WO2004041929A1 - Composition de resine thermoplastique et article forme a partir de ladite composition - Google Patents

Composition de resine thermoplastique et article forme a partir de ladite composition Download PDF

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Publication number
WO2004041929A1
WO2004041929A1 PCT/JP2003/014104 JP0314104W WO2004041929A1 WO 2004041929 A1 WO2004041929 A1 WO 2004041929A1 JP 0314104 W JP0314104 W JP 0314104W WO 2004041929 A1 WO2004041929 A1 WO 2004041929A1
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Prior art keywords
thermoplastic resin
resin composition
poly
styrene
mass
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PCT/JP2003/014104
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English (en)
Japanese (ja)
Inventor
Shinobu Yamao
Manabu Nomura
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Idemitsu Kosan Co., Ltd.
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Publication of WO2004041929A1 publication Critical patent/WO2004041929A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene

Definitions

  • the present invention relates to a thermoplastic resin composition having excellent elastic modulus, mechanical strength, and fluidity, and a molded product thereof.
  • SPS syndiotactic structure
  • the present invention has been made in view of the above circumstances and provides a thermoplastic resin composition having excellent mechanical strength and fluidity, which has been difficult to achieve with a conventional reinforcing agent without lowering the elastic modulus, and a molded article thereof.
  • the purpose is. Disclosure of the invention
  • the present inventors have found that fiber strength used as a reinforcing agent to achieve the above object is As a result of intensive studies on the agent, it was found that a flat fiber reinforcing agent having a long cross section and a short cross section was effective instead of a fiber reinforcing agent having a circular cross section, and the present invention was completed. .
  • thermoplastic resin composition comprising the following components (A) to (F)
  • (E) A flat cross-section fiber reinforcing agent whose cross section perpendicular to the length direction has a major axis and a minor axis.
  • thermoplastic resin composition 10 to 65% by mass based on the thermoplastic resin composition
  • (F) is 0 to 50% by mass based on the thermoplastic resin composition. /. (Including 0), provided that (E) + (F) is 10 to 65 mass based on the thermoplastic resin composition. / 0 .
  • the minor axis (the longest linear distance in the direction perpendicular to the major axis) of the fiber reinforcement is 3 m or more, and the major axis (the linear distance of the longest part of the cross section) Z
  • the minor axis is 2.5 or more
  • the syndiotactic structure of the styrene polymer mainly having a syndiotactic structure which is the component (A) of the present invention, is defined as having a stereochemical structure of syndiotactic. It has a three-dimensional structure in which phenyl groups, which are side chains, are alternately located in opposite directions to the main chain formed from carbon-carbon bonds, and its tacticity is nuclear magnetic properties due to isotope carbon. It is determined by the resonance method (1 3 C one NMR method).
  • the tacticity measured by the 13 C_NMR method is the percentage of the presence of multiple consecutive structural units.For example, in the case of two, 'is diat, three is triad, and five is pentad.
  • the styrenic polymer having a syndiotactic structure according to the present invention is usually 75% or more, preferably 85% or more in racemic diamond, or 30% in racemic pentad.
  • Polystyrene poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (alkoxystyrene) having a syndiotacticity of preferably 50% or more (Benzoic acid ester), a hydrogenated polymer thereof, a mixture thereof, or a copolymer containing these as a main component.
  • poly (alkylstyrene) examples include poly (methylstyrene) and poly (methylstyrene).
  • poly (halogenated alkylstyrene) examples include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
  • preferred styrene polymers having a syndiotactic structure include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), and poly (p-methylstyrene).
  • Styrene-based polymers having such a syndiotactic structure can be prepared, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing a monomer (a monomer corresponding to the styrene-based polymer) (Japanese Patent Application Laid-Open No. Sho 62-18770).
  • poly (halogenated alkylstyrene) is produced by the method described in JP-A-1-46912, and these hydrogenated polymers are produced by the method described in JP-A-11178505. You can do it.
  • these styrene-based polymers having mainly a syndiotactic structure can be used alone or in combination of two or more.
  • the amount of the component (A) is selected in the range of 25 to 90% by mass, preferably 40 to 90% by mass, based on (A) + (B) + (C) + (D). . If the amount is less than 25% by mass, moldability, If the strength and heat resistance decrease, and if the content exceeds 90% by mass, the strength and heat resistance may decrease.
  • the component (B) of the present invention contains a chain having compatibility or affinity with the component (A) in the polymer chain.
  • a chain having compatibility or affinity with the component (A) in the polymer chain examples thereof include syndiotactic polystyrene, atactic polystyrene, and isotactic.
  • examples include polymers having polystyrene, styrene-based polymer, polyphenylene ether, polyvinylinolemethinoleatel, or the like as a main chain, a block chain, or a graft chain.
  • the polar group as used herein may be any group that improves the adhesiveness with the inorganic filler as the component (F), and specifically includes, for example, an acid anhydride group, a carboxylic acid group, and a carboxylic ester group. , Carboxylic acid halide group, carboxylic acid amide, carboxylic acid group, sulfonic acid group, sulfonic acid ester group, sulfonic acid chloride group, sulfonic acid amide group, sulfonic acid group, epoxy group, amino group, imid And oxazoline groups.
  • styrene-maleic anhydride copolymer S MA
  • styrene-dalicidyl methacrylate copolymer terminal carboxylic acid-modified polystyrene, terminal epoxy-modified polystyrene, terminal oxazoline-modified polystyrene, terminal amine-modified polystyrene, Sulfonated polystyrene, Styrene-based monomer, Styrene-methinomethylacrylate copolymer, (styrene-glycidyl methacrylate) monomethyl methacrylate monograph copolymer, acid-modified acrylic-styrene monograph polymer, (Styrene-dalicydyl methacrylate) Styrene-graft polymer, polybutylene terephthalate-polystyrene-grafted poly, maleic anhydride-modified SPS, fumaric acid-modified SPS,
  • the polymer of the component (B) may be used alone or in combination of two or more.
  • modified polyphenylene ether is obtained by modifying the following polyphenylene ether with a modifying agent, but is not limited by the modification method as long as it meets the object of the present invention.
  • Polyphenylene ether is a known compound.
  • U.S. Pat. Nos. 3,306,874, 3,306,875, and 3,257,35 Reference can be made to the specifications of JP-A No. 7 and JP-A Nos. 3,257, 358.
  • Polyphenylene ethers can usually be prepared by an oxidative coupling reaction to form a homopolymer or copolymer in the presence of a copper amine complex, one or more di- or tri-substituted phenols.
  • Copper amine complexes include copper ammine complexes derived from primary, secondary and tertiary amines.
  • polyphenylene ether examples include, for example, poly (2,3-dimethinole 6-ethynole_1,4_phenylene ether), poly (2-methyl-16-chloromethinole 1, 4_phenylene ethereol) ), Poly (2-methynole 1-6-hydroxy-1,4-fu-lenethenole), poly (2-methino 1-6-n-butynole _ 1, 4, 1-fenerene enole), poly (2-echine) / Le 6-isopropinole 1'4 1 feninolee tenor), poly (2-ethinole) 1 6—n—Propylene / Lae 1,4 Hue-Lene Tegre), Poly (2,3,6—Trimethinole 1,4_Fu-Lene Athenole), Poly [2— (4'-Methinole Feline) 1 1,4 1-Fu-Len-Etenore], Pori (2-Promo 6-F
  • copolymers derived from two or more of the phenolic compounds used in the preparation of the homopolymer are also suitable.
  • a graft copolymer and a block copolymer of a vinyl aromatic compound such as polystyrene and the above-mentioned polyphenylene ether may be mentioned.
  • poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used.
  • modifiers used for modifying these polyphenylene ethers include compounds having an ethylenic double bond and a polar group in the same molecule.
  • maleic anhydride maleic acid, Estenole maleate, maleimide and its substituted product
  • maleic acid derivatives such as maleate
  • Fumaric acid derivatives such asucic acid, fumaric acid ester and fumarate
  • itaconic acid derivatives such as itaconic anhydride, itaconic acid, itaconic acid ester and itaconic acid salt
  • acrylic acid, acrylic acid ester, acrylic acid amide, acrylic And methacrylic acid derivatives such as methacrylic acid esters, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, and glycidyl methacrylate.
  • maleic anhydride fumaric acid or glycidyl methacrylate is particularly preferably used.
  • the modified polyphenylene ether can be obtained, for example, by reacting the polyphenylene ether with a modifying agent in the presence of a solvent or another resin.
  • a modifying agent for example, a method of melt-kneading and reacting at a temperature in the range of 150 to 350 ° C. using a roll mill, Banbury mixer, extruder, or the like.
  • a method of performing a heat reaction in a solvent such as benzene, toluene, or xylene can be used.
  • the reaction system should contain benzoyl peroxyde; di-t-butyl peroxide; dicumyl peroxide; t-butinoreoxybenzoate; It is also effective to use a radical generator such as thyronitrile; azobisisopareronitrile; 2,3-diphenyl-2,3-dimethylbutane.
  • a radical generator such as thyronitrile; azobisisopareronitrile; 2,3-diphenyl-2,3-dimethylbutane.
  • maleic anhydride-modified polyphenylene ether, fumaric acid-modified polyphenylene ether or glycidyl methacrylate-modified polyphenylene ether is particularly preferably used.
  • a modified SPS having a polar group can also be used as the component (II). This modified SPS can be obtained, for example, by modifying the SPS of the component (A) with a denaturing agent, but is not limited to this method as long as it can be used for the purpose of the present invention. .
  • the SPS used for the modification is not particularly limited, and it is possible to use the SPS of the above component (A), but in particular, the copolymer of styrene and the substituted styrene is compatible with other components. It is preferably used.
  • composition ratio of the copolymer is preferably in the range of 3-5 0 mol% content of substituted styrene units, more preferably in the range from 3 2 5 mole 0/0 is there.
  • Particularly preferred substituted styrenes include, for example, alkylstyrenes such as methylstyrene, ethylstyrene, isopropynolestyrene, tertiary butynolestyrene, and biel styrene; halogenated styrenes such as chlorostyrene, promostyrene, and chloromethylstyrene; And phenolic styrene such as methoxystyrene, ethoxystyrene and the like.
  • alkylstyrenes such as methylstyrene, ethylstyrene, isopropynolestyrene, tertiary butynolestyrene, and biel styrene
  • halogenated styrenes such as chlorostyrene, promostyrene, and chloromethylsty
  • One of these substituted styrenes may be used, or two or more of them may be used in combination.
  • a modifying agent used for modifying the SPS a compound having an ethylenic double bond and a polar group in the same molecule can be used.
  • a modifying agent examples include maleic anhydride, maleic acid, maleic ester, maleimide and its N-substituted product, maleic acid derivatives such as maleic acid salt, fumaric acid, fumaric ester, and bumaric acid.
  • Fumaric acid derivatives such as salts, itaconic anhydride, itaconic acid, itaconic acid esters, itaconic acid derivatives such as itaconic acid salts, acrylic acid, acrylic esters, acrylic acid Acrylic acid derivatives such as mid and acrylates; methacrylic acid derivatives such as methacrylic acid, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, and glycidyl methacrylate;
  • maleic anhydride fumaric acid or glycidyl methacrylate is particularly preferably used.
  • the modified SPS can be obtained, for example, by reacting the SPS with a modifying agent in the presence of a solvent or another resin.
  • the method of modification is not particularly limited, and known methods, for example, a method of melt-kneading and reacting at a temperature in the range of 150 to 350 ° C. using a roll mill, a Pampari mixer, an extruder, or the like, Alternatively, a method of performing a heat reaction in a solvent such as benzene, toluene, or xylene can be used.
  • a method of melt-kneading and reacting at a temperature in the range of 150 to 350 ° C. using a roll mill, a Pampari mixer, an extruder, or the like Alternatively, a method of performing a heat reaction in a solvent such as benzene, toluene, or xylene can be used.
  • benzoyl peroxide g-tert-butyl peroxide, dicumyl peroxide, t-ptinoleperoxybenzoate, azobisisod It is also effective to use a radical generator such as ptyronitrinole, azobis isonorelononitrile, 2,3-dipheninole-1,2,3-dimethylbutane.
  • a radical generator such as ptyronitrinole, azobis isonorelononitrile, 2,3-dipheninole-1,2,3-dimethylbutane.
  • maleic anhydride-modified SPS, fumaric acid-modified SPS and dalicidyl methacrylate-modified SPS are particularly preferably used.
  • the component (B) may be used alone or in combination of two or more.
  • the polar group content in the component (B) is 0.01 to 20 mass%. /. It is preferably in the range of 0.05 to 10% by mass.
  • the content is less than 0.01% by mass, it is necessary to incorporate a large amount of the component (B) in order to exhibit the effect as a compatibilizer.
  • the mechanical properties and heat resistance of the water-soluble resin composition decrease, which is not preferable.
  • the amount of the component (B) is from 0.2 to 10% by mass, and preferably from 0.5 to 8% by mass, based on (A) + (B) +. (C) + (D). To be elected. If the amount is less than 0.2% by mass, the affinity between the E component and the F component and the resin component is reduced, so that the strength of the thermoplastic resin composition is reduced. The heat resistance and moldability of the plastic resin composition are undesirably reduced.
  • Thermoplastic resins other than styrene polymers having a syndiotactic structure include linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, and block.
  • Polyolefin resin including polypropylene, random polypropylene, polybutene, 1,2-polybutadiene, 4-methylpentene, cyclic polyolefin, atactic polystyrene, isotactic polystyrene, HIPS, ABS, AS Polystyrene resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate and other polyester resins, polyamide 6, polyamide 6,6 and other polyamide resins, polyphenylene N'eteru, may be selected arbitrarily from p p S or those such as known ones they were modified.
  • thermoplastic resins can be used alone or in combination of two or more.
  • Styrene polymers having an atactic three-dimensional structure (hereinafter referred to as “Atactic Tick polystyrene) is obtained by polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, etc.
  • R represents a substituent containing at least one of 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 tin atom; Represents an integer of 1 to 3. When m is plural, each R may be the same or different.
  • Preferred aromatic butyl compounds include styrene, ⁇ -methylstyrene, methylstyrene, ethynolestyrene, isopropynolestyrene, tertiary butynolestyrene, phenyl / styrene, bininolestyrene, chlorostyrene, bromostyrene, phenololerostyrene, Chloromethinolestyrene, methoxystyrene, ethoxystyrene and the like are used, and these are used alone or in combination of two or more.
  • aromatic vinyl compounds include styrene, ⁇ -methylstyrene, m-methinolestyrene, p-tert-butylinolestyrene, p-chlorostyrene, m-chlorostyrene and monofluorostyrene.
  • Other copolymerizable vinyl monomers include acrylonitrile and methacrylic acid.
  • Vinyl cyanide compounds such as mouth-tolyl, methyl acrylate, ethyl acrylate, propinorea acrylate, ptinorea acrylate, amino acrylate, hexino acrylate, octyl acrylate, 2-ethyl hexino acrylate, cyclic Mouthhexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, and other acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and amide methacrylate , Hexyl methacrylate, octinole methacrylate, 2-ethylenoxy hexinole methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate , Methacryl
  • copolymerizable rubbery polymers examples include polybutadienes, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, gen-based rubbers such as polyisoprene, ethylene-co-olefin copolymers, ethylene- ⁇ - olefins.
  • Non-gen-based rubbers such as polyene copolymers and polyacrylates, styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-propylene elastomer, styrene-graft ethylene
  • examples include propylene elastomer, ethylene ionomer resin, and hydrogenated styrene-isoprene copolymer.
  • the molecular weight of atactic polystyrene is not particularly limited, but generally has a weight average molecular weight of at least 10,000, preferably at least 50,000.
  • weight-average molecular weight is less than 100,000, thermal The properties and mechanical properties deteriorate, which is not desirable.
  • polyphenylene ether is used for this purpose in U.S. Pat. Nos. 3,306,874, 3,306,875, and 3,25. Reference can be made to the specifications of JP-A-7,357.
  • Polyphenylene ethers are usually prepared by an oxidative coupling reaction to form a homopolymer or copolymer in the presence of a copper amine complex, one or more di- or tri-substituted phenols.
  • Copper amine complexes include copper ammine complexes derived from primary, secondary and tertiary amines.
  • polyphenylene ethers examples include poly (2,3-dimethinol-1-6-ethynole-1,4-phenyleneatenole), poly (2-methinolate 6-chloromethinele 1,4-phenyleneatenole), and poly ( 2-Methinole 6-Hydroxyshetinole 1, 4 _phenylene ether, poly (2-methinolate 6-n-butyl-1,4-phenylene ether), poly (2-ethene / ole 6-isopropyl) 1,4-phenylene ether), poly (2-ethynole 6-n-propynolee 1,4-phenylene ether), poly (2,3,6-trimethylenole 1,4-phenylene ether), poly (2- (4,1-Methylpheninole) 1-1,4-phenyleneatenole), poly (2-bromo-6-phenyleneoleate 1,4-phenyleneatenole), poly (2-met-met
  • copolymers such as copolymers derived from two or more phenolic compounds used in the preparation of the homopolymer are also suitable.
  • a graft copolymer and a block copolymer of a Bier aromatic compound such as polystyrene and the above-mentioned polyphenylene ether can be mentioned.
  • poly (2,6-dimethyl-1,4-phenylene ether) is used.
  • the rubber-like elastic material include, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysnolide rubber, thiocol rubber, acryl rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer.
  • SBR hydrogenated styrene-butadiene block copolymer
  • SEB hydrogenated styrene-butadiene block copolymer
  • SBS hydrogenated styrene-butadiene-styrene block copolymer
  • SEBS hydrogenated styrene-butadiene-styrene block copolymer
  • SIR Styrene-isoprene block copolymer
  • SEP hydrogenated styrene-isoprene block copolymer
  • SIS hydrogenated styrene-isoprene-styrene block copolymer
  • SEPS hydrogenated styrene-isoprene-styrene block copolymer Body
  • E PM d Len propylene rubber
  • E PDM ethylene pro Pilet Njengomu
  • Orefin rubbers such as ethylene-Otaten copolymer Heras Tomah one
  • SBR SBR
  • SEB SEB
  • SEBS SEBS
  • SIR SEP
  • SIS SEPS
  • core shell rubber EPM
  • EPDM ethylene octene copolymer elastomer or these Rubber
  • These rubber-like elastic bodies can be used alone or in combination of two or more.
  • the compounding amount of the component (C) is 0 to 60 mass based on (A) + (B) + (C) + (D). / 0 , preferably in the range of 0 to 45% by mass.
  • thermoplastic resin composition If the amount is more than 60% by mass, the heat resistance, moldability, chemical resistance, and the like of the thermoplastic resin composition are lowered depending on the added components, which is not preferable.
  • the components (nucleating agent) that accelerate the crystallization rate of the styrene polymer having a syndiotactic structure include metal salts of carboxylic acids such as aluminum di (pt-butyl benzoate) and methylene bis (2 , 4-di-t-butylphenol) Metal salts of phosphoric acid such as acid phosphate, talc, phthalocyanine derivatives, etc. Can be used.
  • nucleating agents can be used alone or in combination of two or more.
  • the compounding amount of the component (D) is selected in the range of 0 to 5% by mass, preferably 0 to 3% by mass based on (A) + (B) + (C) + (D).
  • the D component acts as a foreign substance, resulting in a decrease in strength and a decrease in thermal stability.
  • a cross-section perpendicular to the length direction has a flat cross-section fiber strengthening agent having a major axis (the longest linear distance in the direction perpendicular to the major axis) and a minor axis (the longest linear distance in a direction perpendicular to the major axis).
  • the glass fiber as the fiber reinforcing agent of the component (E) will be described.
  • Glass fiber with a flat cross section is manufactured by using an elliptical hole-shaped pusher instead of a circular hole-shaped pusher in the glass fiber manufacturing process. Publication No. 300).
  • the major axis and the minor axis be 2.5 or more.
  • the upper limit of the major axis / minor axis is about 6.
  • the cross-sectional shape has no corners so as not to cause excessive stress concentration.
  • a small amount of glass fiber is not sufficient to reflect the reinforcement reinforcement in the direction perpendicular to the length direction of the glass fiber on the heat resistance.
  • a blend of 5% by mass is required.
  • the blending amount is 1 o mass. If it is less than / 0 , the capturing effect is insufficient, and the heat resistance and rigidity are reduced. If it exceeds 65% by mass, the appearance is reduced due to poor dispersion of the glass fiber, and the fluidity is reduced.
  • the glass fiber used for the purpose of the present invention is preferably a glass fiber which has been subjected to a surface treatment in order to secure adhesion to a resin and exhibit a reinforcing effect.
  • the coupling agent used for the surface treatment is used for improving the adhesion between the glass fiber and the resin, and may be selected from conventionally known ones such as a so-called silane coupling agent and a titanium coupling agent. Any one can be selected and used.
  • a film-forming substance for glass can be used in combination with the above-mentioned 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.
  • these fiber reinforcements can be used alone or in combination of two or more.
  • the inorganic filler examples include glass fiber (except one in which one fiber has a flat cross-sectional shape), carbon fiber, whiskers, my strength, and the like, and include fibrous, granular, and powdery materials. .
  • Shapes include cloth, mat, bundle cut, short fiber, filament And a whisker.
  • the length is preferably 0.055 mm to 50 mm and the fiber diameter is 5 to 20 m.
  • granular and powdery fillers include, for example, talc, carbon black, graphite, titanium dioxide, silica, My power, calcium sulfate, calcium carbonate, barium carbonate, magnesium carbonate, magnesium sulfate, and sulfuric acid.
  • examples include barium, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, and glass beads.
  • organic filler examples include organic synthetic fibers and natural fibers.
  • organic synthetic fibers examples include polyamide fibers, wholly aromatic polyamide fibers, polyimide fibers, and LCP (liquid crystal polymer) fibers.
  • the above-mentioned filler is preferably a surface-treated filler.
  • the coupling agent used for the surface treatment is used to improve the adhesiveness between the filler and the resin, and may be selected from conventionally known ones such as a so-called silane coupling agent and a titanium coupling agent. Any one can be selected and used.
  • ⁇ -aminopropyl trimethoxysilane, ⁇ —] 3- (aminoethyl) -1- ⁇ -aminopropyl trimethoxysilane, ⁇ -glycidoxypropyl pyritrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) Aminosilanes such as tinoletrimethoxysilane, epoxysilane, and isopropyl tri ( ⁇ -amidoethyl, aminoethyl) titanate are preferred.
  • a film-forming substance for glass can be used together with the above-mentioned 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 biel acetate-based polymers.
  • the compounding amount of the component (F) is 0 to 50% by mass (including 0) based on the thermoplastic resin composition.
  • the total amount of (E) + (F) ranges from 10 to 65% by mass.
  • the organic filler or the inorganic filler may be used alone or in combination of two or more.
  • thermoplastic resin composition of the present invention may contain additives such as an antioxidant, a plasticizer, a flame retardant, a flame retardant auxiliary, a pigment and an antistatic agent, as long as the object of the present invention is not impaired. it can.
  • the antioxidant can be arbitrarily selected from phosphorus, phenol, zeolite and other known antioxidants.
  • Antioxidants can be used alone or in combination of two or more.
  • plasticizer it is possible to arbitrarily select and use a known plasticizer such as polyethylene glycol, polyamide oligomer, ethylene bis stearamide, phthalate ester, polystyrene oligomer, polyethylene wax, and silicone oil. it can.
  • Flame retardants include brominated polymers such as brominated polystyrene, brominated syndiotactic polystyrene, brominated polyphenylene ether, brominated diphenylalkane, and brominated diphenyl ether. family compounds also c can be selected arbitrarily from known ones, as a flame retardant aid, antimony compounds including antimony oxide, can be selected arbitrarily from other known ones .
  • antioxidants plasticizers, flame retardants, flame retardant aids, pigments, antistatic agents, etc. Can be used alone or in combination of two or more.
  • thermoplastic resin composition of the present invention is not particularly limited, and can be prepared by a known method.
  • the components may be blended by various methods such as mixing at room temperature or melt-kneading, and the method is not particularly limited.
  • melt kneading using a twin-screw extruder is preferably used.
  • melt kneading using a twin-screw extruder kneading at a temperature equal to or higher than the melting point of SPS to be used and lower than 350 ° C. is preferable.
  • the kneading temperature is lower than the melting point of the used SPS, the viscosity of the resin is too high, so that the productivity may be lowered. If the mixing temperature is higher than 350 ° C, the resin may be thermally decomposed.
  • thermoplastic resin composition of the present invention is not particularly limited, and the thermoplastic resin composition can be molded by a known method such as injection molding or extrusion molding.
  • the molding temperature is preferably equal to or higher than the melting point of the SPS used and lower than 350 ° C.
  • the fluidity may decrease, and if it exceeds 350 ° C, the resin may be thermally decomposed.
  • the mold temperature is preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 180 ° C.
  • the mold temperature is lower than 40 ° C, SPS may not be sufficiently crystallized, and the SPS characteristics may not be sufficiently exhibited. If the mold temperature is higher than 200 ° C, the rigidity at the time of mold release is reduced. The ejector may be cracked or deformed.
  • the resin temperature at this time was about 331 ° C.
  • the modification rate was 1.45% by weight.
  • HH30 Homopolystyrene (Idemitsu Sekiyu styrene HH30)
  • Circle GF Glass fiber with a circular cross section [Asahi Fiberglass Co., Ltd. C S 03 MA F T 164 G]
  • Eyebrows type GF aminosilane / urethane surface treatment [Nitto Boseki Co., Ltd., CSH-3 Pa-256] 3 G (glass) flakes: Nippon Sheet Glass RE FG302 (G) Other components ''
  • Irg. 10 10 Antioxidant ilganox 10 1 0 manufactured by Chipagaigi Co., Ltd.
  • ATOX Flame retardant aid (antimony trioxide) [PATO X-M manufactured by Nippon Seiko Co., Ltd.]
  • thermoplastic resin compositions of each of the examples and comparative examples were prepared by dry blending predetermined raw materials except for glass fibers with a Hensile mixer, and then using a twin-screw extruder [TEM-35, manufactured by Toshiba Machine Co., Ltd.].
  • the cylinder temperature was set at 290 ° C, and glass fibers were supplied from the side to perform melt-kneading to pelletize.
  • the obtained pellet was injected into an injection molding machine (SH100A manufactured by Sumitomo Heavy Industries, Ltd.), with a cylinder temperature of 290 ° C, an injection speed of 18%, a cooling time of 20 seconds, and a mold temperature of 144 ° C, each test piece was prepared using a family test piece mold, the maximum molding (injection) pressure at that time was used as an index of fluidity, and the bending strength and tensile strength were determined from the test piece. It was measured.
  • SH100A manufactured by Sumitomo Heavy Industries, Ltd.
  • the mold shrinkage was determined by comparing the mold dimensions.
  • Mold shrinkage (Die size-Molded product size) / (Die size)
  • dumbbells are bonded with an epoxy adhesive (ME 268: manufactured by Pernox Japan, curing conditions: 150 ° C, 1 hour, adhesive thickness: 10 mmX 12 mmX 0.2 mm), and 2 3 After curing at 24 ° C for 24 hours, a tensile test was performed to determine the force at which the bonded surface was peeled off.
  • ME 268 manufactured by Pernox Japan
  • One of the purposes of adding the inorganic filler is to reduce the molding shrinkage and improve the dimensional accuracy of the molded part.However, the addition of the inorganic filler has problems with strength and fluidity.
  • Comparative Example 7 calcium carbonate (P-30) and G (glass) flakes were added to obtain a glass fiber alone. Compared with (Comparative Example 4), the molding shrinkage rate is lower, but the fluidity is lower (the molding pressure is higher) and the strength is lower.
  • Example 6 and Example 7 the use of flat glass fibers improved the strength and moldability as compared with the circular glass fiber type.
  • Example 9 and Comparative Example 9 Example 10 and Comparative Example 10
  • the SPS + other resin system has the same flat GF as the SPS-only system. Has higher tensile strength and bending strength, and has better fluidity.
  • Comparative Examples 8 to 10 Compared with Comparative Example 4, Comparative Examples 8 to 10 have improved adhesive strength to the epoxy adhesive, but Comparative Example 8 has reduced strength, and Comparative Examples 9 and 10 have reduced fluidity. .
  • SPS is flammable (HB) when no flame retardant is added.
  • HB flammable
  • flame retardancy is required for some applications such as electric and electronic parts, so it is necessary to add a flame retardant. May decrease.
  • Example 11 using a flat glass fiber has high tensile strength and bending strength and good fluidity.
  • thermoplastic resin composition having improved strength and fluidity, which has been difficult to achieve with a conventional reinforcing agent system, without deteriorating complicated molding and mass productivity (manufacturing of a large number of molds).
  • a molded article can be easily obtained.
  • thermoplastic resin composition of the present invention can be used in the following fields.
  • printers housesing, chassis, ribbon cassette, tray, ink peripheral parts, etc.
  • copiers personal computers
  • personal computers housing, floppy disk shell, keyboard, etc.
  • projector parts telephones, communication equipment (housing, Handset, etc., mechanical chassis, machines, registers, typewriters, calculators, optical equipment, musical instruments and other miscellaneous goods, toys, leisure, sports equipment, remote control cars, blocks, pachinko machine parts, surfboards, helmets, Toilet seats, toilet lids, tanks, shower parts, pump parts, plumbing outlets, lunch boxes, various containers, pots, building material housing parts, containers, furniture, stationery (ballpoint pens, magic, writing implement trays, etc.), stamp stands, etc.
  • Various parts, pipes, Over door, tray it includes the industrial materials such as a film.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une composition de résine thermoplastique qui comprend : (A) un polymère à base de styrène présentant une structure syndiotactique comme structure primaire ; (B) un polymère présentant une certaine compatibilité ou une bonne affinité avec un composant (A) et présentant un groupe polaire ; (C) une résine thermoplastique et/ou un élastomère thermo-élastique autre qu'un polymère à base de styrène présentant une structure syndiotactique ; (D) un composant accélérant la cristallisation du polymère à base de styrène présentant une structure syndiotactique ; (E) une fibre de contrainte de résine présentant une section transversale perpendiculaire à la direction longitudinale d'une forme possédant un diamètre long et un diamètre court ; et (F) une charge organique ou inorganique. L'invention concerne également un article formé à partir de ladite composition de résine thermoplastique. Ladite composition de résine et ledit article ne présentent pas une réduction du module d'élasticité et combinent une résistance mécanique élevée avec une fluidité remarquable, ce qui était difficile à obtenir avec un agent de renforcement classique.
PCT/JP2003/014104 2002-11-07 2003-11-05 Composition de resine thermoplastique et article forme a partir de ladite composition WO2004041929A1 (fr)

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JP2002-323612 2002-11-07
JP2002323612A JP2004155928A (ja) 2002-11-07 2002-11-07 熱可塑性樹脂組成物及びその成形体

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JP4971590B2 (ja) * 2004-12-21 2012-07-11 出光興産株式会社 芳香族ポリカーボネート樹脂組成物及びその成形体
JP2006328230A (ja) * 2005-05-26 2006-12-07 Asahi Kasei Chemicals Corp 重合体組成物からなる光学材料
JP4787547B2 (ja) * 2005-06-06 2011-10-05 帝人株式会社 ポリエステル組成物およびそれからなる二軸配向フィルム
JP2008001744A (ja) * 2006-06-20 2008-01-10 Sumitomo Bakelite Co Ltd 熱可塑性樹脂組成物及びそれを用いた成形品
TWI355401B (en) * 2006-09-29 2012-01-01 Cheil Ind Inc Thermoplastic resin composition and plastic articl
US8324308B2 (en) 2007-04-20 2012-12-04 Idemitsu Kosan Co., Ltd. Resin composition for encapsulating an electronic tag, a resin-encapsulated electronic tag and a method for producing the same
EP2060596B1 (fr) * 2007-11-16 2012-06-13 Ems-Patent Ag Compositions de moulage renforcées à base de polyamide chargé
JP2009185150A (ja) * 2008-02-05 2009-08-20 Idemitsu Kosan Co Ltd 伝熱性樹脂組成物及びその樹脂成形体
JP2010084007A (ja) * 2008-09-30 2010-04-15 Mitsubishi Engineering Plastics Corp 携帯電子機器用ポリアミド樹脂組成物及び携帯電子機器部品
EP2617772B1 (fr) * 2010-09-16 2020-02-12 Mitsubishi Engineering-Plastics Corporation Composition de résine d'éther de polyphénylène et article moulé de ladite composition
WO2024024653A1 (fr) * 2022-07-26 2024-02-01 出光興産株式会社 Composition de résine thermoplastique renforcée par des fibres et composite résine-métal

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EP0546497A2 (fr) * 1991-12-10 1993-06-16 Idemitsu Kosan Company Limited Composition de résine thermoplastique
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EP0246620B1 (fr) * 1986-05-19 1992-02-26 Nitto Boseki Co., Ltd. Objet moulé en résine renforcée de fibres de verre et son procédé de fabrication
EP0376616A2 (fr) * 1988-12-26 1990-07-04 Polyplastics Co. Ltd. Composition de résine thermoplastique renforcée de fibres
EP0384208A2 (fr) * 1989-02-10 1990-08-29 Idemitsu Kosan Company Limited Composition de résine
EP0546497A2 (fr) * 1991-12-10 1993-06-16 Idemitsu Kosan Company Limited Composition de résine thermoplastique
EP0587100B1 (fr) * 1992-09-10 1996-08-21 Idemitsu Kosan Company Limited Composition de polystyrène
JPH06116454A (ja) * 1992-10-07 1994-04-26 Idemitsu Kosan Co Ltd 熱可塑性樹脂組成物
JPH0718186A (ja) * 1993-06-29 1995-01-20 Nitto Boseki Co Ltd 扁平な断面形状を有するガラス繊維の粉末強化熱可塑 性樹脂組成物
JPH0762175A (ja) * 1993-08-31 1995-03-07 Idemitsu Kosan Co Ltd 熱可塑性樹脂組成物
JPH11181195A (ja) * 1997-12-25 1999-07-06 Asahi Chem Ind Co Ltd 耐熱性に優れた樹脂組成物及びそれからなるポンプ部品
US6348540B1 (en) * 1998-04-22 2002-02-19 Idemitsu Petrochemical Co., Ltd. Styrenic resin composition and semiconductor carrier device
JP2000164038A (ja) * 1998-11-27 2000-06-16 Idemitsu Petrochem Co Ltd 電気絶縁用ポリスチレン系樹脂フィルム

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