JP6640540B2 - Thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition and a molded article, and more particularly, to a thermoplastic resin composition and a molded article having excellent fluidity and strength, and excellent weld strength and dimensional stability.

  Polycarbonate resins are excellent in mechanical strength, electrical properties, transparency, and the like, and are widely used as engineering plastics in various fields such as electric and electronic devices and automobiles. Further, with the reduction in size and weight of electric / electronic devices, automobile parts, and the like, materials having higher rigidity are required.

  As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fibers are added in order to improve mechanical strength and dimensional stability is known (for example, see Patent Document 1). In order to further increase the rigidity of the glass fiber reinforced polycarbonate resin, the content of the glass fiber has been increased, but there is a problem that the weld strength is reduced as the content of the glass fiber is increased. In recent years, this problem is important because the shape of molded articles has become more complicated and the strength of the entire part is often governed by weld strength.

  On the other hand, although the glass fiber reinforced polycarbonate resin composition is excellent in rigidity and mechanical strength, the fluidity is reduced, so that the injection molding temperature needs to be set to a high temperature, and it is difficult to obtain a thin molded product. In addition, in order to obtain a thin molded product, when injection molding is performed using a mold of a multi-point gate having, for example, six or more points, there is a problem that the strength of a weld portion is significantly reduced.

  As described above, various small-sized precision parts and the like typified by various portable terminals such as smartphones, digital cameras, and the like, which are becoming smaller, thinner and more complex in shape, have not only rigidity and mechanical strength, but also greater There is a strong need for a resin material having both fluidity and weld strength.

JP 2004-256581 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and has excellent fluidity, high strength, and a glass fiber capable of obtaining a molded article having good weld strength and excellent dimensional stability. An object is to provide a reinforced thermoplastic resin composition.

The present inventors have conducted extensive studies on various resin materials in order to achieve the above object, and as a result, in a resin composition of a polyester resin and a polycarbonate resin, a polyethylene terephthalate resin and a specific copolymerized polyethylene terephthalate were used as the polyester resin. A glass fiber reinforced resin composition containing a resin, containing a polycarbonate resin in a specific small amount, and further compounding a specific elastomer, has excellent fluidity, high strength, weld strength and dimensional stability. They have found that a good molded product can be manufactured, and have completed the present invention.
The present invention is as follows.

[1] Based on a total of 100 parts by mass of the following (A), (B) and (C), 20 to 65 parts by mass of the polyethylene terephthalate resin (A), and 15 to 30 mol% of all diol constituent units are as follows: Thermoplastic resin (D) containing 20 to 60 parts by mass of copolymerized polyethylene terephthalate resin (B) and 2 to 20 parts by mass of polycarbonate resin (C), which are structural units derived from a diol represented by general formula (1). A thermoplastic resin composition comprising 2 to 8 parts by mass of a core / shell type elastomer (E) and 65 to 110 parts by mass of a glass fiber (F) based on 100 parts by mass.
(Wherein, R ¹ and R ² are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms) [2] The thermoplastic resin composition according to the above [1], wherein the core / shell type elastomer (E) has a butadiene rubber as a core and a number average particle size of 100 to 350 nm. object.
[3] The thermoplastic resin composition according to the above [1] or [2], wherein the glass fiber (F) is a glass fiber having a flat cross section.
[4] A molded product obtained by outsert molding the thermoplastic resin composition according to any of [1] to [3] above on a metal sheet having a thickness of 0.1 to 0.4 mm.
[5] The molded article according to the above [4], which is outsert molded using a mold having six or more gates per molded article.

  The thermoplastic resin composition of the present invention has excellent fluidity, has high strength and excellent dimensional stability, and can produce a molded product having a good weld strength. It can be particularly suitably used for injection molding, insert molding or outsert molding using a mold.

Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition of the present invention comprises 20 to 65 parts by mass of the polyethylene terephthalate resin (A) based on 100 parts by mass of the total of (A), (B) and (C), and 15 to 30% by mole of a copolymer containing 20 to 60 parts by mass of a copolymerized polyethylene terephthalate resin (B) and 2 to 20 parts by mass of a polycarbonate resin (C), which are structural units derived from a diol represented by the following general formula (1). It is characterized by containing 2 to 8 parts by mass of the core / shell type elastomer (E) and 65 to 110 parts by mass of the glass fiber (F) with respect to 100 parts by mass of the plastic resin (D).

[Polyethylene terephthalate resin (A)]
In the polyethylene terephthalate resin, the ratio of oxyethylene oxyterephthaloyl units (hereinafter may be referred to as “ET units”) composed of terephthalic acid and ethylene glycol to all the constituent repeating units (hereinafter may be referred to as “ET ratio”). ) Is preferably a polyethylene terephthalate resin having a content of 90 equivalent% or more, and the polyethylene terephthalate resin in the invention may contain a constitutional repeating unit other than an ET unit in a range of less than 10 equivalent%. Polyethylene terephthalate resin is produced using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as main raw materials, but other acid components and / or other glycol components may also be used as raw materials.

  Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids and derivatives thereof such as malonic acid, succinic acid and adipic acid, and oxyacids and derivatives thereof such as p-hydroxybenzoic acid and glycolic acid.

  Examples of the diol component other than ethylene glycol include aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, and neopentyl glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-deca Fats such as hydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7-decahydronaphthalenedimethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, and pentacyclododecan dimethanol Wherein diols; bisphenol A, the aromatic dihydroxy compound derivative such as bisphenol S, and the like.

  Examples of the copolymerized polyethylene terephthalate resin include ethylene glycol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymerized polyethylene terephthalate) and 1,4-butanediol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymer). Polymerized polybutylene terephthalate), 1,4-butanediol / isophthalic acid / decanedicarboxylic acid copolymer and the like, among which alkylene terephthalate copolyester is preferable.

  The raw material containing terephthalic acid or its ester-forming derivative and ethylene glycol as described above is obtained by subjecting bis (β-hydroxyethyl) terephthalate and bis (β-hydroxyethyl) terephthalate to an esterification reaction or an ester exchange reaction in the presence of an esterification catalyst or a transesterification catalyst. And / or an oligomer thereof is formed, and then subjected to melt polycondensation under high temperature and reduced pressure in the presence of a polycondensation catalyst and a stabilizer to obtain a polymer.

  The esterification catalyst does not need to be particularly used because terephthalic acid serves as an autocatalyst for the esterification reaction. Further, the esterification reaction can be carried out in the coexistence of an esterification catalyst and a polycondensation catalyst described later, and can be carried out in the presence of a small amount of an inorganic acid or the like. As the transesterification catalyst, alkali metal salts such as sodium and lithium, alkaline earth metal salts such as magnesium and calcium, and metal compounds such as zinc and manganese are preferably used. Among them, manganese is preferable in terms of the appearance of the obtained polyethylene terephthalate. Compounds are particularly preferred.

  As the polycondensation catalyst, a compound soluble in a reaction system such as a germanium compound, an antimony compound, a titanium compound, a cobalt compound, a tin compound or the like is used alone or in combination. As the polycondensation catalyst, germanium dioxide is particularly preferred from the viewpoint of color tone and transparency. These polycondensation catalysts may be used in combination with a stabilizer in order to suppress a decomposition reaction during the polymerization. Examples of the stabilizer include phosphates such as trimethyl phosphate, triethyl phosphate, and triphenyl phosphate, and triphenyl phosphate. Phosphites such as phyto and trisdodecyl phosphites, and one kind of phosphorus compounds such as methyl acid phosphate, dibutyl phosphate, monobutyl phosphate acid phosphate, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc. Or two or more types are preferable.

  The use ratio of the above-mentioned catalyst is usually in the range of 1 to 2,000 ppm, preferably 3 to 500 ppm as mass of the metal in the catalyst in the whole polymerization raw material, and the use ratio of the stabilizer is The mass of the phosphorus atom therein is usually in the range of 10 to 1000 ppm, preferably 20 to 200 ppm. The supply of the catalyst and the stabilizer can be performed at any stage of the esterification reaction or the transesterification reaction in addition to the preparation of the raw material slurry. Furthermore, it can be supplied at the beginning of the polycondensation reaction step.

Although the intrinsic viscosity (IV) of the polyethylene terephthalate resin (A) is usually in the range of 0.3 to 1.5 dl / g, the polyethylene terephthalate resin (A) used in the present invention has an IV of 0.4 to 1. Those having 2 dl / g are preferred. If the IV is less than 0.4, the strength tends to decrease, and if it exceeds 1.2, the fluidity tends to be insufficient. The more preferred IV is 0.45 to 1.0 dl / g, and more preferably 0.5 to 0.9 dl / g.
In addition, the intrinsic viscosity of the polyethylene terephthalate resin (A) is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

[Copolymerized polyethylene terephthalate resin (B)]
The thermoplastic resin composition of the present invention contains a copolymerized polyethylene terephthalate resin (B) having a constitutional unit derived from ethylene glycol and a diol represented by the following general formula (1). In addition, the copolymerized polyethylene terephthalate resin (B) is a resin different from the polyethylene terephthalate resin (A).

(Wherein, R ¹ and R ² are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms) Represents a group hydrocarbon group.)

In the general formula (1), R ¹ and R ² are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and A hydrocarbon group selected from the group consisting of 6 to 10 aromatic hydrocarbon groups, preferably a methylene group, an ethylene group, a propylene group, a butylene group or a structural isomer thereof, for example, an isopropylene group, an isobutylene Group. As the diol compound having a cyclic acetal skeleton represented by the general formula (1), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] Undecane is particularly preferred.

  The constituent unit derived from the diol represented by the general formula (1) is preferably 15 to 30 mol% in all the diol constituent units of the copolymerized polyethylene terephthalate resin (B). If it is less than 15 mol%, the dimensional stability tends to be poor, and if it exceeds 30 mol%, the dimensional stability tends to be poor.

  The structural units derived from ethylene glycol and the diol other than the diol represented by the general formula (2) in the copolymerized polyethylene terephthalate resin (B) are not particularly limited, but may be trimethylene glycol, 1,4-butane. Aliphatic diols such as diol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol, and neopentyl glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2 -Decahydronaphthalenedimethanol, 1,3-decahydronaphthalenedimethanol, 1,4-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 1,6-decahydronaphthalenedimethanol, 2,7 -Decahydrona Alicyclic diols such as tarendmethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, and pentacyclododecane dimethanol; polyether compounds such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; Bisphenols such as'-(1-methylethylidene) bisphenol, methylenebisphenol (bisphenol F), 4,4'-cyclohexylidenebisphenol (bisphenol Z), 4,4'-sulfonylbisphenol (bisphenol S); Alkylene oxide adducts; hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphene Aromatic dihydroxy compounds such as Le benzophenone; and the structural unit derived from a diol alkylene oxide adducts of the aromatic dihydroxy compounds can be exemplified.

  The carboxylic acid component of the copolymerized polyethylene terephthalate resin (B) is terephthalic acid, but may contain a dicarboxylic acid structural unit other than terephthalic acid. Isophthalic acid, phthalic acid; tetrabromophthalic acid, tetrabromo Halogen-substituted phthalic acids such as terephthalic acid; alkyl-substituted phthalic acids such as methylisophthalic acid; naphthalenedicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid Diphenyldicarboxylic acids such as 4,4'-diphenyldicarboxylic acid and 3,4'-diphenyldicarboxylic acid; aromatic dicarboxylic acids such as 4,4'-diphenoxyethanedicarboxylic acid; succinic acid, adipic acid, sebacic acid , Azelaic acid, decadic acid, cyclohexene Aliphatic or alicyclic dicarboxylic acids such as sandicarboxylic acid; aliphatic or alicyclic diols such as trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, etc. Dihydroxybenzenes such as hydroquinone and resorcin; bisphenols such as 2,2'-bis (hydroxyphenyl) propane and 2,2'-bis (4-hydroxyphenyl) -sulfone; bisphenols and ethylene glycol; Aromatic diols such as ether diols obtained from glycols; and polyoxytetramethylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxytetramethylene glycol. Polyoxyalkylene glycols; .epsilon. hydroxycaproic acid, hydroxybenzoic acid, oxycarboxylic acids such as such as such as hydroxy-ethoxy benzoic acid.

  These copolymer components can be used alone or in combination of two or more. The proportion thereof is not more than 20 mol%, especially not more than 10 mol%, based on the total amount of dicarboxylic acid (oxycarboxylic acid is half the amount calculated as carboxylic acid). Preferably

  The copolymerized polyethylene terephthalate resin (B) can be produced by a conventionally known method. For example, a melt polymerization method such as a transesterification method and a direct esterification method or a solution polymerization method can be mentioned.

When producing the copolymerized polyethylene terephthalate resin (B), a conventionally known catalyst can be used. For example, sodium and magnesium alkoxides; fatty acid salts and carbonates such as zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, germanium, antimony, and tin. , Phosphates, hydroxides, chlorides, oxides; metallic magnesium and the like. These can be used alone or a plurality of them can be used simultaneously.
Among the above-mentioned catalysts, fatty acid salts, carbonates, phosphates, hydroxides, chlorides and oxides of titanium and germanium are more preferred.

  The intrinsic viscosity of the copolymerized polyethylene terephthalate resin (B) may be in the range of 0.4 to 1.5 dl / g when measured at 25 ° C. with a mixed solvent of phenol and tetrachloroethane at a mass ratio of 6/4. Preferably, it is more preferably 0.45 to 1.2 dl / g, and further preferably 0.5 to 1.0 dl / g.

[Polycarbonate resin (C)]
The thermoplastic resin composition of the present invention contains a polycarbonate resin (C).
The specific type of the polycarbonate resin (C) is not limited, and examples thereof include a polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. At this time, a polyhydroxy compound or the like may be reacted in addition to the dihydroxy compound and the carbonate precursor. Also, a method of reacting carbon dioxide with a cyclic ether as a carbonate precursor may be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, various copolymer forms such as a random copolymer and a block copolymer can be selected as the copolymer. Usually, such a polycarbonate polymer is a thermoplastic resin.

  Among the monomers that are the raw materials of the aromatic polycarbonate resin, examples of the aromatic dihydroxy compound include:

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (that is, resorcinol), and 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl and 4,4′-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, Dihydroxynaphthalenes such as 2,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene;

2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxydiaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes;

9,9-bis (4-hydroxyphenyl) fluorene,
Bisphenols having a cardo structure such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone;
And the like.

Among these, bis (hydroxyaryl) alkanes are preferred, and bis (4-hydroxyphenyl) alkanes are particularly preferred. In particular, 2,2-bis (4-hydroxyphenyl) propane ( That is, bisphenol A) is preferred.
One type of aromatic dihydroxy compound may be used, or two or more types may be used in any combination and in any ratio.

Further, to give examples of monomers that are the raw materials of the aliphatic polycarbonate resin,
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;

  Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

  Glycols such as ethylene glycol, 2,2'-oxydiethanol (i.e., diethylene glycol), triethylene glycol, propylene glycol, and spiro glycol;

  1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie, ethylene oxide), 1,2-epoxypropane (ie, propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl Cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, 1,3-epoxypropane; and the like.

  Among the monomers used as the raw material of the polycarbonate resin, examples of the carbonate precursor include carbonyl halide and carbonate ester. One type of carbonate precursor may be used, or two or more types may be used in any combination and in any ratio.

  Specific examples of the carbonyl halide include phosgene; a haloformate such as a bischloroformate of a dihydroxy compound and a monochloroformate of a dihydroxy compound.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and cyclic carbonates. And the like, carbonates of dihydroxy compounds.

Method for Producing Polycarbonate Resin The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, particularly preferable ones among these methods will be specifically described.

Interfacial polymerization method First, a case where a polycarbonate resin is produced by an interfacial polymerization method will be described.
In the interfacial polymerization method, the pH is usually maintained at 9 or more in the presence of an organic solvent and an aqueous alkali solution which are inert to the reaction, and the dihydroxy compound is reacted with a carbonate precursor (preferably, phosgene). A polycarbonate resin is obtained by performing interfacial polymerization in the presence. In the reaction system, a molecular weight modifier (terminal terminator) may be added as necessary, or an antioxidant may be added to prevent oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. It is preferable to use phosgene among the carbonate precursors, and the method using phosgene is particularly called the phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene, and xylene. Can be In addition, an organic solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  Examples of the alkali compound contained in the aqueous alkali solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, and alkaline earth metal compounds. Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and 2 or more types may be used together by arbitrary combinations and ratios.

  Although the concentration of the alkali compound in the aqueous alkali solution is not limited, it is usually used at 5 to 10% by mass in order to control the pH in the aqueous alkali solution of the reaction to 10 to 12. For example, when phosgene is blown, the molar ratio between the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11. In particular, it is preferably 1: 2.0 or more, and usually 1: 3.2 or less, particularly preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine and trihexylamine; and alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N'-dimethylaniline and N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Pyridine; guanidine salts; and the like. One type of polymerization catalyst may be used, or two or more types may be used in any combination and in any ratio.

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; and phthalimides. Among them, aromatic phenols are preferred. Specific examples of such aromatic phenol include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenol. Substituted phenols; vinyl group-containing phenols such as isopropanylphenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; One type of molecular weight modifier may be used, or two or more types may be used in combination in any combination and in any ratio.

  The amount of the molecular weight modifier to be used is generally 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, based on 100 mol of the dihydroxy compound. When the amount of the molecular weight modifier used falls within this range, the thermal stability and hydrolysis resistance of the resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additives, and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the time of the reaction (phosgenation) of the dihydroxy compound and phosgene and the time of the start of the polymerization reaction.
The reaction temperature is usually from 0 to 40 ° C., and the reaction time is usually from several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

Melt transesterification method Next, a case where a polycarbonate resin is produced by a melt transesterification method will be described.
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonates such as ditolyl carbonate. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, 1 type of carbonic acid diester may be used and 2 or more types may be used together by arbitrary combinations and ratios.

  The ratio between the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and to use 1.01 mol or more. Is more preferable. The upper limit is usually 1.30 mol or less. By setting it in such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In a polycarbonate resin, the amount of terminal hydroxyl groups tends to have a large effect on thermal stability, hydrolysis stability, color tone, and the like. Therefore, the amount of terminal hydroxyl groups may be adjusted as required by any known method. In the transesterification reaction, usually, by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound; the degree of reduced pressure during the transesterification reaction, etc., it is possible to obtain a polycarbonate resin having an adjusted amount of terminal hydroxyl groups. In addition, by this operation, the molecular weight of the usually obtained polycarbonate resin can also be adjusted.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, a method of separately mixing a terminal terminator at the time of the reaction may be mentioned. At this time, examples of the terminal terminator include monohydric phenols, monohydric carboxylic acids, and carbonic acid diesters. In addition, 1 type may be used for a terminal stopper, and 2 or more types may be used together by arbitrary combinations and ratios.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound may be used in combination. One transesterification catalyst may be used, or two or more transesterification catalysts may be used in any combination and in any ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above conditions while removing by-products such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by any of a batch method and a continuous method. In the case of performing the batch method, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additive, and the like is arbitrary as long as a desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, among others, the melt polycondensation reaction is preferably performed in a continuous manner in consideration of the stability and the like of the polycarbonate resin.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, any compound that neutralizes the transesterification catalyst can be used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, 1 type may be used for a catalyst deactivator and 2 or more types may be used together by arbitrary combinations and ratios.

  The amount of the catalyst deactivator to be used is usually 0.5 equivalent or more, preferably 1 equivalent or more, and usually 10 equivalent or less, based on the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Further, it is usually at least 1 ppm, usually at most 100 ppm, preferably at most 20 ppm, based on the polycarbonate resin.

  The viscosity average molecular weight (Mv) of the polycarbonate resin (C) is preferably from 13,000 to 28,000. When the viscosity average molecular weight is in this range, a molded article having good fluidity and moldability and high mechanical strength is easily obtained, and when it is less than 13,000, impact resistance is apt to be remarkably reduced, and 28,000. If it exceeds, the melt viscosity increases, and injection molding tends to be difficult. The lower limit of the molecular weight of the polycarbonate resin (C) is more preferably 13,500, further preferably 14,000, and the upper limit is more preferably 26,000, particularly preferably 25,000.

The viscosity average molecular weight [Mv] of the polycarbonate resin was determined by using methylene chloride as a solvent, determining the intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, and calculating the Schnell viscosity equation. That is, it means a value calculated from η = 1.23 × 10 ⁻⁴ Mv ^0.83 . Further, the intrinsic viscosity [η] is a value obtained by measuring a specific viscosity [η _sp ] at each solution concentration [C] (g / dl) and calculating by the following equation.

  The concentration of terminal hydroxyl group of the polycarbonate resin (C) is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. This makes it possible to further improve the retention heat stability and color tone of the polycarbonate resin. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for a polycarbonate resin produced by a melt transesterification method. Thereby, a decrease in the molecular weight can be suppressed, and the mechanical properties of the resin composition can be further improved.

  In addition, the unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group in ppm with respect to the mass of the polycarbonate resin. The measurement method is colorimetric determination by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88 215 (1965)).

  Polycarbonate resin is a polycarbonate resin alone (the term “polycarbonate resin alone” is not limited to an embodiment including only one type of polycarbonate resin, and is used in a sense including, for example, an embodiment including a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. ), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, a polycarbonate resin is copolymerized with an oligomer or a polymer having a siloxane structure for the purpose of further increasing the flame retardancy and impact resistance; and a phosphorus atom for the purpose of further improving the thermal oxidation stability and the flame retardancy. A copolymer with a monomer, oligomer or polymer having the following; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving the thermal oxidation stability; polystyrene or the like for improving the optical properties Copolymers with an oligomer or polymer having an olefin structure; copolymers with polyester resin oligomers or polymers for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance and fluidity of the molded product, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and is usually 9,500 or less, preferably 9,000 or less. Further, the content of the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin material but also a polycarbonate resin recycled from a used product (so-called material-recycled polycarbonate resin).
However, the recycled polycarbonate resin is preferably 80% by mass or less of the polycarbonate resin, and more preferably 50% by mass or less. Recycled polycarbonate resin is highly likely to have undergone deterioration such as thermal deterioration or aging deterioration.If such a polycarbonate resin is used in an amount larger than the above range, hue and mechanical properties may be reduced. It is because there is.

The proportions of the contents of the polyethylene terephthalate resin (A), the copolymerized polyethylene terephthalate resin (B) and the polycarbonate resin (C) are based on the total of (A), (B) and (C) being 100 parts by mass. 20 to 65 parts by mass, (B) 20 to 60 parts by mass, and (C) 2 to 20 parts by mass. In the system containing the polyethylene terephthalate resin (A), the copolymerized polyethylene terephthalate resin (B) and the polycarbonate resin (C), it was found that the properties were drastically changed in the composition region. That is, when the content of the copolymerized polyethylene terephthalate resin (B) is less than 20 parts by mass, the dimensional stability is deteriorated, and when it exceeds 60 parts by mass, the dimensional stability and weld strength are deteriorated, and the content of the polycarbonate resin (C) is decreased. When the amount exceeds 20 parts by mass, the weld strength is deteriorated. When the amount is less than 2 parts by mass, the weld strength is good but the strength is not sufficient.
Preferable contents are (A) 22 to 58 parts by mass, (B) 22 to 58 parts by mass, and (C) 3 to 3 parts by mass based on a total of 100 parts by mass of (A), (B) and (C). 19 parts by mass, more preferably (A) is 25 to 55 parts by mass, (B) is 25 to 55 parts by mass, and (C) is 5 to 18 parts by mass.

[Core / shell type elastomer (E)]
As the core / shell type elastomer (E), a graft copolymer obtained by graft-polymerizing a rubber component with a monomer component copolymerizable therewith is preferable. By containing a predetermined amount of the core / shell type elastomer (E), the weld strength can be effectively increased.

  As a method for producing such a graft copolymer, any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization may be used, and the copolymerization method may be a single-stage graft or a multi-stage graft. Is also good. Among them, the emulsion polymerization is the easiest and the preferred method.

  The rubber component generally has a glass transition temperature of 0 ° C or lower, preferably -20 ° C or lower, more preferably -30 ° C or lower. Specific examples of the rubber component include polybutadiene rubber, butadiene-acryl composite rubber, styrene-butadiene rubber, and ethylene-propylene-butadiene rubber. These may be used alone or in combination of two or more.

  Specific examples of the monomer component capable of being graft-copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylate compounds, (meth) acrylate compounds, and glycidyl (meth) acrylate. Epoxy group-containing (meth) acrylic ester compounds, maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid, and their anhydrides (For example, maleic anhydride and the like). One of these monomer components may be used alone, or two or more thereof may be used in combination. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylate compounds, and (meth) acrylate compounds are preferred from the viewpoint of mechanical properties and surface appearance, and more preferred are (meth) acrylate esters. Compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate. be able to. Here, “(meth) acryl” refers to one or both of “acryl” and “methacryl”. The same applies to “(meth) acrylate”.

  The core / shell type elastomer (E) used in the present invention is preferably a butadiene elastomer from the viewpoint of weld strength. Above all, a core / shell type graft copolymer comprising a shell layer formed by copolymerizing a methacrylic acid ester around the core layer with a polybutadiene-containing rubber component is particularly preferred. In the core / shell type graft copolymer, those containing 40% by mass or more of a butadiene rubber component are preferable, and those containing 60% by mass or more are more preferable. The methacrylic acid component preferably contains 10% by mass or more.

  Preferred specific examples of such a core / shell type elastomer (E) include methyl methacrylate-butadiene-styrene graft copolymer, methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer, and methyl methacrylate-butadiene graft copolymer. And a methyl methacrylate-acryl-butadiene rubber graft copolymer, a methyl methacrylate-acryl-butadiene rubber-styrene graft copolymer, and the like. Such rubbery polymers may be used alone or in combination of two or more.

  The method for producing a core / shell type elastomer having a butadiene rubber as a core and a methacrylate copolymer as a shell is not limited, but usually, the above methacrylate is contained in a latex of a butadiene rubber component. Addition of components, radical polymerization initiators such as redox polymerization initiators combining peroxide initiators, azo initiators or oxidizing or reducing agents, anionic emulsifiers, emulsifiers such as nonionic emulsifiers and chain transfer Preferably, a method of producing the composition by emulsion graft polymerization using an agent or the like is used.

The core / shell type elastomer (E) preferably has an average particle diameter of 350 nm or less. By setting the average particle diameter to 350 nm or less, the weld strength is further improved. The preferred lower limit of the average particle size is 80 nm, more preferably 100 nm.
Here, the number average particle size of the core / shell type elastomer (E) is measured by a scanning electron microscope (SEM). Specifically, the thermoplastic resin composition (pellet) of the present invention is obtained by using Hitachi High-Technologies Corporation. It is defined as the number average particle diameter of 300 particles from an image observed at an applied voltage of 2.0 kV and a magnification of 10,000 times using a scanning electron microscope “SU8020”.

  The content of the core / shell type elastomer (E) is 2 parts per 100 parts by mass of the thermoplastic resin (D) containing the polyethylene terephthalate resin (A), the copolymerized polyethylene terephthalate resin (B) and the polycarbonate resin (C). To 8 parts by mass, preferably 2.5 parts by mass or more, preferably 7 parts by mass or less, more preferably 6 parts by mass or less. If the content of the core / shell type elastomer (E) is too small, the weld strength is poor, and if it is too large, the weld strength and non-weld strength decrease.

[Glass fiber (F)]
The thermoplastic resin composition of the present invention is characterized by containing the glass fiber (F) in a high content of 65 to 110 parts by mass with respect to 100 parts by mass of the thermoplastic resin (D). By containing the glass fiber (F) at such a ratio, the strength and dimensional stability of the non-weld portion can be effectively increased. The preferable content of the glass fiber (F) is 68 parts by mass or more and 105 parts by mass or less based on 100 parts by mass of the thermoplastic resin (D).

  As the glass fibers, those which are usually used for thermoplastic resins, such as A glass, E glass, alkali-resistant glass composition containing zirconia component, chopped strand, roving glass, thermoplastic resin and glass fiber (Long fiber) Any known glass fiber can be used irrespective of the form of the glass fiber at the time of blending the masterbatch or the like. Among them, as the glass fiber used in the present invention, alkali-free glass (E glass) is preferable for the purpose of improving the thermal stability of the thermoplastic resin composition of the present invention.

The number average fiber length of the glass fibers is preferably from 1 mm to 10 mm, more preferably from 1.5 to 6 mm, even more preferably from 2 to 5 mm.
If the number average fiber length exceeds 10 mm, the glass fibers are likely to fall off from the surface of the molded product, and the productivity is likely to be reduced. When the number average fiber length is less than 1 mm, the aspect ratio of the glass fiber is small, so that the mechanical strength tends to be insufficiently improved.

  The diameter of the glass fiber is preferably 3 to 20 μm. These can be produced by crushing glass fiber strands, for example, with a hammer mill or a ball mill, according to any conventionally known method. When the diameter of the glass fiber is less than 3 μm, the mechanical strength is similarly insufficiently improved, and when it exceeds 20 μm, the appearance tends to deteriorate. The diameter of the glass fiber is more preferably 5 to 15 μm, and still more preferably 6 to 14 μm.

  The glass fiber can be subjected to a surface treatment with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion with the polyethylene terephthalate resin and the polycarbonate resin.

In addition, it is usually preferable to use a glass fiber obtained by bundling a large number of these fibers as a chopped strand (chopped glass fiber) cut into a predetermined length, and the glass fiber used at this time contains a sizing agent. Is preferred. By adding a sizing agent, good mechanical properties can be obtained in addition to the advantage that the production stability of the molded article is enhanced.
The sizing agent is not particularly limited, and examples thereof include urethane-based, epoxy-based, and acrylic-based sizing agents. Of these, urethane-based and epoxy-based sizing agents are more preferred, and epoxy-based sizing agents are even more preferred.

  The cut length of the chopped strand (chopped glass fiber) is not particularly limited, but is usually 1 to 10 mm, preferably 1.5 to 6 mm, and more preferably 2 to 5 mm.

  The glass fiber may be a glass fiber having a substantially perfect circular cross section, specifically, a cross section having an oblateness (major axis / minor axis) of 1 or more and less than 1.5 in the cross section of the fiber. The flatness at this time is preferably 1 to 1.4, more preferably 1 to 1.2, and particularly preferably 1 to 1.1.

  The glass fiber is also preferably a glass fiber having a flat cross-sectional shape from the viewpoint of fluidity. Specifically, the average value of the major axis of the fiber section is 10 to 50 μm, and the ratio of the major axis to the minor axis (major axis) (Short diameter) is a glass fiber having a flat cross section having an average value of 1.5 or more and 8 or less.

  As the glass fiber, what is called a glass fiber milled fiber (Milled Fiber) is also preferable. More specifically, the milled glass fiber is a strand of glass fiber obtained by bundling tens to thousands of single glass fibers (filaments). Is cut into glass fiber chopped strands cut to a predetermined length. At this time, the glass fiber chopped strand is preferably surface-treated with a sizing agent as described above.

The milled glass fiber is preferably a short fiber having an average fiber length to average fiber diameter ratio (aspect ratio) of 10 or less. The aspect ratio of the milled glass fiber is preferably 8 or less, more preferably 7 or less, preferably 2.5 or more, and more preferably 3 or more. If the aspect ratio exceeds 10, warpage and anisotropy increase, and the appearance of a molded article tends to deteriorate.
Further, the average fiber diameter of the milled glass fiber is preferably a number average fiber diameter of 1 to 25 μm, more preferably 5 to 17 μm, the average length is preferably 1 to 500 μm, more preferably 10 to 300 μm And more preferably 20 to 200 μm. In the short fiber milled glass fiber having an average fiber diameter of less than 1 μm, the formability tends to be impaired, and when the average fiber diameter is more than 25 μm, the appearance is impaired and the reinforcing effect tends to be insufficient.

[Stabilizer]
It is preferable that the thermoplastic resin composition of the present invention contains a stabilizer, because it improves thermal stability and prevents deterioration of mechanical strength and hue.
As the stabilizer, a phosphorus-based stabilizer, a sulfur-based stabilizer and a phenol-based stabilizer are preferable. In particular, when a phosphorus-based stabilizer is contained, the transesterification reaction between the polyethylene terephthalate resin and the polycarbonate resin can be effectively suppressed, and mechanical properties such as impact resistance tend to be improved, which is preferable.

  Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, a phosphite, a phosphate, and the like. Among them, an organic phosphate compound, an organic phosphite compound, or an organic phosphonite compound is preferable.

As the organic phosphate compound, preferably, the following general formula:
_{^{(R 1 O) 3-n}} P (= O) OH n
(In the formula, R ¹ is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2.)
Or a metal salt thereof. More preferably, R ¹ can be mentioned long chain alkyl acid phosphate compound of having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, Examples include a hexadecyl group, an octadecyl group, an eicosyl group, and a triacontyl group. The metal salt is preferably an alkaline earth metal, or a salt of zinc, lead, or tin, particularly a zinc salt.

  Examples of the long-chain alkyl acid phosphate compound include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, and nonylphenyl acid. Cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate Dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and a bis-nonylphenyl acid phosphate, etc., or a metal salt thereof. Among them, octadecyl acid phosphate is preferable. For example, octadecyl acid phosphate is a trade name of "ADEKA STAB AX-71" (octadecyl acid phosphate) manufactured by ADEKA, and "JP-518Zn" (octadecyl acid phosphate Zn salt manufactured by Johoku Chemical Co., Ltd.). )).

As the organic phosphite compound, preferably, the following general formula:
R ² O-P (OR ³ ) (OR ⁴ )
(Wherein, R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ² , R ³ and R ⁴ , At least one is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite , Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phosphite, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like. Among these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable, and this is commercially available, for example, from ADEKA under the trade name “PEP-36”. .

As the organic phosphonite compound, preferably, the following general formula:
^{R 5 -P (OR 6) (} OR 7)
(Wherein, R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ⁵ , R ⁶ and R ⁷ , At least one is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite and tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonate Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2 -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite and tetrakis (2,6- Di-tert-butylphenyl) -3,3′-biphenylenediphosphonite and the like.

  As the sulfur-based stabilizer, any conventionally known sulfur atom-containing compound can be used, and among them, thioethers are preferable. Specifically, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis (N-phenyl-β-naphthylamine) ), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyl dithiocarbamate, nickel isopropyl xanthate, and trilauryl trithiophosphite. Among these, pentaerythritol tetrakis (3-dodecylthiopropionate) is preferable.

  Examples of the phenolic stabilizer include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and octadecyl-3- (3,5-di-tert-butyl-4). -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like. Among these, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred.

  One type of stabilizer may be contained, or two or more types may be contained in any combination and ratio.

  The content of the stabilizer is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the thermoplastic resin (D). When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect improvement in the thermal stability and compatibility of the resin composition, and a decrease in the molecular weight and deterioration of the hue during molding are likely to occur. When the amount exceeds the above range, the amount becomes excessive, and the generation of silver and the deterioration of hue tend to occur more easily. The content of the stabilizer is more preferably 0.001 to 0.7 parts by mass, and still more preferably 0.005 to 0.6 parts by mass.

[Release agent]
The thermoplastic resin composition of the present invention preferably contains a release agent.
Examples of the release agent include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil.

  Examples of the aliphatic carboxylic acid include a saturated or unsaturated aliphatic mono-, di- or tri-valent carboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and more preferred are aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotinic acid, melicic acid, tetraliacontanic acid, montanic acid, adipine Acid, azelaic acid and the like.

  As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same aliphatic carboxylic acids as described above can be used. On the other hand, examples of the alcohol include a saturated or unsaturated monohydric or polyhydric alcohol. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 carbon atoms or less is more preferable. Here, the term "aliphatic" also includes an alicyclic compound.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Is mentioned.

  Note that the above ester may contain an aliphatic carboxylic acid and / or an alcohol as impurities. Further, the ester may be a pure substance or a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and the alcohol that combine to form one ester may be used alone or in combination of two or more in any combination and in any ratio.

  Specific examples of the ester of an aliphatic carboxylic acid and an alcohol include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monostearate. And glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, micro wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. In addition, alicyclic hydrocarbon is also included here as an aliphatic hydrocarbon. These hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax or partial oxides of polyethylene wax are preferred, and paraffin wax and polyethylene wax are more preferred.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, or may be a mixture of various constituent components and various molecular weights as long as the main component is within the above range.

  In addition, the above-mentioned release agent may be contained only by 1 type, and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 100 parts by mass of the thermoplastic resin (D). It is at most 1 part by mass, more preferably at most 0.6 part by mass. When the content of the release agent is less than the lower limit of the above range, the effect of the releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, the hydrolysis resistance And mold contamination during injection molding may occur.

[Dye and pigment]
The thermoplastic resin composition of the present invention may optionally contain a dye or pigment. By containing a dye or pigment, a molded product obtained by molding the aromatic polycarbonate resin composition of the present invention can impart color, light leakage prevention, light reflection, concealment, weather resistance, and the like. .

  Examples of dyes and pigments include inorganic pigments, organic pigments, and organic dyes.

  Examples of inorganic pigments include white pigments such as titanium oxide, zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, calcined kaolin, magnesium carbonate, muscovite, and calcium sulfate; carbon black; sulfides such as cadmium red and cadmium yellow. Silicate pigments such as ultramarine blue; titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium cobalt green, cobalt green, cobalt blue, copper chromium Oxide pigments such as black and copper-iron black; chromic acid pigments such as graphite and molybdate orange; and ferrocyan pigments such as navy blue.

  Examples of the organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isooxane. Condensed polycyclic dyes such as indolinone type and quinophthalone type; anthraquinone type, heterocyclic type and methyl type dyes and pigments.

  Among these, white pigments such as titanium oxide, zinc sulfide, zinc oxide, barium sulfate, and calcium carbonate, carbon black, cyanine compounds, quinoline compounds, anthraquinone compounds, and phthalocyanine compounds are preferable.

In addition, the dye / pigment may contain one kind, or two or more kinds may be contained in an optional combination and ratio.
Further, as the dye / pigment, for the purpose of improving the handleability at the time of extrusion and the dispersibility in the resin composition, a masterbatch with a polyethylene terephthalate resin, a polycarbonate resin or the like may be used.

  When the thermoplastic resin composition of the present invention contains a dye / pigment, its content may be appropriately selected depending on the required properties, but is usually 0.1 to 100 parts by mass of the thermoplastic resin (D). 001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 1 part by mass or more, and preferably 8 parts by mass. Parts by mass, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 1.7 parts by mass or less, particularly preferably 1.5 parts by mass or less.

  In particular, when the above-mentioned white pigment is contained, the content is preferably 2 to 8 parts by mass, more preferably 2.5 parts by mass or more, and still more preferably 100 parts by mass of the thermoplastic resin (D). Is at least 3 parts by mass, more preferably at most 7.5 parts by mass, even more preferably at most 7 parts by mass. When the content exceeds 8 parts by mass, mechanical properties, particularly strength, decrease, and when the content is less than 2 parts by mass, sufficient whiteness tends not to be obtained. As the white pigment, titanium oxide is particularly preferable.

[Additives, etc.]
Thermoplastic resin composition of the present invention, other additives other than the above, for example, ultraviolet absorbers, antistatic agents, additives such as flame retardants, polyethylene terephthalate resin, copolymerized polyethylene terephthalate resin, polycarbonate resin, Other resins other than the core / shell type elastomer can be contained. These may be used alone or in combination of two or more.

[Method for producing thermoplastic resin composition]
The thermoplastic resin composition of the present invention can be produced according to a conventional method for preparing a resin composition. Usually, the components and various additives, if desired, are combined and mixed well and then melt-kneaded in a single or twin screw extruder. Alternatively, the resin composition can be prepared without preliminarily mixing the components, or preliminarily mixing only a part of the components, and supplying the mixture to an extruder using a feeder to melt and knead the components. Further, a polyethylene terephthalate resin (A), a copolymerized polyethylene terephthalate resin (B), a polycarbonate resin (C), or a mixture of a part of another thermoplastic resin and a part of another component is melt-kneaded. A masterbatch may be prepared, and then the remaining other components may be blended and melt-kneaded.
The fibrous reinforcing filler such as glass fiber (F) is preferably supplied from a side feeder in the middle of the cylinder of the extruder.

The heating temperature at the time of melt-kneading can be appropriately selected usually from the range of 260 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause molding failure. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation and the like. The use of a stabilizer is desirable in order to suppress decomposition during kneading and during molding in a later step.
The pellets obtained by pelletizing the above resin composition are molded by various molding methods to obtain molded articles. Also, the resin melt-kneaded by an extruder can be directly molded into a molded product without passing through a pellet.

[Molding]
The method for producing a molded article using the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally employed for the thermoplastic resin composition can be arbitrarily adopted. Examples include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding such as gas assist, molding using an insulated mold, and rapid heating mold. Molding method, foam molding (including supercritical fluid), insert molding, outsert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminating molding method, Press molding, blow molding and the like can be mentioned.

  The shape of the molded article is not particularly limited and can be appropriately selected depending on the use and purpose of the molded article. For example, a plate, a plate, a rod, a sheet, a film, a cylinder, a ring, Examples include a circular shape, an elliptical shape, a polygonal shape, a deformed product, a hollow product, a frame shape (a square, a circular shape, an elliptical shape or a frame of a special shape), a box shape, and a panel shape.

The thermoplastic resin composition of the present invention is particularly suitable for injection molding, insert molding or outsert molding of a thin molded product using a multipoint gate mold having two or more gates of a molten resin injection section. It can be used particularly preferably. The gate structure of the mold itself is not limited, and examples include a side gate structure, a film gate structure (sometimes called a flash gate structure), a direct gate structure, a pin gate structure, a submarine gate structure, a diaphragm gate structure, and a tunnel gate structure. be able to.
The number of gates is 2 or more, and although it depends on the degree of thickness reduction and complexity of the molded product, about 2 to 15 is preferable.

Further, a thin molded article refers to a molded article having a maximum thickness of 2 mm or less, and a maximum thickness of 2 mm, preferably 1.8 mm, more preferably 1.6 mm, further preferably 1.5 mm, and especially 1 mm. And 0.7 mm, particularly 0.5 mm or less, and most preferably 0.4 mm or less.
The shape of the molded product is not limited, and may be a flat plate, a curved plate, a bent plate, a cylinder, a box, a curved surface, or the like. The cross section may be inclined, or may be a wedge-shaped cross section.

  The molding conditions at the time of injection molding vary depending on the specifications of the molding machine, but the thermoplastic resin composition of the present invention is usually set at a cylinder temperature of 280 to 340 ° C and a mold temperature of 50 to 70 ° C. Are each preferred.

  The thermoplastic resin composition of the present invention is excellent in fluidity, high in strength at welds and portions other than the welds, and excellent in dimensional stability. It is suitable for use in molding by injection molding, insert molding or outsert molding using a mold having a point gate.

  Outsert molding is a method in which a metal sheet metal is housed in a mold cavity into which a molten resin is poured at the time of injection molding, and a frame-shaped molded product is formed directly on the metal sheet metal. This method is a type of insert molding in that a metal member is set in a mold and then resin is injected, but it is a molding method in which a resin is adhered and integrated with a part of a metal sheet metal by molding to form a composite part. Outsert molding is a molding technique that is called in the industry.

The injection molding machine used for outsert molding is not particularly limited, and various known injection molding machines can be used, and a metal sheet metal is housed in a mold cavity before injection molding. When outsert molding the resin composition of the present invention, the metal sheet is preferably made of aluminum, iron, stainless steel, copper, or the like, particularly preferably stainless steel, and has a thickness of 0.1 to 0.4 mm. Are preferred.
It is preferable to provide a mold with a large number of gates, such as 6 or more, more preferably 8 or more, especially 10 or more per molded product. In such a case, there is a high risk that a large number of welds will occur in the molded product and the strength of the molded product will be significantly reduced. However, in the resin composition of the present invention, the molded product obtained even in the case of such a large number of gates Can maintain a high weld strength.

  The thermoplastic resin composition of the present invention can produce a molded article having high strength (rigidity) and excellent impact resistance even in a small and thin-walled part. It can be suitably used as a storage frame or a case.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

  The raw materials used in the following Examples and Comparative Examples are as follows. The method of measuring the intrinsic viscosity of the polyethylene terephthalate resin (A) and the copolymerized polyethylene terephthalate resin (B) and the method of measuring the viscosity average molecular weight of the polycarbonate resin are as described above.

(Examples 1 to 10, Comparative Examples 1 to 17)
[Production of thermoplastic resin composition pellets]
After blending each component other than glass fiber in the ratio (mass ratio) shown in the following Tables 2 and 3 among the components shown in the following Tables 2 and 3 and uniformly mixing with a tumbler mixer for 20 minutes, Nippon Steel Corporation In addition to the twin-screw extruder “TEX30α” manufactured by Toshosha, glass fibers were fed by side feed into the molten resin from the middle of the twin-screw extruder at the ratio shown in Table 2 below. The molten resin extruded into strands was kneaded under the conditions of a screw rotation speed of 300 rpm and a barrel temperature of 260 ° C., rapidly cooled in a water bath, and pelletized using a pelletizer to obtain pellets of a thermoplastic resin composition.

[Evaluation of fluidity by bar flow length measurement]
After the pellets obtained above were dried at 100 ° C. for 5 hours, an injection molding machine (mold clamping force 55T) manufactured by Nippon Steel Works Co., Ltd. was used, and the resin flow portion was helical, the thickness was 1 mm, and the width was 6 mm. Was molded under the conditions of a cylinder temperature of 300 ° C., an injection speed of 200 mm / s, an injection pressure upper limit of 150 MPa, and a mold temperature of 60 ° C., and the flow length (unit: mm) was measured.

[Measurement of non-weld strength]
After the pellets obtained above were dried at 100 ° C. for 5 hours, a dumbbell was used at a cylinder temperature of 320 ° C. and a mold temperature of 60 ° C. using an injection molding machine (mold clamping force 55T) manufactured by Japan Steel Works, Ltd. A shape test piece (thickness 1 mm, width of a thin portion 6 mm, length 115 mm including a grip portion) was injection molded.
The tensile strength at break (unit: MPa) was measured using the above dumbbell-shaped test piece.

[Measurement of weld strength]
After the pellets obtained above were dried at 100 ° C. for 5 hours, using an injection molding machine manufactured by Nippon Steel Works Co., Ltd. (mold clamping force 55T), the cylinder temperature was 320 ° C. and the mold temperature was 60 ° C. Test pieces measuring 1.6 mm x 13 mm x 100 mm were molded. The mold used for the main molding is provided with gates at both ends of the test piece, and a weld is formed at the center of the test piece.
For the measurement, a digital impact tester “DG-CB” manufactured by Toyo Seiki Seisaku-sho, Ltd. was used. Under a temperature condition of 23 ° C., this test piece was placed on the above-described apparatus such that the hammer hits the weld portion when the hammer was swung down with the 1.6 mm × 100 mm surface down, and the hammer was swung down. The impact strength (no notch, unit: kJ / m ² ) at the central weld portion of the test piece was measured.

[Dimensional stability-Measurement of molding shrinkage and heat shrinkage]
Mold shrinkage:
Using an injection molding machine manufactured by Nippon Steel Works (mold clamping force: 55T), a rectangular flat plate having a length of 120 mm, a width of 10 mm and a thickness of 1 mm was machined at a cylinder temperature of 300 ° C. and a mold temperature of 60 ° C. (MD direction) is formed by a side gate mold and left standing at 23 ° C. and 50% humidity for 24 hours. Then, the dimension (dimension a) in the flow direction (MD direction) is measured, and the flow direction is formed. The shrinkage rate (unit:%) was calculated.
Heat shrinkage:
After keeping the rectangular flat plate obtained above at a temperature of 85 ° C. for 24 hours, it was allowed to stand at 23 ° C. and a 50% humidity environment for 24 hours. Thereafter, the dimension (dimension b) in the flow direction (MD direction) was measured, and what percentage of the dimension b was smaller than the dimension a, that is, the heat shrinkage rate (unit:%) in the flow direction was calculated.

  The above results are shown in Table 2 below. In the table, Example 1 is abbreviated as “actual 1”, and Comparative Example 1 is abbreviated as “ratio 1”.

  Since the thermoplastic resin composition of the present invention can produce a molded product having high strength (rigidity) and excellent impact resistance even in a small and thin wall, these characteristics are strictly required for parts of electric and electronic equipment, for example, in various portable terminals and the like. It is very useful for parts storage frames and cases.

Claims (5)

Based on a total of 100 parts by mass of the following (A), (B) and (C), 20 to 65 parts by mass of the polyethylene terephthalate resin (A), and 15 to 30 mol% of all diol structural units are represented by the following general formula ( 100 parts by mass of a thermoplastic resin (D) containing 20 to 60 parts by mass of a copolymerized polyethylene terephthalate resin (B) and 2 to 20 parts by mass of a polycarbonate resin (C), which are structural units derived from a diol represented by 1). A thermoplastic resin composition comprising 2 to 8 parts by mass of a core / shell type elastomer (E) and 65 to 110 parts by mass of a glass fiber (F).
(Wherein, R ¹ and R ² are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms) Represents a group hydrocarbon group.)   The thermoplastic resin composition according to claim 1, wherein the core / shell type elastomer (E) is a core / shell type elastomer having a butadiene rubber as a core and having a number average particle size of 100 to 350 nm.   The thermoplastic resin composition according to claim 1, wherein the glass fiber (F) is a glass fiber having a flat cross section.   A molded product obtained by outsert molding the thermoplastic resin composition according to claim 1 on a metal sheet having a thickness of 0.1 to 0.4 mm. A metal sheet metal having a thickness of 0.1 to 0.4 mm using the thermoplastic resin composition according to any one of claims 1 to 3 using a mold having six or more gates per molded article. A method for producing a molded article on which outsert molding is performed.