JP2002060527A - Polycarbonate resin compostion molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition molded article laminated with hard coating layer(s) in high adhesion even if subjected to high-speed injection molding. SOLUTION: This polycarbonate resin composition molded article is such that at least one side of a molded product of a polycarbonate resin composition (A component) <=6 ppm by weight in the total volatiles of methylene chloride at 150 deg.C detected on and after T1 (T1 is the retention time of methylene chloride) is subjected to hard coating treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a molded article of a polycarbonate resin composition. More specifically, the hard coat treatment (preferably a layer provided with a hard coat layer via a primer layer) is excellent in adhesiveness, and even when high-speed injection molding is performed, the hard coat layer is kept in good adhesiveness. The present invention relates to a molded article of a polycarbonate resin composition on which is laminated.

[0002]

2. Description of the Related Art Polycarbonate resin compositions are used in a wide range of fields because of their excellent properties such as transparency and impact resistance. However, since the polycarbonate resin composition is inferior in surface hardness, a hard coat is often formed particularly in applications utilizing transparency.

On the other hand, in recent years, due to the variety of various designs,
Conventionally, in a field where a bent product of an extruded sheet has been used, an attempt has been made to manufacture such a product by injection molding. Such fields include helmets and vehicle windshields, and vehicle glazing materials.

[0004] However, such injection molded articles are usually
There is a tendency that the strain due to various remaining factors is higher than that of the extruded product. On the other hand, such distortion can cause poor adhesion to the hard coat agent, particularly in the case of the polycarbonate resin composition, and the acrylic resin as the primer layer, and can cause poor appearance of the hard coat. In addition, since the injection-molded article may be heated to a high temperature in order to crosslink the crosslinkable group at the time of the primer layer treatment, if a volatile component in a specific amount or more is contained in the polycarbonate resin composition, the injection during the treatment is performed. The specific volatile components volatilized from the surface of the molded product accumulate between the surface of the injection molded product and the acrylic resin serving as the primer layer, which may be a factor in reducing the adhesion between the molded product and the acrylic resin.

In particular, in the case of a large molded product, a molding method having a remarkably high injection speed, such as so-called ultra-high-speed injection molding, has been studied in order to ensure a uniform thermal history of the entire molded product. In such a case, the filling of the resin is extremely short, so that the resin is filled in an extremely high strain state,
Various problems with the acrylic resin, which is cooled and solidified, and is therefore a primer layer accompanying such distortion, have become more prominent. Therefore, there has been a need to improve such a problem from the viewpoint of the polycarbonate resin composition material.

[0006]

An object of the present invention is to reduce distortion during molding of a polycarbonate resin composition in an injection-molded polycarbonate resin composition which has been subjected to a had coating treatment (in particular, an acrylic resin is used as a primer layer). It is an object of the present invention to improve poor adhesion and appearance with a hadcoat treatment and particularly to an ultra-high-speed injection molded article in which distortion during molding is remarkable.

The inventor of the present invention has considered that one of the causes of the remaining distortion is as follows.
Components having a low volatility to some extent are likely to cause turbulence in flow at the time of molding, and furthermore, due to the presence of volatile components volatilizing from the polycarbonate resin composition, in the lamination with a hadcoat treatment layer (in particular, an acrylic resin is used as a primer layer). They found that defects were more likely to occur, and focused on improving such points. It has also been found that stable flow can be achieved by including a specific stabilizer. Further, such an effect becomes more remarkable as the injection speed becomes higher, and finds that the effect of the present invention is more exhibited.
It has become possible to achieve a polycarbonate resin composition molded article with reduced defects in the case of performing the hadcoat treatment (in particular, using an acrylic resin as the primer layer).

[0008]

Means for Solving the Problems The volatile components at 150 ° C. measured by the measurement method specified in the text are the total of the volatile components detected after T1 when the retention time of methylene chloride is T1. The present invention relates to a molded article of a polycarbonate resin composition obtained by subjecting at least one surface of a molded article composed of a polycarbonate resin composition (A component) having an amount of not more than 6 ppm by weight to a hard coating treatment.

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 the reaction by the 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. These may be used alone or in combination of two or more. Can be mixed and used.

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

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

In producing the polycarbonate 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 may be used. 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 which produces such a branched polycarbonate resin is contained, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably, in 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 be generated as a side reaction. The amount of such a branched structure is also 3, and 0.001 to 1 mol%, preferably 0.005 mol%, of the total amount of the aromatic polycarbonate.
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. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amine compounds such as pyridine.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as tertiary amine such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, a quaternary ammonium compound, and a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

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

[0018]

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

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

[0021]

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

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

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is 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
It is about an hour.

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

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

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
Compounds such as 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, dodecylbenzenesulfone 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, and if it exceeds 40,000, the moldability deteriorates and it becomes difficult to reduce optical distortion. 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
Those having a molecular weight of 000 to 30,000 are particularly preferred. Also, two or more polycarbonate resins may be mixed. In the present invention, the viscosity average molecular weight is 100 methylene chloride.
The specific viscosity (η _SP ) obtained from a solution of 0.7 g of a polycarbonate resin 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

In the polycarbonate resin composition used for the component A of the present invention, when the volatile component at 150 ° C. measured by the measurement method specified below is defined as T1 after the retention time of methylene chloride is T1, Is a polycarbonate resin composition in which the total amount of volatile components detected is 6 ppm or less in terms of weight. More preferably, the content is 3 ppm or less, further preferably 1 ppm or less. If the content of the volatile component exceeds 6 ppm, turbulence of the flow during molding is large, which may not be desirable for reducing distortion.

Here, as a method of measuring the volatile component,
It is based on the following conditions. That is, using a GC (gas chromatography) measuring device HP6890 manufactured by Hewlett-Packard Company, HS40XL manufactured by Perkin Elmer Co., Ltd. as an HS (head space) sampler, and CP-SIL 19CB manufactured by Chrome Pack Co., Ltd. as a column.
(Length 50m, inner diameter 0.25mm, film thickness 0.2μm),
A flame ionization detector (FID) is used as a detector. A part of the molded product was cut out to a size of about 10 mm square, and a sample adjusted so that the total weight of the sample became about 3 g was inserted into a glass sealed container, and the sample was placed in an HS sampler.
The volatile gas generated after heating at 1 ° C. for 1 hour is analyzed by GC, and the amount of volatile components per 1 g of sample (μg / g = ppm) is calculated. Here, as the GC analysis conditions, the inlet temperature was 300 ° C., the detector temperature was 300 ° C., and the oven temperature was 5 ° C.
After holding at 0 ° C. for 2 minutes, the sample is heated to 250 ° C. at a rate of 10 ° C./min and held for 10 minutes.

In order to obtain a molded article of the polycarbonate resin composition having a volatilization amount equal to or less than a specific value, it is necessary to reduce a highly volatile component contained in the polycarbonate resin which is a main resin or to volatilize a stabilizer to be compounded. And the amount of addition may be considered. Examples of a method for reducing a highly volatile component contained in the polycarbonate resin include the following methods. That is, (i) a method of extracting a polycarbonate resin with a poor solvent of acetone, methanol, heptane or the like to reduce low molecular weight components (acetone is particularly preferred as the poor solvent), (ii)
A method of forcibly injecting water into a vented extruder when pelletizing polycarbonate resin powder to remove particularly chlorine compounds, etc .; And (iv) a method of strengthening the drying treatment. In addition, it is possible to obtain a polycarbonate resin having a volatilization amount of a specific value or less by using various conventionally known methods.

The following method is also effective in reducing volatile components. That is, the organic solvent solution of the polycarbonate resin is continuously supplied to the container in which the mixture of the polycarbonate resin particles and the warm water is present under stirring.
In the method for producing a polycarbonate resin powder from an organic solvent solution of a polycarbonate resin by evaporating the solvent at the same time, the method is further performed under the following conditions.

As such conditions, the temperature in the vessel is kept within the range of T1 (° C.) or T2 (° C.), the stirring speed is 60 to 100 rpm, and the stirring capacity is 5 to 10 kw / hr · m ³ . Such a production method not only reduces volatile components such as residual chlorine compounds,
It can be preferably used because it produces a polycarbonate resin having a small amount of powder, good filterability, and excellent drying properties. That is, the obtained granules have good filterability, so that the volatile components washed at the time of filtration do not re-adsorb, and since the dryness is excellent, the volatile components contained therein can be sufficiently removed. It becomes possible. It is more preferable to combine such methods in order to sufficiently remove volatile components. 0.0018 × M1 + 37 ≦ T1 (° C.) ≦ 0.0018
× M1 + 42 (M1: viscosity average molecular weight 10,000 to 20,000
0) 0.0007 × M2 + 59 ≦ T2 (° C.) ≦ 0.0007
× M2 + 64 (M2: viscosity average molecular weight 20,000 or more)

As a method of enhancing the drying treatment, it is effective to raise the drying temperature. However, it is not preferable to set the temperature at or above the softening point of the polycarbonate resin, and drying is usually performed at 60 to 130 ° C. Further, there is a method of extending the drying time or increasing the stirring efficiency of the polycarbonate resin during drying.

Another way to enhance drying is to increase the surface area of the polycarbonate resin. A production method that satisfies the specific conditions described above is preferable, but another method specifically includes forming the polycarbonate resin into a powder shape with a small particle diameter. For this purpose, a method of strengthening the pulverization of the polycarbonate resin is used. In particular, it is preferable to grind a slurry containing an organic solvent or water after granulation, because the particles are too hard to grind a dry resin and the efficiency is low. It is also effective to use a porous powder. There is a way to do that.

Further, as a preferred embodiment of the present invention, there is provided a molded article of a polycarbonate resin composition produced under molding conditions in which the injection speed for filling the component A into a mold cavity is 300 mm / sec or more. Is done. In such a case, since the conditions are extremely high shear, the effect of the specific low volatile component content of the present invention can be more effectively exerted, and usually occurs to achieve such a high shear rate. Since distortion can be suppressed, it is possible to obtain a molded article of a polycarbonate resin composition having reduced defects in the case of performing the hadcoat treatment (in particular, using an acrylic resin as a primer layer).

In the present invention, more preferably 350 mm / sec
c or higher, particularly preferably 400 m
m / sec or more. 800mm as upper limit of speed
/ Sec or so. 300-800mm / se
In the range of c, it is possible to achieve the object of the present invention and to obtain a good molded product with little burnt generated on the molded product due to high speed. Here, the injection speed refers to an average speed from the start to the end of filling into the mold cavity, and is not necessarily required to be a constant speed, and molding at a multistage injection speed is also possible.

Here, various methods can be used as a method for setting the injection speed to 300 mm / sec. The injection horsepower is increased by a method such as increasing the capacity of the accumulator or increasing the horsepower of the motor. Basically, it is necessary to optimize the structure of the injection cylinder, the hydraulic control system, the motor control system, and the like in order to achieve control and response of the screw speed and position at extremely high speed and short time. As such a system, various currently known methods can be used.

The power source may be a system using a hydraulic pump or a system using an electric motor (including a linear motor), but a system using a hydraulic pump is more preferable for large molded products. In addition, the injection device
Even if it is an in-line system by advancing a general plasticizing screw, any of a so-called pre-plastic system in which a plasticizing screw and a plunger for filling are separated can be used.

On the other hand, on the surface of the mold, a groove having a sufficient gas release for forming a smooth gas release in the mold, a porous sintered metal, a vacuum pump through a vent hole, etc. A pressure-reducing device is preferably used.

Furthermore, in the present invention, in order to meet the above molding conditions at a specific injection speed or more, the stabilizer represented by the following general formula (1) is added to the polycarbonate resin composition of the component A in an amount of 0% by weight in 100% by weight of the component A. It is preferably contained at 0.0001 to 0.5% by weight. More preferably 0.0
05 to 0.3% by weight, particularly preferably 0.01 to 0.2% by weight.
% By weight.

[0046]

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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 are all the same, two are the same,
Alternatively, any of the three different cases can be selected. )

Since the stabilizer represented by the general formula (1) has an excellent stabilizing effect on thermal oxidation, it can stabilize the polycarbonate resin composition against shear heat at a high injection speed, and It has the advantage that it has excellent resistance to environmental degradation, which is the object of the present invention, because of its excellent heat and moisture resistance. Further, even when another phosphorus-based heat stabilizer is contained, it is preferable that the other phosphorus-based heat stabilizer is contained without inducing hydrolysis or the like. Specific examples of such a stabilizer include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, and tris (di-n-butylphenyl) phosphite. (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-t
tert-butylphenyl) phosphite;
Tris (dialkyl-substituted phenyl) phosphite is preferred, tris (di-tert-butylphenyl) phosphite is more preferred, and tris (2,4-di-tert)
-Butylphenyl) phosphite is particularly preferred.

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

Examples of the resin forming the primer layer include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, 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 coating agent of the present invention includes a light stabilizer and an ultraviolet absorber described later, a catalyst for the silicone resin hard coating agent, a heat / photopolymerization initiator, Inhibitors, silicone defoamers,
It may contain a leveling agent, a thickener, an anti-settling agent, an anti-dripping agent, a flame retardant, various additives of organic / inorganic pigment / dye, and an auxiliary additive.

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

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

[0054]

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

In the present invention, the acrylic resin used as the primer layer of the silicone resin-based hard coating agent is 0.0
It is desirable to contain a monomer having a reactive group with 1 to 50 mol% of the alkoxysilane compound. Examples of such a vinyl monomer having a crosslinkable 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 the primer layer 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 molar ratio of the repeating unit represented by the formula (2) to the repeating unit represented by the following formula (3) is 99.9.
9: 0.01 to 50:50, preferably 9
9: 1 to 60:40, more preferably 9:60.
An acrylic resin in the range of 7: 3 to 70:30 is employed.

[0060]

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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 is at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight of the resin forming the primer layer, and typically, the resin forming the primer layer substantially contains the resin. Desirably, it is an acrylic resin.

Such an 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 ratio. Specific examples of such an acrylate or methacrylate monomer having an alkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyl. Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and the like, and 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyl. Dimethoxysilane is preferred, and 3-methacryloxypropyltrimethoxysilane is particularly preferred.

One preferred embodiment of the acrylic resin used as the primer layer of the silicone resin-based hard coating agent in the present invention is a copolymer comprising a repeating unit represented by 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 99: 1 to 5:
Acrylic resin having a ratio of 0:50 (hereinafter sometimes referred to as “hydroxy group-containing acrylic resin”) of 99 to 60% by weight and a hydrolyzed condensate of a compound represented by the following formula (5) of 1 to 40% by weight ( However mixture or reaction product of ^{_{R 5 a R 6 b SiO 4-}} (a + b) / 2 weight in terms of) can also be mentioned.

[0064]

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

[0066]

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

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. 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 formula (5) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. , Tetraisobutoxysilane, silanes such as tetraacetosilane, methyltrimethoxysilane,
Methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyl Trimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercapto B pills trimethoxysilane, gamma
-Mercaptopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane , Chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β Glycidoxyethyltrimethoxysilane, β
-Glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane,
γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-
Glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ- Glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-
Glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-
Epoxycyclohexyl) methyltriethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β-
(3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3
4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-
Trialkoxy, triacyloxy or triphenoxysilanes such as (epoxycyclohexyl) butyltriethoxysilane or hydrolysates thereof, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloro Propylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethyldimethoxysilane, γ-mercapto Propyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, vinylmethyldimethoxy Silane, vinylmethyldiethoxysilane, glycidoxymethyldimethoxysilane,
Glycidoxymethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α -Glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypro Pilmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ- Examples thereof include alkoxysilanes or diacyloxysilanes such as glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, and γ-glycidoxypropylphenyldiethoxysilane, and hydrolysates thereof. These organic siloxanes can be used alone or in combination of two or more.

More preferably, R ⁵ and R ⁶ in the above formula (5) 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
It is an alkyl group having 1 to 3 carbon atoms substituted with the above groups, and R ⁷ is a case of an alkyl group having 1 to 4 carbon atoms. Specifically, for example, tetramethoxysilane, tetraethoxysilane, tetra- n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, 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, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ-
Methacryloxypropylmethyldimethoxysilane, γ-
Glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane and the like can be mentioned, among which alkyltrialkoxysilane is preferable, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferable. These can be used alone or in combination.

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

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

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

The preferable mixing ratio of the melamine resin is 1 to 100 parts by weight of a mixture or a reaction product of a hydrolysis-condensation product of an alkoxysilane and an 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 the primer layer of the silicone resin-based hard coat agent of the present invention, in the case of the acrylic resin (b), the molecular weight of the acrylic resin is determined by GPC (gel permeation chromatography). )), The weight average molecular weight is preferably 20,000 or more, more preferably 50,000 or more, and the weight average molecular weight is preferably 10,000,000 or less, as measured on the basis of a calibration curve calculated with monodisperse standard polystyrene. used. The acrylic resin having such a molecular weight range is preferable because performance such as adhesion and strength as a primer layer is sufficiently exhibited.

In the method of forming the primer layer in the present invention, in the case of the acrylic resin (a), the 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 layer composition, apply the primer layer composition, then polymerize the monomer component by ultraviolet light or heat, and remove the solvent to obtain a primer. Form a layer.

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

Further, if necessary, it is preferable to heat the mixture to 40 to 140 ° C. after the removal of the solvent to crosslink the crosslinkable group.

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

The solvents used above include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran,
Ethers such as 1,4-dioxane and 1,2-dimethoxyethane, esters such as ethyl acetate and ethoxyethyl acetate, methanol, ethanol, 1-propanol, 2
-Propanol, 1-butanol, 2-butanol, 2
Alcohols such as -methyl-1-propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, gas oil, Hydrocarbons such as kerosene, acetonitrile,
Examples thereof include nitromethane and water, which may be used alone or as a mixture of two or more. The concentration of the solid content of the primer layer composition in the primer layer composition is preferably 1 to 50% by weight, and 3 to 3% by weight.
0% by weight is more preferred.

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

Examples of the resin forming the primer layer include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, 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 for the silicone resin hard coat agent, a heat / photopolymerization initiator, Inhibitors, silicone defoamers,
It may contain a leveling agent, a thickener, an anti-settling agent, an anti-dripping agent, a flame retardant, various additives of organic / inorganic pigment / dye, and an auxiliary additive.

In the present invention, the acrylic resin forming the primer layer of the silicone resin-based hard coat agent can be obtained by applying (a) a primer composition mainly composed of a monomer component to the surface of a molded body and then heating or applying ultraviolet rays. 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 is further improved, and the effect in the present invention is large.

[0086]

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(Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms.) The acrylic resin is copolymerizable 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 from the viewpoint of durability such as adhesion and weather resistance. Specifically, acrylic acid, methacrylic acid, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl (meth) acrylate,
-Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2
-Ethoxyethyl) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, trimethoxysilyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, glycidyl (meth) Acrylate, 3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropyltriethoxysilane, 3-
Examples thereof include (meth) acrylates such as methacryloxypropylmethyldimethoxysilane, N-vinylpyrrolidone, N-vinylcaprolactam, styrene, and acrylonitrile, and these can be used alone or as a mixture of two or more. Further, a mixture of two or more acrylic resins may be used.

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

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 reactive group include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, Methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and the like can be mentioned.

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

[0092]

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

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

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

[0097]

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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)

[0099]

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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.

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

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

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

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

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

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

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

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

In the acrylic resin used as a primer of the silicone resin-based hard 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 performance such as adhesion and strength as a primer layer is sufficiently exhibited.

In the method of forming a primer layer in the present invention, in the case of the acrylic resin (a), the 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.

Further, if necessary, it is preferable to heat the mixture to 40 to 140 ° C. after the removal of the solvent to crosslink the crosslinkable group.

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

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

Further, the above 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 dibutyldithiocarbamate; Complexes. These agents may be used alone or in combination of two or more, and preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the resin forming the primer layer. .

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

Further, the primer composition may contain a catalyst capable of curing the silicone resin-based hard coat agent, whereby the effect of various functional agents such as a resin and a stabilizer contained in the primer layer can 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 ; Any compound or mixture selected from the group consisting of Lewis acids such as TiCl ₄ and ZnCl ₄ can be mentioned.

The above primer composition is applied to a polycarbonate resin molded body 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.

The thickness of such a primer layer is a film thickness necessary for sufficiently bonding the polycarbonate resin molded body and the silicon resin-based hard coat layer and maintaining a necessary amount of the additive. Good, preferably dry, 0.
It is 1 to 10 μm, 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 ones as described above can be used. . More preferably, an organosiloxane resin comprising a hydrolysis condensate of a trialkoxysilane compound and a hydrolysis condensate of a tetraalkoxysilane compound can be exemplified.

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

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

Specific examples of other metal oxide fine particles include a metal oxide sol 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, Optolake 1130F-2 (A-8) manufactured by Catalyst Chemical Industry Co., Ltd.
As a composite metal oxide sol composed of O ₂ —CeO ₂ —SiO _2, Optolake 1130A-2 (A-
8) As the composite metal oxide sol composed of SnO ₂ -WO ₃ , a metal colloid sol composed of Nissan Chemical Co., Ltd.'s Sun Colloid HIS-30M, which is a sol dispersed in methanol, having a solid content of 30%, and Al ₂ O ₃ Examples thereof include alumina sol-200 manufactured by Nissan Chemical Co., Ltd., which is an aqueous dispersion sol having a solid content of 10%.

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

[0127]

Embedded image

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

[0129]

Embedded image

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

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

In order to obtain a hard coat composition which forms a hard coat layer having particularly excellent abrasion resistance, it is preferable that 70% by weight or more is methyltrialkoxysilane, and substantially the entirety 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): A 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 the aqueous dispersion type colloidal silica dispersion when it 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 carried out under acidic conditions, and an acid is generally used as a hydrolyzing agent in order to carry out hydrolysis under such conditions. Such an acid may be added in advance to the trialkoxysilane or colloidal silica dispersion, or may be added after mixing both. Further, the addition can be divided into one time or two or more times. Such acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, inorganic acids such as sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid,
Oxalic acid, succinic acid, maleic acid, lactic acid, organic acids such as paratoluenesulfonic acid, and the like, formic acid, acetic acid, propionic acid, butyric acid,
Organic carboxylic acids such as oxalic acid, succinic acid and maleic acid are preferred, and acetic acid is particularly preferred.

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

The conditions for the hydrolysis and condensation of the trialkoxysilane can 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 above formula (7) is added to the reaction solution obtained by the reaction of the process (1) to cause a hydrolysis condensation reaction, or (ii) the process (1) ) Is mixed with a reaction solution obtained by previously subjecting the tetraalkoxysilane of the formula (7) to a hydrolytic condensation reaction.

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

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

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

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

The mixing ratio of the components x, y, and z, which are the solid components of the organosiloxane resin, depends on the stability of the hard coat composition solution, the transparency of the cured film obtained, 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 for the above-mentioned silicone resin-based hard coat layer usually further contains a curing catalyst. Examples of such a catalyst include lithium salts of aliphatic carboxylic acids such as formic acid, propionic acid, butyric acid, lactic acid, tartaric acid, and succinic acid, alkali metal salts such as sodium salt and potassium salt, benzyltrimethylammonium salt, tetramethylammonium salt, and tetraethylammonium salt. Examples thereof include quaternary ammonium salts such as ammonium salts, and sodium acetate, potassium acetate and benzyltrimethylammonium acetate are preferably used. When using a basic aqueous dispersion type 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. Such alcohols include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol,
-Methyl-2-pentanol, 2-butoxyethanol, etc. are preferable, and a low-boiling alcohol having 1 to 4 carbon atoms is preferable, and 2-propanol is particularly preferable in terms of solubility, stability, and coating properties. In the solvent, water that does not participate in the hydrolysis reaction with water in water-dispersed colloidal silica, lower alcohol generated by the hydrolysis of alkoxysilane, when organic solvent-dispersed colloidal silica is used, Organic solvent of dispersion medium, pH of hard coat composition
Acids added for control are also included. Examples of acids used for pH adjustment include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid. Organic acids such as acid, lactic acid, and paratoluenesulfonic acid are exemplified, and organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are preferable from the viewpoint of easy control of pH. Other solvents must be miscible with water / alcohol, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and acetic acid. Esters such as ethyl and ethoxyethyl acetate are exemplified. The solvent is preferably used in an amount of 50 to 900 parts by weight, more preferably 150 to 70 parts by weight, based on 100 parts by weight of the solid content of the organosiloxane resin composed of the x, y and z components.
0 parts by weight.

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

The hard coat composition is coated on 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 in a dry state. When the thickness of the coat layer is within the above range, cracks are generated in the coat layer due to stress generated during thermosetting, and the adhesion between the coat layer and the base material is not reduced, and the present invention The intended coat layer having sufficient wear resistance can be obtained.

Further, a known leveling agent can be added to 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 may be a resin or oil as a main component, and may be a natural resin such as rosin, gilsonite, shellac or copearl, or 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. Particularly, when printing is performed on the surface of the first layer or the second layer on the interface side with the third layer, an ink component having high heat resistance is required. In such a case, a resin such as a polycarbonate resin or an amorphous resin is used. Preferable examples include polyarylate resins. In addition, a desired color can be adjusted by using a pigment or a dye in the printing ink.

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

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

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

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

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

To the resin of the present invention, an antioxidant generally known can be added for the purpose of preventing oxidation. Examples thereof include phenolic antioxidants, and specifically, for example, vitamin E, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-ter
t-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-
6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert)
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-cyclohexylphenol), 2,2′-
Dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-
tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t
tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-
Hexanediol bis [3- (3,5-di-tert-
Butyl-4-hydroxyphenyl) propionate, bis [2-tert-butyl-4-methyl 6- (3-te
rt-butyl-5-methyl-2-hydroxybenzyl)
Phenyl] terephthalate, 3,9-bis {2- [3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4 -Thiobis (6-ter
t-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol),
2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6- Di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-ter
t-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-te
rt-butylanilino) -1,3,5-triazine,
N, N'-hexamethylenebis- (3,5-di-ter
t-butyl-4-hydroxyhydrocinnamide), N,
N'-bis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyl] hydrazine,
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-ter
t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-
Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate; tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane; The composition ratio of these antioxidants is 0.0001 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 the light stabilizer is 0.00 0.00 parts by weight of the polycarbonate resin.
01 to 10 parts by weight, preferably 0.001 to 5 parts by weight Also, in the polycarbonate resin composition of the present invention,
In particular, in the case of having transparency, a bluing agent can be blended in order to cancel the yellow color due to an ultraviolet absorber or the like. As the bluing agent, any one can be used without any particular difficulty as long as it is used in a polycarbonate resin composition. Generally, anthraquinone dyes are easily available and preferred. As a specific bluing agent, for example, a common name Solvent Violet 13
[CA. No (color index No) 60725;
Trade name "Macrolex Violet B" manufactured by Bayer, "Diaresin Blue G" manufactured by Mitsubishi Chemical Corporation, "Sumiplast Violet B" manufactured by Sumitomo Chemical Co., Ltd.], generic name Solvent Violet 31 [C
A. No. 68210; Trade name "Diaresin Violet D" manufactured by Mitsubishi Chemical Corporation], generic name Solvent
Violet 33 [CA. No. 60725; Trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name S
solvent Blue 94 [CA. No 61500;
Trade name: Mitsubishi Chemical Corporation "Diaresin Blue N"], Generic name: Solvent Violet 36 [C
A. No. 68210; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Solvent
Blue97 [trade name “Macrolex Blue RR” manufactured by Bayer AG] and generic name Solvent Blue
45 [CA. No. 61110; Trade name “Tetrazol Blue RLS” manufactured by Sando Co., Ltd.], Ciba Specialty
Examples include Macrolex Violet and Triazole Blue RLS from Chemicals, and particularly preferred are Macrolex Violet and Triazole Blue RLS.

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

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

[0168]

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) Adhesion The molded body shown in FIG. 2 was placed in a pressure cooker (TPC-411 manufactured by Espec Corporation), and the temperature was 65 ° C. and the pressure was 0.1 mm.
After performing the treatment for 1,000 hours under the conditions of 2 MPa and a humidity of 85% RH, 100 cross-cuts (1 mm ² ) are formed on the coating film, and a cellophane tape is adhered to the cross-cut portion, and then the adhered cellophane tape is adhered. At a right angle and sharply. 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)

(2) Distortion of Molded Product The plate-shaped molded product before the hard coat treatment was sandwiched between two orthogonal polarizing plates, and the distortion was visually observed. The evaluation was made based on the color change of the striped pattern and uneven density. ：: No large optical distortion is observed. ×: Large optical distortion is observed.

[Examples 1 to 4, Comparative Example 1] A cylinder capable of achieving an injection speed of 800 mm / sec after drying a polycarbonate resin composition shown in Table 1 at 120 ° C. for 5 hours using a hot air drier. Ultra high-speed injection molding machine equipped with an injection device with an inner diameter of 45 mmφ (SG manufactured by Sumitomo Heavy Industries, Ltd.)
260M-HP), and was molded.

The molding conditions were as follows: the cylinder temperature was 300 ° C., the back pressure was 19.6 MPa, and the injection speed was 350 mm / sec (first speed) at a constant injection speed. Such a molded product is a plate-shaped molded product having a length of 149 mm, a width of 152 mm and a thickness of 2 mm, and has a film-shaped gate (gate portion having a thickness of 1.0 mm). The mold temperature was kept at 130 ° C. using a mold temperature controller. One of the surfaces of the obtained molded product was subjected to various silicon hard coat treatments (HC-1 to HC-3) shown below, and the above-mentioned evaluation was performed. Table 1 shows combinations of the polycarbonate resin composition and the hard coat agent. Table 1 shows the evaluation results.

The symbols indicating the components shown in Table 1 are as follows. Polycarbonate resin composition (i) PC-1 Organic solvent supply port, hot water supply port of polycarbonate resin,
A stirrer having a ribbon-shaped shape as a stirring blade was mounted on a biaxial container of a 500 L effective internal volume horizontal-shaft rotary mixer equipped with a steam inlet, an exhaust port for a vaporized organic solvent, and an overflow outlet. 7 mm average particle size
50 g of polycarbonate resin powder and water 250
g, while stirring at a stirring speed of 80 rpm, when the temperature in the container reached 77 ° C., the average molecular weight was 2
A methylene chloride solution having a concentration of 16% by weight of polycarbonate resin of 4,700 was supplied at a rate of 10 kg / min, and hot water was supplied at a rate of 10 kg / min. During the supply, the amount of hot water in the container / polycarbonate resin powder (volume ratio) is maintained at about 5, and the temperature in the container is set at a pressure of 2.7 k.
The temperature was maintained at 77 ° C. by heating the steam inlet and the jacket using steam of g / cm ² . The stirring capacity is 6k
w / hr · m ³ . After the start of the supply, the level of the slurry in the container was increased, and the generated polycarbonate resin particles and hot water were discharged from a discharge port provided in an upper portion of the container. At this time, the residence time of the polycarbonate resin particles was 1 hour.

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

After drying the powder, powder 99.
78 parts by weight, 0.02 parts by weight of Irgafos 168 (manufactured by Nippon Ciba Geigy Co., Ltd.) and 0.2 parts by weight of pentaerythritol tetrastearate are blended, and a twin-screw extruder provided with a hydrogenation point and a vent immediately after the hydrogenation point While adding 1% by weight of ion-exchanged water to 100% by weight of the polycarbonate resin powder at 1330 Pa from the vent port.
The resin was pelletized at 280 ° C. by suction at a reduced pressure. The pellet was molded under the above-mentioned molding conditions to obtain a molded product. The polycarbonate resin composition obtained as a molded product had a viscosity average molecular weight of 24,700, and the amount of the low volatile component contained in the polycarbonate resin composition molded product was 1.3 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 viscosity average molecular weight of the polycarbonate resin composition obtained as a molded product was 24,600, and the amount of the low volatile component contained in the polycarbonate resin composition molded product was 5.
It was 8 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, pentaerythritol tetrastearate was added to 99.8 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 substance outlet in a bearing portion. 0.2 parts by weight of 280
The mixture was pelletized by a twin-screw extruder at ℃ to obtain a molded product under the above molding conditions. The polycarbonate resin composition obtained as a molded article had a viscosity average molecular weight of 24,500, and the amount of low volatile components contained in the molded article of the polycarbonate resin composition was 12.1 ppm.

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

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

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

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

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

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

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

The coating composition (i-2) was applied to one surface of a plate-shaped molded product made of a polycarbonate resin composition with a wire bar, allowed to stand 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 (dry). Next, the coating composition (ii-2) was applied on the surface of the coating of the plate-like molded product using a wire bar, allowed to stand at 25 ° C for 20 minutes, and then thermally cured at 120 ° C for 1 hour. The thickness of the second layer was 5.0 μm (dry).

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

The coating composition (i-3) was applied to one surface of a plate-shaped molded product made of a polycarbonate resin composition with a wire bar, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 30 minutes. . The thickness of the first layer was 2.5 μm (dry). Next, the coating composition (ii-2) was applied on the surface of the coating of the plate-like molded product using a wire bar, allowed to stand at 25 ° C for 20 minutes, and then thermally cured at 120 ° C for 1 hour. The thickness of the second layer was 5.0 μm (dry).

As a result of the above evaluation, the content of low volatile components in the polycarbonate resin composition was 6 ppm or less (PC-
In the case of using 1-PC-2), it was found that the molding distortion was good even in the ultra-high speed molding, and the smaller the content of the low volatile component, the better the effect was obtained. When a specific compound was added as a stabilizer to a polycarbonate resin and a specific hard coat agent was coated, a decrease in adhesion after promotion of wet heat was suppressed. Table 1 shows the results.

[0189]

[Table 1]

[0190]

According to the present invention, it is possible to obtain a molded article of a polycarbonate resin composition provided with a hard coat which has a small molding distortion even in ultra-high-speed molding, has high resistance, and has good adhesion at an interface. This makes it possible to use a molded article obtained by applying a hard coat to a polycarbonate resin composition more widely than in the past, so that the industrial effect achieved is extremely large.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a plate-like molded product.

FIG. 2 is a schematic diagram showing a layer configuration of a plate-like molded body.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Plate-shaped molded product main body 2 Plate-shaped molded object 3 Gate 4 Sprue 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 220/18 C08F 220/18 4J029 220/26 220/26 4J035 230/08 230/08 4J038 C08G 64/40 C08G 64/40 4J100 77/04 77/04 C08J 5/00 C08J 5/00 C08K 5/524 C08K 5/524 C08L 69/00 C08L 69/00 // C09D 5/00 C09D 5/00 Z 133/04 133 / 04 183/02 183/02 183/04 183/04 183/07 183/07 B29K 69:00 B29K 69:00 F term (reference) 4F006 AA36 AA56 AB24 AB32 AB34 AB35 AB36 AB37 AB39 AB43 BA02 CA00 CA04 DA04 EA01 EA03 4F071 AA50 AC15 AE05 AH11 AH19 BA01 BB05 BB12 4F100 AA20D AA20E AH02A AH02H AK25D AK25E AK45A AK52D AK52E AL05A AS00B AS00C BA02 BA03 BA04 BA05 BA06 BA07 BA10B BA10E BA10E46E10E C EH462 EJ08 EJ082 GB33 GB76 JK12B JK12C JL11 JM01D JM01E YY00A YY00D YY00E 4F206 AA28 JA07 JL02 JN11 4J002 CG011 CG021 EW066 FA040 FD010 FD040 FD050 FD060 FD070 FD090 FD160 GF00 GN00 GT00 4J029 AA10 AB05 AB07 AC01 AD01 AD10 AE01 BB04A BB05A BB10A BB12A BB12B BB12C BB13A BB13B BB13C BD09A BD09B BD09C BE05A BE07 BF14A BG08X BH02 DB07 DB11 DB13 FA07 FC32 FC33 FC35 FC36 HA01 HC01 HC02 HC04A HC05A JA091 JB131 JB171 JC031 JC091 JC231 JC631 JC711 JC731 JCF1FJFJFJFJFJF131F KE11 KH03 KH05 KH06 KH08 4J035 BA15 CA01K CA01U CA11K CA11U CA112 CA14K CA14U CA142 CA19K CA19U CA192 EA01 EB03 LB02 4J038 CG141 DA161 DA231 DD001 DG001 DG031 DG211 DL021 DL031 AL12 PA03 AL01 PA03

Claims (6)

[Claims] When the retention time of methylene chloride at 150 ° C. measured by the measurement method specified in the text is defined as T1, the total amount of volatile components detected after T1 is expressed in terms of weight. A molded article of a polycarbonate resin composition obtained by subjecting at least one surface of a molded article composed of the polycarbonate resin composition (component A) to a hard coat treatment of 6 ppm or less. 2. The polycarbonate resin composition contains a compound represented by the following formula (1) in an amount of 0.000% in 100% by weight of the component A.
The molded article of the polycarbonate resin composition 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, wherein Ar ¹ , Ar ² and Ar ³ are all the same, two are the same, or all three are different. ) 3. The hard coat layer has a primer layer, and the primer layer contains at least 50 mol% of a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3): The molar ratio of the repeating units represented by the following formulas (2) and (3) is 99.99:
The polycarbonate resin molded product according to claim 1, which is an acrylic resin of 0.01 to 50:50. Embedded image (Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms.) (Where X is a hydrogen atom or a methyl group;
² is an alkylene group having 2 to 5 carbon atoms, R ³ is C 1 -C
And n is an integer of 0 or 1. ) 4. The hard coat layer has a primer layer, and the primer layer contains at least 50 mol% of a repeating unit represented by the above formula (2) and a repeating unit represented by the following formula (4): The molar ratio of the repeating unit represented by the above formula (2) and the following formula (4) is 99: 1 to 5
99 to 60% by weight of a 0:50 acrylic resin and 1 to 40% by weight of a hydrolytic condensate of a compound represented by the following formula (5) (provided that R ⁵ _a R ⁶ _b SiO _{4- (a + b) / 2} The polycarbonate resin molded article according to claim 1, wherein the mixture is a mixture or a reaction product with the polycarbonate resin molded body. Embedded image (Where Y is a hydrogen atom or a methyl group;
⁴ is an alkylene group having 2 to 5 carbon atoms. ) (Wherein, R ⁵ and R ⁶ are the same or different from each other;
An alkyl group having 10 or less carbon atoms, an alkenyl group, an aryl group, or a hydrocarbon atom having a halogen atom, an epoxy group, an amino group, a mercapto group, a methacryloxy group, or a cyano group, and R ⁷ is an alkyl group having 1 to 8 carbon atoms. , An aryl group, an alkoxyalkyl group, or an acyl group, wherein a and b are 0, 1 or 2, and a + b is 0, 1
Or 2. ) 5. The hard coat layer as the upper layer of the primer is composed of 5 to 45% by weight of colloidal silica (x component) and 50 to 80% by weight of a hydrolyzed condensate of a trialkoxysilane represented by the following formula (6) (y component). (Weight in terms of R ³ SiO _3/2 ), 2 to 30% by weight of a hydrolyzed condensate (z component) of a tetraalkoxysilane represented by the following formula (7):
The polycarbonate resin molded article according to claim 3 or 4, which is a layer obtained by curing an organosiloxane resin composed of (weight in terms of SiO ₂ ). Embedded image (Wherein R ⁸ is substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, vinyl groups, methacryloxy groups, amino groups, glycidoxy groups, and 3,4-epoxycyclohexyl groups) R ⁹ is an alkyl group having 1 to 4 carbon atoms, and R ⁹ is an alkyl group having 1 to 4 carbon atoms.) (However, in the formula, R ¹⁰ is an alkyl group having 1 to 4 carbon atoms.) 6. A molded article of the polycarbonate resin composition according to claim 1, wherein the molded article of the polycarbonate resin composition is injection-molded at an injection speed of 300 mm / sec or more.