JP2017149817A - Thermoplastic resin composition and molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that is used in applications requiring impact resistance and low haze like in a building material field, an electric/electronic field, an automobile field, an optical component field, a miscellaneous field and the like, and accordingly of which a molded article is excellent in impact resistance and has low haze, and to provide a molded article formed by molding the same.SOLUTION: There is provided a thermoplastic resin composition which contains a polycarbonate resin (A) containing a structural unit derived from a specific dihydroxy compound and an acrylic resin composition (B), where the acrylic resin composition (B) contains an acrylic resin (B-1) and a rubbery graft polymer (B-2).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition having excellent impact resistance and low haze when formed into a molded product, and a molded product formed by molding the same.

  Polycarbonate is generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and there is a demand for providing polycarbonate using raw materials obtained from biomass resources such as plants. In addition, it is feared that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., so that carbon-neutral plant-derived monomers are used as raw materials even after disposal after use. There is a need to develop polycarbonate. In particular, it is used for applications that require impact resistance and low haze, such as the building materials field, electrical / electronic field, automotive field, optical parts field, and sundries field. There has been a demand for a resin composition having excellent impact properties and low haze.

Conventionally, various polycarbonates using plant-derived monomers as raw materials have been developed. For example, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (see, for example, Patent Document 1).
Here, in the case of the aromatic polycarbonate resin that has been widely used heretofore, the resin itself was excellent in impact resistance, but in the case of using isosorbide, it was inferior in impact resistance and improved compared to the aromatic polycarbonate resin. Is required. In response to this problem, a polycarbonate resin composition containing a polycarbonate resin having a high glass transition temperature and a rubbery polymer has been proposed as one that improves impact resistance (see, for example, Patent Document 2).

British Patent No. 1079686 JP 2014-201679 A

However, in the invention described in the cited document 1, no attention has been paid to the viewpoint of impact resistance of polycarbonate using isosorbide as a raw material, and since no measures are taken to improve impact resistance, It is not satisfactory from the viewpoint of impact resistance.
In addition, although each cited document 2 describes that a rubber-like graft polymer is added to a polycarbonate using isosorbide as a raw material, further improvement in impact resistance and reduction in haze have been demanded.
That is, an object of the present invention is to provide a thermoplastic resin composition having excellent impact resistance and low haze when formed into a molded product, and a molded product formed by molding the same.

As a result of investigations by the present inventors, a polycarbonate resin (A) containing a structural unit derived from a specific dihydroxy compound (A) and an acrylic resin composition (B) are contained,
When the acrylic resin composition (B) is a thermoplastic resin composition containing the acrylic resin (B-1) and the rubber-like graft polymer (B-2), it has excellent impact resistance and haze. The inventors have found that the molded product is low and have completed the present invention.

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) and an acrylic resin composition (B),
A thermoplastic resin composition in which the acrylic resin composition (B) contains an acrylic resin (B-1) and a rubbery graft polymer (B-2).

[2] In the acrylic resin composition (B), the constituent weight ratio of the acrylic resin (B-1) and the rubber-like graft polymer (B-2) is in the range of 95/5 to 5/95 [1. ] The thermoplastic resin composition as described in.
[3] The thermoplastic resin composition according to [1] or [2], wherein the rubber graft polymer (B-2) has a rubber part having an alkyl acrylate structural unit.
[4] A molded product comprising the thermoplastic resin composition according to any one of [1] to [3].
[5] The rubbery graft polymer (B-2) is mixed with the acrylic resin (B-1),
The manufacturing method of the thermoplastic resin composition mixed with the polycarbonate resin (A) containing the structural unit derived from the dihydroxy compound represented by following General formula (1).
[6] In the acrylic resin composition (B), the constituent weight ratio of the acrylic resin (B-1) and the rubber-like graft polymer (B-2) is in the range of 95/5 to 5/95 [5. ] The manufacturing method of the thermoplastic resin composition of description.
[7] The method for producing a thermoplastic resin composition according to [5] or [6], wherein the rubber graft polymer (B-2) has a rubber part having an alkyl acrylate structural unit.

  According to the present invention, it is suitable for applications requiring excellent impact resistance and low haze molding (for example, building material field, electric / electronic field, automobile field, optical part field, miscellaneous goods field, etc.). A thermoplastic resin composition that can be used and a molded product formed by molding the same can be provided.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

<Polycarbonate resin (A)>
The polycarbonate resin (A) used for this invention is a polycarbonate resin characterized by including the structural unit (a) derived from the dihydroxy compound represented by following formula (1).

  Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be. Among them, isosorbide obtained by dehydrating and condensing sorbitol produced from various starches that are abundant as plant-derived resources is easy to obtain and manufacture, moldability, heat resistance, and impact resistance. Most preferable from the viewpoints of properties, surface hardness, and carbon neutral.

  Since the dihydroxy compound represented by the above formula (1) has a cyclic ether structure, it is likely to be gradually oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger and 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, there is a possibility that the resulting polycarbonate resin and thermoplastic resin composition may be colored, and not only the physical properties may be significantly degraded, The polymerization reaction may be affected, and a high molecular weight polymer may not be obtained.

  In addition to the structural unit (a) derived from the dihydroxy compound represented by the formula (1), the polycarbonate resin (A) used in the present invention is an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, an aromatic bisphenol, and a formula. Structural units derived from one or more dihydroxy compounds selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compounds represented by (1) (hereinafter sometimes referred to as “other dihydroxy compounds”) (b In view of the impact resistance of the polycarbonate resin (A), a copolymer polycarbonate resin containing Of these, 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 the light resistance of the polycarbonate resin, the molecular structure has an aromatic ring structure. In particular, an aliphatic dihydroxy compound and / or an alicyclic dihydroxy compound are more preferable, and an alicyclic dihydroxy compound is most preferable in consideration of heat resistance.

  The aliphatic dihydroxy compound may be a linear aliphatic dihydroxy compound or a branched aliphatic dihydroxy compound. For example, 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, Examples include 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and the like.

Examples of the alicyclic dihydroxy compound include 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane di Examples include methanol, 1,3-adamantane dimethanol, and limonene.

  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-hydride) Xylphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 ′ -Dichlorodiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 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 to 2000), poly-1,3-propylene glycol, and polytetramethylene glycol.
The content ratio of the structural unit (b) derived from other dihydroxy compounds in the polycarbonate resin (A) used in the present invention is 10 mol% or more in the structural units derived from all dihydroxy compounds in the polycarbonate resin (A). Preferably, 20 mol% or more is more preferable, and 30 mol% or more is particularly preferable. Moreover, 60 mol% or less is preferable, 50 mol% or less is more preferable, and 45 mol% or less is especially preferable. If the structural unit (b) derived from the other 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.

  The polycarbonate resin (A) of the present invention may be a mixture of two or more, but the content ratio of the structural unit (b) derived from another dihydroxy compound in the polycarbonate resin (A) in that case is the polycarbonate resin If each of the polycarbonate resins corresponding to (A) is averaged according to the content and within the above range, it is similarly preferable.

  The polycarbonate resin (A) used in the present invention can be produced by a generally used production method of a polycarbonate resin, and the production method is a solution polymerization method using phosgene, a melt in which a carbonic acid diester and a dihydroxy compound are reacted. Any polymerization method may be used, but a melt polymerization method is preferred in which a dihydroxy compound containing the dihydroxy compound represented by the formula (1) is reacted with a diester carbonate having lower toxicity to the environment in the presence of a polymerization catalyst. . In addition, as a polymerization catalyst (transesterification catalyst) in melt polymerization, a known alkali metal compound and / or alkaline earth metal compound is used. It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound together with an alkali metal compound and / or an alkaline earth metal compound.

  The polycarbonate resin (A) used in the present invention can be produced by subjecting a dihydroxy compound containing the dihydroxy compound represented by the formula (1) and a carbonic acid diester such as diphenyl carbonate to an ester exchange reaction as described above. More specifically, it can be obtained by transesterification to remove by-product monohydroxy compounds and the like 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 reaction 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 a long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Basic compounds such as metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds of Group 1 or Group 2 (hereinafter simply referred to as “Group 1” or “Group 2”) Compounds. 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.

It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination 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, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound 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 borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate 2 potassium potassium phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, and disodium salt, dipotassium salt, dilithium salt, and dicesium salt of bisphenol A. Among these, cesium compounds and lithium compounds are preferred.

  Examples of the Group 2 metal compound include 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 still more preferable.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron. It is done.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
Examples of the basic ammonium compound 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 Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound 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 these, the use of at least one metal compound selected from the group consisting of Group 2 metal compounds as a catalyst is excellent in various physical properties such as transparency, hue, and light resistance of the obtained polycarbonate resin (A). It is preferable for the purpose.
In order to make the polycarbonate resin (A) particularly excellent in transparency, hue, and light resistance, at least one metal compound selected from the group consisting of a magnesium compound, a calcium compound, and a barium compound is used as the catalyst. It is preferable that it is 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 as a metal equivalent with respect to 1 mol of all dihydroxy compounds subjected to the reaction. It is in the range of 0.1 to 100 μmol, more preferably 0.5 to 50 μmol, particularly preferably 1 to 25 μmol.
Among the above, when using a compound containing at least one metal selected from the group consisting of group 2 metals, the amount in terms of metal is preferably 0.1 μmol or more, more preferably, per 1 mol of all dihydroxy compounds subjected to the reaction. Is 0.5 μmol or more, particularly preferably 0.7 μmol or more. Further, 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 necessary for producing the polycarbonate resin (A) having a desired molecular weight cannot 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 will the hue of the resulting polycarbonate resin (A) be deteriorated, but also by-products may be generated, resulting in a decrease in fluidity and the generation of gel, resulting in brittle fracture. This may cause the production of polycarbonate resin (A) having a target quality.

In the thermoplastic resin composition of the present invention, the amount of the metal used as the catalyst is derived from the catalyst used for the production of the polycarbonate resin and contained in the thermoplastic resin composition. Therefore, the usage amount of the metal of the catalyst in the thermoplastic resin composition is the same usage amount as the range specified above.
As the polymerization reaction, a known method can be used, and any method of a batch method, a continuous method, or a combination of a batch method and a continuous method may be used.

  Moreover, when manufacturing the polycarbonate resin (A) used for this invention, in order to prevent mixing of a foreign material, it is desirable to install a filter. The filter installation position is preferably on the downstream side of the extruder, and the filter foreign matter removal size (opening) is usually preferably 100 μm or less as 99% removal filtration accuracy. In particular, in the case of disagreeing with the entry of minute foreign matters for film applications, 40 μm or less is preferable, and 10 μm or less is more preferable.

Extrusion of the polycarbonate resin (A) used in the present invention is preferably class 7 as defined in JIS B 9920 (2002), more preferably higher than class 6 in order to prevent foreign matter from being mixed after extrusion. It is desirable to carry out in a clean room.
Moreover, when cooling the extruded polycarbonate resin (A) to form chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

The molecular weight of the polycarbonate resin (A) used in the present invention can be represented by a reduced viscosity, and the reduced viscosity is usually preferably 0.30 dL / g or more, and more preferably 0.35 dL / g or more. The upper limit of the reduced viscosity is usually preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.
If the reduced viscosity of the polycarbonate resin (A) is too low, the toughness of the resin composition may be small. If the reduced viscosity is too large, the flow when molding electrical / electronic equipment parts and automotive interior / exterior parts There is a tendency that the productivity is lowered and the productivity and moldability are lowered. In addition, the molding temperature must be higher than appropriate, and the color tone may deteriorate.
The reduced viscosity of the polycarbonate resin is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent, precisely adjusting the polycarbonate resin concentration to 0.6 g / dL. .

The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 90 ° C. or higher and 145 ° C. or lower, more preferably 100 ° C. or higher and 135 ° C. or lower, and particularly preferably 110 ° C. or higher and 125 ° C. or lower. If the glass transition temperature is less than 90 ° C, the heat resistance is insufficient, and if it is 145 ° C or more, the fluidity is insufficient at the time of molding, and the resin composition is not filled to the end of the product, or the strength at the weld part is reduced 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 polycarbonate resin in a molten state is continuously supplied to a twin-screw extruder provided with three vent ports and water injection equipment, and Irganox 1010 (as an antioxidant is added to 100 parts by mass of the polycarbonate resin. BASF Japan Ltd., pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) 0.1 parts by mass, ADK STAB 2112 (manufactured by ADEKA Corporation, Tris ( 2,4-di-tert-butylphenyl) phosphite) and 0.05 part by mass of Unistar E-275 (manufactured by NOF Corporation) as a release agent were added continuously. After devolatilizing low molecular weight substances such as phenol under reduced pressure at each vent section provided in the screw extruder, the pelletizer Pelletize more.

(2) Injection molding About pellets kneaded by a twin screw extruder, pellets preliminarily dried at 80 ° C. for 4 hours were subjected to a J75EII type injection molding machine manufactured by Nippon Steel, with a cylinder temperature of 230 ° C., a molding cycle of 45 seconds, a mold temperature of 60 At 60 ° C., a flat plate of 60 mm × 60 mm × 3 mmt is formed.

(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 with a D65 light source taking measurement. 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. When this light transmittance is higher than the said minimum, the total light transmittance when it is set as a thermoplastic resin composition will become high. Details of the method for measuring the light transmittance will be described in the Examples section.

The haze according to JIS K7105 of the polycarbonate resin (A) of the present invention is usually 2 or less, preferably 1.5 or less, and most preferably 1 or less. If haze is the said range, when it is set as a thermoplastic resin composition, high total light transmittance and high haze can be made compatible.
In the thermoplastic resin composition of the present invention, one type of polycarbonate resin (A) may be used alone, and the types, copolymerization ratios, physical properties, etc. of structural units derived from other dihydroxy compounds are different. You may mix and use 2 or more types.

<Acrylic resin composition (B)>
[Acrylic resin (B-1)]
As the acrylic resin (B-1) used in the present invention, an acrylic resin as a thermoplastic resin is used. The following compounds are mentioned as a monomer used for acrylic resin. For example, methyl methacrylate, methacrylic acid, 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, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopenteni Oxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyl maleate Oxyethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meta ) Acrylate, diethylaminoethyl (meth) acrylate and the like. These may be used by polymerizing alone or in combination of two or more. Among these, those using at least one of alkyl methacrylate and alkyl acrylate are preferable from the viewpoint of impact resistance and low haze. Further, other monomers that can be polymerized with these acrylic monomers, for example, polyolefin monomers, vinyl monomers, and the like may be used in combination.
The molecular weight of the acrylic resin (B-1) 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, the appearance such as flow unevenness when molded as a multilayer body. A multilayer body excellent in mechanical properties and heat resistance can be provided without causing defects.

<Rubber graft polymer (B-2)>
In the rubbery graft polymer (B-2) of the present invention, the rubber part preferably has an alkyl acrylate structural unit, and more preferably the rubber part has a butadiene structural unit and an alkyl acrylate structural unit. . Further, the rubber-like graft polymer latex obtained by emulsion polymerization using an aliphatic emulsifier is obtained by coagulation using an alkaline earth metal salt and recovery. This rubber-like graft polymer latex preferably contains a vinyl monomer (G), preferably a vinyl monomer (P) having a polar group, in the presence of a rubber latex having a butadiene structural unit and an alkyl acrylate structural unit. It is obtained by polymerizing the vinyl monomer (G) contained.

As said rubber latex, it is preferable to use an elastomer, and it is preferable to use a thermoplastic elastomer among them. As the thermoplastic elastomer, various copolymer resins are used, and those having a glass transition temperature of usually −20 ° C. or lower, preferably −30 ° C. or lower, more preferably −50 ° C. or lower, more preferably −70 ° C. The following are preferred.
The rubber latex having a butadiene structural unit and an alkyl acrylate structural unit has a butadiene structural unit of 1 to 99% by weight, an alkyl acrylate structural unit of 99 to 1% by weight, and other vinyl monomer structural units of 0 to 30% by weight (provided that The total solid content in the rubber latex is preferably 100% by weight). It is more preferable to have 1 to 99% by weight of butadiene structural units, 99 to 1% by weight of alkyl acrylate structural units, and 0 to 10% by weight of other vinyl monomer structural units. If the content of the butadiene structural unit in the rubber latex is 1% by weight or more, it is preferable from the viewpoint of impact resistance, and if it is 99% by weight or less, it is preferable from the viewpoint of the YI value (thermal colorability). If the other vinyl monomer structural unit is 30% by weight or less, the difference in refractive index between the rubbery graft polymer of the present invention and the polycarbonate resin of the present invention is preferably reduced.

  Here, the butadiene structural unit refers to a structural unit derived from a butadiene monomer used in the production of rubber latex, and the alkyl acrylate structural unit refers to an alkyl alkylate monomer used in the production of rubber latex. It refers to a structural unit derived from, and the vinyl monomer structural unit refers to a structural unit derived from another vinyl monomer used as necessary in the production of rubber latex.

The rubber latex is obtained by polymerizing a butadiene monomer, an alkyl acrylate monomer, and other vinyl monomers used as necessary.
The butadiene monomer is not particularly limited, and examples thereof include diene monomers such as butadiene and isoprene, such as 1,3-butadiene.
The alkyl acrylate monomer is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and t-butyl acrylate.

These monomers may be used individually by 1 type, and may use 2 or more types together. For reasons of polymerization stability of emulsion polymerization, the alkyl acrylate monomer is preferably an alkyl acrylate having 2 to 8 carbon atoms, more preferably an alkyl acrylate having 3 to 6 carbon atoms, and particularly preferably butyl acrylate.
As another vinyl monomer, a monofunctional or polyfunctional vinyl monomer copolymerizable with a butadiene monomer or an alkyl acrylate monomer can be used. Examples of other vinyl monomers include monofunctional monomers represented by acrylonitrile and alkyl methacrylate; divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, Examples thereof include polyfunctional monomers such as methylolpropane triacrylate and pentaerythritol tetraacrylate. Other vinyl monomers may be used alone, or 2
More than one species may be used in combination.

The method for polymerizing the rubber latex is not particularly limited, but emulsion polymerization is preferred because it is easy to control the particle size of the rubber latex and to form a core / shell structure.
The polymerization initiator used for the polymerization of the rubber latex is not particularly limited, and for example, an azo initiator or a peroxide initiator can be used. These polymerization initiators may be used individually by 1 type, and may use 2 or more types together. The amount of the polymerization initiator used is preferably 0.05 to 1.0 part by weight, particularly about 0.1 to 0.3 part by weight, based on 100 parts by weight of the monomer used as a normal raw material.

  The emulsifier used for the polymerization of the rubber latex is not particularly limited, and for example, an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, and a nonionic anionic emulsifier can be used. These polymerization initiators may be used individually by 1 type, and may use 2 or more types together. For the reason of reducing thermal coloring, it is preferable to use an aliphatic emulsifier such as sodium N-lauroyl sarcosinate or potassium oleate as the emulsifier. The use amount of an emulsifier such as an aliphatic emulsifier is preferably 0.05 to 3 parts by weight, more preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of a monomer used as a normal raw material.

  The volume average particle diameter of the rubber particles in the rubber latex is preferably 0.1 to 1 μm, more preferably 0.15 μm or more. Further, the volume average particle diameter of the rubber particles in the rubber latex is more preferably 0.7 μm or less, and further preferably 0.5 μm or less. When the volume average particle diameter of the rubber particles in the rubber latex is 0.1 μm or more, the impact at low temperature of the polycarbonate resin composition of the present invention obtained by adding the rubber graft polymer of the present invention to the polycarbonate resin of the present invention is low. Therefore, the thickness is preferably 1 μm or less because cullet is hardly generated during the production of the rubbery graft polymer of the present invention. Here, the volume average particle diameter of the rubber particles in the rubber latex refers to the 50% volume average particle diameter of the rubber particles in the rubber latex measured using a light scattering particle meter. It is measured by the method described in the section.

The volume average particle diameter of the rubber particles in the rubber latex is about 0.1 μm according to ordinary emulsion polymerization. In order to adjust the volume average particle diameter to 0.1 to 1 μm, a method of enlarging rubber particles in the rubber latex with a thickening agent is used.
The enlargement of the rubber particles can be performed by adding a thickening agent to the rubber latex.
The thickening agent can be arbitrarily selected from known ones, but it is preferable to use an acid group-containing copolymer (K) and / or an oxyacid salt (M).

The acid group-containing copolymer (K) is preferably obtained by polymerizing an unsaturated acid, an alkyl acrylate, and other copolymerizable monomers used as necessary.
Examples of the unsaturated acid used for the polymerization of the acid group-containing copolymer (K) include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid, and p-styrene sulfone. Examples include acids. Of these, acrylic acid and methacrylic acid are preferable in terms of availability and ease of handling. These unsaturated acids may be used individually by 1 type, and may use 2 or more types together.

The alkyl acrylate used for the polymerization of the acid group-containing copolymer (K) is preferably an alkyl acrylate having 1 to 12 carbon atoms in the alkyl group, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate. Hexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate. These alkyl acrylates may be used alone or in combination of two or more.

Examples of other copolymerizable monomers used as needed for the polymerization of the acid group-containing copolymer (K) include styrene derivatives such as styrene and α-methylenestyrene, alkyl methacrylate, and acrylonitrile. It is done. These other copolymerizable monomers may be used alone or in combination of two or more.
The proportion of the monomer used in the acid group-containing copolymer (K) is 3 to 40% by weight of unsaturated acid, 97 to 35% by weight of alkyl acrylate, and 0 to 40% by weight of other copolymerizable monomers. Preferably, the unsaturated acid is 5 to 35% by weight, the alkyl acrylate is 95 to 30% by weight, and other copolymerizable monomers are 0 to 35% by weight. When the composition is within the above range, the stability of the latex during enlargement is excellent, and the rubber particle diameter of the rubber latex obtained by enlargement can be easily controlled.

The acid group-containing copolymer (K) can be obtained by polymerizing the monomer mixture having the above composition by a known emulsion polymerization method. The polymerization may be performed in one stage or in multiple stages. By polymerizing in multiple stages, an acid group-containing copolymer (K) having a multilayer structure of two or more layers can be obtained.
The oxyacid salt (M) is preferably at least one oxyacid salt (M) selected from an alkali metal salt or alkaline earth metal salt of oxyacid, or a salt of zinc, nickel and aluminum. Examples of such oxyacid salts (M) include salts of sulfuric acid, nitric acid, phosphoric acid and the like with potassium, sodium, magnesium, calcium, nickel, and aluminum. Oxygenate (M) is potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, sodium phosphate in terms of ease of particle size control during enlargement, availability, and ease of handling. Magnesium phosphate and the like are preferable.

Each of these acid group-containing copolymers (K) and oxyacid salts (M) may be used alone or in combination of two or more.
When each of these acid group-containing copolymer (K) and oxyacid salt (M) is used alone, the addition amount of the acid group-containing copolymer (K) is 100 parts by weight of the solid content of the rubber latex as the polymer solid content. It is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, and still more preferably 0.5 to 3 parts by weight. Moreover, 0.1-5 weight part is preferable with respect to 100 weight part of solid content of rubber latex, and, as for the addition amount of oxyacid salt (M), 0.1-4 weight part is more preferable. By adding the acid group-containing copolymer (K) and the oxyacid salt (M) within these ranges, the rubber particles in the rubber latex can be enlarged more efficiently, and the resulting enlarged rubber latex can be stabilized. The characteristics are also greatly improved.

In addition, when performing an enlargement process using an acid group containing copolymer (K), it is preferable that pH of rubber latex is 7 or more. When the pH is on the acidic side, the enlargement efficiency may be low even when the acid group-containing copolymer (K) is added.
The pH of the rubber latex may be adjusted during the production of the rubber latex, or may be separately performed before the enlargement treatment.

The rubbery graft copolymer latex is obtained by graft polymerization of the vinyl monomer (G) on the rubber latex.
As the vinyl monomer (G), a component obtained by polymerizing the vinyl monomer is used so that the glass transition temperature of the polymer is 70 to 120 ° C. The rubber graft polymer latex is coagulated and recovered as a powder. This is preferable in terms of recoverability.

As a vinyl monomer (G), as a vinyl monomer which does not have a polar group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl ( (Meth) acrylate, phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, Examples include bromostyrene, vinyl toluene, vinyl naphthalene, vinyl anthracene, vinyl benzoate, and vinyl acetate. Here, “(meth) acrylate” refers to one or both of “acrylate” and “methacrylate”. These monomers may be used individually by 1 type, and may use 2 or more types together.

  The vinyl monomer (G) preferably contains a vinyl monomer (P) having a polar group. When the vinyl monomer (G) contains the vinyl monomer (P) having a polar group, the rubber-like graft polymer of the present invention can be uniformly dispersed in the polycarbonate resin of the present invention. Thereby, the impact resistance of the polycarbonate resin composition obtained can be improved.

  Examples of the vinyl monomer (P) having a polar group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, dimethylacrylamide, and dimethylaminoethyl acrylate methyl chloride 4 Grade salt, acryloylmorpholine, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, isopropylacrylamide, diethylacrylamide, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (Meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, 2-vinyl-2-oxazo Emissions, p- methoxystyrene, o- methoxystyrene, maleic anhydride, N- phenylmaleimide, cyclohexyl maleimide. 2-Hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are preferred because of the ease of emulsion polymerization (generation of cullet and copolymerization with other graft monomers). These monomers may be used individually by 1 type, and may use 2 or more types together.

  The proportion of the vinyl monomer (P) having a polar group in the vinyl monomer (G) can be arbitrarily set, but is preferably 0.1 to 20% by weight, and 0.5 to 5% by weight. More preferable (however, the entire vinyl monomer (G) is 100% by weight). When the vinyl monomer (G) contains 0.1% by weight or more of the vinyl monomer (P) having a polar group, the rubber graft polymer of the present invention is uniformly dispersed in the polycarbonate resin of the present invention. be able to. On the other hand, the difference in refractive index between the polycarbonate resin of the present invention and the rubbery graft polymer of the present invention is that the vinyl monomer (G) contains a vinyl monomer (P) having a polar group of 20% by weight or less. Or the amount of cullet during polymerization.

  The proportion of the rubber latex in the rubber graft copolymer latex can be arbitrarily set, but the amount of each solid content is preferably 50 to 90% by weight (however, the total solid content of the rubber graft copolymer latex is 100% by weight). If the rubber latex in the rubber graft polymer latex is 50% by weight or more, it is preferable in terms of strength development. Further, if the rubber latex in the rubber graft polymer latex is 90% by weight or less, it is preferable in view of dispersibility in the polycarbonate resin of the present invention and coagulation recovery of the rubber graft polymer.

The method of graft polymerization of the vinyl monomer (G) onto the rubber latex is not particularly limited, but emulsion polymerization is preferred because of control of the rubber particle diameter and easy formation of the core / shell structure.
As the emulsion polymerization method, generally known emulsion polymerization methods such as batch addition polymerization of monomers, continuous addition polymerization of monomers, and multistage polymerization can be employed. Can be added.

  The graft layer may be one layer or two or more layers. When a rubber having a butadiene structural unit is copolymerized with a vinyl monomer having high hydrophobicity and low polymerizability, such as styrene, butadiene rubber and styrene are copolymerized, and the rubber becomes hard and the refractive index tends to swing. May be. Therefore, in the graft polymerization of the rubbery graft polymer in the present invention, a monomer having a high hydrophilicity and a high polymerization property and a high glass transition temperature, for example, a monomer mainly composed of methyl methacrylate is grafted. Then, it is preferable to polymerize a highly hydrophobic vinyl monomer (G) such as styrene.

The polymerization initiator used for the polymerization of the rubber graft copolymer latex can be the same as the polymerization initiator used to polymerize the rubber latex, and the amount used is usually 100 parts by weight of the monomer used as a raw material. The amount is preferably 0.05 to 1.0 part by weight, particularly about 0.1 to 0.3 part by weight.
Moreover, the emulsifier used for the polymerization of the rubber graft copolymer latex can be the same as the emulsifier used for polymerizing the rubber latex, and the amount used is 100 parts by weight of the monomer used as a normal raw material. On the other hand, it is preferably 0.05 to 3 parts by weight, particularly about 0.1 to 2 parts by weight.

The rubbery graft polymer of the present invention is obtained by coagulating from the rubbery graft polymer latex obtained as described above and collecting it as a powder.
As coagulants for coagulating rubber graft polymer latex, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid; organic acids such as acetic acid; sodium, potassium, calcium, magnesium, aluminum and inorganic acids Further, salts with organic acids can be used. These coagulants can be used alone or in combination of two or more. Among them, an alkaline earth metal salt is preferable because yellowing of the obtained polycarbonate resin composition can be prevented, an alkaline earth metal salt containing no sulfate is more preferable, and calcium acetate is particularly preferable. These coagulants are used as an aqueous solution, and the addition amount is not particularly limited, but an amount capable of sufficiently coagulating the latex is used. For example, when the polymer in the latex is 100 parts by weight, the addition amount of the coagulant is preferably 2 parts by weight or more, and more preferably 4 parts by weight or more. Moreover, 10 weight part or less is preferable and 8 weight part or less is more preferable.

<Compositional weight ratio of acrylic resin (B-1) and rubbery graft polymer (B-2) in acrylic resin composition (B)>
In the acrylic resin composition (B), the composition weight ratio of the acrylic resin (B-1) and the rubbery graft polymer (B-2) is in the range of 95/5 to 5/95. It is preferable because the property becomes favorable, more preferably in the range of 90/10 to 20/80, more preferably in the range of 80/20 to 30/70, and in the range of 70/30 to 40/60. Most preferably it is.

  In addition, it can be guessed with the following method that it is a polycarbonate resin composition which made the polycarbonate resin contain what was contained in the acrylic resin as the rubber-like graft polymer like this invention. That is, the dispersion state of the rubber graft polymer in the polycarbonate resin composition is confirmed with a transmission electron microscope or the like, and the polycarbonate resin composition obtained by mixing the polycarbonate resin, the acrylic resin, and the rubber graft polymer at the same time. If the dispersion state of the rubbery graft polymer is good, the polycarbonate resin composition is a polycarbonate resin composition in which a rubbery graft polymer is contained in an acrylic resin. It can be inferred.

<Content of acrylic resin composition in polycarbonate resin composition>
In the polycarbonate resin composition of the present invention, the content of the acrylic resin composition of the present invention relative to a total of 100 parts by weight of the polycarbonate resin (A) and the acrylic resin composition (B) of the present invention is 10 parts by weight or more and 60% by weight. Part or less. If the content of the acrylic resin composition of the present invention is too small outside the above range, a sufficient impact strength modification effect cannot be obtained, and the molded member may be broken. On the other hand, if the amount is too large outside the above range, good moldability may be impaired and burns may occur during molding, or transparency may be impaired. The content of the acrylic resin composition of the present invention in the polycarbonate resin composition of the present invention is more preferably based on 100 parts by weight of the total of the polycarbonate resin (A) and the acrylic resin composition (B) of the present invention. 15 parts by weight or less, more preferably 50 parts by weight or less.

<Content of Rubber Graft Polymer in Polycarbonate Resin Composition>
In the polycarbonate resin composition of the present invention, the content of the rubber graft polymer of the present invention relative to 100 parts by weight of the total of the polycarbonate resin (A) and the acrylic resin composition (B) of the present invention is 1 part by weight or more, 20 It is preferable that it is below the weight part. When the content of the rubber-like graft polymer of the present invention is too small outside the above range, a sufficient impact strength modification effect cannot be obtained, and the molded member may be broken. On the other hand, if the amount is too large outside the above range, good moldability may be impaired and burns may occur during molding, or transparency may be impaired. The content of the rubber-like graft polymer of the present invention in the polycarbonate resin composition of the present invention is more preferably based on 100 parts by weight of the total of the polycarbonate resin (A) and the acrylic resin composition (B) of the present invention. Is 15 parts by weight or less, more preferably 12.5 parts by weight or less.

<Additives>
In the thermoplastic resin composition of the present invention, an antioxidant, a light stabilizer, an ultraviolet absorber, a release agent, a colorant, a neutralizer, an antistatic agent, as long as the effect of suppressing the occurrence of stagnation noise can be maintained. Lubricants, lubricants, 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 in order to further improve the release from the cooling roll during sheet molding or the mold release from the mold during injection molding. A release agent may be blended within the range.
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 anhydride groups, silicone oils, Examples include organopolysiloxane. A mold release agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, behenic acid monoglyceride, 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. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used. A stearic acid ester is more preferable as a mold release agent from the viewpoints of mold release and transparency.

  As the stearic acid ester, a partial or total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and stearic acid is preferable. Such partial esters or total esters of monohydric or polyhydric alcohols and stearic acid include ethylene glycol distearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, pentaerythritol. More preferred are monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, 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. Of these, 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 using a mold release agent, the compounding quantity is 0.001 weight part or more normally with respect to a total of 100 weight part of polycarbonate resin (A) of this invention, and an acrylic resin composition (B), Preferably it is 0.00. 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 content of the release agent is excessively large, the amount of deposits on the mold may increase during molding, and if molding is carried out in large quantities, there is a possibility that labor may be required for mold maintenance. There is a possibility that the appearance will be defective. When the content of the release agent in the thermoplastic resin composition is not less than the above lower limit, there is an advantage that the molded product can be easily released from the mold at the time of molding, and the molded product can be easily obtained.

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

When adding an antioxidant to the thermoplastic resin composition of the present invention, the addition amount is usually preferably 0.001 part by mass or more, more preferably 0.002 with respect to 100 parts by mass of the polycarbonate resin (A). It is more than mass part, More preferably, it is 0.005 mass part or more, Usually, 5 mass part or less is preferable, More preferably, it is 3 mass part or less, More preferably, it is 2 mass part or less.
When the addition amount of the antioxidant is more than 5 parts by mass, the mold may be contaminated during molding, and a molded product having an excellent surface appearance may not be obtained. On the other hand, when it is less than 0.001 part by mass, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained.

<Phosphite antioxidant>
Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl Phosphite,
Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4 -Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-) tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol 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 use only 1 type and may use 2 or more types together.

<Sulfur-based antioxidant>
Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester 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, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6 -Methylbenzui Imidazole, 1,1'-thiobis (2-naphthol), and the like.
Among these, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.
These compounds may use only 1 type and may use 2 or more types together.

<Phenolic antioxidant>
Examples of the phenolic antioxidant include 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 ( , 5-Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl 2-[[beta]-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, 2,6- Examples of the compound include di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-ethylphenol.

Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. 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, preferably pentaerythritol- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] A further preferred.
These compounds may use only 1 type and may use 2 or more types together.

(Light stabilizer)
Examples of the light stabilizer include hindered amine light stabilizers, and the molecular weight is preferably 1000 or less, and more preferably 900 or less. When the molecular weight exceeds 1000, there is a possibility that sufficient weather resistance cannot be obtained when formed into a molded product. 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 at the time of molding, and a molded product having an excellent surface appearance may not be obtained.

Furthermore, a compound having a piperidine structure is preferable. The piperidine structure defined here may be a saturated 6-membered amine structure, and includes a structure in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable.
As the hindered amine light stabilizer, a compound having a plurality of piperidine structures is particularly preferable, and a compound in which the plurality of piperidine structures are linked by an ester structure is preferable.

  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-pyridinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-pyridinol and methanol, 1,2,3, 4-Butanetetracarboxylic acid condensate, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyl Nyl] 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-hydroxyphenyl) propionyloxy] ethyl] -2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane Tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-te Lamethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (2,2,6,6-tetramethyl-4 -Piperidyl) -1,6-hexanediamine polymer and 2,4,6-trichloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid and 2,2,6 , 6-tetramethyl-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- Condensate with 1,3,5-triazine Condensates of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl piperidine.

  When adding a light-resistant stabilizer to the thermoplastic resin composition of the present invention, the addition amount is usually 0.001 part by mass or more and 5 parts by mass or less, preferably 100 parts by mass of the polycarbonate resin (A), preferably It is 0.005 mass part or more and 3 mass parts or less, More preferably, it is 0.01 mass part or more and 1 mass part or less. When the addition amount of the light-resistant stabilizer is more than 5 parts by mass, it tends to be colored, and even if a colorant is added, it is difficult to obtain, for example, jet black with depth and clarity. On the other hand, when it is less than 0.001 part by mass, there is a possibility that sufficient weather resistance may not be obtained when an automobile interior / exterior product is obtained.

<Method for producing thermoplastic resin composition>
In the thermoplastic resin composition of the present invention, the above components are mixed at a predetermined ratio simultaneously or in an arbitrary order by a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. Can be manufactured.

<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. The runner used at that time can use not only a normal cold runner system but also a hot runner system. Also, insert molding, in-mold coating molding, two-color molding, sandwich molding, and the like are possible. Furthermore, in order to obtain a design property, it is also possible to use heat insulating mold forming and rapid heating / cooling mold forming.

(1) Measurement of Charpy impact strength The pellets of the polycarbonate resin composition were dried at 90 ° C for 6 hours using a hot air dryer. Next, the dried polycarbonate copolymer or resin composition pellets are supplied to an injection molding machine (manufactured by Nippon Steel Co., Ltd .: J75EII type), resin temperature 240 ° C., mold temperature 60 ° C., molding cycle 40 seconds. Under these conditions, an ISO test piece for mechanical properties was molded. The ISO test piece for mechanical properties obtained above was subjected to a notched Charpy impact test according to ISO 179 (2000). Higher values indicate higher impact resistance.

(2) Haze measurement The pellets of the polycarbonate resin composition were dried at 90 ° C for 6 hours using a hot air dryer. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (manufactured by Nippon Steel Co., Ltd .: J75EII type), and injection molding is performed under conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. A plate (width 60 mm × length 60 mm × thickness 2 mm) was molded. Based on JIS K7105 (1981), the haze of the test piece was measured with a D65 light source using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).

(3) Comprehensive judgment What satisfy | filled all the following conditions was set as the pass.
Notched Charpy impact strength: 15 kJ / m ² or more Haze: 60% or less

(Production Example 1)
In a polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled at 100 ° C., isosorbide (ISB, Rocket Fleure Co., Ltd .: POLYSORB) and cyclohexanedimethanol (CHDM, Eastman Co.) were purified by distillation and chloride. Diphenyl carbonate (DPC, manufactured by Mitsubishi Chemical Corporation) and calcium acetate monohydrate having an ion concentration of 10 ppb or less,
Prepared so that the molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ , sufficiently substituted with nitrogen, and the oxygen concentration It adjusted to 0.0005-0.001 volume%. Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed to maintain this temperature, and at the same time, pressure reduction was started, After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes.

The phenol vapor produced as a by-product along with the polymerization reaction is led to a reflux condenser using a steam controlled to 100 ° C. as an inlet temperature to the reflux condenser, and dihydroxy compounds and carbonic acid diesters contained in the phenol vapor in a slight amount. Returning to the polymerization reactor, the non-condensed phenol vapor was subsequently recovered by directing it to a condenser using 45 ° C. warm water as the refrigerant. After the contents thus oligomerized are once restored to atmospheric pressure, they are transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes.
Thereafter, the internal temperature is set to 230 ° C. over 20 minutes, the pressure is 133 Pa or less, the pressure is restored to atmospheric pressure when the predetermined stirring power is reached, the contents are extracted in the form of strands, and the pellets of the carbonate copolymer with a rotary cutter I made it.

(Production Example 2)
Manufacture except that in Preparation Example 1, the charge composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.50 / 0.50 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, pellets of carbonate copolymer were prepared.
In addition, the symbol of the compound used by the following example and the comparative example is as follows.
ISB: Isosorbide (Rocket Fleure, trade name: POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Eastman)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

<Acrylic resin>
VRL40: Polymethyl methacrylate (PMMA) resin (trade name: Acrypet VRL40, manufactured by Mitsubishi Rayon Co.) containing rubbery graft polymer (alkyl methacrylate / alkyl acrylate / styrene copolymer)
VH: rubber-like graft polymer-free polymethyl methacrylate (PMMA) resin (Mitsubishi Rayon Co., Ltd., trade name: Acrypet VH)

<Rubber graft polymer>
W-450A: Acrylic rubber (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Metabrene W-450A)
<Antioxidant>
AS2112: Phosphite antioxidant (manufactured by ADEKA, trade name: ADK STAB 2112)
IRGANOX 1010: phenolic antioxidant (manufactured by BASF Japan, trade name: IRGANOX 1010)

<Light resistance stabilizer>
LA-29: Benzotriazole UV absorber (manufactured by ADEKA, trade name: ADK STAB LA-29)
LA-77: Hindered amine light stabilizer (manufactured by ADEKA, trade name: ADK STAB LA-77)
<Release agent>
E-275: Glycol distearate (manufactured by NOF Corporation, trade name: Unistar E-275)

(Examples 1-2)
Using the carbonate copolymer pellets and PMMA resin VRL40 produced in Production Example 1, each component was blended with the polycarbonate resin composition shown in Table 1, and a twin screw extruder manufactured by Nippon Steel Works, Ltd. having two vent ports. Using (LABOTEX30HSS-32), the resin was extruded in a strand shape so that the resin temperature at the exit of the extruder was 250 ° C., cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The thermoplastic resin composition was evaluated and the results are shown in Table 1.

(Examples 3 to 4)
Using the carbonate copolymer pellets produced in Production Example 1 and Production Example 2 and PMMA resin VRL40, the same procedure as in Example 1 was conducted except that the composition shown in Table 1 was used. Manufactured and evaluated. The results are shown in Table 1.

(Comparative Examples 1-2)
The same procedure as in Example 1 was carried out except that the carbonate copolymer pellets and PMMA resin VH produced in Production Example 1 and Production Example 2 were used and the compositions shown in Table 1 were used. The results are shown in Table 1.

(Comparative Example 3)
Using the carbonate copolymer pellets produced in Production Example 1 and PMMA resin VH and rubbery graft polymer W-450A, the same procedure as in Example 1 was carried out except that the composition shown in Table 1 was obtained. Production and evaluation of a polycarbonate resin composition were performed. The results are shown in Table 1.

(Comparative Example 4)
A polycarbonate resin composition was prepared in the same manner as in Example 1, except that the carbonate copolymer pellets and rubber-like graft polymer W-450A produced in Production Example 2 were used, and the composition shown in Table 1 was used. Was manufactured and evaluated. The results are shown in Table 1.

Claims (7)

Containing a polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following general formula (1) and an acrylic resin composition (B),
A thermoplastic resin composition in which the acrylic resin composition (B) contains an acrylic resin (B-1) and a rubbery graft polymer (B-2).

  The constituent weight ratio of the acrylic resin (B-1) and the rubber-like graft polymer (B-2) in the acrylic resin composition (B) is in the range of 95/5 to 5/95. Thermoplastic resin composition.   The thermoplastic resin composition according to claim 1 or 2, wherein the rubber graft polymer (B-2) has a rubber part having an alkyl acrylate structural unit.   The molded article formed by containing the thermoplastic resin composition as described in any one of Claims 1-3. The rubbery graft polymer (B-2) is mixed with the acrylic resin (B-1),
The manufacturing method of the thermoplastic resin composition mixed with the polycarbonate resin (A) containing the structural unit derived from the dihydroxy compound represented by following General formula (1).   The constituent weight ratio of the acrylic resin (B-1) and the rubber-like graft polymer (B-2) in the acrylic resin composition (B) is in the range of 95/5 to 5/95. A method for producing a thermoplastic resin composition.   The method for producing a thermoplastic resin composition according to claim 5 or 6, wherein the rubber graft polymer (B-2) has a rubber part having an alkyl acrylate structural unit.