JP2009221472A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having low linear expansion coefficient and excellent in impact resistance, especially planar impact strength at low temperature and surface appearance; shaped articles and exterior parts for vehicles. <P>SOLUTION: The present invention provides a thermoplastic resin composition comprising 1 to 99 wt.% of aromatic polycarbonate resin (A), 1 to 99 wt.% of aromatic polyester resin (B) based on 100 wt.% total of (A) and (B), 1 to 50 parts by weight of graft copolymer (C) obtained by graft polymerization of rubbery polymer with a vinyl monomer, and 30 to 200 parts by weight of talc (D), provided that the total amount of (A) the aromatic polycarbonate resin and (B) the aromatic polyester resin should be 100 parts by weight. In the composition, the aromatic polycarbonate resin (A) and the aromatic polyester resin (B) have continuous structure of the two phase with structural period of 0.001 to 1.0 μm or dispersed structure with interparticle distance of 0.001 to 1 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition, a molded product, and a vehicle exterior part having a small linear expansion coefficient and excellent impact resistance, particularly surface impact strength at low temperatures, and surface appearance.

  In recent years, it has been desired to reduce the weight of the vehicle body for the purpose of improving the fuel efficiency of automobiles and preventing global warming. For automobile exterior parts, replacement of aluminum and steel materials with thermoplastic resins has been studied. However, the thermoplastic resin has a larger linear expansion coefficient than aluminum and steel materials, and therefore has a problem of inferior dimensional accuracy.

  On the other hand, blends of aromatic polycarbonate resins and aromatic polyester resins are widely used as engineering plastics because of their excellent 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.

  Patent Document 1 proposes a resin composition obtained by blending an aromatic polycarbonate resin, an aromatic polyester, talc and an elastomer.

  Patent Document 2 proposes a resin composition comprising an aromatic polycarbonate resin, an aromatic polyester, a rubber-like elastic body, and an inorganic filler.

  However, since the resin compositions described in Patent Documents 1 and 2 do not form a high shear stress state during kneading by a twin screw extruder, the aromatic polycarbonate resin and the aromatic polyester resin have a sea island structure of several μm. A certain dispersion structure is formed. For this reason, the aromatic polyester resin is likely to thermally expand, so that the linear expansion coefficient is large, and the filler floating is likely to occur, so that an excellent surface appearance cannot be obtained.

  Patent Document 3 proposes a resin composition comprising a polycarbonate resin, a polybutylene terephthalate resin, a wollastonite having a specific structure, and a rubbery polymer. As Comparative Example 6, an aromatic polycarbonate resin and an aromatic polyester resin are proposed. The composition which mix | blended 10 weight part of talc with respect to a total of 85 weight part is described. However, since the blending amount of talc is small, the linear expansion coefficient is large.

  Patent Document 4 proposes a resin composition formed by blending a polycarbonate resin and a polybutylene terephthalate resin to form a specific structure. However, there is no description regarding the blending of the rubber-like elastic body, and there is a general description regarding the addition of talc, but there is no description of the preferred blending amount, and there is no description of the excellent effects associated therewith.

JP-A-6-49343 JP-A-5-222283 JP 2007-254611 A JP 2004-231935 A

  Therefore, an object of the present invention is to provide a thermoplastic resin composition having a small coefficient of linear expansion and excellent impact resistance, particularly surface impact strength at low temperatures, and surface appearance.

  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) an aromatic polycarbonate resin, (B) an aromatic polyester resin, (C) a graft copolymer obtained by graft-polymerizing a vinyl monomer to a rubbery polymer, (D) talc A resin composition comprising:
The total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin is 100% by weight, and (A) aromatic polycarbonate resin is 1 to 99% by weight, and (B) aromatic polyester resin is 1 to 99% by weight. (A) A graft copolymer obtained by graft-polymerizing a vinyl monomer to a rubbery polymer, with the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin being 100 parts by weight, 1 to 50 parts by weight, (D) talc is a resin composition comprising 30 to 200 parts by weight,
The (A) aromatic polycarbonate resin and the (B) aromatic polyester resin have a biphasic continuous structure having a structural period of 0.001 to 1.0 μm, or a dispersed structure having a distance between particles of 0.001 to 1 μm. A thermoplastic resin composition,
(2) (C) The rubbery polymer of the graft copolymer obtained by graft polymerization of a vinyl monomer to a rubbery polymer is selected from organosiloxane rubbers, acrylic rubbers and diene rubbers. The thermoplastic resin composition as described in (1) above, which is at least one kind,
(3) (C) The rubbery polymer of the graft copolymer obtained by graft-polymerizing a vinyl monomer to the rubbery polymer is a composite rubber comprising an organosiloxane and an acrylic polymer. The thermoplastic resin composition as described in (1) or (2) above,
(4) (C) The above-mentioned (1) or (1), wherein the rubber polymer of the graft copolymer obtained by graft polymerization of a vinyl monomer to the rubber polymer is an acrylic rubber (2) The thermoplastic resin composition according to any one of the above.
(5) The above (1) to (4), wherein the graft copolymer obtained by graft polymerizing a vinyl monomer to (C) a rubbery polymer has a hard polymer phase in the innermost layer. The thermoplastic resin composition according to any one of the above.
(6) Further, (F) 0.01 to 4 parts by weight of a polyfunctional compound having three or more functional groups, with the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin being 100 parts by weight The thermoplastic resin composition according to any one of (1) to (5).
(7) A molded article comprising the thermoplastic resin composition described in any of (1) to (6) above,
(8) The molded product according to (7) above, wherein the molded product is a vehicle part,
(9) The molded article according to (7) or (8), wherein the molded article is a vehicle exterior part.

  The thermoplastic resin composition of the present invention can provide a composition having a small coefficient of linear expansion and excellent impact resistance, particularly surface impact strength at low temperatures and surface appearance. In addition, the thermoplastic composition can be suitably used as various molded articles, vehicle parts, vehicle exterior parts, and the like.

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 15,000-30,000.

  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 (A) aromatic polycarbonate resin used in the present invention may contain an aromatic polycarbonate oligomer. The aromatic polycarbonate oligomer can be obtained, for example, by reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester using a terminal terminator or a molecular weight regulator. As the aromatic dihydroxy compound, bisphenol A or a mixture of bisphenol A and another divalent phenol is preferable.

  Examples of the terminal terminator or molecular weight regulator include phenol, pt-alkylphenol, 2,4,6-tribromophenol, long-chain alkylphenol, aliphatic carboxylic acid, hydroxybenzoic acid, and aliphatic carboxylic acid chloride. Can be mentioned. Specific examples of aromatic polycarbonate oligomers are preferably bisphenol A polycarbonate oligomers terminated with pt-butylphenol, copolycarbonate oligomers from tetrabromobisphenol A and bisphenol A terminated with pt-butylphenol. However, it is not always necessary that the oligomer is produced by the same raw materials and reaction method as (A) the aromatic polycarbonate resin.

  The viscosity average molecular weight of the aromatic polycarbonate oligomer is a value calculated from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 1,500 to 9,500, more preferably 2,000. -9,000, most preferably 2500-8,500.

  The content of the polycarbonate oligomer is 0 to 25% by weight, preferably 3 to 20% by weight in the (A) aromatic polycarbonate resin. When an aromatic polycarbonate resin containing a polycarbonate oligomer in the above range is used, the adhesion of a paint, printing ink or the like to the surface of a molded product produced from the resin composition of the present invention can be improved. If the content of the aromatic polycarbonate oligomer exceeds 25% by weight, the impact resistance of the resulting molded article is remarkably lowered.

  The (B) aromatic polyester resin constituting the present invention includes (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, ) A polymer or copolymer obtained by polycondensation of one or more selected from lactones, 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) glyco , 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 3 It is preferably 0.0 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 150 ° C. or higher, and 180 ° C. from the viewpoint of heat resistance. More preferably, it is more preferably 220 ° C. or higher. 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 (A) 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. Both can be applied both by transesterification and by direct polymerization, but continuous polymerization is preferred in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity is increased. In view of cost, direct polymerization is preferable.

  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, (A) 40 to 80% by weight of aromatic polycarbonate resin, (B) aromatic polyester resin 20 ˜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 resin composition tends to decrease or the surface appearance tends to decrease. If it exceeds 99% by weight, the chemical resistance is low. Decrease or formability becomes poor.

  The (C) graft copolymer in the present invention is obtained by graft polymerization of a vinyl monomer to a rubbery polymer.

  There is no particular limitation as long as it has at least the outermost vinyl polymer phase. Specifically, the graft copolymer having a rubbery polymer phase in the inner layer and a vinyl polymer phase in the outer layer (outermost layer). Or a multi-layer graft copolymer such as a graft copolymer having a hard polymer phase in the innermost layer, a rubbery polymer phase in the intermediate layer, and a vinyl polymer phase in the outermost layer (outermost layer). A polymer can be suitably exemplified. These may be used alone or in combination of two or more.

  In the present invention, the term “hard” in the hard polymer phase that is preferably included from the viewpoint of the linear expansion coefficient means that the glass transition temperature of the polymer is 20 ° C. or higher. The glass transition temperature of the coalescence is preferably 30 ° C. or higher, and more preferably 50 ° C. or higher. When the glass transition temperature of the hard polymer is less than 20 ° C., the effect of suppressing the thermal expansion of the rubbery polymer phase may not be sufficient when the graft copolymer in the present invention is blended with a thermoplastic resin.

The glass transition temperature of the polymer can be measured by, for example, a differential scanning calorimeter. In the present invention, the value described in a polymer handbook (Polymer Hand Book (J. Brandrup, Interscience 1989)) is used. The value calculated using the Fox equation is used. (For example, polymethyl methacrylate is 105 ° C. and polybutyl acrylate is −54 ° C.)
The graft copolymer (C) in the present invention is a graft copolymer having a hard polymer phase in the innermost layer, a soft polymer phase in the intermediate layer, and a vinyl polymer phase in the outermost layer. Examples of the hard polymer phase include 40 to 100% by weight of methacrylic acid ester, 0 to 60% by weight of acrylic acid ester, 0 to 60% by weight of aromatic vinyl monomer, and 0 to 0% of polyfunctional monomer. A rigid polymer composed of 10% by weight and 0 to 20% by weight of a vinyl monomer copolymerizable with a methacrylic acid ester, an acrylic acid ester, and an aromatic vinyl monomer can be suitably exemplified.

  Rubber polymers include acrylic rubber such as polyalkyl (meth) acrylate rubber, polyorganosiloxane rubber, organosiloxane rubber such as polyorganosiloxane / acrylic composite rubber, polybutadiene rubber, styrene-butadiene Examples thereof include diene rubbers such as rubbers, butadiene / acrylic copolymer rubbers, and butadiene / acrylic composite rubbers. As a method for producing these rubbery polymers, an emulsion polymerization method is optimal.

  The acrylic rubber used in the (C) graft copolymer of the present invention is a polymer of monomers having an alkyl (meth) acrylate and a polyfunctional monomer as main components.

  Examples of alkyl (meth) acrylate used for polymerization of acrylic rubber include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, and tridecyl acrylate. And alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, and tridecyl methacrylate.

  Examples of the polyfunctional monomer used for the polymerization of acrylic rubber include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanide. Examples thereof include nurate, triallyl isocyanurate, divinylbenzene and the like, and these can be used alone or in combination of two or more.

  The acrylic rubber may be any of a homopolymer, a copolymer, and a composite rubber composed of two or more types of acrylic rubber.

  Examples of the other monomer used as a copolymerization component in the case of a copolymer in the acrylic rubber include diene monomers such as 1,3-butadiene, isoprene and chloroprene; styrene, α-methyl Aromatic vinyls such as styrene; (meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl (meth) acrylate and n-butyl acrylate; unsaturated nitriles such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; Examples include vinyl halides such as vinyl and vinyl bromide; vinylidene halides such as vinylidene chloride and vinylidene bromide; glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. . These monomers can be used alone or in combination of two or more. Among these, it is preferable to contain 1,3-butadiene from the viewpoint of strength development. The amount of other monomers used is preferably 30% by weight or less with respect to 100% by weight of the rubbery polymer.

  The organosiloxane rubber used in the graft copolymer (C) of the present invention has a rubber component containing polyorganosiloxane.

  Any polyorganosiloxane may be used as long as it has an organosiloxane unit, and an organosiloxane monomer or an oligomer obtained by polymerizing an organosiloxane monomer can be obtained as a raw material.

  As the oligomer obtained by polymerizing the organosiloxane monomer, for example, a cyclic body (dimethylsiloxane-based cyclic body) using dimethylsiloxane as a main raw material can be used. In particular, a 3- to 7-membered dimethylsiloxane-based ring is preferably used. The dimethylsiloxane-based cyclic body is particularly preferably used when a later-described composite rubber is used as the rubber component.

  Specific examples of the 3- to 7-membered dimethylsiloxane ring include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexa Siloxane (D6) etc. are mentioned. These may be used alone or in combination of two or more.

  Here, examples of the method for making the latex into fine particles include a method using a homomixer that makes fine particles by a shearing force by high-speed rotation, a method using a homogenizer that makes fine particles by jetting power from a high-pressure generator, and the like.

  Examples of the method for adding the acid catalyst used in the polymerization include a method of adding and mixing together with a siloxane mixture, an emulsifier and water, and a method of dropping a latex in which the siloxane mixture is finely divided into an aqueous solution of an acid catalyst. A method of adding them together with an emulsifier and water is preferably used. As a more preferable addition method, after the acid catalyst is added to the latex, a forced emulsification step is performed simultaneously with the temperature rise, and a preliminary emulsifier and a forced emulsifier capable of generating a pressure of 5 MPa or more are used in the forced emulsification step. Thus, the particle size distribution of the polyorganosiloxane can be easily controlled.

  The method of mixing the siloxane mixture, emulsifier, water and / or acid catalyst includes high-speed stirring and high-pressure emulsification equipment such as a homogenizer. After pre-emulsification using a pre-emulsifier such as an in-line mixer. A method using a device such as a homogenizer capable of generating a pressure of 5 MPa or more is a preferable method because the particle size distribution of the polyorganosiloxane latex can be controlled to a desired distribution.

  The polymerization time for obtaining the polyorganosiloxane is usually 2 hours or more, preferably 5 hours or more after reaching the desired temperature when the method of adding the acid catalyst together with the siloxane mixture, emulsifier and water is used. It is. In the case of dropping the latex in which the siloxane mixture is finely divided into the aqueous solution of the acid catalyst, it is preferable to hold for about 1 hour after the end of dropping of the latex. When the acid catalyst is added all together with the siloxane mixture, the emulsifier and water, the equilibrium state is reached in about 5 hours after reaching the desired temperature, so about 6 hours is appropriate as the polymerization time, but it is lengthened. There is no problem with the polymerization itself.

  The polymerization can be stopped by cooling the reaction solution and neutralizing the latex with an alkaline substance such as caustic soda (sodium hydroxide), caustic potash (potassium hydroxide) or sodium carbonate.

  As the emulsifier used in the production of the polyorganosiloxane, an anionic emulsifier is preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

  Examples of the acid catalyst used in the production of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, aliphatic substituted naphthalenesulfonic acid and sulfonic acid containing aromatics; sulfuric acid, hydrochloric acid, nitric acid And mineral acids. These acid catalysts are used alone or in combination of two or more. Among these acid catalysts, aliphatic substituted benzenesulfonic acid is preferable in that it has an excellent stabilizing effect on the polyorganosiloxane latex. Among aliphatic substituted benzenesulfonic acids, n-dodecylbenzenesulfonic acid is particularly preferable. In addition, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the appearance defect of the resin composition due to the emulsifier component of the polyorganosiloxane latex can be reduced.

  As the siloxane-based crosslinking agent, trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane can be used.

  There are various types of components other than polyorganosiloxane constituting the rubber component, but when impact resistance is required, diene polymers, olefin polymers, vinyl polymers, etc. may be mentioned. In particular, acrylic polymers are preferably used.

  In particular, the rubber component is preferably a composite rubber made of polyorganosiloxane and an acrylic polymer. Specifically, the acrylic polymer component is a polymer of (meth) acrylates. The composite rubber here has a structure in which the polyorganosiloxane and the acrylic polymer are intertwined so that they cannot be separated from each other.

  The graft copolymer using the above-mentioned composite rubber as a rubber component increases the impact resistance when used in a resin composition, in particular, the impact resistance under low temperature and other effects that improve mechanical properties. Can do.

  When a composite rubber is used as the rubber component, the polyorganosiloxane preferably contains a vinyl polymerizable functional group-containing siloxane as a constituent component. In order to obtain such a polyorganosiloxane, a vinyl polymerizable functional group-containing siloxane may be added to the siloxane mixture in the above-described method for producing a polyorganosiloxane.

  The vinyl-polymerizable functional group-containing siloxane contains a vinyl-polymerizable functional group and can be bonded to dimethylsiloxane or a dimethylsiloxane-based cyclic body via a siloxane bond, so that it can be easily combined with an acrylic polymer. Is.

  As the vinyl polymerizable functional group-containing siloxane, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable in consideration of reactivity with dimethylsiloxane.

Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysilane such as γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; vinylphenylsilane such as p-vinylphenyldimethoxymethylsilane ; Mercaptosy such as γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane; Emissions, and the like can be used. In addition, these vinyl polymerizable functional group containing siloxane can be used individually or in mixture of 2 or more types.

  When a composite rubber is used as the rubber component, the method for producing the composite rubber includes a polyorganosiloxane latex neutralized in the polyorganosiloxane production method described above (meth) such as alkyl (meth) acrylate. A method in which acrylates, a cross-linking agent, and a graft crossing agent are added and the polyorganosiloxane is impregnated with an alkyl (meth) acrylate and then polymerized by causing a known radical polymerization initiator to act thereon can be used.

  Examples of (meth) acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate ( Dodecyl methacrylate), stearyl methacrylate (octadecyl methacrylate), and the like. These (meth) acrylates may be used alone or in combination of two or more.

  Further, in the monomer for obtaining the composite rubber, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methacrylic acid-modified silicone; fluorine-containing Various vinyl monomers other than alkyl (meth) acrylates such as vinyl compounds may be included as a copolymerization component in a range of 30% by mass or less.

  Moreover, as a crosslinking agent or a graft crossing agent, the monomer which has a 2 or more unsaturated bond in a molecule | numerator can be used individually or in mixture, for example. Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, and polyfunctional methacrylic group-modified silicone.

  Examples of the graft crossing agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent.

  The cross-linking agent or graft crossing agent needs to be used in the polyalkyl (meth) acrylate part so as to be 0.1 to 2.5% based on the mass. If the amount used is less than 0.1%, it is difficult to recover the powder as a powder, and if it exceeds 2.5%, impact resistance is deteriorated.

  The polymerization method for obtaining the composite rubber is not particularly limited, but can be usually carried out by emulsion polymerization, and if necessary, forced emulsion polymerization. For example, when 2-ethyl acrylate, lauryl methacrylate, or stearyl methacrylate is selected as the monomer constituting the acrylic polymer, these monomers are poor in water solubility. Is preferably generated.

  The ratio of the polyorganosiloxane / acrylic polymer constituting the composite rubber is usually in the range of 1/99 to 99/1 by weight, preferably 1/99 to 80/20, more preferably 2/98. It is the range of -60/40, More preferably, it is the range of 5 / 95-60 / 40. If the polyorganosiloxane is less than 1% by mass with respect to 100% by mass of the composite rubber, the low-temperature impact resistance of the thermoplastic resin composition tends to decrease. There is a tendency for the physical characteristics to decline.

  In the method for producing a composite rubber, as a method for adding an alkyl (meth) acrylate to a polyorganosiloxane latex, a method of adding the whole amount to the polyorganosiloxane latex at once, dropping it into the polyorganosiloxane latex at a constant rate. The method of adding is mentioned.

  Further, as the radical polymerization initiator used for producing the composite rubber, a peroxide, an azo initiator, or a redox initiator combined with an oxidizing agent / reducing agent is used. Among these, a redox initiator is preferable, and a redox initiator combined with ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide is particularly preferable.

  The diene rubber used in the graft copolymer (C) of the present invention is a polymer containing diene monomer units such as 1,3-butadiene, isoprene and chloroprene, and the diene monomer unit is 100 wt. %. Among the diene rubber polymers, when the total monomer unit constituting the diene rubber polymer is 100% by weight, the diene monomer is preferably 60% by weight or more, and more preferably 65% by weight or more. Are preferred.

  When the diene monomer unit in the diene rubber polymer is less than 100% by weight, examples of other vinyl monomers copolymerized with the diene monomer include styrene and α-methylstyrene. Methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate, alkyl acrylates such as ethyl acrylate and n-butyl acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether , Vinyl halides such as vinyl chloride and vinyl bromide, vinylidene halides such as vinylidene chloride and vinylidene bromide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and glycols such as ethylene glycol glycidyl ether. Vinyl monomers having a Jill group, divinylbenzene, ethylene glycol dimethacrylate, can be used a polyfunctional monomer such as 1,3-butylene glycol dimethacrylate. These other vinyl monomers can be used alone or in combination of two or more.

  The graft copolymer (C) of the present invention is obtained by emulsion polymerization using an emulsifier containing a sulfonic acid-type metal salt or a sulfate-type metal salt having a 10% weight reduction temperature higher than 250 ° C. in measurement of thermogravimetry in air. It is preferable to obtain.

  A sulfonic acid type metal salt or a sulfuric acid type metal salt having a 10% weight loss temperature higher than 250 ° C. in the measurement of thermal weight loss in air is less likely to undergo thermal decomposition and has high thermal stability. Moreover, even if a thermal decomposition product is generated by thermal decomposition, the amount is small.

  Examples of the sulfonic acid metal salt having a 10% weight loss temperature higher than 250 ° C. in the measurement of thermal weight loss in the air include sodium dodecylbenzene sulfonate, which is an alkali metal salt of sulfonic acid. Examples of the salt include sodium alkyldiphenyl ether disulfonate, which is a sulfuric acid alkali metal salt.

  The sulfonic acid metal salt or sulfuric acid alkali metal salt can be used alone or in combination of two or more.

  In the present invention, the 10% weight loss temperature in the measurement of thermogravimetry in air is a temperature obtained by performing thermogravimetric analysis (TGA).

  The weight average particle diameter of acrylic rubber, organosiloxane rubber, diene rubber, butadiene / acrylic copolymer rubber, and butadiene / acrylic composite rubber used in the present invention is in the range of 0.01 μm to 2.0 μm. The range of 0.05 μm to 1.0 μm is more preferable, and the range of 0.15 μm to 0.5 μm is most preferable. The weight average particle size is 0.1 ml of latex diluted to about 3% solid content with distilled water, and a flow rate of 1.4 ml / min and a pressure of about 2.76 MPa using a CHDF2000 particle size distribution meter manufactured by MATEC USA. It is a value measured using a capillary cartridge for particle separation and a carrier liquid under the conditions of (about 4000 psi) and a temperature of 35 ° C. The calibration curve of the particle size is prepared by measuring the particle size of a total of 13 points from 0.02 μm to 1.0 μm using, for example, monodispersed polystyrene with a known particle size manufactured by DUKE Co., USA as the standard particle size substance. If the weight average particle diameter is less than 0.01 μm, the impact resistance of the thermoplastic composition tends to decrease and the linear expansion coefficient tends to increase. On the other hand, even when the thickness exceeds 2.0 μm, the impact resistance tends to decrease.

  In the graft copolymer (C) of the present invention, examples of the vinyl monomer constituting the graft portion include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, methyl methacrylate, and 2-ethylhexyl methacrylate. And methacrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more.

  Moreover, you may use together a crosslinking agent or a graft crossing agent, for example, the monomer which has a 2 or more unsaturated bond in a molecule | numerator as needed. Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, polyfunctional methacrylic group-modified silicone, and the like. Examples of the graft crossing agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. About the lower limit of those usage-amounts, 0.1 to 10 weight% is preferable with respect to 100 weight% of vinyl-type monomers which comprise a graft part, and 5 weight% or less is more preferable.

  (C) The content of the rubbery polymer in the graft copolymer is preferably 40 to 95% by weight, more preferably 50 to 92% by weight, and still more preferably 70 to 90% by weight. When the content of the rubbery polymer is less than 40% by weight, the impact resistance of the thermoplastic resin composition may be lowered. When the content of the rubbery polymer exceeds 95% by weight, the linear expansion coefficient is May grow.

  (C) The polymerization of the rubbery polymer in the graft copolymer can be prepared by subjecting a normal radical polymerization initiator to emulsion polymerization. Further, as the radical polymerization initiator used for polymerization, a peroxide, an azo initiator, or a redox initiator combined with an oxidizing agent / reducing agent is used. Of these, redox initiators are preferable, and sulfoxylate initiators in which sodium salt, longalite, and hydroperoxide are combined with ferrous sulfate / ethylenediaminetetraacetic acid are particularly preferable.

  (C) The rubbery polymer in the graft copolymer is, for example, a method in which each monomer described above is emulsion-polymerized in one step (one-step polymerization method) in the presence of an emulsifier, or a method in which emulsion polymerization is performed in two or more steps. (Multi-stage polymerization method).

  As the emulsifier in the graft polymerization, the emulsifier contained in the diene rubber polymer-containing latex may be used as it is, or may be newly added. As an emulsifier newly added at the time of graft polymerization, since the thermal stability of the obtained polyvinyl chloride resin composition is further improved, a 10% weight reduction temperature in the measurement of thermal weight loss in air is 250 ° C. Higher sulfonic acid-based metal salts or sulfuric acid-based alkali metal salts are preferred, but are not limited thereto. Moreover, the emulsifier in the case of graft polymerization can be used individually or in combination of 2 or more types.

  In the graft polymerization, a polymerization initiator is preferably used. Examples of the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, and the like. Organic peroxides, azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, and the like.

  In the graft polymerization, the vinyl monomer may be polymerized in one stage, or may be polymerized in two or more stages.

  (C) The graft copolymer is recovered by putting the graft copolymer latex produced as described above into hot water in which a coagulant is dissolved, and coagulating and solidifying the graft copolymer. Can do. Moreover, it can also collect | recover in powder form by spray-drying graft copolymer latex.

  As a coagulant for recovering the graft copolymer by coagulation and solidification, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid; metal salts such as calcium chloride, calcium acetate and aluminum sulfate should be used. Can do. Of these, calcium chloride and calcium acetate are preferred, and calcium acetate is particularly preferred from the viewpoint of the thermal stability and impact resistance of the thermoplastic resin composition obtained.

  The rubbery polymer used for the graft copolymer (C) in the present invention is preferably a polyorganosiloxane rubber, an acrylic rubber, or a diene rubber, and is excellent in impact resistance and has a small linear expansion coefficient. Polyorganosiloxane rubber or acrylic rubber is more preferable. Among them, a polyorganosiloxane rubber, particularly a composite rubber composed of an organosiloxane and an acrylic polymer, is most preferable from the viewpoint of low-temperature impact resistance, and an acrylic rubber, particularly a hard polymer phase in the innermost layer, from the viewpoint of linear expansion coefficient. A multilayer structure graft copolymer having a rubbery polymer phase in the intermediate layer and a vinyl polymer phase in the outermost layer (outermost layer) is most preferable.

  The blending amount of the (C) graft copolymer in the present invention is 1 to 50 parts by weight, preferably 1 to 30 parts, based on 100 parts by weight of the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin. Part by weight, more preferably 5 to 20 parts by weight. When the amount of the graft copolymer (C) is less than 1 part by weight, the impact strength is insufficient, and when it exceeds 50 parts by weight, the linear expansion coefficient is increased.

The (D) talc used in the present invention is a natural product generally composed of MgO and a silicate represented by the chemical composition formula Mg ₃ (Si ₄ O ₁₀ ) (OH) ₂ , and particularly iron-containing or nickel-containing species. There may be. The crystal shape of the talc particles is not particularly limited, and may be a plate crystal or a columnar crystal.

  The average primary particle size of talc is preferably 0.5 to 6 μm, and it is preferable to use a particle that does not substantially contain particles having a particle size larger than 100 μm. The average primary particle diameter of talc was determined by using a LA-700 laser diffraction / scattering particle size distribution measuring apparatus manufactured by Horiba, Ltd., and the median diameter corresponding to 50% in volume ratio was defined as the average primary particle diameter.

  Further, the talc surface may be treated with various silane coupling agents such as epoxy silane and amino silane.

  In the present invention, (D) talc preferably has a bulk specific gravity of 0.1 to 0.9, more preferably 0.4 to 0.8. When the bulk specific gravity is less than 0.1, the productivity at the time of compounding is lowered and the residence time is lengthened, so that the thermal stability and impact resistance of the resulting thermoplastic resin composition tend to be lowered. If the bulk specific gravity is greater than 0.9, talc does not collapse during kneading, resulting in poor dispersion, and the surface appearance tends to deteriorate, such being undesirable.

  The blending amount of (D) talc used in the present invention needs to be 30 to 200 parts by weight, preferably 40 parts, based on 100 parts by weight of the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin. It is -150 weight part, More preferably, it is 50-120 weight part. If the amount is less than 30 parts by weight, the coefficient of linear expansion is not sufficiently improved.

  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 a two-component resin.

  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 with each other is determined by, for example, an electron microscope, a differential scanning calorimeter (DSC), as described in Polymer Alloys and Blends, Leszek A Utacki, Hans Publishers, Munich Vie New York, P64, and others. 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.

  In the present invention, the two-phase continuous structure refers to a structure in which both components of the resin to be mixed 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 .2 μm or a dispersed structure in the range of a distance between particles of 0.005 to 0.2 μm.

  When the structural period is less than 0.001 μm or the interparticle distance is less than 0.001 μm, the heat resistance and other characteristics deteriorate, and when the structural period exceeds 1 μm or the interparticle distance is 1 μm, the linear expansion coefficient increases, and the surface Appearance also deteriorates.

  On the other hand, in the nucleation and growth, which is 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 compatible and incompatible branching temperatures in this low-temperature compatible phase diagram is called the lower critical solution temperature (LCST for short). The highest temperature among the incompatible branching temperatures is called the upper critical solution temperature (UCST).

  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 constituting 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. The dispersion structure must be 1 μm, and as a measuring method thereof, the polycarbonate component is dyed by an iodine dyeing method and then observed with a transmission electron microscope. Further, as a method for measuring the structure period, specifically, as an X-ray generator, for example, RU-200 manufactured by Rigaku Corporation, using CuKα ray as a radiation source, output 50 KV / 150 mA, slit diameter 0.5 mm, camera radius 405 mm, exposure At 120 minutes, a scattering photograph is taken with the film Kodak DEF-5, and the structure period is determined by small-angle X-ray scattering. In small-angle X-ray scattering, the structural period (Λm) is calculated from the peak position (θm) by the following equation.
Λm = (λ / 2) / sin (θm / 2)

  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 can be obtained 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 using the above-described 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 present invention, an organic acid can be blended for the purpose of neutralizing the alkali component of (D) talc in the thermoplastic resin composition.

  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, maleic anhydride Examples of typical compounds include acid-modified siloxanes. In particular, maleic anhydride and capric acid are preferably used.

  The blending amount of the organic acid is preferably 0.001 to 1 part by weight based on 100 parts by weight of the total of (A) the aromatic polycarbonate resin and (B) the aromatic polyester resin from the viewpoint of the addition effect and fluidity. More preferably, the content is 0.01 to 0.5 parts by weight.

  In the present invention, in order to improve the fluidity of the thermoplastic resin, (F) a polyfunctional compound having three or more functional groups can be blended. The component (F) 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. The component (F) may be any compound having three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound, but has excellent fluidity and mechanical properties. The trifunctional compound or the tetrafunctional compound is more preferable, and the tetrafunctional compound is more preferable.

  In the polyfunctional compound having three or more functional groups (F) 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 (F) 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 (F) has three or more functional groups that are the same or different from these. Preferably it is. In the present invention, the component (F) is (F) 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.

  (F) As a preferable example of the 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.

  (F) 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.

  (F) 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. (F) As a preferable 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.

  (F) As a preferred example of a polyfunctional compound having three or more functional groups, when the functional group is a glycidyl group, a monomer such as triglycidyl triazolidine-3,5-dione or 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.

  (F) 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.

  (F) As a preferable 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, Examples include ester derivatives of compounds having three or more carboxylic acid groups.

  (F) 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 (F) having three or more functional groups contains one or more alkylene oxide units. In the present invention, the component (F) is (F) 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 respect, as the component (F), (F) a polyfunctional compound having three or more functional groups and most preferably a polyfunctional compound containing an alkylene oxide unit is preferred. 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 (F) used in the present invention, (F) 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 preferable example of the polyfunctional compound having three or more functional groups (F) 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 (F) 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 unit, cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide unit, (poly) tetramethylene oxide unit 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 (F) 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 (F) 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 (F) 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 (F) 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 (F) used in the present invention is preferably 15000 m · Pa or less at 25 ° C., and is 5000 m · Pa or less in terms 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 at the time of 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 (F) 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, (F) 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 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 (F). A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.

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

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

  In the present invention, an antioxidant can be blended.

  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] and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate are preferred, and pentaerythrityl-tetrakis [3- (3 , 5-di-tert-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, distearyl pentaerythritol diphosphite, preferably 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 , Especially bis (2,4-di -t- butyl-phenyl) 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.

  The thermoplastic resin composition of the present invention includes a release agent, a stabilizer, an ultraviolet absorber, a colorant, a flame retardant, a flame retardant aid, an anti-dripping agent, a lubricant, and a fluorescent material as long as the effects of the present invention are not impaired. Additives such as brighteners, phosphorescent pigments, fluorescent dyes, flow modifiers, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers, photochromic agents, other thermoplastic resins and thermosetting resins Can be added.

  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, silicone-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 (D) at a cylinder temperature of 150 to 250 ° C., preferably 180 to 230 ° 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.

  Pellets whose structure is fixed in a state where the aromatic polycarbonate resin phase and the aromatic polyester phase are compatibilized by once compatibilizing the aromatic polycarbonate resin and the aromatic polyester resin, and cooling it immediately after discharging from the extruder. Alternatively, after producing 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 is further advanced in the injection molding process. This is a method of forming a polyester resin molded product having a biphasic continuous structure with a period of 0.001 to 1 μm or a dispersed structure with 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 strong 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. Various electronic / electric equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, transport containers, packaging containers, It is also useful for various applications such as 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.

  Vehicle interior parts include, for example, 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. And display housings for car navigation and car television.

  Examples of the vehicle exterior parts include an outer door handle, a fender panel, a door panel, a spoiler, a garnish, a pillar cover, a front grille, a rear body panel, a motorcycle cowl, and a truck bed cover.

  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”. As the reagent, a commercially available good product was used.

(1) Confirmation of structural period Under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C., SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. was used to produce a square plate of 80 mm × 80 mm × 3 mm. A sample having a thickness of 100 μm was cut out from the square plate, stained with polycarbonate by iodine staining method, and then cut out an ultrathin slice, and the sample was observed with a transmission electron microscope at a magnification of 50,000 times. In addition, with respect to a sample obtained by cutting a 100 μm-thick section from the molded product obtained by the injection molding, the structure period in the case of the biphasic continuous structure or the interparticle distance in the case of the dispersed structure is expressed by small-angle X-ray scattering (less than 0.4 μm It was measured by structure period or interparticle distance) or light scattering (in the case of structure period or interparticle distance of 0.4 μm or more). The X-ray generator is RU-200 manufactured by Rigaku Corporation, using CuKα rays as the radiation source, output 50 KV / 150 mA, slit diameter 0.5 mm, camera radius 405 mm, exposure time 120 minutes, scattered photograph with film Kodak DEF-5 Was taken. Peaks were observed in all samples, and the structural period or interparticle distance (Λm) calculated by the following equation was obtained from the peak position (θm).
Λm = (λ / 2) / sin (θm / 2)

(2) Falling ball impact test (Vertical) 85 mm x (horizontal) 85 mm x (height) Using a falling ball tester with a cradle of 50 mm, the thickness was 3 mm, which was prepared above on the cradle and conditioned at -30 ° C. A 1 kg hard ball was dropped from the height of 100 cm to the center of the square plate, and the presence or absence of cracks or cracks was confirmed. After performing the test on 10 sheets, the height was changed by 10 cm, the same test was performed, and the height at which 5 or more test pieces were broken was obtained.

(3) Surface appearance About the 3 mm-thick square plate produced above, surface appearance is evaluated by measuring Ra (center line average roughness, μm) using a surface roughness measuring device (manufactured by ACCRTECH). It was.

(4) Linear expansion coefficient (Linear expansion coefficient) Using the central portion of the square plate having a thickness of about 3 mm produced above, cut into about 5 mm x 12 mm in the resin flow direction (MD), and cut the cut surface with a paper file. Polished. The measurement was performed using TMA-100 manufactured by Seiko Electronics Co., Ltd., and the measurement conditions were held at −50 ° C. for 10 minutes in a nitrogen atmosphere, and then the temperature range from −50 ° C. to 120 ° C. was increased at a rate of temperature increase of 5 ° C. / The temperature was raised in minutes, and the linear expansion coefficient in the range of -30 to 80 ° C was calculated.

(5) A strip-shaped molded product having a fluid thickness of 1 mm and a width of 10 mm was used, and the determination was made based on the flow length. 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.

(6) Weight average particle diameter of rubbery polymer 0.1 ml of a latex prepared by diluting with distilled water to a solid content concentration of about 3% was used as a sample, and a flow rate of 1.4 ml using a CHDF2000 type particle size distribution meter manufactured by MATEC USA. The weight average particle size was measured using a capillary cartridge for particle separation and a carrier liquid under the conditions of / min, pressure of about 2.76 MPa (about 4000 psi), and temperature of 35 ° C. The calibration curve of the particle size was prepared by measuring the particle size of a total of 13 points from 0.02 μm to 1.0 μm using, for example, monodispersed polystyrene with a known particle size manufactured by DUKE, USA as the standard particle size material.

[Production Example 1] Production of polyorganosiloxane graft copolymer (C-1) Production of polyorganosiloxane (S-1) latex 2.0 parts of siloxane crosslinking agent (tetraethoxysilane), vinyl polymerizable functional group Containing siloxane (γ-methacryloyloxypropyldimethoxymethylsilane) 0.5 part and dimethylsiloxane-based cyclic (hexamethylcyclotrisiloxane about 5%, octamethylcyclotetrasiloxane about 75%, decamethylcyclohexasiloxane about 20% The mixture of 97.5 parts) was mixed to obtain 100 parts of a siloxane mixture. 200 parts of distilled water in which 0.7 part of sodium alkylbenzene sulfonate is dissolved as an emulsifier and 100 parts of the above siloxane mixture are pre-emulsified with an in-line mixer manufactured by Tokushu Kika Co., Ltd. and then forcibly emulsified with a homogenizer. And a pre-emulsion was obtained. The pressure of the homogenizer was 20 MPa. Next, the above pre-emulsion was charged into a separable flask previously charged with 0.7 part of alkylbenzenesulfonic acid as an acid catalyst, heated to 80 ° C., maintained at that temperature for 5 hours, then cooled to 20 ° C., 10 The pH of this latex was adjusted to 7.2 with an aqueous sodium hydroxide solution to complete the polymerization reaction, and a polyorganosiloxane (S-1) latex was obtained.

Production of polyorganosiloxane-based graft copolymer (C-1) Polyorganosiloxane (S-1) latex was collected so that the solid content was 20 parts, and placed in a separable flask equipped with a stirrer. Distilled water was added so that the amount of distilled water in the flask was 195 parts, and then a mixture of 60 parts of n-butyl acrylate containing 1.0% allyl methacrylate and 0.48 parts of tert-butyl hydroperoxide was charged. The mixture was stirred for 10 minutes, and the mixture was impregnated with polyorganosiloxane (S-1). Further, 0.4 part of polyoxyethylene ether sulfate was added, and the mixture was further stirred for 10 minutes, followed by nitrogen substitution, and the temperature in the separable flask was raised to 50 ° C., and 0.002 part of ferrous sulfate, ethylenediamine A mixed solution of 0.006 part of disodium tetraacetate, 0.26 part of Rongalite and 5 parts of distilled water was charged, radical polymerization was started, and then held at an internal temperature of 70 ° C. for 2 hours to complete the polymerization and composite rubber Latex was obtained. A part of this latex was sampled and the particle size distribution of the composite rubber was measured. The weight average particle size was 180 nm.

  To this composite rubber latex, 0.06 part of tert-butyl hydroperoxide and 20 parts of a vinyl monomer mixture (methyl methacrylate: n-butyl acrylate = 95: 5 weight ratio) were added dropwise at 70 ° C. over 60 minutes. Then, it was kept at 70 ° C. for 4 hours to complete the graft polymerization of the vinyl monomer onto the composite rubber. The polymerization rate of the vinyl monomer was 99.1%. The obtained latex of the graft copolymer is dropped into 200 parts of hot water in which 5 parts of calcium acetate is dissolved, and the graft copolymer is solidified, separated, washed, dried at 75 ° C. for 8 hours, and then grafted. A powder of crude copolymer product (C-1) was obtained.

[Production Example 2] Production of polyorganosiloxane-based graft copolymer (C-2) The same procedure as in Production Example 1 was carried out except that sodium alkylbenzenesulfonate used as an emulsifier was changed to 3 parts. A copolymer (C-2) was obtained. When the particle size distribution of the composite rubber was measured, the weight average particle size was 90 nm.

[Production Example 3] Production of acrylic rubber-based graft copolymer (C-3) 195 parts of distilled water and 1 part of sodium lauryl sulfate were added to a separable flask equipped with a stirrer, and the atmosphere was replaced with nitrogen. did. Next, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of ethylenediaminetetraacetic acid disodium salt, 0.26 part of Rongalite and 5 parts of distilled water was added, and further 2% allyl methacrylate substituted with nitrogen was contained. A mixture of 80 parts of n-butyl acrylate and 0.40 part of t-butyl hydroperoxide was added to initiate radical polymerization. Thereafter, the polymerization was completed by maintaining the liquid temperature at 70 ° C. for 2 hours to obtain a rubber latex.

  To this rubber latex, a mixed solution of 0.3 part of sodium lauryl sulfate, 0.10 part of t-butyl hydroperoxide, 19 parts of methyl methacrylate and 1 part of n-butyl acrylate was added dropwise at 65 ° C. over 30 minutes, Thereafter, the temperature was maintained at 70 ° C. for 1 hour to complete the graft polymerization to the rubber latex, and an acrylic graft copolymer latex was obtained. A part of this graft copolymer latex was sampled and the weight average particle diameter was measured. The polymerization rate of methyl methacrylate was 99.2%. Thereafter, a powdery acrylic rubber-based graft copolymer (C-3) was obtained in the same manner as in Production Example 1.

[Production Example 4] Production of butadiene-based graft copolymer (C-4) In a pressure-resistant autoclave, 150 parts by weight of deionized water, 95 parts by weight of 1,3-butadiene, 5 parts by weight of styrene, and 0.5 parts of t-dodecyl mercaptan. 5 parts by weight, 0.4 parts by weight diisopropylbenzene hydroperoxide, 1.5 parts by weight sodium pyrophosphate, 0.02 parts by weight ferrous sulfate, 1.0 part by weight dextrose, and 1.0 part by weight potassium oleate Was reacted at 50 ° C. for 24 hours with stirring to produce a butadiene rubber polymerized latex. The rubber latex had a weight average particle diameter of 80 nm.

70 parts by weight (as solid content) of this butadiene-based rubber polymerized latex was charged into a flask and purged with nitrogen. Then, 1.2 parts by weight of NaHCO ₃ was added to a 10% aqueous solution and stirred for 30 minutes. To this solution, 1 part by weight of potassium oleate was added as a 7% aqueous solution and stabilized. Thereafter, 0.6 parts by weight of Rongalite was added and the liquid temperature was maintained at 70 ° C., and a mixed solution of 29 parts by weight of methyl methacrylate, 1 part by weight of n-butyl acrylate and 0.2 part by weight of cumene hydroperoxide. Was graft polymerized to a butadiene rubber polymerized latex.

  After adding 0.5 parts by weight of dibutylhydroxytoluene (BHT) to the obtained graft copolymer latex, 0.2% sulfuric acid aqueous solution is added to coagulate the graft copolymer and heat treatment at 90 ° C. Solidified. Thereafter, the solidified product was washed with warm water and further dried to obtain a butadiene-based graft copolymer (C-4) powder.

[Production Example 5] Production of acrylic rubber-based graft copolymer (C-5) In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen blowing port, monomer addition port, and thermometer, the following component 1 Put.
(Component 1)
Deionized water 200 parts SFS (sodium formaldehyde sulfoxylate) 0.4 part Ferrous sulfate 0.4 x 10 ^-4 parts Disodium ethylenediaminetetraacetate 1.2 x 10 ^-4 parts

Next, the temperature of the system was raised to 80 ° C. while mixing and stirring with nitrogen, and 4 parts (about 20% by mass of (a-1)) of the mixture (a-1) having the following composition were charged. And kept at 80 ° C. for 15 minutes. Next, the remainder of (a-1) was added over 50 minutes and held for 1 hour while maintaining at 80 ° C. to complete the polymerization of the innermost layer polymer. The polymerization rate of the obtained latex (L-1) (unreacted monomer was measured by gas chromatography, the same shall apply hereinafter) was 99% or more.
(Mixture (a-1))
Methyl methacrylate 11.2 parts Styrene 0.8 parts n-butyl acrylate 8.0 parts 1,3-butanediol dimethacrylate 0.6 parts allyl methacrylate 0.08 parts t-butyl hydroperoxide 0.04 parts Emulsifier A ( Polyoxyethylene alkyl ether phosphate ester salt: Phosphanol RS-610NA, trade name, manufactured by Toho Chemical Co., Ltd.) 0.72 parts

Subsequently, 0.27 parts of SFS dissolved in 5.0 parts of deionized water was added to the latex (L-1) and held for 15 minutes, and then a mixture (b-1) having the following composition was added for 4 hours. The solution was added dropwise and held for 2 hours to complete the polymerization of the intermediate layer polymer. The polymerization rate of the obtained latex (L-2) was 99% or more, and the mass average particle diameter of the polymer formed up to the intermediate layer polymer was 250 nm.
(Mixture (b-1))
Styrene 14.0 parts n-Butyl acrylate 66.0 parts Allyl methacrylate 0.72 parts Cumene hydroperoxide 0.23 parts Emulsifier A 2.4 parts

Subsequently, 0.23 parts of SFS dissolved in 5.0 parts of deionized water was added to the latex (L-2) and held for 15 minutes, and then a mixture (c-1) having the following composition was added for 2 hours. The solution was dropped over 20 minutes and held for 1 hour to complete the polymerization of the outer layer polymer. The polymerization rate of the obtained final latex (L-3) was 99% or more.
(Mixture (c-1))
Methyl methacrylate 65 parts n-butyl acrylate 5 parts t-butyl hydroperoxide 0.12 parts n-octyl mercaptan 0.14 parts

  Subsequently, a stainless steel container was charged with 370 parts of a 1.4% calcium acetate aqueous solution as a recovery agent aqueous solution, heated to 60 ° C. with mixing and stirring, and 370 parts of the latex (L-3) was continuously added for 10 minutes. Added. Thereafter, the temperature was raised to 90 ° C. and held for 5 minutes. Cool to room temperature, filter with centrifugal dehydration (1300 G, 3 minutes) while washing with deionized water to obtain a wet resin, and dry at 75 ° C. for 48 hours to obtain a white powdered polyacrylic rubber graft copolymer (C-5) was obtained.

The compounding composition used for the Example and the comparative example below is shown.
(A-1) Aromatic polycarbonate resin (PC); trade name “Taflon A2600”, manufactured by Idemitsu Chemical Co., Ltd., viscosity average molecular weight 26,000
(A-2) Aromatic polycarbonate resin (PC); trade name “Taflon A1900”, manufactured by Idemitsu Chemical Co., Ltd., viscosity average molecular weight 19,000
(B-1) Polybutylene terephthalate resin (PBT); trade name “Trecon 1200S”, manufactured by Toray Industries, Inc., intrinsic viscosity 1.26, melting point 228 ° C.
(B-2) Polybutylene terephthalate resin (PBT); trade name “Toraycon 1100M”, manufactured by Toray Industries, Inc., intrinsic viscosity 1.41, melting point 225 ° C.
(C-1) to (C-5); graft copolymer produced in Production Examples 1 to 5 above (C-6) ethylene elastomer; trade name “Bond First 7M”, manufactured by Sumitomo Chemical Co., Ltd. (D -1) Talc; Trade name “LMS200F”, manufactured by Fuji Talc Kogyo Co., Ltd., bulk specific gravity 0.50, median diameter 5 μm
(D-2) Talc; Trade name “LMS300”, manufactured by Fuji Talc Kogyo Co., Ltd., bulk specific gravity 0.10, median diameter 4.5 μm
(E-1) Antioxidant: Phenolic antioxidant (Adeka manufactured by ADEKA)
(E-2) Antioxidant: Phosphorus compound (PEP-36 manufactured by ADEKA Corporation)
(F) Compound F-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
F-2: trimethylolpropane; molecular weight 134, 0 alkylene oxide units per functional group, ARDRICH F-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
F-4: Polyoxypropylene diglycerin (molecular weight 750, number of alkylene oxide (propylene oxide) units 2.3 per functional group, SC-P750 by Sakamoto Yakuhin)
(F ′) Compound F-5 having less than three functional groups: 1,6-hexanediol; manufactured by ARDRICH

Examples 1-27, Comparative Examples 1-3, 6-7
TEX30α biaxial shafts with three kneading block parts with the cylinder temperature set at 220-240 ° C and the screw speed set at 300 rpm after blending the raw materials so as to have the compositions shown in Tables 1 to 4 and dry blending It melt-kneaded so that the resin pressure of a die | dye part might be 2-3 MPa with an extruder (made by Nippon Steel Works), and after cooling the strand discharged from die | dye in a cooling bath, it pelletized with the strand cutter. Each pellet obtained was dried by a hot air dryer at 130 ° C. for 3 hours or more, and then molded by the evaluation method described above for evaluation.

Comparative Example 4
Except that the cylinder temperature was set to 300 ° C., the mixture was melt-kneaded by the same method as in Example 1 to produce pellets. The resin pressure in the kneading block at this time was 0.7 MPa. Thereafter, evaluation was performed in the same manner as in Example 1.

Comparative Example 5
Pellets were produced by melt-kneading in the same manner as in Example 1 except that a PCM30 extruder without a kneading block part set at a cylinder temperature of 280 ° C. and a screw speed of 200 rpm was used. The resin pressure at this time was 0.2 MPa. Thereafter, evaluation was performed in the same manner as in Example 1.

  The thermoplastic resin compositions of Examples 1 to 27 have a small coefficient of linear expansion, and are excellent in surface impact strength and surface appearance at low temperatures. On the other hand, it can be seen that the thermoplastic resin compositions of Comparative Examples 1 to 7 are inferior in any of linear expansion coefficient, surface impact strength at low temperature, and surface appearance.

Claims (9)

(A) Aromatic polycarbonate resin, (B) Aromatic polyester resin, (C) Graft copolymer obtained by graft polymerization of vinyl monomer to rubbery polymer, (D) Blending talc A resin composition comprising:
The total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin is 100% by weight, and (A) aromatic polycarbonate resin is 1 to 99% by weight, and (B) aromatic polyester resin is 1 to 99% by weight. (A) A graft copolymer obtained by graft-polymerizing a vinyl monomer to a rubbery polymer, with the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin being 100 parts by weight, 1 to 50 parts by weight, (D) talc is a resin composition comprising 30 to 200 parts by weight,
The (A) aromatic polycarbonate resin and the (B) aromatic polyester resin have a biphasic continuous structure having a structural period of 0.001 to 1.0 μm, or a dispersed structure having a distance between particles of 0.001 to 1 μm. A thermoplastic resin composition. (C) The rubbery polymer of the graft copolymer obtained by graft polymerization of a vinyl monomer to a rubbery polymer is at least one selected from organosiloxane rubbers, acrylic rubbers and diene rubbers The thermoplastic resin composition according to claim 1, wherein: (C) The rubbery polymer of the graft copolymer obtained by graft polymerization of a vinyl monomer to a rubbery polymer is a composite rubber made of polyorganosiloxane and acrylic rubber. The thermoplastic resin composition according to claim 1 or 2. (C) The rubbery polymer of the graft copolymer obtained by graft-polymerizing a vinyl monomer to a rubbery polymer is an acrylic rubber. Thermoplastic resin composition. (C) The graft copolymer obtained by graft-polymerizing a vinyl monomer to a rubbery polymer has a hard polymer phase in the innermost layer. The thermoplastic resin composition described in 1. Further, 0.01 to 4 parts by weight of (F) a polyfunctional compound having three or more functional groups is blended, with the total of (A) aromatic polycarbonate resin and (B) aromatic polyester resin being 100 parts by weight. The thermoplastic resin composition according to any one of claims 1 to 5. The molded article which consists of a thermoplastic resin composition as described in any one of Claims 1-6. The molded article according to claim 7, wherein the molded article is a vehicle part. The molded article according to claim 7 or 8, wherein the molded article is a vehicle exterior part.