JP2015218282A - Thermoplastic resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has fluidity (fluidity when molten) suitable for production of a molding, is excellent in molding processability, is suppressed in occurrence of warp due to shrinkage of the molten resin in the cooling process after molding and provides a molding excellent in balance between impact resistance and rigidity.SOLUTION: A thermoplastic resin composition comprises (A) a polycarbonate resin, (B) a compound having a polyorganosiloxane-based polymer part and a vinyl-based (co)polymer part and (C) a filler, and ingredient (C) is a glass fiber having an average value of the ratio (major diameter/minor diameter) of the major diameter to the minor diameter of the fiber cross section of 1.5-8.0 and an average value of the long diameter of 10-50 μm. The contents of ingredients (B) and (C) to 100 pts. mass of ingredient (A) is 1-25 pts. mass and 1-160 pts. mass, respectively.

Description

  The present invention has excellent fluidity (fluidity at the time of melting) suitable for the production of a molded article and is excellent in moldability, and the occurrence of warpage due to shrinkage of the molten resin in the cooling process after molding is suppressed, Furthermore, it is related with the thermoplastic resin composition which gives the molded article excellent in the balance of impact resistance and rigidity.

  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 the fiber reinforced polycarbonate resin (composition), 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 discloses a resin composition containing a polycarbonate resin, a thermoplastic polyurethane resin, and glass fibers. Patent Document 3 discloses a polycarbonate-polyorganosiloxane copolymer having a specific structural unit, an average value of the major axis of the fiber cross section of 10 to 50 μm, and an average ratio of major axis to minor axis (major axis / minor axis). The glass fiber reinforced resin composition containing the flat cross-section glass fiber whose value is 1.5-8.0 is disclosed.

Japanese Patent Laid-Open No. 3-27352 JP-A-6-41415 JP 2012-116915 A

  In recent years, fiber reinforced polycarbonate resin (composition) has impact resistance and rigidity, which is not achieved by conventional unreinforced polycarbonate resin or fiber reinforced polycarbonate resin, and clearly reflects the cavity shape of the molding die. There is a need for elaborate moldings. Under such circumstances, the present invention has fluidity (fluidity at the time of melting) suitable for the production of molded products, has excellent moldability, and is caused by shrinkage of the molten resin in the cooling process after molding. It is an object of the present invention to provide a thermoplastic resin composition that suppresses the occurrence of warping and further provides a molded article having an excellent balance between impact resistance and rigidity.

The present invention is as follows.
1. (A) Polycarbonate resin (hereinafter also referred to as “component (A)”), (B) a compound having a polyorganosiloxane polymer part and a vinyl (co) polymer part (hereinafter “component (B) ) "And (C) a filler (hereinafter also referred to as" component (C) "), the component (C) is the ratio of the major axis to the minor axis of the fiber cross section. The average value of (major axis / minor axis) is 1.5 to 8.0 and the average value of the major axis is 10 to 50 μm, and the content of component (B) is the component (A 1) to 25 parts by mass with respect to 100 parts by mass, and the content of component (C) is 1 to 160 parts by mass with respect to 100 parts by mass of component (A). object.
2. In the above 1, the component (B) 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. The thermoplastic resin composition as described.
3. Further, (D) glass flakes, mica, graphite, talc, wollastonite, carbon fibers, and other fillers selected from glass fibers excluding the component (C) (hereinafter also referred to as “component (D)”). 3. The thermoplastic resin composition according to 1 or 2 above, which contains.
4). 4. A molded article comprising the thermoplastic resin composition according to any one of 1 to 3 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. And since the molded product obtained is also excellent in the balance between impact resistance and rigidity and the occurrence of warpage is suppressed, the thermoplastic resin composition of the present invention is, for example, a vehicle, a ship, an OA device, a home appliance, It is suitable for the production of molded products having elaborate shapes, such as electric / electronic devices, building materials, daily goods, sports equipment, stationery, and the like.

It is a schematic perspective view which shows the external appearance of a component (C). It is a schematic perspective view which shows the external appearance of a component (C). It is a schematic perspective view which shows the external appearance of a component (C). It is a schematic perspective view which shows the external appearance of a component (C). It is a schematic sectional drawing which shows the modification of the cross section of the component (C) in FIG.

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 contains components (A), (B), and (C), and the content of the component (B) is 1 to 25 with respect to 100 parts by mass of the component (A). It is a mass part, Content of the said component (C) is 1-150 mass parts with respect to 100 mass parts of said components (A), It is characterized by the above-mentioned.

  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 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 component (B) is rubbery at 25 ° C. and a polyorganosiloxane polymer having a polymerizable unsaturated bond (carbon-carbon double bond) (hereinafter “polyorganosiloxane rubber”). Resin composition (silicone rubber reinforced) obtained by polymerizing (grafting) a vinyl monomer (hereinafter also referred to as “vinyl monomer (b1)”) in the presence of Resin), a polyorganosiloxane rubber part in which at least a part of the carbon-carbon double bond is cleaved, and a vinyl (co) resin part containing a structural unit derived from the vinyl monomer (b1) And is preferably a silicone-based rubber-reinforced graft resin.
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 (b1) used in the production of the silicone rubber reinforced graft resin is a compound having one polymerizable unsaturated bond, and includes an aromatic vinyl compound, a vinyl cyanide compound, and (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 (b1) according to the present invention preferably contains an aromatic vinyl compound. This vinyl monomer (b1) 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 (b1) 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 (b1) 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 (b1) 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 (b1) is preferably 70% by mass, more preferably 80% by mass, 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 (b1) 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 vinyl monomer (b1) is polymerized (graft polymerization) in the presence of a polyorganosiloxane rubber, and 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 (b1) 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 (b1) 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 (b1) 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 (b1).
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 (b1) whole quantity.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (b1), 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 (B) according to the present invention. This resin composition is a polyorganosiloxane rubber that remains without being grafted; a vinyl (co-polymer) containing a structural unit derived from the vinyl monomer (b1) 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 (B) may be included singly or in combination of two or more.

  Since the content of the component (B) contained in the composition of the present invention is excellent in the balance of molding processability, impact resistance and rigidity, 1 to 25 when the component (A) is 100 parts by mass. It is a mass part, Preferably it is 3-17 mass parts, More preferably, it is 5-14 mass parts.

The component (C) has an average value of the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross-section of 1.5 to 8.0 (hereinafter, this form is referred to as “an irregular shape”), and A glass fiber having an average value of the major axis of 10 to 50 μm. In addition, this irregular shape should just be formed in the cross section of at least one part of the length direction of a component (C), and can be set as the aspect formed over several parts or the whole. When the component (C) in which all the fiber cross sections in the length direction have an irregular shape is used, the effect of the present invention can be sufficiently obtained. In addition, when providing the fiber cross section of an irregular shape over multiple parts or the whole, the irregular shape may be the same and may differ.
As said component (C), it can use with the glass fiber which has the external appearance shown by FIGS. 1-4, what these deform | transformed, etc., for example. For example, the cross-sectional shape (rectangle) of the flat plate-like component (C) shown in FIG. 4 is a “>” character (see FIG. 5), or the cross-sectional shape is a curved line. It can also be a thing (not shown) etc. which provided a convex part or a recessed part partially (not shown).

上記式では、平均繊維長は、本発明の熱可塑性樹脂組成物又は成形品において、繊維長を、例えば、走査型電子顕微鏡（ＳＥＭ）により、一定量の数の成分（Ｃ）に対して測定した後の数平均値を用いることができる。また、平均繊維径は、異形形状の断面を同一面積の真円形に換算したときの数平均繊維径をいう。
本発明の熱可塑性樹脂組成物又は成形品から、成分（Ｃ）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（Ｃ）を回収する方法等を適用すればよい。 The relationship between the major axis and the minor axis of the fiber cross section in the component (C) will be described with reference to FIGS. 1 to 4. In the present invention, the ratio between the average value of the major axis d2 and the average value of the minor axis d1 (major axis / The minor axis) is 1.5 to 8.0, preferably 2.0 to 2.0 because the molded article obtained has little anisotropy of the shrinkage rate, is excellent in impact resistance and rigidity, and warpage is suppressed. It is -6.0, More preferably, it is 2.5-5.0.
Moreover, the average value of the major axis of the fiber cross section is 10 to 50 μm, preferably 15 because the molded article obtained has little anisotropy of the shrinkage rate, is excellent in impact resistance and rigidity, and warpage is suppressed. It is -40 micrometers, More preferably, it is 20-35 micrometers.
Furthermore, the said component (C) is a glass fiber which has a long shape, The average value (average fiber length) of the length L shown by FIGS. 1-4 is preferably 0.1-2.0 mm, More preferably, it is 0.15-1.0 mm, More preferably, it is 0.2-0.8 mm. In addition, the aspect ratio represented by the following formula is preferably 2 to 120, more preferably 2.5 to 70, because the molded article obtained has little shrinkage anisotropy and is excellent in mechanical strength. Preferably it is 3-50. The shape in the length direction is usually a linear shape as shown in FIGS. 1 to 4, but may be a wavy shape, a zigzag shape, a curved shape, a spiral shape, or the like.

In the above formula, the average fiber length is measured with respect to a certain number of components (C) by, for example, a scanning electron microscope (SEM) in the thermoplastic resin composition or molded article of the present invention. The number average value after this can be used. Moreover, an average fiber diameter says the number average fiber diameter when converting the cross section of a deformed shape into the perfect circle of the same area.
When isolating component (C) 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 (C) may be applied.

The glass constituting the component (C) may be one 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, phosphate glass and the like. Is mentioned. 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 component (C) is not particularly limited and may be a single fiber, or a chopped strand obtained by twisting a number of long single fibers, bundling them with a glass fiber bundling agent, and then cutting them. , Roving, milled fiber and the like. Moreover, you may have the part or layer by the surface treating agent for glass fibers on the surface of the said component (C).

As the sizing agent for glass fiber, 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, Composition containing urethane 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 Products, compositions containing polyvinyl acetate, compositions containing polyester resins, compositions containing polyacrylates, compositions containing modified polyolefin resins, compositions containing starch or polyvinyl alcohol, and fats and the like.
Examples of the surface treatment agent include reactive coupling agents; higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants.

  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 component (C) may be modified by both the sizing agent and the surface treatment agent.

  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 molding processability, impact resistance and rigidity, and a molded product in which the occurrence of warpage is suppressed is obtained. ) Is 100 parts by mass, it is 1 to 160 parts by mass, preferably 5 to 130 parts by mass, and more preferably 10 to 120 parts by mass.

In order to further improve the impact resistance and rigidity, the composition of the present invention can contain a filler other than the component (C), that is, the component (D) which is another filler.
Examples of the component (D) include glass flake, mica, graphite, talc, wollastonite, carbon fiber, and glass fiber excluding the component (C). Of these, glass flakes and carbon fibers are preferred.
In the composition of the present invention, the component (D) may be included singly or in combination of two or more.

  The content of the component (D) contained in the composition of the present invention is 1 to 100 parts by mass when the component (A) is 100 parts by mass because the impact resistance and rigidity are further improved. , Preferably it is 3-70 mass parts, More preferably, it is 5-50 mass parts.

  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.

The composition of the present invention may further contain other resins.
The other resin is a resin not included in the component (B), and includes a vinyl (co) polymer (aromatic vinyl (co) polymer containing a structural unit derived from a vinyl monomer, Acrylic (co) polymer, polyvinyl chloride resin, polyvinylidene chloride resin, fluorine resin, etc., rubber reinforced resin (ABS resin, AES resin, ASA resin, etc.), polyester resin (polyethylene terephthalate, polyethylene (terephthalate / adipate) ), Polyethylene naphthalate, polybutylene terephthalate, polybutylene (terephthalate / adipate), polybutylene (terephthalate / decane dicarboxylate), polybutylene naphthalate, polycyclohexanedimethylene terephthalate, etc., polyolefin resin, polyamide resin, etc. It is done. These resins may be used alone or in combination of two or more.
When the composition of the present invention contains other resin, the upper limit of the content is preferably 60 parts by mass, more preferably 100 parts by mass relative to the total of 100 parts by mass of the component (A) and the component (B). 45 parts by mass.

  In the present invention, another preferable resin is a diene rubber, a hydrogenated diene rubber, an acrylic rubber, and a rubber polymer selected from ethylene / α-olefin rubber, or a non-rubber polymer. Resin (hereinafter “component”) obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound (hereinafter also referred to as “vinyl monomer (e1)”) in the presence. (E) ") and polyester resin. Hereinafter, the resin (rubber reinforced resin) obtained by polymerizing the vinyl monomer (e1) in the presence of the rubber polymer is referred to as component (E1), and in the absence of the rubber polymer. The resin (vinyl copolymer) obtained by polymerizing the vinyl monomer (e1) is referred to as component (E2).

  The component (E1) is a vinyl monomer (e1) 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, 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 (e1) used in the production of the component (E1) may be a monomer composed of an aromatic vinyl compound and a vinyl cyanide compound, or an aromatic vinyl compound, a vinyl cyanide compound, and A monomer composed of another 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 (e1), the explanation of the aromatic vinyl compound exemplified as the vinyl monomer (b1) used for forming the component (B) 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 (e1), the explanation of the vinyl cyanide compound that can be used as the vinyl monomer (b1) used for forming the component (B) 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 (e1), (meth) acrylic acid which can be used as the vinyl monomer (b1) 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.

  The manufacturing method of the said component (E1) 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 (B).

In the rubber-reinforced resin produced as described above, a vinyl (co) polymer containing a structural unit derived from the vinyl monomer (e1) 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 (e1) And a (co) polymer.
The graft ratio of the graft resin contained in the rubber reinforced resin is measured in the same manner as in the case of the silicone rubber reinforced graft resin contained in the component (B), from the viewpoint of impact resistance, molded appearance, and rigidity. Preferably it is 20% or more, More preferably, it is 30% or more, More preferably, it is 40 to 150%.

Preferred examples of the component (E1) are shown below.
(1) Diene rubber reinforced resin obtained by polymerizing vinyl monomer (e1) composed of aromatic vinyl compound and vinyl cyanide compound in the presence of diene rubber (2) Presence of diene rubber Below, diene rubber reinforced resin obtained by polymerizing vinyl monomer (e1) consisting of aromatic vinyl compound, vinyl cyanide compound and (meth) acrylic acid ester compound (3) Presence of diene rubber Below, diene rubber reinforced resin obtained by polymerizing vinyl monomer (e1) composed of aromatic vinyl compound, vinyl cyanide compound and maleimide compound (4) Presence of ethylene / α-olefin rubber Below, an ethylene / α-olefin rubber-reinforced resin obtained by polymerizing a vinyl monomer (e1) comprising an aromatic vinyl compound and a vinyl cyanide compound

  In the composition of the present invention, the component (E1) may be included singly or in combination of two or more.

  When the composition of the present invention contains the component (E1), the content of the component (E1) is excellent in the balance of molding processability, impact resistance, and rigidity, so the component (A) and the component (B ) Is preferably 3 to 30 parts by mass, more preferably 5 to 25 parts by mass, and still more preferably 8 to 15 parts by mass.

  Next, the component (E2) is a vinyl copolymer obtained by polymerizing a vinyl monomer (e1) containing an aromatic vinyl compound and a vinyl cyanide compound. That is, this vinyl copolymer has 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 “structure”). Unit (ey) "), and may optionally contain a structural unit derived from another vinyl monomer (hereinafter also referred to as" structural unit (ez) "). Good copolymer.

The explanation of the aromatic vinyl compound exemplified as the vinyl monomer (b1) used for forming the component (B) is applied to the aromatic vinyl compound forming the structural unit (ex). The structural unit (ex) contained in the component (E2) 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 (E2) is preferably 40 to 85% by mass, more preferably 50 to 50% when the total of the structural units constituting the component (E2) is 100% by mass. 80 mass%, More preferably, it is 60-75 mass%. When the content of the structural unit (ex) is 40 to 85% 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 (b1) used for forming the component (B) is applied to the vinyl cyanide compound that forms the structural unit (ey). The structural unit (ey) contained in the component (E2) 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 (E2) is preferably 15 to 60% by mass, more preferably 20 to 20%, assuming that the total of structural units constituting the component (E2) is 100% by mass. It is 50 mass%, More preferably, it is 25-40 mass%. When the content of the structural unit (ey) is 15 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 (E2) includes a structural unit (ez), the upper limit of the content is the sum of the structural units constituting the component (E2), that is, the structural units (ex), (ey), and (ez) ) Is 100% by mass, preferably 40% by mass, more preferably 25% by mass.

  The component (E2) is preferably a vinyl copolymer composed of structural units (ex) and (ey), and a vinyl copolymer composed of structural units (ex) and (ey) and a structural unit ( ex), (ey) and a combination with a vinyl copolymer consisting of (ez) may be used.

The weight average molecular weight (Mw) of the component (E2) 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 (E2) 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 (E2) 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 (E2) may be included singly or in combination of two or more.

  When the composition of the present invention contains the component (E2), the content of the component (E2) is excellent in the balance of molding processability, impact resistance, and rigidity. Therefore, the component (A) and the component (B ) Is preferably 3 to 30 parts by mass, more preferably 5 to 25 parts by mass, and still more preferably 8 to 15 parts by mass.

  The composition of the present invention may further comprise a plasticizer, an antioxidant, an ultraviolet absorber, an anti-aging agent, a flame retardant, a lubricant, a stabilizer, a weathering agent, a light stabilizer, a heat stabilizer, depending on the purpose and application. , Antistatic agents, water repellents, oil repellents, antifoaming agents, antibacterial agents, preservatives, colorants (pigments, dyes, etc.), fluorescent whitening agents, conductivity-imparting agents, etc. .

  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 (hereinafter also referred to as “component (F)”) include halogen-containing compounds, phosphorus-containing compounds, guanidine-based compounds, silicone-based compounds, and the like. These can be used alone or in combination of two or more.

As halogen-containing compounds,
(F1) Brominated polyethylene, tetrabromoethane, tetrabromocyclooctane, hexabromocyclododecane, dibromoethyldibromocyclohexane, dibromodimethylhexane, 2- (bromomethyl) -2- (hydroxymethyl) -1,3-propanediol, Dibromoneopentyl glycol, tribromoneopentyl alcohol, pentaerythrityl tetrabromide, monobromodipentaerythritol, dibromodipentaerythritol, tribromodipentaerythritol, tetrabromodipentaerythritol, pentabromodipentaerythritol, hexabromodipentaerythritol Brominated aliphatic compounds such as hexabromotripentaerythritol, polybrominated pentaerythritol, or derivatives thereof, Bromine cycloaliphatic compound or a derivative thereof;
(F2) Tribromo of tetrabromobisphenol A, tetrabromobisphenol S, tetrabromobisphenol A-diallyl ether, tetrabromobisphenol A-dimethallyl ether, tetrabromobisphenol A-diglycidyl ether, tetrabromobisphenol A-diglycidyl ether Phenol adduct, tetrabromobisphenol A-bis (2-hydroxydiethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (2-bromoethyl ether), tetrabromo Bisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), tetra Romo bisphenol A- polycarbonate oligomer, tetrabromobisphenol A- diglycidyl ethers such as brominated bisphenol adduct epoxy oligomer, brominated bisphenols or derivatives thereof;
(F3) hexabromobenzene, pentabromotoluene, ethylenebispentabromodiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, bis (2,4,6-tribromophenoxy) ethane, tetrabromophthalic anhydride, octabromotrimethylphenylindane, Tribromophenyl allyl ether, 2,3-dibromopropyl pentabromophenyl ether, octabromo-1,1,3-trimethyl-1-phenylindane, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, ethane-1 , 2-bis (pentabromophenyl), bis (2,4,6-tribromophenoxy) ethane, ethylenebistetrabromophthalimide, polydibromophenylene Oxide, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, tris (2,3-dibromopropyl-1) isocyanurate, tris (tribromophenyl) cyanurate, atactic Brominated aromatic compounds or derivatives thereof, such as brominated polystyrene having a structure and brominated styrene / propylene copolymer having an atactic structure;
(F4) Pentabromobenzyl acrylate, atactic brominated styrene / methyl methacrylate copolymer, atactic brominated styrene / methyl methacrylate / glycidyl methacrylate copolymer, atactic brominated styrene / glycidyl methacrylate copolymer Brominated (meth) acrylic compounds such as polymers and polypentabromobenzyl acrylate;
(F5) Bromine atom and nitrogen atom-containing compounds such as ethylenebisdibromonorbornanedicarboximide and tris (2,3-dibromopropyl) isocyanurate;
(F6) Chlorine atom-containing compounds such as chlorinated paraffin, chlorinated naphthalene, perchloropentadecane, chlorinated aromatic compounds, and chlorinated alicyclic compounds;
(F7) Brominated inorganic compounds such as ammonium bromide are listed.

（式中、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７は、それぞれ、互いに独立して、アリール基又はアラルキル基であり、Ｘはアリーレン基であり、ｊ、ｋ、ｌ及びｍは、それぞれ、互いに独立して、０又は１であり、Ｎは１〜５の整数である。） As phosphorus-containing compounds, phosphoric acid esters represented by the following general formula (4) and salts thereof, phosphorous acid esters represented by the following general formula (5) and salts thereof, and represented by the following general formula (6) Phosphonic acid esters and salts thereof, condensed phosphoric acid esters represented by the following general formula (7), phosphazene derivatives, and the like.
O = P (OR ¹¹ ) _s (OM ^{n +} _{1 / n} ) _3-s (4)
(In the formula, each R ¹¹ is independently a hydrocarbon group having 1 to 30 carbon atoms, and each M is independently a hydrogen atom, or Group 1A, Group 1B of the periodic table, (It is a metal atom selected from Group 2A and Group 2B, s is 1, 2 or 3, and n is 1 or 2.)
_{^{P (OR 11) t (OM}} n + 1 / n) 3-t (5)
(In the formula, each R ¹¹ is independently a hydrocarbon group having 1 to 30 carbon atoms, and each M is independently a hydrogen atom, or Group 1A, Group 1B of the periodic table, (It is a metal atom selected from Group 2A and Group 2B, t is 1, 2, or 3, and n is 1 or 2.)
_{^{O = P (R 12) (}} OM n + 1 / n) 2 (6)
(In the formula, R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and each M is independently a hydrogen atom or group 1A, group 1B of the periodic table, (It is a metal atom selected from Group 2A and Group 2B, and n is 1 or 2. However, the case where all of R ² and M are hydrogen atoms is excluded.)

(Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently an aryl group or an aralkyl group, X is an arylene group, j, k, l and m are Independently from each other, it is 0 or 1, and N is an integer of 1 to 5.)

In the phosphoric acid ester represented by the general formula (4), R ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms, but may be an aliphatic hydrocarbon group (which may be linear or branched). , An alicyclic hydrocarbon group (which may have a substituent) and an aromatic hydrocarbon group (which may have a substituent), and a saturated type or an unsaturated type But you can. The number of carbon atoms is preferably 6 to 28, more preferably 10 to 24. In addition, when s = 2 or s = 3, a ring structure may be formed by two R ¹¹ .

When s = 1, the phosphate ester represented by the general formula (4) is a monoester such as methyl dihydrogen phosphate, ethyl dihydrogen phosphate, hexyl dihydrogen phosphate, octyl dihydrogen. Examples include phosphate, nonyl dihydrogen phosphate, decyl dihydrogen phosphate, dodecyl dihydrogen phosphate, octadecyl dihydrogen phosphate, nonylphenyl dihydrogen phosphate, and the like. When s = 2, it is a diester such as dimethyl phosphate, diethyl phosphate, dihexyl phosphate, dioctyl phosphate, di (2-ethylhexyl) phosphate, dinonyl phosphate, didecyl phosphate, didodecyl phosphate, ditetradecyl phosphate, diester Examples include octadecyl phosphate, diphenyl phosphate, dibenzyl phosphate and the like. It can also be a metal salt of each compound. Further, when s = 3, it is a triester, for example, trimethyl phosphate, triethyl phosphate, trihexyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, Examples include cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate and the like.
Furthermore, in the case of s = ^2, to form a ring structure with ^{R 11} to each other, sodium 2,2-methylenebis (4,6-di -tert- butylphenyl) phosphate, sodium 2,2'-methylenebis ( 4,6-di-tert-butylphenyl) phosphate, lithium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, sodium-2,2'-ethylidenebis (4,6-di) -Tert-butylphenyl) phosphate, lithium-2,2'-ethylidenebis (4,6-di-tert-butylphenyl) phosphate, and the like can also be used.

In the phosphite represented by the above general formula (5), R ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms, but may be an aliphatic hydrocarbon group (straight or branched). ), An alicyclic hydrocarbon group (which may have a substituent) and an aromatic hydrocarbon group (which may have a substituent), and may be saturated or unsaturated. It may be a mold. The number of carbon atoms is preferably 6 to 28, more preferably 10 to 24.

  The phosphite ester represented by the general formula (5) is a monoester when t = 1, for example, methyl dihydrogen phosphite, ethyl dihydrogen phosphite, hexyl dihydrogen phosphite, Octyl dihydrogen phosphite, nonyl dihydrogen phosphite, decyl dihydrogen phosphite, dodecyl dihydrogen phosphite, octadecyl dihydrogen phosphite, hexacosyl dihydrogen phosphite, dodecyl phenyl dihydrogen phosphite Etc. When t = 2, it is a diester, for example, dimethyl hydrogen phosphite, diethyl hydrogen phosphite, dihexyl hydrogen phosphite, dioctyl hydrogen phosphite, di (2-ethylhexyl) hydrogen phosphite, dinonyl hydro Genphosphite, didecyl hydrogen phosphite, didodecyl hydrogen phosphite, ditetradecyl hydrogen phosphite, dioctadecyl hydrogen phosphite, octyl benzyl hydrogen phosphite, nonyl tridecyl hydrogen phosphite, butyl eico Examples thereof include silhydrogen phosphite, diphenyl hydrogen phosphite, dibenzyl hydrogen phosphite and the like. When t = 3, it is a triester, for example, trimethyl phosphite, triethyl phosphite, trihexyl phosphite, trioctyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tridodecyl phosphite Phyto, trioctadecyl phosphite, triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, diphenyl decyl Examples thereof include phosphite and phenyl didecyl phosphite. It can also be a metal salt of each compound.

In the phosphonate represented by the general formula (6), R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. In the latter case, an aliphatic hydrocarbon group (straight chain) Or an alicyclic hydrocarbon group (which may have a substituent) and an aromatic hydrocarbon group (which may have a substituent). Also, it may be saturated or unsaturated. The number of carbon atoms is preferably 6 to 28, more preferably 10 to 24.

  Examples of the phosphonic acid ester represented by the general formula (6) include dimethyl phosphonate, diethyl phosphonate, dibutyl phosphonate, dihexyl phosphonate, dioctyl phosphonate, didecyl phosphonate, didodecyl phosphonate, dioctadecyl phosphonate, and phosphonic acid. Examples include diphenyl acid, ditolyl phosphonate, dimethyl methyl phosphonate, diethyl ethyl phosphonate, diisopropyl methyl phosphonate, dioctyl phenyl phosphonate, and diphenyl methyl phosphonate. It can also be a metal salt of each compound.

In the condensed phosphate compound represented by the general formula (7), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are an aryl group or an aralkyl group, preferably a cresyl group, a phenyl group, a xylenyl group, a propyl group. A phenyl group and a butylphenyl group; X is an arylene group, preferably a hydrocarbon group derived from resorcinol, hydroquinone or bisphenol A.

  Examples of the phosphazene derivatives include cyclic phosphazene compounds (cyclophosphazene compounds), chain phosphazene compounds, and crosslinked phenoxyphosphazene compounds.

  In addition, aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based compound, molybdenum-based compound, zinc stannate, and the like can be used.

  When the composition of the present invention contains the component (F), the content thereof is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (C) and other resins. More preferably, it is 5-20 mass parts, More preferably, it is 7-15 mass parts.

As the stabilizer, inorganic phosphorus-containing compounds such as hydrogen phosphate compounds, phosphorus oxides or halides, and phosphate compounds are preferably used. When the rubber-reinforced resin such as component (B) 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) It 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.
Examples of the hydrogen phosphate compound include a monohydrogen phosphate compound and a dihydrogen phosphate compound, and salts thereof are particularly preferable. The salt is preferably a metal salt or an ammonium salt. The metal atom constituting the metal salt is preferably an element belonging to Groups 1 to 3 of the periodic table, and examples thereof include lithium, sodium, potassium, calcium, copper, zinc, and aluminum. Specific examples of preferable hydrogen phosphate compounds include sodium dihydrogen phosphate, disodium 1 hydrogen phosphate, diammonium hydrogen phosphate, zinc hydrogen phosphate, potassium dihydrogen phosphate, calcium hydrogen phosphate, phosphoric acid Examples include magnesium hydrogen and dilithium monohydrogen phosphate. In addition, the hydrate of these compounds can also be used.
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 part derived from the component (B) (that is, the content of the polyorganosiloxane polymer (polyorganosiloxane rubber)) is impact resistance and From the viewpoint of rigidity, it is preferably 0.1 to 6% by mass, more preferably 0.2 to 4% by mass, and still more preferably 0.3 to 2% by mass with respect to the entire composition.

  The thermoplastic resin composition of the present invention preferably has a melt mass flow rate value (hereinafter referred to as “MFR”) measured in accordance with ISO 1133 under the conditions of a temperature of 240 ° C. and a load of 98 N, preferably 5 to 120 g / 10. Minutes. In addition, MFR in case the thermoplastic resin composition of this invention does not contain a component (F) becomes like this. Preferably it is 5-50 g / 10min, More preferably, it is 6-30 g / 10min, More preferably, it is 7-20 g / 10 Minutes. Moreover, MFR in case the thermoplastic resin composition of this invention contains a component (F) becomes like this. Preferably it is 20-100g / 10min, More preferably, it is 30-85g / 10min, More preferably, it is 35-70g / 10 Minutes. Since the MFR of the thermoplastic resin composition of the present invention is in the range of 5 to 120 g / 10 min, the occurrence of warpage due to the shrinkage of the molten resin in the cooling process after molding is suppressed, and the appearance is excellent. A molded product having an excellent balance between impact resistance and rigidity can be obtained.

  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. The shape, size, and the like of the raw material are appropriately selected depending on the production apparatus, but the length of the raw material for containing the component (C) having a preferable size is preferably 0.1 to 6 mm.

  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 (C) and the raw material for component (D), Mix thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc., then melt-knead, and then continue to supply the component (C) raw material, etc. Method (side feed method); and the like. In the case of batch kneading the raw material components, the shear stress applied during melt kneading may cause significant breakage of the raw material for component (C), and may not include the component (C) having the preferred aspect ratio. It is preferable to apply the side feed method.

  As a suitable example of the side feed method, using an extruder with side feed, all the raw material components (mainly resin) except the raw material for component (C) and the raw material for component (D) are used as the main of the extruder. A side feeder that is supplied from a hopper (the most upstream part) and sufficiently melted and kneaded, and then the component (C) raw material and the like are disposed in the extruder, for example, near the center in the extrusion direction of the cylinder (the middle stream part). And is kneaded with a molten 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 manufacturing a molded article using the above molding apparatus, the molding temperature and the mold temperature are determined depending on the types of the component (A) raw material and the component (C) raw material, or the raw material components used (including other resins). ), Etc., as appropriate.
When manufacturing a molded article, the cylinder temperature of the molding apparatus is usually 250 ° C to 280 ° 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, glass flake, carbon 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]
As a raw material [P] for the component (A), polycarbonate “NOVAREX 7022PJ” (trade name) manufactured by Mitsubishi Engineering Plastics Co., Ltd. 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]
As a raw material [Q] for component (B), 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.

1-3. Raw material [R]
As a raw material [R] for the component (C), 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.

1-4. Raw material [S]
The following three types were used as the raw material [S] for component (D).
(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 (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.
(3) Raw material S3 (carbon fiber)
Carbon fiber (chopped strand) “CFU” (trade name) manufactured by Nippon Polymer Industries 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.

1-5. Raw material [T]
As other resins, the styrene-acrylonitrile copolymer (raw material T1) obtained in Synthesis Example 2 below, the diene rubber reinforced resin (raw material T2) obtained in Synthetic Example 3, and the synthetic example 4 were obtained. Ethylene / α-olefin rubber reinforced resin (raw material T3) was 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.

Synthesis Example 4 (Synthesis of raw material T3)
A 20 liter stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc. was placed in an ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Mooney viscosity (ML _{1 + 4).} , 100 ° C.) = 20) 25 parts, 10.95 parts of styrene, 4.05 parts of acrylonitrile, 0.5 part of tert-dodecyl mercaptan and 110 parts of toluene were heated and heated. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.09 part of tert-butyl peroxyisopropyl monocarbonate was added, and the temperature was further increased. While maintaining the internal temperature at 100 ° C., the polymerization was started at a stirring rotation speed of 100 rpm. After polymerization for 1 hour, 43.8 parts of styrene, 16.2 parts of acrylonitrile, and 0.36 part of tert-butylperoxyisopropyl monocarbonate were continuously added over 3 hours. After 4 hours from the start of polymerization, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion rate was 97%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Subsequently, the reaction liquid was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. Thereafter, the volatile matter was substantially degassed using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), and pelletized to obtain an ethylene / propylene copolymer rubber reinforced resin T3. This ethylene / propylene copolymer rubber reinforced resin was used as a raw material T3. The graft ratio in the graft resin contained in this raw material T3 is 46%, and the content of the ungrafted (co) polymer (acetone-soluble component) is 64%. The intrinsic viscosity [η] ( 30 ° C. in methyl ethyl ketone) was 0.45 dl / g.

1-6. Raw material [U]
The following two flame retardants were used.
(1) Raw material U1 (flame retardant)
1,3-phenylene-bis (dixylenyl) phosphate “PX-200” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd. was used.
(2) Raw material U2 (anti-drip agent)
A polytetrafluoroethylene “Polyflon FA500C” (trade name) manufactured by Daikin Industries, Ltd. was used.

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1-22 and Comparative Examples 1-13
After mixing the raw materials [P], [Q], [R], [S], [T] and [U] at the ratios shown in Tables 1 to 4, 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 4.
(1) Fluidity As an index of molding processability, 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”.
(2) Impact resistance Charpy impact strength was measured at a temperature of 23 ° C. according to ISO 179. The unit is “kJ / m ² ”.
(3) Tensile properties The tensile strength was measured at a temperature of 23 ° C. according to ISO 527. The unit is “MPa”.
(4) Bending properties In accordance with ISO 178, the bending strength and bending modulus were measured at a temperature of 23 ° C. The units are “MPa” and “MPa”, respectively.
(5) Warpage A flat molded product (150 mm x 150 mm x 2 mm) was produced under the following conditions by injection molding using a one-point gate mold, the state of warpage was visually evaluated, and judged according to the following criteria.
<Molding conditions>
Melting temperature of thermoplastic resin composition: 280 ° C
Mold temperature: 50 ℃
Injection / pressure holding time: 10 seconds Cooling time: 40 seconds <Criteria>
○: No warpage Δ: Warpage is small ×: Warpage is large (6) Combustibility Predetermined shape according to Subject 94 of Underwriters Laboratories (UL) using pellets made of a thermoplastic resin composition And a test piece having a size (125 mm × 13 mm × 1 mm) was prepared and subjected to a vertical combustion test.

From Tables 1 to 4, the following can be understood.
Comparative Examples 1 and 2 are examples that do not contain the component (C) according to the present invention, and are inferior in fluidity, and warpage of the molded product was confirmed. The comparative example 3 is a case where the content rate of the component (B) which concerns on this invention is too few, and was inferior to impact resistance. Comparative Example 4 is an example in which the content ratio of the component (B) according to the present invention is too large, the bending modulus is not sufficient, and the rigidity is inferior. Comparative Examples 5 to 9 were cases where the content of the component (B) according to the present invention was too small, and the impact resistance was poor. Comparative Example 10 is an example in which the content ratio of the component (C) according to the present invention is too small, the bending modulus is not sufficient, and the rigidity is inferior. Comparative Example 11 is an example in which the content ratio of the component (C) according to the present invention is too large, the fluidity and the impact resistance are inferior, and the warpage of the molded product was confirmed. The comparative example 12 is a case where the content rate of the component (B) which concerns on this invention is too few, and was inferior to impact resistance. Comparative Example 13 is an example in which the content ratios of components (B) and (C) according to the present invention are both too large, and the impact resistance and rigidity were not sufficient.
On the other hand, according to Examples 1-22, the curvature of the molded product was not confirmed, and Charpy impact strength, tensile strength, bending strength, and bending modulus were all at high levels.

  The thermoplastic resin composition of the present invention is excellent in molding processability, has a good balance of impact resistance and rigidity, and suppresses the occurrence of warping, so that the obtained molded product is a vehicle, ship, OA equipment, home appliance. It is particularly suitable as a molded product having an elaborate shape, such as equipment, electrical and electronic equipment, building materials, daily goods, sports equipment, stationery, and the like.

Claims (4)

In the composition containing (A) a polycarbonate resin, (B) a compound having a polyorganosiloxane polymer part, and a vinyl (co) polymer part, and (C) a filler,
In the component (C), the average value of the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section is 1.5 to 8.0, and the average value of the major axis is 10 to 50 μm. Glass fiber,
Content of the said component (B) is 1-25 mass parts with respect to 100 mass parts of said components (A),
Content of the said component (C) is 1-160 mass parts with respect to 100 mass parts of said components (A), The thermoplastic resin composition characterized by the above-mentioned.   2. The silicone rubber-reinforced graft resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polyorganosiloxane polymer in the component (B). The thermoplastic resin composition described in 1.   Furthermore, (D) Glass flakes, mica, graphite, talc, wollastonite, carbon fiber, and other fillers selected from glass fibers excluding the component (C) are contained. Thermoplastic resin composition.   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 3.

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