JP2010031283A - Styrene resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a syndiotactic styrene resin composition which has high mold-release performance in molding, allows little bleedout onto molds and exerts little effect on the appearance of molded articles. <P>SOLUTION: The styrene resin composition comprises (A) 98-10 wt.% of a syndiotactic styrene polymer, (B) 2-90 wt.% of a thermoplastic resin and/or rubber-like elastic body other than the syndiotactic styrene polymer, and (C) 0.01-2.0 pts.wt. of an alkyl-modified silicone oil based on 100 pts.wt. of the total of (A)+(B) above. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a styrenic resin composition, and more particularly to a styrenic resin composition comprising a styrenic polymer mainly having a syndiotactic structure and comprising a specific silicone oil.

  Styrene polymers mainly having a syndiotactic structure (hereinafter simply referred to as “syndiotactic polystyrene”, “syndiotactic styrene polymer”, or “SPS”) have excellent chemical resistance and heat resistance. , Electrical characteristics, and water absorption dimensional stability, and used in various industrial parts as engineering plastics.

  By the way, when plastic industrial parts are produced by injection molding, press molding, vacuum / compression molding, etc., it may be required to shorten the molding cycle in order to reduce production cost and mass production. However, in the molding of syndiotactic polystyrene, if the molding cycle is excessively shortened, deformation may occur due to a protruding pin or the like when the product is taken out from the mold, and there is a difficulty in shortening this molding cycle. Therefore, further expansion of the application range of SPS to the plastic industry field has been limited.

  In general, in order to suppress the extrusion deformation of a product in a short molding cycle, a method of improving the rigidity of the product by adding an inorganic filler to the resin composition, or a mold release agent is added to release the mold. A method for improving the lubricity between a product and a mold is known. By the way, when using a mold release agent, delicate control is requested | required about the affinity between resin used as a base and a mold release agent. That is, if the affinity is excessively good, the release agent is taken into the resin and does not localize on the product surface, so that a release effect cannot be expected. On the other hand, if the affinity is poor, it is not taken into the resin and exhibits a releasing effect, but causes bleed out to the mold and causes a defective appearance of the product.

  Conventionally, in the formation of atactic polystyrene (generally GPPS, HIPS), it is widely known to add dimethyl silicone oil as a release agent or a sliding agent. However, in syndiotactic polystyrene, the kneading temperature, molding temperature, and mold temperature in injection molding are higher than that of atactic polystyrene. The use of the dimethyl silicone oil was not desirable because defects such as bleeding out to the mold occurred.

  Therefore, a high-performance mold release agent that can be preferably applied to the molding of syndiotactic polystyrene has been strongly desired.

  An object of the present invention is to provide a syndiotactic styrene-based resin composition that has high mold release performance at the time of molding and has little influence on bleed out to a mold and product appearance.

  As described above, the present inventors have conducted extensive research to develop a styrenic resin composition containing syndiotactic polystyrene having desirable properties, and as a result, have been conventionally incompatible with styrenic polymers. The inventors have found that the purpose can be achieved by adding a specific amount of the alkyl-modified silicone oil which has been considered, and the present invention has been completed.

That is, the present invention provides the following styrenic resin compositions.
1. (A) Styrene polymer mainly having a syndiotactic structure 98 to 10% by weight, (B) polyethylene, polypropylene, atactic polystyrene, isotactic polystyrene, HIPS, ABS, AS, polyphenylene ether, fumaric acid modified polyphenylene ether And at least one thermoplastic resin selected from maleic acid-modified polyphenylene ether and / or SBR, SEB, SBS, SEBS, SIR, SEP, SIS, SEPS, EPM, EPDM, ethylene / octene copolymer elastomer and maleic acid 2 to 90% by weight of at least one rubber-like elastic body selected from modified SEBS, and (C) an alkyl-modified silicone oil in an amount of 0.01 to 2 with respect to a total of 100 parts by weight of the above (A) + (B). Contains 0.0 part by weight Styrene resin composition comprising a.
2. (A) 95-15% by weight of a styrenic polymer mainly having a syndiotactic structure, (B) polyethylene, polypropylene, atactic polystyrene, isotactic polystyrene, HIPS, ABS, AS, polyphenylene ether, fumaric acid-modified polyphenylene ether And at least one thermoplastic resin selected from maleic acid-modified polyphenylene ether and / or at least one rubber-like elastic body selected from SEBS, SEPS, ethylene-octene copolymer elastomer and maleic acid-modified SEBS 2. The styrenic polymer according to claim 1, comprising 0.2 to 1.5 parts by weight of (C) alkyl-modified silicone oil with respect to a total of 100 parts by weight of (A) + (B). Resin composition.

  According to the present invention, it is possible to obtain a syndiotactic styrene-based resin composition that has high mold release performance during molding and has little influence on bleed out to a mold and product appearance.

Outline sketch of box-shaped molded product for releasability test Conceptual diagram at the time of mold release by protrusion of ejector pin Conceptual diagram of injection molding of flat plate for bleed-out evaluation

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
1. Content of Each Component of Styrenic Resin Composition The styrenic resin composition according to the present invention includes, as an essential component, a syndiotactic styrene polymer, a thermoplastic resin other than a syndiotactic styrene polymer, and / or rubber. In addition to these components, other components may be added as necessary within the range not impairing the object of the present invention.

(1) Syndiotactic styrene polymer The syndiotactic structure in the syndiotactic styrene polymer is a syndiotactic structure, that is, a side chain with respect to a main chain formed from a carbon-carbon bond. In which the phenyl groups are alternately located in opposite directions, and their tacticity is determined by nuclear magnetic resonance ( ¹³ C-NMR) with isotope carbon.
^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of consecutive structural units, for example, a dyad for two, a triad for three, a pentad for five. However, the styrenic polymer having a syndiotactic structure referred to in the present invention is usually 75% or more, preferably 85% or more by racemic dyad, or 30% or more, preferably 50% or more by racemic pentad. Syndiotactic polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoate), their hydrogenated polymers and A mixture thereof or a copolymer containing these as a main component is designated.
Here, as poly (alkyl styrene), poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene) And poly (vinyl styrene). Examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

  Among these, particularly preferable styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiary butyl styrene), poly (p-chlorostyrene), Examples thereof include poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units.

Such a syndiotactic styrenic polymer can be prepared, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum in an inert hydrocarbon solvent or in the absence of a solvent as a catalyst. It can be produced by polymerizing a monomer (corresponding to the styrenic polymer) (Japanese Patent Laid-Open No. 62-187708). Poly (halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912, and these hydrogenated polymers can be obtained by the method described in JP-A-1-178505.
These styrenic polymers mainly having a syndiotactic structure can be used alone or in combination of two or more.

(2) Thermoplastic resins other than syndiotactic styrene-based polymers As thermoplastic resins other than syndiotactic styrene-based polymers, linear high-density polyethylene, linear low-density polyethylene, high-pressure method low-density polyethylene, Polyolefin resins including isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene, 4-methylpentene, cyclic polyolefin, atactic polystyrene, isotactic polystyrene, HIPS, Polystyrene resins such as ABS and AS, polyester resins such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide 6, polyamide 6 , 6 and other known resins such as polyamide resins, polyphenylene ether, PPS or modified ones thereof can be used. Among these thermoplastic resins, polyethylene resins such as polyethylene, polypropylene, atactic polystyrene, isotactic polystyrene, HIPS, ABS, AS and other polystyrene resins, polyphenylene ether, fumaric acid modified polyphenylene ether, maleic acid modified polyphenylene ether are Particularly preferably used. In addition, these thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.

  A styrenic polymer having an atactic three-dimensional structure (hereinafter sometimes referred to as “atactic polystyrene”) is obtained by a polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, or bulk-suspension polymerization. A polymer composed of one or more aromatic vinyl compounds represented by the following general formula (1), or one or more other vinyl monomers copolymerizable with one or more aromatic vinyl compounds: Copolymers, hydrogenated polymers of these polymers, and mixtures thereof. (In the formula, R represents a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, and a substituent containing at least one kind of tin atom; Represents an integer of 1 to 3. However, when m is plural, each R may be the same or different.

  Preferred aromatic vinyl compounds used here include styrene, α-methyl styrene, methyl styrene, ethyl styrene, isopropyl styrene, tertiary butyl styrene, phenyl styrene, vinyl styrene, chlorostyrene, bromostyrene, fluorostyrene, chloro There are methyl styrene, methoxy styrene, ethoxy styrene and the like, and these are used alone or in combination of two or more. Among these, particularly preferred aromatic vinyl compounds are styrene, p-methylstyrene, m-methylstyrene, p-tertiary butylstyrene, p-chlorostyrene, m-chlorostyrene, and p-fluorostyrene.

  Other vinyl monomers that can be copolymerized include vinylcyan compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. , Acrylates such as cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, Octadecyl methacrylate , Methacrylates such as phenyl methacrylate, benzyl methacrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromo And maleimide compounds such as phenyl) maleimide.

  Further, copolymerizable rubber-like polymers include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene and other diene rubber, ethylene-α-olefin copolymer, ethylene-α- Non-diene rubber such as olefin-polyene copolymer, polyacrylic acid ester, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene elastomer, styrene-graft-ethylene-propylene elastomer, Examples thereof include ethylene ionomer resins and hydrogenated styrene-isoprene copolymers.

  The molecular weight of the atactic polystyrene is not particularly limited, but generally has a weight average molecular weight of 10,000 or more, preferably 50,000 or more. Here, when the weight average molecular weight is less than 10,000, the thermal properties and mechanical properties of the obtained molded product are deteriorated, which is not preferable. Furthermore, there is no limitation on the molecular weight distribution, and various types can be used.

  In addition, polyphenylene ether is a known compound, and is used for this purpose. US Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358 Each specification can be referred to. Polyphenylene ethers are usually prepared by an oxidative coupling reaction that produces a homopolymer or copolymer in the presence of a copper amine complex, one or more two or three substituted phenols. Here, the copper amine complex can be a copper amine complex derived from a primary, secondary and / or tertiary amine.

Examples of suitable polyphenylene ethers include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1,4-phenylene ether). ), Poly (2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6) -Isopropyl-1,4-phenylene ether), poly (2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether) ), Poly (2- (4′-methylphenyl) -1,4-phenylene ether), poly (2-bromo-6-phenyl-1,4-phenylene ether), poly (2-methyl-6- Phenyl-1,4 Phenylene ether), poly (2-phenyl-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether), Poly (2-chloro-6-ethyl-1,4-phenylene ether), poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-di-n-propyl-) 1,4-phenylene ether), poly (2-methyl-6-isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-phenylene ether), poly (2 -Methyl-6-ethyl-1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), Poly (2,6-diethyl -1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether) and the like.
Copolymers such as copolymers derived from two or more phenolic compounds such as those used in the preparation of the homopolymer are also suitable. Further examples include a graft copolymer and a block copolymer of a vinyl aromatic compound such as polystyrene and the above-mentioned polyphenylene ether. Of these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used.

(3) Rubber-like elastic body Specific examples of the rubber-like elastic body include, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber. , Styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer ( SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block Copolymer (SEPS), olefin rubber such as ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), ethylene octene copolymer elastomer, or butadiene-acrylonitrile-styrene-core shell rubber (ABS) , Methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene- Core shell rubber (ABS), butadiene-styrene-core shell rubber (SBR), methyl methacrylate-butyl acrylate-siloxane Examples thereof include a core-shell type particulate elastic body such as siloxane-containing core-shell rubber, or a rubber obtained by modifying these.
Of these, SBR, SEB, SBS, SEBS, SIR, SEP, SIS, SEPS, core-shell rubber, EPM, EPDM, ethylene / octene copolymer elastomers or rubbers modified with these are preferably used. These rubber-like elastic bodies can be used alone or in combination of two or more.

(4) Alkyl-modified silicone oil The alkyl-modified silicone oil in the present invention has a structure in which some or all of the side chain methyl groups in the dimethyl silicone oil are substituted with alkyl groups. That is, any CH ₃ — moiety in the [(CH ₃ ) ₂ SiO] _n repeating unit in dimethyl silicone oil may be substituted with an alkyl group, and all CH ₃ — moieties in all repeating units may be those substituted with an alkyl group (i.e., modification rate 100 mol% of one) or, CH ₃ - portions repeating units and CH substituted with an alkyl group ₃ - repeating units moiety is not substituted with the alkyl group Also included are so-called random bodies in which and are chained at random, and so-called block bodies in which both are chained together.

CH ₃ - of the part, assuming that called the existence ratio of those substituted in the alkyl group and modification ratio (unit:%), modification ratio is preferably not less than 20 mol%. If it is less than 20 mol%, bleeding out tends to occur. The type of the alkyl group is not particularly limited, and examples thereof include various types such as a linear alkyl group and a branched alkyl group. Specific examples include a linear or branched alkyl group having 2 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, such as an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group.
These alkyl-modified silicone oils can be used alone or in combination of two or more.

(5) Other additive components The resin composition according to the present invention is provided with an inorganic filler, an antioxidant, a nucleating agent, a plasticizer, a flame retardant, a flame retardant aid, a pigment, and an electrification as long as the object of the present invention is not impaired. Additives such as inhibitors can be blended.

(i) Inorganic fillers Inorganic fillers include fibrous ones, granular ones and powdery ones. Examples of the fibrous filler include glass fiber, carbon fiber, whisker, mica and the like. The shape includes a cross shape, a mat shape, a focused cut shape, a short fiber, a filament shape, a whisker, and the like. In the case of the focused cut shape, a length of 0.05 mm to 50 mm and a fiber diameter of 5 to 20 μm are preferable. . On the other hand, as granular and powder fillers, for example, talc, carbon black, graphite, titanium dioxide, silica, mica, calcium sulfate, calcium carbonate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, and oxidation Examples thereof include tin, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flakes, and glass beads.

  Among the various fillers as described above, carbon fibers, mica, calcium carbonate, and glass fillers such as glass powder, glass flakes, glass beads, glass filaments, glass fibers, glass robbing, and glass mats are preferable, among these A glass filler is particularly preferable, and glass fiber is more preferable.

  Further, the above-mentioned filler is preferably a surface-treated one. The coupling agent used for the surface treatment is used for improving the adhesion between the filler and the resin, and so-called silane coupling agents, titanium coupling agents, and the like are conventionally known. Any one can be selected and used. Among them, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Amino silane, epoxy silane, and isopropyl tri (N-amidoethyl, aminoethyl) titanate are preferable.

  Moreover, the film-forming substance for glass can be used together with said coupling agent. The film-forming substance is not particularly limited, and examples thereof include polyester-based, polyether-based, urethane-based, epoxy-based, acrylic-based, and vinyl acetate-based polymers. In addition, these inorganic fillers can be used individually by 1 type or in combination of 2 or more types.

(ii) Antioxidant Antioxidants can be arbitrarily selected from known ones such as phosphorus, phenol and sulfur. In addition, these antioxidants can be used alone or in combination of two or more.

(iii) Nucleating agents As nucleating agents, metal salts of carboxylic acids including aluminum di (pt-butylbenzoate), phosphoric acids including sodium methylenebis (2,4-di-tert-butylphenol) acid phosphate These can be arbitrarily selected from known ones such as metal salts, talc and phthalocyanine derivatives. Specific product names include NA11 and NA21 manufactured by Asahi Denka Co., Ltd., PTBBA-AL manufactured by Dainippon Ink and the like. These nucleating agents can be used alone or in combination of two or more.

(iv) Plasticizer The plasticizer can be arbitrarily selected from known ones such as polyethylene glycol, polyamide oligomer, ethylene bisstearoamide, phthalate ester, polystyrene oligomer, polyethylene wax, and silicone oil. In addition, these plasticizers can be used individually by 1 type or in combination of 2 or more types.

(V) Flame retardants, flame retardant aids Flame retardants include brominated polystyrene, brominated syndiotactic polystyrene, brominated polymers such as brominated polyphenylene ether, bromine-containing diphenylalkane, bromine-containing diphenyl ether. It can be arbitrarily selected from known compounds such as brominated aromatic compounds.
Further, as the flame retardant aid, an antimony compound such as antimony trioxide and other known materials can be arbitrarily selected and used.
These flame retardants and flame retardant aids can be used alone or in combination of two or more.

2. (A) SPS 100 to 5% by weight (including 100), preferably 98 to 10% by weight, more preferably 95 to 15% by weight. (B) Thermoplastic resin other than SPS and / or Alternatively, it is 0 to 95% by weight (including 0), preferably 2 to 90% by weight, and more preferably 5 to 85% by weight, of a rubber-like elastic body. If the SPS is less than 5% by weight, the properties of the SPS may not be exhibited. In (B), when a thermoplastic resin other than SPS and a rubber-like elastic body are used in combination, the blending ratio of both is not particularly limited. What is necessary is just to select a compounding ratio suitably according to the objective.
(C) The addition amount of the alkyl-modified silicone oil is 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the total amount of the thermoplastic resin and / or rubber-like elastic body other than (A) SPS and (B) SPS. The amount is preferably 0.2 to 1.5 parts by weight. When the amount is less than 0.1 parts by weight, the effect of improving the releasability cannot be expected. When the amount is more than 2.0 parts by weight, the effect of improving the releasability can be expected, but the appearance of the product such as silver is poor. There is a risk that problems such as a decrease in continuous productivity due to the occurrence of bleed out to the surface may occur.

3. Method for Preparing Styrenic Resin Composition According to the Present Invention The method for preparing the styrene resin composition according to the present invention is not particularly limited and can be prepared by a known method. For example, the above components may be blended by various methods such as mixing at room temperature or melt kneading, and the method is not particularly limited. Among these mixing / kneading methods, melt kneading using a twin screw extruder is preferably used. In melt kneading using a twin screw extruder, kneading at a temperature higher than the melting point of the SPS used and lower than 350 ° C. is preferred. If the kneading temperature is lower than the melting point of the SPS used, the viscosity of the resin is too high, which is not preferable because the productivity may be lowered, and if it exceeds 350 ° C., the resin may be thermally decomposed.

4). Molding Method Using Styrenic Resin Composition According to the Present Invention The molding method is not particularly limited, and can be molded by a known method such as injection molding or extrusion molding. In injection molding, it is preferable that the molding temperature is not lower than the melting point of SPS used and lower than 350 ° C. If the molding temperature is lower than the melting point of the SPS used, it is not preferable because the fluidity may decrease, and if it exceeds 350 ° C., the resin may be thermally decomposed, which is not preferable. Moreover, as mold temperature, 40 to 200 degreeC is preferable and 50 to 180 degreeC is still more preferable. When the mold temperature is less than 40 ° C., SPS does not crystallize sufficiently, and the characteristics of SPS may not be sufficiently exhibited, which is not preferable. Moreover, when it exceeds 200 degreeC, the rigidity at the time of mold release may fall, and there exists a possibility that an ejector cracks and a deformation | transformation may generate | occur | produce.

5). Uses of Styrenic Resin Composition According to the Present Invention The styrene resin composition according to the present invention can be used for various purposes and is not particularly limited, but in the electrical / electronic field, various connectors (SLOT, PGA, D-SUB, AGP, PCI, USB, audio jack, etc.), printed circuit board, LED parts, terminal block, relay box, F terminal, motor insulator, power module, fan motor parts (frame, fan), lens surrounding parts (CD) Pickup lens holders, DVD pickup lens holders), etc. In the automotive field, in-vehicle connectors, control unit boxes, fuse boxes, junction boxes, reflectors, extensions, canisters, various valves, radiator grills Grills, marks, back panels, door mirrors, wheel caps, air spoilers, motorcycle cowls, cylinder head covers, instrument panels, meter hoods, pillars, glove boxes, console boxes, speaker boxes, lids, etc. In the appliance field, housing, chassis, cassette case, CD magazine, remote control case, connector, fan, refrigerator parts (lining, tray, arm, door cap, handle, fan, etc.), vacuum cleaner parts (housing, handle, pipe) , Suction port, fan guide, etc.), air conditioner parts (housing, fan, remote control case, etc.), pot, fan, ventilation fan, washing machine, parts for lighting equipment, parts for dish dryer, parts for microwave oven (choke cover, roller) Ring), bag Examples include terry cases.

  Other general equipment includes printers (housing, chassis, ribbon cassette, tray, ink peripheral parts, etc.), copiers (computers (housing, floppy disk shell, keyboard, etc.)), projector parts, telephones, communication equipment (housing, Handset, mechanical chassis, sewing machine, register, typewriter, computer, optical equipment, musical instruments, etc., toys, leisure, sports equipment, remote control car, block, pachinko machine parts, surfboard, helmet, toilet seat, toilet Various parts including lids, tanks, shower parts, pump parts, water supply / drains, lunch boxes, various containers, pots, building material housing parts, containers, furniture, stationery (ballpoint pens, magic, writing instrument trays, etc.), stamp stands, etc. , Pipes, sheets, trays, films, etc. And the like.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
(1) Raw material used (A) Syndiotactic styrene polymer / SPS1: Weight average in terms of polystyrene measured by GPC method at 150 ° C. using homosyndiotactic polystyrene 1,2,4-trichlorobenzene as a solvent Molecular weight Mw = 200,000, Mw / Mn = 2.20
SPS2: Syndiotactic styrene-paramethylstyrene copolymer 1,2,4-trichlorobenzene as solvent, weight average molecular weight in terms of polystyrene measured by GPC method at 150 ° C. Mw = 190,000, Mw / Mn = 2.30

(B1) Thermoplastic resin other than syndiotactic styrenic polymer FAPPO: Fumaric acid-modified polyphenylene ether produced in Production Example 1 PPO1: Poly (2,6-dimethyl-1,4-phenylene ether) Mitsubishi Gas YPX-100H manufactured by Kagakusha
-PPO2: Poly (2,6-dimethyl-1,4-phenylene ether) YPX-100L manufactured by Mitsubishi Gas Chemical Company
・ HH30: GPPS Idemitsu styrene HH30 made by Idemitsu Petrochemical Co., Ltd.
・ 640UF: High density polyethylene Idemitsu Petrochemical Co., Ltd. IDEMITSU HD 640UF

(B2) Rubber-like elastic body M1962: Maleic acid-modified SEBS type elastomer, Asahi Kasei Kogyo Co., Ltd. Tuftec M1962
G1651: Crayton G1651 manufactured by SEBS type elastomer shell company
・ Sep. 8006: Septon 8006 manufactured by SEBS type elastomer Kuraray
・ Sep. 2104: Septon 2104 manufactured by SEPS type elastomer Kuraray
・ ENG. 8150: Ethylene / octene copolymer elastomer ENGAGE 8150 manufactured by DuPont Dow Elastomer Co., Ltd.

(C) Alkyl-modified silicone oil / SF8416: modified by Toray Dow Corning Silicone Co., Ltd. = 50 mol%
SH203: Toray Dow Corning Silicone Co., Ltd. modification rate = 38 mol%
SH230: Toray Dow Corning Silicone Co., Ltd. modification rate = 38 mol%

(D) Other silicone oils SH510: Methylphenyl silicone oil Toray Dow Corning Silicone Co., Ltd. SH550: Methylphenyl silicone oil Toray Dow Corning Silicone Co., Ltd.

(E) Other components NA21: Nucleating agent, manufactured by Asahi Denka Co., Ltd., Irg. 1010: Irganox 1010 made by antioxidant Ciba Geigy
PEP36: Antioxidant, manufactured by Asahi Denka Co., Ltd. 8010: Flame retardant, SAYTEX 8010 manufactured by 1,2-di (pentabromophenyl) ethaneethyl
・ PATOX: Flame retardant aid, PATOX-M manufactured by Nippon Antimine Co., Ltd.
DHT-4A: Halogen scavenger, manufactured by Kyowa Chemical Co., Ltd. GF: Glass fiber manufactured by Asahi Fiber Glass Co., Ltd. CS 03 JA FT 164G

(2) Evaluation method
(i) Releasability Using an injection molding machine (SH100A manufactured by Sumitomo Heavy Industries, Ltd.), under the following molding conditions, 97 mm (length) x 60 mm (width) x 30 mm (depth), as shown in FIG. A box-shaped molded body having a thickness of 1 mm was molded, and the deformation of the product due to the ejector pin protrusion at the time of product release was observed. The ejector pins are arranged so as to hit the four corners of the bottom plate portion of the box-shaped molded body. The cooling time (molding cycle) is shortened and the shortest cooling time until the protrusion of the ejector pin causes a large visible deformation or the bottom plate of the box-shaped molded product is pierced by the ejector pin. Compared. That is, the shorter the minimum cooling time is, the higher (good) the releasability is. The molding conditions are as follows.
・ Cylinder temperature: 260 ℃ or 290 ℃
-Mold temperature: 80 ° C or 140 ° C
・ Filling time: 1.0 seconds ・ Holding pressure time: 2.0 seconds ・ Holding pressure: 1,900 kgf / cm ²
・ Ejector protrusion speed: 35%

(ii) Product appearance defect The box-shaped molded product produced at the time of the above-mentioned releasability evaluation was visually observed to check for appearance defects such as silver and gas burn.

(iii) Bleed out Using an injection molding machine (SH100A manufactured by Sumitomo Heavy Industries, Ltd.), 500 shots were molded so as to fill the 80 × 80 × 3 mmt flat plate shown in FIG. The deposits near the flow end of the mold were observed. The case where nothing was observed was marked with ○, and the case where oil droplets were observed was marked with ×.
The molding conditions are as follows.
・ Cylinder temperature: 260 ℃ or 290 ℃
-Mold temperature: 80 ° C or 140 ° C

[Production Example 1] Production of fumaric acid-modified polyphenylene ether 1 kg of polyphenylene ether (intrinsic viscosity 0.45 dL / g in chloroform, 25 ° C), 30 g of fumaric acid, 2,3-dimethyl-2,3-diphenyl as a radical generator 20 g of butane (Japanese fats and oils, NOFMER BC) was dry blended and melt kneaded using a 30 mm twin screw extruder at a screw rotation speed of 200 rpm and a set temperature of 300 ° C. At this time, the resin temperature was about 331 ° C. The strands were cooled and pelletized to obtain fumaric acid-modified polyphenylene ether.
In order to measure the modification rate, 1 g of the obtained modified polyphenylene ether was dissolved in ethylbenzene and then reprecipitated in methanol. The recovered polymer was subjected to Soxhlet extraction with methanol, and after drying, the modification rate was determined by the intensity and titration of carbonyl absorption in the IR spectrum. Asked. At this time, the modification rate was 1.45% by weight.

[Example 1]
88 parts by weight of SPS1, 1.5 parts by weight of SF8416 (modification rate 50 mol%), 2 parts by weight of FAPPO, 6 parts by weight of ENGAGE 8150, 2 parts by weight of Septon 2104, 2 parts by weight of G1651, and 0.17 of NA21. After 6 parts by weight, 0.3 parts by weight of Irganox 1010 and 0.3 parts by weight of PEP36 were dry blended, 49 parts by weight of glass fiber (FT164G) was side fed at a cylinder temperature of 290 ° C. using a twin screw extruder. The resulting strand was cooled through a water bath and then pelletized. The obtained pellets were evaluated for releasability, product appearance, and bleed out at a cylinder temperature of 290 ° C. and a mold temperature of 140 ° C. Table 1 shows the results.

[Examples 2-3, Comparative Examples 1-3]
The same operation as in Example 1 was performed except that the mixture was blended as shown in Table 1. The results are shown in Table 1.

[Examples 4-6, Comparative Examples 4-6]
The same procedure as in Example 1 was performed except that the mixture was blended as shown in Table 2. The results are shown in Table 2.

[Examples 7 to 9, Comparative Examples 7 to 9]
They were blended as shown in Table 3 and were carried out in the same manner as in Example 1 except that the cylinder temperature during molding was 260 ° C. and the mold temperature was 80 ° C. The results are shown in Table 3.

[Examples 10-12, Comparative Examples 10-12]
Compounding was carried out as shown in Table 4, and the same procedure as in Example 1 was performed except that the cylinder temperature during molding was 260 ° C. and the mold temperature was 80 ° C. The results are shown in Table 4.

Example 13
76 parts by weight of SPS1, 1.5 parts by weight of SF8416, 4 parts by weight of PPO1, 16 parts by weight of G1651, 4 parts by weight of M1962, 0.6 parts by weight of NA21, 0.3 parts by weight of Irganox 1010, PEP36 After dry blending 0.3 part by weight, melt-kneading is performed while side-feeding 49 parts by weight of glass fiber (FT164G) at a cylinder temperature of 290 ° C. using a twin screw extruder, and the resulting strand is passed through a water bath. After cooling, it was pelletized. The obtained pellets were evaluated for releasability, product appearance, and bleed out at a cylinder temperature of 290 ° C. and a mold temperature of 140 ° C. Table 5 shows the results.

[Examples 14-15, Comparative Examples 13-15]
The same operation as in Example 13 was performed except that the mixture was blended as shown in Table 5. The results are shown in Table 5.

[Examples 16 to 18, Comparative Examples 16 to 19]
They were blended as shown in Table 6 and were carried out in the same manner as in Example 1 except that the cylinder temperature during molding was 260 ° C. and the mold temperature was 80 ° C. The results are shown in Table 6.

1: Vertical length of box-shaped molded body 97 mm
2: Horizontal length of box-shaped molded body 60 mm
3: Depth of box-shaped molded product 30 mm
4: Thickness of box-shaped molded body 1 mm
5: Eject turbine trace 6: Gate direction 7: Ejector pin 8: Box-shaped molded body 9: Mold 10: Vertical length of bleed-out evaluation flat plate 80mm
11: Horizontal length of flat plate for bleed out evaluation 80mm
12: Flow stop end 13: Gate direction

Claims (2)

  (A) 98 to 10% by weight of a styrenic polymer mainly having a syndiotactic structure, (B) polyethylene, polypropylene, atactic polystyrene, isotactic polystyrene, HIPS, ABS, AS, polyphenylene ether, fumaric acid-modified polyphenylene ether And at least one thermoplastic resin selected from maleic acid-modified polyphenylene ether and / or SBR, SEB, SBS, SEBS, SIR, SEP, SIS, SEPS, EPM, EPDM, ethylene / octene copolymer elastomer and maleic acid 2 to 90% by weight of at least one rubber-like elastic body selected from modified SEBS, and (C) an alkyl-modified silicone oil in an amount of 0.01 to 2 with respect to a total of 100 parts by weight of the above (A) + (B). Contains 0.0 part by weight Styrene resin composition comprising a.   (A) 95-15% by weight of a styrenic polymer mainly having a syndiotactic structure, (B) polyethylene, polypropylene, atactic polystyrene, isotactic polystyrene, HIPS, ABS, AS, polyphenylene ether, fumaric acid-modified polyphenylene ether And at least one thermoplastic resin selected from maleic acid-modified polyphenylene ether and / or at least one rubber-like elastic body selected from SEBS, SEPS, ethylene-octene copolymer elastomer and maleic acid-modified SEBS 2. The styrenic polymer according to claim 1, comprising 0.2 to 1.5 parts by weight of (C) alkyl-modified silicone oil with respect to a total of 100 parts by weight of (A) + (B). Resin composition.

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