JP6420061B2 - Thermoplastic resin composition and molded article - Google Patents

Description

  The present invention has a fluidity (fluidity at the time of melting) suitable for processing a molded article, has excellent moldability, and gives a molded article having an excellent balance of impact resistance and rigidity of the resulting molded article. The present invention relates to a plastic resin composition.

  Polycarbonate resins are excellent in transparency, heat resistance and mechanical properties, and are used in vehicles, OA (office automation) devices, home appliances, electrical / electronic devices, building materials and the like. In addition, a polycarbonate resin reinforced by blending a fibrous filler is superior in dimensional stability, rigidity, and heat resistance compared to a non-reinforced polycarbonate resin. It is used as a molding material for housings.

  As a fiber reinforced resin composition containing a polycarbonate resin, for example, Patent Document 1 discloses a resin composition containing a polycarbonate resin, a hydrogenated styrene-butadiene block copolymer, and glass fibers. . Patent Document 2 includes (A) 95 to 55% by weight of a modified polybutylene terephthalate resin having 5 to 40 mol% of a comonomer unit and (B) 100 parts by weight of a resin component consisting of 5 to 45% by weight of a polycarbonate resin. , (C) 0.001 to 5 parts by weight of a crystal nucleating agent, (D) 40 to 200 parts by weight of an inorganic filler such as glass fiber, and (E) 0.1 to 5 parts by weight of a coloring component. A terephthalate resin composition is disclosed. Patent Document 3 discloses (c) polycarbonate oligomer 3 to 100 parts by weight of (a) polyalkylene terephthalate resin 95 to 50% by weight and (b) aromatic polycarbonate resin 5 to 50% by weight. A thermoplastic polyester resin composition comprising 50 parts by weight, (d) 0.01 to 0.5 parts by weight of an organophosphorus compound, and (e) 70 to 350 parts by weight of an inorganic filler such as glass fiber is disclosed. Yes. Patent Document 4 discloses (A) a polybutylene terephthalate-based resin containing a polybutylene terephthalate / isophthalate copolymer, wherein the polyphthalene terephthalate resin has a content of 3-30 mol% of isophthalic acid component with respect to all dicarboxylic acid components. 30 to 95 parts by weight of a butylene terephthalate resin, (B) 1 to 30 parts by weight of a polycarbonate resin, (C) 1 to 30 parts by weight of an elastomer, (D) 3 to 60 parts by weight of a fibrous reinforcing material such as glass fiber, A polyester-based resin composition in which the total amount of (A) to (D) is 100 parts by weight is disclosed. Patent Document 5 discloses (A) 95 to 55% by weight of a modified polybutylene terephthalate resin containing 5 to 30 mol% of isophthalic acid units and having an intrinsic viscosity of 0.60 to 0.80 dl / g, and (B ) For 100 parts by weight of the resin component comprising 5 to 45% by weight of polycarbonate resin, (C) 60 to 150 parts by weight of glass fiber having a flat cross-sectional shape, (D) Particle or plate shape with an average particle size of 10 to 60 μm A polybutylene terephthalate resin composition comprising 10 to 50 parts by weight of a filler and 0.1 to 5 parts by weight of (E) a montanic acid compound is disclosed.

Japanese Patent Laid-Open No. 3-27352 Japanese Patent Laid-Open No. 9-291204 JP 2000-53848 A JP 2002-356611 A JP 2008-120925 A

The composition of Patent Document 1 is insufficient in fluidity (molding processability), and is improved by the composition of Patent Documents 2 to 5 which further contains a polybutylene terephthalate resin. However, the actual situation is that the effect of improving impact resistance and rigidity is not sufficient.
An object of the present invention is a thermoplastic resin having fluidity (fluidity at the time of melting) suitable for processing of a molded article, excellent molding processability, and excellent balance of impact resistance and rigidity of the obtained molded article. It is to provide a composition.

The present invention is as follows.
1. (A) polycarbonate resin, (B) aromatic polyester resin, (C) a compound having a polyorganosiloxane polymer part and a vinyl (co) polymer part, and (D) a fibrous filler And
The content ratios of the polycarbonate resin (A) and the resin (B) are 18 to 40 % by mass and 60 to 82 % by mass, respectively, when the total of both is 100% by mass,
The content of the compound (C) is 3 to 17 parts by weight per 100 parts by weight of the polycarbonate resin (A) and the resin (B),
The content of the fibrous filler (D) is the polycarbonate resin (A) and the thermoplastic resin composition, which is a 40 to 150 parts by weight per 100 parts by weight of the resin (B) .
2. Thermoplastic resin sets composition as the resin (B) is described in the above 1 is polybutylene terephthalate.
3 . The compound (C), the presence of the polyorganosiloxane-based polymer rubber, the one or a silicone rubber-reinforced graft resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound 2. The thermoplastic resin composition according to 2.
4 . The thermoplastic resin composition according to any one of 1 to 3 above, wherein the fibrous filler (D) contains glass fibers.
5 . A molded article comprising the thermoplastic resin composition according to any one of 1 to 4 above.

  According to the thermoplastic resin composition of the present invention, since it is excellent in fluidity (molding processability), it is possible to smoothly manufacture a molded product. The resulting molded product is also excellent in the balance between impact resistance and rigidity, and it is suitable for parts such as vehicles, ships, OA equipment, home appliances, electrical / electronic equipment, building materials, daily goods, sports equipment, stationery, etc. Is preferred.

It is the schematic which shows the irregular cross section of the fibrous filler which can be used.

The present invention will be described in detail below.
In this specification, “(meth) acryl” means acryl and methacryl, “(meth) acrylate” means acrylate and methacrylate, “(meth) acryloyl group” means acryloyl group and methacryloyl group, “Polymer” means homopolymers and copolymers.
The weight average molecular weight (Mw) of the polymer excluding the polycarbonate resin is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

The thermoplastic resin composition of the present invention comprises (A) a polycarbonate resin (hereinafter also referred to as “component (A)”), (B) an aromatic polyester resin (hereinafter also referred to as “component (B)”), (C) a compound having a polyorganosiloxane polymer part and a vinyl (co) polymer part (hereinafter referred to as “compound (C)” or “component (C)”), and (D) fiber. In the case where the content ratio of the polycarbonate resin (A) and the resin (B) is 100% by mass, 18 to 40 % by mass and 60 to 82 % by mass, and the content of the compound (C) is 3 to 17 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the resin (B). Including the fibrous filler (D). The content is 40 to 150 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the resin (B).

  The component (A) is not particularly limited as long as it is a polycarbonate resin having a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, and the like. In addition, this component (A) may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). Good.

  Examples of the aromatic polycarbonate include those obtained by melting a transesterification (transesterification reaction) of an aromatic dihydroxy compound and a carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, and pyridine and phosgene. What was obtained by the pyridine method using a reaction product etc. can be used.

  The aromatic dihydroxy compound may be any compound having two hydroxyl groups in the molecule, such as dihydroxybenzene such as hydroquinone and resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis ( -Hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-methyl) Phenyl) fluorene, 4,4 ′-(p-phenylenediisopropylidene) bisphenol, 4,4 ′-(m-phenylenediisopropylidene) bisphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxyphenyl) Ketone, bis (p-hydroxyphenyl) ether, bis (p-hydride) Xylphenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Examples thereof include bis (p-hydroxyphenyl) sulfoxide. These can be used alone or in combination of two or more.

  Of the aromatic hydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. The benzene ring may be one in which a hydrogen atom bonded to a carbon atom constituting the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like. Of these, bisphenol A is particularly preferred.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

The average molecular weight and molecular weight distribution of the component (A) are not particularly limited as long as the composition has molding processability. The molecular weight of the component (A) is a viscosity average molecular weight (Mv) converted from the solution viscosity measured at 25 ° C. using methylene chloride as a solvent, preferably 10,000 to 50,000, more preferably 15,000 to 30,000, more preferably 17,500 to 27,000. When the viscosity average molecular weight is 10,000 to 50,000, the moldability and mechanical strength are excellent.
The MFR (temperature 240 ° C., load 10 kg) of the component (A) is preferably 1 to 70 g / 10 minutes, more preferably 2.5 to 50 g / 10 minutes, and further preferably 4 to 30 g / 10 minutes. is there.

  In the composition of the present invention, the component (A) may be included singly or in combination of two or more.

  The component (B) is an aromatic polyester resin, preferably an acid component containing an aromatic dicarboxylic acid and / or an ester-forming derivative of an aromatic dicarboxylic acid, a diol compound and / or an ester-forming property of a diol compound. A resin obtained by a reaction with a diol component containing a derivative can be used. This resin may be a homopolyester or a copolyester.

Among the above acid components, aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4, Examples include 4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, and the like. These substitution products (alkyl group substitution products such as methyl isophthalic acid) and derivatives (alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used.
Furthermore, oxyacids and their ester-forming derivatives such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid can also be used.
The said acid component can be used individually by 1 type or in combination of 2 or more types.

Examples of the diol component include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and neopentyl glycol; and alicyclic glycols such as 1,4-cyclohexanedimethanol. In addition, these substitution bodies and derivatives can also be used. A cyclic ester compound such as ε-caprolactone can also be used.
Furthermore, long-chain diol compounds (polyethylene glycol, polytetramethylene glycol, etc.), alkylene oxide addition polymers of bisphenols, etc. (ethylene oxide addition polymers of bisphenol A, etc.), etc. can be used as necessary. .
The said diol component can be used individually by 1 type or in combination of 2 or more types.

  When the component (B) is a homopolyester, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, polyneopentyl terephthalate, polyethylene Isophthalate, polyethylene naphthalate, polybutylene naphthalate, polyhexamethylene naphthalate and the like can be used. Of these, polybutylene terephthalate is preferable from the viewpoint of moldability.

When the component (B) is a copolyester, the acid component used for the formation thereof preferably contains an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid, and if necessary, further contains adipic acid. , Aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, and sebacic acid. The diol component is preferably an aliphatic alkylene glycol such as a linear alkylene glycol such as ethylene glycol, propylene glycol or 1,4-butanediol; a poly (oxy-alkylene) unit such as diethylene glycol or polytetramethylene glycol. And a polyoxyalkylene glycol having an oxyalkylene unit having about 2 to 4 repetitions.
Furthermore, in addition to the above compounds, hydroxycarboxylic acids such as glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, etc., as necessary And monofunctional components such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butylbenzoic acid, and benzoylbenzoic acid, or ester derivatives thereof; tricarballylic acid, trimellitic acid, trimesic acid, pyro Polyhydric carboxylic acids such as merit acid; polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol; one or two polyfunctional components such as gallic acid or ester derivatives thereof The above components for polycondensation It may be used in.

  For the above component (B), the intrinsic viscosity measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (mass ratio) is not particularly limited, but molding processing From a viewpoint of property, Preferably it is 0.2-2.0 dl / g, More preferably, it is 0.4-1.3 dl / g.

  In the composition of the present invention, the component (B) may be included singly or in combination of two or more.

In the present invention, the content ratio of the component (A) and the component (B) is, among molding processability, impact resistance and rigidity , particularly from the viewpoint of molding processability , when the total of both is 100% by mass And 18 to 40 % by mass and 60 to 82 % by mass, respectively.

  The component (C) is a compound having a polyorganosiloxane polymer part and a vinyl (co) polymer part, preferably a polyorganosiloxane polymer part and a vinyl (co) polymer part. Are directly bound compounds.

In the present invention, the compound (C) is rubbery at 25 ° C., and a polyorganosiloxane polymer having a polymerizable unsaturated bond (carbon-carbon double bond) (hereinafter referred to as “polyorganosiloxane rubber”). Resin composition (silicone rubber reinforced) obtained by polymerizing (grafting) a vinyl monomer (hereinafter also referred to as “vinyl monomer (c1)”) in the presence of Resin), a polyorganosiloxane polymer part having a carbon-carbon double bond cleaved, and a vinyl (co) polymer part containing a structural unit derived from the vinyl monomer (c1). A bonded silicone rubber reinforced graft resin is preferred.
Hereinafter, the silicone rubber reinforced graft resin which is a preferred embodiment will be described.

The polyorganosiloxane rubber used for forming the silicone rubber-reinforced graft resin has a polymerizable unsaturated bond (carbon-carbon double bond) and is represented by the following general formula (1). A modified polyorganosiloxane rubber obtained by cocondensation of one or more kinds of organosiloxane (i) having a structural unit and a graft crossing agent (ii) is preferably used.
[R ¹ _n SiO] _{(4-n) / 2} (1)
(In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, and n represents an integer of 0 to 3. When there are a plurality of R ^{1 s} , they may be the same as or different from each other.)

R ¹ in the general formula (1), that is, the monovalent hydrocarbon group includes an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aryl group such as a phenyl group and a tolyl group; a vinyl group; An alkenyl group such as an allyl group; and a group in which a part of hydrogen atoms bonded to carbon atoms in these hydrocarbon groups is substituted with a halogen atom, a cyano group, or the like; and at least one hydrogen atom of an alkyl group is a mercapto group And a group substituted with.

The organosiloxane (i) is linear, branched or cyclic and preferably has a cyclic structure. Specifically, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, etc. Is mentioned. These can be used alone or in combination of two or more.
In addition, the said organosiloxane (i) was condensed beforehand using 1 or more types of the compound represented by the said General formula (1), for example, the weight average molecular weight (Mw) is about 500-10,000. Polyorganosiloxane may be used. The polyorganosiloxane may be a polyorganosiloxane whose molecular chain end is sealed with a functional group such as a hydroxyl group, an alkoxy group, a trimethylsilyl group, or a methyldiphenylsilyl group.

Examples of the graft crossing agent (ii) include vinylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 1- (p-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, allylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxy A compound having a carbon-carbon unsaturated bond and an alkoxysilyl group, such as silane; a silane compound having a mercapto group (thiol group), such as γ-mercaptopropylmethylmethyldimethoxysilane; a silane compound having an amino group; tetravinyl Tetramethyl And cyclosiloxane.
When the organosiloxane (i) contains a polymerizable unsaturated bond, the graft crossing agent (ii) to be used may or may not have a polymerizable unsaturated bond.

In the case of producing the modified polyorganosiloxane rubber, the organosiloxane (i) and the graft crossing agent (ii) are subjected to shear mixing in the presence of an emulsifier such as alkylbenzene sulfonic acid using a homomixer or the like to condense. It can be a method or the like. The upper limit of the amount of the graft crossing agent (ii) used is preferably 50% by mass, more preferably 10% by mass, and still more preferably 5% when the total amount with the organosiloxane (i) is 100% by mass. % By mass.
In the production of the modified polyorganosiloxane rubber, a crosslinking agent may be added in order to improve impact resistance. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. When a crosslinking agent is used, the upper limit of the amount used is usually 10 parts by mass, preferably 5 parts by mass when the total amount of the organosiloxane (i) and the graft crossing agent (ii) is 100 parts by mass. .
The weight average molecular weight (Mw) of the modified polyorganosiloxane rubber is preferably 30,000 to 1,000,000, more preferably 50,000 to 300,000. Within this range, the balance of impact resistance and fluidity in the composition of the present invention is excellent.

  The volume average particle diameter of the polyorganosiloxane rubber is preferably 20 to 500 nm, more preferably 50 to 400 nm, and still more preferably 150 to 350 nm from the viewpoint of impact resistance.

The vinyl monomer (c1) used in the production of the silicone rubber reinforced graft resin is a compound having one polymerizable unsaturated bond, and is an aromatic vinyl compound, a vinyl cyanide compound, (meth) acrylic. An acid ester compound, a maleimide compound, an unsaturated acid anhydride, a carboxyl group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, an oxazoline group-containing unsaturated compound, and the like can be used. The vinyl monomer (c1) according to the present invention preferably contains an aromatic vinyl compound. This vinyl monomer (c1) may be a monomer composed only of an aromatic vinyl compound, an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylate compound exemplified above, Consists of other vinyl monomers such as maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds It may be a monomer.
The lower limit of the ratio of the aromatic vinyl compound contained in the vinyl monomer (c1) is preferably 50% by mass, more preferably 60% by mass, and still more preferably 65% from the viewpoint of molding processability and molding appearance. % By mass.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, tribromostyrene, and fluorostyrene. These compounds can be used alone or in combination of two or more. Moreover, as said aromatic vinyl compound, styrene and (alpha) -methylstyrene are preferable and styrene is especially preferable.

  When the vinyl monomer (c1) is composed of an aromatic vinyl compound and another vinyl monomer, the use ratio of the aromatic vinyl compound and the other vinyl monomer is determined according to mechanical strength and From the viewpoint of molding appearance, when these totals are 100% by mass, preferably 50 to 85% by mass and 15 to 50% by mass, more preferably 60 to 80% by mass and 20 to 40% by mass, respectively. Preferably they are 65-75 mass% and 25-35 mass%.

  In the present invention, the vinyl monomer (c1) preferably contains an aromatic vinyl compound and a vinyl cyanide compound because of excellent molding processability and impact resistance. In this case, the lower limit of the ratio of the total amount of the aromatic vinyl compound and the vinyl cyanide compound contained in the vinyl monomer (c1) is preferably 70% by mass, more preferably 80% by mass, and still more preferably. Is 90% by mass.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These compounds can be used alone or in combination of two or more. The vinyl cyanide compound is preferably acrylonitrile.

Hereinafter, compounds that may be contained in the vinyl monomer (c1) are exemplified.
Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) ) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. Of these, N-phenylmaleimide is preferred. Moreover, these compounds can be used individually or in combination of 2 or more. In addition, as another method for introducing a structural unit derived from a maleimide compound into the silicone rubber-reinforced graft resin, for example, a method of copolymerizing an unsaturated dicarboxylic anhydride of maleic anhydride and then imidizing it But you can.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic (Meth) acrylic acid ester having a hydroxyl group such as a compound obtained by adding ε-caprolactone to 2-hydroxyethyl acid; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α -Methylstyrene M-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4 -Hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy- 2-butene, 3-hydroxy-2-me Examples include til-1-propene. These compounds can be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These compounds can be used alone or in combination of two or more.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.

  In order to produce the silicone rubber-reinforced graft resin, the method of polymerizing (graft polymerization) the vinyl monomer (c1) in the presence of a polyorganosiloxane rubber includes emulsion polymerization, suspension polymerization, Solution polymerization, bulk polymerization, or a polymerization method combining these can be applied.

  In the case of producing the above silicone rubber reinforced resin, the polymerization may be started by adding the vinyl monomer (c1) all together in the reaction system in the presence of the total amount of the polyorganosiloxane rubber. Alternatively, the polymerization may be performed while continuously adding. Further, in the presence or absence of a part of the polyorganosiloxane rubber, the polymerization may be started by adding the vinyl monomer (c1) all at once, or may be added in portions or continuously. May be. At this time, the remainder of the polyorganosiloxane rubber may be added in a batch, divided or continuously during the reaction.

  When a silicone rubber reinforced resin is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (c1) whole quantity.
When using the said polymerization initiator, it can add to a reaction system collectively or continuously.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer (c1).
When the chain transfer agent is used, it can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (c1) whole quantity.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (c1), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.
In addition, when making the said silicone rubber reinforced resin consist of 2 or more types of silicone rubber reinforced resin, after isolating resin from each latex, you may mix, but as another method, There are methods such as coagulating a latex mixture containing each resin.

  In the case of producing a silicone rubber reinforced resin by solution polymerization, bulk polymerization and bulk-suspension polymerization, known methods can be applied.

  The silicone rubber reinforced resin (resin composition) produced as described above mainly contains a silicone rubber reinforced graft resin, that is, the component (C) according to the present invention. This resin composition is a polyorganosiloxane rubber that remains without being grafted; a vinyl-based (co-polymer) containing a structural unit derived from the vinyl monomer (c1) that is formed without grafting. ) A polymer; or a composite of these intertwined.

The graft ratio of the silicone rubber-reinforced graft resin is preferably 10% or more, more preferably 20% or more, and further preferably 30 to 150% from the viewpoint of impact resistance and molding appearance.
The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the above formula, S represents 1 gram of silicone rubber-reinforced resin in 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then centrifuged under a temperature condition of 5 ° C. This is the mass (g) of the insoluble matter obtained by centrifuging at 60 rpm (rotation speed: 23,000 rpm) and separating the insoluble matter and the soluble matter, and T is contained in 1 gram of the silicone rubber reinforced resin. This is the mass (g) of the polyorganosiloxane rubber. The mass of the polyorganosiloxane rubber can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  In the composition of the present invention, the component (C) may be included singly or in combination of two or more.

The content of the component (C) contained in the composition of the present invention is excellent in the balance of impact resistance, rigidity and molding processability, so that the total amount of the component (A) and the component (B) is 100 parts by mass. 3 to 17 parts by mass , and more preferably 5 to 14 parts by mass.

上記式では、繊維長、繊維径、長径及び短径を、例えば、走査型電子顕微鏡（ＳＥＭ）により、一定量の数の充填剤に対して測定した後の数平均値を用いることができる。
上記成分（Ｄ）の平均繊維長は、好ましくは０．０２〜２．８ｍｍ、より好ましくは０．０５〜２．２ｍｍ、更に好ましくは０．１〜１．５ｍｍである。
尚、上記成分（Ｄ）の断面形状は、特に限定されず、円形、楕円形、多角形（長方形等）や、これらが変形したもの又は複合化した異形等とすることができる。本発明においては、図示していない、扁平率の高い楕円形や、図１（１）若しくは（２）に示される形状又はそれが変形した形状、の断面を有する成分（Ｄ）を含む組成物を用いることにより、流動性が向上し、成形加工性に優れ、成形収縮性の異方性（ＭＤ方向及びＴＤ方向）を低減させることができ、反り又はねじれの抑制された成形品を得ることができる。特に、断面の短径ｄ１に対する長径ｄ２の比（ｄ２／ｄ１）が１．２以上である、円に対して扁平な形状の断面を有する部分を備える成分（Ｄ）を含むことが好ましい。
本発明の熱可塑性樹脂組成物又は成形品から、成分（Ｄ）を単離する場合には、例えば、空気中、５００℃〜８００℃の温度で加熱して、樹脂成分を灰化させた後、成分（Ｄ）を回収する方法等を適用すればよい。 The component (D) is a fibrous filler, and the aspect ratio represented by the following formula is preferably 2 to 200, more preferably 2 to 120, still more preferably 2.5 to 70, and particularly preferably 3. It is a filler having a long shape of ˜50. When the aspect ratio is 2 to 200, an excellent mechanical strength can be obtained, and a molded product having excellent molded appearance can be obtained while suppressing anisotropy. The shape in the longitudinal direction can be a straight line, a wavy line, a zigzag, a curve, a spiral, or the like.

In the above formula, the number average value after measuring the fiber length, fiber diameter, major axis, and minor axis with respect to a certain number of fillers using, for example, a scanning electron microscope (SEM) can be used.
The average fiber length of the component (D) is preferably 0.02 to 2.8 mm, more preferably 0.05 to 2.2 mm, and still more preferably 0.1 to 1.5 mm.
In addition, the cross-sectional shape of the component (D) is not particularly limited, and may be a circular shape, an elliptical shape, a polygonal shape (rectangular shape, etc.), a deformed shape or a complex shape. In the present invention, a composition containing a component (D) having a cross section of an ellipse with a high flatness, a shape shown in FIG. 1 (1) or (2), or a deformed shape thereof, which is not shown. By using, the fluidity is improved, the molding processability is excellent, the molding shrinkability anisotropy (MD direction and TD direction) can be reduced, and a molded product in which warpage or twisting is suppressed is obtained. Can do. In particular, the ratio (d2 / d1) of the major axis d2 to the minor axis d1 of the cross section is preferably 1.2 or more, and the component (D) including a portion having a cross section that is flat with respect to a circle is preferably included.
When isolating component (D) from the thermoplastic resin composition or molded article of the present invention, for example, after heating in air at a temperature of 500 ° C. to 800 ° C., the resin component is incinerated. A method for recovering the component (D) may be applied.

  The component (D) may be composed only of fibers having a structure such as a solid body, a porous body, and a tubular body, or a base fiber having a structure such as a solid body, a porous body, and a tubular body, and the surface thereof. And a layer formed by performing a predetermined surface treatment or the like on at least a part of the surface. That is, the constituent material of the component (D) is appropriately selected depending on the structure, and may be one kind or two or more kinds. And the cross-sectional shape of the said component (D) can be made into circular, an ellipse, a polygon, an indeterminate form, etc.

  The constituent material of the component (D) or its base fiber includes glass, carbon, boron, gypsum, asbestos, silica, silica / alumina, alumina, zirconia, boron nitride, silicon nitride, silicon carbide, potassium titanate, wollast Knight, zonolite, sepiolite, magnesium sulfate, zinc oxide, aluminum borate, calcium carbonate, calcium oxalate, stainless steel, aluminum, titanium, copper, brass and other inorganic materials, as well as aliphatic polyamide, aromatic polyamide, fluororesin, Examples thereof include high melting point organic materials such as polyester and acrylic resin. A fibrous material (including what is called “whisker”) processed from these materials is used.

  In the composition of the present invention, the component (D) may be included singly or in combination of two or more.

It is preferable that the said component (D) contains glass fiber. The glass constituting this glass fiber may be made of any of alkali-containing glass, low alkali glass and non-alkali glass, and examples of the raw glass include silicate glass, borate silicate glass, and phosphate glass. It is done. Moreover, as a kind of raw material glass, E glass, C glass, A glass, S glass, M glass, AR glass, L glass, etc. are mentioned.
The form of the glass fiber is not particularly limited, and any form such as chopped strand, roving, milled fiber, etc. obtained by twisting a number of long single fibers, converging them with a glass fiber sizing agent, and then cutting them. It may be. Of these, chopped strands are preferred from the viewpoint of the balance between mechanical strength and elastic modulus. As the glass fiber used for the chopped strand, a single fiber having an average fiber diameter of preferably 6 to 23 μm, more preferably 9 to 16 μm is preferably used. The number of single fibers bundled is preferably 100 to 4,000, more preferably 800 to 3,000.

The glass fiber is a portion made of a glass fiber sizing agent, a surface treatment agent, or the like in order to improve rigidity in the composition of the present invention or interfacial contact with the component (A) in the composition of the present invention. Or you may have a layer.
As a sizing agent for glass fibers, a composition containing an epoxy resin such as a bisphenol type epoxy resin or a novolac type epoxy resin, a composition containing a urethane resin, a composition containing a urethane resin and a coupling agent, a novolak type epoxy resin, urethane Composition containing resin and coupling agent, novolac epoxy resin, composition containing phenoxy resin and coupling agent, composition containing copolymer of aromatic vinyl compound and vinyl cyanide compound, composition containing amino resin , A composition containing polyvinyl acetate, a composition containing a polyester resin, a composition containing polyacrylate, a composition containing a modified polyolefin resin, a composition containing starch or polyvinyl alcohol, and an oil. Among these, a composition containing an epoxy resin is preferable.
Examples of the surface treatment agent include reactive coupling agents; higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, fluorocarbon surfactants, and the like.

  Examples of the reactive coupling agent include silane coupling agents, titanate coupling agents, aluminate coupling agents, and borane coupling agents.

As said silane coupling agent, the compound represented by following General formula (2) can be used, for example.
R ² Si (OR ³ ) ₃ (2)
(Wherein R ² is an amino group, glycidoxy group, chlorine atom, vinyl group, (meth) acryloyl group, 3,4-epoxycyclohexyl group, mercapto group, N-aminoethylamino group, isocyanate group and ureido group) A selected group or atom, or an alkyl group having the above-mentioned group at its terminal, and R ³ is a hydrocarbon group.)

  Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, γ- Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropylmethyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropylmethyltriethoxy Silane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycine Doxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyl Methyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysila , Β-mercaptoethyltrimethoxysilane, β-mercaptoethyltriethoxysilane, β-mercaptoethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxy-ethoxy) silane, γ Examples include-(methacryloyloxypropyl) trimethoxysilane, γ-chloropropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, γ-allylaminopropyltrimethoxysilane, and γ-allylthiopropyltrimethoxysilane.

As said titanate coupling agent, the compound represented by following General formula (3) can be used, for example.
(R ⁴ O) Ti (OR ⁵ ) (OR ⁶ ) (OR ⁷ ) (3)
(Wherein R ⁴ is an alkyl group, and R ⁵ , R ⁶ and R ⁷ are the same or different from each other, and are a substituted or unsubstituted alkyl group, an alkanoyl group, a (meth) acryloyl group, a dialkylpyrophosphate group, A divalent ethylene group in which R ³ and R ⁴ are a group selected from an N-aminoethyl-aminoethyl group, an alkylbenzenesulfonyl group, a dialkyl phosphate group, a dialkyl phosphite group, and a cumylphenyl group; An oxalyl group or a —CO—CH ₂ — group.)

Examples of the titanate coupling agent include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditri). Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl tris ( Dioctyl pyrophosphate) titanate, isopropyl dioctyl pyrophosphate titanate, isopropyl tri (N Aminoethyl - aminoethyl) titanate, isopropyl tris (dodecylbenzene sulfonyl) titanate, titanium - isopropoxyphenyl glycolate, tetra -n- butoxy, include tetrakis 2-ethylhexoxy) or the like.
Examples of the above-mentioned aluminate coupling agent include aluminum alkyl acetoacetate and dichelate such as aluminum ethyl acetoacetate and diisopropylate; aluminum alkenyl acetoacetate and dialchelate; aluminum trisethyl acetoacetate, aluminum bisethyl acetoacetate and monoacetylacetate And aluminum trisacetylacetonate.

  The glass fiber may be modified with both a sizing agent and a surface treatment agent.

  When the said component (D) contains carbon fiber, electroconductivity can be provided to a composition and electrostatic coating can be performed to the molded article obtained.

When the said component (D) consists of glass fiber and carbon fiber, when these sum totals shall be 100 mass%, from a viewpoint of impact resistance and electroconductivity, respectively, Preferably it is 10-90 mass%, respectively. And 10 to 90 mass%, more preferably 40 to 80 mass% and 20 to 60 mass%.
In the case where the component (D) includes a plurality of types of glass fibers, when a combination having a circular cross section and a cross section having a flat shape with respect to a circle (an irregular cross section) is used, The content ratio is preferably 10 to 90% by mass and 10 to 90% by mass, and more preferably 20 to 60% by mass, from the viewpoint of molding processability and molding shrinkage, when the total of both is 100% by mass. And 40 to 80% by mass.

Since the content of the component (D) contained in the composition of the present invention is excellent in the balance of impact resistance, rigidity and molding processability, the total amount of the component (A) and the component (B) is 100 parts by mass. 40 to 150 parts by mass, preferably 50 to 150 parts by mass, and more preferably 80 to 150 parts by mass.

The composition of the present invention may further contain another polymer (other resin).
Other polymers include vinyl (co) polymers containing structural units derived from vinyl monomers (aromatic vinyl (co) polymers, acrylic (co) polymers, polyvinyl chloride resins, Polyvinylidene chloride resin, fluororesin, etc.), polyolefin resin, polyamide resin, and rubber reinforced graft resin obtained by polymerizing vinyl monomer in the presence of rubbery polymer other than polyorganosiloxane rubber Etc.
When the composition of the present invention contains another polymer (other resin), the upper limit of the content is preferably 60 with respect to a total of 100 parts by mass of the component (A) and the component (B). Part by mass, more preferably 40 parts by mass.

  In the present invention, another preferred polymer (other resin) is a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the absence of a rubbery polymer (hereinafter referred to as “vinyl monomer”). A copolymer (hereinafter referred to as “component (E)”), a diene rubber, a hydrogenated diene rubber, an acrylic rubber, or ethylene / α. A rubber obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound (hereinafter also referred to as “vinyl monomer (f1)”) in the presence of an olefin rubber. It is a reinforced resin (hereinafter referred to as “component (F)”). The composition of the present invention may contain both component (E) and component (F), or may contain only one of them.

  The component (E) is a copolymer obtained by polymerizing a vinyl monomer (e1) containing an aromatic vinyl compound and a vinyl cyanide compound. That is, the copolymer includes a structural unit derived from an aromatic vinyl compound (hereinafter also referred to as “structural unit (ex)”) and a structural unit derived from a vinyl cyanide compound (hereinafter referred to as “structural unit ( ey) ")), and may optionally contain structural units derived from other vinyl monomers (hereinafter also referred to as" structural units (ez) "). It is a polymer.

The explanation of the aromatic vinyl compound exemplified as the vinyl monomer (c1) used for forming the component (C) is applied to the aromatic vinyl compound forming the structural unit (ex). The structural unit (ex) contained in the component (E) may be only one type or two or more types. As the aromatic vinyl compound, styrene and α-methylstyrene are preferable.
The content of the structural unit (ex) contained in the component (E) is preferably 40 to 90% by mass, more preferably 50 to 50% when the total of the structural units constituting the component (E) is 100% by mass. It is 85 mass%, More preferably, it is 65-80 mass%. When the content of the structural unit (ex) is 40 to 90% by mass, excellent mechanical strength and molded appearance can be obtained.

The description of the vinyl cyanide compound that can be used as the vinyl monomer (c1) used for forming the component (C) is applied to the vinyl cyanide compound that forms the structural unit (ey). The structural unit (ey) contained in the component (E) may be only one type or two or more types. As the vinyl cyanide compound, acrylonitrile is preferable.
The content of the structural unit (ey) contained in the component (E) is preferably 10 to 60% by mass, more preferably 15 to 15%, assuming that the total of the structural units constituting the component (E) is 100% by mass. It is 50 mass%, More preferably, it is 20-35 mass%. When the content of the structural unit (ey) is 10 to 60% by mass, excellent mechanical strength and molded appearance can be obtained.

Other vinyl monomers that form the structural unit (ez) include (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated monomers. Examples thereof include saturated compounds and oxazoline group-containing unsaturated compounds. Of these, (meth) acrylic acid ester compounds are preferred.
When the component (E) includes the structural unit (ez), the upper limit of the content is the sum of the structural units constituting the component (E), that is, the structural units (ex), (ey), and (ez). ) Is preferably 70% by mass, more preferably 50% by mass.

  The component (E) is preferably a copolymer composed of the structural units (ex) and (ey). The copolymer composed of the structural units (ex) and (ey) and the structural units (ex), ( It may be a combination with a copolymer consisting of (ey) and (ez).

The weight average molecular weight (Mw) of the component (E) is preferably 30,000 to 500,000, more preferably 40,000 to 350,000, and still more preferably 50,000 to 300,000.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component (E) is preferably 0.2 to 0.8 dl / g, more preferably 0.25, from the viewpoint of impact resistance and moldability. It is -0.7 dl / g, More preferably, it is 0.3-0.6 dl / g.

  Here, the intrinsic viscosity [η] is obtained by dissolving the component (E) in methyl ethyl ketone, preparing five different concentrations, and measuring the reduced viscosity of each concentration at 30 ° C. using an Ubbelohde viscosity tube. Can be sought.

  In the composition of the present invention, the component (E) may be included singly or in combination of two or more.

  When the composition of the present invention contains the component (E), the content of the component (E) is superior in the balance of impact resistance, rigidity and molding processability, so that the component (A) and the component (B ) Is preferably 2 to 60 parts by mass, more preferably 3 to 45 parts by mass, and still more preferably 5 to 35 parts by mass.

  The component (F) is a vinyl monomer (f1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber, hydrogenated diene rubber, acrylic rubber or ethylene / α-olefin rubber. ) Is a rubber-reinforced resin obtained by polymerizing.

The diene rubber may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C. Further, the diene rubber may be a crosslinked polymer or a non-crosslinked polymer.
Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymer rubbers such as styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymer rubbers such as acrylonitrile / styrene / isoprene copolymers, natural rubber, etc. Is mentioned. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The diene rubber can be used singly or in combination of two or more.

The hydrogenated diene rubber is a (co) polymer obtained by hydrogenating a (co) polymer containing a structural unit derived from a conjugated diene compound (however, the hydrogenation rate is 50% or more).
Examples of the hydrogenated diene rubber include hydrogenated conjugated diene block copolymers having the following structure. That is, a polymer block A composed of a structural unit derived from an aromatic vinyl compound; a double bond portion of a polymer composed of a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content exceeding 25 mol%. Polymer block B formed by hydrogenation of 95 mol% or more; 95 mol% or more of a double bond portion of a polymer composed of a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content of 25 mol% or less Hydrogenated polymer block C formed by hydrogenation; and 95 mol% or more of a double bond portion of a copolymer composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound. It is a block copolymer which consists of what combined 2 or more types among the polymer blocks D formed.

The molecular structure of the block copolymer may be branched, radial, or a combination thereof. The block structure may be a diblock, triblock, multiblock, or a combination thereof.
As the structure of the block copolymer, A- (BA) n, (AB) n, A- (BC) n, C- (BC) n, (BC) n , A- (DA) n, (AD) n, A- (DC) n, C- (DC) n, (DC) n, A- (BCD) ) N, (A-B-C-D) n [n is an integer of 1 or more. Etc., preferably AB-A, A-B-A-B, A-B-C, A-D-C, and C-B-C.

The aromatic vinyl compound used for forming the polymer blocks A and D constituting the block copolymer is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. . Examples thereof include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and the like. . These compounds can be used alone or in combination of two or more. Of these, styrene is preferred.
The content ratio of the polymer block A constituting the block copolymer is preferably 0 to 65% by mass, more preferably 10 to 40% by mass with respect to the whole polymer.

  The polymer blocks B, C and D are formed by hydrogenating a pre-hydrogenation block copolymer obtained using a conjugated diene compound and an aromatic vinyl compound. Examples of the conjugated diene compound used for forming the polymer blocks B, C, and D include 1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, and the like. These compounds can be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are preferred because they can be utilized industrially and have excellent physical properties.

The hydrogenation rates of the polymer blocks B, C and D are all 95 mol% or more, preferably 96 mol% or more.
The 1,2-vinyl bond content in the polymer block B is preferably more than 25 mol% and 90 mol% or less, more preferably 30 to 80 mol%.
The 1,2-vinyl bond content in the polymer block C is preferably 25% mol or less, more preferably 20 mol% or less.

The 1,2-vinyl bond content in the polymer block D is preferably 25 to 90 mol%, more preferably 30 to 80 mol%.
The amount of the aromatic vinyl compound unit in the polymer block D is preferably 25% by mass or less, more preferably 20% by mass or less.

  Examples of the hydrogenated diene rubber include hydrogenated polybutadiene, hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / styrene block polymer, Examples thereof include a hydrogenated product of a butadiene / acrylonitrile copolymer.

  The weight average molecular weight (Mw) of the hydrogenated diene rubber is preferably 10,000 to 1,000,000, more preferably 30,000 to 800,000, and still more preferably 50,000 to 500,000.

The acrylic rubber is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate, It is a rubber obtained by (co) polymerizing a monomer containing a (meth) acrylic acid alkyl ester compound such as stearyl methacrylate. These (meth) acrylic acid alkyl ester compounds can be used alone or in combination of two or more.
In addition to the (meth) acrylic acid alkyl ester compounds, the monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methacrylic acid Various vinyl monomers such as modified silicone and fluorine-containing vinyl compound may be contained in the range of 30% by mass or less.

The ethylene / α-olefin rubber is a copolymer including an ethylene unit and a structural unit composed of an α-olefin having 3 or more carbon atoms, and includes an ethylene / α-olefin copolymer and an ethylene / α-olefin. -Non-conjugated diene copolymers are exemplified.
Examples of the ethylene / α-olefin copolymer include an ethylene / propylene copolymer and an ethylene / butene-1 copolymer. Examples of the ethylene / α-olefin / non-conjugated diene copolymer include an ethylene / propylene / non-conjugated diene copolymer and an ethylene / butene-1 / non-conjugated diene copolymer.

  The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, Examples include 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. In the α-olefin, the number of carbon atoms is more preferably 3 to 12, and further preferably 3 to 8.

  The proportions of ethylene units and α-olefin units constituting the ethylene / α-olefin rubber are preferably 5 to 95% by mass and 5 to 95% by mass, respectively, when the total of these is 100% by mass. More preferably, they are 50-90 mass% and 10-50 mass%, More preferably, they are 60-88 mass% and 12-40 mass%, Most preferably, they are 70-85 mass% and 15-30 mass%. When there is too much content rate of the said alpha olefin unit, the flexibility of a film may fall.

When the ethylene / α-olefin rubber is an ethylene / α-olefin / non-conjugated diene copolymer, examples of the non-conjugated diene include alkenyl norbornene such as 5-ethylidene-2-norbornene; cyclic such as dicyclopentadiene Diene; aliphatic diene and the like. These compounds can be used alone or in combination of two or more.
The content of the structural unit derived from the non-conjugated diene is preferably 1 to 30% by mass, more preferably 2 with respect to the total amount of the structural unit constituting the ethylene / α-olefin / non-conjugated diene copolymer. ˜20 mass%. When there is too much content rate of a nonconjugated diene unit, shaping | molding external appearance property and weather resistance may fall.

The amount of unsaturated groups in the ethylene / α-olefin rubber is preferably 4 to 40 in terms of iodine value.
The Mooney viscosity (ML _{1 + 4} , 100 ° C .; conforming to JIS K6300) of the ethylene / α-olefin rubber is preferably 5 to 80, more preferably 10 to 65, and still more preferably 15 to 45. When the Mooney viscosity is in the above range, the film has excellent flexibility and impact resistance.

  The vinyl monomer (f1) used in the production of the rubber-reinforced resin may be a monomer composed of an aromatic vinyl compound and a vinyl cyanide compound, an aromatic vinyl compound, a vinyl cyanide compound and others. A monomer composed of a vinyl monomer may be used. In the latter case, the lower limit of the total amount of the aromatic vinyl compound and the vinyl cyanide compound is preferably 30% by mass, more preferably 20% by mass, and still more preferably 10% by mass.

  For the aromatic vinyl compound contained in the vinyl monomer (f1), the explanation of the aromatic vinyl compound exemplified as the vinyl monomer (c1) used for forming the component (C) is applied. The The aromatic vinyl compound may be only one type or two or more types. As the aromatic vinyl compound, styrene and α-methylstyrene are preferable.

  For the vinyl cyanide compound contained in the vinyl monomer (f1), the explanation of the vinyl cyanide compound that can be used as the vinyl monomer (c1) used for forming the component (C) is applied. The The vinyl cyanide compound may be only one type or two or more types. As the vinyl cyanide compound, acrylonitrile is preferable.

  As the other vinyl monomer contained in the vinyl monomer (f1), (meth) acrylic acid which can be used as the vinyl monomer (c1) used for forming the component (B). An ester compound, a maleimide compound, an unsaturated acid anhydride, a carboxyl group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound, an oxazoline group-containing unsaturated compound, or the like can be used.

Preferred examples of the component (F) are shown below.
(F1) Diene rubber reinforced resin obtained by polymerizing a vinyl monomer (f1) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber (F2) Presence of a diene rubber Below, presence of diene rubber reinforced resin (F3) diene rubber obtained by polymerizing vinyl monomer (f1) consisting of aromatic vinyl compound, vinyl cyanide compound and (meth) acrylic acid ester compound Below, a diene rubber reinforced resin obtained by polymerizing a vinyl monomer (f1) comprising an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound

  The manufacturing method of the said component (F) can be made to be the same as that of the manufacturing method of the silicone type rubber reinforced resin which is the said component (C).

In the rubber-reinforced resin produced as described above, a vinyl (co) polymer containing a structural unit derived from the vinyl monomer (f1) is usually a diene rubber, a hydrogenated diene rubber, From a structural unit derived from a resin (graft resin) grafted on acrylic rubber or ethylene / α-olefin rubber and an ungrafted component not grafted on the rubber, that is, the remaining vinyl monomer (f1) And a (co) polymer.
The graft ratio of the graft resin contained in the diene rubber reinforced resin is measured in the same manner as in the case of the silicone rubber reinforced graft resin contained in the component (C). From the viewpoint of impact resistance, molding appearance, and rigidity. Therefore, it is preferably 20% or more, more preferably 30% or more, and further preferably 40 to 150%.

  In the composition of the present invention, the component (F) may be included singly or in combination of two or more.

  When the composition of the present invention contains the component (F), the content of the component (F) is excellent in the balance of impact resistance, rigidity and molding processability. Therefore, the component (A) and the component (B) ) Is preferably 2 to 60 parts by mass, more preferably 3 to 45 parts by mass, and still more preferably 5 to 35 parts by mass.

  The composition of the present invention may further comprise a filler (hereinafter referred to as “other filler”), a plasticizer, an antioxidant, an ultraviolet absorber, an anti-aging agent, a flame retardant, a lubricant, depending on the purpose and application. , Stabilizers, weathering agents, light stabilizers, heat stabilizers, antistatic agents, water repellents, oil repellents, antifoaming agents, antibacterial agents, preservatives, colorants (pigments, dyes, etc.), fluorescent whitening agents, It may contain a conductivity imparting agent or the like.

  As said other filler, if it does not have the property of the said component (D), it will not specifically limit, Heavy calcium carbonate, Collagen calcium carbonate, Light calcium carbonate, Magnesium carbonate, Zinc carbonate, Hydroxide Aluminum, magnesium hydroxide, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, ground silica, fused silica, kaolin, diatomaceous earth, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide , Aluminum oxide, magnesium oxide, aluminum sulfate, glass flake, glass balloon, shirasu balloon, saran balloon, phenol balloon and the like. These can be used alone or in combination of two or more.

  When the thermoplastic resin composition of the present invention contains other fillers, when the total of the component (D) and other fillers is 100% by mass, these ratios are preferably 10 to 90 masses, respectively. % And 10 to 90 mass%, more preferably 30 to 85 mass% and 15 to 70 mass%.

  In the present invention, when a scale-like component is included as another filler, that is, when a composition containing the component (D) and the scale-like component is used as the filler, molding shrinkability anisotropy ( MD direction and TD direction) can be reduced, and a molded product having excellent molded appearance can be obtained. As such a filler, glass flakes are suitable.

When the thermoplastic resin composition of the present invention contains glass fibers as the component (D) and glass flakes as other fillers, the content ratio of these is 100% by mass. From the viewpoints of impact resistance and mold shrinkage, they are preferably 10 to 90 mass% and 10 to 90 mass%, more preferably 40 to 80 mass% and 20 to 60 mass%, respectively.
Moreover, when the thermoplastic resin composition of the present invention contains glass fibers and carbon fibers as the component (D) and glass flakes as other fillers, the glass fibers, carbon fibers and glass flakes are contained. The proportions are preferably 20 to 90% by mass, 5 to 70% by mass, and 5 to 70% by mass, respectively, from the viewpoint of impact resistance, conductivity, and mold shrinkage when the total of both is 100% by mass. Preferably they are 40-80 mass%, 10-50 mass%, and 10-50 mass%.

  Examples of the plasticizer include phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, aliphatic monobasic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, polyhydric alcohol ester, epoxy plasticizer, high Examples include molecular plasticizers and chlorinated paraffins. These can be used alone or in combination of two or more.

  Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds. These can be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and triazine compounds. These can be used alone or in combination of two or more.

  Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiols. Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphoric compounds, and the like. These can be used alone or in combination of two or more.

  Examples of the flame retardant include halogen-containing compounds, phosphorus-containing compounds, guanidine compounds, and silicone compounds. These can be used alone or in combination of two or more.

  When the composition of the present invention contains a flame retardant, the content thereof is preferably 5 to 30 mass with respect to 100 mass parts of the total amount of the components (A) to (D) and other resins or polymers. Parts, more preferably 10 to 25 parts by mass, still more preferably 15 to 20 parts by mass.

As the stabilizer, inorganic phosphorus-containing compounds such as hydrogen phosphate compounds, phosphorus oxides or halides, and phosphate compounds are preferably used. When a silicone rubber-reinforced graft resin such as component (C) is produced by emulsion polymerization, an emulsifier, a coagulant, an acid, a base, etc. may remain. If these coexist in the composition, the component ( A) may cause a decrease in molecular weight, and when an inorganic phosphorus-containing compound is used, a decrease in physical properties may be suppressed.
The said inorganic type phosphorus-containing compound may be used independently and may be used in combination of 2 or more type.
The inorganic phosphorus-containing compound can be used at the time of producing the composition and before kneading the raw material components or during kneading.

  In the composition of the present invention, the content of the polyorganosiloxane polymer (polyorganosiloxane rubber) forming the polyorganosiloxane polymer component constituting the component (C) is high in impact resistance and rigidity. From the viewpoint, it is preferably 0.05 to 15% by mass, more preferably 0.3 to 7% by mass, and particularly preferably 0.5 to 4% by mass with respect to the entire composition.

  The composition of this invention can be manufactured by kneading | mixing a raw material component using an extruder, a Banbury mixer, a kneader, a roll, etc. In kneading, the raw material components may be kneaded all at once, or may be kneaded by a multistage addition method. In addition, although the shape, size, etc. of the raw material are appropriately selected by the production apparatus, the length of the raw material for component (D) for containing the component (D) having a preferable size is preferably 0.1. ~ 6mm.

  As a specific method for producing the composition of the present invention, all the raw material components are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, and the like. Accordingly, a method of granulating the preliminary mixture using an extrusion granulator and the like, and then melt-kneading the granulated product; raw material components excluding the raw material for component (D) are made into a V-type blender, a Henschel mixer, A method of thoroughly mixing using premixing means such as a mechanochemical apparatus or an extrusion mixer, followed by melt-kneading, and then supplying a raw material for component (D) and continuing the melt-kneading (side feed method); etc. Is mentioned. In the case of batch kneading raw material components, the shearing stress applied during melt kneading may cause significant breakage of the raw material for component (D), but the side feed method can suppress this. it can.

  As a suitable example of the side feed method, all the raw material components (mainly resin) except the raw material for component (D) are removed from the main hopper (upstream part) of the extruder by using an extruder with side feed. Supply and sufficiently melt-knead, and then feed the component (D) raw material from an extruder, for example, from a side feeder disposed near the center in the extrusion direction of the cylinder (middle stream portion) This is a method of kneading with a resin.

  The molded product of the present invention comprises the above-described thermoplastic resin composition of the present invention or the raw material components that will form the constituent components of an injection molding device, an extrusion molding device, a profile extrusion molding device, a hollow molding device, a compression molding device. Molding device, vacuum molding device, foam molding device (including the method of injecting supercritical fluid), blow molding device, injection compression molding device, gas assist molding device, water assist molding device, heat insulating mold molding device, rapid heating and cooling It can be manufactured by processing with a known molding apparatus such as a mold molding apparatus, a two-color molding apparatus, a sandwich molding apparatus, or an ultra-high speed injection molding apparatus. That is, the molded article of the present invention contains the thermoplastic resin composition of the present invention.

When a molded product is produced using the molding apparatus, the molding temperature and the mold temperature are appropriately selected depending on the type of raw material components (including other polymers) used.
The cylinder temperature of the molding apparatus in the case of producing a molded product is usually 240 ° C to 300 ° C. The mold temperature is usually 40 ° C to 80 ° C.
In any of the above cases, when the molded product is large, the cylinder temperature is generally set higher than the above temperature.

  The molded product of the present invention may be provided with a through hole, a groove, a concave portion, a convex portion, and the like at an arbitrary position according to the purpose and application. Moreover, various surface treatments can be performed on the molded article of the present invention. “Surface treatment” means vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), coating (hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared ray) It means a process of forming a new layer or part on the surface of a conventionally known resin molded product, such as absorption coating and printing.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Production raw materials The raw materials (resin or copolymer, glass fiber, etc.) used for the production of the thermoplastic resin composition are as follows. The measurement of the graft ratio, intrinsic viscosity [η] and the like were performed according to the above-described methods.
1-1. Raw material [P]
A polycarbonate “NOVAREX 7022PJ” (trade name) manufactured by Mitsubishi Engineering Plastics was used. The viscosity average molecular weight (Mv) is 22,000, and the MFR (temperature 240 ° C., load 10 kg) is 9 g / 10 min.

1-2. Raw material [Q]
Polybutylene terephthalate “DURANEX 200FP” (trade name) manufactured by Wintech Polymer Co., Ltd. was used. The intrinsic viscosity measured at 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (mass ratio) is 0.6 dl / g.

1-3. Raw material [R]
A silicone rubber reinforced resin obtained in Synthesis Example 1 below was used.

Synthesis Example 1 (Synthesis of silicone rubber reinforced resin)
A mixture of 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane was added to 300 parts of an aqueous solution in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved in distilled water. The mixture was stirred and emulsified for 3 minutes. The emulsified dispersion is transferred to a separable flask equipped with a condenser, a nitrogen gas inlet, and a stirrer. Under stirring, the emulsion is heated at 90 ° C. for 6 hours to undergo a condensation reaction, and cooled at 5 ° C. for 24 hours to complete the reaction. It was. As a result, a latex containing a modified polyorganosiloxane rubber with a condensation rate of 92.8% was obtained. Thereafter, the latex was neutralized to pH 7 by adding an aqueous sodium carbonate solution. The volume average particle diameter of the modified polyorganosiloxane rubber was 280 nm.
Next, in a glass flask equipped with a stirrer, 40 parts of the modified polyorganosiloxane rubber, 100 parts of ion exchange water, 1.5 parts of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecyl mercaptan, 15 parts of styrene and Acrylonitrile (5 parts) was accommodated and heated to 45 ° C. with stirring. Thereafter, an activator aqueous solution comprising 0.1 part of ethylenediaminetetraacetic acid sodium salt, 0.003 part of ferrous sulfate, 0.2 part of sodium formaldehyde sulfoxylate dihydrate and 15 parts of ion-exchanged water, and diisopropylbenzene 0.1 part of hydroperoxide was added to initiate polymerization. And after 1 hour, incremental polymerization consisting of 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecyl mercaptan, 0.2 part of diisopropyl hydroperoxide, 30 parts of styrene and 10 parts of acrylonitrile. The ingredients were added continuously over 3 hours and polymerization was continued. After the addition was complete, stirring was continued for 1 hour.
Thereafter, 0.2 part of 2,2-methylene-bis (4-ethylene-6-tert-butylphenol) was added to terminate the polymerization, and a latex containing a silicone rubber reinforced resin was obtained. Subsequently, 2 parts of calcium chloride was added to the latex to coagulate the resin component, washed with water and dried (75 ° C., 24 hours) to recover a white powder (silicone rubber reinforced resin). The polymerization conversion was 97.2%, the grafting rate was 90%, and the intrinsic viscosity [η] (30 ° C. in methyl ethyl ketone) of the acetone soluble component was 0.47 dl / g.

1-4. Raw material [S]
The raw materials S1 to S3 were used as the fibrous filler, and the raw material S4 was used as the other filler.
(1) Raw material S1 (glass fiber)
Glass fiber (chopped strand) “CS03MA FT665” (trade name) manufactured by Owens Corning Japan was used. This product is a chopped strand adjusted to a fiber length of 3 mm after bundling single fibers having a strand diameter of 13 μm with a sizing agent made of an epoxy resin composition.
(2) Raw material S2 (carbon fiber)
Carbon fiber (chopped strand) “CFU” (trade name) manufactured by Nippon Polymer Sangyo Co., Ltd. was used. This product is a chopped strand adjusted to a fiber length of 6 mm after bundling single fibers having a strand diameter of 7 μm with a sizing agent made of a polyurethane resin composition.
(3) Raw material S3 (glass fiber having an irregular cross section)
A flat section chopped glass fiber “CSG 3PA830” (trade name, cut length 3 mm, flat length 28 μm, flat short 7 μm) manufactured by Nitto Boseki Co., Ltd. was used.
(4) Raw material S4 (glass flakes)
Granular glass flake “Micrograss Freka REFG-101” (trade name, average diameter 600 μm, average thickness 5 μm) manufactured by Nippon Sheet Glass Co., Ltd. was used.

1-5. Raw material [T]
The styrene / acrylonitrile copolymer (raw material T1) obtained in Synthesis Example 2 below and the diene rubber reinforced resin (raw material T2) obtained in Synthetic Example 3 were used.

Synthesis Example 2 (Synthesis of raw material T1)
A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, the first reactor was charged with a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and 0.4 part of tert-dodecyl mercaptan as a molecular weight regulator. And a solution in which 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, is dissolved in 5 parts of toluene, are continuously supplied. Polymerization was carried out at 0 ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the styrene / acrylonitrile copolymer. This styrene / acrylonitrile copolymer was used as raw material T1.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this raw material T1 was 0.42 dl / g.

Synthesis example 3 (synthesis of raw material T2)
In a glass flask equipped with a stirrer, in a nitrogen stream, 42 parts of ion-exchanged water, 0.35 part of potassium rosinate, 0.2 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 80 parts of latex containing 32 parts, 19 parts of latex containing 8 parts of styrene / butadiene copolymer rubber (styrene unit amount 30%) having an average particle size of 600 nm, 14 parts of styrene and 6 parts of acrylonitrile are accommodated and stirred. The temperature rose. When the internal temperature reached 40 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.3 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization.
After polymerizing for 30 minutes, 45 parts of ion-exchanged water, 0.7 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.13 part of tert-dodecyl mercaptan and 0.1 part of cumene hydroperoxide were added for 3 hours. Over time. Thereafter, the polymerization was further continued for 1 hour, and 0.2 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to the reaction system to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and wash it with water. Thereafter, it was washed and neutralized with an aqueous potassium hydroxide solution, further washed with water and then dried to obtain a diene rubber reinforced resin. This diene rubber reinforced resin was used as raw material T2. The graft ratio of the graft resin contained in the raw material T2 is 55%, and the content of ungrafted (co) polymer (hereinafter referred to as “acetone soluble content”) is 38%. The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) was 0.45 dl / g.

1-6. Raw material [U]
The following two types were used as antioxidants.
(1) Raw material U1 (antioxidant)
Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name “ADK STAB PEP-36”, manufactured by ADEKA)
(2) Raw material U2 (antioxidant)
2- [1- (2-Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate (trade name “Sumilyzer GS (F)”, manufactured by Sumitomo Chemical Co., Ltd. )

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1 to 12 Comparative Examples 1 to 6 and Reference Examples 1 to 9
After mixing the raw materials [P], [Q], [R], [S], [T] and [U] at the ratios shown in Tables 1 to 3, using a Henschel mixer, A twin-screw extruder “TEX44αII” (model name) manufactured by Steel Manufacturing Co., Ltd. was supplied and melt-kneaded to obtain a thermoplastic resin composition. In addition, the cylinder preset temperature at the time of melt-kneading was 200 to 250 degreeC.

The obtained composition was subjected to the following evaluation test. The results are shown in Tables 1 to 3.
(1) Impact resistance In accordance with ISO 179, Charpy impact strength was measured at a temperature of 23 ° C. The unit is “kJ / m ² ”.
(2) Tensile properties The tensile strength was measured at a temperature of 23 ° C. according to ISO 527. The unit is “MPa”.
(3) Bending properties According to ISO 178, the bending strength and bending modulus were measured at a temperature of 23 ° C. The units are “MPa” and “MPa”, respectively.
(4) Fluidity As an index of moldability, the melt mass flow rate was measured in accordance with ISO 1133 under conditions of a temperature of 240 ° C. and a load of 98N. The unit is “g / 10 minutes”.
(5) Mold shrinkage According to JIS K7152-4, the mold shrinkage was measured at a temperature of 23 ° C. in the MD direction and the TD direction, respectively.
○: Less than 0.5% Δ: 0.5% to 0.7%
×: Over 0.7%

From Tables 1 to 3, the following can be understood.
The comparative example 1 is an example which does not contain the component (A) based on this invention, was inferior to impact resistance, and had a high mold shrinkage rate. Comparative Examples 2 and 3 are examples not containing the component (C) according to the present invention, and the impact resistance was poor. Comparative Example 4 is an example in which the content ratio of the component (C) according to the present invention is too large, and the melt mass flow rate is too low and the molding processability is poor. Comparative Example 5 is an example in which the content ratio of the component (D) according to the present invention is too small, and the rigidity was not sufficient. Comparative Example 6 is an example in which the content ratio of the component (D) according to the present invention is too large, and the fluidity (molding processability) was not sufficient.
On the other hand, according to Examples 1 to 12 , Charpy impact strength, tensile strength, bending strength and bending modulus are all improved, and the melt mass flow rate is in the range of 2.3 to 50 g / 10 min. It can be seen that the balance of impact resistance, rigidity and molding processability is excellent.

  Since the thermoplastic resin composition of the present invention provides a molded product having excellent molding processability and improved balance between impact resistance and rigidity, the molded product obtained is a vehicle, a ship, an OA device, a home appliance, an electric machine. -Suitable for electronic devices, building materials, etc., daily goods, sports equipment, stationery, etc.

Claims (5)

(A) polycarbonate resin, (B) aromatic polyester resin, (C) a compound having a polyorganosiloxane polymer part and a vinyl (co) polymer part, and (D) a fibrous filler And
The above compound (C) is a silicone rubber reinforced graft resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polyorganosiloxane polymer (however, polyorgano Polyorganosiloxane graft copolymer obtained by graft polymerizing at least one vinyl monomer containing at least an epoxy group-containing vinyl monomer to a composite rubber comprising a siloxane rubber component and a polyalkyl (meth) acrylate rubber component Is excluded.)
The content ratios of the polycarbonate resin (A) and the resin (B) are 18 to 40% by mass and 60 to 82% by mass, respectively, when the total of both is 100% by mass,
Content of the said compound (C) is 3-17 mass parts with respect to a total of 100 mass parts of the said polycarbonate resin (A) and the said resin (B),
Content of the said fibrous filler (D) is 40-150 mass parts with respect to a total of 100 mass parts of the said polycarbonate resin (A) and the said resin (B), The thermoplastic resin composition characterized by the above-mentioned. .   The thermoplastic resin composition according to claim 1, wherein the resin (B) is polybutylene terephthalate. The vinyl monomer includes the aromatic vinyl compound and the vinyl cyanide compound,
The thermoplastic resin composition according to claim 1 or 2, wherein a lower limit of a ratio of a total amount of the aromatic vinyl compound and the vinyl cyanide compound contained in the vinyl monomer is 70% by mass .   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the fibrous filler (D) contains glass fibers.   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 4.

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