JP2017036426A - Thermoplastic resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass fiber-reinforced thermoplastic resin composition which has excellent fluidity and high strength and is capable of giving a molded article having good weld strength.SOLUTION: The thermoplastic resin composition contains 2-8 pts.mass of a core/shell type elastomer (D) having a butadiene rubber as a core and 65-110 pts.mass of glass fibers (E) with respect to 100 pts.mass of a thermoplastic resin (C) which contains 80-98 pts.mass of a polyethylene terephthalate resin (A) and 2-20 pts.mass of a polycarbonate resin (B) based on 100 pts.mass of the total of (A) and (B). The polyethylene terephthalate resin (A) contains 50 mass% or more of a polyethylene terephthalate resin having an intrinsic viscosity of 0.6 dL/g or less. The core/shell type elastomer (D) has a number average particle diameter of 100-350 nm.SELECTED DRAWING: None

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 excellent in fluidity and strength, and weld strength.

  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 electrical and electronic equipment fields and automobile fields. With the reduction in size and weight of electrical and electronic equipment, automotive parts, etc., a material with higher rigidity is required.

  As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fiber is 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, it has been attempted to increase the blending amount of the glass fiber. However, there is a problem that the weld strength decreases as the blending amount of the glass fiber increases. In recent years, the shape of molded parts has become complex, and this problem is important because the strength of the entire part is often dominated by the weld strength.

  On the other hand, the glass fiber reinforced polycarbonate resin composition is excellent in rigidity and mechanical strength, but its fluidity is lowered. Therefore, it is necessary to set the injection molding temperature to a high temperature, and it becomes difficult to obtain a thin molded product. In addition, in order to obtain a thin molded product, for example, when injection molding is performed using a multi-point gate mold such as 6 points or more, a large number of welds are formed in the molded product, so that the strength of the molded product is increased. There was a problem of significant decrease.

  Various small precision parts represented by various portable terminals such as smartphones and digital cameras that are becoming smaller, thinner and more complicated in this way are not only rigid and mechanical strength, but also at the time of molding There is a strong demand for resin materials having both fluidity and weld strength.

JP 2004-256581 A

  The present invention was devised in view of the above problems of the prior art, and is a glass fiber reinforced thermoplastic resin composition capable of obtaining a molded article having excellent fluidity, high strength, and good weld strength. The purpose is to provide.

As a result of extensive studies on various resin materials in order to achieve the above-mentioned problems, the present inventors used a polyethylene terephthalate resin having a specific intrinsic viscosity as a polyester resin in a resin composition of a polyester resin and a polycarbonate resin. The glass fiber reinforced resin composition containing a specific amount of a polycarbonate resin and further blended with a specific elastomer has excellent fluidity and high strength, and can produce a molded product with good weld strength. As a result, the present invention has been completed.
The present invention is as follows.

[1] Thermoplastic resin (C) containing 80 to 98 parts by mass of polyethylene terephthalate resin (A) and 2 to 20 parts by mass of polycarbonate resin (B) based on a total of 100 parts by mass of (A) and (B). 2 to 8 parts by mass of core / shell type elastomer (D) having butadiene rubber as a core and 65 to 110 parts by mass of glass fiber (E) with respect to 100 parts by mass, and polyethylene terephthalate resin (A) A thermoplastic resin composition comprising 50% by mass or more of a polyethylene terephthalate resin having an intrinsic viscosity of 0.6 dl / g or less and a core / shell type elastomer (D) having a number average particle diameter of 100 to 350 nm.
[2] The thermoplastic resin composition according to [1], wherein the glass fiber (E) is a glass fiber having a flat cross-sectional shape.
[3] A molded product obtained by outsert-molding the thermoplastic resin composition according to [1] or [2] on a metal sheet having a thickness of 0.1 to 0.4 mm.
[4] The molded article according to the above [3], which is outsert molded using a mold having 6 or more gates per molded article.

  The thermoplastic resin composition of the present invention can produce a molded product having excellent fluidity, high strength, and good weld strength. In particular, a thin molded product is injected using a multi-point gate mold. It can be particularly suitably used for molding, insert molding or outsert molding.

Hereinafter, the present invention will be described in detail.
The thermoplastic resin composition of the present invention contains 80 to 98 parts by mass of polyethylene terephthalate resin (A) and 2 to 20 parts by mass of polycarbonate resin (B) on the basis of a total of 100 parts by mass of (A) and (B). 2 to 8 parts by mass of core / shell type elastomer (D) having butadiene rubber as a core and 65 to 110 parts by mass of glass fiber (E) with respect to 100 parts by mass of thermoplastic resin (C) The terephthalate resin (A) contains 50% by mass or more of a polyethylene terephthalate resin having an intrinsic viscosity of 0.6 dl / g or less, and the core / shell type elastomer (D) has a number average particle diameter of 100 to 350 nm. .

[Polyethylene terephthalate resin (A)]
The intrinsic viscosity (IV) of the polyethylene terephthalate resin is usually in the range of 0.3 to 1.5 dl / g, but the polyethylene terephthalate resin (A) used in the present invention has a IV of 0.6 dl / g or less. The resin is characterized by containing 50% by mass or more in the polyethylene terephthalate resin (A). By containing a polyethylene terephthalate resin having an IV of 0.6 dl / g or less, the fluidity of the thermoplastic resin composition of the present invention containing a large amount of glass fibers can be further improved. The preferable upper limit of the content of polyethylene terephthalate resin with an IV of 0.6 dl / g or less is 100% by mass, but a polyethylene terephthalate resin with an IV of 0.6 dl / g or less and other polyethylene terephthalate resins are used in combination. In this case, the IV of other polyethylene terephthalate resin is preferably more than 0.6 dl / g to 1.0 dl / g, more preferably 0.6 dl / g to 0.9 dl / g, and even more than 0.6 dl / g to It is preferably 0.9 dl / g, particularly more than 0.6 dl / g to 0.8 dl / g. The blending amount when a polyethylene terephthalate resin having an IV of 0.6 dl / g or more is mixed is preferably 10 to 50% by mass.

The intrinsic viscosity of the polyethylene terephthalate resin can be adjusted by appropriately selecting the production conditions for the known polyethylene terephthalate resin. For example, the polymerization time, the amount of catalyst, the degree of vacuum during polymerization, etc. may be set appropriately.
In the present invention, the intrinsic viscosity of the polyethylene terephthalate resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  Polyethylene terephthalate resin is a ratio of oxyethyleneoxyterephthaloyl units (hereinafter sometimes referred to as “ET units”) composed of terephthalic acid and ethylene glycol with respect to all constitutional repeating units (hereinafter sometimes referred to as “ET ratio”). .) Is preferably a polyethylene terephthalate resin of 90 equivalent% or more, and the polyethylene terephthalate resin in the present invention may contain a constitutional repeating unit other than the ET unit in a range of less than 10 equivalent%. The 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 be used together as raw materials.

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

  Examples of diol components other than ethylene glycol include aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and bisphenol. A, aromatic dihydroxy compound derivatives 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 them, alkylene terephthalate copolyester is preferable.

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

  The esterification catalyst is not particularly required because terephthalic acid serves as an autocatalyst for the esterification reaction. The esterification reaction can be carried out in the presence 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. Compounds are particularly preferred.

  As the polycondensation catalyst, compounds soluble in a reaction system such as a germanium compound, an antimony compound, a titanium compound, a cobalt compound, and a tin compound are used alone or in combination. As the polycondensation catalyst, germanium dioxide is particularly preferable from the viewpoints of color tone and transparency. These polycondensation catalysts may be used in combination with a stabilizer in order to suppress the decomposition reaction during polymerization. Examples of the stabilizer include phosphate esters such as trimethyl phosphate, triethyl phosphate and triphenyl phosphate, and triphenyl phosphate. Phosphites such as phyto, trisdodecyl phosphite, methyl acid phosphate, dibutyl phosphate, monobutyl phosphate acidic phosphate, phosphorous compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid Or 2 or more types are preferable.

  The use ratio of the above catalyst is usually in the range of 1 to 2000 ppm, preferably 3 to 500 ppm as the weight of the metal in the catalyst in the total polymerization raw material, and the use ratio of the stabilizer is the stabilizer in the total polymerization raw material. The weight of the phosphorus atom is usually 10 to 1000 ppm, preferably 20 to 200 ppm. The catalyst and the stabilizer can be supplied at any stage of the esterification reaction or transesterification reaction in addition to the preparation of the raw slurry. Further, it can be supplied at the beginning of the polycondensation reaction step.

[Polycarbonate resin (B)]
Although there is no restriction | limiting in the specific kind of polycarbonate resin (B), For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. 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, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

  Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:

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

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 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) Dihydroxy diaryl 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,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
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 such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardio structure-containing bisphenols 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;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (especially from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

In addition, when an example of a monomer that is a raw material of the aliphatic polycarbonate resin is given,
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- 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 (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;

  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 And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  Among the monomers used as the raw material for the polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  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; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

Manufacturing method of polycarbonate resin The manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. 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, a particularly preferable one of these methods will be described in detail.

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, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

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

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

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of 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 be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; 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, triethylbenzylammonium chloride, etc. Pyridine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. 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 reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

Melt transesterification method Next, the case where a polycarbonate resin is produced by the 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; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of 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 above all, 1.01 mol or more is used. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

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, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  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, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a 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-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the polycarbonate resin and the like, the melt polycondensation reaction is preferably carried out continuously.

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

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

  The viscosity average molecular weight (Mv) of the polycarbonate resin (B) is preferably 13,000 to 28,000. When the viscosity average molecular weight is within this range, a molded product having good fluidity and moldability and high mechanical strength is easily obtained. When the viscosity average molecular weight is less than 13,000, impact resistance is remarkably lowered and 28,000 is obtained. If it exceeds 1, the melt viscosity increases and injection molding tends to be difficult. The lower limit of the molecular weight of the polycarbonate resin (A) is more preferably 13,500, still more preferably 14,000, and the upper limit thereof is more preferably 26,000, particularly preferably 25,000.

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

  The terminal hydroxyl group concentration of the polycarbonate resin (B) 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. Thereby, the residence heat stability and color tone of polycarbonate resin can be improved more. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a resin composition can be improved more.

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

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, 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 usually 9,500 or less, preferably 9,000 or less. Furthermore, 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 raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin).
However, the regenerated 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 likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

  The ratio of the content of the polyethylene terephthalate resin (A) and the polycarbonate resin (B) is based on a total of 100 parts by mass of (A) and (B), and 80 to 98 parts by mass of the polyethylene terephthalate resin (A), polycarbonate resin ( B) is 2 to 20 parts by mass. In the system containing the polyethylene terephthalate resin (A) and the polycarbonate resin (B), it has been found that the properties change dramatically in the composition region. That is, when the content of the polycarbonate resin (B) exceeds 20 parts by mass, the weld strength is deteriorated. When the content is less than 2 parts by mass, the weld strength is good, but the strength of the non-weld part is not sufficient. The preferred content of the polycarbonate resin (B) is 3 parts by mass or more, more preferably 4 parts by mass or more, particularly preferably 5 parts by mass or more, and preferably 19 parts by mass or less, more preferably 18 parts by mass or less. .

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

  Such a graft copolymer may be produced by any production method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be a single-stage graft or a multi-stage graft. Also good. Of these, the emulsion polymerization is the easiest and preferred method.

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

  Specific examples of monomer components that can be graft copolymerized with a butadiene rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates. Epoxy group-containing (meth) acrylic acid ester compounds such as maleimide, maleimide compounds such as N-methylmaleimide and N-phenylmaleimide, α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid, and the like (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. 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 (D) used in the present invention is a core / shell comprising a shell layer formed by copolymerizing a methacrylic acid ester around a polybutadiene-containing rubber component as a core layer from the viewpoint of weld strength. A type graft copolymer is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a butadiene rubber component, more preferably 60% by mass or more. Moreover, what contains 10 mass% or more of methacrylic acid components is preferable.

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

  There is no limitation on a method for producing a core / shell type elastomer having a butadiene rubber as a core and a methacrylic acid ester copolymer as a shell. Usually, the above methacrylate is contained in a latex of a butadiene rubber component. Ingredients added, radical initiators such as peroxide initiators, azo initiators or redox initiators combined with oxidizing agents or reducing agents, emulsifiers such as anionic emulsifiers, nonionic emulsifiers, and chain transfer The method of manufacturing by emulsion graft polymerization etc. using an agent etc. is mentioned preferably.

The core / shell type elastomer (D) has an average particle size of 350 nm or less. By setting the average particle size to 350 nm or less, the weld strength is improved. The minimum of a preferable average particle diameter is 80 nm, More preferably, it is 100 nm.
Here, the number average particle diameter 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 used as Hitachi High-Technology Corporation. It is defined as the number average particle diameter of 300 particles from an image observed using a scanning electron microscope “SU8020” at an applied voltage of 2.0 kV and a magnification of 10,000 times.

  The content of the core / shell type elastomer (D) is 2 to 8 parts by mass with respect to 100 parts by mass of the thermoplastic resin (C) containing the polyethylene terephthalate resin (A) and the polycarbonate resin (B), preferably It is 2.5 parts by mass or more, preferably 7 parts by mass or less, more preferably 6 parts by mass or less. When the content of the core / shell type elastomer (D) is too small, the weld strength is poor, and when it is too large, the weld strength and the non-weld strength are lowered.

[Glass fiber (E)]
The thermoplastic resin composition of the present invention is characterized in that the glass fiber (E) is contained at a high content of 65 to 110 parts by mass with respect to 100 parts by mass of the thermoplastic resin (C). By containing glass fiber (E) 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 (E) is 68 parts by mass or more and 105 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (C).

  As glass fiber, if it is normally used for thermoplastic resin, 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 regardless of the form of the glass fiber at the time of blending a masterbatch or the like. Especially, as a glass fiber used for this invention, an alkali free glass (E glass) is preferable from the objective of improving the thermal stability of the thermoplastic resin composition of this invention.

The number average fiber length of the glass fibers is preferably 1 mm or more and 10 mm or less, more preferably 1.5 to 6 mm, and further preferably 2 to 5 mm.
When 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 tends to be lowered. If the number average fiber length is less than 1 mm, the glass fiber has a small aspect ratio, and therefore mechanical strength is likely to be insufficiently improved.

  The glass fiber preferably has a diameter of 3 to 20 μm. These can be produced by pulverizing glass fiber strands using, for example, 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 improvement of the mechanical strength is similarly insufficient, and when it exceeds 20 μm, the appearance tends to deteriorate. The diameter of the glass fiber is more preferably 5 to 15 μm, 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 between the polyethylene terephthalate resin and the polycarbonate resin.

Moreover, it is preferable to use a glass fiber that is usually a bundle of many of these fibers as a chopped strand (chopped glass fiber) cut into a predetermined length. The glass fiber used at this time contains a sizing agent. It is preferable to do. In addition to the advantage of improving the production stability of the molded product by blending the sizing agent, good mechanical properties can be obtained.
The sizing agent is not particularly limited, and examples thereof include urethane-based, epoxy-based, acrylic-based sizing agents. Of these, urethane-based and epoxy-based sizing agents are more preferable, and epoxy-based sizing agents are more preferable.

  Although there is no restriction | limiting in particular also about the cut length of a chopped strand (chopped glass fiber), Usually, 1-10 mm, Preferably it is 1.5-6 mm, More preferably, it is 2-5 mm.

  The glass fiber may be a glass fiber having a substantially circular cross section, specifically a glass fiber having a substantially circular cross section with a flatness (major axis / minor axis) of 1 to less than 1.5. In this case, the aspect ratio 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 cross section is 10 to 50 μm, and the ratio of major axis to minor axis (major axis) / Minor axis) is a flat cross-section glass fiber having an average value of 1.5 or more and 8 or less.

  As the glass fiber, a so-called glass fiber milled fiber is also preferable. Specifically, the milled glass fiber is a strand of glass fibers in which dozens to thousands of glass single fibers (filaments) are bundled. The glass fiber chopped strand cut into a predetermined length is pulverized. In this case, 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. When the aspect ratio exceeds 10, warpage and anisotropy increase and the appearance of the molded product tends to deteriorate.
The average fiber diameter of the milled glass fiber is preferably 1 to 25 μm in terms of number average fiber diameter, more preferably 5 to 17 μm, and the average length is preferably 1 to 500 μm, more preferably 10 to 300 μm. More preferably, it is 20-200 micrometers. In the short glass milled glass fiber having an average fiber diameter of less than 1 μm, the moldability is likely to be impaired, and when the average fiber diameter is greater than 25 μm, the appearance is impaired and the reinforcing effect tends to be insufficient.

[Stabilizer]
It is preferable for the thermoplastic resin composition of the present invention to contain a stabilizer because it improves thermal stability and prevents mechanical strength and hue deterioration.
As the stabilizer, a phosphorus stabilizer, a sulfur stabilizer and a phenol stabilizer are preferable. In particular, it is preferable to contain a phosphorus-based stabilizer because 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 good.

  Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphite ester, and phosphate ester. Among them, organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds are preferable.

The organic phosphate compound is 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 is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group, etc. are mentioned. The metal salt is preferably an alkaline earth metal, zinc, lead, or tin salt, particularly a zinc salt.

  Examples of long-chain alkyl acid phosphate compounds 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, nonyl phenyl 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 these, octadecyl acid phosphate is preferable, and this is, for example, trade name “ADEKA STAB AX-71” (octadecyl acid phosphate) manufactured by ADEKA, trade name “JP-518Zn” (octadecyl acid phosphate Zn salt, manufactured by Johoku Chemical Co., Ltd.) ) And the like.

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 of them 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, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (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, di 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 product is commercially available, for example, under the trade name “PEP-36” manufactured by ADEKA. .

The organic phosphonite compound is preferably the following general formula:
R ⁵ -P (OR ⁶ ) (OR ⁷ )
(In the formula, 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 of them is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho 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- And di-tert-butylphenyl) -3,3′-biphenylenediphosphonite.

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

  Examples of the phenol-based stabilizer include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 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 (C). When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect an improvement in the thermal stability and compatibility of the resin composition, and a decrease in molecular weight and a deterioration in hue during molding are likely to occur. When it exceeds, it will become excess amount and there exists a tendency for generation | occurrence | production of silver and a hue deterioration to occur further 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 aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  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.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine and comprise one ester may each be used only by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol 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, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

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

  In addition, the mold release agent mentioned above 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 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 100 parts by mass of the thermoplastic resin (C). 1 part by mass or less, more preferably 0.6 part by mass or less. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, 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 / pigment. By containing the dye / pigment, it is possible to impart color, light leakage prevention property, light reflectivity, concealability, weather resistance, etc. to the molded product obtained by molding the aromatic polycarbonate resin composition of the present invention. .

  Examples of the dye / pigment 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, dial, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium Examples thereof include oxide pigments such as black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; ferrocyan pigments such as bitumen.

  Examples of 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, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

  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, phthalocyanine compounds, and the like are preferable.

In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.
In addition, the dyed pigment may be used as a master batch with a polyethylene terephthalate resin, a polycarbonate-based resin, or the like for the purpose of improving the handleability during extrusion and improving the dispersibility in the resin composition.

  In the case where the thermoplastic resin composition of the present invention contains a dye / pigment, the content thereof may be appropriately selected according to the required characteristics, but it is usually 0. 100 parts by mass of the thermoplastic resin (C). 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 or less, 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 part by mass or less, and particularly preferably 0.5 parts by mass or less.

  In particular, the content when the above-described white pigment is contained is preferably 2 to 8 parts by mass, more preferably 2.5 parts by mass or more, and further preferably 100 parts by mass of the thermoplastic resin (C). Is 3 parts by mass or more, more preferably 7.5 parts by mass or less, and still more preferably 7 parts by mass or less. When the content exceeds 8 parts by mass, the mechanical properties, particularly the strength, are lowered, and when the content is less than 2 parts by mass, sufficient whiteness is not easily obtained. As the white pigment, titanium oxide is particularly preferable.

[Additives, etc.]
The thermoplastic resin composition of the present invention includes other additives other than those described above, for example, additives such as ultraviolet absorbers, antistatic agents, flame retardants, and the above-described polyethylene terephthalate resins, polycarbonate resins, and core / shell types. Resins other than elastomers can be contained. These may be used alone or in combination of two or more.

[Method for producing thermoplastic resin composition]
As a manufacturing method of the thermoplastic resin composition of this invention, it can carry out in accordance with the conventional method of resin composition preparation. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Moreover, it is also possible to prepare a resin composition without mixing each component in advance, or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Furthermore, a polyethylene terephthalate resin (A), a polycarbonate resin (B), or a part of another thermoplastic resin blended with a part of other components is melt-kneaded to prepare a master batch, and then The remaining other components may be blended and melt kneaded.
In addition, it is also preferable to supply the fibrous reinforcing filler of glass fiber (D) 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 from the range of usually 260 to 300 ° C. If the temperature is too high, decomposition gas tends to be generated, which may cause molding defects. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. It is desirable to use a stabilizer in order to suppress decomposition during kneading or molding in the subsequent process.
The pellets obtained by pelletizing the resin composition described above are molded into various molded products by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets.

[Molding]
The method for producing a molded product 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. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. 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, laminate molding method, Examples include a press molding method and a blow molding method.

  The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, 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 specially shaped frame), 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 article using a multi-point gate mold having two or more gates for the molten resin injection part. It can be particularly preferably used. There is no limitation on the gate structure of the mold itself, 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 it is preferably about 2 to 15 although it depends on the degree of thinning and complexity of the molded product.

The thin molded product refers to a molded product having a maximum thickness of 2 mm or less, and the maximum thickness is 2 mm, preferably 1.8 mm, more preferably 1.6 mm, still more preferably 1.5 mm, especially 1 mm. In addition, it refers to a molded product of 0.7 mm, particularly 0.5 mm or less, most preferably 0.4 mm or less.
Further, the shape of the molded product is not limited, and may be a flat plate shape, a curved plate shape, a folded plate shape, a cylindrical shape, a box shape, a curved surface shape, etc. The cross section may be inclined or 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 usually has a cylinder temperature of 280 to 340 ° C and a mold temperature of 50 to 70 ° C. Each is preferred.

  The thermoplastic resin composition of the present invention is excellent in fluidity, has high strength other than the weld part and the weld part, and is 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 technique in which a metal sheet metal is accommodated in advance in a mold cavity into which molten resin is poured during injection molding, and a frame-shaped molded product is directly molded on the metal sheet metal. This method is a kind of insert molding in that a metal member is set in a mold and then a resin is injected. However, this method is a molding method in which a resin is attached to and integrated with a part of a metal sheet metal to form a composite part. So is outsert molding and molding technology called in the industry.

The injection molding machine used for the outsert molding is not particularly limited, and various known injection molding machines can be used, and the metal sheet metal is accommodated in the mold cavity in advance prior to the injection molding. When the resin composition of the present invention is subjected to outsert molding, the metal sheet metal is preferably made of aluminum, iron, stainless steel, copper or the like, particularly stainless steel, and the thickness is in the range of 0.1 to 0.4 mm. Are preferred.
The mold is preferably provided with a large number of gates such as 6 points or more, further 8 points or more, particularly 10 points or more per molded product. In such a case, there is a high risk that a large number of welds are generated in the molded product and the strength of the molded product is significantly reduced. High weld strength can be maintained.

  Since the thermoplastic resin composition of the present invention can produce a molded product having high strength (rigidity) and excellent impact resistance even with a small thin wall, parts for electric and electronic equipment, such as parts for various portable terminals, which are required to have these characteristics severely. 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 examples, 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. In addition, the measuring method of the intrinsic viscosity of polyethylene terephthalate resin and the viscosity average molecular weight of polycarbonate resin is as having mentioned above.

(Examples 1-14, Comparative Examples 1-23)
[Production of thermoplastic resin composition pellets]
Of the components described below in Table 2 and below, each component other than glass fiber is blended in the proportions (mass ratio) described in Table 2 and below and mixed uniformly for 20 minutes with a tumbler mixer, and then Nippon Steel Corporation. While supplying it to the twin screw extruder “TEX30α” manufactured by Tosho Co., Ltd., glass fibers were supplied by side feed into the molten resin from the middle of the twin screw extruder at the ratio described in Table 2 below. The molten resin kneaded under the conditions of a screw rotation speed of 300 rpm and a barrel temperature of 260 ° C. and extruded into a strand shape was quenched in a water tank and pelletized using a pelletizer to obtain a pellet of a thermoplastic resin composition.

[Evaluation of fluidity by measuring bar flow length]
After drying the pellet obtained above at 100 ° C. for 5 hours, the Nippon Steel Works injection molding machine (clamping force 55T) and the resin flow part are spiral, the thickness is 1 mm, and the width is 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 under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 60 ° C. using an injection molding machine (clamping force 55T) manufactured by Nippon Steel Works. A shape test piece (thickness 1 mm, narrow portion width 6 mm, length including grip portion 115 mm) was injection molded.
The tensile strength at break (unit: MPa) was measured using the dumbbell-shaped test piece.

[Measurement of weld strength]
After the pellets obtained above were dried at 100 ° C. for 5 hours, using a Nippon Steel Works injection molding machine (clamping force 55T), a cylinder temperature of 320 ° C. and a mold temperature of 60 ° C. were used. A test piece measuring 1.6 mm long × 13 mm wide × 100 mm long was molded. The metal mold used for the main molding is provided with gates at both ends of the rod-shaped 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 Seisakusho was used. Under the temperature condition of 23 ° C., the test piece is 1.6 mm × 100 mm side down, and when the hammer is shaken down, it is left in the above-mentioned apparatus so that the hammer hits the weld part, and the hammer is shaken down. The impact strength (no notch, unit: kJ / m ² ) at the central weld of the test piece was measured.
The above results are shown in Table 2 below. In the table, Example 1 is abbreviated as “Real 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 with a small thin wall, it can be used in parts of electric and electronic equipment, such as various portable terminals, which require these characteristics. It is very useful for parts storage frames and cases.

Claims (4)

  Thermoplastic resin (C) 100 containing 80 to 98 parts by mass of polyethylene terephthalate resin (A) and 2 to 20 parts by mass of polycarbonate resin (B) based on a total of 100 parts by mass of the following (A) and (B). 2-8 parts by mass of core / shell type elastomer (D) having butadiene rubber as a core, 65-110 parts by mass of glass fiber (E), and polyethylene terephthalate resin (A) has an intrinsic viscosity with respect to parts by mass. A thermoplastic resin composition comprising a polyethylene terephthalate resin of 0.6 dl / g or less in an amount of 50% by mass or more and a core / shell type elastomer (D) having a number average particle diameter of 100 to 350 nm.   The thermoplastic resin composition according to claim 1, wherein the glass fiber (E) is a glass fiber having a flat cross-sectional shape.   A molded product obtained by outsert molding the thermoplastic resin composition according to claim 1 or 2 onto a metal sheet having a thickness of 0.1 to 0.4 mm.   The molded article according to claim 3, which is outsert molded using a mold having six or more gates per molded article.