, or a cyano group, and R ⁷ is an alkyl group having 1 to 8 carbon atoms. , An aryl group, an alkoxyalkyl group, or an acyl group, wherein a and b are 0, 1 or 2, and a + b is 0, 1
Or 2. ) 5. The hard coat layer as the upper layer of the primer is composed of 5 to 45% by weight of colloidal silica (x component) and 50 to 80% by weight of a hydrolyzed condensate of a trialkoxysilane represented by the following formula (6) (y component). (Weight in terms of R ³ SiO _3/2 ), 2 to 30% by weight of a hydrolyzed condensate (z component) of a tetraalkoxysilane represented by the following formula (7):
The molded article of the polycarbonate resin composition according to claim 3 or 4, which is a layer obtained by curing an organosiloxane resin composed of (weight in terms of SiO ₂ ). Embedded image (Wherein R ⁸ is substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, vinyl groups, methacryloxy groups, amino groups, glycidoxy groups, and 3,4-epoxycyclohexyl groups) R ⁹ is an alkyl group having 1 to 4 carbon atoms, and R ⁹ is an alkyl group having 1 to 4 carbon atoms.) (However, in the formula, R ¹⁰ is an alkyl group having 1 to 4 carbon atoms.)