JP2001353832A - Polycarbonate resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin laminate reduced in the generation of stain, and excellent in strength and resistance to environmental deterioration even when the laminate is molded by inset molding. SOLUTION: The polycarbonate resin laminate consists of a layer (A-layer) comprising a polycarbonate resin (A-component) which contains a component, of which the mol.wt. measured in terms of monodisperse standard polystyrene by a GPC (gel permeation chromatography) method is 3,000 or less, in an amount of 0.5-2.8% as an area ratio in a GPC chart wherein a logarithm of a mol.wt. is plotted on the transverse and of which the weight average mol.wt. is 30,000-60,000 and the layer (B-layer) laminated to the A-layer and comprising a polycarbonate resin (B-component) of which the weight average mol.wt. measured by GPC is 50,000-80,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin laminate. More specifically, the present invention relates to a laminate of a polycarbonate resin having a specific molecular weight component and a molecular weight distribution, which is a laminate obtained by laminating polycarbonate resins having low distortion and sufficient strength, and having excellent long-term properties such as wet heat resistance. Things.

[0002]

2. Description of the Related Art Polycarbonate resins are used in a wide variety of fields because of their excellent properties such as transparency and impact resistance. For example, they are used for optical information media, optical lenses, and glazing materials for buildings and vehicles. Can be mentioned.

On the other hand, in recent years, the design of a product has been regarded as one of the factors of commercial value more than ever, and as one of means for responding to such a demand, a sheet or a film, or a secondary processing thereof. Insert molding is performed in which a resin is filled into a mold cavity into which a molded product inserted is inserted. However, in the case of such insert molding, since there are many unstable elements at the time of filling with resin, especially in applications having transparency, a sufficient product may not be obtained with respect to residual strain after molding. There are many at present. One of the techniques from the material side for reducing such distortion is a method of reducing the molecular weight of the polycarbonate resin, but this is not a sufficient solution because the strength of the entire product is impaired.

[0004] That is, there is a demand for a polycarbonate resin laminate having little distortion generated in a product and excellent in strength and resistance to environmental degradation.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin laminate excellent in strength and environmental resistance even when a laminate is formed by a method such as insert molding. Is to provide the body. The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a laminate in which a polycarbonate resin having a specific molecular weight and its distribution can be solved can solve the above-mentioned problems, and have reached the present invention.

[0006]

According to the present invention, components having a molecular weight of 3,000 or less as measured by the GPC (gel permeation chromatography) method defined in the text have the logarithm of the molecular weight on the horizontal axis. A layer (A layer) made of a polycarbonate resin (A component) having an area ratio of 0.5 to 2.8% in a GPC chart and a weight average molecular weight of 33,000 to 60,000, and the A layer The present invention relates to a polycarbonate resin laminate comprising a layer (B layer) composed of a polycarbonate resin (component B) having a weight average molecular weight of 50,000 to 80,000 as measured by GPC laminated on the laminate.

[0007] The polycarbonate resin of the present invention is generally prepared by interfacial polycondensation of a dihydric phenol and a carbonate precursor,
In addition to those obtained by a reaction by a melt transesterification method, those obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method or those obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.

[0008] Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) phenyl}
Propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis} (4-
(Hydroxy-3-phenyl) phenyl} propane, 2,
2-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxyphenyl) -3-methylbutane,
2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α′-bis (4- Hydroxyphenyl) -o-
Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α
α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester and the like, and these may be used alone or in combination of two or more. Can be mixed and used.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. Particularly, a homopolymer of bisphenol A, and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl ｝ Propane and α, α'-
A copolymer with at least one selected from bis (4-hydroxyphenyl) -m-diisopropylbenzene is 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 are required. An inhibitor or the like may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

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

When a polyfunctional compound producing such a branched polycarbonate resin is contained, the proportion is preferably from 0.001 to 1 mol%, more preferably from 0.005 to 0.5 mol%, particularly preferably from the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may be generated as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

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

In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (2) can be shown.

[0016]

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

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among them, phenols having a long-chain alkyl group represented by the following general formulas (3) and (4) as a substituent are preferably used.

[0019]

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[0020]

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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 (3), those having n of 10 to 30, especially 10 to 26 are preferred. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (4), compounds wherein X is -R-CO-O- and R is a single bond are suitable, and n is 10-30, especially 10-26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Further, the terminal stoppers may be used alone or in combination of two or more.

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

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

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

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

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

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

The polycarbonate resin used for the component A of the present invention has a molecular weight of 3, as measured by the following GPC (gel permeation chromatography) method.
GP with the components below 000 taking the logarithm of the molecular weight on the horizontal axis
0.5 to 2.8% in area ratio in the C chart;
It is a polycarbonate resin having a weight average molecular weight of 33,000 to 60,000. More preferably, the area ratio is 0.5 to 2%, still more preferably 0.5 to 1%, and the weight average molecular weight is preferably 45,000 to 5%.
5,000, more preferably 48,000 to 52,000
0.

The GPC measurement method is based on the following conditions. That is, using a GPC measuring device placed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, MIXED-C (length 300 mm, inner diameter 7.5 mm) manufactured by Polymer Laboratories as a column,
Using chloroform as a mobile phase, Easycal PS-2 manufactured by Polymer Laboratories as a standard substance, and a differential refractometer as a detector, using chloroform as a developing solvent, 1 mg per 1 ml of the chloroform
100 μl of the solution obtained by dissolving the sample
After injection, GPC measurement is performed under the conditions of a column temperature of 35 ° C. and a flow rate of 1 ml / min. Based on the obtained data, a base line is determined by connecting the rising point and the convergence point of the chart. From this, the weight average molecular weight of the polycarbonate resin used for the component A and the area ratio of the component having a molecular weight of 3,000 or less are determined. calculate.

0.5% of components having a molecular weight of 3,000 or less
If it is less than 30%, a sufficient effect on lowering the distortion is not recognized. If it exceeds 2.8%, it is not preferable in terms of strength and environmental degradation resistance. The weight average molecular weight is 33,00.
If it is less than 0, it is not preferable in terms of strength and environmental degradation resistance, and if it exceeds 60,000, it may not be desirable for low distortion.

In order to produce the component A of the present invention, it is essential to suppress the generation of a component having a low degree of polymerization. For this purpose, it is important to achieve homogeneous polymerization conditions.
Increasing the polymerization rate is also effective. Therefore, in the interfacial polycondensation, a method using an amine catalyst or the like can be more preferably selected.

As a method for achieving homogeneous polymerization conditions,
In the case of interfacial polycondensation, use of a stirrer capable of strong stirring such as a homomixer is used. In order to increase the polymerization rate, a method of raising the polymerization temperature or the like to such an extent that depolymerization does not occur may be mentioned. In order to obtain a uniform and fine dispersion phase, a method of passing the dispersion through a porous material such as a glass porous filter may be used in addition to the vigorous stirring using the homomixer.
Further, a method in which polymerization is carried out in a static state by an interfacial polycondensation method, and only a portion close to the interface is extracted, may be mentioned.

On the other hand, there is also a method of obtaining the component A of the present invention by a method of removing low molecular weight components from the obtained polycarbonate resin without particular consideration of polymerization conditions. Specific examples of such a method include non-solvent precipitation and non-solvent extraction. In such a case, the separation efficiency can be improved by using the separation based on the solubility and the separation using a porous filter in combination.

Here, as a method for precipitating the polycarbonate resin in a non-solvent, a methylene chloride solution containing about 5 to 30% by weight of the polycarbonate resin is added to about 1 to 30% by weight.
/ 2 to 20 times the volume of an aliphatic hydrocarbon, an aliphatic alcohol, an aliphatic ketone, an aliphatic ester, an aliphatic ether, or the like, is added, and the polymer precipitate formed is filtered.

On the other hand, in the non-solvent extraction, the solid polycarbonate resin is obtained by adding about 2 to 20 times the volume of aromatic hydrocarbon, aliphatic hydrocarbon, chlorinated aliphatic hydrocarbon, aliphatic ketone, these non-solvent and methylene chloride. It is extracted using a mixture of the above.

Incidentally, such a non-solvent precipitation or non-solvent extraction method may be a method of extracting a polycarbonate resin satisfying the condition of the component A from a polycarbonate resin having a low molecular weight component but a small molecular weight.

On the other hand, the polycarbonate resin used as the component B of the present invention is a polycarbonate resin having a weight average molecular weight of 50,000 to 80,000 measured by the above-specified GPC method. By adjusting various reaction conditions, the target weight average molecular weight can be appropriately achieved. More preferably, it is a polycarbonate resin having a weight average molecular weight of 50,000 to 65,000.

If the number-average molecular weight of the B component is less than 50,000, the strength and environmental degradation resistance of the entire laminate will not be sufficient. Low distortion tends to be difficult.

According to the present invention, there is provided a polycarbonate resin laminate obtained by laminating the layer A composed of the component A and the layer B composed of the component B.
Provided is a polycarbonate resin laminate in which the thickness of the layer B is smaller than the thickness of the layer A and the total thickness of the laminate is 0.5 to 5 mm. More preferably, the thickness of the layer B is 100 to 100.
0 μm, more preferably 200 to 700 μm.

In the above case, sufficient strength and environmental degradation resistance can be efficiently obtained while achieving low distortion. B
When the thickness of the layer is within a specific thickness range, the balance between the reduction in the overall strain and the degree of freedom in processing is particularly good.

Although the structure of the polycarbonate laminate of the present invention is particularly suitable for insert injection molding, such a structure can be obtained by another manufacturing method. Other methods include, for example, multilayer extrusion, insert compression molding, multicolor molding, simultaneous composite molding (a method of filling the mold cavity from two or more points), and sandwich molding (molding from one point). (A method of filling the cavity).

That is, according to the present invention, as a more preferred embodiment, the layer B is inserted into the mold cavity,
Provided is a polycarbonate resin laminate obtained by filling the components into a mold cavity.

In the insert molding, a molded product, a sheet, etc., which forms various B layers by extrusion molding, injection molding, rotational molding, etc. of the B component in a separate step, is mounted in a mold cavity, and the A component is formed. It is to be filled with polycarbonate resin. A printed layer, a metal thin film layer, a hard coat layer, a water / oil repellent layer, an antistatic layer, an ultraviolet / infrared absorbing layer, a polarizing layer, and the like are provided on the surface of the layer B, which is a molded article formed from the B component. It may be. As the printing method, a known printing method such as gravure printing, flat plate 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 metal thin film layer can be formed by a method such as vapor deposition, sputtering, or gas spraying. still,
These layers may be formed on the interface side with the layer A.

When these various functional layers are on the interface side, the chemical influence of the functional layers extends not only to the polycarbonate resin of the layer B but also to the polycarbonate resin of the layer A. Such a chemical effect may cause a decrease in interfacial adhesion during long-term use in some cases. However, since the component A of the present invention has long-term properties, that is, properties in which microcracks and the like in environmental degradation hardly occur, even when various functional layers are provided at the interface,
Thereby, the strength of the interface does not decrease.

More preferably, the layer B of the present invention is a sheet-like molded article provided with these various functional layers and a molded article obtained by subjecting them to secondary processing such as thermoforming. Further, in such molding, molding by a hot runner is also possible.

Further, as a preferred embodiment of the present invention, in the insert molding, the injection speed at the time of filling such a component A into the mold cavity is 300 mm / sec.
A polycarbonate resin laminate manufactured under the above molding conditions is provided. In such a case, since the conditions are extremely high shear, the effect that the low molecular weight component of the present invention is a specific amount can be more effectively exerted. In addition, it is possible to suppress the breaking of the molecular chain that occurs to achieve such a high shear rate, and thus it is possible to obtain a laminate that is more stable in characteristics.

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 the high speed. Here, the injection speed refers to an average speed from the start to the end of filling into the mold cavity, and does not necessarily have to be a constant speed, and molding can be performed at multiple injection speeds.

Here, various methods can be used to set the injection speed to 300 mm / sec, but 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-plaster 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 vent to allow gas to escape smoothly in the mold, a porous sintered metal, a vacuum pump through a vent hole, etc. A pressure-reducing device is preferably used.

Further, in the present invention, a stabilizer represented by the following general formula (1) is added to the polycarbonate resin of the component A in an amount of 0.001% by weight of 100% by weight of the component A in order to cope with the above-mentioned molding conditions at a specific injection speed or more. Preferably, the content is 0.5 to 0.5% by weight. More preferably 0.005 to
0.3% by weight, particularly preferably 0.01 to 0.2% by weight
It is.

[0054]

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Wherein Ar ¹ , Ar ² and Ar ³ are dialkyl-substituted aromatic groups having 8 to 20 carbon atoms,
r ¹ , Ar ² and Ar ³ may be the same or different. )

Since the stabilizer represented by the general formula (1) is excellent in stabilizing action against thermal oxidation, it is possible to stabilize the polycarbonate resin against shear heat generation at a high injection speed. In addition, it has the advantage that it also has excellent resistance to environmental degradation, which is the object of the present invention, because of its excellent wet heat resistance and the like. 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-isopropylpropyl) phosphite, and tris (di-n-butylphenyl) phosphite. Fight, Tris (2,4-di-tert)
-Butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, and the like. Tris (dialkyl-substituted phenyl) phosphite is preferred, and tris (di-tert-butylphenyl) phosphite is preferred. More preferably, tris (2,4-di-te
(rt-butylphenyl) phosphite is particularly preferred.

The surface of the molded body for forming the layer B of the present invention which is in contact with the layer A may have a three-dimensional pattern formed on the surface. By giving such a three-dimensional pattern, it becomes possible to obtain a polycarbonate laminate having a high design property, an optical function and good adhesion.
In addition, when such a three-dimensional pattern is applied, the resin flow may flow from a substantially thick portion, and it may be difficult to completely fill the resin due to the final accumulation of gas. However, when filling is performed at a specific injection speed or more suitable for the present invention, such a problem can be sufficiently coped with.

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

A preferred embodiment of the polycarbonate resin laminate of the present invention is a case where the total light transmittance of the laminate satisfies 70% or more. When such transparency is required, lower distortion is required, and the effects of the present invention can be exhibited more effectively. It should be noted that such transparency only needs to have a portion where such transparency is required in the polycarbonate resin laminate, and does not necessarily indicate only when the entire surface satisfies such conditions.

A releasing agent can be blended with the polycarbonate resin of the component A and the component B of the present invention. As the release agent, a saturated fatty acid ester is generally used. Esters, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the polycarbonate resin.

Further, a phosphorus-based heat stabilizer other than the phosphite compound represented by the above formula (1) can be added to the polycarbonate resin of the present invention, if necessary. As the phosphorus-based heat stabilizer, a phosphite compound and a phosphate compound, and furthermore, a phosphonite compound are preferably used.

As the phosphite compound, distearyl pentaerythritol diphosphite, bis (2,4
-Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite Phosphite, and the like, preferably distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter
(t-butyl-4-methylphenyl) pentaerythritol diphosphite and 4,4′-isopropylidene diphenol ditridecyl phosphite.

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

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

To the polycarbonate resin of the present invention, an antioxidant commonly known for the purpose of preventing oxidation can be added. When such an antioxidant is used in combination with the above-mentioned phosphorus-based heat stabilizer, improvement in hue and the like can be achieved without blending a phosphorus-based heat stabilizer more than necessary. This makes it possible to further enhance the balance with the hydrolysis resistance characteristic caused by the phosphorus-based heat stabilizer.

The antioxidants include phenolic antioxidants. Specifically, for example, vitamin E, n-octadecyl-β- (4′-hydroxy-
3 ′, 5′-di-tert-butylfell) propionate, 2-tert-butyl-6- (3′-tert-
Butyl-5'-methyl-2'-hydroxybenzyl)-
4-methylphenyl acrylate, 2,6-di-ter
t-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-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'-dimethylenebis (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-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-tert-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-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-ter
t-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-t
tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,
4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-tert-butylanilino) -1,
3,5-triazine, N, N'-hexamethylenebis-
(3,5-di-tert-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-tert-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-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-t)
tert-butyl-4-hydroxyphenyl) propionate] methane and the like.

Further, examples of the antioxidant include a sulfur-based antioxidant. Specifically, dilauryl-
3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate , Laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4- (3
-Laurylthiopropionyloxy) -5-tert-
Butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-
Examples thereof include 6-methylbenzimidazole and 1,1′-thiobis (2-naphthol).

The composition ratio of these antioxidants is 0.0001 to 0.1 with respect to 100 parts by weight of the polycarbonate resin.
5 parts by weight are 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, as the ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxy-phenol, 2- (4,
6-bis- (2,4-dimethylphenyl-1,3,5-
Examples thereof include hydroxyphenyltriazine compounds such as triazin-2-yl) -5-hexyloxy-phenol.

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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.
The amount is from 0.01 to 10 parts by weight, preferably from 0.001 to 5 parts by weight.

Further, a bluing agent can be added to the polycarbonate resin of the present invention in order to cancel a yellowish 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 for a polycarbonate resin. Generally, anthraquinone dyes are easily available and preferred. As a specific bluing agent, for example, the common name Solven
t Violet 13 [CA. No. (color index No.) 60725; Trade name “Macrolex Violet B” manufactured by Bayer Corporation, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Viol
et31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name S
Solvent Violet 33 [CA. No. 6072
5; trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA.
No. 61500; Trade name "Diaresin Blue N" manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet
t36 [CA. No. 68210; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Sol
vent Blue 97 [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., and Macrolex Violet and Triazole Blue RLS manufactured by Ciba Specialty Chemicals.

The polycarbonate resin of the present invention may contain other 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 particles, aramid fiber, polyarylate fiber, Graphite, conductive carbon black, various whiskers, etc.), flame retardant (halogen, phosphate ester, metal salt, red phosphorus, silicon, fluorine, metal hydrate, etc.), heat resistant agent, coloring agent ( Pigments such as carbon black and titanium oxide, dyeing ), Light diffusing agents (crosslinked acrylic particles, crosslinked silicon particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, luminous pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic Further, an organic antibacterial agent, a photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, and the like), an impact modifier represented by a graft rubber, an infrared absorber, and a photochromic agent can be blended. It is preferable that the amount of these fillers is such that the total light transmittance is 70% or more, which is a preferred embodiment of the polycarbonate resin laminate of the present invention.

In the present invention, by laminating the above-mentioned specific polycarbonate resin, it is possible to obtain a laminate having less distortion and excellent environmental resistance such as strength and wet heat resistance. It is suitable for long-term use under severe conditions such as glazing products, outer panel parts, exterior materials such as electronic / electrical equipment and mechanical devices typified by portable information terminals and electric tools.

[0078]

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) Surface Impact Strength At 23 ° C., 50%
Under a RH atmosphere, a high-speed surface impact tester is used at a punching speed of 7 m / sec using a punch for punching with a semicircular tip and a radius of 1/4 inch, and a circular cradle with a radius of 1/2 inch. (Hydroshot HT manufactured by Shimadzu Corporation)
Using M-1), the punch was made to collide with the center part of the substantially plate-shaped molded product, and the energy (J) required to break through the sample was measured.

(2) Moisture / heat resistance The plate-like molded product was treated with an environmental tester (Platinum Subzero Lucifer manufactured by Tabai Espec Co., Ltd.) at 65 ° C. and 85% RH for 500 hours, and then the same as (1) above. The surface impact strength was measured by the above method, and compared with the impact strength before the wet heat treatment. In addition, the ratio of the value after the wet heat treatment to the value before the wet heat treatment was represented by% as the retention ratio, and those with a retention ratio of 90% or more were evaluated with “○”, and those with less than 90% were evaluated with “X”.

(3) Distortion of Molded Product The plate-like molded product 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.

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

[Examples 1 to 3 and Comparative Examples 1 to 3] A cylinder capable of achieving an injection speed of 800 mm / sec after drying the polycarbonate resin 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 (SG2 manufactured by Sumitomo Heavy Industries, Ltd.)
60M-HP) was used for molding.

Before filling with the resin, the polycarbonate resin sheet cut to the size corresponding to each of the mold core surface sides was mounted by charging.

Using a vacuum pump (combination of ULVAC PMB006CM mechanical booster manufactured by Nippon Vacuum Engineering Co., Ltd. and an EC803 rotary pump) with the mold closed, evacuation was performed for 10 seconds, followed by molding. The evacuation was performed through a gas vent clearance provided around the mold cavity.

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 248 mm, a width of 178 mm and a thickness of 5 mm, and has a film-shaped gate (gate portion having a thickness of 1.5 mm). The mold temperature was kept at 130 ° C. using a mold temperature controller. The obtained molded article was evaluated as described above. Table 1 shows the evaluation results.

The symbols indicating the components shown in Table 1 are as follows. (A component: polycarbonate resin) (i) PC-1 Molecular weight of 3,000 measured by the GPC method described below.
A polycarbonate resin pellet having the following components in a GPC chart with the logarithm of the molecular weight on the horizontal axis being 0.7% in area ratio and having a weight average molecular weight of 50,100.
In addition, such pellets were obtained in the following manner.

That is, a mixture obtained by adding 10 times the amount of acetone to the powdered polycarbonate resin was placed in a stainless steel container, and the mixture was stirred at room temperature for 3 hours, and then filtered and dried under reduced pressure to obtain a purified polycarbonate resin powder. Obtained. To 99.78 parts by weight of the polycarbonate resin, 0.02 parts by weight of Irgafos 168 (manufactured by Nippon Ciba Geigy Co., Ltd.) and 0.2 parts by weight of pentaerythritol tetrastearate were blended.
To obtain a resin composition pelletized by a twin-screw extruder. In the above purification, only the acetone solution is pumped from the mixture in the stainless steel container through the filter to the evaporator, and the vaporized and purified acetone is returned to the stainless steel container again, and the circulation of the acetone is established. Went in shape.

(Ii) PC-2 A molecular weight of 3,000 measured by the GPC method shown below
A polycarbonate resin pellet comprising the following components in an area ratio of 2.6% in a GPC chart in which a logarithm of a molecular weight is plotted on a horizontal axis and a weight average molecular weight is 46,000.
In addition, such pellets were obtained in the following manner. That is,
97.78 parts by weight of a purified polycarbonate resin powder purified in the same manner as PC-1, 2 parts by weight of a polycarbonate oligomer shown below, 0.02 parts by weight of Irgafos168 (manufactured by Nippon Ciba Geigy Co., Ltd.), and pentaerythritol tetrastea The resin composition was blended with a rate of 0.2 part by weight and pelletized at 280 ° C. with a twin-screw extruder.

(Iii) PC-3 Molecular weight of 3,000 measured by GPC method shown below
A polycarbonate resin pellet comprising the following components in an area ratio of 2.6% in a GPC chart in which a logarithm of a molecular weight is plotted on a horizontal axis and a weight average molecular weight is 46,000.
In addition, such pellets were obtained in the following manner. That is,
97.8 parts by weight of a purified polycarbonate resin powder purified in the same manner as PC-1 was mixed with 2 parts by weight of a polycarbonate oligomer shown below and 0.2 parts by weight of pentaerythritol tetrastearate, and the mixture was biaxially heated at 280 ° C. A resin composition pelletized by an extruder was obtained.

(Iv) PC-4 A molecular weight of 3,000 measured by the GPC method shown below
A polycarbonate resin pellet having the following components in an area ratio of 0.3% in a GPC chart in which the logarithm of the molecular weight is plotted on the horizontal axis and having a weight average molecular weight of 61,000.
In addition, such pellets were obtained in the following manner. That is,
10 times the amount of acetone was added to the powdered polycarbonate resin, and the mixture was stirred at room temperature for 3 hours in the same manner as in PC-1, and then filtered and dried under reduced pressure to obtain a purified polycarbonate resin powder. 99.8 parts by weight of the polycarbonate resin powder and 0.2 parts by weight of pentaerythritol tetrastearate were blended to obtain a resin composition pelletized at 280 ° C. by a twin-screw extruder.

(V) PC-5 Molecular weight of 3,000 measured by GPC method shown below
A polycarbonate resin pellet having the following components in an area ratio of 4.6% in a GPC chart in which a logarithm of a molecular weight is plotted on a horizontal axis and a weight average molecular weight of 32,000.
In addition, such pellets were obtained in the following manner. That is,
10 times the amount of acetone was added to the powdered polycarbonate resin, and the mixture was stirred at room temperature for 3 hours in the same manner as in PC-1, and then filtered and dried under reduced pressure to obtain a purified polycarbonate resin powder. After drying the polycarbonate resin, 95.8 parts by weight of the polycarbonate resin, 4 parts by weight of the polycarbonate oligomer shown below, and 0.2 parts by weight of pentaerythritol tetrastearate are blended and pelletized at 280 ° C. by a twin screw extruder. A resin composition was obtained.

(Component B: Polycarbonate resin sheet) (i) PCS-1 Bisphenol A and phosgene, and p-tert-butylphenol as a terminal stopper were synthesized by a conventional method without using an amine-based catalyst. GP shown below
C. Irgaf was added to 100 parts by weight of a polycarbonate resin having a weight average molecular weight of 55,700 measured by the C measurement method.
0.0168 parts by weight of os168 (manufactured by Nippon Ciba Geigy KK), 0.2 parts by weight of pentaerythritol tetrastearate, and TINUVIN as a UV absorber
1577 (manufactured by Nippon Ciba Geigy) 1 part by weight, Macrolex Violet B (manufactured by Bayer) 0.000
3 parts by weight were blended and melt-extruded at 280 ° C. under a reduced pressure of 1330 Pa by a T-die extruder having a gear pump to obtain a polycarbonate resin sheet having a thickness of 0.5 mm. 2. The polycarbonate resin sheet of FIG. 2 having an acrylic primer having a thickness of 2.5 μm on one surface and a silicon hard coat treatment of 5.0 μm further thereon.

(Ii) PCS-2 A polycarbonate resin sheet obtained by subjecting the above PC-2 to sheet preparation and hard coating in the same manner as PCS-1.

(Polycarbonate oligomer) As a polycarbonate oligomer, bisphenol A
And phosgene, and p-tert-butylphenol as a terminal stopper, and the pH of the system during the phosgenation reaction.
Is 10.2 to 11.3, and then p-tert-butylphenol and aqueous sodium hydroxide are added, and the mixture is reacted for 60 minutes at pH 12 or higher and at a reaction temperature of 38 to 41 ° C., and the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. After washing with water until the product became water, an oligomer having a weight average molecular weight of about 2,900 as measured by GPC shown below was obtained. The terminal chlorine content of such an oligomer is not detected by an ultraviolet-visible spectrophotometer (U-3200 manufactured by Hitachi, Ltd.) having a detection limit of 0.2 ppm. Not detected in the ¹ H-NMR measurement of 0.0003 mol.

(GPC Measurement Method) A Gulliver series manufactured by JASCO Corporation was used as a measuring device, and MIXE manufactured by Polymer Laboratories was used as a column in an environment of clean air at a temperature of 23 ° C. and a relative humidity of 50%.
DC (length: 300 mm, inner diameter: 7.5 mm), chloroform as a mobile phase, Easycal PS-2 manufactured by Polymer Laboratories as a standard substance, and a differential refractometer as a detector, and chloroform as a developing solvent. Then, 100 μl of a solution in which 1 mg of the sample was dissolved per 1 ml of chloroform was injected into a GPC measuring apparatus, and GPC measurement was performed under the conditions of a column temperature of 35 ° C. and a flow rate of 1 ml / min. A baseline was determined by connecting the rising point and the convergence point of the obtained GPC chart, and the weight average molecular weight of the polycarbonate resin and the area ratio of components having a molecular weight of 3,000 or less were calculated from this.

[0097]

[Table 1]

As is evident from Table 1, when the polycarbonate resin having a specific molecular weight component of the present invention is used, a molded product excellent in long-term properties such as impact strength and wet heat resistance and low distortion property is obtained. It can be seen that is obtained.

[0099]

According to the present invention, it is possible to obtain a polycarbonate resin laminate having low distortion and excellent strength and long-term properties. Such laminates can be used in buildings,
BACKGROUND ART In a variety of fields such as aircraft, ships, vehicles, electric / electronic devices, machinery and other fields, a molded article having a small distortion and a good design can be obtained, so that the industrial effect achieved is extremely large.

[Brief description of the drawings]

FIG. 1 is a view schematically showing an outline of a plate-like molded product used in Examples.

FIG. 2 is a diagram schematically illustrating an outline of a layer configuration of a sheet molded product forming a layer B used in an example.

[Explanation of symbols]

1 Plate-shaped molded product main body (layer A, length 248 mm parallel to runner, length 178 mm in flow direction, overall thickness 5 mm) 2 Insert film (layer B) 3 Gate (thickness and width of gate entrance portion 1. 5m
m) 4 Runner (length 195 mm, thickness 7 mm) 5 Sprue (diameter of runner portion 8 mm) 6 Polycarbonate resin forming B layer 7 Primer layer 8 Hard coat layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AH01A AH02A AK45A AK45B BA02 BA16 EH31 EH36 JA07A JA07B JD04 JJ03 JK01 JK10 JL00 JL04 JN01 YY00A YY00B 4F206 AA28A AB22 AD05 AE10 J03J07 J05 J05

Claims (5)

[Claims] 1. A component having a molecular weight of 3,000 or less as measured by a GPC (gel permeation chromatography) method defined in the text is defined as an area ratio in a GPC chart in which the logarithm of the molecular weight is plotted on the horizontal axis. 5 to 2.8%
Having a weight average molecular weight of 33,000 to 6
A layer (A layer) composed of a polycarbonate resin (A component) having a molecular weight of 0000, and GPC laminated on the A layer
Weight average molecular weight of 50,000 to 8
A polycarbonate resin laminate comprising a layer (B layer) composed of a polycarbonate resin (component B) of 000. 2. The polycarbonate resin laminate according to claim 1, wherein the polycarbonate resin laminate is obtained by inserting the layer B into a mold cavity and filling the component A into the mold cavity. 3. The polycarbonate resin laminate according to claim 2, wherein the injection speed at the time of filling the component A into the mold cavity is 300 mm / sec or more. 4. The polycarbonate according to claim 1, wherein the component A contains the compound represented by the following general formula (1) in an amount of 0.0001 to 0.5% by weight based on 100% by weight of the component A. Resin laminate. Embedded image (Wherein, Ar ¹ , Ar ² and Ar ^{3 each} have 8 to ² carbon atoms)
0 is a dialkyl-substituted aromatic group, and Ar ¹ , Ar ^2, and Ar ³ can be each the same or different. ) 5. The method according to claim 1, wherein the polycarbonate resin laminate has a total light transmittance of 70% or more.
Item 10. The polycarbonate resin laminate according to item 1.