JP2001294693A - Polycarbonate resin molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin molded article applied with a hard coat having a higher resistance to a bend-processing and a good closely adhering property at boundary. SOLUTION: This polycarbonate resin molded article is provided by having a hard coat layer on at least one surface of a molded article consisting of a polycarbonate resin (component A) having <=100 ppm total amount of free divalent phenol and monovalent phenol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a molded article of a polycarbonate resin. More specifically, it is a resin molded article obtained by subjecting a polycarbonate resin, which is a total amount of a specific free dihydric phenol and monohydric phenol, to a hard coat treatment, and has a good adhesion to a hard coat layer, especially for bending. The present invention relates to a polycarbonate resin molded body.

[0002]

2. Description of the Related Art In recent years, products with different functions have been added to each layer of the product in order to increase the value of the product, such as enhancing the functionality and design of the product, and saving resources and environmental measures by recycling and eliminating painting. Design is desired. In particular, there is the highest demand for adding a specific function to the product surface to increase 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] According to such a production method, for example, a polycarbonate resin laminate having a hard coat is produced, and a polycarbonate resin 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 polycarbonate resin molded article having a higher resistance to bending and the like and having a hard coat having good interface adhesion. .

The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a polycarbonate resin having a free dihydric phenol of a specific amount or less is subjected to a hard coat treatment, and particularly to a specific hard coat. Thus, the present invention has been found to have better resistance to bending.

[0008]

According to the present invention, the total content of free dihydric phenol and monohydric phenol is 100 p.
The present invention relates to a polycarbonate resin molded article having a hard coat layer on at least one surface of a molded article composed of a polycarbonate resin (component A) having a pm or less.

The polycarbonate resin of the present invention is usually prepared by interfacial polycondensation of a dihydric phenol and a carbonate precursor,
In addition to those obtained by a reaction by a melt transesterification method, those obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method or those obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.

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, and 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, dihaloformate of dihydric phenol and the like.

In producing the polycarbonate resin 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. Further, the polycarbonate resin may be a branched polycarbonate resin 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 resins 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 resin is contained, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.001 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of such a branched structure is also 3;
It is preferably from 0.5 to 0.5 mol%, particularly preferably from 0.01 to 0.3 mol%. The ratio is ¹
It 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. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
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 a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or 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, such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (8) can be shown.

[0018]

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Wherein A is a hydrogen atom or a group having 1 to 9 carbon atoms.
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and 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. Among these, phenols having a long-chain alkyl group represented by the following general formulas (9) and (10) as a substituent are preferably used.

[0021]

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[0022]

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(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 such substituted phenols of the general formula (9), those having n of 10 to 30, especially 10 to 26 are preferable. Specific examples thereof include decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, and the like. Octadecyl phenol, eicosyl phenol, docosyl phenol, triacontyl phenol 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 and the carbonate ester while heating in the presence of an inert gas. It is carried out 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 adjusted to 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. 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 the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
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 bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl 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 such a catalyst is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, the strength becomes insufficient. Those having a viscosity average molecular weight of 10,000 to 40,000 are preferred, more preferably 13,000 to 35,000, and more preferably 17,000 to 35,000.
Those having a size of 000 to 30,000 are particularly preferred. Also, two or more polycarbonate resins may be mixed. The viscosity average molecular weight referred to in the present invention is 100 methylene chloride.
The specific viscosity (η _SP ) obtained from a solution in which 0.7 g of a polycarbonate resin is dissolved in 20 ml at 20 ° C. is inserted 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 of the present invention can be used in any of the above-mentioned interfacial polycondensation method and melt transesterification method. The amount of free dihydric phenol and monohydric phenol can be controlled by the interfacial polycondensation method. In this case, it is important to increase the reactivity and suppress the decomposition reaction, and since a large amount of free dihydric phenol and monohydric phenol can be removed by a washing step after the reaction, the pH and the It can be adjusted by appropriately controlling the reaction conditions such as the reaction temperature, the type and amount of the catalyst, and the washing conditions. In the case of the melt transesterification method, it can be adjusted by adding a reaction-active monomer, for example, methoxycarbonylphenylphenyl carbonate, to react and remove most of the free dihydric phenol and the like.

The polycarbonate resin used in the present invention, which is produced by the above-mentioned method and whose amounts of free dihydric phenol and monohydric phenol are adjusted, has a free dihydric phenol and monohydric phenol content of 100 ppm or less, preferably 100 ppm or less. Is 70 ppm or less, more preferably 30 ppm, particularly preferably 5 ppm or less. The total content of free dihydric phenol and monohydric phenol is 100
If the content exceeds ppm, the bending cannot be sufficiently improved. still,
The content of the dihydric phenol and the monohydric phenol of the present invention is a value obtained by an HPLC (high-performance liquid chromatography) method.

Here, the cause of the content of free dihydric phenol or monohydric phenol related to the resistance to bending is not known, but after the forming of a sheet or the like, the free dihydric phenol or monohydric phenol remaining in the polycarbonate remains. It is thought that phenol components and the like remain to some extent, but when various solvent components are applied on such a surface, aggregation of dihydric phenol components and the like is induced, coating is performed in such a state, and bending stress is applied. Since the strength of the interface at a portion where the dihydric phenol component and the like are aggregated to some extent is low, it is considered that the difference may occur particularly in a severe acceleration test for long-term characteristics such as a moist heat test.

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. This is thought to be because the long-term decomposition reaction of the polycarbonate resin induced by the presence of free dihydric phenol or monohydric phenol can be suppressed, and such a compound itself is hardly affected by the components of the hard coat agent. It is thought that.

[0037]

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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 may be the same or different from each other. )

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 0.0001 to 100% by weight of the polycarbonate resin of the component A.
0.5 wt% is preferred, more preferably 0.0005.
To 0.1% by weight, more preferably 0.001 to 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 silicone 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, for example, a mixture of trialkoxysilane and tetraalkoxysilane or a partial hydrolyzate of an alkylated product thereof, and a mixture of methyltrialkoxysilane and phenyltrialkoxysilane. Decomposed products, partially hydrolyzed condensates of colloidal silica-filled organotrialkoxysilanes and the like can be mentioned. 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. Note that various surfactants, for example, siloxane-based or alkyl fluoride-based surfactants, may be added to the hard coat layer in order to obtain a smooth surface state. Examples of the organic resin-based hard coat 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 silicone resin hard coat agent is formed thereon. It is preferable to form a cured layer adjusted 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, and polyester acrylates, urethane acrylates, epoxy acrylates comprising 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 of the silicone resin hard coat agent, a heat / photopolymerization initiator, Inhibitor, silicone defoamer,
It may contain leveling agents, thickeners, sedimentation inhibitors, anti-sagging agents, flame retardants, various additives for organic / inorganic pigments / dyes, and auxiliary additives.

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 irradiating an active energy ray such as an electron beam or radiation (hereinafter sometimes referred to as an acrylic resin (a)); 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 and the upper silicon hard coat layer becomes better, and the effect in the present invention is also large.

[0046]

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(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 such an 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 compounding 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.

The acrylic resin used as a primer of the silicone resin-based hard coat agent in the present invention 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 crosslinking reactive group include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyl trimethoxysilane, and 3-methacryloxypropyl trimethoxysilane. ,
3-methacryloxypropyltriethoxysilane, 3-
Methacryloxypropylmethyldimethoxysilane and the like can be mentioned.

One preferred embodiment of the acrylic resin used as a primer of the silicone resin-based hard coat agent in the present invention is a copolymer comprising a repeating unit represented by the above formula (2) and the following formula (3). And the repeating unit represented by the above formula (2) and the following formula (3)
Is a molar ratio of 99.99: 0.
01:50:50, preferably 99: 1
60:40, more preferably 97: 3 to 7
An acrylic resin in the range of 0:30 is employed.

[0052]

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(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 copolymer comprises at least 50% by weight, preferably at least 70% by weight, more preferably at least 9% by weight of the resin forming the primer layer.
0% by weight, and typically, it is desirable that the resin forming the primer layer is substantially this acrylic resin copolymer.

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. As the acrylate or methacrylate monomer having such an alkoxysilyl group, specifically, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and the like, and 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyl. Dimethoxysilane is preferred, and 3-methacryloxypropyltrimethoxysilane is particularly preferred.

In one preferred embodiment of the acrylic resin used as the primer of the silicone resin-based hard coating agent in the present invention, the above formula (2) and the following formula (4)
And a molar ratio of the repeating unit represented by the formula (2) to the repeating unit represented by the following formula (4) is from 99: 1 to 50:50.
99 to 60% by weight of an acrylic resin (hereinafter may be referred to as "hydroxy group-containing acrylic resin"), and a hydrolyzed condensate of a compound represented by the following formula (5):
0 wt% mixture or reaction product of (wherein ^{_{R 5 a R 6 b -SiO 4-}} (a + b) / 2 weight in terms of) can also be mentioned.

[0057]

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

[0059]

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(Wherein, R ⁵ and R ⁶ are the same or different from each other and are an alkyl group, alkenyl group, aryl group having 10 or less carbon atoms, halogen atom, epoxy group, amino group, mercapto group, 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. Further, specific examples of the monomer corresponding to the formula (4) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. Methacrylate is preferably employed.

On the other hand, specific examples of the alkoxysilane represented by the above 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, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycid Xymethyltriethoxysilane, 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) methyl Triethoxysilane, 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,
trialkoxy or trialkoxy such as γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane; Acyloxy or triphenoxysilanes or a hydrolyzate thereof, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-
Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethyldimethoxysilane, γ-mercaptopropyldiethoxysilane, γ- Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane , Α-glycidoxyethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypro Pillmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-gly Sidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxy Silane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glyci Examples include alkoxysilanes or diacyloxysilanes such as doxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, 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, vinyl group, methacryloxy group, amino group, glycidoxy group, 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 (Ami Ethyl)-.gamma.-aminopropyltrimethoxysilane, N-beta (aminoethyl)-.gamma.-
Aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, etc., among which alkyl Trialkoxysilanes are preferred, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferred. These can be used alone or in combination.

The hydrolysis condensate of this alkoxysilane is generally 0.2 to 4 equivalents, preferably 0.5 to 2 equivalents, more preferably 1 to 1 equivalent to 1 equivalent of the alkoxy group of the alkoxysilane under acidic conditions. 20 using 5 equivalents of water
It is obtained by performing a hydrolytic condensation reaction at 〜40 ° C. for 1 hour to several days. Acids are used in the hydrolysis-condensation reaction. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid. And organic acids such as succinic acid, maleic acid, lactic acid and p-toluenesulfonic acid, and volatile acids such as acetic acid and hydrochloric acid are preferred. When an inorganic acid is used, the acid is usually used at a concentration of 0.0001 to 2N, preferably 0.001 to 0.1N. When an organic acid is used, 0 to 100 parts by weight of alkoxysilane is used. 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight.

The mixing ratio of the hydrolysis-condensation product 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). -(a + b) / 2} ).
The latter is 99 to 60% by weight, preferably 95 to 70% by weight.
It is. By adjusting the resin to such a composition, the layer made of the acrylic resin has good adhesion to the polycarbonate resin and the upper silicon hard coat layer. Further, a mixture of the above hydrolyzed condensate of alkoxysilane and the above-mentioned hydroxy group-containing acrylic resin in the above-mentioned ratio or a partially condensed reaction product can be used.

Further, as one preferred embodiment of the acrylic resin used as a primer of the silicone resin-based hard coating agent in the present invention, a mixture or reaction of a hydrolysis-condensation product of the above alkoxysilane and a hydroxy group-containing acrylic resin is preferred. A product obtained by further mixing a melamine resin with the product can also be mentioned. The melamine resin to be used includes, for example, fully alkylated methylated melamine represented by hexamethoxymethyl melamine, a resin in which a part of the methoxymethyl group of hexamethoxymethyl melamine becomes a methylol group, an imino group, and 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 hydrolyzed condensate of alkoxysilane and the acrylic resin having a hydroxy group.
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 coating 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 the performance such as adhesion and strength as a primer layer is sufficiently exhibited.

As a 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 mixed with a volatile solvent which does not react with or dissolve the polycarbonate resin. After dissolving or homogenizing without using a solvent to prepare a primer composition, apply the primer composition, then polymerize the monomer component by ultraviolet light or heat, and remove the solvent to form a primer layer. Form.

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

In addition, if necessary, it is preferable to crosslink the crosslinkable group by heating to 40 to 140 ° C. after removing the solvent, if necessary.

Further, it is possible to activate the surface by subjecting the primer layer to an alkali treatment so as to enhance the adhesion to the silicon 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,
Hydrocarbons such as isooctane, benzene, toluene, xylene, gasoline, light oil, kerosene, acetonitrile, nitromethane, water, etc., may be used alone or in combination of two or more. Good. The concentration of the solid content of the resin forming the primer layer in the primer composition is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

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

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 such as nickel dibutyl dithiocarbamate 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, for example, 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; These agents may be used alone or in combination of two or more, and preferably used in an amount of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the resin forming the primer layer. .

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 resins and stabilizers contained in the primer layer may be 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 ; Examples include any compound or mixture selected from the group consisting of Lewis acids such as TiCl ₄ and ZnCl ₄ .

The above primer composition is applied to a polycarbonate resin molded product 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,
Spin coating, roller coating (gravure roll coating, transfer roll coating), etc.
It can be appropriately selected according to the shape of the substrate to be coated. The polycarbonate resin molded body coated with such a primer composition is usually dried and removed at a temperature from room temperature to a temperature equal to or lower than the thermal deformation temperature of the base material. C. to crosslink the crosslinkable group by heating to obtain a polycarbonate resin molded article in which the resin forming the primer layer is laminated.

[0079] The thickness of the primer layer is such that the polycarbonate resin molded body and the silicone resin-based hard coat layer are sufficiently adhered to each other and that the necessary amount of the additive can be maintained. Well, preferably 0.1 to 10
μm, and more preferably 1 to 5 μm.

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 as those described above. Although it can be used, more preferred are an organosiloxane resin composed of a hydrolysis condensate of a trialkoxysilane compound and a hydrolysis condensate of a tetraalkoxysilane compound.

Further, 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 kind of metal oxide fine particles selected from n, Zr, Al, W, Sb, Ta, La, and In; composite particles or solid solutions composed of such two or more kinds of metal oxides or mixtures 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. Among these metal oxide fine particles, colloidal silica is the most typical, and is most preferably used in the present invention. More specifically, as a product dispersed in an acidic aqueous solution, Snowtex O of Nissan Chemical Industries, Ltd. is used. ,
Products dispersed in a basic aqueous solution include Snowtex 30, Snowtex 40 from Nissan Chemical Industry Co., Ltd., and Cataloid S30 and Cataloid S4 from Catalyst Kasei Kogyo Co., Ltd.
0. Nissan Chemical Industries' MA-ST, IPA-ST, NBA-ST, I
BA-ST, EG-ST, XBA-ST, NPC-S
T, DMAC-ST and the like.

Specific examples of other metal oxide fine particles include a metal oxide sol made of CeO ₂ having a solid content of 15% and 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, Optrake 1130F-2 (A-8) manufactured by Catalyst Chemical Industry Co., Ltd., which is a sol dispersed in methanol with a solid content of 30%, Ti
As the 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 oxide sol composed of Nissan Chemical Co., Ltd.'s Sun Colloid HIS-30M, which is a methanol-dispersed sol 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 composed of a hydrolyzed condensate (z component) of a tetraalkoxysilane represented by the following formula:

[0085]

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(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. )

[0087]

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(Wherein, R ¹⁰ is an alkyl group having 1 to 4 carbon atoms) As the x-component colloidal silica, 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 can be mentioned, and these 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 wholly 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): The trialkoxysilane of the above 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 a water-dispersed colloidal silica dispersion when the dispersion is used, and water may be further added if necessary. Usually, 1 to 10 equivalents, preferably 1.5 to 7 equivalents, more preferably 3 to 5 equivalents of water 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 2N, preferably 0.001 to 0.
It is used at a concentration of 1N. When an organic acid is used, it is used in an amount of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of trialkoxysilane.

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

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

The 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 specified unconditionally.
４０40 ° C., and the reaction time is 10 minutes to several days.

On the other hand, when (ii) the reaction solution obtained by the reaction of the process (1) is mixed with the reaction solution in which the tetraalkoxysilane of the formula (7) has been subjected to a hydrolysis condensation reaction, First, it is necessary to hydrolyze and condense tetraalkoxysilane. This hydrolysis-condensation reaction is usually carried out under an acidic condition under the conditions of 1 to 1 equivalent of tetraalkoxysilane.
The reaction is carried out by 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 the same acids as described above, and volatile acids such as acetic acid and hydrochloric acid are preferable. The acid is usually 0.000 when an inorganic acid is used.
It is used at a concentration of 1 to 2N, preferably 0.001 to 0.1N, and when an organic acid is used, 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of tetraalkoxysilane. Used in parts by weight.

The mixing ratio of each of the x component, y component and z component, which are the solid components of the organosiloxane resin, depends on the stability of the hard coat composition solution, 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 catalysts 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 a 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. Examples of such alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol,
-Methyl-2-pentanol, 2-butoxyethanol and the like 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 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. 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 a primer layer formed on a polycarbonate resin molded article, and cured by heating to form a hard coat layer. Examples of the coating method include 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, and a roller coating method (gravure roll coating method, transfer roll coating method). ) Can be appropriately selected according to the shape of the substrate to be coated. The substrate coated with such a composition is usually heated and cured after drying and removing the solvent at a temperature from room temperature to a temperature not higher than the thermal deformation temperature of the substrate. It is preferable to perform such thermal curing at a high temperature within a range in which there is no problem with the heat resistance of the substrate because curing can be completed earlier. At room temperature,
Thermal curing 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. The thermosetting is preferably performed at 50 ° C to 20 ° C.
0 ° C. range, more preferably 80 ° C. to 160 ° C. range,
More preferably, the composition is cured by heating in the range of 100 ° C to 140 ° C, preferably for 10 minutes to 4 hours, more preferably for 20 minutes to 3 hours, and still more preferably for 30 minutes to 2 hours.

The thickness of the silicone resin-based hard coat layer is
It is usually 2 to 10 μm, preferably 3 to 8 μm. When the thickness of the coat layer is within the range, cracks are generated in the coat layer due to stress generated at the time of 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 the coating property and the 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 application.

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, saturated polyester resin, amorphous polyarylate resin, Amorphous polyolefin resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride
Synthetic resins such as vinyl acetate copolymer, butyral resin, methylcellulose resin, ethylcellulose resin, and urethane resin can be used. In particular, when the molded article is used for insert molding of a thermoplastic resin, an ink component having high heat resistance is required. In such a case, a resin such as a polycarbonate resin or an amorphous 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 or the like can be used.

Although the polycarbonate resin molded article of the present invention can take various forms, it is particularly preferable in the present invention that it has the form of a sheet or a film, and in particular, such a sheet or the like is bent. This is a case where insert molding is performed in a 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 is easy to handle in various steps such as application of a hard coat, insertion into a mold, or bending before insertion.

The interface between the resin sheet and the like according to the present invention, which is in contact with the resin by insert molding, is not limited to a mere plane, but may have a three-dimensional pattern formed on the surface. In the case where such a three-dimensional pattern is provided, if it has optical transparency, it becomes possible to obtain a polycarbonate resin molded article having a high degree of design and optical functions.

Here, the three-dimensional pattern refers to three-dimensional irregularities in which optical changes and non-uniformities 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 design properties but also optically usable regular figures 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 that cannot be obtained on a normal plane (such as iridescent light). What is necessary is just to have.

A releasing agent can be added to the polycarbonate resin of the component A of the present invention. As the release agent, a saturated fatty acid ester is generally used. Esters, 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.

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 of the present invention. As the phosphorus-based heat stabilizer, a phosphite compound and a phosphate compound, and furthermore, a phosphonite compound are preferably used.

As the phosphite compound, distearyl pentaerythritol 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 Phosphite, and the like, preferably distearyl pentaerythritol 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. 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 0.0001 to 100 parts by weight of the polycarbonate resin.
0.5 parts 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 light stabilizer is 0.00 0.00 parts by weight of the polycarbonate resin.
0.01 to 10 parts by weight, preferably 0.001 to 5 parts by weight. The polycarbonate resin of the present invention has a bluing agent in order to cancel a yellowish color due to an ultraviolet absorber or the like, particularly when it has transparency. Can be blended. As the bluing agent, any one can be used without any particular difficulty as long as it is used for a polycarbonate resin. Generally, anthraquinone dyes are easily available and preferred. Specific blueing agents include, for example, 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 S
solvent Violet 31 [CA. No.6821
0; 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 Solvent
Blue 94 [CA. No. 61500; Trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation], generic name Sol
vent Violet 36 [CA. No. 68210;
Trade name Bayer Corporation “Macrolex Violet 3
R "], generic name Solvent Blue 97 [trade name" Macrolex Blue RR "manufactured by Bayer AG] and generic name Solvent Blue 45 [CA. No61
110; Trade name "Tetazole Blue RL" manufactured by Sando Co., Ltd.
S "], Macrolex Violet and Triazole Blue RLS from Ciba Specialty Chemicals, and particularly Macroxole Violet B and Triazole Blue RLS are preferred.

The polycarbonate resin 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 bead, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particles , Ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc., flame retardants (halogen, phosphate, metal salt, red phosphorus, silicon, fluorine, Metal hydrates), heat-resistant agents, colorants (pigments and dyes such as carbon black and titanium oxide), light diffusing agents (cross-linked acrylic particles, cross-linked silicon particles, ultra-thin glass flakes,
Calcium carbonate particles, fluorescent whitening agents, luminous 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), an impact modifier represented by a graft rubber, an infrared absorber, and a photochromic agent.

In the present invention, a polycarbonate resin molded article having good adhesion to the hard coat layer is provided by subjecting the above-mentioned specific polycarbonate resin to a hard coat treatment, and particularly to a good adhesion even to bending. Therefore, the degree of freedom in design for various applications can be increased.In particular, in the field of transparency, high optical characteristics such as glazing products for vehicles are required, and the degree of freedom in design is increased. It is suitable for the required field.

[0131]

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 sheet test piece was mounted on a semicircular stainless steel bending jig having a radius of curvature of 50 mm shown in FIG. 1 so that the hard-coated surface was on the front side (thickness of the test piece). Was 0.5 mm, a maximum strain of 0.5% occurred). In such a state,
Pressure cooker (TPC-41 manufactured by Espec Corporation)
1) Put inside, temperature 65 ° C, pressure 0.2MPa, humidity 8
The treatment was performed for 1,000 hours under the condition of 5% RH, and the haze before and after the treatment was measured using a reflection / transmittance meter (HR-100 type, manufactured by Murakami Color Research Laboratory) as a measuring instrument, according to JIS K710.
The haze change before and after the treatment was measured in accordance with No. 5. 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 formed on the coating film, and a cellophane tape was adhered to the cross-cut portion, and then the adhered cellophane tape was squared. 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)

(3) Light fastness and discoloration Using a sunshine weather meter (S300) manufactured by Suga Test Machine Co., Ltd., the test piece was subjected to a cycle of repeated rainfall for 18 minutes for 120 minutes at a constant black panel temperature of 63 ° C. for 2 minutes. , 500 hours. The yellowness of the test piece before and after exposure is measured at an ambient temperature of 23 ° C. in accordance with JIS K-7103, and the change in yellowness before and after exposure is indicated as yellowing degree. Yellowness = (Yellowness after exposure)-(Initial yellowness)

[Examples 1 to 6, Comparative Example 1] A test piece was prepared as follows. The following various polycarbonate resins (PC-1 to PC-5) were melt-extruded at 280 ° C. under a reduced pressure of 1330 Pa by a T-die extruder having a gear pump to obtain a polycarbonate resin sheet having a width of 1,000 mm and a thickness of 0.5 mm. . After that, one of the surfaces is treated with various silicon hard coat treatments (HC-1
HC-3) was applied and a test piece of 110 mm × 50 mm was punched out with a punching jig, and the above evaluation was performed.
Table 1 shows combinations of the polycarbonate resin and the hard coat agent.

(Polycarbonate resin) (i) PC-1 Bisphenol A and phosgene, and p-tert-butylphenol as a terminal stopper were used, and were synthesized by an ordinary method using an amine-based catalyst. To obtain a solution having a concentration of 14% by weight, and further, using a centrifugal extractor with a perforated plate (KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.), a 0.5% aqueous sodium hydroxide solution at a flow rate of 1000 ml / min, and the organic phase. Flow rate 1000ml /
After supplying at a rate of 3 min and treating at 3500 rpm, the organic phase was acidified with hydrochloric acid, and then repeatedly washed with water.
When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated to obtain a polycarbonate resin powder.

After drying the powder, powder 99.
78 parts by weight, 0.02 parts by weight of Sandstab P-EPQ (manufactured by Sandoz) and 0.2 parts by weight of pentaerythritol tetrastearate were blended, and a vent port was provided immediately after the hydrogenation point. While adding 1% by weight of ion-exchanged water to the polycarbonate resin with a screw extruder, 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 polycarbonate resin obtained as a sheet had a viscosity average molecular weight of 24,700, and contained bisphenol A and p-ter contained in the polycarbonate resin.
The total amount of t-butylphenol was 19 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 obtained as a sheet had a viscosity average molecular weight of 24,600, and the total amount of bisphenol A and p-tert-butylphenol contained in the polycarbonate resin was 21 ppm.

(Iii) PC-3 Bisphenol A and phosgene, and p-tert-butylphenol as a terminal stopper were synthesized by a conventional method without using an amine-based catalyst. Was substantially the same as ion-exchanged water, and Sandsta was added to 99.78 parts by weight of a polycarbonate resin powder produced by removing a methylene chloride by a kneader provided with an isolation chamber having a foreign matter take-out port in a bearing portion.
b. P-EPQ (manufactured by Sandoz) 0.
02 parts by weight and 0.2 parts by weight of pentaerythritol tetrastearate were blended and pelletized at 280 ° C. using a twin screw extruder to obtain a resin. Thereafter, the sheet was extruded again under the above conditions to obtain a sheet. The polycarbonate resin obtained as a sheet had a viscosity average molecular weight of 24,5.
00, the total amount of bisphenol A and p-tert-butylphenol contained in the polycarbonate resin was 58 ppm.

(Iv) PC-4 Resin obtained by the same treatment as PC-3 except that 99.8 parts by weight of powder used in PC-3 and 0.2 part by weight of pentaerythritol tetrastearate were blended. .
The viscosity average molecular weight of the polycarbonate resin obtained as a sheet was 24,500, and the total amount of bisphenol A and p-tert-butylphenol contained was 6
It was 7 ppm.

(V) PC-5 99.8 parts by weight of a polycarbonate resin powder and pentaerythritol tetrastearate prepared in substantially the same manner as PC-3 and obtained by reducing the number of washing steps.
2 parts by weight were blended, and a resin pelletized by a twin-screw extruder at 280 ° C. was obtained, and then formed into a sheet under the above conditions. The viscosity average molecular weight of the polycarbonate resin obtained as a sheet was 24,500, and bisphenol A contained in the polycarbonate resin and p-tert-
The total amount of butylphenol was 127 ppm.

(Hard Coating Method) (Hereinafter, “parts” indicate parts by weight) (i) Methyl methacrylate (hereinafter abbreviated as MMA) in a flask equipped with a HC-1 reflux condenser and a stirrer and purged with nitrogen. 7
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 N hydrochloric acid are mixed under cooling with ice water, the mixture is stirred at 25 ° C. for 3 hours, diluted with 11 parts of isopropanol, and a solution of the hydrolyzed condensate of tetraethoxysilane ( Y) 300 parts were obtained.

Next, as the composition for the first layer of the hard coat,
8 parts of the acrylic resin (I) is methyl ethyl ketone 40
Parts, methyl isobutyl ketone 20 parts, ethanol 5.2
, 14 parts of isopropanol and 10 parts of 2-ethoxyethanol, and then dissolved in a solution of the hydrolyzed condensate of methyltrimethoxysilane (X).
10 parts were added and stirred at 25 ° C. for 5 minutes. Further, 1 part of a melamine resin (Cymel 303 manufactured by Mitsui Cytec Co., Ltd.) was added to the solution, and the mixture was stirred at 25 ° C. for 5 minutes. -1) was prepared.

Further, as the composition for the second layer of the hard coat,
Water-dispersed colloidal silica dispersion (Nissan Chemical Industries, Ltd.)
Made Snowtex 30 solid content concentration 30% by weight) 10
To 12 parts of distilled water and 20 parts of acetic acid were added and stirred.
4 parts were added. This mixture was stirred at 25 ° C. for 1 hour. To the reaction mixture obtained, 20 parts of a tetraethoxysilane hydrolyzed condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added, diluted with 200 parts of isopropanol, and coated. Composition (ii-1) was prepared.

The coating composition (i-1) was applied to one surface of a polycarbonate resin sheet with a wire bar.
After leaving still at 25 ° C. for 20 minutes, it was thermally cured at 120 ° C. for 30 minutes. The thickness of the first layer was 2.5 μm. Next, the coating composition (ii-1) is formed on the coating surface of the sheet.
Is further applied with a wire bar, and allowed to stand at 25 ° C. for 20 minutes.
Heat cured at 120 ° C. for 2 hours. The thickness of the second layer is 5.0
μm.

(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) were 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 applied to the 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).

On one side of the polycarbonate resin sheet,
The coating composition (i-2) was applied with a wire bar, left at 25 ° C. for 20 minutes, and thermally cured at 120 ° C. for 30 minutes. The thickness of the first layer was 2.5 μm. Then, the coating composition (i
i-2) was applied with a wire bar, left standing at 25 ° C. for 20 minutes, and thermally cured at 120 ° C. for 1 hour. The 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).

On one side of the polycarbonate resin sheet,
The coating composition (i-3) was applied with a wire bar, left at 25 ° C. for 20 minutes, and thermally cured at 120 ° C. for 30 minutes. The thickness of the first layer was 2.5 μm. Then, the coating composition (i
i-2) was applied with a wire bar, left standing at 25 ° C. for 20 minutes, and thermally cured at 120 ° C. for 1 hour. The thickness of the second layer was 5.0 μm.

As a result of the above evaluation, when the total content of free dihydric phenol and monohydric phenol was 100 ppm or less (PC-1 to PC-4) as the polycarbonate resin, the haze change after the three-point bending wet heat treatment was used. And the adhesiveness was not reduced, indicating that it was good for bending. The smaller the total content of free dihydric phenol and monohydric phenol, the better the effect was obtained. When a specific compound was added to a polycarbonate resin as a stabilizer and a specific hard coat agent was coated, light discoloration resistance was also suppressed. Table 1 shows the results.

[0153]

[Table 1]

[0154]

According to the present invention, it is possible to obtain a polycarbonate resin molded body having a higher resistance to bending and the like, and having a hard coat having good interface adhesion. Since the use of the molded article provided with the hard coat can be broadened more than before, 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 article.

[Description of Signs] 1 Strip-shaped molded product main body 2 Stainless steel bending jig 3 Fixing plate 4 Polycarbonate resin layer 5 Primer layer 6 Hard coat layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 230/08 C08F 230/08 4J100 C08G 64/40 C08G 64/40 C08K 5/524 C08K 5/524 C08L 69 / 00 C08L 69/00 C09D 5/00 C09D 5/00 Z 133/10 133/10 133/14 133/14 143/04 143/04 183/02 183/02 183/04 183/04 F-term (reference) 4F006 AA36 AB24 AB39 AB76 BA01 BA02 CA00 DA00 DA04 4F100 AA20B AA20H AH02A AH02H AK25C AK25J AK45A AK52B AK52C AL01C AL05B AL05C AL08C BA02 BA03 BA05 BA10A BA10B CA08A CA23B CC00B EJ65C JK06 JK12B JL01 YY00A YY00B YY00C 4J002 CG001 CG011 EW086 FD036 4J029 AA09 AB07 AC01 AE01 BB05A BB05B BB12A BB12B BB13A BB13B BE05A BE05B BH02 DB07 DB13 DB15 FA07 FC02 HC03 HC04A HC05A JA091 JB131 JB171 JC021 JC091 JC353 JC373 JC633 JF031 JF041 JF141 JF16 1 JF221 JF331 JF361 JF371 JF381 JF471 JF541 JF581 KB22 KE02 KE05 KE11 KH05 4J038 CG141 CH031 CJ131 CJ181 DL021 DL031 DL051 DL081 DL111 GA01 GA02 GA03 GA07 GA09 GA15 HA216 HA446 KA07 KA12 PA18 BA08 HC78 JA01

Claims (5)

[Claims] 1. A molded article made of a polycarbonate resin (component (A)) having a total content of free dihydric phenol and monohydric phenol of 100 ppm or less and having a hard coat layer on at least one surface. . 2. The polycarbonate resin contains a compound represented by the following formula (1) in an amount of 0.000% in 100% by weight of component A.
The polycarbonate resin molded article according to claim 1, comprising 1 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, and Ar ¹ , Ar ² and Ar ³ may be the same or different from each other. ) 3. A hard coat layer having a primer layer, wherein the resin component of the primer composition comprises a repeating unit represented by the following formula (2) and the following formula (3), and the molar ratio thereof is 99. 99: 0.01-50: 5
The polycarbonate resin molded product according to any one of claims 1 and 2, wherein the polycarbonate resin molded product is a copolymer. 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. A hard coat layer having a primer layer, wherein the resin component of the primer composition comprises a repeating unit represented by the above formula (2) and the following formula (4), and the molar ratio thereof is 99: 1 to 50:50 99 to 60% by weight of a copolymer 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 -S
3. The polycarbonate resin molded product according to claim 1, which is a mixture or a reaction product thereof with iO _{4- (a + b) / 2)} . 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, 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 converted to R ⁸ SiO _3/2 ), 2 to 30% by weight of a hydrolyzed condensate (z component) of a tetraalkoxysilane represented by the following formula (7):
The polycarbonate resin molded product according to any one of claims 3 and 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.)