JP2010132893A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in impact resistance, especially in low-temperature planar impact strength and excellent in fluidity, and to provide a molded product thereof. <P>SOLUTION: The thermoplastic resin composition is a resin composition formed by compounding 1 to 99 wt.% of an aromatic polycarbonate resin (A), 1 to 99 wt.% of an aromatic polyester resin (B) based on 100 wt.% total of the aromatic polycarbonate resin (A) and the aromatic polyester resin (B), and 0.01 to 4 pts.wt. of a polyfunctional compound (C), having three or more functional groups, provided that the total amount of (A) the aromatic polycarbonate resin and (B) the aromatic polyester resin is 100 pts.wt., wherein the aromatic polycarbonate resin (A) and a polybutylene terephthalate resin (B) have a bicontinuous structure of the two phases with a structural period of 0.01 to 1.0 μm, or a dispersed structure with intergranular distance of 0.001 to 1 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition and a molded product that give a molded product having excellent impact resistance, particularly low-temperature surface impact strength, and excellent fluidity.

  Conventionally, polycarbonate resins have excellent impact resistance, but are inferior in chemical resistance and fluidity. Therefore, improvement studies have been made by polymer alloys with various resins.

  Among them, blends of polycarbonate resin and polybutylene terephthalate resin are widely used because they are excellent in impact resistance, mechanical properties, heat resistance, chemical resistance, and the like. Further, in recent years, in order to improve impact resistance and rigidity, those containing a fine inorganic filler such as rubber polymer, glass fiber, talc, mica, whisker or the like are widely used. On the other hand, there has been a problem that impact resistance, which is a characteristic of polycarbonate, is lowered.

  In recent years, there has been an increasing demand for large-scale molding, weight reduction and thinning of industrial molded products. Especially, blends of aromatic polycarbonate resin and aromatic polyester resin used for automobiles and electrical / electronic equipment applications. In response to these demands, it is desired to improve the fluidity at the time of melting without deteriorating the characteristics.

In order to solve these problems, Patent Document 1 proposes a resin composition obtained by blending a thermoplastic resin and a polyfunctional compound having three or more functional groups. However, there is no description regarding a blend of an aromatic polycarbonate resin and an aromatic polyester resin, and no method for obtaining a resin composition having a high compatibility between low-temperature impact strength and fluidity is shown.
Patent Document 2 proposes a resin composition comprising an aromatic polycarbonate resin, an aromatic polyester resin, a basic inorganic filler, and a specific phosphite stabilizer.

  However, since a high shear stress state is not formed at the time of kneading with a twin-screw extruder, the aromatic polycarbonate resin and the aromatic polyester resin are not compatible with each other, and the structural period of 0.01 to 1.0 μm accompanying spinodal decomposition A two-phase continuous structure is not formed. Therefore, there is a problem that the low-temperature surface impact strength is not sufficiently developed.

  Patent Document 3 proposes a resin composition comprising a polybutylene terephthalate resin, a polycarbonate resin, a wollastonite having a specific structure, and a rubbery polymer. However, the fluidity is not sufficient, and when the size of the molded product is large, molding may not be possible, which may be a problem.

JP 2008-31439 A JP 2004-359913 A JP 2007-254611 A

  An object of the present invention is to obtain a thermoplastic resin composition and a molded product that give a molded product having excellent impact resistance, particularly low-temperature surface impact strength, and excellent fluidity.

  The present invention has been obtained as a result of intensive studies by the present inventors in order to solve the above problems.

That is, the present invention
(1) A thermoplastic resin composition comprising (A) an aromatic polycarbonate resin, (B) an aromatic polyester resin, and (C) a polyfunctional compound having three or more functional groups. The total of the aromatic polycarbonate resin and (B) aromatic polyester resin is 100% by weight, and (A) the aromatic polycarbonate resin is 1 to 99% by weight, (B) the aromatic polyester resin is 1 to 99% by weight, (A Thermoplastic obtained by blending 0.01 to 4 parts by weight of (C) a polyfunctional compound having 3 or more functional groups, with 100 parts by weight of the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin. A resin composition, wherein (A) an aromatic polycarbonate resin and (B) a polybutylene terephthalate resin have a biphasic continuous structure having a structural period of 0.01 to 1.0 μm, or an interparticle distance The thermoplastic resin composition characterized by having a dispersion structure of 0.001 to,
(2) (C) The polyfunctional compound having three or more functional groups is a compound in which at least one of the terminal structures having a functional group is a structure represented by the formula (1). A thermoplastic resin composition,

(3) (C) The thermoplastic compound according to any one of (1) to (2), wherein the polyfunctional compound having three or more functional groups contains one or more alkylene oxide units. object,
(4) (C) The functional group of the polyfunctional compound having three or more functional groups is at least one selected from a hydroxyl group, a carboxylic acid group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group. The thermoplastic resin composition according to any one of (1) to (3), which is a functional group,
(5) The thermoplastic resin composition according to any one of (1) to (4), further comprising (D) a filler,
(6) The thermoplastic resin composition according to (5), wherein (D) the filler is at least one selected from a plate shape, a granular shape, and a fibrous shape,
(7) A molded article comprising the thermoplastic resin composition according to any one of (1) to (6),
Is to provide.

  The thermoplastic resin composition of the present invention can provide a thermoplastic resin composition that gives a molded article having excellent impact resistance, particularly low-temperature surface impact strength, and excellent fluidity. In addition, the above thermoplastic composition can be suitably used as various molded articles.

  Hereinafter, the present invention will be described in detail.

  The (A) aromatic polycarbonate resin used in the present invention is easily produced by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester. For the reaction, a known method, for example, an interfacial method when phosgene is used, or a transesterification method in which the reaction is performed in a molten state when diester carbonate is used is adopted.

  2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is a typical example of the aromatic dihydroxy compound as the raw material. In addition, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) Octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2, 2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) Bis (hydroxyaryl) alkanes such as propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-biphenyl Bis (hydroxyaryl) cycloalkanes such as (4-hydroxyphenyl) cyclohexane; Dihydroxydiaryl ethers such as 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; 4 , 4′-dihydroxydiphenyl sulfide, dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3 Dihydroxy diaryl sulfoxides such as' -dimethyldiphenyl sulfoxide; dihydroxy such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Aryl sulfones and the like. These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyl may be used in combination. Furthermore, a branched aromatic polycarbonate resin using a polyfunctional compound such as phloroglucin can also be used.

  Examples of the carbonate precursor to be reacted with the aromatic dihydroxy compound include phosgene, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

  (A) The molecular weight of the aromatic polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 10,000 to 50,000, more preferably It is 15,000-40,000, Most preferably, it is 18,000-30,000.

  In order to obtain an aromatic polycarbonate resin having a desired molecular weight, a known method such as a method using a terminal terminator or a molecular weight regulator or a selection of polymerization reaction conditions is employed.

  The (B) aromatic polyester resin used in the present invention comprises (a) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, (c) a lactone It is a polymer or copolymer obtained by polycondensation of one or more selected from the above, and is a polyester that does not exhibit liquid crystallinity.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acid units such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Dioxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and the like And La ester forming derivatives.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Examples thereof include ester-forming derivatives. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  Specific examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene terephthalate, polypropylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), bisphenol A (Terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polypropylene (terephthalate / naphthalate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene (terephthalate / isophthalate) Phthalate), poly (cyclohexanedimethylene / ethylene) terephthalate , Aromatic polyesters such as poly (cyclohexanedimethylene / ethylene) (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate) / bisphenol A, polyethylene (terephthalate / isophthalate) / bisphenol A, and polybutylene (terephthalate / succinate) ), Polypropylene (terephthalate / succinate), polyethylene (terephthalate / succinate), polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate), polyethylene ( Terephthalate / sulfoisophthalate / succinate), polypropylene ( Terephthalate / sulfatoisophthalate / succinate), polybutylene (terephthalate / sebate), polypropylene (terephthalate / sebate), polyethylene (terephthalate / sebate), polybutylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polyethylene terephthalate / polyethylene glycol, poly Butylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene) Oxide) glycol , Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polypropylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polybutylene (terephthalate / isophthalate) / Poly (propylene oxide / ethylene oxide) glycol, Polypropylene (terephthalate / isophthalate)・ Poly (propylene oxide / ethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polybutylene terephthalate, poly-ε-caprolactone, etc. Blends, polyethylene oxalate, polypropylene oxalate, Butylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polybutylene adipate, polypropylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polypropylene (succinate / adipate), polyethylene ( Succinate / adipate), polyhydroxyalkanoates such as polyhydroxybutyric acid and copolymers of β-hydroxybutyric acid and β-hydroxyvaleric acid, aliphatic polyesters such as polycaprolactone, polyglycolic acid, polylactic acid, polybutylene succinate carbonate And aliphatic polyester carbonates.

  Among these, a polymer obtained by polycondensation of aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components is preferable. Specifically, polybutylene terephthalate, polypropylene terephthalate , Polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polypropylene naphthalate, polybutylene naphthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene (terephthalate / isophthalate), polybutylene terephthalate・ Polyethylene glycol, polypropylene terephthalate ・ Polyethylene glycol, polyethylene terephthalate ・ polyethylene glycol Polybutylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, Polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polypropylene (terephthalate / succinate) , Polyethylene (terephthalate / succinate It can be mentioned preferably. Ratio of aromatic dicarboxylic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of the above aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components Is more preferably 30 mol% or more, and further preferably 40 mol% or more.

  Among these, a polymer obtained by polycondensation of terephthalic acid or an ester-forming derivative thereof and an aliphatic diol selected from ethylene glycol, propylene glycol, or butanediol or an ester-forming derivative thereof as a main component is more preferable. Specifically, polypropylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate・ Poly (tetramethylene oxide) glycol, polypropylene terephthalate ・ Poly (teto Methylene oxide) glycol, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate) / Isophthalate) -poly (tetramethylene oxide) glycol, polyethylene (terephthalate / succinate), polyethylene (terephthalate / adipate), polypropylene (terephthalate / succinate), polypropylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polybutylene ( Terephthalate / adipate), polybutylene (terephthalate) Over DOO / sebacate), polybutylene (terephthalate / decane dicarboxylate), it may be mentioned poly (cyclohexane dimethylene terephthalate / isophthalate). The ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as a main component is 30 mol% or more. It is more preferable that it is 40 mol% or more.

  Further preferred examples of the specific examples of the (B) aromatic polyester resin in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyester elastomer, polypropylene terephthalate, and polybutylene succinate. In view of the properties, at least one selected from polybutylene terephthalate or polyethylene terephthalate is preferably the main component, and more preferably polybutylene terephthalate is the main component.

  The (B) thermoplastic polyester resin may be a copolymer. Specific examples include polybutylene (terephthalate / isophthalate), poly (cyclohexanedimethylene terephthalate / isophthalate), polybutylene (terephthalate / adipate), polyethylene (terephthalate / Succinate), polybutylene (terephthalate / succinate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene (terephthalate / naphthalate), and the like. May be.

  The viscosity of the (B) aromatic polyester resin used in the present invention is not particularly limited as long as it can be melt-kneaded. Usually, the intrinsic viscosity when an o-chlorophenol solution is measured at 25 ° C. is 0.36 to It is preferably 3.0 dl / g. In particular, those in the range of 0.9 to 2.0 dl / g are preferable from the viewpoint of moldability. If the intrinsic viscosity is less than 0.36 dl / g, the mechanical properties are poor, and if the intrinsic viscosity exceeds 3.0 dl / g, the moldability tends to be poor.

  The melting point of the (B) aromatic polyester resin used in the present invention is not particularly limited, but is preferably 120 ° C. or higher, more preferably 180 ° C. or higher, particularly 220 ° C. from the viewpoint of heat resistance. It is preferable that the temperature is not lower than ° C. The upper limit is 350 ° C. Furthermore, it is preferable that it exists in the range of 220 to 250 degreeC at the point of a moldability and productivity. In the present invention, the melting point of the aromatic polyester resin (B) is a value measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.

  The (B) aromatic polyester resin used in the present invention has a COOH end group amount determined by potentiometric titration of an m-cresol solution with an alkaline solution in a range of 1 to 50 eq / t (end group amount per ton of polymer). Some can be preferably used from the viewpoint of durability.

  The production method of the aromatic polyester resin (B) used in the present invention is not particularly limited, and can be produced by a known polycondensation method or ring-opening polymerization method, and any of batch polymerization and continuous polymerization can be used. In addition, both the transesterification reaction and the reaction by direct polymerization can be applied. Continuous polymerization is preferred in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased, and direct polymerization is preferred in terms of cost.

  The blending amount of (A) aromatic polycarbonate resin and (B) aromatic polyester resin in the present invention is (A) aromatic, with the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin being 100% by weight. 1 to 99% by weight of an aromatic polycarbonate resin, and 1 to 99% by weight of (B) an aromatic polyester resin. (A) 10 to 90% by weight of aromatic polycarbonate resin, (B) 10 to 90% by weight of aromatic polyester resin are more preferable, (A) 60 to 80% by weight of aromatic polycarbonate resin, (B) aromatic polyester resin 40 ˜60% by weight is most preferred. (A) If the blending amount of the aromatic polycarbonate resin is less than 1% by weight, the impact strength of the thermoplastic resin composition tends to decrease, and if it exceeds 99% by weight, the fluidity decreases, or the thermoplastic resin. The chemical resistance of the composition is reduced.

  The polyfunctional compound having three or more functional groups (C) used in the present invention is a component necessary for improving the fluidity of the thermoplastic resin of the present invention. The component (C) is not limited as long as it has three or more functional groups in the molecule, and may be a low molecular compound or a polymer. In addition, the component (C) may be any compound as long as it has three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound, but is excellent in fluidity and mechanical properties. In this respect, a trifunctional compound or a tetrafunctional compound is more preferable, and a tetrafunctional compound is further preferable.

  In the polyfunctional compound having three or more functional groups (C) used in the present invention, at least one of the terminal structures having a functional group is represented by the formula (1) from the viewpoint of excellent fluidity and impact resistance. It is preferable that the compound is a compound having a structure represented by formula (1), in which two or more of the terminal structures having a functional group are particularly preferable in terms of excellent fluidity and mechanical properties. More preferably, the compound is a compound in which three or more of the terminal structures having a functional group are structures represented by the formula (1), and all the terminal structures having a functional group are represented by the formula (1). Most preferably, the compound is a structure.

  Here, R represents a hydrocarbon group having 1 to 15 carbon atoms, n represents an integer of 1 to 10, X represents a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, It represents at least one functional group selected from an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group, and a silyl ether group.

  In the present invention, R represents an alkylene group, n represents an integer of 1 to 7, and X represents a hydroxyl group, a carboxylic acid group, or an amino group in terms of excellent fluidity, durability, and mechanical properties. , Preferably represents at least one functional group selected from a glycidyl group, an isocyanate group, an ester group, and an amide group, R represents an alkylene group, n represents an integer of 1 to 5, and X represents More preferably, it represents at least one functional group selected from a hydroxyl group, a carboxylic acid group, an amino group, a glycidyl group, and an ester group, R represents an alkylene group, n represents an integer of 1 to 4, More preferably, X represents at least one functional group selected from a hydroxyl group, an amino group, a glycidyl group, and an ester group, R represents an alkylene group, n represents an integer of 1 to 3, Is It is particularly preferred is a hydroxyl group. In the present invention, when R is an alkylene group, the structure represented by the formula (1) indicates a structure containing an alkylene oxide unit.

  In the present invention, the polyfunctional functional group in the component (C) is a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, It is preferably at least one selected from an amide group, a silanol group, and a silyl ether group, and the functional group in component (C) has three or more functional groups that are the same or different from these. Preferably it is. In the present invention, the component (C) is (C) a polyfunctional compound having three or more functional groups, and two or more terminal structures having functional groups are represented by the formula (1). In the case of a compound having a structure, the functional group may be the same or different from the above, but in terms of fluidity, mechanical properties, durability, heat resistance and productivity, It is preferable that they are the same.

  (C) As a preferable example of a polyfunctional compound having three or more functional groups, when the functional group is a hydroxyl group, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2, 6-hexanetriol, 1,2,3,6-hexanetetrol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, triethanolamine, trimethylolethane, trimethylolpropane, ditrimethylolpropane , Tritrimethylolpropane, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, methylglucoside, sorbitol, mannitol, sucrose, 1,3,5- Trihydroxybe Zen, polymers such as polyhydric alcohol or a polyvinyl alcohol having a carbon number of 3 to 24 such as 1,2,4-trihydroxy benzene. Of these, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol having a branched structure are preferable from the viewpoint of fluidity and mechanical properties.

  (C) As a preferable example of the polyfunctional compound having three or more functional groups, when the functional group is a carboxylic acid group, propane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2, 3-triscarboxylic acid, butane-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid , Cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, naphthalene- 2,5,7-tricarboxylic acid, pyridine-2,4,6-tricarboxylic acid, naphthalene-1,2,7,8-tetracarboxylic acid, naphthalene-1, , 5,8 polycarboxylic acid or acrylic acid, such as tetracarboxylic acid, include polymers such as methacrylic acid, it may be used acid anhydrides thereof. Of these, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid and acid anhydrides having a branched structure are preferable from the viewpoint of fluidity.

  (C) When the functional group of the polyfunctional compound having three or more functional groups is an amino group, at least one of the three or more substituents is preferably a primary or secondary amine, Is more preferably a primary or secondary amine, and both are particularly preferably primary amines. (C) As a preferred example of a polyfunctional compound having three or more functional groups, when the functional group is an amino group, 1,2,3-triaminopropane, 1,2,3-triamino-2-methyl Propane, 1,2,4-triaminobutane, 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-tri Aminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4 5-tetraminobenzene, 1,2,4-triaminonaphthalene, 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene, 1,4 5 8 tetra amino naphthalene. Of these, 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane and 1,3,5-triaminobenzene having a branched structure are preferable from the viewpoint of fluidity.

  (C) As a preferred example of a polyfunctional compound having three or more functional groups, when the functional group is a glycidyl group, monomers such as triglycidyl triazolidine-3,5-dione, triglycidyl isocyanurate And polymers such as poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate, glycidyl group-containing acrylic polymer, and glycidyl group-containing acrylic / styrene polymer.

  (C) As a preferred example of a polyfunctional compound having three or more functional groups, when the functional group is an isocyanate group, nonane triisocyanate (for example, 4-isocyanatomethyl-1,8-octane diisocyanate (TIN)) , Decane triisocyanate, undecane triisocyanate, dodecane triisocyanate and the like.

  (C) As a preferred example of a polyfunctional compound having three or more functional groups, when the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of the compound having three or more hydroxyl groups, And ester derivatives of compounds having three or more carboxylic acid groups.

  (C) As a preferable example of the polyfunctional compound having three or more functional groups, when the functional group is an amide group, an amide derivative of the compound having three or more carboxylic acid groups may be mentioned.

  From the viewpoint of fluidity and mechanical properties, it is preferable that the compound (C) having three or more functional groups contains one or more alkylene oxide units. In the present invention, the component (C) is (C) a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having a functional group is represented by the formula (1) In the case where R in the formula (1) is an alkylene group, the structure represented by the formula (1) indicates a structure containing an alkylene oxide unit and is particularly excellent in fluidity. In this regard, as the component (C), (C) a polyfunctional compound having three or more functional groups, and most preferably a polyfunctional compound containing an alkylene oxide unit. In the present invention, an aliphatic alkylene oxide unit having 1 to 4 carbon atoms is effective as a preferred example of the alkylene oxide unit. Specific examples include a methylene oxide unit, an ethylene oxide unit, a trimethylene oxide unit, a propylene oxide unit, Examples include tetramethylene oxide units, 1,2-butylene oxide units, 2,3-butylene oxide units, and isobutylene oxide units. In the present invention, in particular, fluidity, recyclability, durability, heat resistance and It is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit in terms of excellent mechanical properties, and a compound containing a propylene oxide unit in terms of excellent impact resistance. In particular Masui.

  In the component (C) used in the present invention, (C) the number of alkylene oxide units contained in the polyfunctional compound having three or more functional groups is one per functional group in terms of excellent fluidity and mechanical properties. It is preferable that it is 0.1-20, It is more preferable that it is 0.5-10, It is further more preferable that it is 1-2.

  As a preferred example of the polyfunctional compound having three or more functional groups (C) containing one or more alkylene oxide units, when the functional group is a hydroxyl group, (poly) oxymethylene glycerol, (poly) oxyethylene glycerol, (Poly) oxytrimethylene glycerol, (Poly) oxypropylene glycerol, (Poly) oxyethylene- (Poly) oxypropylene glycerol, (Poly) oxytetramethylene glycerol, (Poly) oxymethylene diglycerol, (Poly) oxyethylene di- Glycerin, (poly) oxytrimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylenetrimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, (poly) Xylpropylene trimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethyleneditrimethylolpropane, ( Poly) oxytrimethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly) oxypropylene pentaerythritol , (Poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol, ( Re) oxymethylene dipentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxytrimethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol, (poly) oxymethylene glucose, (poly) oxyethylene glucose, (Poly) oxytrimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, (poly) oxytetramethylene glucose and the like.

  In addition, as a preferred example of the polyfunctional compound having three or more functional groups (C) containing one or more alkylene oxide units, propane-1 containing (poly) methylene oxide units when the functional group is a carboxylic acid , 2,3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) trimethylene oxide units, (poly) propylene Propane-1,2,3-tricarboxylic acid containing an oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly) tetramethylene oxide unit, 2-methylpropane-1, containing a (poly) methylene oxide unit, 2,3-triscarboxylic acid, 2-methylpropane-1,2,3-triscal containing (poly) ethylene oxide units Acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) trimethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) propylene oxide units, Contains 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) tetramethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) methylene oxide units, and (poly) ethylene oxide units Butane-1,2,4-tricarboxylic acid, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, Butane-1,2,4-tricarboxylic acid containing (poly) tetramethylene oxide units, containing (poly) methylene oxide units Butane-1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) ethylene oxide units, butane-1,2, containing (poly) trimethylene oxide units 3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, butane-1,2,3,4-tetra containing (poly) tetramethylene oxide units Carboxylic acid, trimellitic acid containing (poly) methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) trimethylene oxide units, trimellitic acid containing (poly) propylene oxide units , Trimellitic acid containing (poly) tetramethylene oxide units, trimesic acid containing (poly) methylene oxide units , Trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) trimethylene oxide units, trimesic acid containing (poly) propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, (poly) methylene Hemimellitic acid containing oxide units, Hemimellitic acid containing (poly) ethylene oxide units, Hemimellitic acid containing (poly) trimethylene oxide units, Hemimellitic acid containing (poly) propylene oxide units, (Poly) tetramethylene oxide Hemimellitic acid containing units, pyromellitic acid containing (poly) methylene oxide units, pyromellitic acid containing (poly) ethylene oxide units, pyromellitic acid containing (poly) trimethylene oxide units, (poly) propylene oxide units Including Piromel Tolic acid, pyromellitic acid containing (poly) tetramethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) methylene oxide units, cyclohexane-1,3,5-containing (poly) ethylene oxide units Tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid containing (poly) trimethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide units, (poly) tetramethylene oxide units Examples thereof include cyclohexane-1,3,5-tricarboxylic acid.

  In addition, as a preferable example of the polyfunctional compound having three or more functional groups (C) including one or more alkylene oxide units, when the functional group is an amino group, 1,2,2 including (poly) methylene oxide units Contains 3-triaminopropane, 1,2,3-triaminopropane containing (poly) ethylene oxide units, 1,2,3-triaminopropane containing (poly) trimethylene oxide units, (poly) propylene oxide units 1,2,3-triaminopropane, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) methylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) ethylene oxide units, containing (poly) trimethylene oxide units , 2,3-triamino-2-methylpropane, 1,2,3-triamino-2-methylpropane containing (poly) propylene oxide units, 1,2,3-triamino- containing (poly) tetramethylene oxide units 2-methylpropane, 1,2,4-triaminobutane containing (poly) methylene oxide units, 1,2,4-triaminobutane containing (poly) ethylene oxide units, 1 containing (poly) trimethylene oxide units , 2,4-triaminobutane, 1,2,4-triaminobutane containing (poly) propylene oxide units, 1,2,4-triaminobutane containing (poly) tetramethylene oxide units, (poly) methylene 1,2,3,4-tetraminobutane containing oxide units, 1,2,3,4-tetramibutane containing (poly) ethylene oxide units Contains butane, 1,2,3,4-tetraminobutane containing (poly) trimethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) propylene oxide units, (poly) tetramethylene oxide units 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane containing (poly) methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, (poly) tri 1,3,5-triaminocyclohexane containing methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triamino containing (poly) tetramethylene oxide units Cyclohexane, 1,2,4-triaminocyclohexane containing (poly) methylene oxide units 1,2,4-triaminocyclohexane containing (poly) ethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) trimethylene oxide units, 1,2,4 containing (poly) propylene oxide units -Triaminocyclohexane, 1,2,4-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) methylene oxide units, (poly) ethylene oxide units included 1,2,4,5-tetraminocyclohexane, 1,2,4,5-tetraminocyclohexane containing (poly) trimethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) propylene oxide units, 1,2,4,5 containing (poly) tetramethylene oxide units Tetraminocyclohexane, 1,3,5-triaminobenzene containing (poly) methylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, 1,3 containing (poly) trimethylene oxide units , 5-triaminobenzene, 1,3,5-triaminobenzene containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, (poly) methylene oxide units 1,2,4-triaminobenzene containing 1,2,4-triaminobenzene containing (poly) ethylene oxide units, 1,2,4-triaminobenzene containing (poly) trimethylene oxide units, (poly ) 1,2,4-triaminobenzene containing propylene oxide units, (poly) tetramethylene oxy Including de units 1,2,4-aminobenzene, and the like.

  In addition, as a preferable example of the polyfunctional compound having three or more functional groups (C) including one or more alkylene oxide units, when the functional group is an ester group, three or more hydroxyl groups including the alkylene oxide unit are used. And an aliphatic acid ester or an aromatic acid ester of the compound having an ester derivative of a compound having three or more carboxylic acid groups containing the alkylene oxide unit.

  In addition, as a preferred example of the polyfunctional compound having three or more functional groups (C) containing one or more alkylene oxide units, when the functional group is an amide group, three or more carboxylic acids containing the alkylene oxide units And amide derivatives of compounds having a group.

  As a particularly preferred example of the polyfunctional compound having three or more functional groups (C) containing one or more alkylene oxide units from the viewpoint of fluidity, when the functional group is a hydroxyl group, (poly) oxyethylene glycerin, ( (Poly) oxypropylene glycerol, (poly) oxyethylene diglycerol, (poly) oxypropylene diglycerol, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane, (poly) oxyethylene ditrimethylolpropane, ( Poly) oxypropylene ditrimethylolpropane, (poly) oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol When the functional group is carboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide units, (poly ) Trimellitic acid containing ethylene oxide units, trimellitic acid containing (poly) propylene oxide units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, cyclohexane containing (poly) ethylene oxide units -1,3,5-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid containing a (poly) propylene oxide unit, and when the functional group is an amino group, 1,2 containing a (poly) ethylene oxide unit , 3-triaminopropane, (poly) propylene oxide 1,2,3-triaminopropane containing 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, (poly) Examples include 1,3,5-triaminobenzene containing an ethylene oxide unit and 1,3,5-triaminobenzene containing a (poly) propylene oxide unit.

  The viscosity of the polyfunctional compound having three or more functional groups (C) used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and is 5000 m · Pa or less from the viewpoint of fluidity and mechanical properties. More preferably, it is particularly preferably 2000 m · Pa or less. Although there is no particular lower limit, it is preferably 100 m · Pa or more from the viewpoint of bleeding property during molding. When the viscosity at 25 ° C. is larger than 15000 m · Pa, the fluidity improving effect is insufficient, which is not preferable.

  The molecular weight or weight average molecular weight (Mw) of the compound having three or more functional groups (C) used in the present invention is preferably in the range of 50 to 10,000, and in the range of 150 to 8,000 in terms of fluidity. It is more preferable that it is in the range of 200 to 3000. In the present invention, (B) Mw of a polyfunctional compound having three or more functional groups is converted to polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent. Value.

  The moisture content of the polyfunctional compound having (C) three or more functional groups used in the present invention is preferably 1% or less. More preferably, the moisture content is 0.5% or less, and further preferably 0.1% or less. There is no particular lower limit for the moisture content of the component (C). A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.

  In the present invention, (C) the blending amount of the polyfunctional compound having three or more functional groups is (C) with the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin being 100 parts by weight. It is essential that the component is in the range of 0.01 to 4 parts by weight, and in terms of fluidity and impact resistance, it is preferably blended in the range of 0.05 to 2 parts by weight. More preferably, it is blended in the range of 7 parts by weight.

  In the present invention, the component (C) preferably has at least one hydroxyl group or carboxylic acid group from the viewpoint of fluidity, and the component (C) has three or more hydroxyl groups or carboxylic acid groups. It is more preferable that the component (C) has three or more hydroxyl groups, and it is particularly preferable that all functional groups of the component (C) are hydroxyl groups.

  In the present invention, in order to impart other properties such as mechanical strength of the resin composition, (D) a filler can be blended.

  (D) As the type of filler, any filler such as fibrous, needle-like, plate-like, and granular can be used. Specifically, glass fibers, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers Fibrous fillers such as alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, etc., acicular fillers such as wollastonite, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker , Talc, mica, glass flakes, synthetic hydrotalcite, platy fillers such as graphite, kaolin, clay, various beads such as silica, calcium carbonate, glass beads, silica beads, various balloons such as glass microballoons, two Molybdenum sulfide, montmorillona DOO, titanium oxide, fillers in granular, such as barium sulfate is exemplified.

  When talc is used in the filler (D) of the present invention, the bulk density of talc is preferably 0.1 to 2.0, more preferably 0.3 to 1.5, and 0.5 to 1.0. Most preferred. When the bulk specific gravity is 0.1 or more, the rigidity, impact resistance and thermal stability of the resin composition tend to be further improved. When the bulk specific gravity is 2.0 or less, the appearance of the molded product of the resin composition And impact resistance tends to be further improved.

Here, the bulk density is a value obtained by the following method.
(1) Place talc on a sieve with an opening of 1.4 mm, and pass the sieve while sweeping lightly with a brush.
(2) The talc passed through the sieve is put into a receiver attached to the bulk density measuring device specified in JISK5101 until it reaches a heap.
(3) The top pile of talc is scraped off with a spatula from the inlet of the receiver, the weight of the talc in the receiver is measured, and the bulk density is calculated by the following equation.
Bulk density = weight of talc in the receiver (g) / capacity of receiver (ml)

  As a method of increasing the bulk density using raw material talc, any conventionally known granulation method can be used, and there are a case where a binder is not used and a method where a binder is used.

  As an example of a method not using a binder, there is usually a method of deaeration compression. A typical example of such a method is a method of performing roller compression with a briquetting machine or the like while degassing.

  As an example of a method using a binder, there is a method in which a liquid in which a resin or the like serving as a binder is dissolved or dispersed and talc are uniformly mixed with a mixer such as a super mixer and granulated through a granulator. Further, it is preferable to dry the talc and remove components such as water from the talc.

  The talc can be surface-treated in advance. Examples of surface treatment include chemical treatment with various treatment agents such as silane coupling agents, higher fatty acids, fatty acid metal salts, and polyalkylene glycols, as well as physical surfaces such as mechano-fusion methods and high-speed air-flow impact methods. Processing is also possible.

  Specific examples of suitable talc include HT-7000 manufactured by Harima Kasei Co., Ltd., and B-10 and R-10 manufactured by Matsumura Sangyo Co., Ltd.

  When carbon fiber is used in the filler (D) of the present invention, there is no particular limitation, and carbonaceous fibers manufactured using various known carbon fibers such as polyacrylonitrile, pitch, rayon, lignin, hydrocarbon gas, etc. It is a graphite fiber, and a fiber obtained by coating these fibers with a metal may be used. The carbon fibers are usually in the form of chopped strands, roving strands, milled fibers, etc., and have a diameter of 15 μm or less, preferably 5 to 10 μm.

  The carbon fiber used in the present invention is preferably a chopped strand, and the number of filaments of the carbon fiber strand which is a precursor of the chopped carbon fiber is preferably 1,000 to 150,000. If the number of filaments is less than 1,000, the production cost increases, and if it exceeds 150,000, the production cost increases and stability in the production process may be greatly impaired.

  The carbon fibers used in the present invention can be suitably used that are bundled with various sizing agents. Sizing agents include epoxy resin, urethane-modified epoxy resin, epoxy-modified urethane resin, phenol resin, polyamide resin, polycarbonate resin, polyimide resin, polyetherimide resin, bismaleimide resin, polysulfone resin, polyethersulfone resin, polyvinylpyrrolidone resin And at least one resin component selected from the group consisting of a polyacrylic resin and a polyurethane resin. In the present invention, among these resin components, those containing an epoxy resin and a polyurethane resin are preferably used from the viewpoint of compatibility with the thermoplastic resin.

  When glass fiber is used in the filler (D) of the present invention, there is no particular limitation, but chopped strand type or roving type glass fiber can be used, and silane coupling agents such as aminosilane compounds and epoxysilane compounds and / or Alternatively, glass fibers treated with a sizing agent containing one or more epoxy compounds such as urethane, vinyl acetate, bisphenol A diglycidyl ether, and novolac epoxy compounds are preferably used. The silane coupling agent and / or sizing agent is You may use it, mixing with an emulsion liquid. The fiber diameter is 1 to 30 μm, preferably 5 to 15 μm. In addition, although the fiber cross section is circular, a fiber reinforcing material having an arbitrary cross section such as an elliptical glass fiber, a flat glass fiber and an eyebrow-shaped glass fiber having an arbitrary aspect ratio can be used. It is characterized by improved fluidity at the time and a molded product with less warping.

  Among these (D) fillers, in the obtained thermoplastic resin composition, when a good surface appearance, excellent surface impact strength and low coefficient of linear expansion are required, a plate-like or granular filler is preferable, A plate-like filler is more preferable, and talc is particularly preferable. Moreover, when high rigidity and a low linear expansion coefficient are required, a fibrous filler is preferable and glass fiber is particularly preferable. Furthermore, when high rigidity, low specific gravity, and a low linear expansion coefficient are required, a fibrous filler is preferable and carbon fiber is particularly preferable.

  The above (D) filler can be used in combination of two or more kinds, and by using two kinds of talc / glass fiber and talc / carbon fiber in combination, a good surface appearance and high rigidity are achieved. It becomes possible to achieve both.

  The filler (D) may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be subjected to a surface treatment in advance. it can. Examples of surface treatment include chemical treatment with various treatment agents such as silane coupling agents, higher fatty acids, fatty acid metal salts, and polyalkylene glycols, as well as physical surfaces such as mechano-fusion methods and high-speed air-flow impact methods. Processing is also possible.

  The blending amount of (D) filler is such that the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin is 100 parts by weight, and it is blended in the range of 0.1 to 200 parts by weight. It is preferable at a point, It is more preferable to mix | blend in the range of 1-150 weight part, It is further more preferable to mix | blend in the range of 20-100 weight part.

  In the present invention, in order to impart mechanical strength and other characteristics of the resin composition, (E) an impact resistance improver can be blended.

  (E) As the impact resistance improver, those known for thermoplastic resins can be used. Specifically, natural rubber, polyethylene such as low density polyethylene and high density polyethylene, polypropylene, impact resistance Modified polystyrene, polybutadiene, styrene / butadiene copolymer, ethylene / propylene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer Polymers, polyester elastomers such as polyethylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, butadie such as MBS It includes core-shell elastomer system core shell elastomers or acrylic, which can be used alone or in combination. Examples of the butadiene-based or acrylic-based core-shell elastomer include “Metablene” manufactured by Mitsubishi Rayon, “Kaneace” manufactured by Kaneka, “Paralloid” manufactured by Rohm & Haas, and the like.

  Since the linear expansion coefficient of the resulting thermoplastic resin composition is excellent, it is preferable to use a butadiene-based core-shell elastomer or an acrylic-based core-shell elastomer.

  (E) The blending amount of the impact modifier may be blended in the range of 0.1 to 100 parts by weight, with the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin being 100 parts by weight. It is preferable from the point of fluidity | liquidity and impact resistance, It is more preferable to mix | blend in the range of 1-70 weight part, It is further more preferable to mix | blend in the range of 1-50 weight part.

  In the present invention, an organic acid (F) can be used for the purpose of improving the thermal stability and the like of the thermoplastic resin composition.

  (F) Various types of organic acids can be used, for example, fatty acids having 6 to 30 carbon atoms such as caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, arachidic acid, Examples of representative compounds include maleic anhydride and acid-modified siloxane. In particular, maleic anhydride and capric acid are preferably used.

  (F) The blending amount of the organic acid is 0.001 to about 100 parts by weight of the total of (A) the aromatic polycarbonate resin and (B) the aromatic polyester resin from the viewpoint of improving the thermal stability and fluidity. The amount is preferably 5 parts by weight, and more preferably 0.01 to 1 part by weight. (F) When the compounding amount of the organic acid is less than 0.001 part by weight, the effect of improving the melt stability is not exhibited, and when it exceeds 5 parts by weight, the fluidity and impact resistance are lowered.

  Thus, by blending the organic acid (F), the melt stability is improved, and a molded product excellent in impact resistance and appearance can be obtained.

  In the present invention, (A) an aromatic polycarbonate resin and (B) an aromatic polyester resin have a biphasic continuous structure having a structural period of 0.01 to 1.0 μm, or a dispersed structure having an interparticle distance of 0.001 to 1 μm. It is necessary to have.

  In order to obtain a resin composition having such a structural period, it is preferable that (A) the aromatic polycarbonate resin and (B) the aromatic polyester resin are once dissolved and formed into a structure by spinodal decomposition described later. Furthermore, in order to realize this structure formation, (A) an aromatic polycarbonate resin and (B) an aromatic polyester resin, a partial miscible system described later, a system that undergoes shear field-dependent phase dissolution / phase decomposition, a reaction, A system that induces phase decomposition is preferred.

  In general, polymer alloys composed of two-component resins include compatible systems, incompatible systems, and semi-compatible systems. The compatible system is a system that is compatible in the entire range of practical temperatures above the glass transition temperature and below the thermal decomposition temperature under non-shearing in an equilibrium state. The incompatible system is a system that is incompatible in the entire region, contrary to the compatible system. A semi-compatible system is a system that is compatible in a certain temperature and composition region and incompatible in another region. Furthermore, in this semi-compatible system, there are those that undergo phase separation by spinodal decomposition depending on the conditions of the phase separation state and those that undergo phase separation by nucleation and growth.

  Furthermore, in the case of a polymer alloy composed of three or more components, a system in which all three or more components are compatible, a system in which all three or more components are incompatible, a compatible phase having two or more components, and the rest There is a system in which one or more phases are incompatible, two components are partially compatible, and the remaining components are distributed in a partially compatible system composed of these two components. In the present invention, in the case of a polymer alloy comprising three or more components other than (A) aromatic polycarbonate resin and (B) aromatic polyester resin, (A) aromatic polycarbonate resin and (B) 3 other than aromatic polyester resin. The component is preferably a system distributed to at least one of (A) an aromatic polycarbonate resin and (B) an aromatic polyester resin. In this case, the structure of the polymer alloy is equivalent to the incompatible structure composed of two components. The following description will be made on behalf of a polymer alloy composed of two-component resins.

  Phase separation by spinodal decomposition refers to phase separation that occurs in an unstable state inside the spinodal curve in phase diagrams for different two-component resin compositions and temperatures, and phase separation by nucleation and growth refers to the phase separation. In the figure, it refers to phase separation that occurs in the metastable state inside the binodal curve and outside the spinodal curve.

  The spinodal curve refers to the difference (ΔGmix) between the free energy when compatibilized and the sum of the free energies in two phases that are not compatible (ΔGmix) when two different resins are mixed with respect to the composition and temperature. φ) is a curve in which the partial differential twice (∂2ΔGmix / ∂φ2) is 0, and inside the spinodal curve is an unstable state of ∂2ΔGmix / ∂φ2 <0, and outside is ∂ 2ΔGmix / ∂φ2> 0.

  The binodal curve is a boundary curve between the region where the system is compatible and the region where the system is separated with respect to the composition and temperature.

  Here, the case of being compatible in the present invention is a state in which they are uniformly mixed at the molecular level. Specifically, both phases having different two-component resins as main components are 0.001 μm or more. The case where the phase structure is not formed is indicated, and the case where the phase is incompatible is the case where the phase is not in a compatible state, that is, the phases mainly composed of two different resin components are 0.001 μm or more. It refers to the state of forming a phase structure. Whether or not they are compatible is determined by various methods such as an electron microscope, a differential scanning calorimeter (DSC), and the like, as described in Polymer Alloys and Blends, Leszek A Utacki, Hans Publishers, Munich Vie New York, P64, etc. be able to.

  According to detailed theory, in spinodal decomposition, once the temperature of a mixed system that has been uniformly mixed at the temperature of the compatible region is rapidly increased to the temperature of the unstable region, the system will rapidly phase-separate toward the coexisting composition. To start. At that time, the concentration is monochromatized at a constant wavelength, and a two-phase continuous structure is formed in which both separated phases are continuously intertwined regularly with a structure period (Λm). After the formation of the two-phase continuous structure, the process in which only the concentration difference between the two phases increases while keeping the structure period constant is called the initial process of spinodal decomposition.

Furthermore, the structural period (Λm) in the initial process of the above-mentioned spinodal decomposition has a thermodynamic relationship as shown in the following equation.
Λm to [| Ts-T | / Ts] -1/2 (where Ts is the temperature on the spinodal curve)

  In spinodal decomposition, after going through such an initial process, it goes through a medium-term process in which an increase in wavelength and an increase in concentration difference occur simultaneously, and a later process in which an increase in wavelength occurs in a self-similar manner after the concentration difference reaches the coexisting composition. In order to obtain the structure defined in the present invention, the desired structural period before the final separation into the macroscopic two phases has been reached. What is necessary is just to fix a structure in a step.

  In addition, in the process of increasing the wavelength from the mid-stage process to the late-stage process, depending on the influence of the composition and the interfacial tension, the continuity of one phase may be interrupted and the above-described biphasic continuous structure may be changed to a dispersed structure. In this case, the structure may be fixed when the desired interparticle distance is reached.

  The two-phase continuous structure referred to in the present invention refers to a structure in which both components of the resin to be mixed each form a continuous phase and are entangled three-dimensionally. A schematic diagram of this two-phase continuous structure is described, for example, in “Polymer Alloy Fundamentals and Applications (Second Edition) (Chapter 10.1)” (edited by the Society of Polymer Science: Tokyo Kagaku Dojin).

  The dispersion structure referred to in the present invention refers to a so-called sea-island structure in which particles mainly composed of the other resin component are interspersed in a matrix mainly composed of the other resin component. .

  The thermoplastic resin composition of the present invention needs to be structurally controlled to have a two-phase continuous structure with a structural period of 0.001 to 1 μm or a dispersed structure with a distance between particles of 0.001 to 1 μm. . It is preferable to control to a two-phase continuous structure with a structural period of 0.001 to 0.5 μm or a dispersed structure with a distance between particles of 0.001 to 0.5 μm. It is more preferable to control to a two-phase continuous structure in the range of 0.1 μm, or a dispersed structure in the range of a distance between particles of 0.005 to 0.1 μm.

  When the structure period is less than 0.001 μm or the distance between particles is less than 0.001 μm, characteristics such as heat resistance may deteriorate. When the structure period exceeds 1 μm, or when the distance between particles exceeds 1 μm, falling ball impact The strength may decrease.

  On the other hand, in the nucleation and growth, which is the phase separation in the metastable region described above, a dispersed structure that is a sea-island structure is formed from the initial stage, and it grows. It is difficult to form a biphasic continuous structure in the range of 0.001 to 1 μm or a dispersed structure in the range of a distance between particles of 0.001 to 1 μm.

  In order to realize the spinodal decomposition, it is necessary to bring each thermoplastic resin into a compatible state and then to an unstable state inside the spinodal curve.

  First, as a method of realizing a compatible state with a resin composed of two or more components, after dissolving in a common solvent, spray drying, freeze drying, coagulation in a non-solvent substance, film formation by solvent evaporation, etc. from this solution is used. Examples thereof include a solvent casting method and a melt-kneading method in which a partially compatible system is melt-kneaded under compatible conditions. Among these, compatibilization by melt kneading, which is a dry process that does not use a solvent, is preferably used in practice.

  For compatibilization by melt kneading, an ordinary extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing step of the injection molding machine. The temperature for compatibilization needs to be a condition in which the partially compatible resin is compatible.

  Next, when the resin composition made into a compatible state by the above melt kneading is in an unstable state inside the spinodal curve, the temperature for making the unstable state when the spinodal decomposition is performed, and other conditions vary depending on the combination of the resins. Although it cannot be generally stated, it can be set by performing a simple preliminary experiment based on the phase diagram.

  As a method of immobilizing the structure product by spinodal decomposition, one or both components of the phase-separated phase can be fixed in a short period of time by rapid cooling or the like, or if one is a component that is thermosetting, the phase of the thermosetting component May be fixed by utilizing the fact that they cannot move freely due to reaction, and when the other is a crystalline resin, it may be fixed by utilizing the fact that the crystalline resin phase cannot be freely moved by crystallization.

  In the present invention, in order to phase-separate the (A) aromatic polycarbonate resin and the (B) aromatic polyester resin by the above spinodal decomposition into the thermoplastic resin composition of the present invention, as described above, a partially compatible system, It is preferable to combine a resin that is a shear field-dependent phase dissolution / phase decomposition system or a reaction-induced phase decomposition system.

  In general, partial compatible systems are known to have a low-temperature compatible phase diagram that is easy to be compatible on the low temperature side in the same composition, and a high temperature compatible phase diagram that is easy to be compatible on the high temperature side. It has been. The lowest temperature between the miscible and incompatible branch temperatures in this low-temperature compatible phase diagram is called the lower critical solution temperature (abbreviated as LCST), and is compatible in the high-temperature compatible phase diagram. The highest temperature among the incompatible branching temperatures is called the upper critical solution temperature (UCST for short).

  In the case of a low-temperature compatible phase diagram, a resin of two or more components that have become compatible using a partially compatible system can be brought to a temperature higher than the LCST and a temperature inside the spinodal curve. In the case of the figure, spinodal decomposition can be performed by setting the temperature below UCST and the temperature inside the spinodal curve.

  In addition to spinodal decomposition by this partially compatible system, spinodal decomposition is also induced by melt kneading in non-compatible systems, for example, once compatible under shearing during melt kneading, etc., and then in an unstable state again under non-shearing. Phase separation by spinodal decomposition is also possible by so-called shear field-dependent phase dissolution / phase decomposition in which phase decomposition occurs, and in this case as well, in the same manner as in the case of a partially miscible system, decomposition proceeds in a spinodal decomposition mode and both phases are ordered. Has a continuous structure. Furthermore, this shear field-dependent phase dissolution / phase decomposition is the same as the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the shear field and the unstable region expands. The substantial degree of supercooling (| Ts−T |) also increases in the temperature change range, and as a result, it is easy to reduce the structural period in the initial process of spinodal decomposition in the above relational expression, so that it is preferably used. It is done. In order to achieve compatibilization by shearing during such melt kneading, a normal extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing step of the injection molding machine. In this case, the temperature for compatibilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions differ depending on the combination of the resins, and cannot be generally stated. The conditions can be set by performing a simple preliminary experiment based on the phase diagram under the shear conditions. Also, as a method of reliably realizing the compatibilization in the plasticizing process of the injection molding machine, it is melt-kneaded with a twin-screw extruder in advance and compatibilized, and after discharging, it is rapidly cooled in ice water or the like to fix the structure in the compatibilized state. A preferred example is a method of injection molding using a paste.

  In addition, the addition of a third component that is a copolymer such as a block copolymer, a graft copolymer, or a random copolymer that further includes a component that constitutes a polymer alloy to the thermoplastic resin composition that constitutes the present invention In order to reduce the free energy of the interface, it is preferably used in order to easily control the structural period in the biphasic continuous structure and the distance between dispersed particles in the dispersed structure. In this case, the third component such as the copolymer is usually distributed to each phase of the polymer alloy composed of the two-component resin except the copolymer, and thus can be handled in the same manner as the polymer alloy composed of the two-component resin.

  In the thermoplastic resin composition of the present invention, the (A) aromatic polycarbonate resin and the (B) aromatic polyester resin are a two-phase continuous structure having a structural period of 0.001 to 1.0 μm, or a distance between particles of 0.001 to 0.001. A 1 μm dispersion structure is preferable, and the measurement method is a portion where the structure can be observed by observing with a transmission electron microscope a sample obtained by staining a polycarbonate component by iodine staining and then cutting out an ultrathin section. 100 are arbitrarily selected, and the average value is calculated after measuring the structure period or interparticle distance.

  In order to realize the spinodal decomposition, it is necessary that the resin having two or more components is once in a compatible state and then in an unstable state inside the spinodal curve. In spinodal decomposition in a general semi-compatible system, spinodal decomposition can be caused by temperature jumping to an incompatible region after melt-kneading under compatible conditions. On the other hand, in the above-described shear field-dependent spinodal decomposition, in the non-compatible system, since it is compatibilized under shear in the range of a shear rate of 100 to 10000 sec-1 at the time of melt kneading, the spinodal only by non-shearing. Degradation can occur.

  The polymer alloy formed by blending the (A) aromatic polycarbonate resin and the (B) aromatic polyester resin of the present invention belongs to the above shear field-dependent spinodal decomposition, and has a shear rate of 100 to 10000 sec-1 during melt-kneading. Since it is compatibilized under a range of shear, spinodal decomposition can be caused only by non-shearing. In the above, the shear rate is, for example, when using a parallel disk type shear applicator, a resin heated to a predetermined temperature and put in a molten state is put between the parallel disks, the distance (r) from the center, and between the parallel disks It can be obtained as ω × r / h from the interval (h) and the angular velocity (ω) of rotation.

  As a specific method for producing such a polymer alloy, a method utilizing the above-mentioned shear field-dependent spinodal decomposition is mentioned as a preferred example. As a method for realizing compatibilization during melt-kneading, (A) an aromatic polycarbonate resin and A preferred method is (B) a method in which an aromatic polyester resin is melt-kneaded under a high shear stress in a kneading zone of a twin-screw extruder.

  When using such a twin-screw extruder, a higher shear stress state is formed by screw arrangement using a kneading block, lowering the resin temperature, increasing the screw rotation speed, or increasing the viscosity of the polymer used. Therefore, it can be adjusted appropriately.

  In the thermoplastic resin composition of the present invention, an antioxidant, a mold release agent, a stabilizer, an ultraviolet absorber, a colorant, a flame retardant, a flame retardant aid, and an anti-dripping agent are added as long as the effects of the present invention are not impaired. , Lubricants, fluorescent brighteners, phosphorescent pigments, fluorescent dyes, flow modifiers, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers, photochromic additives, other thermoplastic resins and heat A curable resin can be added.

  Examples of the antioxidant include sulfur compounds such as phenol compounds, phosphorus compounds, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate.

  Examples of phenolic compounds include 2,6-di-t-butyl-p-cresol, 2,2'-methylene-bis- (4-methyl-6-di-t-butylphenol), 4, 4'- Thiobis (3-methyl-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, pentaerythrityl-tetrakis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

  One type or two or more types of phenolic compounds can be used simultaneously. The blending amount of the phenolic compound is preferably 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin.

  Examples of phosphorus compounds include triphenyl phosphite, trioctadecyl phosphite, trisnonylphenyl phosphite, trilauryl trithiophosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, Bis (3-methyl-1,5-di-t-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, and distearyl pentaerythritol diphosphite are preferred.

  One type or two or more types of phosphorus compounds can be used simultaneously. The compounding amount of the phosphorus compound is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin.

  Examples of mold release agents include plant waxes such as carnauba wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax, petroleum waxes such as paraffin wax and polyethylene wax, castor oil And oil-based waxes such as fatty acids and derivatives thereof.

  Examples of stabilizers include benzotriazole-based compounds including 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, as well as benzophenone-based compounds such as 2,4-dihydroxybenzophenone, mono- or distearyl phosphate, Examples thereof include phosphate esters such as trimethyl phosphate.

  These various additives may have a synergistic effect by combining two or more kinds, and may be used in combination.

  For example, the additive exemplified as the antioxidant may act as a stabilizer or an ultraviolet absorber. Some of those exemplified as stabilizers also have an antioxidant action and an ultraviolet absorption action. In other words, the classification is for convenience and does not limit the action.

  Examples of UV absorbers include, for example, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Benzophenone ultraviolet absorbers typified by methane and the like, as well as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′methylenebis [4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-tert-butyl The benzotriazole type ultraviolet absorber represented by the condensate with -5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl propionate-polyethylene glycol can be mentioned.

  Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane. It can also include hindered amine light stabilizers represented by, such light stabilizers in combination with the ultraviolet absorber and various antioxidants, exhibit better performance in terms of weather resistance.

  Examples of flame retardants are halogen-based, phosphate ester-based, metal salt-based, red phosphorus, silicon-based, metal hydrate-based, etc., and flame retardant aids are antimony compounds typified by antimony trioxide. , Zirconium oxide, molybdenum oxide and the like.

  Examples of the thermoplastic resin include, for example, polyethylene, polyamide, polyphenylene sulfide, polyether ether ketone, liquid crystal polyester, polyacetal, polysulfone, polyether sulfone, polyphenylene oxide, etc. Examples of the thermosetting resin include phenol resin, Examples include melamine resin, unsaturated polyester resin, silicone resin, and epoxy resin.

  These other thermoplastic resins and thermosetting resins can be blended at any stage for producing the polyester resin composition constituting the polyester resin molded article of the present invention. For example, an aromatic polycarbonate resin and A method of adding the aromatic polyester resin at the same time, a method of adding the aromatic polycarbonate resin and the aromatic polyester resin after melt-kneading in advance, or one of the aromatic polycarbonate resin and the aromatic polyester resin at the beginning For example, a method of adding the remaining resin to the resin and melt-kneading the remaining resin may be used.

  In the thermoplastic resin composition of the present invention, these blending components are preferably dispersed uniformly, and any blending method can be used. A typical example is a method of melt-kneading at a temperature of 200 to 350 ° C. using a known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Each component may be mixed in advance and then melt kneaded. In addition, although it is better that the water | moisture content adhering to each component is less and it is desirable to dry beforehand, not all the components need to be dried.

  A preferable method for producing the thermoplastic resin composition of the present invention is as follows. (A) to (C) at a cylinder temperature of 150 to 300 ° C, preferably 180 to 250 ° C, in a twin screw extruder capable of imparting high shear. ) And other additives are fed to the extruder, the aromatic polycarbonate resin and the aromatic polyester resin are once compatibilized and melt kneaded using shear field dependent spinodal decomposition.

  Therefore, in order to stably obtain the above-mentioned specific phase separation structure under practical molding conditions, it can be obtained by melt-kneading each component, but the melt-kneading can be performed at a resin pressure of 1.5 to 10 MPa. preferable.

  The resin pressure in the production method of the present invention is a value measured with a resin pressure gauge attached to the melt-kneading apparatus, and the gauge pressure is taken as the resin pressure.

  The resin pressure at the time of melt kneading does not need to be consistently 1.5 MPa or more, and it is sufficient that there is at least one region where the resin pressure is 1.5 MPa or more, and melt kneading is performed using an extruder. In this case, it is preferable that the resin pressure be 2 MPa or more at a location where the resin pressure is usually highest, for example, at a location where the resin stays by reverse full flight or kneading block.

  The resin pressure at the time of melt kneading is not particularly limited as long as the mechanical performance permits as long as the pressure is 1.5 MPa or more, but is preferably used in the range of 2 to 10 MPa, and particularly in the range of 2 to 5 MPa, the two-phase continuous Since the structure can be obtained more stably and the deterioration of the resin is small, it is preferably used.

  The method for adjusting the resin pressure at the time of melt kneading is not particularly limited. For example, (b) improvement of the resin viscosity by lowering the melt kneading temperature, (b) selection of a polymer having a molecular weight that achieves the desired resin pressure. (C) Resin retention by changing screw arrangements such as reverse full flight and kneading block introduction, (d) Improving the feed rate of raw materials, and increasing the polymer filling rate in the barrel by introducing mesh into the die part. (F) Improvement of resin viscosity by mixing arbitrary additives, (g) Supercritical state such as introduction of carbon dioxide gas, and the like.

  The structure was fixed in a state in which the aromatic polycarbonate resin phase and the aromatic polyester resin phase were compatibilized by once compatibilizing the aromatic polycarbonate resin and the aromatic polyester resin and cooling it immediately after discharging from the extruder. After producing pellets or pellets having a continuous structure with a structure period of 0.4 μm or less, which is the initial state of spinodal decomposition, the pellets are injection-molded, and the spinodal decomposition further proceeds in the injection molding process, This is a method for forming a polyester resin molded article having a biphasic continuous structure having a structural period of 0.001 to 1 μm or a dispersed structure having a distance between particles of 0.001 to 1 μm.

  The thermoplastic resin composition of the present invention can be usually produced by injection molding the pellets produced as described above to produce various products. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The thermoplastic resin composition of the present invention can also be used in the form of various shaped extruded products, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the thermoplastic resin composition of the present invention can be made into a hollow molded product by rotational molding or blow molding.

  The thermoplastic resin composition of the present invention thus obtained can be used in a wide range of fields, such as automobile parts, electronic / electric equipment parts, OA equipment parts, machine parts, other agricultural materials, transport containers, and packaging containers. It is also useful for various uses such as miscellaneous goods and miscellaneous goods. In particular, the present invention is suitable for vehicle interior parts and vehicle exterior parts that are required to satisfy both heat resistance, rigidity, and impact resistance and to have a long molded product life.

  Examples of automotive parts include center panels, instrument panels, dashboards, console boxes, inner door handles, rear boards, inner pillar covers, inner door covers, inner door pockets, seat back covers, inner roof covers, luggage floor boards, Interior parts such as car navigation and car television display housings, outer door handles, fender panels, door panels, spoilers, garnishes, pillar covers, front grills, roof rails, bumpers, rear body panels, motorcycle cowls, truck bed covers Exterior parts such as, alternator terminal, alternator connector, IC regulator, potentiometer base for light deer Air intake nozzle snorkel, intake manifold, air flow meter, air pump, fuel pump, engine coolant joint, thermostat housing, carburetor main body, carburetor spacer, engine mount, ignition hobbin, ignition case, clutch bobbin, sensor housing, idle speed control valve , Vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, top and bottom of radiator tank, cooling fan, fan shroud, engine cover, cylinder Head cover, oil cap , Oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing, timing belt cover, brake booster parts, various cases, fuel related / exhaust system / intake system tubes, Various tanks, various hoses for fuel / exhaust / intake systems, various clips, various valves such as exhaust gas valves, various pipes, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pad wear sensors, brake pad wear sensors , Throttle position sensor, crankshaft position sensor, thermostat base for air conditioner, air conditioner panel switch board, heating hot air flow control valve, radiator motor Rush holder, water pump impeller, turbine vane, wiper motor related parts, step motor rotor, brake piston, solenoid bobbin, engine oil filter, ignition device case, torque control lever, starter switch, starter relay, safety belt parts, register blade, Washer lever, window regulator handle, knob of window regulator handle, passing light lever, distributor, sun visor bracket, various motor housings, door mirror stay, horn terminal, window washer nozzle, hood louver, wheel cover, wheel cap, grill apron Cover frame, lamp reflector, lamp socket, lamp how Ring, lamp bezels, wire harness connector, SMJ connector, PCB connector, door grommet connector, such as various types of connectors, such as connector for a fuse, and the like.

  Examples of electronic / electrical equipment components include connectors, coils, various sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, and transformers. Device, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts, generator, electric motor , Transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, other pole rods, electrical parts cabinets, VTR parts, TV parts, irons, hair dryers, Rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disc / compact disc / DVD, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office computer related parts, telephone equipment related Parts, mobile phone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriter-related parts, microscopes, binoculars, cameras, watches and other optical equipment / precision machine-related parts It is done.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

  The evaluation method of an Example and a comparative example is shown next. Unless otherwise specified, “part” indicates “part by weight” and “%” indicates “% by weight”.

(1) Fluidity Using a strip-shaped molded product having a thickness of 1 mm and a width of 10 mm, the fluidity was judged. SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. is used, and the injection conditions are a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and an injection pressure of 50 MPa.

(2) Drop weight impact strength SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. was used under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., and a square plate of 80 mm × 80 mm and a thickness of 1 to 3 mm was produced.
Using Shimadzu's high-speed instrumented surface impact device (Hydroshot), set the test conditions to a falling weight speed of 3.3 mm / second, a punch tip diameter of 1/2 inch, and a sample receiving part diameter of 3 inches. = 5, Test temperature was -30 ° C. The test was performed under each condition, and the hole from which the punch was removed was whitened, and the case where no crack was generated as a whole was determined to be ductile, and the case where the entire plate was cracked was determined to be brittle.

(3) Falling ball impact strength The 3 mm-thick square plate produced above is placed on a (vertical) 85 mm × (horizontal) 85 mm × (height) 50 mm cradle, and a 200 g hard ball from a height of 100 cm is placed in the center. It dropped and checked for cracks and cracks. After testing 10 samples prepared at −30 ° C., the height was changed and the same test was performed to obtain the height at which five or more test pieces were broken.

(4) Surface appearance The surface appearance of the 3 mm thick square plate produced above is evaluated by measuring Ra (centerline average roughness, μm) using a surface roughness measuring device (manufactured by ACCRTECH). It was.

(5) Linear expansion coefficient Using the central part of the square plate having a thickness of about 3 mm produced above, a sample was cut into about 5 mm × 12 mm in the resin flow direction, and the surface was polished with a paper file. The measurement was performed using SSC-5200 and TMA-120C manufactured by Seiko Electronics Co., Ltd., and the measurement conditions were held at −30 ° C. for 10 minutes in a nitrogen atmosphere, and then the temperature was raised from −40 ° C. to 100 ° C. The temperature was increased at a rate of 5 ° C./min, and the linear expansion coefficient in the range of −30 to 80 ° C. was calculated.

(6) Flexural modulus Measured according to ASTM-D-790 using a 1/8 inch bending test piece produced by injection molding.

(7) Measurement of structural period or interparticle distance A sample with a thickness of 100 μm was cut out from the square plate prepared above, and after staining with polycarbonate by iodine staining, an ultrathin section was cut out with a transmission electron microscope. Observation was performed at a magnification of 10,000 times, and 100 locations where the structure could be observed were arbitrarily selected, and after measuring each structural period, an average value was calculated.

  The compounding composition used for the Example and the comparative example below is shown.

(A) Aromatic polycarbonate resin A-1: Aromatic polycarbonate resin; trade name “Taflon A1900”, manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight 19,000.

(B) Aromatic polyester resin B-1: Polybutylene terephthalate resin; trade name “Toraycon 1100M”, manufactured by Toray Industries, Inc., melting point 225 ° C.
B-2: Polybutylene terephthalate resin; trade name “Trecon 1200M”, manufactured by Toray Industries, Inc., melting point 222 ° C.

(C) Compound C-1 having three or more functional groups: Oxypropylene trimethylolpropane; trade name “TMP-F32”, manufactured by Nippon Emulsifier, molecular weight 308, number of alkylene oxide (propylene oxide) units per functional group 1
C-2: trimethylolpropane; molecular weight 134, 0 alkylene oxide units per functional group, ARDRICH C-3: polyoxyethylene diglycerin; trade name “SC-E450”, Sakamoto Yakuhin, molecular weight 410, 1 Number of alkylene oxide (ethylene oxide) units per functional group 1.5
C-4: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, Sakamoto Pharmaceutical SC-P750).

(C ′) Compound C′-1 having less than three functional groups: 1,6-hexanediol; manufactured by ARDRICH.

(D) Filler D-1: Talc; Trade name “B-10”, Matsumura Sangyo Co., Ltd. D-2: Talc; Trade name “LMS200F”, Fuji Talc Kogyo Co., Ltd. D-3: Mica; Trade name “A-21”, manufactured by Yamaguchi Mika Kogyo Co., Ltd. D-4: glass fiber; trade name “CS3J948”, manufactured by Nitto Boseki Co., Ltd., chopped strand shape with a fiber diameter of about 10 μm D-5: carbon fiber Product name “TS-15”, manufactured by Toray Industries, Inc.

(E) Impact resistance improver E-1: Trade name “EXL2600”, manufactured by Rohm and Haas, MBS resin E-2: Trade name “S2001”, manufactured by Mitsubishi Rayon, silicone acrylic core shell rubber.

(F) Organic acid F-1: Maleic anhydride; trade name “CRYSTAL MAN AB”, manufactured by NOF Corporation.

Examples 1-26, Comparative Examples 1-3, Comparative Examples 5-7, Comparative Examples 9-10
A TEX30α twin screw extruder having three kneading block parts, in which the raw materials were blended so as to have the composition shown in Tables 1 to 3 and dry blended, the cylinder temperature was set to 220 ° C., and the screw rotation speed was set to 200 rpm. (Nippon Steel Works) was melt-kneaded so that the resin pressure of the die part would be 2 to 5 MPa, and the strand discharged from the die was cooled in a cooling bath and then pelletized with a strand cutter. Each pellet obtained was dried by a hot air dryer at 110 ° C. for 8 hours, and then molded by the evaluation method described above and evaluated.

Comparative Example 4, Comparative Example 8, Comparative Examples 11-13
Except for using a PCM30 extruder which does not have a kneading block part in which the raw materials are blended so as to have the composition shown in Tables 1 to 3, the cylinder temperature is set to 220 ° C., and the screw rotation speed is set to 200 rpm, Pellets were prepared by melt kneading in the same manner. The resin pressure at this time was 0.2 MPa. Each pellet obtained was evaluated in the same manner as in Example 1.

  The thermoplastic resin compositions of Examples 1 to 12 are excellent in low-temperature surface impact strength and excellent in fluidity. On the other hand, it can be seen that the thermoplastic resin compositions of Comparative Examples 1 to 4 are inferior in either low-temperature surface impact strength or fluidity.

  The thermoplastic resin compositions of Examples 13 to 20 are excellent in low-temperature surface impact strength, and are excellent in surface appearance, linear expansion coefficient, and fluidity. On the other hand, it can be seen that the thermoplastic resin compositions of Comparative Examples 5 to 8 are inferior in any of low temperature surface impact strength, surface appearance, linear expansion coefficient and fluidity.

  The thermoplastic resin compositions of Examples 21 to 26 are excellent in low-temperature surface impact strength and excellent in rigidity, surface appearance, linear expansion coefficient, and fluidity. On the other hand, it can be seen that the thermoplastic resin compositions of Comparative Examples 9 to 13 are inferior in any of rigidity, low-temperature surface impact strength, surface appearance, linear expansion coefficient, and fluidity.

Claims (7)

(A) an aromatic polycarbonate resin, (B) an aromatic polyester resin, (C) a thermoplastic resin composition comprising a polyfunctional compound having three or more functional groups, and (A) an aromatic polycarbonate. The total of the resin and (B) aromatic polyester resin is 100% by weight, and (A) aromatic polycarbonate resin is 1 to 99% by weight, (B) aromatic polyester resin is 1 to 99% by weight, and (A) aromatic A thermoplastic resin composition comprising 100 parts by weight of the total of the polycarbonate resin and (B) aromatic polyester resin, and (C) 0.01 to 4 parts by weight of a polyfunctional compound having three or more functional groups. (A) Aromatic polycarbonate resin and (B) polybutylene terephthalate resin are both-phase continuous structure having a structural period of 0.01 to 1.0 μm, or the distance between particles is 0.00. The thermoplastic resin composition characterized by having a dispersion structure 01～1Myuemu. (C) The thermoplastic resin according to claim 1, wherein the polyfunctional compound having three or more functional groups is a compound in which at least one of the terminal structures having a functional group is a structure represented by the formula (1). Composition.

(R represents a hydrocarbon group having 1 to 15 carbon atoms, n represents an integer of 1 to 10, and X represents a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, or an isocyanate group. And represents at least one functional group selected from a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group, and a silyl ether group.) (C) The thermoplastic resin composition according to any one of claims 1 to 2, wherein the polyfunctional compound having three or more functional groups contains one or more alkylene oxide units. (C) The functional group of the polyfunctional compound having three or more functional groups is at least one functional group selected from a hydroxyl group, a carboxylic acid group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group. The thermoplastic resin composition according to any one of claims 1 to 3. Furthermore, (D) The thermoplastic resin composition of any one of Claims 1-4 formed by mix | blending a filler. (D) The thermoplastic resin composition according to claim 5, wherein the filler is at least one selected from a plate shape, a granular shape, and a fibrous shape. The molded article which consists of a thermoplastic resin composition as described in any one of Claims 1-6.