JP2022151565A - Thermoplastic resin composition, and molded article obtained by molding the same - Google Patents

Abstract

To provide a thermoplastic resin composition which uses an environmentally-friendly raw material, is excellent in light transmittance and is small in a phase difference, and a molded article obtained by molding the same.SOLUTION: A thermoplastic resin composition contains a polycarbonate resin (A) including a structural unit derived from a predetermined dihydroxy compound, a resin (B) having a structural unit derived from a (meth)acrylate-based monomer component, and at least one kind of a resin (C) having a structural unit derived from acrylonitrile and a structural unit derived from an aromatic vinyl-based monomer, wherein the resin (B) and the resin (C) are mutually incompatible, and a weight ratio of the resin (B) to the resin (C) is 99:1 to 1:99.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having good light transmittance and small retardation when formed into a molded article, and a molded article obtained by molding the same.

Polycarbonates are generally manufactured using raw materials derived from petroleum sources. However, in recent years, the depletion of petroleum resources is a concern, and there is a demand for providing polycarbonates using raw materials obtained from biomass resources such as plants. In addition, there are concerns that global warming due to the increase and accumulation of carbon dioxide emissions will cause climate change. There is a demand for the development of a polycarbonate with In particular, it is used in applications that require impact resistance and low haze, such as building materials, electrical/electronics, automobiles, optical parts, and miscellaneous goods. There is a demand for a resin composition that has excellent impact resistance and low haze.

Conventionally, various polycarbonates using plant-derived monomers as raw materials have been developed. For example, it has been proposed to obtain a polycarbonate by using isosorbide as a plant-derived monomer and transesterifying it with diphenyl carbonate (Patent Document 1). Here, in the case of the aromatic polycarbonate resin, which has been widely used in the past, the resin itself was excellent in impact resistance, but when isosorbide is used, the impact resistance is inferior to that of the aromatic polycarbonate resin. Is required. To address this problem, methods have been proposed to improve the impact resistance by incorporating a rubbery graft polymer or a styrenic resin into a polycarbonate made from isosorbide (Patent Documents 2, 3, etc.).

British Patent No. 1079686 JP 2017-149817 A JP 2009-144016 A

By the way, the inventions described in Patent Documents 2 and 3 are studied for impact resistance and are described as being useful in the field of OA equipment, optical parts, etc. However, the molding made of the obtained thermoplastic resin The phase difference of the body is large, and there is a possibility that the image passing through the molded body may be doubled or distorted such as blurring.
Therefore, the present invention solves these problems, uses environmentally friendly raw materials, has excellent light transmittance, and has a small retardation thermoplastic resin composition, and a molded product obtained by molding this. is to provide

As a result of studies by the present inventors, a polycarbonate resin (A) containing a structural unit derived from a specific dihydroxy compound and a thermoplastic resin containing a compatibilizing resin composed of at least two types of specific resins compatible with each other The present inventors have completed the present invention based on the finding that a molded product having excellent light transmittance and a small retardation can be obtained by using a resin composition.

That is, the gist of the present invention is as follows.
[1] A polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following general formula (1), a resin having a structural unit (b) derived from a (meth)acrylic acid ester-based monomer component ( B), and at least one resin (C) having a structural unit (c1) derived from acrylonitrile and a structural unit (c2) derived from an aromatic vinyl monomer, wherein the resin (B) and the resin (C ) are compatible with each other, and the weight ratio of the resin (B) to the resin (C) is B:C=99:1 to 1:99.

[2] The thermoplastic resin composition according to [1], wherein the resin (C) is a resin (C1) having both the structural unit (c1) and the structural unit (c2).
[3] The thermoplastic resin composition according to [1] or [2], wherein the resin (C) is an acrylonitrile-styrene copolymer.

[4] When the total amount of the resin (A), the resin (B), and the resin (C) is 100 parts by weight, the total amount of the resin (B) and the resin (C) is 1 part by weight or more and 50 The thermoplastic resin composition according to any one of [1] to [3], which is part by weight or less.
[5] The content ratio of the resin (B) and the resin (C) according to any one of [1] to [4], wherein the weight ratio of B:C is 99:1 to 65:35. A thermoplastic resin composition.

[6] Polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the above general formula (1), a resin having a structural unit (b) derived from a (meth)acrylic acid ester-based monomer component (B), and a resin (C1′) consisting only of structural units (c1) derived from acrylonitrile and structural units (c2) derived from an aromatic vinyl monomer, the resin (B), A thermoplastic resin composition in which the weight ratio of the resin (C1′) is B:C1′=99:1 to 1:99.
[7] A molded article containing the thermoplastic resin composition according to any one of [1] to [6].

[8] Polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the above general formula (1) and a structural unit (b) derived from a (meth)acrylic acid ester-based monomer component A thermoplastic resin composition is prepared by mixing a resin (B) and at least one resin (C) having a structural unit (c1) derived from acrylonitrile and a structural unit (c2) derived from an aromatic vinyl monomer. A method for producing a thermoplastic resin composition, wherein the weight ratio of the resin (B) to the resin (C) is B:C=99:1 to 1:99.
[9] The resin (C) is a resin (C1′) consisting only of structural units (c1) derived from acrylonitrile and structural units (c2) derived from an aromatic vinyl monomer [8] A method for producing the thermoplastic resin composition according to 1.
[10] The method for producing a thermoplastic resin composition according to [8], wherein the resin (B) and the resin (C) are compatible with each other.

According to the present invention, the molded article molded from the obtained thermoplastic resin composition has excellent light transmittance and a small phase difference. A clear image can be obtained by suppressing distortion such as distortion.

Embodiments of the present invention will be described in detail below. is not limited to the contents of
The present invention provides a thermoplastic resin composition containing a specific polycarbonate resin (A) (hereinafter sometimes simply referred to as "resin (A)"), a predetermined resin (B) and a resin (C), and this This invention relates to a molded article containing a thermoplastic resin composition.

<Polycarbonate resin (A)>
The polycarbonate resin (A) (resin (A)) used in the present invention is a polycarbonate resin containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1).

Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide, and isoidet, which have a stereoisomeric relationship, and these may be used alone or in combination of two or more. may Among them, isosorbide, which is obtained by dehydration condensation of sorbitol produced from various easily available starches, which exists abundantly as a plant-derived resource, is easy to obtain and produce, moldability, heat resistance, and impact resistance. It is the most preferable in terms of properties, surface hardness, and carbon neutrality.

Since the dihydroxy compound represented by the above formula (1) has a cyclic ether structure, it is easily oxidized by oxygen. It is important to use oxygen scavengers, etc., and to handle under a nitrogen atmosphere. For example, when isosorbide is oxidized, decomposition products such as formic acid may be generated. When isosorbide containing these decomposition products is used as a raw material for producing a polycarbonate resin, the obtained polycarbonate resin and thermoplastic resin composition may be colored, and the physical properties may be significantly deteriorated. In some cases, the polymerization reaction is affected and a high molecular weight polymer cannot be obtained.

The polycarbonate resin (A) used in the present invention is not particularly limited as long as it contains the structural unit (a) derived from the dihydroxy compound represented by the above formula (1). A homopolycarbonate resin containing only the unit (a) may be used, or a copolymerized polycarbonate resin further containing a structural unit other than the structural unit (a) may be used. The polycarbonate resin (A) is preferably a copolymerized polycarbonate resin from the viewpoint that the molded article obtained from the thermoplastic resin is more excellent in impact resistance. When the polycarbonate resin (A) is a copolymerized polycarbonate resin, the content of the structural unit (a) in the polycarbonate resin (A) is 30 in the structural units derived from all dihydroxy compounds in the polycarbonate resin (A). mol % or more is preferable, 40 mol % or more is more preferable, 50 mol % or more is still more preferable, and 60 mol % or more is particularly preferable. Moreover, it is preferably 90 mol % or less, more preferably 80 mol % or less, and particularly preferably 70 mol % or less. If the structural unit (a1) derived from another dihydroxy compound in the polycarbonate resin (A) is too small, the heat resistance may be insufficient, and if it is too large, the impact resistance may be insufficient.

Polycarbonate resin (A) used in the present invention, in addition to the structural unit (a) derived from the dihydroxy compound represented by formula (1), aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, aromatic bisphenols and formula Structural units (a1 ) may be a copolymer polycarbonate resin containing. This copolymerized polycarbonate resin can improve impact resistance. Among this structural unit (a1), one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and aromatic bisphenols are preferred. From the viewpoint of light resistance of the polycarbonate resin, a dihydroxy compound having no aromatic ring structure in the molecular structure, that is, an aliphatic dihydroxy compound and/or an alicyclic dihydroxy compound is preferable. Cycloaliphatic dihydroxy compounds are most preferred.

The aliphatic dihydroxy compound may be a linear aliphatic dihydroxy compound or a branched aliphatic dihydroxy compound, such as ethylene glycol, 1,3-propanediol, 1,2-propanediol. , 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and the like.

Examples of the alicyclic dihydroxy compounds include 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Methanol, Tricyclodecanedimethanol, Pentacyclopentadecanedimethanol, 2,6-Decalindimethanol, 1,5-Decalindimethanol, 2,3-Decalindimethanol, 2,3-Norbornanedimethanol, 2,5- norbornane dimethanol, 1,3-adamantane dimethanol, limonene and the like.

Examples of the aromatic bisphenols include 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2- Bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5- dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1 , 1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4 '-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-(2-hydroxy ethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene.

Examples of the ether group-containing dihydroxy compound include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150-2000), poly-1,3-propylene glycol, polytetramethylene glycol and the like.

When the polycarbonate resin (A) used in the present invention contains the structural unit (a1) derived from the other dihydroxy compound, the content ratio is the structural unit derived from all the dihydroxy compounds in the polycarbonate resin (A). WHEREIN: 10 mol% or more is preferable, 20 mol% or more is more preferable, 30 mol% or more is especially preferable. Moreover, it is preferably 90 mol % or less, more preferably 80 mol % or less, and particularly preferably 70 mol % or less. If the structural unit (a1) derived from another dihydroxy compound in the polycarbonate resin (A) is too small, the impact resistance may be insufficient, and if it is too large, the heat resistance may be insufficient.

From the viewpoint of optical properties, the polycarbonate resin (A) used in the present invention preferably does not contain an aromatic component as a structural unit. That is, it is preferable to use only compounds having non-aromatic structures as copolymerizable monomers. If the main chain of the polymer contains an aromatic component, there is a concern that the weather resistance, transparency and retardation of the resin composition may deteriorate. Employing the other structural unit containing no aromatic component can prevent the aromatic component from being incorporated into the main chain due to the structural unit.

On the other hand, in some cases, it is effective to incorporate an aromatic component into the main chain or side chain of the polymer in order to balance heat resistance, mechanical properties, etc. while ensuring optical properties. From the viewpoint of balancing various properties, the content of the structural unit containing an aromatic group in the resin is preferably 30 mol% or less, more preferably 10 mol% or less, and 5 mol% or less. is more preferable, and it is particularly preferable that it is 1 mol % or less.

Two or more kinds of the polycarbonate resin (A) of the present invention can be mixed, and in that case, the content of the structural unit (a1) derived from another dihydroxy compound in the polycarbonate resin (A) is It is similarly preferable if the average content of the polycarbonate resins corresponding to (A) falls within the above range.

The polycarbonate resin (A) used in the present invention can be produced by a commonly used method for producing a polycarbonate resin, and the production method is a solution polymerization method using phosgene, a melting method in which a diester carbonate and a dihydroxy compound are reacted. Although any polymerization method may be used, a melt polymerization method is preferred in which a dihydroxy compound containing a dihydroxy compound represented by formula (1) is reacted with a carbonic acid diester that is less toxic to the environment in the presence of a polymerization catalyst. . As a polymerization catalyst (transesterification catalyst) in melt polymerization, a known alkali metal compound and/or alkaline earth metal compound is used. Basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used together with the alkali metal compounds and/or alkaline earth metal compounds.

The polycarbonate resin (A) used in the present invention can be produced by transesterifying a dihydroxy compound containing a dihydroxy compound represented by formula (1) and a carbonic acid diester such as diphenyl carbonate as described above. More specifically, it is obtained by transesterification and removing by-products such as monohydroxy compounds out of the system. In this case, melt polymerization is usually carried out by transesterification in the presence of a transesterification catalyst.

Examples of the transesterification catalyst (hereinafter sometimes referred to as "catalyst") that can be used in the production of the polycarbonate resin (A) used in the present invention include the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Group 1 or Group 2 (hereinafter simply referred to as "Group 1" and "Group 2") metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, basic compounds such as amine compounds compound. Among these, Group 1 metal compounds and/or Group 2 metal compounds are preferably used, and Group 2 metal compounds are particularly preferably used from the viewpoint of transparency and weather resistance.

A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used together with the group 1 metal compound and/or the group 2 metal compound. It is particularly preferred to use only group 1 metal compounds and/or group 2 metal compounds.
In addition, as the form of the group 1 metal compound and/or the group 2 metal compound, it is usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. Hydroxides, carbonates and acetates are preferred from the standpoint of ease, and acetates are preferred from the viewpoint of hue and polymerization activity.

Examples of Group 1 metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride , Sodium phenylate, Potassium phenylate, Lithium phenylate, Cesium phenylate, Sodium benzoate, Potassium benzoate, Lithium benzoate, Cesium benzoate, Disodium hydrogen phosphate, Dipotassium hydrogen phosphate, Phosphorus dilithium oxyhydrogen, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, sodium, potassium, lithium, cesium alcoholates, phenolates, bisphenols Disodium salt, dipotassium salt, dilithium salt, dicesium salt and the like of A, among which cesium compounds and lithium compounds are preferred.

Group 2 metal compounds include, for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like, among which magnesium compounds, calcium compounds and barium compounds are preferred, magnesium compounds and/or Or a calcium compound is more preferable.

Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, and tributylbenzylboron. sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, or strontium salts of boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, butyltriphenyl boron, etc.; be done.

Examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
Examples of basic ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide and the like.

Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

Among the above, it is preferable to use at least one metal compound selected from the group consisting of Group 2 metal compounds as a catalyst to improve various physical properties such as transparency, hue, and light resistance of the resulting polycarbonate resin (A). It is preferable to make
In order to make the polycarbonate resin (A) particularly excellent in transparency, hue, and light resistance, the catalyst is at least one metal compound selected from the group consisting of magnesium compounds, calcium compounds, and barium compounds. and particularly preferably at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds.

In the case of a Group 1 metal compound and/or a Group 2 metal compound, the amount of the catalyst used is preferably 0.1 to 300 μmol, more preferably 0.1 to 300 μmol in terms of metal, per 1 mol of all dihydroxy compounds to be subjected to the reaction. It is in the range of 0.1 to 100 µmol, more preferably 0.5 to 50 µmol, and particularly preferably 1 to 25 µmol.
Among the above, when a compound containing at least one metal selected from the group consisting of Group 2 metals is used, the amount in terms of metal is preferably 0.1 μmol or more, more preferably 0.1 μmol or more, per 1 mol of the total dihydroxy compound to be subjected to the reaction. is 0.5 μmol or more, particularly preferably 0.7 μmol or more. The upper limit is preferably 20 µmol, more preferably 10 µmol, particularly preferably 3 µmol, and most preferably 2.0 µmol.

If the amount of the catalyst used is too small, the polymerization activity required to produce the polycarbonate resin (A) having the desired molecular weight may not be obtained, and sufficient breaking energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only does the resulting polycarbonate resin (A) have a poor hue, but also by-products are generated, resulting in decreased fluidity and increased gel generation, leading to brittle fracture. may be caused, and it may be difficult to produce the polycarbonate resin (A) with the desired quality.

In addition, in the thermoplastic resin composition of the present invention, the amount of the catalyst metal is contained in the thermoplastic resin composition derived from the catalyst used in the production of the polycarbonate resin. Therefore, the amount of the catalyst metal used in the thermoplastic resin composition is the same amount as the range defined above.
The polymerization reaction can be carried out in a known manner, and may be batch, continuous, or a combination of batch and continuous.

Moreover, when producing the polycarbonate resin (A) used in the present invention, it is desirable to install a filter in order to prevent contamination by foreign matter. The installation position of the filter is preferably on the downstream side of the extruder, and the size (opening) of the filter for removing foreign matter is preferably 100 μm or less as filtration accuracy for 99% removal. In particular, in the case of film applications, etc., where contamination with minute foreign matter is to be avoided, the thickness is preferably 40 μm or less, more preferably 10 μm or less.

Extrusion of the polycarbonate resin (A) used in the present invention is preferably class 7 defined in JIS B 9920 (2002), more preferably class 6, in order to prevent contamination after extrusion. It is desirable to carry out in a clean room.
When the extruded polycarbonate resin (A) is cooled and chipped, it is preferable to use a cooling method such as air cooling or water cooling. It is desirable to use air from which foreign matter in the air has been previously removed by a hepa filter or the like for the air used for air cooling to prevent reattachment of foreign matter in the air. When water cooling is used, it is desirable to use water from which metals are removed with an ion-exchange resin or the like and foreign matter is removed from the water with a filter. The mesh size of the filter to be used is preferably 10 μm to 0.45 μm as filtration accuracy for 99% removal.

The molecular weight of the polycarbonate resin (A) used in the present invention can be represented by the reduced viscosity, and the reduced viscosity is usually preferably 0.30 dL/g or more, more preferably 0.35 dL/g or more. The upper limit of the reduced viscosity is generally preferably 1.20 dL/g or less, more preferably 1.00 dL/g or less, and even more preferably 0.80 dL/g or less.
If the reduced viscosity of the polycarbonate resin (A) is too low, the toughness of the resulting resin composition may be low. It tends to lower productivity and reduce moldability. In addition, the molding temperature must be higher than appropriate, which may deteriorate the color tone.
The reduced viscosity of the polycarbonate resin is measured using methylene chloride as a solvent, precisely adjusting the polycarbonate resin concentration to 0.6 g / dL, and using an Ubbelohde viscosity tube at a temperature of 20.0 ° C. ± 0.1 ° C. .

The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 70° C. or higher and 145° C. or lower, more preferably 80° C. or higher and 135° C. or lower, and particularly preferably 90° C. or higher and 125° C. or lower. If the glass transition temperature is less than 70°C, the heat resistance is insufficient, and if it is 145°C or more, the fluidity during molding is insufficient, and the resin composition may not be filled to the end of the product, or the strength at the weld portion may decrease. There is
The total light transmittance and haze of the polycarbonate resin (A) of the present invention can be measured by the following methods.

(1) Pellet production A molten polycarbonate resin is continuously supplied to a twin-screw extruder equipped with three vent ports and water injection equipment, and Irganox 1010 ( BASF Japan Co., Ltd., pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) 0.1 parts by mass, ADEKA STAB 2112 (manufactured by ADEKA Corporation, 0.05 parts by mass of tris (2,4-di-tert-butylphenyl) phosphite) and 0.3 parts by mass of Unistar E-275 (manufactured by NOF Corporation) as a release agent are continuously added. At the same time, low-molecular-weight substances such as phenol are devolatilized under reduced pressure at each vent section provided in the twin-screw extruder, and then pelletized by a pelletizer.

(2) Injection molding Pellets kneaded with a twin-screw extruder are pre-dried at 100°C for 6 hours and then molded using a J85AD injection molding machine manufactured by Japan Steel Works, Ltd. with a cylinder temperature of 240°C, a molding cycle of 40 seconds, and a metal mold. A flat plate of 100 mm x 100 mm x 2 mmt is molded at a mold temperature of 60°C.

(3) Haze and total light transmittance measurement Using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd., the haze (Haze (%)) and total light transmittance (%) of the above test piece were measured with a D65 light source. Measure. The total light transmittance of the polycarbonate resin (A) of the present invention is preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more. If the total light transmittance is higher than the above lower limit, the total light transmittance of the thermoplastic resin composition will be high. The details of the method for measuring the total light transmittance will be described in the section of Examples.

The haze of the polycarbonate resin (A) of the present invention according to JIS K 7105 is usually 2% or less, preferably 1.5% or less, most preferably 1% or less. If the haze is within the above range, it is possible to achieve both a high total light transmittance and a high haze when the thermoplastic resin composition is formed.
In addition, in the thermoplastic resin composition of the present invention, one type may be used alone as the polycarbonate resin (A), and other types of structural units derived from dihydroxy compounds, copolymerization ratios, physical properties, etc. Two or more kinds of substances may be mixed and used.

<Resin (B)>
The resin (B) used in the present invention is a resin having a structural unit (b) derived from a (meth)acrylic acid ester-based monomer component, that is, an acrylic resin.

As the acrylic resin used in the present invention, an acrylic resin as a thermoplastic resin is used. Examples of the structural unit (b) of the (meth)acrylic acid ester-based monomer component, which is a structural unit of the acrylic resin, include methyl (meth)acrylate, (meth)acrylic acid, benzyl (meth)acrylate, n -butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclo Pentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, acrylic (meth)acrylate, 2-hydroxyethyl (meth)acrylate, succinic acid 2-(meth)acryloyloxyethyl, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, pentamethyl Piperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and the like are exemplified. These may be used by polymerizing alone, or may be used by polymerizing two or more kinds. Among these, those using at least one of alkyl methacrylate and alkyl acrylate are preferable because of their low impact resistance and haze. Other monomers that can be polymerized with these acrylic monomers, such as polyolefin monomers and vinyl monomers, may also be used in combination.

In addition, in this specification, "(meth)acrylate" means "acrylate" or "methacrylate."
The molecular weight of the acrylic resin is not particularly limited, but if the weight average molecular weight is in the range of 30,000 or more and 300,000 or less, appearance defects such as flow unevenness may occur when molding as a multilayer body. It is possible to provide a multilayer body having excellent mechanical properties and heat resistance.

<Resin (C)>
The resin (C) used in the present invention is at least one resin having a structural unit (c1) derived from acrylonitrile and a structural unit (c2) derived from an aromatic vinyl monomer. As the resin (C), a resin (C1) having both the structural unit (c1) and the structural unit (c2) may be used, or a resin (C2-1) having the structural unit (c1) and a resin (C2-2) having the structural unit (c2) may be used in combination.

[Compatibility]
By the way, it is preferable that the resin (C) and the resin (B) are compatible with each other. Here, the term "compatible" refers to the property that when a plurality of substances are mixed, they do not separate but mix together.
In the present invention, since the resin (B) and the resin (C) are compatible with each other, it is possible to easily match the refractive index of the resin (A) and maintain high transparency. .
The fact that the resin (B) and the resin (C) are compatible with each other means that, for example, the resin (B) and the resin (C) have different glass transition temperatures than the respective glass transition temperatures of the thermoplastic resin composition. can be confirmed by showing

[Structural unit (c1), structural unit (c2)]
Examples of the structural unit (c1) include acrylonitrile and the like. Examples of the structural unit (c2) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, Examples include styrene derivatives such as monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, with styrene being particularly preferred. Furthermore, these can be used singly or in combination of two or more.

[Resin (C1)]
The resin (C1) is a resin having both a structural unit (c1) derived from acrylonitrile and a structural unit (c2) derived from an aromatic vinyl monomer. As the resin (C1) having both of these structural units and compatible with the resin (B) as described above, the structural unit (c1) derived from acrylonitrile and the structural unit derived from the aromatic vinyl monomer A resin (C1') consisting only of both structural units of (c2), specifically an acrylonitrile-styrene copolymer can be mentioned.

[Resin (C2-1), Resin (C2-2)]
The resin (C2-1) is a resin having the structural unit (c1) derived from acrylonitrile and does not contain the structural unit (c2). Examples of this resin (C2-1) include polyacrylonitrile.
Further, the resin (C2-2) is a resin having a structural unit (c2) derived from an aromatic vinyl-based monomer and does not contain the structural unit (c1). Examples of this resin (C2-2) include polystyrene and poly-α-methylstyrene.

<Mixing ratio of resin (B) and resin (C)>
The mixing ratio (weight ratio) of the resin (B) and the resin (C), expressed as B/C, is preferably 99/1 or less, preferably 95/5 or less. If the amount of the resin (B) is too large, there is a risk that the total light transmittance will decrease and the haze will increase. Also, the lower limit of B/C is preferably 1/99 or more, preferably 65/35 or more. If the amount of the resin (C) is too large, there is a risk that the total light transmittance will decrease and the haze will increase.

<Mixing ratio of resin (A), resin (B) and resin (C)>
The mixing ratio (weight ratio) of the resin (A), the resin (B) and the resin (C) is, when the total amount of the resin (A), the resin (B) and the resin (C) is 100 parts by weight, The total amount of resin (B) and resin (C) is preferably 1 part by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and particularly preferably 20 parts by weight or more. If the total amount of the resin (B) and the resin (C) is too small, there is a risk that the retardation will be insufficiently reduced. Moreover, the upper limit of the total amount of the resin (B) and the resin (C) is preferably 50 parts by weight or less, preferably 45 parts by weight or less, and more preferably 40 parts by weight or less. If the total amount of the resin (B) and the resin (C) is too large, there is a risk that the impact resistance will be lowered.

<Difference in refractive index between resin (A) and mixed resin of resin (B) and resin (C)>
The difference between the refractive index of the resin (A) and the refractive index of the mixed resin of the resin (B) and the resin (C), that is, (refractive index of the resin (A))−(resin (B) and resin (C) (refractive index of the mixed resin) is preferably within the range of ±0.007, preferably within the range of ±0.005. If the refractive index difference is too large, the total light transmittance may decrease and the haze may increase.

<Method for producing a thermoplastic resin composition according to the present invention>
The thermoplastic resin composition of the present invention is prepared by mixing the resin (A), resin (B) and resin (C) in a predetermined ratio at the same time or in any order in a tumbler, a V-type blender, a Nauta mixer, or a Banbury mixer. , a kneading roll, or an extruder.

<Additive>
The thermoplastic resin composition of the present invention may optionally contain antioxidants, light stabilizers, ultraviolet absorbers, release agents, colorants, neutralizers, antistatic agents, lubricants, lubricants and plasticizers. , flame retardants, fillers and the like can also be added.

(Release agent)
The thermoplastic resin composition of the present invention does not impair the purpose of the present invention, such as for improving roll release from the cooling roll during sheet molding or release from the mold during injection molding. A release agent may be blended within the range.
Examples of such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefinic waxes, olefinic waxes containing carboxy groups and/or carboxylic acid anhydride groups, silicone oils, organopolysiloxane and the like. The releasing agent may be used singly or in combination of two or more.

The higher fatty acid ester is preferably a partial or full ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of partial or full esters of monohydric or polyhydric alcohols with saturated fatty acids include monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbitate stearate, stearyl stearate, monoglyceride behenate, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate , sorbitan monostearate, 2-ethylhexyl stearate and the like. Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used. From the viewpoint of releasability and transparency, stearic acid ester is more preferable as a release agent.

The stearic acid ester is preferably a partial or full ester of a substituted or unsubstituted monohydric or polyhydric alcohol having 1 to 20 carbon atoms and stearic acid. Partial or full esters of monohydric or polyhydric alcohols and stearic acid include ethylene glycol distearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, and pentaerythritol. More preferred are monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate and stearyl stearate are more preferred, and ethylene glycol distearate and stearic acid monoglyceride are particularly preferred.

As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable. Among them, unsubstituted saturated fatty acids having 10 to 30 carbon atoms are more preferable, and examples of such higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid. Of these, saturated fatty acids having 16 to 18 carbon atoms are more preferred, and examples of such saturated fatty acids include palmitic acid and stearic acid, with stearic acid being particularly preferred.

When a release agent is used, the amount thereof is usually 0.001 part by weight or more, preferably 0.001 part by weight, per 100 parts by weight of the total amount of resin (A), resin (B) and resin (C). 01 parts by weight or more, more preferably 0.1 parts by weight or more, and usually 2 parts by weight or less, preferably 1 part by weight or less, more preferably 0.5 parts by weight or less. If the release agent content is excessively high, deposits on the mold may increase during molding. There is a possibility that the appearance of the product may be damaged. When the content of the release agent in the thermoplastic resin composition is at least the above lower limit, there is an advantage that the molded product can be easily released from the mold during molding, and the molded product can be obtained easily.

(Antioxidant)
As the antioxidant, a general antioxidant used for resins can be used, but from the viewpoint of oxidation stability, thermal stability, jet blackness, etc., phosphite antioxidant, sulfur antioxidant, and Phenolic antioxidants are preferred.

When an antioxidant is added to the thermoplastic resin composition of the present invention, the amount added is usually preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass, relative to 100 parts by mass of the resin (A). parts or more, more preferably 0.005 parts by mass or more, and usually preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.
If the amount of the antioxidant added is more than 5 parts by mass, the mold may be contaminated during molding, failing to obtain a molded product with excellent surface appearance. On the other hand, when the content is less than 0.001 parts by mass, there is a tendency that sufficient improvement effect on the weather resistance test cannot be obtained.

<Phosphite-based antioxidant>
Phosphite-based antioxidants include triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecyl Phosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert
-Butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2, 4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite and the like.

Among these, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6 -di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is preferably used.
These compounds may be used alone or in combination of two or more.

<Sulfur-based antioxidant>
Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, di Stearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate) ), glycerol-3-stearylthiopropionate, bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl]sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6 -methylbenzimidazole, 1,1'-thiobis(2-naphthol) and the like.
Among these, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred.
These compounds may be used alone or in combination of two or more.

<Phenolic antioxidant>
Phenolic antioxidants include, for example, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3, 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis(2, 4-di-tert-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2 ,4,8,10-tetraoxaspiro(5,5)undecane, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol and other compounds. be done.

Among these compounds, aromatic monohydroxy compounds substituted with one or more alkyl groups having 5 or more carbon atoms are preferred. Specifically, octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert -Butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and the like are preferred, and pentaerythritol- Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is more preferred.
These compounds may be used alone or in combination of two or more.

(light stabilizer)
Hindered amine-based light stabilizers can be used as light stabilizers, and the molecular weight thereof is preferably 1,000 or less, more preferably 900 or less. If the molecular weight exceeds 1,000, there is a possibility that sufficient weather resistance cannot be obtained when formed into a molded product. Also, the molecular weight is preferably 300 or more, more preferably 400 or more. If the molecular weight is less than 300, the heat resistance is poor, the mold is contaminated during molding, and a molded product with excellent surface appearance may not be obtained.

Furthermore, compounds having a piperidine structure are preferred. The piperidine structure defined here may be a saturated six-membered amine structure, and includes a piperidine structure partially substituted with a substituent. Examples of substituents include alkyl groups having 4 or less carbon atoms, and methyl groups are particularly preferred.
As the hindered amine light stabilizer, a compound having a plurality of piperidine structures is particularly preferred, and a compound in which the plurality of piperidine structures are linked by an ester structure is preferred.

Such light stabilizers include 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis(2,2,6,6-tetramethyl-piperidyl) sebacate, bis(1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethylpiperidine-4-carboxylic acid) 1,2,3,4-butanetetrayl, 2,2, condensate of 6,6-tetramethyl-pyrelidinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-pyrelidinol, methanol and 1,2,3, Condensate of 4-butanetetracarboxylic acid, bis(1,2,3,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl ] butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, 1 -[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4,4-hydroxy Phenyl)propionyloxy]ethyl]-2,2,6,6-tetramethylpiperidine, 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-tetramethyl-4- piperidyl)imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}], N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)- Condensation product of 1,6-hexanediamine polymer and 2,4,6-trichloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Condensation product of methyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-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]-6-chloro-1,3, Condensation with 5-triazine and condensates of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine.

When a light stabilizer is added to the thermoplastic resin composition of the present invention, the amount added is usually 0.001 parts by mass or more and 5 parts by mass or less, preferably 0 parts by mass, relative to 100 parts by mass of the resin (A). .
005 mass parts or more and 3 mass parts or less, more preferably 0.01 mass parts or more and 1 mass part or less.
If the amount of the light fastness stabilizer added is more than 5 parts by mass, it tends to be colored, and even if a coloring agent is added, it is difficult to obtain, for example, a deep and clear jet black. On the other hand, if it is less than 0.001 parts by mass, there is a possibility that sufficient weather resistance cannot be obtained when used as interior and exterior parts for automobiles.

<Physical properties of thermoplastic resin composition>
The thermoplastic resin composition of the present invention preferably has the following physical properties.
- Total light transmittance The thermoplastic resin composition of the present invention preferably has a total light transmittance of 80% or more. In this case, the transparency of the polycarbonate resin composition is even more excellent. From the same point of view, it is particularly preferable that the total light transmittance is 85% or more. The total light transmittance is measured by the method described below.

Haze The thermoplastic resin composition of the present invention preferably has a haze of 45% or less, more preferably 25% or less, particularly preferably 15% or less, and 5% or less. Most preferred. In this case, the transparency of the thermoplastic resin composition is even more excellent. Haze is measured by the method described later.

• Retardation The thermoplastic resin composition of the present invention preferably has a retardation of 150 nm or less, more preferably 130 nm or less, and particularly preferably 125 nm or less. In this case, the molded article molded from the thermoplastic resin composition has a smaller retardation, so that the effect of suppressing distortion such as double or blurred images through the molded article is more effective. Excellent. The phase difference is measured by the method described below.

<Molded product>
When molding a molded article using the thermoplastic resin composition of the present invention, any molding method can be used, but injection molding, injection compression, and injection press molding are preferably used. As for the runner used at that time, it is possible to use not only the usual cold runner system but also the hot runner system. Insert molding, in-mold coating molding, two-color molding, sandwich molding, etc. are also possible. Furthermore, in order to obtain designability, it is also possible to use adiabatic mold molding and rapid heating and cooling mold molding.

Next, the present invention will be described in more detail with reference to examples. The present invention is by no means limited by these examples. First, the evaluation method will be explained.

[Evaluation method]
(1) Refractive index Pellets were dried at 80°C for 6 hours using a vacuum dryer. Next, the dried pellets were pressed at 230° C. using a mini test press (MP-2FH manufactured by Toyo Seiki Seisakusho Co., Ltd.) to prepare a press-molded plate (width 7 mm×length 15 mm×thickness 1 mm). The obtained press-molded plate was cut into a predetermined size (width 160 mm x length 160 mm x thickness 1 mm), and an interference filter of 589 nm (D line) was passed using an Abbe refractometer ("DR-M4" manufactured by Atago Co., Ltd.). was used to measure the refractive index nD.

(2) Measurement of Total Light Transmittance The obtained pellets of the thermoplastic resin composition were dried at 100° C. for 6 hours using a hot air dryer. Next, the dried pellets of the thermoplastic resin composition are supplied to an injection molding machine (manufactured by Japan Steel Works, Ltd.: J85AD type), under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. , an injection-molded plate (width 100 mm x length 100 mm x thickness 2 mm) was molded. The obtained injection molded plate was measured for total light transmittance of the test piece according to JIS K7361-1 using NDH-7000II manufactured by Nippon Denshoku Industries Co., Ltd.

(3) Haze Measurement Using the same test piece as the total light transmittance measurement, the haze of the test piece was measured using NDH-7000II manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136.

(4) Pencil Hardness Measurement Using the same test piece as the haze measurement described above, pencil hardness was measured using a pencil hardness tester manufactured by Mize Testing Machine Co., Ltd. in accordance with JIS K5600-5-4.

(5) Retardation Measurement Using the same test piece as the pencil hardness measurement, the retardation at a wavelength of 590 nm was measured with a retardation measurement device "KOBRA WWR/XY" manufactured by Oji Scientific Instruments Co., Ltd. The measurement was performed by dividing into meshes of 10 mm×10 mm, and the average of the phase differences of the divided meshes was taken as the average phase difference.

(6) Hue Measurement Using the same test piece as in the above retardation measurement, the lightness L* value was measured with a hue apparatus "CM-5" manufactured by Konica Minolta, Inc. The L* value was measured by a reflection method using a D65/10 light source and a reflection measurement diameter of φ30 mm.

Those that satisfied all of the following conditions were judged to have passed the test.
・Total light transmittance: 80% or more ・Haze: 45% or less ・Pencil hardness: F or more ・Average retardation: 170 nm or less

[raw materials]
<Raw material for polycarbonate resin (A)>
· Isosorbide ... POLYSORB manufactured by Rocket Fleuret, hereinafter referred to as "ISB". • Cyclohexanedimethanol: manufactured by Eastman, hereinafter referred to as "CHDM".
- Diphenyl carbonate: manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as "DPC".

<Resin (B)>
• Polymethyl methacrylate: manufactured by Mitsubishi Chemical Corporation, trade name: ACRYPET VH, refractive index: nd = 1.492, hereinafter referred to as "PMMA".
<Resin (C)>
Acrylonitrile-styrene copolymer resin: manufactured by Techno UMG, refractive index: nd=1.569, trade name: Sunrex, hereinafter referred to as "AS".

[Production of polycarbonate resin (A-1)]
(Production example 1)
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100° C., ISB, CHDM, DPC purified by distillation to reduce the chloride ion concentration to 10 ppb or less, and calcium acetate monohydrate were added in a molar ratio. ISB/CHDM/DPC/calcium acetate monohydrate = 0.70/0.30/1.00/1.3×10 ⁻⁶ , sufficiently replaced with nitrogen, oxygen concentration 0.0005 Adjusted to ~0.001 vol%.
Subsequently, heating was performed with a heat medium, and when the internal temperature reached 100°C, stirring was started, and the contents were melted and made uniform while controlling the internal temperature to 100°C. After that, the temperature was started to rise, and the internal temperature was raised to 210°C in 40 minutes. When the internal temperature reached 210°C, the temperature was controlled to be maintained. After 90 minutes, the pressure was increased to 13.3 kPa (absolute pressure, hereinafter the same), and the pressure was maintained for an additional 60 minutes.

Phenol vapor, which is a by-product of the polymerization reaction, is led to a reflux condenser using a refrigerant whose inlet temperature is controlled at 100°C, and a small amount of dihydroxy compounds and carbonic acid diesters contained in the phenol vapor are removed. After returning to the polymerization reactor, uncondensed phenol vapor was subsequently introduced to a condenser using hot water of 45° C. as a refrigerant and recovered. After the content thus oligomerized is once restored to atmospheric pressure, it is transferred to another polymerization reactor equipped with a stirring blade and a reflux condenser controlled in the same manner as described above, and the temperature is raised and the pressure is reduced. was started, and the internal temperature was set to 220° C. and the pressure to 200 Pa in 60 minutes.
After that, the internal temperature is 230° C. and the pressure is 133 Pa or less over 20 minutes, and when the predetermined stirring power is reached, the pressure is restored to atmospheric pressure, the contents are extracted in the form of strands, and the pellets of the carbonate copolymer are cut with a rotary cutter. made it The obtained resin (A-1) was used in the following examples and comparative examples. The refractive index (nD) of resin (A-1) was 1.50.

[Production of polycarbonate resin (A-2)]
(Production example 2)
It was produced in the same manner as in Production Example 1 except that the molar ratio of ISB and CHDM was set to ISB/CHDM=0.30/0.70. The obtained resin (A-2) was used in the following examples and comparative examples. The refractive index (nD) of resin (A-2) was 1.50.

[Production of polycarbonate resin (A-3)]
(Production example 3)
It was produced in the same manner as in Production Example 1 except that CHDM was changed to TCDDM. The obtained resin (A-3) was used in the following examples and comparative examples. The refractive index (nD) of resin (A-3) was 1.511.

(Examples 1 to 13, Comparative Examples 1 to 6, Reference Examples 1 to 3)
Using the resins (A-1), (A-2), (A-3), PMMA, and AS produced in Production Examples 1 to 3, each component was blended according to the polycarbonate resin composition formulation shown in Table 1, and 2 Using a twin-screw extruder (LABOTEX30HSS-32) manufactured by Japan Steel Works, Ltd., which has two vent ports, the resin temperature at the extruder outlet is extruded in a strand shape so that the resin temperature is 250 ° C., cooled and solidified with water, and then rotated. Pelletized with a type cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa. Reference Example 3 is colored black based on the formulation of Example 5.
The obtained thermoplastic resin composition was evaluated by the method described above, and the results are shown in Table 1.
The retardation of PMMA and AS is shown in Reference Examples 1 and 2, and the difference from each example was confirmed.

[result]
From the above results, it is clear that in Examples 1 to 13, sufficiently high transparency and low average retardation can be obtained. Furthermore, as is clear from Reference Examples 1 and 2, although the average retardation of resin (C) alone is extremely high, Example 1 containing a compatibilizing resin for resin (B) and resin (C) ~ 13, while maintaining higher transparency than Comparative Example 1 or Comparative Example 4 containing only resin (A-1) or resin (A-3) and resin (B), the same or less average retardation was gotten.
On the other hand, in Comparative Examples 2 and 5, the average retardation could not be measured because the transparency of the samples was too poor. In addition, it was found that Comparative Examples 3 and 6 provided sufficiently high transparency as in Examples 1 to 13, but provided an average retardation higher than those in Examples 1 to 13.
In Reference Example 3, the L* value was 0.74, and it was clarified that jet-blackness can be expressed by obtaining sufficiently high transparency and low average retardation.

Claims (10)

a polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following general formula (1);
A resin (B) having a structural unit (b) derived from a (meth)acrylic acid ester-based monomer component, and
At least one resin (C) having a structural unit (c1) derived from acrylonitrile and a structural unit (c2) derived from an aromatic vinyl monomer,
The resin (B) and the resin (C) are compatible with each other,
A thermoplastic resin composition wherein the weight ratio of the resin (B) to the resin (C) is B:C=99:1 to 1:99.

2. The thermoplastic resin composition according to claim 1, wherein the resin (C) is a resin (C1) having both the structural unit (c1) and the structural unit (c2). 3. The thermoplastic resin composition according to claim 1, wherein the resin (C) is an acrylonitrile-styrene copolymer. When the total amount of the resin (A), the resin (B), and the resin (C) is 100 parts by weight, the total amount of the resin (B) and the resin (C) is 1 part by weight or more and 50 parts by weight or less. The thermoplastic resin composition according to any one of claims 1 to 3. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the content ratio of the resin (B) and the resin (C) is B:C = 99:1 to 65:35 by weight. . a polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following general formula (1);
A resin (B) having a structural unit (b) derived from a (meth)acrylic acid ester-based monomer component, and
A resin (C1′) consisting only of both structural units (c1) derived from acrylonitrile and structural units (c2) derived from an aromatic vinyl monomer,
A thermoplastic resin composition in which the weight ratio of the resin (B) to the resin (C1′) is B:C1′=99:1 to 1:99.

A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 6. A polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following general formula (1), and a resin (B) having a structural unit (b) derived from a (meth)acrylic acid ester-based monomer component. and at least one resin (C) having a structural unit (c1) derived from acrylonitrile and a structural unit (c2) derived from an aromatic vinyl monomer to produce a thermoplastic resin composition. have
A method for producing a thermoplastic resin composition, wherein the weight ratio of the resin (B) to the resin (C) is B:C=99:1 to 1:99.

9. The resin (C) according to claim 8, wherein the resin (C) is a resin (C1′) consisting only of structural units (c1) derived from acrylonitrile and structural units (c2) derived from an aromatic vinyl monomer. A method for producing a thermoplastic resin composition. 9. The method for producing a thermoplastic resin composition according to claim 8, wherein the resin (B) and the resin (C) are compatible with each other.