JP2008231440A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition with controlled molding processability, particularly occurrence of flow mark and jetting during molding, and composed of an aromatic polycarbonate resin and an aromatic polyester resin. <P>SOLUTION: The thermoplastic resin composition is composed of 100 wt.% in total, of 30-98.99 wt.% of an aromatic polycarbonate resin (A component) composed of (A-1) 40-95 wt.% of an aromatic polycarbonate resin and (A-2) 5-60 wt.% of an aromatic polyester resin, 1-50 wt.% of at least one filler (B component) selected from a group composed of an inorganic filler, a heat-resistant organic filler and a rubbery filler, 0.01-20 wt.% of a fluorinated olefinic polymer (D component) with a weight-average molecular weight of 5,000,000-50,000,000 calculated from dynamic shear elasticity rate determined at 380°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition. More specifically, even when an aromatic polycarbonate resin composed of an aromatic polycarbonate resin and an aromatic polyester resin is blended with an inorganic filler, a heat-resistant organic filler, or a rubber-like filler, at the time of injection molding The present invention relates to a thermoplastic resin composition in which the occurrence of jetting, flow marks and the like is suppressed.

  An aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin and an aromatic polyester resin is widely used in various industrial fields because it has excellent mechanical properties, dimensional stability, and chemical resistance.

  In order to improve the rigidity and linear expansion coefficient of the resin composition, a method of blending glass fibers (Patent Document 1-2), a method of blending scale-like and plate-like inorganic fillers such as talc and mica ( Patent Literature 3-4) and a method of blending fine fibrous inorganic fillers such as wollastonite (Patent Literature 5) have been proposed. An aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin and an aromatic polyester resin blended with these inorganic fillers is a material having improved chemical resistance and excellent chemical resistance and high temperature characteristics. In some cases, a heat-resistant organic filler such as an aramid fiber or an aramid powder is blended in place of the inorganic filler.

  On the other hand, in order to improve the impact strength of an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin and an aromatic polyester resin, it is common practice to add a rubbery filler. Furthermore, when an inorganic filler is blended in the aromatic polycarbonate resin composition described above, there is a problem that impact strength is lowered. In order to solve this problem, a rubber-like filler is generally blended, and the obtained resin composition has a good impact strength.

  However, an aromatic polycarbonate resin composition composed of an aromatic polycarbonate resin and an aromatic polyester resin contains components that are incompatible with the aromatic polycarbonate resin composition, such as an inorganic filler and a rubber-like filler. In such a case, there is a problem that jetting and flow marks are likely to occur on the surface of the injection molded product.

  In general, it is possible to cope with such poor surface appearance of an injection-molded product by measures for improving flow characteristics such as improvement of molding temperature or reduction of molecular weight. However, in such an aromatic polycarbonate resin composition, the former measure induces decomposition of the aromatic polycarbonate resin composition derived from the transesterification reaction, while the latter measure is sufficient because it leads to a decrease in mechanical properties. Can not respond.

  That is, these are extremely serious and inherent problems for a thermoplastic resin composition in which an inorganic filler or a rubber-like filler is blended with an aromatic polycarbonate resin composed of an aromatic polycarbonate resin and an aromatic polyester resin. This is a problem that does not occur in a resin composition that can be applied widely depending on molding conditions, such as a resin composition comprising an aromatic polycarbonate and a graft polymer described in JP-A-61-91248.

  Therefore, it consists of aromatic polycarbonate and aromatic polyester with excellent rigidity, high temperature characteristics, chemical resistance, impact strength, and other mechanical properties, and also suppresses molding processability, especially flow marks and jetting during molding. There is a strong demand for aromatic polycarbonate resin compositions.

JP 54-94556 A JP-A-6-29344 JP 55-129444 A JP-A-5-222283 Japanese Patent Laid-Open No. 7-149948

  An object of the present invention is an aromatic polycarbonate resin having excellent chemical properties such as chemical resistance, rigidity and high temperature characteristics, impact strength, and molding processability, in particular, occurrence of flow marks and jetting during molding, and The object is to provide a thermoplastic resin composition comprising an aromatic polyester resin.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have added an inorganic filler, a heat-resistant organic filler, or a rubber-like resin to an aromatic polycarbonate resin comprising an aromatic polycarbonate resin and an aromatic polyester resin. In a filler-containing resin composition containing a filler or the like, when a specific polymer having a very high molecular weight is further added, the molding processability, particularly the generation of flow marks and jetting during molding is suppressed. The present invention has been reached.

  The present invention relates to an aromatic polycarbonate resin (component A) comprising 100% by weight in total of (A-1) 40 to 95% by weight of an aromatic polycarbonate resin and (A-2) 5 to 60% by weight of an aromatic polyester resin. 30 to 99.99% by weight, 1 to 50% by weight of at least one filler (component B) selected from inorganic fillers, heat-resistant organic fillers, and rubber-like fillers, and dynamic shear elasticity at 380 ° C. This relates to a thermoplastic resin composition comprising 0.01 to 20% by weight of a fluorinated olefin polymer (component D) having a weight average molecular weight of 5 to 50 million calculated from rate measurement.

  The polycarbonate resin used as (A-1) of the present invention is an aromatic carbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the dihydric phenol used here include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), bis (4hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, Examples include 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- (4-hydroxy-3-methylphenyl) propane, and bis (4-hydroxyphenyl) sulfone. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, with bisphenol A being particularly preferred. Examples of the carbonate precursor include carbonyl halald, carbonyl ester, haloformate, and the like, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like. In producing the polycarbonate resin, the above dihydric phenol may be used alone or in combination of two or more, and the polycarbonate resin is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Or it may be a mixture of two or more kinds of polycarbonate resins.

If the molecular weight of the polycarbonate resin is too low, the strength is not sufficient, and if it is too high, the melt viscosity becomes high and it becomes difficult to mold, so it is usually 10,000 to 50,000, preferably 15,000 in terms of viscosity average molecular weight. ~ 30,000. The viscosity average molecular weight (M) here is obtained by inserting the specific viscosity (ηsp) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
ηsp / C = [η] + 0.45 × [η] ² C
[η] = 1.23 × 10 ⁻⁴ M ^0.83
([Η] is the intrinsic viscosity, C is the polymer concentration of 0.7)

  Next, a basic means for producing a polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used, and examples of the molecular weight regulator include alkyl-substituted phenols such as phenol and p-tert-butylphenol and 4- (2 It is desirable to use terminal terminators such as alkyl-substituted phenols such as -phenylisopropyl) phenol. The reaction temperature is preferably 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. In addition, it is not necessary that all of the resulting molecular chain ends have a structure derived from a terminal terminator.

  In a transesterification reaction (melting method) using carbonic acid diester as a carbonate precursor, it is produced by stirring a dihydric phenol component in a predetermined proportion and, if necessary, a branching agent and the like with carbonic acid diester under an inert gas atmosphere. It is carried out by a method of distilling off alcohols or phenols. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst used for now well-known transesterification reactions, such as an alkali metal compound and a nitrogen-containing basic compound, can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred. In addition, diphenyl carbonate, methyl (2-phenyloxycarbonyloxy) benzenecarboxylate or the like is added as an end terminator in the initial stage of the reaction or in the middle of the reaction, and various conventionally known catalyst deactivations immediately before the end of the reaction. It is also preferable to add an agent.

  The aromatic polyester resin used as (A-2) in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof. It is a polymer.

  As the aromatic dicarboxylic acid here, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether Dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid Aromatic dicarboxylic acids such as acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid are preferably used, In particular, terephthalic acid and 2,6-naphthalenedicarboxylic acid can be preferably used.

  Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. together with the dicarboxylic acid. .

  Examples of the diol that is a component of the aromatic polyester of the present invention include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1, Contains aromatic diols such as 2,2-bis (β-hydroxyethoxyphenyl) propane, aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol Diols and the like, and mixtures thereof. If the amount is even smaller, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.

  The aromatic polyester of the present invention can be branched by introducing a small amount of a branching agent. Although there is no restriction | limiting in the kind of branching agent, A trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, etc. are mentioned.

  Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1, In addition to 2-bis (phenoxy) ethane-4,4′-dicarboxylate, and the like, copolymer polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like can be given. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof having a good balance of mechanical properties and the like can be preferably used.

  Further, the terminal group structure of the obtained aromatic polyester resin is not particularly limited, and may be a case where the ratio of one of the hydroxyl groups and the carboxyl group in the terminal group is large in addition to the case where the ratio is almost the same. . Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

  About the manufacturing method of this aromatic polyester resin, according to a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., the dicarboxylic acid component and the diol component are polymerized while heating to produce by-products. It is carried out by discharging water or lower alcohol out of the system. Examples of germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, and the like. Can be illustrated.

  Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc. used in the transesterification reaction, which is the former stage of the conventionally known polycondensation, can be used together, and phosphoric acid or phosphorous acid after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like.

  The molecular weight of the aromatic polyester resin is not particularly limited, but the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.2, preferably 0.65 to 1.15.

  Examples of the inorganic filler used as the component B in the present invention include glass fiber (chopped strand), carbon fiber, metal-coated carbon fiber, metal fiber, wollastonite, zonotlite, potassium titanate whisker, aluminum borate whisker, and basic sulfuric acid. Fibrous fillers such as magnesium whiskers, plate fillers such as talc, mica, glass flakes, graphite flakes, short glass fibers (milled fibers), short carbon fibers, glass beads, glass balloons, silica particles, titania particles, alumina Particulate fillers such as particles, kaolin, clay, calcium carbonate, titanium oxide and the like can be mentioned.

  Further, the heat-resistant organic filler used as the B component of the present invention refers to one that does not melt at the molding processing temperature of the aromatic polycarbonate resin that is the A component of the present invention. Such fillers include aramid fibers and polyarylate fibers. And the like, and particulate fillers such as aramid powder, phenol resin particles, crosslinked styrene particles, and crosslinked acrylic particles.

  Examples of the rubber-like filler used as the component B in the present invention include polymers of conjugated diene monomers such as polybutadiene and polyisoprene, copolymers such as butadiene-styrene and butadiene-acrylonitrile, alkyl acrylate monomers, Polymer or copolymer of alkyl methacrylate monomer, and acrylate-diene copolymer copolymerized with conjugated diene, EPDM rubber, and composite rubber having a structure in which polyorganosiloxane rubber and acrylate rubber are entangled with each other A rubbery substrate such as a polymer is copolymerized with at least one component selected from an aromatic vinyl monomer, a vinyl cyanide monomer, an alkyl acrylate monomer, an alkyl methacrylate monomer, and the like. The rubber-like filler obtained in this way can be used. These rubber-like fillers can be produced by known emulsion polymerization, suspension polymerization, bulk polymerization, and bulk suspension polymerization.

  Examples of the conjugated diene monomer that can be used in the present invention include butadiene, isoprene, 1,3-heptadiene, 2,3-dimethylbutadiene, and among them, butadiene and isoprene are preferable.

  Examples of the acrylate monomer that can be used in the rubbery substrate in the present invention include n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and the like, and examples of the methacrylate monomer include hexyl methacrylate and 2-ethylhexyl methacrylate. Can do. A rubbery substrate obtained by copolymerizing these acrylates and the above conjugated dienes can also be used. Further, the polyorganosiloxane rubber is polymerized in a state where the acrylate monomer or methacrylate monomer is swollen in the presence of the polyorganosiloxane rubber component, or the polyorganosiloxane rubber and the acrylate monomer are polymerized at the same time. A composite rubber polymer having a structure in which rubber and acrylate rubber are entangled with each other can also be used as the rubbery substrate.

  Furthermore, examples of the aromatic vinyl monomer that can be used in the rubber-like filler of the present invention include styrene, α-methylstyrene, 4-methylstyrene, and 3,5-diethylstyrene. Among them, styrene is preferable. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile. Among them, acrylonitrile is preferable. Examples of the acrylate monomer and methacrylate monomer copolymerized with the rubbery substrate include methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, propyl acrylate, and isopropyl acrylate. Among them, ethyl acrylate, methyl methacrylate Is preferred.

  When at least one monomer is copolymerized on a rubbery substrate, the substrate contains at least 10% by weight when the total amount of the rubbery filler is 100% by weight. Is contained at least 25% by weight, more preferably 50 to 80% by weight. Further, when the component copolymerized on the substrate is a mixture of an aromatic vinyl monomer and at least one selected from a vinyl cyanide monomer, an acrylate monomer, and a methacrylate monomer, The aromatic vinyl monomer is preferably 60 to 90% by weight in 100% by weight of the total amount of the aromatic vinyl monomer and the other monomer. Furthermore, a functional monomer such as maleic anhydride, maleimide, N-methylmaleimide and the like can be copolymerized in the range of 10% by weight or less in 100% by weight of the whole rubber filler.

  In addition, when other monomers are copolymerized on the rubber-like substrate, usually such other monomer components are mixed without being copolymerized on the substrate, but the molecular weight of such components is usually standard polystyrene. It is a thing of 50,000-500,000 in the weight average molecular weight computed by conversion GPC measurement.

Examples of the fluorinated olefin polymer having a weight average molecular weight of 5 to 50 million calculated from the dynamic shear modulus measurement at 380 ° C. used as the D component in the present invention include polytetrafluoroethylene and tetrafluoroethylene. -Fluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene-fluoroalkyl vinyl ether copolymer, Of these, polytetrafluoroethylene can be preferably used. Such fluorinated olefin-based polymers include solid forms obtained by coagulating and washing the dispersion during emulsion polymerization, those using the dispersion concentrate as it is, and other polymers. Various forms such as a mixture obtained by coagulation with a dispersion can be used. If the weight average molecular weight of component D exceeds 5 million, the improvement effect such as jetting is insufficient, and if it exceeds 50 million, the decrease in fluidity increases with respect to the improvement effect.
The molecular weight of such a fluorinated olefin polymer can be calculated by a method using a dynamic shear modulus at 380 ° C. Furthermore, it is preferable to use dedicated calculation software.

  In the present invention, jetting that occurs when a resin composition in which an aromatic polycarbonate resin, which is the A component of the present invention is blended with a B component such as an inorganic filler, is injection molded by blending the D component. It becomes possible to reduce the appearance defect.

  The proportions of the A component, B component, and D component used in the present invention are 30 to 99.99 wt.% A component, 1 to 50 wt.% B component, and 0.01 to 20 wt. %. If the A component is less than 30% by weight, the molding processability in the injection molding is inferior, the appearance is deteriorated, and the strength is also inferior. On the other hand, when the component A exceeds 99.99% by weight, the improvement effects such as strength and impact resistance are insufficient. On the other hand, if the component B is less than 1% by weight, the strength and impact resistance are insufficient, and if it exceeds 50% by weight, the molding processability in the injection molding is inferior and the appearance is deteriorated. If the D component is less than 0.01% by weight, the effect of improving such as jetting is insufficient, and if it exceeds 20% by weight, the molding processability is inferior and the appearance deteriorates.

  Moreover, the ratio of the aromatic polycarbonate which is (A-1) in A component, and (A-2) aromatic polyester is (A-1) 40 to 95 weight% in 100 weight% of this A component, and (A -2) 5 to 60% by weight, preferably (A-1) 60 to 90% by weight and (A-2) 10 to 30% by weight. When (A-1) is less than 40% by weight and (A-2) is more than 60% by weight, the impact strength and dimensional accuracy are inferior, while (A-2) is less than 5% by weight and (A-1) If it exceeds 95% by weight, the chemical resistance and molding processability are inferior.

  Furthermore, in the present invention, various heat stabilizers are preferably used in order to suppress thermal deterioration during the molding process of the component A. Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4 -Di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite Monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentae Thritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) ) Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenyl Rangephosphosphinic acid tetrakis (2,4-di-tert-butylphenyl), benzenephosphonate dimethyl, benzenephosphonate diethyl, benzenephosphonate dipropiate Etc. The. These heat stabilizers may be used alone or in admixture of two or more. The blending amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin as the component A, 0.001 -0.1 weight part is still more preferable.

  The thermoplastic resin composition of the present invention can also be blended with an antioxidant generally known for the purpose of preventing oxidation. Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4,6-tris (3,5-di- -Butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy -Benzylphosphonate-diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphosphinic acid tetrakis (2,4-di-t-butylphenyl) 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxa Spiro (5,5) undecane and the like can be mentioned. The blending amount of these antioxidants is preferably 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin that is the component A.

  In the thermoplastic resin composition of the present invention, in order to further improve the releasability from the mold at the time of melt molding, a mold release agent can be blended within a range that does not impair the object of the present invention. Examples of the mold release agent include olefin wax, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax and the like. The compounding amount of the release agent is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the A component aromatic polycarbonate resin.

  The thermoplastic resin composition of the present invention can be blended with a light stabilizer as long as the object of the present invention is not impaired. Examples of such a light stabilizer include 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo. Triazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2 Examples include '-methylenebis (4-cumyl-6-benzotriazolephenyl) and 2,2'-p-phenylenebis (1,3-benzoxazin-4-one). The blending amount of the light stabilizer is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin that is the component A.

  An antistatic agent can be blended with the thermoplastic resin composition of the present invention as long as the object of the present invention is not impaired. Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like.

  The thermoplastic resin composition used in the present invention is produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. be able to. Furthermore, a nucleating agent, a flame retardant, a foaming agent, and a dye / pigment that are usually used in the resin composition may be contained within a range not impairing the object of the present invention. The thermoplastic resin composition obtained in the present invention is particularly suitable for injection molding, but such injection molding methods include not only ordinary injection molding but also injection compression molding, gas injection hollow molding, two-color molding. It is also useful in high-speed injection molding and other various injection molding methods.

  In addition to mechanical properties and chemical resistance, the resin composition of the present invention is further excellent in impact strength and rigidity, and can provide a molded product in which appearance defects such as jetting during molding are suppressed.・ Electric / information equipment field, construction machinery / machine tools, various machine fields, automotive field, etc., industrially useful, especially outer shells of electronic / electrical equipment, etc. It is useful in fields requiring relatively large members such as outer plate members for construction machines and outer plate members for houses.

The following examples further illustrate the present invention. In addition, the part and% in an Example are a weight part and weight%, and evaluation was based on the following method.
(1) Appearance: Tensile dumbbells described in ASTM D638 were molded, and the presence or absence of jetting and flow marks was determined visually. The determination was made according to the following.
○: No appearance defect of jetting and flow mark ×: Defect appearance of jetting or flow mark (2) Impact strength: Measured in accordance with ASTM D256 at a thickness of 1/8 ”.
(3) Weld retention ratio: Tensile strength was measured by using a tensile dumbbell described in ASTM D638, forming gates at both ends of the dumbbell, and forming a weld at the center of the dumbbell. Further, in accordance with ASTM D638, the normal tensile strength was measured, and the weld strength retention was calculated according to the following formula. The weld retention is preferably 70% or more, particularly preferably 75% or more.

[Example 1 and Comparative Example 1]
0.1 weight of phosphorus stabilizer (distearyl pentaerythritol diphosphite) (Asahi Denka Kogyo Co., Ltd. PEP-8) with respect to each component shown in Table 1 and 100 parts by weight in total. 0.5 parts by weight of carbon black and carbon black were mixed, and pelletized at a cylinder temperature of 270 ° C. using a vent type extruder with a diameter of 30 mm [VSK-30 manufactured by Nakatani Co., Ltd.]. After the pellets were dried at 120 ° C. for 5 hours, a test piece was molded at a cylinder temperature of 270 ° C. and a mold temperature of 90 ° C. by using an injection molding machine [T-150D manufactured by FANUC Corporation], and the evaluation results were shown. .

In addition, the symbol which shows each component of Table 1 is as follows.
(A component)
(A-1) Aromatic polycarbonate resin Bisphenol A type polycarbonate obtained by the phosgene method: Panlite L-1250; manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 25,000
(A-2) Aromatic polyester resin PBT / PET: Polybutylene terephthalate resin (TRB-H, Teijin Ltd., intrinsic viscosity 1.07) and polyethylene terephthalate resin (TR-8580, Teijin Ltd., intrinsic viscosity 0) .8) mixed at a weight ratio of 7/3 (component B) inorganic filler WSN: wollastonite; NYCO NYGLOS4
(D component)
PTFE: a mixture of 20% by weight of polytetrafluoroethylene having a weight average molecular weight of 20 million calculated from dynamic shear modulus measurement and 80% by weight of methacrylic resin; manufactured by Mitsubishi Rayon Co., Ltd. (acrylic modified PTFE), methabrene A-3000

  As is clear from these tables, the resin composition comprising an aromatic polycarbonate, an aromatic polyester resin, and an inorganic filler and / or a rubber-like filler causes jetting and flow marks in the molded product, and is practically sufficient. While a molded article cannot be obtained, it can be seen that in a composition in which a small amount of a polymer having a specific molecular weight of the present invention is added, they are eliminated and a good molded article is obtained.

Claims (1)

  (A-1) Aromatic polycarbonate resin (component A) 30 to 98. The resin is composed of 100% by weight in total of 40 to 95% by weight of aromatic polycarbonate resin and (A-2) 5 to 60% by weight of aromatic polyester resin. 99% by weight, 1 to 50% by weight of at least one filler (component B) selected from inorganic filler, heat-resistant organic filler, and rubber-like filler, and calculated from dynamic shear modulus measurement at 380 ° C. A thermoplastic resin composition comprising a total of 100% by weight of a fluorinated olefin polymer (component D) having a weight average molecular weight of 5 to 50 million and 0.01 to 20% by weight.