JP6957905B2 - A thermoplastic resin composition and a molded product using the same. - Google Patents

Description

The present invention relates to a thermoplastic resin composition having high transparency, low haze, and high surface hardness when made into a molded product, and a molded product obtained by molding the same.

Polycarbonate is generally manufactured using raw materials derived from petroleum resources. However, in recent years, there is concern about the depletion of petroleum resources, and there is a demand for the provision of polycarbonate using raw materials obtained from biomass resources such as plants. In addition, since there is a concern that global warming due to increased carbon dioxide emissions and accumulation will bring about climate change, etc., carbon-neutral plant-derived monomers are used as raw materials even if they are disposed of after use. Development of polycarbonate is required. Among them, high transparency, low haze, high surface hardness such as building materials field, electrical / electronic field, automobile field, optical parts field, miscellaneous goods field, etc., and more preferably, there is no appearance defect and is good. Since it is used in applications that require the appearance of a molded product, there has been a demand for a resin composition having good characteristics when it is used as a molded product.

Conventionally, various polycarbonates made from plant-derived monomers have been developed.
For example, it has been proposed to use isosorbide as a plant-derived monomer and to obtain polycarbonate by transesterification with diphenyl carbonate (see, for example, Patent Document 1).
Here, in the case of the acrylic resin which has been widely used in the above-mentioned applications, the transparency of the resin itself is high, the haze is low, and the surface hardness is high. However, when isosorbide is used, it is used. Further improvement of these characteristics is required. To solve this problem, a polycarbonate resin composition containing a polycarbonate resin having a high glass transition temperature and a specific rubbery polymer has been proposed as having high transparency, low haze, and enhancing impact resistance (for example). , Patent Document 2).

British Patent No. 1079686 Japanese Unexamined Patent Publication No. 2014-201679

However, in the invention described in Cited Document 1, attention has not been paid to the viewpoints that the polycarbonate made from isosorbide has high transparency, low haze, and high surface hardness, and these characteristics are improved. It is not satisfactory from the viewpoint of high transparency, low haze, and high surface hardness because it has not been treated as possible.
Further, in Reference Document 2, although it is described that a rubbery graft polymer is added to polycarbonate made from isosorbide, the properties are further improved, that is, the transparency is high, the haze is low, and the surface is surface. It has been required that the hardness is high, and more preferably, the appearance of the molded product is not defective and the appearance of the molded product is good.
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 made into a molded product, and further, a molded product obtained by molding the thermoplastic resin composition. It is preferable to provide a thermoplastic resin composition which does not have a poor appearance when it is made into a molded product and can obtain a good appearance of the molded product, and a molded product obtained by molding the thermoplastic resin composition.

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

［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), and a polycarbonate resin (A).
A thermoplastic resin composition containing a methyl methacrylate / maleic anhydride / styrene copolymer (B).

[2] The thermoplastic resin composition according to [1], which comprises a methyl methacrylate / methyl acrylate copolymer (C).
[3] The thermoplastic resin composition according to [1] or [2], which has a melt flow rate (MFR) of 6 g / 10 min or more at 230 ° C. and 2.16 kg according to JIS K7210 (1999).
[4] Methyl methacrylate / maleic anhydride / styrene copolymer (B) or methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) used for the thermoplastic resin. The thermoplastic according to any one of [1] to [3], wherein the mixture of) has a melt flow rate (MFR) of 10 g / 10 min or more at 230 ° C. and 3.80 kg according to JIS K7210 (1999). Resin composition.
[5] The thermoplastic resin composition according to any one of [1] to [4], which contains an acrylic resin (D).
[6] The description in [5], wherein the melt flow rate (MFR) at 230 ° C. and 3.80 kg according to JIS K7210 (1999) of the acrylic resin (D) 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 claims [1] to [6], which comprises a rubbery graft polymer (E) other than a methyl methacrylate / maleic anhydride / styrene copolymer.
[8] In the polycarbonate resin composition, when the total of the above components (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, the polycarbonate resin (A) The polycarbonate resin composition according to any one of [1] to [7], which contains 40 parts by weight or more and 95 parts by weight or less.
[9] In the above-mentioned polycarbonate resin composition, when the total of the above-mentioned component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, methyl methacrylate. Rubberic 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 contains 5 parts by weight or more and 60 parts by weight or less in total of E).
[10] A type in which the polycarbonate resin (A) is selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, aromatic bisphenols, 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], which contains a structural unit derived from the above dihydroxy compound. [11] A molded product containing the thermoplastic resin composition according to any one of [1] to [10].

According to the present invention, applications are required to have high transparency, low haze, high surface hardness, more preferably no appearance defects, and a good appearance of a molded product (for example, in the field of building materials, electrical / electronic). It is possible to provide a thermoplastic resin composition that can be suitably used in a field, an automobile field, an optical component field, a miscellaneous goods field, etc., and a molded product obtained by molding the thermoplastic resin composition.

Hereinafter, embodiments of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described below as long as the gist of the present invention is not exceeded. It is not limited to the contents of.

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

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

Since the dihydroxy compound represented by the above formula (1) has a cyclic ether structure, it is easily oxidized by oxygen. Therefore, in order to prevent decomposition by oxygen during storage and production, moisture should not be mixed in. , It is important to use an oxygen scavenger or handle it in 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, not only may the resulting polycarbonate resin and the thermoplastic resin composition be colored, but also the physical properties may be significantly deteriorated. It may affect the polymerization reaction and a high molecular weight polymer may not be obtained.

The polycarbonate resin (A) used in the present invention has an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, aromatic bisphenols and a formula in addition to the structural unit (a) derived from the dihydroxy compound represented by the formula (1). A structural unit (b) derived from one or more dihydroxy compounds (hereinafter, may be referred to as "other dihydroxy compounds") selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound represented by (1). ) Is preferable in terms of impact resistance of the polycarbonate resin (A). Among them, one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and aromatic bisphenols are preferable, and from the viewpoint of light resistance of the polycarbonate resin, the aromatic ring structure is present in the molecular structure. Dihydroxy compounds that do not, that is, aliphatic dihydroxy compounds and / or alicyclic dihydroxy compounds are more preferable, and alicyclic dihydroxy compounds are most preferable in consideration of heat resistance.

The aliphatic dihydroxy compound may be a linear aliphatic dihydroxy compound or a branched chain 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 thereof include 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

Examples of the alicyclic dihydroxy compound include 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol. Tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornandimethanol, 2,5-norbornandi Examples thereof include methanol, 1,3-adamantandimethanol, limonene and the like.

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

Examples of the ether group-containing dihydroxy compound include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150 to 2000), poly-1,3-propylene glycol, polytetramethylene glycol and the like.
The content ratio of the structural unit (b) derived from the other dihydroxy compound in the polycarbonate resin (A) used in the present invention is 10 mol% or more in the structural unit derived from the total dihydroxy compound in the polycarbonate resin (A). Preferably, 20 mol% or more is more preferable, and 30 mol% or more is particularly preferable. Further, 60 mol% or less is preferable, 50 mol% or less is more preferable, and 45 mol% or less is particularly 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.

Although two or more kinds of the polycarbonate resin (A) of the present invention can be mixed, 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 the polycarbonate resin corresponding to (A) is averaged in the above range according to the content, it is similarly preferable.

The polycarbonate resin (A) used in the present invention can be produced by a generally used method for producing a polycarbonate resin, which is a solution polymerization method using phosgen, melting by reacting a carbonic acid diester with a dihydroxy compound. Any of the polymerization methods may be used, but a melt polymerization method in which a dihydroxy compound containing the dihydroxy compound represented by the formula (1) is reacted with a carbonic acid diester having a lower toxicity to the environment in the presence of a polymerization catalyst is preferable. .. Further, as a polymerization catalyst (ester exchange catalyst) in melt polymerization, known alkali metal compounds and / or alkaline earth metal compounds are 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 in combination 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 transesterifying a dihydroxy compound containing the dihydroxy compound represented by the formula (1) and a carbonic acid diester such as diphenyl carbonate as described above. More specifically, it is obtained by subjecting it to a transesterification reaction to remove by-produced monohydroxy compounds and the like from the system. In this case, melt polymerization is usually carried out by a transesterification reaction in the presence of a transesterification reaction 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 periodic table (Nomenclature of Organic Chemistry IUPAC Recommendations 2005). Group 1 or Group 2 (hereinafter, simply referred to as "Group 1" or "Group 2") metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine-based compounds, etc. Examples include 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 also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with a group 1 metal compound and / or a group 2 metal compound. It is particularly preferable to use only group 1 metal compounds and / or group 2 metal compounds.
Further, as the form of the group 1 metal compound and / or the group 2 metal compound, it is usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt, but it is easy to obtain and can be handled. Hydroxide, carbonate, and acetate are preferable from the viewpoint of ease, and acetate is preferable from the viewpoint of hue and polymerization activity.

Examples of Group 1 metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, cesium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, and the like. Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium boron hydride, potassium borohydride, lithium boron hydride, cesium hydride , Sodium phenylated, potassium phenylated, lithium phenylated boron, cesium phenylated, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus 2 lithium hydrogen acid, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, cesium alcoholate, phenolate, bisphenol Examples thereof include a disodium salt, a dipotassium salt, a dilithium salt and a dicesium salt of A, and among them, a cesium compound and a lithium compound are preferable.

Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogencarbonate, barium carbonate, magnesium hydrogencarbonate, strontium hydrogencarbonate, calcium carbonate, barium carbonate, magnesium carbonate, and the like. Examples thereof include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. Among them, magnesium compounds, calcium compounds and barium compounds are preferable, and magnesium compounds and / Alternatively, a calcium compound is more preferable.

Examples of the basic boron compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron and tributylbenzyl. Examples include sodium salts such as boron, tributylphenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron, and butyl triphenyl boron, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt, and strontium salt. Be 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, and trimethylphenylammonium hydroxide. Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, Examples thereof include butyltriphenylammonium hydroxide.

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

Among the above, using 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 to make it.
Further, in order to make the transparency, hue and light resistance of the polycarbonate resin (A) particularly excellent, at least one metal compound whose catalyst is selected from the group consisting of magnesium compounds, calcium compounds and barium compounds. It is particularly 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 0.1 to 300 μmol, as a metal equivalent amount with respect to 1 mol of the total dihydroxy compound to be subjected to the reaction. It is in the range of 0.1 to 100 μmol, more preferably 0.5 to 50 μmol, and particularly preferably 1 to 25 μmol.
When a compound containing at least one metal selected from the group consisting of Group 2 metals is used among the above, the amount in terms of metal is preferably 0.1 μmol or more, more preferably 0.1 μmol or more, per 1 mol of the total dihydroxy compound to be subjected to the reaction. Is 0.5 μmol or more, particularly preferably 0.7 μmol or more. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2.0 μmol.

If the amount of the catalyst used is too small, the polymerization activity required to produce the polycarbonate resin (A) having a desired molecular weight may not be obtained, and sufficient fracture energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only the hue of the obtained polycarbonate resin (A) deteriorates, but also by-products are generated to reduce the fluidity and generate more gel, resulting in brittle fracture. May cause difficulty in producing the polycarbonate resin (A) of the target quality.

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

Further, when producing the polycarbonate resin (A) used in the present invention, it is desirable to install a filter in order to prevent foreign matter from being mixed. The installation position of the filter is preferably on the downstream side of the extruder, and the size (opening) of removing foreign matter on the filter is usually preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, when it is disliked to mix a minute foreign substance in a film application or the like, it is preferably 40 μm or less, more preferably 10 μm or less.

The extrusion of the polycarbonate resin (A) used in the present invention preferably has a higher cleanliness than Class 7, preferably Class 6, defined in JIS B 9920 (2002) in order to prevent foreign matter from being mixed after extrusion. It is desirable to carry out in a clean room.
Further, when the extruded polycarbonate resin (A) is cooled and formed into 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 using water cooling, it is desirable to use water from which metals in the water have been removed with an ion exchange resin or the like and foreign substances in the water have been removed with a filter. The opening of the filter used is preferably 10 μm to 0.45 μm as the filtration accuracy for 99% removal.

The molecular weight of the polycarbonate resin (A) used in the present invention can be expressed by the reduced viscosity, and the reduced viscosity is usually preferably 0.30 dL / g or more, more preferably 0.35 dL / g or more. The upper limit of the reduction viscosity is usually preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and further preferably 0.80 dL / g or less.
If the reducing viscosity of the polycarbonate resin (A) is too low, the toughness of the resin composition may be low, and if the reducing viscosity is too high, the flow during molding of electrical / electronic equipment parts and automobile interior / exterior parts. The property tends to decrease, and the productivity and moldability tend to decrease. In addition, the molding temperature must be raised more than appropriate, and the color tone may deteriorate.
The reduced viscosity of the polycarbonate resin is measured by using methylene chloride as a solvent, precisely adjusting the polycarbonate resin concentration to 0.6 g / dL, and using an Ubbelohde viscous tube at a temperature of 20.0 ° C. ± 0.1 ° C. ..

The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 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 higher, the fluidity is insufficient during molding, the resin composition is not filled to the end of the product, or the strength at the weld portion is lowered. 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 Irganox 1010 (Irganox 1010) as an antioxidant is continuously supplied to a twin-screw extruder equipped with three vent ports and water injection equipment, and 100 parts by weight of the polycarbonate resin is supplied. 0.1 part by weight of pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by BASF Japan Ltd., Adecastab 2112 (manufactured by ADEKA Co., Ltd., Tris) 2,4-Di-tert-butylphenyl) phosphite) (0.05 parts by weight) and Unistar E-275 (manufactured by Nissui Co., Ltd.) as a mold release agent (0.3 parts by weight) are continuously added, and two Low-molecular-weight substances such as phenol are devolatile under reduced pressure at each vent portion provided in the shaft extruder, and then pelletized with a pelletizer.

(2) Injection molding For pellets kneaded with a twin-screw extruder, pellets pre-dried at 80 ° C. for 4 hours were pre-dried at 80 ° C. using a J75EII type injection molding machine manufactured by Japan Steel Works, with a cylinder temperature of 230 ° C., a molding cycle of 45 seconds, and a mold temperature of 60. A flat plate of 60 mm × 60 mm × 3 mmt is formed at ° C.

(3) Haze and total light transmittance measurement Using a haze meter NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd., the haze (Haze (%)) and total light transmittance (%) of the above test piece were measured 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 above lower limit, the total light transmittance of the thermoplastic resin composition becomes high. Details of this method for measuring the light transmittance will be described in the section of Examples.

The haze of the polycarbonate resin (A) of the present invention in accordance with JIS K7105 is usually 2 or less, preferably 1.5 or less, and most preferably 1 or less. When the haze is in the above range, it is possible to achieve both a high total light transmittance and a high haze when the thermoplastic resin composition is used.
In the thermoplastic resin composition of the present invention, one type may be used alone as the polycarbonate resin (A), and the types of structural units derived from other dihydroxy compounds, the copolymerization ratio, the physical properties, etc. are different. Two or more kinds of the same may be mixed and used.

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

"Physical characteristics of methyl methacrylate / maleic anhydride / styrene copolymer (B)"
The 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 is good. ° C. or higher is more preferable, and 95 ° C. or higher is particularly preferable. Further, 135 ° C. or lower is preferable, 130 ° C. or lower is more preferable, 125 ° C. or lower is further preferable, and 120 ° C. or lower is particularly preferable.
The deflection temperature under load (° C.) of the methyl methacrylate / maleic anhydride / styrene copolymer (B) is 1.80 MPa, 4 mm according to the ISO test method 75, and the deflection temperature under load (° C.) is measured by the flatwise method. 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. This is preferable because the surface hardness becomes high when it is made into a molded product. Further, it is more preferably in the range of 40/60 to 80/20, and most preferably in the range of 50/50 to 70/30.

<Methyl methacrylate / methyl acrylate copolymer (C)>
The thermoplastic resin composition of the present invention is preferable because it further contains the methyl methacrylate / methyl acrylate copolymer (C), so that the transparency is high and the haze can be lowered.
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 either methyl methacrylate / maleic anhydride / styrene copolymer (B) alone, or methyl methacrylate / maleic anhydride / styrene copolymer. It can be obtained as a mixture of the coalescence (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). The following description means that the same physical property values are preferable even in the case of a simple substance of methyl methacrylate, maleic anhydride, and styrene copolymer (B) that does not use methyl methacrylate or 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 not particularly limited. 65 ° C. or higher is preferable, 70 ° C. or higher is further preferable, and 75 ° C. or higher is particularly preferable. Further, 125 ° C. or lower is preferable, 120 ° C. or lower is more preferable, and 115 ° C. or lower is further preferable.
The deflection temperature under load (° C.) of the mixture of methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) is 1.80 MPa, 4 mm in accordance with ISO test method 75. , The deflection temperature under load (° C) can be measured by the flatwise method.

The mixture of methyl methacrylate / maleic anhydride / styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) is a melt flow rate (MFR) at 230 ° C. and 3.80 kg according to JIS K7210 (1999). ) Is 10 g / 10 min or more because the appearance of the molded product is good. 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 further preferably 0.8 g / 10 min or more. The above is particularly preferable, 1.0 g / 10 min or more is most preferable, and the upper limit value is 8 g / 10 m.
In or less is preferable, 6 g / 10 min or less is more preferable, 4 g / 10 min or less is further preferable, 3 g / 10 min or less is particularly preferable, and 2 g / 10 min or less is most preferable.

<Acrylic resin (D)>
It is preferable that the thermoplastic resin of the present invention contains an acrylic resin (D) (hereinafter, may be abbreviated as PMMA resin) because the appearance of the molded product is good.
As the acrylic resin (D), an acrylic resin as a thermoplastic resin is used. Examples of the monomer used for the acrylic resin include the following compounds. 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 (Meta) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acroyloxyethyl succinate, 2- (meth) acroyloxyethyl maleate, 2- (meth) acroyl phthalate Examples thereof include oxyethyl, 2- (meth) acryole oxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate. Will be done. These may be polymerized alone or may be used by polymerizing two or more kinds. Among these, those using at least one of alkyl methacrylate and alkyl acrylate are preferable because of their low impact resistance and low haze. Further, other monomers that can be polymerized with these acrylic monomers, such as polyolefin monomers and vinyl monomers, 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, appearance defects such as uneven flow may occur when molding as a multilayer body. It is possible to provide a multilayer body having excellent mechanical properties and heat resistance without occurring.
The appearance of the molded product of the acrylic resin (PMMA resin) is that the melt flow rate (MFR) at 230 ° C. and 3.80 kg according to JIS K7210 (1999) is 0.1 g / 10 min or more and 50 g / 10 min or less. Is preferable because 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 or more. The above is most preferable, and the upper limit value is preferably 45 g / 10 min or less, more preferably 40 g / 10 min or less, further 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 may contain a rubbery graft polymer (E) in addition to the methyl methacrylate / maleic anhydride / styrene copolymer. The rubbery graft polymer (E) preferably has a rubber portion having an alkyl acrylate structural unit, and more preferably a rubber portion having a butadiene structural unit and an alkyl acrylate structural unit. Further, it is obtained by coagulating and recovering a rubbery graft polymer latex obtained by emulsion polymerization using an aliphatic emulsifier using an alkaline earth metal salt. This rubbery 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 contained vinyl monomer (G).

As the rubber latex, it is preferable to use an elastomer, and it is particularly preferable to use a thermoplastic elastomer. Various copolymer resins are used as the thermoplastic elastomer, and the glass transition temperature is usually −20 ° C. or lower, preferably −30 ° C. or lower, more preferably −50 ° C. or lower, and further preferably −70 ° C. The following are preferred.
Rubber latex having a butadiene structural unit and an alkyl acrylate structural unit has 1 to 99% by weight of a butadiene structural unit, 99 to 1% by weight of an alkyl acrylate structural unit, and 0 to 30% by weight of other vinyl monomer structural units. , The total solid content in the rubber latex is 100% by weight). Further, it is more preferable to have 1 to 99% by weight of the butadiene structural unit, 99 to 1% by weight of the alkyl acrylate structural unit, and 0 to 10% by weight of the other vinyl monomer structural unit. When the content of the butadiene structural unit in the rubber latex is 1% by weight or more, it is preferable in terms of impact resistance, and when it is 99% by weight or less, it is preferable in terms of YI value (heat coloring property). When 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 small, which is preferable.

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 other vinyl monomers used as needed 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 needed.
The butadiene monomer is not particularly limited, and examples thereof include diene-based monomers such as butadiene and isoprene, for example, 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.

One of these monomers may be used alone, or two or more of these monomers may be used in combination. For the reason 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 a butyl acrylate.
As the other vinyl monomer, a monofunctional or polyfunctional vinyl monomer copolymerizable with the butadiene monomer or the alkyl acrylate monomer can be used. Examples of other vinyl monomers include monofunctional monomers typified by acrylonitrile and alkyl methacrylate; divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, and tri. Examples thereof include polyfunctional monomers such as methylolpropane triacrylate and pentaerythritol tetraacrylate. As for other vinyl monomers, one type may be used alone, or two or more types may be used in combination.

The method for polymerizing the rubber latex is not particularly limited, but emulsion polymerization is preferable because the particle size of the rubber latex can be controlled and the core-shell structure can be easily formed.
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. The volume average particle diameter of the rubber particles in the rubber latex is more preferably 0.7 μm or less, 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 resistance at low temperature of the polycarbonate resin composition of the present invention obtained by adding the rubbery graft polymer of the present invention to the polycarbonate resin of the present invention. It is preferable because the property can be improved, and when it is 1 μm or less, cullet is less likely to be generated during the production of the rubbery graft polymer of the present invention, which is preferable. 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, and the details are as described in the examples below. Measured by the method described in the section.

The volume average particle size of the rubber particles in the rubber latex is about 0.1 μm according to the usual emulsion polymerization. In order to make the volume average particle diameter 0.1 to 1 μm, a method such as enlarging the rubber particles in the rubber latex with an enlarging agent is used.
The rubbery graft copolymer latex is obtained by graft-polymerizing a vinyl monomer (G) on the rubber latex.
As the vinyl monomer (G), a component having a glass transition temperature of 70 to 120 ° C. of the polymer obtained by polymerizing the vinyl monomer (G) can be used to coagulate the rubbery graft polymer latex and recover it as a powder. It is preferable in terms of recoverability.

As the vinyl monomer (G), examples of the vinyl monomer having no polar group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, t-butyl (meth) acrylate, isobolonyl (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, vinyl Examples thereof include naphthalene, vinyl anthracene, vinyl benzoate, and vinyl acetate. Here, "(meth) acrylate" refers to one or both of "acrylate" and "methacrylate". One of these monomers may be used alone, or two or more of these monomers may be used in combination.

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 rubbery graft polymer of the present invention can be uniformly dispersed in the polycarbonate resin of the present invention. Further, thereby, the impact resistance of the obtained polycarbonate resin composition 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. Class salt, acryloylmorpholine, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, isopropylacrylamide, diethylacrylamide, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (Meta) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, 2-vinyl-2-oxazoline, p-methoxystyrene, o-methoxystyrene, maleic anhydride, N -Phenylmaleimide, cyclohexylmaleimide can be mentioned. 2-Hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are preferable because of the ease of emulsion polymerization (formation of cullet, copolymerization with other graft monomers). One of these monomers may be used alone, or two or more of these monomers may be used in combination.

The ratio 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, preferably 0.5 to 5% by weight. More preferable (however, the entire vinyl monomer (G) is 100% by weight). By containing 0.1% by weight or more of the vinyl monomer (P) having a polar group in the vinyl monomer (G), the rubbery 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 means that the vinyl monomer (G) contains 20% by weight or less of the vinyl monomer (P) having a polar group. It is preferable because of the amount of cullet during polymerization.

The ratio of the rubber latex in the rubbery graft copolymer latex can be set arbitrarily, but the solid content of each is preferably 50 to 90% by weight (however, the entire solid content of the rubbery graft copolymer latex is used. 100% by weight). When the rubber latex in the rubbery graft polymer latex is 50% by weight or more, it is preferable in terms of strength development. Further, when the rubber latex in the rubbery graft polymer latex is 90% by weight or less, it is preferable in terms of dispersibility in the polycarbonate resin of the present invention and solidification recovery of the rubbery graft polymer.
The method for graft-polymerizing the vinyl monomer (G) onto the rubber latex is not particularly limited, but emulsion polymerization is preferable because the rubber particle size can be controlled and the core-shell structure can be easily formed.

<Thermoplastic resin composition>
The contents of the component (A) to the component (E) are usually not particularly limited, but in the following description, the component (A), the component (B), the component (C), the component (D) and the component (E) The preferable content of each component will be described with the description of 100 parts by weight in total. The following description means that the same content is preferable even when at least one of the component (C), the component (D) and the component (E) is not used.

In the above-mentioned polycarbonate resin composition, when the total of the above-mentioned component (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, the polycarbonate resin (A) is 40 parts by weight. It is preferable to include parts by weight or more and 95 parts by weight or less because the transparency is high, the haze is low, the surface hardness is high, and the appearance of the molded product is improved. Further, 45 parts by weight or more is more preferable, 50 parts by weight or more is further preferable, and 55 parts by weight or more is particularly preferable. Further, 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.

Methyl methacrylate, maleic anhydride, and styrene when the total of the component (A), the component (B), the component (C), the component (D), and the component (E) in the above polycarbonate resin composition is 100 parts by weight. A total of rubbery graft polymers (E) other than the copolymer (B), methyl methacrylate / methyl acrylate (C), acrylic resin (D) and methyl methacrylate / maleic anhydride / styrene copolymer. It is preferable to include 5 parts by weight or more and 60 parts by weight or less because the transparency is high, the haze is low, the surface hardness is high, and the appearance of the molded product is improved. Further, 15 parts by weight or more is more preferable, 20 parts by weight or more is further preferable, 25 parts by weight or more is particularly preferable, and 30 parts by weight or more is most preferable. Further, 55 parts by weight or less is more preferable, 50 parts by weight or less is further preferable, and 45 parts by weight or less is particularly preferable.

Methyl methacrylate / maleic anhydride when the total of the above components (A), (B), component (C), component (D) and component (E) in the above polycarbonate resin composition is 100 parts by weight. -The total content of the styrene copolymer (B) and methyl methacrylate / methyl acrylate (C) is high in transparency, low haze, and high surface hardness when it contains 5 parts by weight or more and 60 parts by weight or less. , It is preferable because the appearance of the molded product is improved. Further, 15 parts by weight or more is more preferable, 20 parts by weight or more is further preferable, 25 parts by weight or more is particularly preferable, and 30 parts by weight or more is most preferable. Further, 55 parts by weight or less is more preferable, 50 parts by weight or less is further preferable, and 45 parts by weight or less is particularly preferable.

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

Further, as the 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. It is preferable because the haze is low, the surface hardness is high, and the appearance of the molded product is improved. Further, 3: 7 to 7: 3 is more preferable, and 4: 6 to 6: 4 is more preferable.
Methyl methacrylate / maleic anhydride when the total of the above components (A), (B), component (C), component (D) and component (E) in the above polycarbonate resin composition is 100 parts by weight. -The content of the rubbery graft polymer (E) other than the styrene copolymer is high in transparency, low haze, high surface hardness, and good appearance of the molded product when it contains 5 parts by weight or more and 60 parts by weight or less. It is preferable because it becomes. Further, 6 parts by weight or more is more preferable, 7 parts by weight or more is further preferable, 8 parts by weight or more is particularly preferable, and 9 parts by weight or more is most preferable. Further, 40 parts by weight or less is more preferable, 30 parts by weight or less is further preferable, and 25 parts by weight or less is particularly preferable.

<Additives>
The thermoplastic resin composition of the present invention contains an antioxidant, a light-resistant stabilizer, an ultraviolet absorber, a mold release agent, a colorant, a neutralizing agent, an antistatic agent, as long as the effect of suppressing the generation 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 object of the present invention in order to further improve the releasability from the cooling roll during sheet molding or the mold releasability during injection molding. A mold release agent may be blended in a range.
Such release agents include higher fatty acid esters of monovalent or polyhydric alcohols, higher fatty acids, paraffin waxes, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic acid anhydride groups, silicone oils, etc. Organopolysiloxane and the like can be mentioned. As the release agent, one type may be used alone, or two or more types may be mixed and used.

As the higher fatty acid ester, a partial ester or a total ester of a monovalent or polyvalent alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of the partial ester or total ester of the monovalent or polyvalent alcohol and the saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, and behenyl behenate. Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate , Sorbitane monostearate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenic behenate are preferably used. From the viewpoint of mold release and transparency, stearic acid ester is more preferable as a mold release agent.

As the stearic acid ester, a partial ester or a total ester of stearic acid with a substituted or unsubstituted monohydric or polyhydric alcohol having 1 to 20 carbon atoms is preferable. Examples of the partial ester or total ester of the monovalent or polyhydric alcohol and stearic acid include ethylene glycol distearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, and pentaerythritol. More preferred are monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and stearyl stearate are more preferable, and ethylene glycol distearate and stearic acid monoglyceride are particularly preferable.

As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable. Among them, unsaturated fatty acids having 10 to 30 carbon atoms which are not substituted are more preferable, and examples of such higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like. Among them, saturated fatty acids having 16 to 18 carbon atoms are more preferable, and examples of such saturated fatty acids include palmitic acid and stearic acid, but stearic acid is particularly preferable.

When a mold release agent is used, the blending amount thereof is the total of the above-mentioned component (A), component (B), component (C), component (D) and component (E) of the present invention with respect to 100 parts by weight. , Usually 0.001 parts by weight or more, preferably 0.01 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. It is 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 a large amount of molding is performed, it may take labor to maintain the mold, and the obtained molding The product may have a poor appearance. When the content of the mold release agent in the thermoplastic resin composition is at least the above lower limit, there is an advantage that the molded product can be easily released from the mold at the time of molding, and the molded product can be easily obtained.

(Antioxidant)
As the antioxidant, a general antioxidant used for resins can be used, but from the viewpoints of oxidation stability, thermal stability, jet blackness, etc., phosphite-based antioxidants, sulfur-based antioxidants, and sulfur-based antioxidants, and Phenolic 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-mentioned component (A), component (B), component (C), component (D) and component (D) of the present invention. 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. It is preferably, more preferably 3 parts by weight or less, still 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, if it is less than 0.001 part by weight, a sufficient improvement effect on the weather resistance test tends not to be obtained.

<Phosphite-based antioxidant>
Examples of the phosphite-based antioxidant include triphenylphosphine, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and the like.
Tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphos Fight, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) ) Pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 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.
Only one of these compounds may be used, or two or more of these compounds may be used in combination.

<Sulfur-based antioxidant>
Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, and di-dipropionic acid ester. Stearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate) ), Glycon-3-stearylthiopropionate, bis [2-methyl-4- (3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6 -Methylbenzimidazole, 1,1'-thiobis (2-naphthol) and the like can be mentioned.
Of these, pentaerythritol tetrakis (3-laurylthiopropionate) is preferred.
Only one of these compounds may be used, or two or more of these compounds may be used in combination.

<Phenolic antioxidant>
Examples of the phenolic antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3). , 5-Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3, 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3, 5-Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis 4,4'-biphenylenediphosphinate (2, 4-Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2-[β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2 , 4,8,10-Tetraoxaspiro (5,5) undecane, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol and other compounds. Be done.

Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable, and 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. Is preferred, and pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is even more preferred.
Only one of these compounds may be used, or two or more of these compounds may be used in combination.

(Light-resistant stabilizer)
Examples of the light resistance stabilizer include hindered amine-based light stabilizers, and the molecular weight thereof is preferably 1000 or less, more preferably 900 or less. If the molecular weight exceeds 1000, sufficient weather resistance may not be obtained when the molded product is formed. The molecular weight is preferably 300 or more, more preferably 400 or more. If the molecular weight is less than 300, the heat resistance is poor, the mold is contaminated during molding, and a molded product having an excellent surface appearance may not be obtained.

Further, a compound having a piperidine structure is preferable. The piperidine structure defined here may be an amine structure having a saturated 6-membered ring, and includes a piperidine 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-based 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 particularly preferable.

Such light-resistant stabilizers include 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis (2,2,6,6-tetramethyl-piperidyl) sebacate, and 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 A condensate of 6,6-tetramethyl-pyrreridineol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-pyreridinol, methanol and 1,2,3 Condensate of 4-butanetetracarboxylic acid, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl ] Butylmalonate, bisdecanoate (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, 1 -[2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4,4-hydroxy) Phenyl) propionyloxy] ethyl] -2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate , Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-diyl} Piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl)- Condensate of 1,6-hexanediamine polymer with 2,4,6-trichloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Condensate of methyl-4-piperidinol with β, β, β, β-tetramethyl-3,9- (2,4,5,10-tetraoxaspiro [5,5] undecane-diethanol, N, N' -Bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3 5-Condensation with triazine Things, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6
, Condensate with 6-tetramethylpiperidine and the like.

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

<Physical characteristics of thermoplastic resin composition>
The thermoplastic resin composition of the present invention has a melt flow rate (MFR) of 6 g / 10 min or more at 230 ° C. and 2.16 kg in accordance with JIS K7210 (1999), which improves the appearance of the molded product. 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 value 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, and 9 g. Most preferably / 10 min or less.

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

<Molded product>
When molding a molded product using the thermoplastic resin composition of the present invention, any molding method can be used, but injection molding, injection compression, and injection press molding are preferably used. As the runner used at that time, not only the normal cold runner method but also the hot runner method can be used. In addition, insert molding, in-mold coating molding, two-color molding, sandwich molding and the like are also possible. Further, in order to obtain designability, it is also possible to use heat insulating mold molding and rapid heating and cooling mold molding.

<Reason why the present invention is effective>
The thermoplastic resin composition of the present invention has high transparency, low haze, and high surface hardness when formed into a molded product.
The reason for this is not yet clear, but it can be inferred as follows. That is, the refractive indexes of the polycarbonate resin, the other resin, and the rubbery graft polymer were the same, the transparency was high, and the haze value was low. Further, since the surface hardness of the other resin is high, it is presumed that the pencil hardness of the molded product becomes good and the above effect is exhibited.

Further, the resin composition of the preferred embodiment of the present invention has high transparency, low haze, increased pencil hardness, no poor appearance, and a good appearance of the molded product can be obtained when it is made into a molded product. .. The reason for this is not yet clear, but it can be inferred as follows. That is, the refractive indexes of the polycarbonate resin, the other resin, and the rubbery graft polymer were the same, the transparency was high, and the haze value was low. In addition, the surface hardness of the other resin is high, the viscosity difference between the polycarbonate resin and the other resin is small, and the sea-island structure is fine, so that the pencil hardness when made into a molded product is good, and the appearance of the molded product is also good. It is presumed that the above effects are 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, pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (manufactured by Japan Steel Works, Ltd .: J75EII type), and injection molding is performed under the 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 formed. The total light transmittance and haze of the test piece were measured with a D65 light source using a haze meter (NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K7105 (1981) for the obtained injection-molded plate.

(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: Tripogia type 14DR) in accordance with JIS-K5600.
Load 750g
Measurement speed 30 mm / min
Measuring distance 7 mm
UNI made by Mitsubishi Pencil was used as a pencil.
As the pencil hardness, 4H, 3H, 2H, H, F, and HB were used.
The measurement was performed 5 times, and the soft hardness, which is one of the scratched pencil hardnesses, was defined as the pencil hardness of the measurement substance two or more times.

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

(4) Appearance of molded product With respect to the injection-molded plate obtained in (1) above, the molded plate having a wrinkled appearance defect was marked with Δ, and the molded plate without wrinkles was marked with ◯.

(5) Melt flow rate (MFR)
For pellets of the polycarbonate resin composition, a melt flow rate (MFR) of 2.16 kg was measured at 230 ° C. using MELT INDEXER (manufactured by Toyo Seiki Seisakusho) in accordance with JIS K7210 (1999).

(6) Comprehensive judgment 2
Those who satisfied the comprehensive judgment 1 and further satisfied the following conditions were regarded as passing 2.
Molded product appearance: In the above-mentioned molded product appearance test, a molded plate having no wrinkled appearance defects was obtained.

(Manufacturing Example 1)
Isosorbide (ISB, Rocket Foil: POLYSORB) and tricyclodecanedimethanol (TCDDM, Oxea) are distilled and purified into a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C. Diphenyl carbonate (DPC, manufactured by Mitsubishi Chemical Corporation) and calcium acetate monohydrate having an ion concentration of 10 ppb or less are mixed in a molar ratio of ISB / TCDDM / DPC / calcium acetate monohydrate = 0.70 / 0. It was charged to be .30 / 1.00 / 1.3 × ^10-6 and sufficiently substituted with nitrogen to adjust the oxygen concentration to 0.0005 to 0.001% by volume. Subsequently, heating was performed with a heat medium, stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to reach 100 ° C. After that, the temperature rise is started, the internal temperature is set to 210 ° C. in 40 minutes, and when the internal temperature reaches 210 ° C., this temperature is controlled to be maintained, and at the same time, the depressurization is started and reaches 210 ° C. The pressure was adjusted to 13.3 kPa (absolute pressure, the same applies hereinafter) in 90 minutes, and the pressure was maintained for another 60 minutes.

The phenol vapor produced as a by-product during the polymerization reaction is guided to a reflux condenser using steam controlled at 100 ° C. as the inlet temperature to the reflux condenser as a refrigerant, and a small amount of dihydroxy compounds and carbon dioxide diesters contained in the phenol vapor are introduced. The mixture was returned to the polymerization reactor, and the non-condensed phenol vapor was subsequently led to a condenser using hot water at 45 ° C. as a refrigerant for recovery. The contents thus oligomerized are once repressurized to atmospheric pressure and then transferred to another polymerization reactor equipped with a stirring blade and a similarly controlled reflux condenser to raise the temperature and reduce the pressure. The internal temperature was 220 ° C. and the pressure was 200 Pa in 60 minutes.
After that, the internal temperature was lowered to 230 ° C. and the pressure was 133 Pa or less over 20 minutes, and when the stirring power became the predetermined stirring power, the pressure was restored to atmospheric pressure, the contents were extracted in the form of strands, and the pellets of the carbonate copolymer were pelleted with a rotary cutter. I made it.

(Manufacturing Example 2)
Isosorbide (ISB, manufactured by Rocket Foil: POLYSORB) and cyclohexanedimethanol (CHDM, manufactured by Eastman) are distilled and purified into a polymerization reactor equipped with a stirring blade and a reflux cooler controlled at 100 ° C. to produce chloride. Diphenyl carbonate (DPC, manufactured by Mitsubishi Chemical Corporation) and calcium acetate monohydrate having an ion concentration of 10 ppb or less were mixed in a molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0. It was charged to be 30 / 1.00 / 1.3 × ^10-6 and sufficiently substituted with nitrogen to adjust the oxygen concentration to 0.0005 to 0.001% by volume. Subsequently, heating was performed with a heat medium, stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to reach 100 ° C. After that, the temperature rise is started, the internal temperature is set to 210 ° C. in 40 minutes, and when the internal temperature reaches 210 ° C., this temperature is controlled to be maintained, and at the same time, the depressurization is started and reaches 210 ° C. The pressure was adjusted to 13.3 kPa (absolute pressure, the same applies hereinafter) in 90 minutes, and the pressure was maintained for another 60 minutes.

The phenol vapor produced as a by-product during the polymerization reaction is guided to a reflux condenser using steam controlled at 100 ° C. as the inlet temperature to the reflux condenser as a refrigerant, and a small amount of dihydroxy compounds and carbon dioxide diesters contained in the phenol vapor are introduced. The mixture was returned to the polymerization reactor, and the non-condensed phenol vapor was subsequently led to a condenser using hot water at 45 ° C. as a refrigerant for recovery. The contents thus oligomerized are once repressurized to atmospheric pressure and then transferred to another polymerization reactor equipped with a stirring blade and a similarly controlled reflux condenser to raise the temperature and reduce the pressure. The internal temperature was 220 ° C. and the pressure was 200 Pa in 60 minutes.
After that, the internal temperature was lowered to 230 ° C. and the pressure was 133 Pa or less over 20 minutes, and when the stirring power became the predetermined stirring power, the pressure was restored to atmospheric pressure, the contents were extracted in the form of strands, and the pellets of the carbonate copolymer were pelleted with a rotary cutter. I made it.

(Manufacturing Example 3)
Production except that the preparation composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.50 / 0.50 / 1.00 / 1.3 × ^{10-6 in Production Example 2.} Pellets of carbonate copolymer were prepared in the same manner as in Example 1.

The abbreviations of the compounds used in the following examples and comparative examples are as follows.
ISB: Isosorbide (manufactured by Rocket Foil, trade name POLYSORB)
TCDDM: Tricyclodecanedimethanol (manufactured by Oxea)
CHDM: 1,4-Cyclohexanedimethanol (manufactured by Eastman)
DPC: Diphenyl carbonate (manufactured by 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 consisting of a methyl methacrylate / methyl acrylate copolymer and a methyl methacrylate / maleic anhydride / styrene copolymer (manufactured by Asahi Kasei Chemicals Co., Ltd., Delpet 981J: Deflection temperature under load 110 ° C., MFR (230 ° C., 3) .80kg): 1.8g / 10min)

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

<Antioxidant>
AS2112: Phosphite-based antioxidant (ADEKA, ADEKA STAB 2112)
IRGANOX1010: Phenolic antioxidant (manufactured by BASF Japan, trade name IRGANOX1010)

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

(Example 1)
Using the carbonate copolymer pellets and SMM resin 980N produced in Production Example 1, each component was compounded with the polycarbonate resin composition composition shown in Table 1, and a twin-screw extruder manufactured by Japan Steel Works, Ltd. having two vent ports. Using (LABOTEX30HSS-32), the resin was extruded into a strand shape so that the resin temperature at the outlet 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 the 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)
Using the pellets of the carbonate copolymer produced in Production Example 1, the same procedure as in Example 1 was carried out except that the compositions shown in Table 1 were obtained, and the polycarbonate resin composition was produced and evaluated. The results are shown in Table 1.

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

(Comparative Example 2)
Using the pellets of the carbonate copolymer produced in Production Example 2, the same procedure as in Example 1 was carried out except that the compositions shown in Table 1 were obtained, and the polycarbonate resin composition was produced and evaluated. The results are shown in Table 1.

(Example 3)
Using the carbonate copolymer pellets and SMM resin 981J produced in Production Examples 2 and 3, the same procedure as in Example 1 was carried out except that the compositions shown in Table 1 were obtained, and the polycarbonate resin composition was prepared. Manufactured and evaluated. The results are shown in Table 1.

(Example 4)
Using the carbonate copolymer pellets produced in Production Example 2, the SMM resin 981J, and the elastic polymer M-590, the same procedure as in Example 1 was carried out except that the compositions shown in Table 1 were obtained, and the polycarbonate resin was used. The composition was produced and evaluated. The results are shown in Table 1.

(Comparative Example 3)
The same procedure as in Example 1 was carried out except that the carbonate copolymer pellets and PMMA resin VH produced in Production Example 2 were used to obtain the composition shown in Table 1, and the production and evaluation of the polycarbonate resin composition were carried out. 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 is blended with the polycarbonate resin composition shown in Table 2, and the product is manufactured by Japan Steel Works, Ltd., which has two vent ports. Using a twin-screw extruder (LABOTEX30HSS-32), the resin was extruded into a strand shape so that the resin temperature at the outlet 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 the 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 that the pellets of the carbonate copolymer produced in Production Example 2, the pellets of the carbonate copolymer produced in Production Example 3, the SMM resin 980N, and the PMMA resin 720V were used to obtain the compositions shown in Table 2. The same as in Example 1 was carried out, and the polycarbonate resin composition was produced and evaluated. The results are shown in Table 2.

(Example 8)
Example 1 and Example 1 except that the carbonate copolymer pellets produced in Production Example 2, SMM resin 980N, PMMA resin 720V, and rubbery graft polymer M-590 were used to obtain the composition shown in Table 2. In the same manner, the polycarbonate resin composition was produced and evaluated. The results are shown in Table 2.

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

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

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

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

Claims (8)

A polycarbonate resin (A) consisting of only a structural unit derived from a dihydroxy compound represented by the following general formula (1) and a structural unit derived from an aliphatic dihydroxy compound and / or an alicyclic dihydroxy compound.
Contains methyl methacrylate, maleic anhydride, styrene copolymer (B),
The content ratio of the constituent units derived from the aliphatic dihydroxy compound and the alicyclic dihydroxy compound in the polycarbonate resin (A) is 10 mol% or more and 50 mol% or less.
A thermoplastic resin composition in which the constituent weight ratio of the polycarbonate resin (A) and the methyl methacrylate / maleic anhydride / styrene copolymer (B) is 30/70 to 90/10.
A width 60 mm × obtained by molding the pellets of the above thermoplastic resin composition dried at 90 ° C. for 6 hours using a hot air dryer under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. The total light transmittance of the injection molded plate having a length of 60 mm and a thickness of 2 mm measured under the following condition (1) is 85% or more, and the haze is 5% or less.
A thermoplastic resin composition having a pencil hardness of F or more measured under the following condition (2) of the injection molded plate.
(1) Total light transmittance and haze: In accordance with JIS K7105 (1981), a haze meter (NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure the total light transmittance and haze of the above test piece with a D65 light source. taking measurement.
(2) Pencil hardness: In accordance with JIS-K5600, the surface hardness is measured under the following conditions with a surface measuring instrument (manufactured by Shinto Kagaku: Tripogia type 14DR).
Load 750g
Measurement speed 30 mm / min
Measuring distance 7 mm
Use Mitsubishi Pencil UNI as a pencil

The thermoplastic resin composition according to claim 1, which comprises a methyl methacrylate / methyl acrylate copolymer (C). The thermoplastic resin composition according to claim 1 or 2, which comprises a polymethyl methacrylate resin (D). The third aspect of the present invention, wherein the melt flow rate (MFR) of the polymethyl methacrylate resin (D) at 230 ° C. and 3.80 kg according to JIS K7210 (1999) is 0.1 g / 10 min or more and 50 g / 10 min or less. Thermoplastic resin composition. The thermoplastic resin composition according to any one of claims 1 to 4, which comprises a rubbery graft polymer (E). In the above thermoplastic resin composition, when the total of the above components (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, the polycarbonate resin (A) is used. The thermoplastic resin composition according to claim 5, which comprises 40 parts by weight or more and 85 parts by weight or less. In the above thermoplastic resin composition, when the total of the above components (A), component (B), component (C), component (D) and component (E) is 100 parts by weight, methyl methacrylate / anhydrous maleine is used. A total of 15 parts by weight or more and 60 parts by weight or more of the acid / styrene copolymer (B), the methyl methacrylate / methyl acrylate copolymer (C), the polymethyl methacrylate resin (D) and the rubbery graft polymer (E). The thermoplastic resin composition according to claim 6, which comprises parts by weight or less. A molded product containing the thermoplastic resin composition according to any one of claims 1 to 7.