JP2017226818A - Thermoplastic resin composition and molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a thermoplastic resin composition having high transparency, low haze and high surface hardness when prepared into a molded article to be used, for example, in building material field, electric and electronic field, automotive field, optical component field and general merchandise field: and a molded article prepared by molding the above composition, and more preferably, to provide: a thermoplastic resin composition giving good appearance of a molded article having no appearance defect when prepared into the molded article, and a molded article prepared by molding the resin composition.SOLUTION: The thermoplastic resin composition comprises: a polycarbonate resin (A) including a structural unit derived from a specific dihydroxy compound; and a methyl methacrylate-maleic acid anhydride-styrene copolymer (B).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition having high transparency, low haze, and high surface hardness 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. Above all, it has high transparency, low haze, high surface hardness, and preferably no appearance defect, such as in the building materials field, electrical / electronic field, automobile field, optical parts field, sundries field, etc. For use in applications where the appearance of a molded product is required, there has been a demand for a resin composition having good properties when formed into a molded product.

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 acrylic resin that has been widely used for the above-mentioned applications, the transparency of the resin itself is high, the haze is low, and the surface hardness is high, but when using isosorbide Further improvements in these properties are needed. In response to this problem, a polycarbonate resin composition containing a polycarbonate resin having a high glass transition temperature and a specific rubber polymer has been proposed as having high transparency, low haze, and high impact resistance (for example, , See Patent Document 2).

British Patent No. 1079686 JP 2014-201679 A

However, in the invention described in the cited document 1, attention is not paid to the viewpoint that the polycarbonate using isosorbide as a raw material has high transparency, low haze, and high surface hardness, and these characteristics are improved. Since no treatment has been made, it is not satisfactory from the viewpoint of high transparency, low haze, and high surface hardness.
In addition, for Cited Document 2, although it is described that a rubbery graft polymer is added to a polycarbonate using isosorbide as a raw material, further improvement in properties, that is, high transparency, low haze, surface It has been demanded that the hardness is high, and more preferably, there is no appearance defect when it is formed into a molded product, and the molded product has a good appearance.
That is, an object of the present invention is to provide a thermoplastic resin composition having high transparency, low haze, and high surface hardness when formed into a molded product, and a molded product formed by molding the thermoplastic resin composition. It is preferable to provide a thermoplastic resin composition that does not have a poor appearance when formed into a molded product and provides a good molded product appearance, and a molded product formed by molding the same.

As a result of studies by the present inventors, a polycarbonate resin (A) containing a structural unit derived from a specific dihydroxy compound,
(B) When a thermoplastic resin composition containing a methyl methacrylate / maleic anhydride / styrene copolymer is used, the transparency is high, the haze is low, and the surface hardness is high. It has been found that there is no appearance defect and the appearance of a good molded product is obtained, and the present invention has been completed.

［２］メタクリル酸メチル・アクリル酸メチル共重合体（Ｃ）を含む［１］に記載の熱可塑性樹脂組成物。
［３］ＪＩＳ Ｋ７２１０（１９９９）に準拠した２３０℃、２．１６ｋｇのメルトフローレイト（ＭＦＲ）が６ｇ／１０ｍｉｎ以上である［１］または［２］に記載の熱可塑性樹脂組成物。
［４］熱可塑性樹脂に用いたメタクリル酸メチル・無水マレイン酸・スチレン共重合体（Ｂ）またはメタクリル酸メチル・無水マレイン酸・スチレン共重合体（Ｂ）とメタクリル酸メチル・アクリル酸メチル（Ｃ）の混合物が、ＪＩＳ Ｋ７２１０（１９９９）に準拠した２３０℃、３．８０ｋｇのメルトフローレイト（ＭＦＲ）が１０ｇ／１０ｍｉｎ以上である［１］〜［３］のいずれか一項に記載の熱可塑性樹脂組成物。
［５］アクリル系樹脂（Ｄ）を含む［１］〜［４］のいずれか一項に記載の熱可塑性樹脂組成物。
［６］アクリル系樹脂（Ｄ）のＪＩＳ Ｋ７２１０（１９９９）に準拠した２３０℃、３．８０ｋｇのメルトフローレイト（ＭＦＲ）が０．１ｇ／１０ｍｉｎ以上５０ｇ／１０ｍｉｎ以上以下である［５］に記載の熱可塑性樹脂組成物。
［７］メタクリル酸メチル・無水マレイン酸・スチレン共重合体以外のゴム質グラフト重合体（Ｅ）を含む請求項［１］〜［６］のいずれか一項に記載の熱可塑性樹脂組成物。
［８］上記ポリカーボネート樹脂組成物中、上記の成分（Ａ）、成分（Ｂ）、成分（Ｃ）、成分（Ｄ）および成分（Ｅ）の合計１００重量部とした際に、ポリカーボネート樹脂（Ａ）を４０重量部以上９５重量部以下含む［１］〜［７］のいずれか１項に記載のポリカーボネート樹脂組成物。
［９］上記ポリカーボネート樹脂組成物中、上記の成分（Ａ）、成分（Ｂ）、成分（Ｃ）、成分（Ｄ）および成分（Ｅ）の合計１００重量部とした際に、メタクリル酸メチル・無水マレイン酸・スチレン共重合体（Ｂ）、メタクリル酸メチル・アクリル酸メチル（Ｃ）、アクリル系樹脂（Ｄ）およびメタクリル酸メチル・無水マレイン酸・スチレン共重合体以外のゴム質グラフト重合体（Ｅ）を合計で、５重量部以上６０重量部以下含む［１］〜［８］のいずれか１項に記載のポリカーボネート樹脂組成物。
［１０］ポリカーボネート樹脂（Ａ）が、脂肪族ジヒドロキシ化合物、脂環式ジヒドロキシ化合物、芳香族ビスフェノール類及び式（１）で表されるジヒドロキシ化合物以外のエ
ーテル基含有ジヒドロキシ化合物からなる群より選ばれる一種以上のジヒドロキシ化合物に由来する構成単位を含む［１］〜［９］のいずれか一項に記載の熱可塑性樹脂組成物。［１１］［１］〜［１０］のいずれか一項に記載の熱可塑性樹脂組成物を含有してなる成形品。 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 thermoplastic resin composition comprising a methyl methacrylate / maleic anhydride / styrene copolymer (B).

[2] The thermoplastic resin composition according to [1], comprising a methyl methacrylate / methyl acrylate copolymer (C).
[3] The thermoplastic resin composition according to [1] or [2], wherein a melt flow rate (MFR) of 230 ° C. and 2.16 kg in accordance with JIS K7210 (1999) is 6 g / 10 min or more.
[4] Methyl methacrylate / maleic anhydride / styrene copolymer (B) or methyl methacrylate / maleic anhydride / styrene copolymer (B) used for thermoplastic resin and methyl methacrylate / methyl acrylate (C) ) Is a thermoplastic according to any one of [1] to [3], wherein a melt flow rate (MFR) of 230 ° C. and 3.80 kg in accordance with JIS K7210 (1999) is 10 g / 10 min or more. Resin composition.
[5] The thermoplastic resin composition according to any one of [1] to [4], including an acrylic resin (D).
[6] The acrylic resin (D) according to [5], wherein a melt flow rate (MFR) of 230 ° C. and 3.80 kg conforming to JIS K7210 (1999) is 0.1 g / 10 min or more and 50 g / 10 min or more. Thermoplastic resin composition.
[7] The thermoplastic resin composition according to any one of [1] to [6], comprising a rubbery graft polymer (E) other than methyl methacrylate / maleic anhydride / styrene copolymer.
[8] When the total amount of the component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight in the polycarbonate resin composition, the polycarbonate resin (A The polycarbonate resin composition according to any one of [1] to [7], comprising 40 parts by weight or more and 95 parts by weight or less.
[9] When the total amount of the component (A), the component (B), the component (C), the component (D) and the component (E) is 100 parts by weight in the polycarbonate resin composition, Rubber graft polymers other than maleic anhydride / styrene copolymer (B), methyl methacrylate / methyl acrylate (C), acrylic resin (D) and methyl methacrylate / maleic anhydride / styrene copolymer ( The polycarbonate resin composition according to any one of [1] to [8], which includes 5 to 60 parts by weight of E) in total.
[10] A type in which the polycarbonate resin (A) is selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, an aromatic bisphenol, and an ether group-containing dihydroxy compound other than the dihydroxy compound represented by the formula (1) The thermoplastic resin composition according to any one of [1] to [9], comprising a structural unit derived from the above dihydroxy compound. [11] A molded article comprising the thermoplastic resin composition according to any one of [1] to [10].

  According to the present invention, it is required to have high transparency, low haze, high surface hardness, more preferably no appearance defect, and good molded article appearance (for example, in the field of building materials, electrical / electronics). Field, automobile field, optical parts field, miscellaneous goods field, etc.) and a molded product formed by molding the thermoplastic resin composition 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 equipped with three vent ports and water injection equipment, and Irganox 1010 (as an antioxidant is added to 100 parts by weight of the polycarbonate resin. BASF Japan Ltd., pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) 0.1 parts by weight, ADK STAB 2112 (manufactured by ADEKA Corporation, Tris ( 2,4-di-tert-butylphenyl) phosphite) and 0.05 part by weight of Unistar E-275 (manufactured by NOF Corporation) as a release agent are continuously added. 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.

<Methyl methacrylate / maleic anhydride / styrene copolymer (B)>
The thermoplastic resin composition of the present invention comprises the polycarbonate resin (A) of the present invention and a methyl methacrylate / maleic anhydride / styrene copolymer (B) (hereinafter sometimes referred to as “SMM resin”). Containing.
The monomer components constituting the methyl methacrylate / maleic anhydride / styrene copolymer (B) are methyl methacrylate, maleic anhydride and styrene.

"Physical properties of methyl methacrylate / maleic anhydride / styrene copolymer (B)"
Preferred physical properties of the methyl methacrylate / maleic anhydride / styrene copolymer (B) of the present invention are shown below.
The deflection temperature under load (° C.) of the methyl methacrylate / maleic anhydride / styrene copolymer (B) is not particularly limited, but is preferably 85 ° C. or higher because the appearance after molding becomes good. More preferably, it is 95 ° C. or higher. Moreover, 135 degrees C or less is preferable, 130 degrees C or less is more preferable, 125 degrees C or less is more preferable, 120 degrees C or less is especially preferable.
The deflection temperature under load (° C) of methyl methacrylate / maleic anhydride / styrene copolymer (B) is 1.80 MPa, 4 mm, measured by the flatwise method according to ISO test method 75. it can.

  In the thermoplastic resin composition of the present invention, the constituent weight ratio of the polycarbonate resin (A) of the present invention and the methyl methacrylate / maleic anhydride / styrene copolymer (B) is in the range of 30/70 to 90/10. It is preferable because the surface hardness increases when a molded product is formed. Moreover, the range of 40/60 to 80/20 is more preferable, and the range of 50/50 to 70/30 is most preferable.

<Methyl methacrylate / methyl acrylate copolymer (C)>
The thermoplastic resin composition of the present invention is preferable because it further contains a methyl methacrylate / methyl acrylate copolymer (C), which has high transparency and can reduce haze.
The monomer components constituting the methyl methacrylate / methyl acrylate copolymer (C) are methyl methacrylate and methyl acrylate.

The commercially available methyl methacrylate / maleic anhydride / styrene copolymer (B) is a methyl methacrylate / maleic anhydride / styrene copolymer (B) alone or a methyl methacrylate / maleic anhydride / styrene copolymer. It can be obtained as a mixture of the union (B) and the methyl methacrylate / methyl acrylate copolymer (C).
Further, in the following description, preferable physical property values will be described by the expression of a mixture of methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C). In addition, the following description means that the same physical property values are preferable even in the case of a methyl methacrylate / maleic anhydride / styrene copolymer (B) alone without using methyl methacrylate / methyl acrylate (C). ing.

The deflection temperature under load (° C.) of the mixture of methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) is not particularly limited, but the appearance after molding Is preferably 65 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 75 ° C. or higher. Moreover, 125 degrees C or less is preferable, 120 degrees C or less is more preferable, and 115 degrees C or less is further more preferable.
The deflection temperature under load (° C.) of the mixture of methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) conforms to ISO test method 75, 1.80 MPa, 4 mm. The deflection temperature under load (° C.) can be measured by the flatwise method.

A mixture of methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) was melted at 230 ° C. according to JIS K7210 (1999) and 3.80 kg of melt flow rate (MFR). ) Is preferably 10 g / 10 min or more because the appearance of the molded product is improved. From the viewpoint of transparency, haze, and surface hardness, the lower limit is preferably 0.1 g / 10 min or more, more preferably 0.4 g / 10 min or more, further preferably 0.6 g / 10 min or more, and 0.8 g / 10 min. The above is particularly preferable, 1.0 g / 10 min or more is most preferable, and the upper limit is 8 g / 10 m.
in or less, preferably 6 g / 10 min or less, more preferably 4 g / 10 min or less, particularly preferably 3 g / 10 min or less, and most preferably 2 g / 10 min or less.

<Acrylic resin (D)>
The thermoplastic resin of the present invention preferably contains an acrylic resin (D) (hereinafter sometimes abbreviated as PMMA resin) because the appearance of the molded product becomes good.
As the acrylic resin (D), 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 (PMMA) 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, poor appearance such as flow unevenness when molded as a multilayer body. The multilayer body excellent in mechanical characteristics and heat resistance can be provided without being generated.
Acrylic resin (PMMA resin) has an appearance of a molded product having a melt flow rate (MFR) of 230 g and 3.80 kg in accordance with JIS K7210 (1999) of 0.1 g / 10 min to 50 g / 10 min. Is preferable because of good. Further, from the viewpoint of transparency, haze, and surface hardness, the lower limit is preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, further preferably 10 g / 10 min or more, particularly preferably 15 g / 10 min or more, and 20 g / 10 min. The upper limit is preferably 45 g / 10 min or less, more preferably 40 g / 10 min or less, still more preferably 35 g / 10 min or less, particularly preferably 30 g / 10 min or less, and most preferably 28 g / 10 min or less.

<Rubber graft polymer (E)>
The resin composition of the present invention can contain a rubbery graft polymer (E) in addition to the methyl methacrylate / maleic anhydride / styrene copolymer. In the rubbery graft polymer (E), 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 in combination of two or more.

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 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 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 the vinyl monomer (G), as a vinyl monomer having no 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, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinylna Array type, vinyl anthracene, vinyl benzoate, vinyl acetate and the like. 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.

<Thermoplastic resin composition>
Although content of a component (A) -component (E) is not specifically limited normally, In the following description, a component (A), a component (B), a component (C), a component (D), and a component (E) The preferable content of each component will be described in the description of the total of 100 parts by weight. In addition, the following description means that the same content is preferable also when not using at least 1 type of a component (C), a component (D), and a component (E).

  When the total amount of the component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight in the polycarbonate resin composition, the polycarbonate resin (A) is 40 It is preferable to contain at least 95 parts by weight because the transparency is high, the haze is low, the surface hardness is high, and the appearance of the molded product is improved. Moreover, 45 weight part or more is more preferable, 50 weight part or more is further more preferable, and 55 weight part or more is especially preferable. Furthermore, 85 parts by weight or less is more preferable, 80 parts by weight or less is further preferable, 75 parts by weight or less is particularly preferable, and 70 parts by weight or less is most preferable.

  When the total of component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight in the polycarbonate resin composition, methyl methacrylate / maleic anhydride / styrene Rubber graft polymer (E) other than copolymer (B), methyl methacrylate / methyl acrylate (C), acrylic resin (D) and methyl methacrylate / maleic anhydride / styrene copolymer in total 5 parts by weight or more and 60 parts by weight or less is preferable because transparency is high, haze is low, surface hardness is high, and appearance of a molded product is improved. Moreover, 15 weight part or more is more preferable, 20 weight part or more is further more preferable, 25 weight part or more is especially preferable, and 30 weight part or more is the most preferable. Furthermore, 55 parts by weight or less is more preferable, 50 parts by weight or less is more preferable, and 45 parts by weight or less is particularly preferable.

In the polycarbonate resin composition, when the total amount of the component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, methyl methacrylate / maleic anhydride -The total content of the styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) is preferably 5 to 60 parts by weight with high transparency, low haze, and high surface hardness. It is preferable because the appearance of the molded product is improved. Moreover, 15 weight part or more is more preferable, 20 weight part or more is further more preferable, 25 weight part or more is especially preferable, and 30 weight part or more is the most preferable. Furthermore, 55 parts by weight or less is more preferable, 50 parts by weight or less is more preferable, and 45 parts by weight or less is particularly preferable.

  In the polycarbonate resin composition, when the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is 100 parts by weight, the acrylic resin (D) The content of 5 parts by weight or more and 60 parts by weight or less is preferable because transparency is high, haze is low, surface hardness is high, and appearance of a molded product is improved. Moreover, 6 weight part or more is more preferable, 7 weight part or more is further more preferable, 8 weight part or more is especially preferable, and 9 weight part or more is the most preferable. Furthermore, 40 parts by weight or less is more preferable, 30 parts by weight or less is more preferable, and 25 parts by weight or less is particularly preferable.

Moreover, as a weight ratio of the total amount of the component (B) and the component (C) and the amount of the component (D) in the polycarbonate resin composition, 1: 9 to 9: 1 is highly transparent, This is preferable because the haze is low, the surface hardness is high, and the appearance of the molded product is improved. Moreover, 3: 7-7: 3 is more preferable and 4: 6-6: 4 is more preferable.
In the polycarbonate resin composition, when the total amount of the component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, methyl methacrylate / maleic anhydride -The content of the rubber-like graft polymer (E) other than the styrene copolymer is preferably 5 to 60 parts by weight with high transparency, low haze, high surface hardness, and good appearance of the molded product. This is preferable. Moreover, 6 weight part or more is more preferable, 7 weight part or more is further more preferable, 8 weight part or more is especially preferable, and 9 weight part or more is the most preferable. Furthermore, 40 parts by weight or less is more preferable, 30 parts by weight or less is more preferable, and 25 parts by weight or less is particularly preferable.

<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 squeaking 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 a mold release agent is used, the blending amount is 100 parts by weight of the total of the above component (A), component (B), component (C), component (D) and component (E) of the present invention. The amount is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, more preferably 0.1 part 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 an antioxidant is added to the thermoplastic resin composition of the present invention, the amount of the antioxidant added is the above component (A), component (B), component (C), component (D) and component ( E) The total of E) is usually preferably 0.001 part by weight or more, more preferably 0.002 part by weight or more, still more preferably 0.005 part by weight or more, and usually 5 parts by weight or less with respect to 100 parts by weight. The amount is preferably 3 parts by weight or less, more preferably 2 parts by weight or less.
If the amount of the antioxidant added is more than 5 parts by weight, 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 weight, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained.

<Phosphite antioxidant>
Examples of the phosphite antioxidant 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 Phyto, 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, etc.

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-t
ert-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, etc. Are preferred, and pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is more preferred.
These compounds may use only 1 type and may use 2 or more types together.

(Light stabilizer)
Examples of the light resistant stabilizer include hindered amine light stabilizers, and the molecular weight thereof 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- A condensate with 1,3,5-triazine, Haq dimethyl and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6
, 6-tetramethylpiperidine and the like.

  When a light-resistant stabilizer is added to the thermoplastic resin composition of the present invention, the added amount thereof is the above-mentioned component (A), component (B), component (C), component (D) and component (E) of the present invention. ) Is usually 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight. It is as follows. If the light stabilizer is added in an amount of more than 5 parts by weight, it tends to be colored, and even if a colorant is added, it is difficult to obtain a jet black with a depth and clarity, for example. On the other hand, when it is less than 0.001 part by weight, there is a possibility that sufficient weather resistance may not be obtained when an automobile interior / exterior product is obtained.

<Physical properties of thermoplastic resin composition>
In the thermoplastic resin composition of the present invention, the appearance of a molded article is good when the melt flow rate (MFR) of 230 ° C. and 2.16 kg in accordance with JIS K7210 (1999) is 6 g / 10 min or more. preferable. From the viewpoint of transparency, haze, and surface hardness, the lower limit is preferably 6.5 g / 10 min or more, more preferably 7 g / 10 min or more, further preferably 7.5 g / 10 min or more, and particularly preferably 8 g / 10 min or more. 8.5 g / 10 min or more is most preferable, and the upper limit is preferably 12 g / 10 min or less, more preferably 11 g / 10 min or less, further preferably 10.5 g / 10 min or less, particularly preferably 10 g / 10 min or less, 9 g / 10 min or less is most preferable.

<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.

<Reason why the present invention is effective>
When the thermoplastic resin composition of the present invention is formed into a molded article, it has high transparency, low haze, and high surface hardness.
The reason for this is not clear yet, but is presumed as follows. That is, the refractive index of polycarbonate resin, other resin, and rubber-like graft polymer was equivalent, transparency became high, and the haze value became low. In addition, since the surface hardness of the other resin is high, it is presumed that the pencil hardness when formed into a molded product is good, and the above effect is exhibited.

  Furthermore, when the resin composition according to a preferred embodiment of the present invention is formed into a molded product, the transparency is high, the haze is low, the pencil hardness is increased, and further, there is no appearance defect and a good molded product appearance can be obtained. . The reason for this is not clear yet, but is presumed as follows. That is, the refractive index of polycarbonate resin, other resin, and rubber-like graft polymer was equivalent, transparency became high, and the haze value became low. In addition, the surface hardness of other resins is high, the difference in viscosity between the polycarbonate resin and other resins is small, and the sea-island structure is fine, so the pencil hardness when molded products are good, and the molded product appearance is also good, It is presumed that the above effect is achieved.

(1) Total light transmittance and 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 obtained injection-molded plate was measured for total light transmittance and haze of the test piece with a D65 light source using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).

(2) Surface hardness (pencil hardness)
The surface hardness of the injection-molded plate obtained in (1) was measured under the following conditions with a surface measuring instrument (manufactured by Shinto Kagaku: Tripogear Type 14DR) in accordance with JIS-K5600.
Load 750g
Measurement speed 30mm / min
Measuring distance 7mm
Mitsubishi pencil UNI was used as the pencil.
As pencil hardness, 4H, 3H, 2H, H, F, and HB were used.
The measurement was made 5 times, and the softness of the pencil hardness that was scratched twice or more was defined as the pencil hardness of the measurement substance.

(3) Comprehensive judgment 1
Those satisfying all of the following conditions were set to pass 1.
Total light transmittance: 85% or more Haze: 5% or less Pencil hardness: Pencil hardness improved by adding SMM resin or PMMA resin compared to polycarbonate resin alone

(4) Appearance of molded product Regarding the injection molded plate obtained in the above (1), a molded plate having a wrinkle-like appearance defect by visual observation was indicated by Δ, and a molded plate having no wrinkled appearance was indicated by ◯.

(5) Melt flow rate (MFR)
The pellets of the polycarbonate resin composition were measured according to JIS K7210 (1999) using a MELT INDEXER (manufactured by Toyo Seiki Seisakusho) and a melt flow rate (MFR) of 230 ° C. and 2.16 kg.

(6) Comprehensive judgment 2
Those satisfying the comprehensive judgment 1 and further satisfying the following conditions were set as pass 2.
Molded product appearance: In the above-mentioned molded product appearance test, a molded plate free from wrinkled appearance defects was obtained.

(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 tricyclodecane dimethanol (TCDDM, Oxea Co.) are purified by distillation and chlorinated. Diphenyl carbonate (DPC, manufactured by Mitsubishi Chemical Co., Ltd.) and calcium acetate monohydrate with a product ion concentration of 10 ppb or less, ISB / TCDDM / DPC / calcium acetate monohydrate = 0.70 / 0 in molar ratio .30 / 1.00 / 1.3 × 10 ⁻⁶ , and nitrogen was sufficiently substituted to adjust the oxygen concentration to 0.0005 to 0.001% by 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 so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. 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)
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) having an ion concentration of 10 ppb or less and calcium acetate monohydrate in a molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0. The mixture was charged so as to be 30 / 1.00 / 1.3 × 10 ⁻⁶ , sufficiently substituted with nitrogen, and adjusted to an oxygen concentration of 0.0005 to 0.001% by 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 so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. 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 3)
Manufacture except that in Preparation Example 2, the charging 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)
TCDDM: Tricyclodecane dimethanol (Oxea)
CHDM: 1,4-cyclohexanedimethanol (Eastman)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

<SMM resin>
980N: Methyl methacrylate / maleic anhydride / styrene copolymer (manufactured by Asahi Kasei Chemicals, Delpet 980N: deflection temperature under load 118 ° C., MFR (230 ° C., 3.80 kg): 1.6 g / 10 min)
981J: A mixture of methyl methacrylate / methyl acrylate copolymer and methyl methacrylate / maleic anhydride / styrene copolymer (manufactured by Asahi Kasei Chemicals Corporation, Delpet 981J: deflection temperature under load 110 ° C., MFR (230 ° C., 3 ° C. .80 kg): 1.8 g / 10 min)

<PMMA resin>
720V: PMMA resin (manufactured by Asahi Kasei Chemicals, Delpet 720V, MFR (230 ° C., 3.80 kg): 25 g / 10 min)
VH: PMMA resin (manufactured by Mitsubishi Rayon Co., Ltd., Acrypet VH, MFR (230 ° C., 3.80 kg): 2.0 g / 10 min)
<Rubber graft polymer>
M-590: butyl acrylate / methyl methacrylate / styrene copolymer (manufactured by Kaneka Corporation, Kane Ace M-590)

<Antioxidant>
AS2112: Phosphite antioxidant (manufactured by ADEKA, ADK STAB 2112)
IRGANOX 1010: Phenolic antioxidant (manufactured by BASF Japan, trade name IRGANOX 1010)

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

Example 1
Using the carbonate copolymer pellets and SMM resin 980N produced in Production Example 1, each component is blended with the polycarbonate resin composition shown in Table 1 and has 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.

(Comparative Example 1)
The polycarbonate resin composition was produced and evaluated in the same manner as in Example 1 except that the carbonate copolymer pellets produced in Production Example 1 were used and the composition shown in Table 1 was used. The results are shown in Table 1.

(Example 2)
Using the carbonate copolymer pellets produced in Production Example 2 and the SMM resin 981J, the production and evaluation of the polycarbonate resin composition were carried out in the same manner as in Example 1 except that the composition shown in Table 1 was used. went. The results are shown in Table 1.

(Comparative Example 2)
A polycarbonate resin composition was produced and evaluated in the same manner as in Example 1 except that the carbonate copolymer pellets produced in Production Example 2 were used and the composition shown in Table 1 was used. The results are shown in Table 1.

(Example 3)
Using the carbonate copolymer pellets produced in Production Example 2 and Production Example 3 and SMM resin 981J, 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.

Example 4
A polycarbonate resin was produced in the same manner as in Example 1 except that the carbonate copolymer pellets produced in Production Example 2 and the SMM resin 981J and elastic polymer M-590 were used and the composition shown in Table 1 was obtained. The composition was manufactured and evaluated. The results are shown in Table 1.

(Comparative Example 3)
Using the carbonate copolymer pellets and PMMA resin VH produced in Production Example 2, except that the composition shown in Table 1 was used, the production and evaluation of the polycarbonate resin composition were conducted in the same manner as in Example 1. went. The results are shown in Table 1.

  As can be seen by comparing Examples 1 to 4 in Table 1 with Comparative Examples, the thermoplastic resin composition of the present invention has high transparency, low haze, and high surface hardness when formed into a molded product. .

(Examples 5 and 6)
Using the carbonate copolymer pellets produced in Production Example 2, SMM resin 980N, and PMMA resin 720V, each component was blended with the polycarbonate resin composition shown in Table 2 and manufactured by Nippon Steel Works, Ltd., which has two vent ports. Using a twin screw extruder (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 2.

(Example 7)
Except for using the carbonate copolymer pellets produced in Production Example 2, the carbonate copolymer pellets produced in Production Example 3 and SMM resin 980N, PMMA resin 720V, the composition shown in Table 2 was used. In the same manner as in Example 1, the polycarbonate resin composition was produced and evaluated. The results are shown in Table 2.

(Example 8)
Example 1 except that the carbonate copolymer pellets produced in Production Example 2 and SMM resin 980N, PMMA resin 720V, and rubbery graft polymer M-590 were used and the composition shown in Table 2 was obtained. It carried out similarly and manufacture and evaluation of the polycarbonate resin composition were performed. The results are shown in Table 2.

(Comparative Example 3)
Using the carbonate copolymer pellets and PMMA resin VH produced in Production Example 2, the same procedure as in Example 1 was conducted except that the composition shown in Table 2 was used, and the production and evaluation of the polycarbonate resin composition were conducted. went. The results are shown in Table 2.

(Comparative Example 4)
Using the carbonate copolymer pellets and PMMA resin 720V produced in Production Example 2, except that the composition shown in Table 2 was used, the production and evaluation of the polycarbonate resin composition were carried out in the same manner as in Example 1. went. The results are shown in Table 2.

Example 9
Using the carbonate copolymer pellets produced in Production Example 2, SMM resin 980N, and PMMA resin 720V, the same procedure as in Example 1 was carried out except that the composition shown in Table 2 was used. Manufactured and evaluated. The results are shown in Table 2.

As can be seen from a comparison of Examples 5 to 8 and Example 2 and Comparative Examples 3 to 5 in Table 2, the resin composition of the preferred embodiment of the present invention has high transparency when formed into a molded product. The haze is low, the pencil hardness is increased, and there is no appearance defect, and a good molded product appearance is obtained.

Claims (11)

A polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following general formula (1);
A thermoplastic resin composition comprising a methyl methacrylate / maleic anhydride / styrene copolymer (B).

  The thermoplastic resin composition according to claim 1, comprising a methyl methacrylate / methyl acrylate copolymer (C).   The thermoplastic resin composition according to claim 1 or 2, wherein a melt flow rate (MFR) of 230 ° C and 2.16 kg in accordance with JIS K7210 (1999) is 6 g / 10 min or more.   Methyl methacrylate / maleic anhydride / styrene copolymer (B) or a mixture of methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) used for thermoplastic resin The thermoplastic resin composition according to any one of claims 1 to 3, wherein a melt flow rate (MFR) of 230 ° C and 3.80 kg in accordance with JIS K7210 (1999) is 10 g / 10 min or more.   The thermoplastic resin composition according to any one of claims 1 to 4, comprising an acrylic resin (D).   The thermoplastic resin according to claim 5, wherein the acrylic resin (D) has a melt flow rate (MFR) of 230 g and 3.80 kg in accordance with JIS K7210 (1999) of 0.1 g / 10 min to 50 g / 10 min. Resin composition.   The thermoplastic resin composition according to any one of claims 1 to 6, comprising a rubbery graft polymer (E) other than methyl methacrylate / maleic anhydride / styrene copolymer.   When the total amount of the component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight in the polycarbonate resin composition, the polycarbonate resin (A) is 40 The polycarbonate resin composition according to any one of claims 1 to 7, comprising from 95 parts by weight to 95 parts by weight.   In the polycarbonate resin composition, when the total amount of the component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, methyl methacrylate / maleic anhydride・ Rubber graft polymer (E) other than styrene copolymer (B), methyl methacrylate / methyl acrylate (C), acrylic resin (D) and methyl methacrylate / maleic anhydride / styrene copolymer The polycarbonate resin composition according to any one of claims 1 to 8, comprising 5 parts by weight or more and 60 parts by weight or less in total.   The polycarbonate resin (A) is one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, aromatic bisphenols, and ether group-containing dihydroxy compounds other than the dihydroxy compounds represented by formula (1). The thermoplastic resin composition according to any one of claims 1 to 9, comprising a structural unit derived from a compound.   The molded article formed by containing the thermoplastic resin composition as described in any one of Claims 1-10.