JP2008214431A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that exhibits excellent mechanical properties, particularly excellent surface impact strength at low temperatures. <P>SOLUTION: The thermoplastic resin composition exhibiting excellent impact strength at low temperatures comprises 99-50 wt.% of a thermoplastic resin (component A) and 1-50 wt.% of a block copolymer (component B) that is constituted of a block S mainly composed of polystyrene, a block B mainly composed of poly(1,4-butadiene) and a block M mainly composed of polymethyl methacrylate and contains at least one linkage unit selected from the group consisting of S-B-M, M-S-B-S-M and M-B-S-B-M. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition having significantly improved impact resistance at low temperatures. More specifically, it contains a copolymer (triblock copolymer) composed of three different compositions, and has high practicality that significantly improves low-temperature impact resistance in the presence of an inorganic filler. It relates to a thermoplastic resin composition having

  The flow from inorganic materials to resin is progressing for reasons such as weight reduction, freedom of design, processability, and cost reduction. In recent years, in the automobile field and the OA field, parts are being made thinner and lighter, and so on. In particular, in the automobile field, cases such as the use of resin as a large member in the front panel of large equipment in the automobile outer plate and the OA field are increasing.

  Among them, in the automobile field, technological developments using resin parts for large parts typified by body panels such as fenders are becoming active again for weight reduction. Other exterior materials include fenders, bumpers, door panels, pillars, side protectors, side moldings, various spoilers, bonnets, roof panels, and trunk lids. Among them, active in outer panels that are still not sufficiently resinized, such as fenders, door panels, bonnets, roof panels, and trunk lids. Among them, so-called vertical outer panels such as fenders and door panels are popular. High impact resistance is required for these parts that are required to be thinner and lighter.

  As a resin that satisfies high impact resistance, an aromatic polycarbonate resin is known among thermoplastic resins. In addition, the resin composition of an aromatic polycarbonate resin and a thermoplastic polyester such as polyethylene terephthalate resin or polybutylene terephthalate resin or ABS resin has improved chemical resistance and molding processability, which are disadvantages of the aromatic polycarbonate resin. Widely used as a material (hereinafter, such a thermoplastic resin composition is referred to as a PC alloy). In particular, a resin composition comprising an aromatic polycarbonate resin and a polyester resin is effectively used in the fields of automobile interior and exterior parts, OA equipment, and the like. However, the resin composition hardly exhibits the excellent impact resistance at room temperature of the polycarbonate-based resin, and the low impact resistance of the polyester-based resin is expressed in the resin composition as it is. Arise.

  Further, when the molded product is made thinner or lighter, a high level of performance is required for the mechanical strength, rigidity, heat resistance, dimensional stability, etc. of the material. It is a common method to add an inorganic filler to a PC alloy as a response to such a requirement. However, the addition of inorganic fillers often results in deterioration of appearance and impact resistance, and can be an obstacle to weight reduction.

  Furthermore, particularly in the OA equipment field, good flame retardancy is required for the resin composition from the viewpoint of product safety. Thinning of the molded product requires higher flame retardancy. The addition of more flame retardant often reduces the impact resistance more.

  A melt elasticity effect modifier is also added to the PC alloy for the purpose of improving the melt elasticity effect. When the melt elasticity effect is improved, the shrinkage at the time of resin combustion becomes strong, so that the effect of preventing melt dripping at the time of combustion is imparted. Further, the improvement of the melt elastic effect leads to suppression of uneven thickness at the time of blow molding or hollow injection molding, and disappearance of the jetting phenomenon at the time of injection molding. However, when a melt elastic effect modifier is added, impact resistance and the like may be reduced.

From these points, a PC alloy having improved impact resistance is required.
As a means for improving the impact resistance of a PC alloy, an impact modifier has been conventionally added. An elastic polymer is often used as the impact modifier. Elastic polymers have different reforming effects depending on the amount of rubber component, and those with relatively little rubber component (ABS resin, AES resin, ASA resin, HIPS resin, etc.) can improve flowability as well as impact resistance. It is. On the other hand, those having a relatively large rubber component can improve impact resistance with a small amount. One or more impact modifiers are used to take advantage of these features.

  However, in recent years, the requirements for material specifications have become more and more severe, and the thermoplastic resin composition obtained by these prior arts cannot sufficiently satisfy the requirements. In particular, the low-temperature impact resistance considering outdoor use in winter and the surface impact strength close to the practical impact test of molded products are particularly insufficient. Therefore, a material excellent in impact resistance, particularly surface impact resistance at low temperatures, is strongly desired.

As a method for improving the impact resistance of such a thermoplastic resin composition, addition of a block copolymer containing a rubbery polymer has been attempted. Furthermore, as a method for modifying a block copolymer containing a rubbery polymer, a method of partially modifying with a partially hydride or the like is known. However, there are problems such as a decrease in molecular weight, a decrease in compatibility, and a deterioration in dispersibility, and the improvement effect is insufficient. It is known that a thermoplastic resin containing a block copolymer having improved compatibility is excellent in impact resistance, gas barrier properties, and vibration damping properties (see Patent Document 1). However, the resin described in Patent Document 1 has a problem that it has poor low-temperature impact resistance.
On the other hand, it is known that a block copolymer that can realize a highly dispersed state in a resin and has excellent compatibility with other resins improves the impact resistance of the thermosetting resin (see Patent Document 2).

JP 2005-225899 A US Pat. No. 6,894,113

  An object of the present invention is to provide an excellent thermoplastic resin composition that has excellent mechanical properties such as Charpy impact strength and surface impact strength, and that has an unprecedented excellent thermoplastic resin composition particularly in surface impact strength at low temperatures. It is to provide. As a result of earnest research, the present inventors have found that the impact resistance at low temperature is improved in a thermoplastic resin containing a triblock copolymer, and completed the present invention. I arrived.

  The present invention relates to a thermoplastic resin, preferably a polycarbonate resin (A-1 component), a styrene unit component-containing resin (A-2 component) and a polyester resin (A-) whose rubber component content is not 40% by weight. A thermoplastic resin (component A) of 99 to 20% by weight selected from the group consisting of 3 components), an S block based on polystyrene, and a poly (1,4-butadiene) as a main component. 1 to 50% by weight of an S / M / B block copolymer (B component) composed of a B block and an M block containing polymethyl methacrylate as a main component. A block copolymer comprising at least one binding unit selected from the group consisting of SBM, MSBMSM, and MBSMSBM. A block copolymer consisting of at least one binding unit selected from the group consisting of SBM, preferably MSBMSM, and MBSMSBM It is a thermoplastic resin composition having excellent surface impact strength at low temperature, characterized in that it is a block copolymer composed of a coalesced unit, more preferably only a bond unit SBM. Here, the symbols S, B and M used in the above-mentioned unit represent the above S block, B block and M block, respectively, and the same notation is used hereinafter. The block copolymer (component B) is preferably 10 to 80% by weight of S block (component B-1), 5 to 60% by weight of B block (component B-2), and 15 to M block (component B-3). It is preferably composed of 80% by weight. Further, the S block (component B-1) preferably contains at least 80% by weight of polystyrene, the B block (component B-2) contains at least 60% by weight of polybutadiene, and the thermoplastic resin (component A) and This is preferably incompatible with the S block (component B-1) and has a glass transition temperature (TgB) of 0 ° C. or lower. The M block (B-3 component) contains at least 60% by weight of polymethyl methacrylate, and includes thermoplastic resin (A component), S block (B-1 component), and B block (B-2 component). It is preferably incompatible and the glass transition temperature (TgS) is higher than the glass transition temperature (TgB) of the B block. The thermoplastic resin having such a structure has excellent mechanical properties, and in particular, has excellent characteristics that are unmatched in terms of surface impact strength at low temperatures.

Hereinafter, the details of the present invention will be described.
(Component A: thermoplastic resin)
The component A is at least selected from the group consisting of a polycarbonate resin, a styrene unit component-containing resin (A-2 component) and a polyester resin (A-3 component) having a rubber component content that is not a block copolymer of less than 40% by weight. One or more thermoplastic resins may be mentioned. Each resin will be described below.

(A-1 component: aromatic polycarbonate)
The aromatic polycarbonate which is A-1 component is a well-known thing which has been conventionally used for various molded articles. That is, it is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  The aromatic polycarbonate may be various polycarbonate resins having a high heat resistance or a low water absorption rate, which are polymerized using other dihydric phenols, in addition to the commonly used bisphenol A type polycarbonate. The aromatic polycarbonate may be produced by any production method, and in the case of interfacial polycondensation, a monohydric phenol end-stopper is usually used. The aromatic polycarbonate may be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further, a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. Polymerized polycarbonate may be used. However, an aromatic polycarbonate composed of a homopolymer of bisphenol A is particularly preferable in terms of excellent impact resistance. The details of the aromatic polycarbonate of the present invention are described in the pamphlet of WO03 / 080728.

As specific examples of the aromatic polycarbonate having a high heat resistance or a low water absorption, which is polymerized using other dihydric phenols, the following compounds are preferably exemplified.
(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, 4,4 '-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") component is 20 to 80 mol% (more preferable) 40 to 75 mol%, more preferably 45 to 65 mol%), and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "BCF") component is 20 to 20 mol. Copolycarbonate which is 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), And a BCF component in an amount of 5 to 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and The 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%). Copolycarbonate.

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

  As the A-1 component aromatic polycarbonate of the present invention, not only virgin raw materials but also aromatic polycarbonate regenerated from used products, so-called material recycled aromatic polycarbonate can be used. Used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and optical recording media Etc. are preferable. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, automobile headlamp lenses, optical recording media, and the like are consumed in large quantities, and regenerated products can be obtained stably. In addition, said virgin raw material is a raw material which is not yet used in the market after the manufacture.

The viscosity average molecular weight of the aromatic polycarbonate of component A-1 is 1.6 × 10 ^{4 to} 2.3 × 10 ⁴ , preferably 1.6 × 10 ^{4 to} 2.2 × 10 ⁴ , more preferably. It is in the range of 1.8 × 10 ^{4 to} 2.1 × 10 ⁴ . An aromatic polycarbonate having a viscosity average molecular weight in such a suitable range is excellent in balance between fluidity, strength and heat resistance.

In addition, what is necessary is just to satisfy this viscosity average molecular weight as the whole A-1 component, and what satisfies this range with the mixture of 2 or more types from which molecular weight differs is included. In particular, mixing of an aromatic polycarbonate having a viscosity average molecular weight exceeding 5.0 × 10 ⁴ (more preferably 8.0 × 10 ⁴ or more, more preferably 1.0 × 10 ⁵ or more) increases the entropy elasticity at the time of melting. There are cases where this is advantageous. For example, it is effective for reducing jetting, gas injection molding, foam molding (including supercritical fluid), and improvement of injection press moldability. Therefore, mixing of aromatic polycarbonates having a viscosity average molecular weight exceeding 5.0 × 10 ⁴ is one of suitable choices when these improvements are required and when these molding methods are applied. Such an effect becomes more pronounced as the molecular weight of the aromatic polycarbonate is higher, but the upper limit of the molecular weight is practically 2.0 × 10 ⁶ , preferably 3.0 × 10 ⁵ , more preferably 2.0 × 10 ⁵ . is there. It is preferable that the high molecular weight component is mixed in such an amount that the molecular weight distribution of two or more peaks can be observed in a measuring method such as GPC (gel permeation chromatography).

  In the aromatic polycarbonate resin (component A) of the present invention, the amount of phenolic hydroxyl group is preferably 30 eq / ton or less, more preferably 25 eq / ton or less, and further preferably 20 eq / ton or less. Such a value can be substantially 0 eq / ton by sufficiently reacting the terminal terminator. The amount of the phenolic hydroxyl group is determined by performing 1H-NMR measurement, and calculating the molar ratio of the dihydric phenol unit having a carbonate bond, the divalent phenol unit having a phenolic hydroxyl group, and the terminal terminator unit. It is determined by converting to the amount of phenolic hydroxyl group per polymer weight.

(A-2 component: styrene unit component-containing resin in which the content of a rubber component that is not a block copolymer is less than 40% by weight)
A styrene unit component-containing resin having a rubber component content of less than 40% by weight, which is not a block copolymer used as the A-2 component in the present invention, can be copolymerized with a styrene monomer and, if necessary, these. It is a styrene unit component-containing resin having a rubber component content of less than 40% by weight obtained by polymerizing one or more selected from the group consisting of other vinyl monomers and rubber components. Here, the difference between the A-2 component and the B component is the structural form. That is, the component B is a block copolymer, and the component A-2 is a structural form represented by other structural forms such as a random copolymer or a graft copolymer.

  Styrene monomers used for the styrene unit component-containing resin component include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, and p-tert-butylstyrene. Styrene derivatives such as vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene. Styrene is particularly preferable. Furthermore, these can be used alone or in combination of two or more.

  Other vinyl monomers copolymerizable with the styrenic monomer include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate, methyl acrylate, ethyl acrylate, Acrylic acid alkyl esters such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate and dodecyl acrylate, aryl methacrylates such as phenyl methacrylate and benzyl methacrylate, methyl methacrylate, ethyl methacrylate, Propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate , Methacrylic acid alkyl esters such as 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, etc., and maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, etc. And α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid, and anhydrides thereof.

  Examples of the rubber component copolymerizable with the styrenic monomer include polybutadiene, polyisoprene, styrene / butadiene random copolymer and block copolymer, acrylonitrile / butadiene copolymer, alkyl acrylate ester and / or methacrylic ester. Copolymers of acid alkyl esters and butadiene, diene copolymers such as butadiene / isoprene copolymers, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers and block copolymers Copolymers of ethylene and α-olefin, etc., ethylene / methacrylate copolymers, copolymers of ethylene and unsaturated carboxylic esters such as ethylene / butyl acrylate copolymers, ethylene / vinyl acetate copolymers, etc. Of ethylene and aliphatic vinyl Polymer, ethylene / propylene / hexadiene copolymer, etc., ethylene / propylene / non-conjugated diene terpolymer, acrylic rubber such as polybutyl acrylate, and polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component Examples thereof include composite rubber (hereinafter referred to as IPN type rubber) having a structure in which they are intertwined so that they cannot be separated.

  Examples of the A-2 component-containing styrene unit component-containing resin include polystyrene, styrene / butadiene / styrene copolymer (SBS resin), hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS resin), and hydrogenated styrene. Isoprene / styrene copolymer (hydrogenated SIS resin), high impact polystyrene (HIPS resin), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / acrylonitrile・ Butadiene / styrene copolymer (MABS resin), acrylonitrile / styrene / acrylic rubber copolymer (ASA resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), styrene / methyl methacrylate copolymer ( MS Fat), methyl methacrylate-acrylonitrile-styrene copolymer (MAS resin), styrene-maleic anhydride copolymer (SMA resin), styrene · IPN type rubber copolymer resin or a mixture thereof. Such a styrenic thermoplastic resin may have a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during the production thereof. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution, block copolymers, polymers with high stereoregularity, and copolymers obtained by anionic living polymerization, radical living polymerization, or the like are used. It is also possible. These may be used alone or in combination of two or more.

  Among these, polystyrene (PS resin), high impact polystyrene (HIPS resin), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene / acrylic rubber copolymer (ASA resin), and one or more selected from the group consisting of acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin) are preferably used. Among them, ABS resin, ASA resin, AES resin is most preferred.

  The ABS resin used in the present invention is a thermoplastic graft copolymer (ABS copolymer) obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, a vinyl cyanide compound and an aromatic vinyl compound. It is a mixture of the copolymer (AS copolymer). The copolymer of the vinyl cyanide compound and the aromatic vinyl compound is used for the production of a resin comprising a thermoplastic graft copolymer obtained by graft copolymerizing a vinyl cyanide compound and an aromatic vinyl compound with a diene rubber component. It may be a copolymer produced as a by-product, or a copolymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. The molecular weight of the copolymer comprising the vinyl cyanide compound and the aromatic vinyl compound is preferably 0.2 to 1.0, more preferably 0.25 to 0.5 in terms of reduced viscosity. The ratio of the AS copolymer can be collected by a technique such as dissolving the ABS resin in a good solvent for the AS copolymer such as acetone and centrifuging the soluble component. On the other hand, the insoluble matter (gel) becomes a net ABS copolymer.

Further, the weight ratio (graft ratio) of the grafted vinyl cyanide compound and aromatic vinyl compound to the diene rubber component is preferably 20 to 200% by weight, more preferably 20 to 70% by weight.
As the diene rubber component forming this ABS resin, for example, a rubber having a glass transition point of 10 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and the ratio thereof is 100% by weight of the ABS resin component. It is preferably 5 to 39.9% by weight, more preferably 10 to 35% by weight, and still more preferably 10 to 25% by weight.

  In the ABS resin of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.3 to 3.0 μm, still more preferably 0.4 to 1.5 μm, and particularly preferably 0.4. ~ 0.9 μm. The rubber particle diameter distribution can be either a single distribution or a rubber having a plurality of peaks of two or more, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  This ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be one-stage copolymerization or multistage copolymerization. Furthermore, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method. In the suspension polymerization method, the aqueous phase and the monomer phase are maintained separately, and both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotational speed of the disperser, and the continuous production is performed. In the method, a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility to control the particle size.

(A-3 component: polyester resin)
Examples of the polyester resin of the present invention include polyethylene terephthalate (PET), cyclohexanedimethanol copolymerized PET, polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). Polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene isophthalate / terephthalate copolymer, polybutylene terephthalate / isophthalate copolymer, polyethylene naphthalate / terephthalate copolymer, And polybutylene naphthalate / terephthalate copolymer. Among them, polyethylene terephthalate (PET) is particularly preferable as an aromatic polyester resin.

  The polyethylene terephthalate of the present invention may contain a dicarboxylic acid component other than the terephthalic acid component as a copolymerization component. In the present invention, the description of “xx component” (“xx” represents the compound name) related to the structural unit of the A-3 component is a polymer derived from the compound “xx” or an ester-forming derivative thereof. Indicates the structural unit. For example, the dicarboxylic acid component refers to a structural unit derived from dicarboxylic acid or an ester-forming derivative thereof.

  Examples of such other dicarboxylic acid components include isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid. Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane Examples thereof include structural units derived from dicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid and the like. These dicarboxylic acid components can be used alone or in admixture of two or more. The dicarboxylic acid component other than the terephthalic acid component is preferably 30 mol% or less, more preferably 20 mol% or less, when the total amount of the dicarboxylic acid component is 100 mol%.

  Furthermore, the polyethylene terephthalate of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30 mol% in addition to the aromatic dicarboxylic acid component. Specific examples of the component include structural units derived from adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like.

  The polyethylene terephthalate of the present invention may contain a diol component other than the ethylene glycol component as a copolymer component. Examples of other diol components include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or -2,2,4,4. -Tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedi Examples include structural units derived from methanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), and the like. These can be used alone or in admixture of two or more.

  Further, polyethylene terephthalate obtained by slightly copolymerizing a polyethylene glycol component can be used as the diol component. The molecular weight of the polyethylene glycol component is preferably in the range of 150 to 6,000.

  The composition ratio of the polyethylene glycol component is preferably 5% by weight or less, more preferably 3% by weight or less, and still more preferably 2% by weight or less in 100% by weight of the diol component. On the other hand, the lower limit is preferably 0.5% by weight or more, and more preferably 1% by weight or more.

  Further, polyethylene terephthalate usually contains about 0.5 mol% or more of diethylene glycol component as a side reaction product during polymerization in 100 mol% of diol component, and such diethylene glycol component is preferably 6 mol% or less. 5 mol% or less is still more preferable.

  In the polyethylene terephthalate of the present invention, a terephthalic acid component and isophthalic acid in a polyethylene terephthalate / isophthalate copolymer (hereinafter sometimes abbreviated as TA / IA copolymer) in which a part of the terephthalic acid component is an isophthalic acid component. The ratio with the acid component is 70 to 99.9 mol%, preferably 75 to 99 mol%, more preferably 80 to 99 mol% of the terephthalic acid component when the total dicarboxylic acid component is 100 mol%. The isophthalic acid component is 0.1 to 30 mol%, preferably 1 to 25 mol%, more preferably 1 to 20 mol%.

  Further, the TA / IA copolymer contains 10 mol% or less, preferably 5 mol% or less of the aromatic dicarboxylic acid component such as naphthalenedicarboxylic acid other than the terephthalic acid component and isophthalic acid component, and adipic acid or the like. The aliphatic dicarboxylic acid component can be copolymerized in an amount of 5 mol% or less, preferably 3 mol% or less, and most preferably the dicarboxylic acid component consists of a terephthalic acid component and an isophthalic acid component. Further, the ethylene glycol component alone is most preferable as the diol component in the TA / IA copolymer, but a diol component other than ethylene glycol can be copolymerized.

  The ethylene glycol component and neo in the polyethylene / neopentyl terephthalate copolymer (hereinafter sometimes abbreviated as EG / NPG copolymer) in which part of the ethylene glycol component in the polyethylene terephthalate of the present invention is a neopentyl glycol component. The ratio with respect to the pentyl glycol component is 90 to 99 mol%, preferably 95 to 99 mol%, more preferably 97 to 99 mol% of the ethylene glycol component when the total diol component is 100 mol%. Moreover, a neopentyl glycol component is 1-10 mol%, Preferably it is 1-8 mol%, More preferably, it is 1-5 mol%. It is also possible to copolymerize diol components other than ethylene glycol and neopentyl glycol.

  In the EG / NPG copolymer, the aromatic dicarboxylic acid component such as isophthalic acid and naphthalenedicarboxylic acid other than the terephthalic acid component is 10 mol% or less, preferably 5 mol% or less, and the above-mentioned adipic acid or the like. The aliphatic dicarboxylic acid component can be copolymerized in an amount of 5 mol% or less, preferably 3 mol% or less, and the dicarboxylic acid component is most preferably a terephthalic acid component alone. It is also possible to copolymerize an aliphatic dicarboxylic acid component.

  About the manufacturing method of the polyethylene terephthalate used for this invention, according to a conventional method, the presence of the polycondensation catalyst containing titanium, germanium, antimony, etc. WHEREIN: The compound which induces | guides | derives a dicarboxylic acid component, and the said diol component are heated. This is carried out by polymerizing the compound to be induced and discharging the by-produced water or lower alcohol out of the system. As the polycondensation catalyst, a germanium-based polymerization catalyst is preferable, and examples thereof include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium dioxide, germanium hydroxide, Examples include germanium tetrachloride and tetramethoxygermanium. Other examples include insoluble catalysts such as antimony trioxide. In particular, a polyethylene terephthalate resin using a germanium-based polymerization catalyst is suitable for the purpose of the present invention, particularly for chemical resistance and thermal stability.

  Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventionally known polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like. The production method of polyethylene terephthalate can be either batch type or continuous polymerization type.

  The IV value of the polyethylene terephthalate resin used in the present invention is 0.45 to 0.57 dl / g, more preferably 0.47 to 0.55 dl / g, and most preferably 0.49 to 0.52 dl / g. When the IV value is high, the fluidity is lowered, and there is a problem that the effect of improving the chemical resistance is hardly exhibited. On the other hand, when the IV value is too low, the strength is greatly reduced and the thermal stability of the thermoplastic resin is lowered due to the large amount of terminal groups of the polyethylene terephthalate resin. In addition, the production of polyethylene terephthalate resin having a low IV value has a problem that pelletization is difficult because the thread is broken.

The IV value of the polyethylene terephthalate resin is a logarithmic viscosity value (IV value) measured at 25 ° C. in o-chlorophenol unless otherwise specified. That is, it is calculated from the solution viscosity measured at 25 ° C. after dissolving 1.2 g of polyethylene terephthalate resin in 15 cm ³ of o-chlorophenol with heating. Density of Polyethylene terephthalate resin obtained after the polycondensation reaction step is preferably 1.35~1.41g / cm ^3, more preferably 1.37~1.39g / cm ^3. In the present invention, the density of the polyethylene terephthalate resin is measured at a temperature of 23 ° C. by a density gradient tube method using a calcium nitrate solution in accordance with D method of JIS K7112.

  The amount of terminal carboxyl groups of the polyethylene terephthalate resin used in the present invention is 20 to 35 eq / ton, preferably 22 to 30 eq / ton, more preferably 23 to 28 eq / ton or less.

  The more preferable polyethylene terephthalate resin of the present invention satisfies that the content of dioxyethylene terephthalate units is in the range of 1.0 to 5.0 mol% (preferably 1.0 to 2.5 mol%). In this way, the polyethylene terephthalate resin obtained from the final polycondensation reactor is usually formed into granules (chips) by a melt extrusion molding method. Such a granular polyethylene terephthalate resin desirably has an average particle diameter of usually 2 to 5 mm (preferably 2.2 to 4 mm). For the polyethylene terephthalate resin of the present invention, it is preferable to use the granular polyethylene terephthalate resin that has undergone the liquid phase polycondensation process as it is.

  As the A-3 component polyethylene terephthalate resin, not only a virgin raw material but also a polyethylene terephthalate resin regenerated from a used product can be used. Particularly suitable polyethylene terephthalate resin can be used effectively because it is consumed in large quantities and its regeneration system has been established. Examples of the used products include containers represented by PET bottles and blisters, various films, and fibers.

(B component: S / M / B block copolymer)
The block copolymer of the B component of the present invention is a combination of S block (B-1 component), B block (B-2 component), and M block (B-3 component) which are three different polymer blocks. And a block copolymer comprising at least one bond unit selected from the group consisting of bond units SBM, MSBMSM, and MBSBM A block co-polymer consisting of only one linking unit preferably selected from the group consisting of linking units SBM, MSBMSM, and MBSMSBM. It is a block copolymer composed of a combination, and more preferably only a bond unit SBM. Here, for example, the bond units SBM, MSBMSM represent bond units in which the S block, the B block, and the M block are linearly bonded in this order. (The following notation of bond units follows this rule.) The S block is a polymer chain mainly composed of polystyrene, and the B block is a polymer chain mainly composed of poly (1,4-butadiene). , M block is a polymer chain mainly composed of polymethyl methacrylate.

  In this block copolymer, the block copolymer (component B) is 10 to 80% by weight of S block (component B-1), preferably 20 to 60% by weight for improving impact value at low temperature, and B block (B -2 component) 5-60% by weight, preferably 10-40% by weight for improving impact value at low temperature, and M block (B-3 component) 15-80% by weight, for improving impact value at low temperature Therefore, it is preferable that it is comprised by 30 to 60 weight%.

  Further, it is desirable that the S block (B-1 component) contains at least 80% by weight, preferably 95% by weight or more of polystyrene. The B block (B-2 component) is preferably polybutadiene, and at least 60%. Those containing polybutadiene of 95% by weight, preferably 95% by weight or more are desirable, and those containing at least 60% by weight, preferably 95% by weight or more of polymethyl methacrylate as the M block (component B-3) are desirable.

  Here, as the copolymer component other than the main component in each block, for example, o-methylstyrene, p-methylstyrene, ethylstyrene, dimethylstyrene and the like are mentioned for the S block, and ethylenepropylene, isoprene, Ethylene and the like can be mentioned, and regarding the M block, hydroxyethyl methacrylate, glycidyl methacrylate, siloxanyl methacrylate and the like can be mentioned.

  Further, it is preferable that the B block (component B-2) is incompatible with the thermoplastic resin (component A) and the S block (component B-1), and the glass transition temperature (TgB) is 0 ° C. or less. The M block (B-3 component) is incompatible with the thermoplastic resin (A component), the S block (B-1 component) and the B block (B-2 component), and the glass transition temperature (TgS) is It is preferably higher than the glass transition temperature (TgB) of the B block. In addition, Tg and compatibility means here Tg of resin comprised only with each block, and mutual compatibility. Moreover, Tg is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

The number average molecular weight of the block copolymer is preferably in the range of 3 × 10 ^{4 to} 5 × 10 ⁵ , and in the range of 8 × 10 ⁴ to 2 × 10 ^{5 in} order to improve the impact value at low temperature. It is more preferable. The number average molecular weight is a value measured by a terminal group quantification method.

(C component: rubbery polymer)
The rubbery polymer of component C is a glass transition temperature that is not a block copolymer of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and the rubber component content is 40% by weight. As mentioned above, it refers to a polymer comprising preferably 45% by weight or more of a rubber component, and a copolymer obtained by bonding other polymer chains to the polymer comprising the rubber component. The upper limit of the content of the rubber component is practically about 90% by weight.

  The rubber polymer is more preferably a copolymer formed by bonding other polymer chains. In the production of a rubbery polymer in which another polymer chain is grafted to a rubber component, it is widely known that not a few polymers or copolymers are not grafted on the rubber component. The component C of the present invention may contain such a free polymer or copolymer.

  More specifically, as the rubbery polymer of component C, SB (styrene-butadiene) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) copolymer MB (methyl methacrylate-butadiene) copolymer, ASA (acrylonitrile-styrene-acrylic rubber) copolymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) copolymer, MA (methyl methacrylate-acrylic rubber) copolymer MAS (methyl methacrylate-acrylic rubber-styrene) copolymer, methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, methyl methacrylate- , And the like Le silicone IPN rubber) copolymer. These copolymers are preferably core-shell type graft copolymers in which a polymer chain composed of the above monomer is bonded to a polymer core composed of a rubber component. Among these, at least one rubber polymer selected from the group consisting of SB copolymer, ABS copolymer, MBS copolymer, and methyl methacrylate- (acryl / silicone IPN rubber) copolymer is preferable.

  The rubber particle diameter of the rubber polymer is preferably 0.05 to 2 [mu] m, more preferably 0.1 to 1 [mu] m, and particularly preferably 0.1 to 0.5 [mu] m in weight average particle diameter. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  In the rubbery polymer of the graft copolymer, the weight ratio of the grafted component to the rubber substrate (graft ratio (% by weight)) is preferably 10 to 100%, more preferably 15 to 70%, still more preferably. 15-40%.

  Examples of the rubbery polymer of the present invention include various thermoplastic elastomers composed of a hard segment and a soft segment. Examples of such thermoplastic elastomers include polyester elastomers, polyurethane elastomers, styrene elastomers, and olefin elastomers.

(D component: inorganic filler)
The inorganic filler which is the component D of the present invention can be freely selected from fibrous, flake, spherical and hollow shapes, and is fibrous for improving the strength and impact resistance of the resin composition and dimensional stability. Flakes are preferred. For example, as the fibrous inorganic filler, glass fiber, carbon fiber, metal fiber, ceramic fiber, slag fiber, rock wool, zonotlite, wollastonite, and various whiskers (potassium titanate whisker, aluminum borate whisker, Boron whisker, basic magnesium sulfate whisker and the like) are exemplified, and examples of the flaky inorganic filler include glass flake, metal flake, graphite flake, smectite, kaolin clay, mica and talc. In addition, for example, a hollow filler such as a glass balloon may be crushed by melt-kneading with a resin to obtain an effect of improving rigidity in the same manner as a plate-like inorganic filler. The flaky filler of the present invention includes those that exhibit such effects. These inorganic fillers include those in which different materials are surface-coated. Typical examples of the different materials include metals, alloys, and metal oxides. A coating such as a metal or an alloy can impart high conductivity and may improve the design. In some cases, the metal oxide coating can provide functions such as photoconductivity, and the design can be improved.
In the present invention, mica, talc, and wollastonite are particularly suitable in terms of impact resistance, appearance, dimensional stability, cost, and the like.

(Mica)
As the average particle diameter of mica, the average particle diameter (D50 (median diameter of particle size distribution)) measured by a laser diffraction / scattering method is preferably 1 to 50 μm, more preferably 2 to 20 μm, still more preferably 2 10 μm can be used. If the average particle diameter of mica is less than 1 μm, the effect of improving the rigidity is not sufficient, and if it exceeds 50 μm, the rigidity is not sufficiently improved, and the mechanical strength such as impact characteristics is not significantly lowered. As the thickness of mica, a thickness measured by observation with an electron microscope is preferably 0.01 to 1 μm, more preferably 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. Mica may be a pulverized natural mineral or a synthetic product. The mica may be pulverized by either dry pulverization or wet pulverization. The dry pulverization method is more inexpensive and more common, while the wet pulverization method is effective for pulverizing mica more thinly and finely. As a result, the rigidity improvement effect of the resin composition becomes higher.

(talc)
In the present invention, talc is hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO2, 3MgO, 2H2O, and is usually a scaly particle having a layered structure. The composition is composed of 56 to 65% by weight of SiO2, 28 to 35% by weight of MgO, and about 5% by weight of H2O. As other minor components, Fe2O3 is 0.03 to 1.2% by weight, Al2O3 is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K2O is 0.2% by weight or less, Na2O contains 0.2 wt% or less. More preferable talc compositions include SiO2: 62 to 63.5 wt%, MgO: 31 to 32.5 wt%, Fe2O3: 0.03 to 0.15 wt%, and Al2O3: 0.05 to 0.25. % By weight and CaO: 0.05 to 0.25% by weight are preferred. Further, the loss on ignition is preferably 2 to 5.5% by weight.

  As for the particle diameter of talc, the average particle diameter measured by the sedimentation method is 0.1 to 50 μm (more preferably 0.1 to 10 μm, still more preferably 0.2 to 5 μm, particularly preferably 0.2 to 3.5 μm). ) Is preferable. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm 3) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

(Wollastonite)
The average fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and still more preferably 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the average fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. A filler to be measured for fiber diameter is randomly extracted from an image obtained by observation with an electron microscope, and the fiber diameter is measured near the center of each filler. The number average fiber diameter is calculated from the obtained measured value. The observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work). On the other hand, the measurement of average fiber length observes a filler with an optical microscope, calculates | requires individual length, and calculates a number average fiber length from the measured value. Observation with an optical microscope begins with the preparation of a dispersed sample so that the fillers do not overlap each other. Observation is performed under the condition of 20 times the objective lens, and the observed image is taken as image data into a CCD camera having about 250,000 pixels. From the obtained image data, the fiber length is calculated using a program for obtaining the maximum distance between two points of the image data using an image analysis apparatus. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurement is 500 or more (600 or less is suitable for work).

The wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible. It is preferable that the iron content in wollastonite is 0.5 wt% or less in terms of Fe2O3 by such magnetic separator processing. Wollastonite may be a pulverized natural mineral or a synthetic product.
The inorganic filler includes silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydride). ) And various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

(Ratio of each component)
It describes about the ratio of each component in this invention.
The ratio of the aromatic polycarbonate (A-1 component) to the ABS resin (A-2 component) or the polyester resin (A-3 component) in the A component is 100% by weight of the total A-1 component / A- 2 component or A-3 component is 10 to 100% by weight / 90 to 0% by weight, preferably 50 to 90% by weight / 50 to 10% by weight, more preferably 60 to 85% by weight / 40 to 15% by weight. . When the amount of the aromatic polycarbonate resin added is small, the impact resistance and heat resistance are insufficient.

  The mixing ratio of the thermoplastic resin (component A) and the block copolymer (component B) is 1 to 50% by weight of the B component with respect to 99 to 50% by weight of the A component, preferably 99 to 80% of the A component. The B component is 1 to 20% by weight with respect to the weight percent, and more preferably the B component is 1 to 10% by weight with respect to the A component 99 to 90% by weight. When the addition amount is small, the improvement in impact resistance at low temperatures is insufficient, and when it is too large, the heat resistance or rigidity is lowered.

  The addition amount of the rubber polymer (component C) is 1 to 45 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 7 parts by weight, based on 100 parts by weight of the thermoplastic resin (component A). It is. When the addition amount is small, the development of impact resistance tends to be insufficient, and when it is too large, the heat resistance or rigidity is lowered.

  The added amount of the inorganic filler (component D) is 1 to 70 parts by weight, preferably 5 to 40 parts by weight, more preferably 7 to 30 parts by weight, based on 100 parts by weight of the thermoplastic resin (component A). is there. When the addition amount is too large, the impact resistance is lowered, and further, the appearance of the molded product is lowered. When the addition amount is small, the effect of improving the rigidity, which is the main purpose of the addition, is not exhibited.

(Other ingredients)
Furthermore, the thermoplastic resin composition of the present invention includes a flame retardant, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), a char-forming compound (for example, a novolak type phenol) within the range satisfying the above characteristics. Resins, condensates of pitches and formaldehyde, etc.), nucleating agents (for example, sodium stearate and ethylene-sodium acrylate), anti-dripping agents (such as fluorinated polyolefins having fibril formation ability), thermal stabilizers, Antioxidants (for example, hindered phenol-based antioxidants and sulfur-based antioxidants), ultraviolet absorbers, light stabilizers, mold release agents, antistatic agents, foaming agents, flow modifiers, antibacterial agents Agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), lubricant, colorant, fluorescent brightener, phosphorescent pigment, fluorescent dye, infrared absorber, It can be blended like Tokuromikku agent.

(I) Thermal stabilizer It is preferable that various thermoplastic stabilizers are mix | blended with a thermoplastic resin composition. A phosphorus-based stabilizer is suitable as such a heat stabilizer. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Such phosphorus stabilizers can be used alone or in combination of two or more.

  Specifically, as the phosphite compound, for example, a trialkyl phosphite such as tridecyl phosphite, a dialkyl monoaryl phosphite such as didecyl monophenyl phosphite, a monoalkyl diaryl phosphite such as monobutyl diphenyl phosphite, Triaryl phosphites such as triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Such as diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Intererythritol phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4- Examples include cyclic phosphites such as (di-tert-butylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate. Triphenyl phosphate and trimethyl phosphate.

  Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite. Tetrakis (2,4-di-tert More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. An example of the tertiary phosphine is triphenylphosphine.

  The amount of the phosphorus stabilizer is preferably 0.0001 to 1% by weight, more preferably 0.0005 to 0.5% by weight, and more preferably 0.002 to 0% in 100% by weight of the thermoplastic resin composition of the present invention. More preferred is 3% by weight.

(Ii) Antioxidant An antioxidant may be blended in the thermoplastic resin composition. The antioxidant can improve the thermal stability and heat aging resistance during molding of the thermoplastic resin composition. Such an antioxidant is preferably a hindered phenol stabilizer. Examples of the hindered phenol stabilizer include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5 ′). -Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl } -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N′-hexamethylenebis- (3,5 Di-tert-butyl-4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis [ And methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane. All of these are readily available. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types. The blending amount of these antioxidants is preferably 0.0001 to 0.05% by weight in 100% by weight of the thermoplastic resin composition.

(Iii) Ultraviolet Absorber Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers. More specifically, for example, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl) Butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6-tert-butylphenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,2′-p-phenylenebis (3,1-benzoxazine-4 − ), And 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane Is exemplified. Further, hindered amine light stabilizers typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like Can also be used. The blending amount of the ultraviolet absorber and light stabilizer is preferably 0.01 to 1% by weight in 100% by weight of the thermoplastic resin composition.

(Iv) Mold Release Agent Examples of the mold release agent include olefin wax, silicone oil, fluorine oil, organopolysiloxane, ester of mono- or polyhydric alcohol and higher fatty acid, paraffin wax, beeswax and the like. Of these, esters of monohydric or polyhydric alcohols and higher fatty acids are preferred. The higher fatty acid preferably contains 60% by weight or more of a fatty acid having 17 or more carbon atoms (more preferably 17 to 32 carbon atoms, still more preferably 26 to 32 carbon atoms). As such a higher fatty acid, a higher fatty acid mainly composed of montanic acid is preferably exemplified. Such higher fatty acids are usually produced by oxidizing montan wax. On the other hand, examples of the monohydric alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol.

Examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin (such as decaglycerin), pentaerythritol, dipentaerythritol, trimethylolpropane, diethylene glycol, and propylene glycol. The alcohol component in the ester of a monohydric or polyhydric alcohol and a higher fatty acid is more preferably a polyhydric alcohol. Among these, glycerin, pentaerythritol, dipentaerythritol, and trimethylolpropane are preferable, and glycerin is particularly preferable.
The blending amount of the release agent is preferably 0.001 to 2% by weight, more preferably 0.005 to 1% by weight, still more preferably 0.01 to 1% by weight, in 100% by weight of the thermoplastic resin composition. Most preferably, it is 0.01 to 0.5 weight%.

(V) Antistatic agent Examples of the antistatic agent include polyether ester amide, glycerin monostearate, naphthalenesulfonic acid formaldehyde highly condensate alkali (earth) metal salt, dodecylbenzenesulfonic acid alkali (earth) metal salt, Examples include dodecylbenzenesulfonic acid ammonium salt, dodecylbenzenesulfonic acid phosphonium salt, maleic anhydride monoglyceride, and maleic anhydride diglyceride. The blending amount of the antistatic agent is preferably 0.01 to 10% by weight in 100% by weight of the thermoplastic resin composition.

(Vi) Flow modifier As the flow modifier, for example, a plasticizer (represented by, for example, phosphate ester, phosphate ester oligomer, phosphazene oligomer, fatty acid ester, aliphatic polyester, and aliphatic polycarbonate), high Other thermoplastic resins and thermoplastic oligomers having rigidity and high fluidity (for example, having a weight average molecular weight of less than 40,000 obtained by polymerizing at least one component selected from styrene, acrylonitrile, and polymethyl methacrylate) Polymers, represented by oligomers of high-rigidity polycarbonate, etc.), liquid crystal polymers (eg, represented by liquid crystal polyester, etc.), rigid molecules (eg, represented by poly-p-phenylene compounds, etc.), and lubricants (eg, minerals) Oil, synthetic oil, higher fatty acid ester, higher fatty acid amino acid And the like, and the like, and the like.
Such a flow modifier can be blended in an amount of 0.1 to 10% by weight, preferably 1 to 8% by weight, in 100% by weight of the thermoplastic resin composition.

(Vii) Flame retardant As the flame retardant, red phosphorus flame retardant represented by stabilized red phosphorus in which red phosphorus or the surface of red phosphorus is microencapsulated using a known thermosetting resin and / or inorganic material; Tetrabromobisphenol A, tetrabromobisphenol A oligomer, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene ether, polydibromophenylene ether , Halogenated flame retardants typified by decabromodiphenyl oxide bisphenol condensate and halogen-containing phosphate ester; triphenyl phosphate as monophosphate compound, reso as condensed phosphate ester Organic phosphate ester flame retardants typified by lucinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) and other pentaerythritol diphenyl diphosphates; polyphosphate ammonium salts, aluminum phosphates, aluminum phosphates, zirconium phosphates, etc. Represented by inorganic metal compound hydrates such as inorganic phosphate, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc metaborate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide, etc. Inorganic flame retardant: potassium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, potassium diphenylsulfone-3-sulfonate, diphenylsulfone-3,3′- Organic alkali (earth) metal salt flame retardant represented by potassium disulfonate; (poly) organosiloxane compound containing aryl group and alkoxy group, (poly) organosiloxane compound containing aryl group and Si-H group And silicone-based flame retardants typified by copolymers of (poly) organosiloxane and polycarbonate resin; phosphazene-based flame retardants typified by phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers.
Such a flame retardant can be blended in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, in 100% by weight of the thermoplastic material.

(Viii) Anti-dripping agent The anti-drip agent of the present invention prevents melt dripping during combustion and further improves flame retardancy. As the anti-drip agent, a fluorine-containing anti-drip agent is more suitable.
Examples of the fluorine-containing anti-dripping agent suitable as the anti-dripping agent include a fluorine-containing polymer having a fibril forming ability. / Hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.
Such an anti-dripping agent can be blended in an amount of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, in 100% by weight of the thermoplastic resin composition.

(Manufacture of thermoplastic materials)
Arbitrary methods are employ | adopted for preparation of the thermoplastic resin composition of this invention. For example, the method of premixing A component, B component, and another component, melt-kneading after that, and pelletizing can be mentioned. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the premixing, granulation can be performed by an extrusion granulator or a briquetting machine as necessary. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred.

  In addition, a method of supplying each component independently to a melt kneader represented by a twin screw extruder without premixing each component can also be employed. Moreover, after premixing some components, the method of supplying to a melt-kneader independently of the remaining components is mentioned. In particular, when an inorganic filler is blended, the inorganic filler is preferably supplied from a supply port in the middle of the extruder into the molten resin using a supply device such as a side feeder. The premixing means and granulation are the same as described above. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

  Furthermore, it is preferable that the moisture contained in the A component and the B component is small before melt kneading. Therefore, it is more preferable to melt-knead after drying either A component or B component, or both by methods, such as various hot air drying, electromagnetic wave drying, and vacuum drying. The vent suction during melt-kneading is preferably in the range of 1 to 60 kPa, preferably 2 to 30 kPa.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  The thermoplastic resin composition of the present invention exhibits unparalleled excellent impact resistance at low temperatures. Since it has high impact resistance even at low temperatures, it can be effectively used in a wide range of industrial fields such as the automobile field, OA equipment field, electronic / electric equipment field, building material field, agricultural material field, and fishery material field. The industrial effect is exceptional.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

(I) Raw material for thermoplastic material (component A-1)
PC-1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 22,400 produced from bisphenol A and phosgene (“Panlite L-1225WP” (trade name) manufactured by Teijin Chemicals Ltd.)
PC-2: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 19,700 produced from bisphenol A and phosgene (“Panlite L-1225WX” (trade name) manufactured by Teijin Chemicals Ltd.)
(A-2 component)
ABS: ABS resin pellet (manufactured by Nippon A & L Co., Ltd., Santac UT-61 (trade name))
(A-3 component)
PET1: Polyethylene terephthalate resin polymerized using a germanium compound polymerization catalyst having an IV value of 0.51 and a terminal carboxyl group amount of 26.3 eq / ton (manufactured by Teijin Chemicals Ltd., TR-MB (trade name))
PBT1: Polybutylene terephthalate having an IV value of 0.87 (manufactured by Polyplastics Co., Ltd., DURANEX 500FP (trade name))

(B component)
SBM1: Polystyrene / polybutadiene / polymethyl methacrylate block copolymer (manufactured by Arkema, A012 (trade name))
SBM2: Polystyrene / polybutadiene / polymethyl methacrylate block copolymer (manufactured by Arkema, A123 (trade name))
SBM3: Polystyrene / polybutadiene / polymethyl methacrylate block copolymer (manufactured by Arkema, A250 (trade name))
In addition, the used B component is a block copolymer comprised only by the bond unit SBM. Table 1 shows the weight percentage of each component of the S block, B block, and M block of the above three block copolymers.

(Other than B component)
SBM4: Butadiene / alkyl methacrylate / styrene copolymer (Rohm and Haas, BTA712 (trade name))
(C component)
IM1: Butadiene / alkyl acrylate / alkyl methacrylate copolymer (Rohm and Haas, Paraloid EXL2602 (trade name))
(D component)
WSN1: Wollastonite (manufactured by NYCO, NYGLOS4 (trade name))
(Other)
WAX: Acid-modified olefin wax comprising a copolymer of maleic anhydride and α-olefin (Diacarna PA30M (trade name) manufactured by Mitsubishi Chemical Corporation)
ST: Phosphorus stabilizer (Asahi Denka Kogyo Co., Ltd., ADK STAB PEP-8 (trade name))
TMP: Trimethyl phosphate (TMP (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)

(Manufacture of thermoplastic resin composition)
The compositions described in Tables 2 to 4 were produced by an extruder. As the extruder, a vent type twin screw extruder (Nippon Steel Works TEX30XSST) having a diameter of 30 mmφ was used. For the A component, the powdered one used a paddle dryer, and the pellet one used a hopper dryer, dried in advance at 120 ° C. for 4 hours or more, and charged from the main feeder. D component, WAX, PET1, and PBT1 were mixed in advance and charged from the side feeder using a weighing machine different from the A component. Other ingredients were pre-blended with a Henschel mixer in advance and charged from the main feeder. A vent was set at the 10th barrel, and suction was performed at a vacuum level of 6 kPa or less. Other extrusion conditions were a cylinder set temperature: 270 ° C., a die set temperature: 270 ° C., a discharge rate: 20 kg / hour, and a screw rotation speed: 165 rpm.

(How to create a test piece)
The produced thermoplastic resin pellets were dried by a hot air dryer at 120 ° C. for 4 hours, and Examples 1 and 2 and Comparative Example 1 were cylinders using a molding machine (manufactured by FANUC: T-150D) with a clamping force of 1470 kN. Molding was performed at a temperature of 280 ° C. and a mold temperature of 70 ° C., and molding was performed at a cylinder temperature of 270 ° C. and a mold temperature of 70 ° C. otherwise. The test piece shape used the test piece based on each specification.

(Characteristic evaluation of thermoplastic resin composition)
(I) High-speed surface impact test (unit: J): flat plate molded product having a length of 150 mm, a width of 150 mm, and a thickness of 2 mmt prepared according to the test piece preparation method described above (temperature after molding 23 ° C., relative humidity 50% RH) The energy (J) required to break through the sample was measured using a high-speed surface impact tester (Hydroshot HTM-1 manufactured by Shimadzu Corporation). . The test conditions are as follows. That is, in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH, two measurements at a substrate temperature of 23 ° C. and −30 ° C. are used as a measuring instrument for punching with a hemispherical tip and a radius of 6.35 mm (1/4 inch). A punch and a circular cradle having a radius of 12.7 mm (1/2 inch) were used, and the punching speed was 7 m / s. The measurement at −30 ° C. was performed as follows. A stainless steel container was prepared and filled with polyethylene beads. In addition, test specimens were embedded in such beads. This is in order to reduce the influence due to the bias of heat conduction. This stainless steel container was stored in a −30 ° C. freezer, and the test piece was set to −30 ° C. During the test, the test piece was quickly taken out from the freezer, mounted on an impact tester, and the test was conducted. It was confirmed by thermography that the test piece was tested at a temperature of approximately −30 ° C.
(Ii) Charpy impact strength (unit: kJ / m ² ): A test piece was prepared in accordance with the test piece preparation method shown above, and Charpy impact values (notched) at 23 ° C. and −30 ° C. in accordance with ISO 179 were obtained. It was measured.
(Iii) Elastic modulus (unit: MPa): A test piece was prepared according to the test piece preparation method described above, and the elastic modulus at 23 ° C. was measured in accordance with ISO178.
(Iv) Spiral flow: Archimedean spiral flow length (channel width 8 mm, channel thickness 2 mm) was measured (the injection molding machine uses “SG150U type” manufactured by Sumitomo Heavy Industries, Ltd.). The measurement was performed in Examples 1 and 2 and Comparative Example 1 at an injection pressure of 150 MPa and a cylinder of 300 ° C. Examples 3, 4 and 5 and Comparative Examples 2 and 3 were performed at an injection pressure of 100 MPa and a cylinder of 260 ° C. Examples 6, 7, and 8 and Comparative Examples 4 and 5 were performed at an injection pressure of 100 MPa and a cylinder temperature of 260 ° C.
(V) Load deflection temperature (unit: ° C.): A test piece was prepared according to the test piece preparation method described above, and the load deflection temperature was measured at a load of 0.45 MPa in accordance with ISO75.

  As shown in Examples 1 and 2, since the polycarbonate resin composition containing the B component increases the low-temperature Charpy impact, a linear triblock polymer containing three different components functions as an impact modifier. It has been shown. In Examples 3-5, injection molding can be easily performed by improving the fluidity by further including an ABS resin (evaluated by spiral flow). Moreover, it was shown that it is effective even when used in combination with other impact modifiers (component C).

  In automobile exterior parts, it is necessary to improve rigidity (elastic modulus) and appearance. When an inorganic filler (D component) is contained as shown in Comparative Examples 4 and 5 to improve the rigidity and appearance, the impact strength at low temperatures, particularly the value of high side impact, decreases. However, as shown in Examples 6 to 9, it can be seen that the high-speed surface impact at a low temperature is remarkably improved by containing SBM (component B).

  As described above, the thermoplastic resin composition of the present invention exhibits excellent impact resistance at low temperatures. Since it has high impact strength even at low temperatures, it can be effectively used in a wide range of industrial fields such as the automotive field, OA equipment field, electronic / electric equipment field, building materials field, agricultural material field, and fishery material field. The above effect is exceptional.

Claims (13)

  S / M / B block copolymer composed of S block mainly composed of polystyrene, B block mainly composed of poly (1,4-butadiene), and M block mainly composed of polymethyl methacrylate. (B component) 1-50% by weight and other thermoplastic resin (A component) 99-50% by weight, the S / M / B block copolymer is SBM, M- It is a block copolymer containing at least one bonding mode selected from the group consisting of S-B-S-M and M-B-S-B-M, and has excellent low temperature impact resistance Thermoplastic resin composition.   The S / M / B block copolymer (B component) is 10 to 80% by weight of S block (B-1 component), 5 to 60% by weight of B block (B-2), and M block (B- 3) The thermoplastic resin composition according to claim 1, comprising 15 to 80% by weight.   The thermoplastic resin composition according to claim 1 or 2, wherein the S block (component B-1) contains at least 80% by weight of polystyrene.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the B block (component B-2) contains at least 60% by weight of poly (1,4-butadiene).   The B block (component B-2) is incompatible with the thermoplastic resin (component A) and the S block (component B-1), and the glass transition temperature (TgB) is 0 ° C. or less. The thermoplastic resin composition in any one of Claims 1-4.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the M block (component B-3) contains at least 60% by weight of polymethyl methacrylate.   M block (B-3 component) is incompatible with thermoplastic resin (A component), S block (B-1 component) and B block (B-2 component), and its glass transition temperature (TgS) Is higher than the glass transition temperature (TgB) of B block, The thermoplastic resin composition in any one of Claims 1-6 characterized by the above-mentioned.   The thermoplastic resin (component A) is a polycarbonate resin (component A-1), a styrene unit component-containing resin (A-2 component) that is not a block copolymer with a rubber component content of less than 40% by weight, and a polyester resin (A The thermoplastic resin composition according to any one of claims 1 to 7, which is at least one thermoplastic resin selected from the group consisting of -3 components.   A rubbery polymer (C component) having a glass transition temperature of 0 ° C. or less and a rubber component content of 40% by weight or more is 1 to 45 wt. The thermoplastic resin composition according to any one of claims 1 to 8, which is contained in a part.   The thermoplastic resin composition according to any one of claims 1 to 9, comprising 1 to 70 parts by weight of an inorganic filler (D component) per 100 parts by weight of the total of the A component and the B component. The thermoplastic resin composition according to any one of claims 1 to 10, wherein the number average molecular weight of the S / M / B block copolymer (component B) is 3 x 10 ^{4 to} 5 x 10 ⁵ .   One in which the S / M / B block copolymer (component B) is selected from the group consisting of linking units SBM, MSBMS, and MBSMSBM. The thermoplastic resin composition according to any one of claims 1 to 11, comprising only one bonding unit.   The thermoplastic resin composition according to any one of claims 1 to 12, wherein the S / M / B-based block copolymer (component B) is composed of only the binding unit SBM.