JP5226326B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, it has high rigidity and high impact resistance by reinforcement with carbon fiber, has a low linear expansion coefficient in the fiber direction, has good crack resistance to heat cycles, and has a low linear expansion coefficient in the direction other than the carbon fiber direction. The present invention relates to an aromatic polycarbonate resin composition that gives a product.

  An aromatic polycarbonate resin is a thermoplastic resin having excellent mechanical properties such as impact strength, and a resin composition of an aromatic polycarbonate resin and a thermoplastic polyester such as polyethylene terephthalate resin or polybutylene terephthalate resin or an ABS resin is aromatic. As a material that maintains the excellent properties of aromatic polycarbonate resins and has improved chemical resistance, moldability, etc., which are disadvantages of aromatic polycarbonate resins, it is widely used in various applications such as the automotive field and OA field. .

  A method of blending a fibrous filler such as carbon fiber or glass fiber as a means for improving the rigidity or the like of the aromatic polycarbonate resin or a resin composition containing the aromatic polycarbonate resin as a main component (see Patent Documents 1 and 2) , A method of blending scale-like and plate-like inorganic fillers such as talc and mica (see Patent Documents 3, 4, and 5) is disclosed.

  However, in order to obtain further high rigidity and high impact resistance, it is necessary to have a processing technique for leaving carbon fibers in a molded product in a long shape. However, if the difference in expansion coefficient between the carbon fiber and the resin is large, the resin stress generated during cooling after thermoforming is large and remains as stress strain inside the resin. There was a problem that the sex became worse.

JP 54-94556 A JP-A-6-49344 JP 55-129444 A U.S. Pat. No. 4,280,949 JP-A-5-222283

  The object of the present invention is to have high rigidity and high impact resistance by reinforcement with carbon fiber, low linear expansion coefficient in the fiber direction, good crack resistance against heat cycle, and linear expansion coefficient other than carbon fiber direction. It is an object to provide an aromatic polycarbonate resin composition that gives a molded article with a small amount.

  As a result of intensive studies to achieve the above object, the present inventor has surprisingly found that relatively fine wollastonite particles satisfying a specific condition with an aspect ratio of a specific value or more and a fiber length. Has found that an aromatic polycarbonate resin composition containing carbon fibers having a specific value or more can achieve the above object, and has completed the present invention.

  The present invention relates to an aromatic polycarbonate resin (component A) 50 to 100% by weight and a thermoplastic polyester resin (component B-1) and a rubber component containing less than 40% by weight of a styrene unit component-containing resin (component B-2) ) The number average fiber length is 10 μm or less and the number average fiber diameter is 100 parts by weight of the resin component consisting of 0 to 50% by weight of the thermoplastic resin (component B) consisting of at least one resin selected from the group consisting of 1.5 μm or less, 5 to 80 parts by weight of wollastonite particles (component C) having an aspect ratio of 4.5 or more converted from the number average fiber length and the number average fiber diameter, and the number average fiber length of 1 mm or more. The present invention relates to an aromatic polycarbonate resin composition containing 10 to 100 parts by weight of carbon fiber (component D), and a molded product comprising the same.

Further, the present invention will be described in detail.
(Component A: aromatic polycarbonate resin)
The A component aromatic polycarbonate resin used in the present invention 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.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl). Phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) ), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3 -Isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4 Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) ) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis (4-hydroxyphenyl) -o-di Sopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) ) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′- Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or in admixture of two or more.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3- Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl)- A homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferred. In particular, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane Sphenol A, a copolymer with 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used. .

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melt transesterification method, catalyst, terminal terminator, dihydric phenol antioxidant, etc., as necessary May be used. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  Examples of the trifunctional or higher polyfunctional aromatic compounds include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2. , 4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1- Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4- Hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof may be mentioned. Among them, 1,1,1-tris ( 4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When a polyfunctional compound that produces such a branched polycarbonate resin is included, the ratio is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.01, based on the total amount of the aromatic polycarbonate. -0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may be generated as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. A content of 5 mol%, particularly preferably 0.01 to 0.3 mol% is preferred. Such a ratio can be calculated by ¹ H-NMR measurement.

  The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.

The molecular weight of the polycarbonate resin is not specified, but if the molecular weight is less than 1 × 10 ⁴ , the high temperature characteristics and the like are lowered, and if it exceeds 4 × 10 ⁴ , the moldability is lowered. 1 × 10 ⁴ to 4 × 10 ⁴ is preferable, 1.4 × 10 ^{4 to} 3 × 10 ⁴ is more preferable, and 1.6 × 10 ^{4 to} 2.5 × 10 ⁴ is more preferable. is there.

  Two or more aromatic polycarbonate resins may be mixed. In this case, it is naturally possible to mix with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range.

In particular, a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ has characteristics derived from its high entropy elasticity (drip prevention characteristics, drawdown characteristics, and characteristics that improve melting characteristics such as jetting improvement). This is preferable when these characteristics are required. More preferably, it is a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight of 8 × 10 ⁴ or more, and further preferably a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight of 1 × 10 ⁵ or more. That is, the one that can observe the molecular weight distribution of two or more peaks by a measuring method such as GPC (gel permeation chromatography) can be preferably used.

The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _SP ) 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.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(B component: at least one thermoplastic resin selected from the group consisting of a thermoplastic polyester resin and a rubber component containing a styrene unit component containing less than 40% by weight)
The B component of the present invention is at least one selected from the group consisting of a thermoplastic polyester resin (B-1 component) and a styrene unit component-containing resin (B-2 component) whose rubber component content is less than 40% by weight. It is a thermoplastic resin containing the thermoplastic resin.

  The reason is as follows. (I) The molding temperature can be lowered. Thereby, the molecular weight fall of aromatic polycarbonate resin by reaction with wollastonite can be suppressed. As a result, good recycling characteristics can be achieved. (Ii) The B-1 component and the B-2 component do not significantly impair the heat resistance and impact resistance expected of the aromatic polycarbonate resin. (Iii) The B-1 component and the B-2 component have good thermal stability of the polymer blend with the aromatic polycarbonate resin.

  The thermoplastic polyester resin used as the B-1 component of 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.

  The aromatic dicarboxylic acid here is 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, and 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. .

  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 aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic rings such as 2,2-bis (β-hydroxyethoxyphenyl) propane 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, a copolymer polyester 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.

  With respect to the method for producing such an aromatic polyester resin, according to a conventional method, in the presence of a polymerization catalyst containing titanium, germanium, antimony or the like, the dicarboxylic acid component and the diol component are polymerized while heating, and water produced as a by-product. Alternatively, the lower alcohol is discharged out of the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. Can be illustrated.

  Preferred examples of the polymerization catalyst for the organic titanium compound include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitic acid, and a reaction product of tetrabutyl titanate and trimellitic anhydride. Can be mentioned. The amount of the organic titanium compound used is preferably such that the titanium atom is 3 to 12 mg atomic% with respect to the acid component constituting the polybutylene terephthalate.

  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 Such a catalyst can be deactivated and polycondensed with an acid compound or the like.

The production method of the aromatic polyester resin can be either a batch method or a continuous polymerization method.
The molecular weight of the aromatic polyester resin is not particularly limited, but the intrinsic viscosity measured at 35 ° C. using o-chlorophenol as a solvent is 0.4 to 1.5, preferably 0.45 to 1.2, and more preferably. 0.5 to 1.15.

  The styrene unit component-containing resin having a rubber component content of less than 40% by weight used as the B-2 component in the present invention is a styrene monomer and other vinyl monomers copolymerizable with these if necessary. A styrene unit component-containing resin having a rubber component content of less than 40% by weight, obtained by polymerizing at least one selected from the group consisting of a body and a rubber component.

  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 epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide , 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 B-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 / butadiene・ Styrene copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / styrene / acrylic rubber copolymer (ASA resin), acrylonitrile / ethylene propylene rubber / styrene copolymer Polymer (AES resin), styrene / methyl methacrylate copolymer (MS resin), methyl methacrylate / acrylonitrile / styrene copolymer (MAS resin), styrene / maleic anhydride copolymer (SMA resin) and styrene / IPN type rubber Examples thereof include a resin such as a copolymer, 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), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), one or more selected from the group consisting of methyl methacrylate / butadiene / styrene copolymer (MBS resin) Preferably, ABS resin, ASA resin, and AES resin are most preferable.

  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 calculated 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.

  Examples of the vinyl cyanide compound grafted onto the diene rubber component include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound grafted onto the diene rubber component, those described above can be used in the same manner, but styrene and α-methylstyrene are particularly preferably used. The proportion of the component grafted to the diene rubber component is preferably 60.1 to 95% by weight, more preferably 65 to 90% by weight, and further preferably 75 to 90% by weight in 100% by weight of the ABS resin component. . Further, the vinyl cyanide compound is 5 to 50% by weight, preferably 10 to 30% by weight, and the aromatic vinyl compound is 95 to 50% by weight with respect to 100% by weight of the total amount of the vinyl cyanide compound and aromatic vinyl compound. , Preferably 90 to 70% by weight. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for some of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally well-known various things can be used for the initiator, chain transfer agent, emulsifier, etc. which are used by reaction as needed.

  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.

  The ASA resin used in the present invention is a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to an acrylic rubber component, or the thermoplastic graft copolymer, a vinyl cyanide compound and an aromatic resin. A mixture with a copolymer of a group vinyl compound. The acrylic rubber referred to in the present invention contains an alkyl acrylate unit having 2 to 10 carbon atoms, and further contains styrene, methyl methacrylate, butadiene as other copolymerizable components as necessary. Also good. Preferred examples of the alkyl acrylate having 2 to 10 carbon atoms include 2-ethylhexyl acrylate and n-butyl acrylate. The alkyl acrylate is preferably contained in an amount of 50% by weight or more in 100% by weight of the acrylate rubber. Further, the acrylate rubber is at least partially crosslinked, and examples of the crosslinking agent include ethylene glycol diacrylate, butylene glycol diacrylate, ethylene glycol dimethacrylate, allyl methacrylate, polypropylene glycol diacrylate, and the like. The crosslinking agent is preferably used in an amount of 0.01 to 3% by weight based on the acrylate rubber. The proportion of the acrylic rubber component 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 100% by weight of the ASA resin.

  The proportion of the vinyl cyanide compound and the aromatic vinyl compound is 5 to 50% by weight of the vinyl cyanide compound and 95 to 50% by weight of the aromatic vinyl compound with respect to the total amount of 100% by weight. It is preferable that the vinyl compound is 15 to 35% by weight and the aromatic vinyl compound is 85 to 65% by weight. As the production method, the same one as the above ABS resin can be used.

  The AES resin used in the present invention is a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound on an ethylene-propylene rubber component or an ethylene-propylene-diene rubber component, or the thermoplastic graft copolymer. And a mixture of a vinyl cyanide compound and a copolymer of an aromatic vinyl compound. As the production method, the same one as the above ABS resin can be used.

The thermoplastic resin composed of the A component and the B component has a melt viscosity measured by a capillary rheometer at 260 ° C. in the range of 0.1 × 10 ^{3 to} 5 × 10 ³ Pa · s at a shear rate of 300 sec ^−1. Preferably, it is more preferably in the range of 0.3 × 10 ^{3 to} 2 × 10 ³ Pa · s, and most preferably in the range of 0.3 × 10 ^{3 to} 1.5 × 10 ³ . By using specific wollastonite particles, the aromatic polycarbonate resin composition of the present invention can achieve good surface appearance and recyclability even for resins in such a range of conditions.

(C component: wollastonite particles)
The wollastonite particles as component C of the present invention have a number average fiber length of 10 μm or less, a number average fiber diameter of 1.5 μm or less, and a number average fiber length and a number average fiber diameter obtained by the following measurement method. It has a particle shape characteristic with a calculated aspect ratio of 4.5 or more.

  The method for measuring the fiber length and fiber diameter is as follows. The fiber length is measured by observing wollastonite particles as a raw material with an optical microscope, obtaining the length of each wollastonite, and calculating the number average fiber length from the measured value. Incidentally, most of the wollastonite particles have a fibrous form even when finely pulverized due to the characteristics derived from the crystal structure.

  Observation with an optical microscope is performed by first preparing a sample dispersed so that wollastonite particles do not overlap each other. Such observation is performed under the condition that the objective lens is 20 times, and the observed image is captured as image data into a CCD camera having about 250,000 pixels. The obtained image data is calculated using a program for obtaining the maximum distance between two points of the image data using an image analysis device. Under such conditions, the size per pixel corresponds to a length of 1.25 μm. Therefore, the minimum fiber length to be measured is 1.25 μm. The number of measurement is 5000 or more.

  On the other hand, the fiber diameter is measured by observing wollastonite particles as a raw material of the composition with an electron microscope, obtaining the fiber diameter of each wollastonite particle, and calculating the number average fiber diameter from the measured value. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level.

  For the fiber diameter, wollastonite for which the fiber diameter is to be measured is randomly extracted from an image obtained by observation with an electron microscope, and the fiber diameter is measured near the center. If the cross section is not a circle, the maximum value is the fiber diameter. The number average fiber diameter is calculated from the obtained measured value. Since recent electron microscopes have a function of calculating the length on the observation screen, the fiber diameter can be calculated relatively easily. The observation magnification is about 1,000 times, and the number of measurement is 1,000 or more.

The aspect ratio of the wollastonite particles is calculated by dividing the number average fiber length calculated by the above method by the number average fiber diameter.
As a pulverizer for pulverizing C component wollastonite so as to satisfy the above-mentioned conditions of the particle shape characteristics, various types can be used, for example, a high-speed rotating mill, a ball mill, a medium stirring mill, a jet mill, etc. Can be mentioned. Among these, a jet mill is preferable. Furthermore, examples of such a jet mill system include an air current suction type, a nozzle suction type, a collision object collision type, a counter jet collision type, and a composite type. Among these, a counter jet collision type pulverizer is preferable.

  Furthermore, it is preferable to classify the pulverized wollastonite particles to remove components having a long fiber length to obtain the desired wollastonite particles. Such classification methods include mesh type sieves, impactor type inertial force classifiers (variable impactors, etc.), Coanda effect type inertial force classifiers (elbow jets, etc.), spiral airflow type centrifugal fields Classifiers (multistage cyclones, etc.), helical airflow type centrifugal field classifiers with free vortex type and guide vanes (microplex, dispersion separator, etc.), helical airflow type centrifugal field classifiers, forced vortex type Classification chamber rotating type (Accucut, turbo classifier, etc.) and helical airflow type centrifugal field classifier, forced vortex type, rotating blade type (micron separator, super separator, etc.) In addition, use of these composite types is also preferable (note that the names in parentheses are trade names or common names) That). Of these, a centrifugal field classifier is preferred as a means for enabling classification of finer particles.

Wollastonite particles can be obtained by pulverizing and classifying natural white minerals having needle-like crystals mainly composed of calcium silicate. Due to this crystal structure, the pulverized mineral also has a fibrous form. Of course, synthesized wollastonite can also be used in the present invention. These wollastonites are substantially represented by the chemical formula CaO.SiO ₂ and contain about 50 wt% SiO ₂ , about 47 wt% CaO, and other impurities such as Fe ₂ O ₃ , Al ₂ O ₃ , CaCO _3. The specific gravity is known to be about 2.9.

The number average fiber length is preferably 1 to 10 μm, more preferably 2 to 9 μm, and further preferably 2 to 8 μm.
The number average fiber diameter is preferably 0.2 to 1.5 μm, more preferably 0.3 to 1.3 μm, and even more preferably 0.5 to 1.2 μm. A number average fiber length of 3 μm or more is advantageous in terms of rigidity and strength.

  Furthermore, the aspect ratio is preferably 4.5 or more and less than 50, more preferably 5 or more and less than 30. A higher aspect ratio is preferable, but wollastonite obtained by pulverizing natural minerals having an aspect ratio of 50 or more is technically difficult to achieve at present.

  The wollastonite particles may be those subjected to surface treatment with a usual surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent. As such a silane coupling agent, an epoxy silane coupling agent can be preferably mentioned. A mixture of polyalkoxysiloxane and epoxy silane coupling agent and / or a reaction product of polyalkoxy siloxane and epoxy silane coupling agent can also be preferably used. It is possible to use wollastonite particles surface-treated with these silane coupling agents.

(D component: carbon fiber)
The D component of the present invention is a carbon fiber having a number average fiber length of 1 mm or more obtained by the following measurement method. The method for measuring the fiber length is as follows. That is, the fiber length is measured by visually observing the carbon fiber, obtaining the length of each carbon fiber, and calculating the number average fiber length from the measured value. In addition, the measuring method shall be 300 or more. The fiber length is preferably 3 mm or more. If the fiber length is less than 1 mm, the impact value is significantly reduced. Moreover, 5-15 micrometers is preferable, as for the several fiber diameter obtained by the following measuring methods of this carbon fiber, 6-8 micrometers is more preferable, and 6.5-7.5 micrometers is more preferable. Aggregation tends to occur when the fiber diameter is less than 5 μm, and breakage tends to occur when the fiber diameter is greater than 15 μm. The method for measuring the fiber diameter is as follows. The fiber diameter is obtained by randomly extracting carbon fibers to be measured with respect to an image obtained by observation with an electron microscope, and measuring the fiber diameter near the center. If the cross section is not a circle, the maximum value is the fiber diameter. The number average fiber diameter is calculated from the obtained measured value. Since recent electron microscopes have a function of calculating the length on the observation screen, the fiber diameter can be calculated relatively easily. The observation magnification is about 1,000 times, and the number of measurement is 1,000 or more.
The carbon fiber of the D component may be either a bread type or pitch type carbon fiber, but generally a bread type is often used.

(Composition of each component)
The composition ratios of the A component, the B component, the C component, and the D component are as follows. Of the total 100% by weight of component A and component B, the component A is 50 to 100% by weight, preferably 50 to 95% by weight, more preferably 60 to 90% by weight. The B component is 0 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the A component is less than 50% by weight of the total of 100% by weight of the A component and the B component, the heat resistance, impact strength and the like are lowered, which is not preferable.

  Component C is 5 to 80 parts by weight, preferably 15 to 60 parts by weight, more preferably 15 to 40 parts by weight, and still more preferably 20 to 30 parts by weight with respect to 100 parts by weight of the resin composition. If the content of the C component wollastonite particles is less than 5 parts by weight, the coefficient of linear expansion becomes large and sufficient dimensional stability cannot be achieved, and if it exceeds 80 parts by weight, impact strength, appearance, etc. are reduced. It is not preferable.

  D component is 10-100 weight part with respect to 100 weight part of said resin components, Preferably it is 15-80 weight part, More preferably, it is 17-70 weight part, More preferably, it is 20-60 weight part. If the content of the carbon fiber of component D is less than 10 parts by weight, high rigidity and impact resistance are insufficient, and if it exceeds 100 parts by weight, quality differences such as mechanical properties and appearance due to molding conditions become large.

  According to the present invention, by using the wollastonite particles having the above specific shape and the carbon fiber having a fiber length of a specific value or more, the carbon fiber is reinforced with high rigidity and high impact resistance, and in the fiber direction. It is possible to provide an aromatic polycarbonate resin composition that has a low coefficient of linear expansion, good crack resistance to heat cycles, and gives a molded product having a low coefficient of linear expansion other than in the direction of carbon fibers.

(E component: impact modifier)
In order to further improve the impact strength and the like of the aromatic polycarbonate resin composition obtained in the present invention, an impact modifier can be used as the E component.
Such an impact modifier contains 40% or more of a rubber component, and in this respect, it is clearly distinguished from the ABS resin of the B component of the present invention.

  As an E component impact modifier usable in the present invention, a rubber component having a glass transition temperature of 10 ° C. or lower, aromatic vinyl, vinyl cyanide, acrylate ester, methacrylate ester, and copolymerizable with these And a graft copolymer obtained by copolymerizing one or more monomers selected from various vinyl compounds.

  Moreover, the rubber component and the block copolymer of the said monomer are also mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomers (hydrogenated styrene / isoprene / styrene elastomers) and hydrogenated styrene / butadiene / styrene elastomers.

  Furthermore, various elastic polymers known as other thermoplastic elastomers such as polyurethane elastomers, polyester elastomers, polyether amide elastomers and the like can also be used.

  As the rubber component having a glass transition temperature of 10 ° C. or less, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicon composite rubber, isobutylene-silicon composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber , Ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicon rubber, epichlorohydrin rubber, fluororubber, and those obtained by adding hydrogen to these unsaturated bonds.

  Among them, impact modifiers containing a rubber component having a glass transition temperature of −10 ° C. or lower, more preferably −30 ° C. or lower are preferable. Particularly, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicon composite rubber are used. Preferred impact modifiers are preferred. The composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure entangled with each other so as not to be separated.

  Examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, and styrene is particularly preferable. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, etc., and examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, methacrylic acid. Examples thereof include butyl, cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable.

  The impact modifier containing a rubber component having a glass transition temperature of 10 ° C. or lower may be produced by any polymerization method of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and is a copolymerization method. May be a single-stage graft or a multi-stage graft. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient. 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 individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation 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.

  Such impact modifiers are commercially available and can be easily obtained. For example, as a rubber component having a glass transition temperature of 10 ° C. or less, butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber is mainly used as Kane Ace B series of Kaneka Chemical Industry Co., Ltd., Mitsubishi Rayon Co., Ltd. Examples include METABLEN C series, Kureha Chemical Industry's EXL series, HIA series, BTA series, KCA series, Ube modifier resin series UCL modifier resin series, and acrylic as a rubber component with a glass transition temperature of 10 ° C or less. -As what mainly has a silicon composite rubber, what is marketed by Mitsubishi Rayon Co., Ltd. by the brand name of Metablen S-2001 or SRK-200 is mentioned.

  The composition ratio of the E component is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, and still more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the total of the A component and optionally the B component. It is. When the proportion of the impact modifier of the E component exceeds 50 parts by weight, the heat resistance and the appearance are deteriorated.

(F component: other thermoplastic resin)
The aromatic polycarbonate resin composition of the present invention can contain a thermoplastic resin (F component) other than the A component and the B component. Examples of such thermoplastic resins include polyamide resins, acrylic resins, and polyolefin resins such as polyethylene resins and polypropylene resins. Furthermore, engineering plastics such as polyphenyl ether and polyacetal, polyether ether ketone, polyether imide, polyether amide, polysulfone, polyether sulfone, and so-called super engineering plastics are included.
The composition ratio in the case of adding the F component is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight per 100 parts by weight of the resin component comprising the A component and optionally the B component.

(G component: flame retardant)
If necessary, the aromatic polycarbonate resin composition of the present invention may further contain a flame retardant in an amount that does not impair the object of the present invention.
Although it does not restrict | limit especially as a flame retardant (G component) which can be used for the aromatic polycarbonate resin composition of this invention, Halogenated bisphenol A polycarbonate type flame retardant, organic salt type flame retardant, aromatic phosphorus An acid ester flame retardant, a halogenated aromatic phosphate ester type flame retardant, or the like can be used, and one or more of them can be blended.

  Specifically, the polycarbonate-type flame retardant of halogenated bisphenol A is a polycarbonate-type flame retardant of tetrachlorobisphenol A, a polycarbonate-type flame retardant of tetrachlorobisphenol A and bisphenol A, a polycarbonate-type flame retardant of tetrabromobisphenol A, A copolymer polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A.

  Specifically, the organic salt flame retardants are dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, Potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, Perfluorobutane sulfonate potassium, sodium lauryl sulfate or Potassium hexadecyl sulfate, sodium or potassium.

  Specifically, the halogenated aromatic phosphate ester type flame retardant is tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, etc. is there.

  Specifically, aromatic phosphate ester flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′- Biphenol bis (dixylenyl phosphate), bisphenol A bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4'-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl) Phosphate), aromatic polyphosphates whose aromatic ring source is resorcin and phenol and does not contain phenolic OH groups, aromatic polyphosphates whose aromatic ring source is resorcin and phenol and contain phenolic OH groups Phosphate, aromatic polyphosphates whose aromatic ring source is hydroquinone and phenol and not containing phenolic OH groups, aromatic polyphosphates containing similar phenolic OH groups, ("aromatic polyphosphates" shown below are phenolic Aromatic polyphosphates with aromatic ring sources of bisphenol A and phenol, and aromatic ring sources of resorcinol and 2,6-xylenol. And aromatic polyphosphates whose aromatic ring source is hydroquinone and 2,6-xylenol, aromatic polyphosphates whose aromatic ring source is bisphenol A and 2,6-xylenol, and the like.

  Among these flame retardants, the polycarbonate type flame retardant of halogenated bisphenol A is preferably a polycarbonate type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate of tetrabromobisphenol A and bisphenol A, and more preferably tetrabromobisphenol A. Polycarbonate flame retardants are preferred. As the organic salt flame retardant, potassium perfluorobutane sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate are preferable. As the aromatic phosphate ester flame retardant, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcinol bis (dixylenyl phosphate), and bisphenol A bis (diphenyl phosphate) are preferable.

  Other flame retardants include halogenated flame retardants such as brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated polystyrene, brominated polystyrene, brominated polyphenylene ether, polydibromophenylene ether, red phosphorus or The red phosphorus surface contains a red phosphorus flame retardant represented by stabilized red phosphorus, which is microencapsulated with a known thermosetting resin and / or inorganic material, a phenyl group, a vinyl group and a methyl group (poly ) Silicone-type flame retardants represented by organosiloxane compounds and copolymers of (poly) organosiloxane and polycarbonate resins, and phosphazene polymer-type flame retardants represented by phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers. It can be mentioned.

  Among the above flame retardants, the 5% weight loss temperature when the temperature is increased from 23 ° C. to 600 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen atmosphere by TGA (Thermogravimetric Analysis) is 300 ° C. or more. An aromatic phosphate ester flame retardant can be cited as a preferred embodiment.

  These flame retardants have a plasticizing effect on the aromatic polycarbonate resin. Therefore, the breakage of the wollastonite particles during melt kneading is further suppressed. Further, since the transferability at the time of molding is improved, it is effective for reducing the occurrence of convex foreign matter. Further, those satisfying the above-mentioned weight reduction temperature condition have good thermal stability. Therefore, even when melt-kneaded repeatedly, there is little volatilization from the resin composition and thermal decomposition of itself. Furthermore, the hydrolyzability (moisture and heat resistance) of the aromatic polycarbonate resin resulting from the hydrolysis of the aromatic phosphate ester flame retardant is greatly improved by the combined use effect with the wollastonite particles. As a result, a resin composition with good recyclability is achieved by the above effect.

  When G component is added, the blending amount is preferably 0.001 to 20 parts by weight, more preferably 0.005 to 18 parts by weight per 100 parts by weight of the total of A component and optionally B component, 0.01 More preferred is ˜15 parts by weight.

(H component: polytetrafluoroethylene having fibril-forming ability)
The aromatic polycarbonate resin composition of the present invention can contain, as an H component, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) having fibril forming ability mainly for the purpose of further improving the flame retardancy.

  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. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. 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 Industries, Ltd., and the like. Commercially available PTFE aqueous dispersions include Fullon AD-1 and AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd., Polyflon D-1 and D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation. As a commercial product of PTFE in a mixed form, there can be mentioned “Metablene A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX 449” (trade name) manufactured by GE Specialty Chemical Co., Ltd.

  When H component is added, the amount of PTFE is preferably 0.05 to 3 parts by weight, more preferably 0.08 to 1.5 parts per 100 parts by weight of the total of A component and optionally B component. Part by weight, more preferably 0.1 to 1.0 part by weight.

(Other additives)
The aromatic polycarbonate resin composition of the present invention may contain a small amount of an inorganic filler or a heat-resistant organic filler in addition to the component C of the present invention.
Examples of the inorganic filler include fiber fillers such as glass fiber (chopped strand), carbon fiber, metal fiber, zonotlite, potassium titanate whisker, aluminum borate whisker, basic magnesium sulfate whisker, talc, mica, and glass flakes. , Platy fillers such as graphite flakes, short glass fibers (milled fibers), short carbon fibers, glass beads, glass balloons, ceramic balloons, carbon beads, silica particles, titania particles, alumina particles, kaolin, clay, calcium carbonate, Various particulate fillers such as titanium oxide, cerium oxide, zinc oxide, and the above-mentioned various inorganic fillers are represented by gold, silver, nickel, copper, chromium, aluminum, etc. by methods such as plating, vapor deposition and sputtering. Various metals, titanium oxide, Iron, tin oxide, zirconium oxide, and inorganic filler coated with a metal oxide typified by cerium oxide.

  The heat-resistant organic filler means a material that does not melt at the molding processing temperature of the aromatic polycarbonate resin that is the component A of the present invention. Such fillers include fibrous fillers such as aramid fibers and polyarylate fibers, and aramid powders. And particulate fillers such as polytetrafluoroethylene powder, phenol resin particles, crosslinked styrene particles, and crosslinked acrylic particles.

  The aromatic polycarbonate resin composition of the present invention may contain a phosphorus-based heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent, a foaming agent, a dye / pigment, and the like. However, it is particularly preferable to include a phosphorus-based heat stabilizer.

  Examples of phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, trisnonylphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite Phyto, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert) -Butyl fluoride Nyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, phosphite compounds, tributyl phosphate, trimethyl phosphate, tri Cresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, phosphate compounds such as diisopropyl phosphate, and other Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphos as a phosphorus heat stabilizer Knight, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, Examples thereof include phosphonite compounds such as bis (2,4-di-tert-butylphenyl) -4-biphenylenephosphonite.

  Of these, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphate, trimethylphosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4 '-Biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenephosphonite are preferred.

  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, more preferably 0.002 to 100 parts by weight of the total of the A component and optionally the B component. -0.3 parts by weight is more preferred.

  Further, among the above, when the resin component is a resin component comprising an aromatic polycarbonate resin (A component) and a thermoplastic polyester resin (B-1 component), distearyl pentaerythritol diphosphite, bis (2,4- Pentaerythritol diphosphite compounds such as di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are preferred.

  The preferred reason is as follows. The resin component composed of the A component and the B-1 component is liable to cause a decrease in the molecular weight of the aromatic polycarbonate resin of the A component due to a transesterification reaction between the A component and the B-1 component during melt kneading. Further, such transesterification is facilitated by the presence of a silicate filler such as wollastonite. Pentaerythritol diphosphite compounds are more susceptible to hydrolysis than other phosphite compounds. The acid component produced by such hydrolysis suppresses the transesterification reaction promoting effect of the wollastonite, and a good aromatic polycarbonate resin composition with less molecular weight reduction is achieved.

  The composition ratio of the pentaerythritol diphosphite compound is preferably 0.005 to 1 part by weight, more preferably 0.05 to 1 part by weight per 100 parts by weight of the total of the component A and the component B-1.

  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], penta Erythritol-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-tert-butyl-4- Roxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-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-tetraoxaspiro (5,5 ) Undecane and the like. The blending amount of these antioxidants is preferably 0.0001 to 1 part by weight with respect to 100 parts by weight as a total of the A component and optionally the B component.

  Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers typified by 2,2′-dihydroxy-4-methoxybenzophenone and, for example, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5. -Chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethyl Butyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and 2- (3 , 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole is exemplified by benzotriazole-based ultraviolet absorbers. The 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. Furthermore, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-bis (2,4-dimethylphenyl) -1,3, Hydroxyphenyltriazine compounds such as 5-triazin-2-yl) -5-hexyloxyphenol can also be used. The blending amount of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight as a total of the component A and optionally the component B.

  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, it is also possible to blend a release agent 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 mold release agent is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight as a total of the A component and optionally the B component.

(Production method of resin composition)
Arbitrary methods are employ | adopted in order to manufacture the thermoplastic resin composition of this invention. For example, there can be mentioned a method of premixing components A to D and optionally other components, and then melt-kneading and pelletizing. Examples of the premixing means include a tumbler, a V-type blender, a Henschel mixer, a Nauta mixer, a ribbon mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt kneaded with a melt kneader typified by a vent type twin screw extruder and pelletized with a device such as a pelletizer.

  In addition, it is possible to adopt a method in which the A component to the D component and optionally other components are independently supplied to a melt-kneader represented by a twin screw rudder. In addition, there is a method in which a part of the components A to D and optionally other components are premixed and then supplied to the melt-kneader independently of the remaining components. For example, the method of supplying C component independently from the middle of an extruder using a side feeder is mentioned. 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. Further, when a compound having a relatively low melting point such as an aromatic phosphate ester flame retardant is supplied, a method of heating it to a liquid state and supplying it to a melt kneader by a liquid injection device or a liquid addition device can also be used.

  When the resin component is composed of the A component and the B-1 component, it is preferable that the moisture contained in the A component and the B-1 component before melt kneading is small. Therefore, it is preferable to melt-knead the dried A component or B-1 component by various methods such as hot air drying, electromagnetic wave drying, and vacuum drying. On the other hand, vent suction during melt kneading is preferably performed without increasing the degree of vacuum so much. For example, a method of discharging volatile components out of the system while circulating nitrogen gas or the like near atmospheric pressure can be used.

(Method for manufacturing molded products)
In general, in the case of a carbon fiber composite resin material, injection molding is not preferred as a molding method because the carbon fiber is broken and shortened by injection molding and the physical properties are lowered. Therefore, a method is preferable in which after the pellets are melted, the discharged product is kept warm and reheated in the residual heat, put into the mold, and pressed under the condition that the D component does not break to form the molded product. Further, a production method including the following steps i) to iii) is more preferable.
i) A resin composition comprising the A component, the B component, and the C component is melt-extruded.
ii) Add D component to the melted resin prepared in i), and knead and discharge A component, B component, C component and D component uniformly and continuously under the condition that D component does not break using a kneader. .
iii) After the discharge product prepared in ii) is weighed and cut, the discharge product is kept warm and reheated in the residual heat, put into the mold, and pressed under the condition that the D component does not break to mold the molded product.

The linear expansion coefficient of the aromatic polycarbonate resin composition comprising the A component, the B component, and the C component used for the matrix component of the present invention is preferably less than 5 × 10 ⁻⁵ / ° C., more preferably 4 Less than 5 × 10 ⁻⁵ / ° C. and 1.0 × 10 ⁻⁵ / ° C. or more, more preferably less than 4 × 10 ⁻⁵ / ° C. and 1.2 × 10 ⁻⁵ / ° C. or more. When the linear expansion coefficient is 5 × 10 ⁻⁵ / ° C. or more, the crack resistance to a heat cycle of a molded product made of an aromatic polycarbonate resin composition composed of A component to D component is deteriorated, and 1.0 × 10 ^−5. Those having a temperature of less than / ° C. are substantially difficult to use due to a substantial decrease in appearance and impact strength.

The linear expansion coefficient is measured by cutting a cubic test piece with a side of 4 mm from the center of a tensile dumbbell used in ISO 527 and measuring the resin flow direction during molding. TMA2940 Thermal Analyst 2200 manufactured by TA Instruments was used for measurement, and an average value of −30 ° C. to 90 ° C. was calculated at a temperature increase rate of 2 ° C./min.
The linear expansion coefficient of the aromatic polycarbonate resin composition of the present invention is preferably less than 3.5 × 10 ⁻⁵ / ° C., more preferably less than 3 × 10 ⁻⁵ / ° C. and 5 × 10 ⁻⁶ / ° C. or more. More preferably, it is less than 1.5 × 10 ⁻⁵ / ° C. and 1 × 10 ⁻⁶ / ° C. or more. When the linear expansion coefficient is 3.5 × 10 ⁻⁵ / ° C. or more, dimensional stability is not sufficient due to large thermal expansion. The linear expansion coefficient is measured by cutting a cubic test piece having a side of 4 mm from the center of the molded body and measuring the resin flow direction during molding. TMA2940 Thermal Analyst 2200 manufactured by TA Instruments was used for measurement, and an average value of −30 ° C. to 90 ° C. was calculated at a temperature increase rate of 2 ° C./min.

  The surface of the molded product in terms of product design when the aromatic polycarbonate resin composition of the present invention is molded into a plate-shaped molded product using a mold whose surface is finished using an abrasive of No. 2000 or more as defined in JIS R6001 The roughness is preferably less than 2.0 μm, more preferably 0.01 μm or more and less than 1.5 μm, and most preferably 0.02 μm or more and less than 1.0 μm. The surface roughness is measured according to JIS B0601-1994 using a universal surface shape measuring instrument (SURFCOM 3B.E-MD-S10A: manufactured by Tokyo Seimitsu Co., Ltd.) under conditions of a stylus diameter of 2 μm and a stylus pressure of 0.07 g. The average surface roughness (Ra) is calculated at a measurement length of 10 mm, a measurement speed of 0.15 mm / s, and a measurement magnification of 10K.

  As described above, according to the present invention, the aromatic polycarbonate resin (component A) 50 to 100% by weight, and the styrene unit component-containing resin having a thermoplastic polyester resin (component B-1) and a rubber component content of less than 40% by weight. Number measured by the method specified in the text with respect to 100 parts by weight of a resin component consisting of 0 to 50% by weight of at least one thermoplastic resin selected from the group consisting of (B-2 component) 5 to 80 parts by weight of wollastonite particles (component C) having a particle shape characteristic of an average fiber length of 10 μm or less, a number average fiber diameter of 1.5 μm or less, and an aspect ratio of 4.5 or more, the fiber length is specified A molded article formed from an aromatic polycarbonate resin composition containing 10 to 100 parts by weight of carbon fiber (D component) having a value equal to or higher than the value is provided.

More specifically, the following molded articles are provided. That is, (i) a molding formed from an aromatic polycarbonate resin composition comprising a resin component comprising the A component, 5 to 80 parts by weight of the C component per 100 parts by weight of the resin component, and 10 to 100 parts by weight of the D component. Product, (ii) an aromatic polycarbonate resin composition comprising 5 to 80 parts by weight of the C component and 10 to 100 parts by weight of the D component per 100 parts by weight of the resin component comprising the A component and the B-1 component. And (iii) a resin component comprising the A component and the B-2 component, 5 to 80 parts by weight of the C component per 100 parts by weight of the resin component, and 10 to 100 parts by weight of the D component. A molded article formed from an aromatic polycarbonate resin composition.
More preferably, a coated molded article formed from the polycarbonate resin composition is provided.

  The aromatic polycarbonate resin composition of the present invention is excellent in mechanical properties such as rigidity and impact properties, and excellent in crack resistance against heat cycle, automobile parts such as automobile outer plates, roofs, structural materials, outer handles, and various OA. It is optimal for applications that require high strength, such as equipment parts and sports parts.

  The form of the invention that the present inventor considers to be the best is an aggregation 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.

Hereinafter, the present invention will be described in more detail with reference to examples.
[Examples 1-6, Comparative Examples 1-7]
Each example and comparative example were evaluated by the following methods.
(Evaluation 1) Surface appearance: A molded product of 150 mm × 150 mm × 4 mmt was prepared by the following method using the pellet prepared by the method described in “Method for producing pellet” below. That is, first, using EC160N-4Y manufactured by Toshiba Machine Co., Ltd., applying a back pressure of 50 kgf / cm ² in the cylinder with the nozzle processed into a 10 mm nozzle hole diameter under the condition of a cylinder temperature of 300 ° C. After filling, the cylinder was backed, and 135 g of the resin composition was injected in a dumpling form at a speed of 16.7 g / sec onto a Teflon (registered trademark) processed hot plate heated to 300 ° C. installed in front of the nozzle. Next, using a mold whose surface was finished using a No. 2000 abrasive defined in JIS R6001, this dumpling-shaped lump was subjected to conditions of a mold temperature of 90 ° C., a pressurization time of 20 seconds, and a pressing force of 360 kgf / cm ² . Was subjected to press molding, the surface temperature was lowered to 90 ° C., and then released to obtain a molded product. The surface roughness of the obtained molded product was measured by the following method. That is, in accordance with JIS B0601-1994, a universal surface shape measuring instrument (SURFCOM 3B.E-MD-S10A: manufactured by Tokyo Seimitsu Co., Ltd.) was used under the conditions of a stylus diameter of 2 μm and a stylus pressure of 0.07 g. The average surface roughness (Ra) was calculated at 10 mm, a measurement speed of 0.15 mm / s, and a measurement magnification of 10K.

(Evaluation 2) Surface impact: A molded article prepared in the same manner as in Evaluation 1 was used, a high-speed surface impact test was performed, and the absorbed energy until the specimen was broken was measured. The measurement was performed at −30 ° C., and the hitting core speed was 7 m / s.

(Evaluation 3) Linear expansion coefficient: A cube having a side of 4 mm was cut out from the central part of a molded product produced by the same method as in Evaluation 1, and the linear expansion coefficient was measured in the resin flow direction during molding by the following method. That is, TMA2940 Thermal Analyst 2200 manufactured by TA Instruments was used, and an average value in a range of −30 ° C. to 90 ° C. under the condition of a temperature rising rate of 2 ° C./min was calculated.

(Evaluation 4) Heat cycle test: The appearance of the test piece was observed after repeating the heat cycle test at −30 ° C. and 80 ° C. for 100 cycles in a cycle of 2 hours at a temperature of 2 hours for each molded product prepared in the same manner as in Evaluation 1. did.
a. There is no problem with no change in the appearance such as cracks.
b. Cracks were observed.

(Pellet making method)
After mixing each component except the D component shown in Table 1 with a V-type blender at a blending ratio shown in the table, the cylinder temperature was measured by a vent type twin screw extruder [KTX-30 manufactured by Kobe Steel Co., Ltd.] with a screw diameter of 30 mm. Kneading and extruding at 270 ° C. and vent suction of 3 kPa, impregnating the molten resin composition into D component carbon fibers continuously fed into a die attached to the tip of the extruder, and pelletizing the carbon fibers impregnated with the resin A pellet was prepared by cutting to a length of 1 mm or more. In addition, among each component, the aromatic polycarbonate resin and the aromatic polyester resin were used after being hot-air dried at 120 ° C. for 5 hours.

Each component indicated by symbols in Table 1 is as follows.
(A component)
1) PC-1: a linear aromatic polycarbonate resin having a viscosity average molecular weight of 25,000 produced from bisphenol A and phosgene (“Panlite L-1250” manufactured by Teijin Chemicals Ltd.)
2) PC-2: A linear aromatic polycarbonate resin having a viscosity average molecular weight of 19,700 produced from bisphenol A and phosgene (“Panlite L-1225L” manufactured by Teijin Chemicals Ltd.)
(B component)
(B-1 component)
1) PET: Polyethylene terephthalate resin (TR-MB; manufactured by Teijin Limited, intrinsic viscosity 0.51)
2) PBT: polybutylene terephthalate resin (500 FP; manufactured by Teijin Limited, intrinsic viscosity 0.86)
(B-2 component)
1) ABS: ABS resin (“Santac UT-61” manufactured by Nippon A & L Co., Ltd.)
(C component)
1) Wallast-1: KGP-H40 manufactured by Kansai Matec (number average fiber length 6.5 μm, number average fiber diameter 1.0 μm, aspect ratio 6.5)
2) Wallast-2: PH330 manufactured by JFE Mineral Co., Ltd. (number average fiber length 6.3 μm, number average fiber diameter 1.1 μm, aspect ratio 5.7)
(Other than C component)
1) Wallast-3: NYGLOS4 manufactured by NYCO (number average fiber length 6.7 μm, number average fiber diameter 1.7 μm, aspect ratio 3.9)
(D component)
1) D-1: Carbon fiber (manufactured by Toho Tenax Co., Ltd., HTA-12K)
(Other)
1) ST: Cyclic neopentanetetraylbis (octadecyl phosphite) (Adeka Stub PEP-8 manufactured by Asahi Denka Kogyo Co., Ltd.)
2) TMP: Trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.)

Claims (11)

  Aromatic polycarbonate resin (component A) 50-100% by weight, thermoplastic polyester resin (component B-1) and rubber component content of less than 40% by weight styrene unit component-containing resin (component B-2) The number average fiber length is 10 μm or less and the number average fiber diameter is 1.5 μm with respect to 100 parts by weight of a resin component consisting of 0 to 50% by weight of a thermoplastic resin (component B) consisting of at least one resin selected from the group Carbon fiber (D) having 5 to 80 parts by weight of wollastonite particles (component C) having an aspect ratio calculated from the number average fiber length and the number average fiber diameter of 4.5 or more and a number average fiber length of 1 mm or more Component) An aromatic polycarbonate resin composition containing 10 to 100 parts by weight.   2. The aromatic polycarbonate resin composition according to claim 1, wherein the resin component is a resin component comprising 50 to 95% by weight of the A component and 5 to 50% by weight of the B component.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the content of component C is 15 to 60 parts by weight.   Content of D component is 15-80 weight part, The aromatic polycarbonate resin composition of any one of Claims 1-3.   Component C has a number average fiber length of 1 to 10 μm, a number average fiber diameter of 0.2 to 1.5 μm, and an aspect ratio calculated from the number average fiber length and the number average fiber diameter of 4.5 or more and less than 50 It is a wollastonite particle, The aromatic polycarbonate resin composition of any one of Claims 1-4.   The aromatic polycarbonate resin composition according to any one of claims 1 to 5, wherein the impact modifier (E component) is contained in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the total of the A component and the B component.   B-1 component is a polyethylene terephthalate, The aromatic polycarbonate resin composition of any one of Claims 1-6.   B-2 component is an ABS resin, The aromatic polycarbonate resin composition of any one of Claims 1-7.   The aromatic polycarbonate resin composition according to any one of claims 1 to 8, wherein the component D is a carbon fiber having a number average fiber length of 1 mm or more and a number average fiber diameter of 5 to 15 µm.   The molded article which consists of an aromatic polycarbonate woody composition of any one of Claims 1-9. The method for producing a molded article according to claim 10, comprising the following steps i) to iii).
i) Melt extrusion of a resin composition comprising an A component, a B component, and a C component.
ii) Add the D component to the molten resin prepared in i), and use the kneader to knead the A component, B component, C component, and D component uniformly and continuously under conditions where the D component does not break. To do.
iii) After the discharge product prepared in ii) is weighed and cut, the discharge product is kept warm and reheated in the residual heat, put into the mold, and pressed under the condition that the D component does not break to mold the molded product.