WO2004041929A1

WO2004041929A1 - Thermoplastic resin composition and formed article formed therefrom

Info

Publication number: WO2004041929A1
Application number: PCT/JP2003/014104
Authority: WO
Inventors: Shinobu Yamao; Manabu Nomura
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2002-11-07
Filing date: 2003-11-05
Publication date: 2004-05-21
Also published as: JP2004155928A

Abstract

A thermoplastic resin composition which comprises (A) a styrene based polymer having a syndiotactic structure as a primary structure, (B) a polymer exhibiting compatibility with or good affinity for (A) component and having a polar group, (C) a thermoplastic resin and/or rubbery elastomer other than a styrene based polymer having a syndiotactic structure, (D) a component accelerating the crystallization of the styrene based polymer having a syndiotactic structure, (E) a rein forcing fiber having a cross section perpendicular to the longitudinal direction of a shape having a longer diameter and a shorter diameter and (F) an organic or inorganic filler; and an article formed therefrom. The resin composition and the article is free from the reduction of modulus of elasticity, and, combines high mechanical strength and excellent fluidity, which has been difficult to be achieved by a conventional reinforcing agent.

Description

Description Thermoplastic resin composition and molded product thereof

The present invention relates to a thermoplastic resin composition having excellent elastic modulus, mechanical strength, and fluidity, and a molded product thereof. Background art

Conventionally, styrene-based polymers having a syndiotactic structure (hereinafter sometimes abbreviated as “SPS”) have excellent mechanical properties, heat resistance, chemical resistance, and moldability. It is used as a material for parts, automobile parts and machine parts.

In recent years, with the miniaturization and high performance of products, the required level of fluidity and strength of materials has been increasing.

Increasing the amount of inorganic filler is generally used to improve heat resistance, but a well-known phenomenon is that increasing the amount of ordinary glass fiber and other reinforcing agents reduces the fluidity (for example, , L.E.Nie 1sen, "Mechanical Properties of Polymers and Composite Materials," published by Kagaku Dojin, 1976, January 15, 1st edition, p. 233).

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. .

That is, the present invention

1. A thermoplastic resin composition comprising the following components (A) to (F)

(A) Styrene-based polymer mainly having syndiotactic structure

(A) + (B) + 2 5~9 0 mass ^{(C) + (D) 0} /0

(B) A polymer having compatibility or affinity with the component (A) and having a polar group

(A) + (B) + (C) + (D) of 0.1 2: 1 0 mass ^_0/0

(C) Thermoplastic resin and / or rubber-like elastic material other than styrenic polymer having syndiotactic structure

(A) + (B) + (C) + ( including 0) 0-6 0 Weight ^_0/0 (D)

(D) A component that promotes the crystallization rate of a styrenic polymer having a syndiotactic structure

0 to 5% by mass of (A) + (B) + (C) + (D) (including 0)

(E) A flat cross-section fiber reinforcing agent whose cross section perpendicular to the length direction has a major axis and a minor axis.

10 to 65% by mass based on the thermoplastic resin composition

(F) Organic or inorganic filler

(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 .

2. 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 thermoplastic resin composition according to 1, 3. The thermoplastic resin composition according to 1 above, wherein the fiber reinforcing agent is glass fiber; 4. a molded article comprising the thermoplastic resin composition according to 1 above.

It is about. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

(A) Styrene polymer mainly having a syndiotactic structure 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.

Examples of poly (alkylstyrene) include poly (methylstyrene) and poly (methylstyrene).

(Ethyl styrene), poly (isopropyl styrene), poly (tertiary butylin styrene), poly (phenylen styrene), poly (bulnaphthale) ), Poly (butylstyrene) and the like, and 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). In particular, preferred styrene polymers having a syndiotactic structure include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), and poly (p-methylstyrene). —Styrenes, poly (m-chlorostyrene), poly (p-styrene, styrene), hydrogenated polystyrene, and copolymers containing these structural units.

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).

In addition, 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.

In addition, 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.

(B) a polymer having compatibility or affinity with a styrenic polymer having a syndiotactic structure and having a polar group

The component (B) of the present invention contains 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.

Specifically, 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, glycidyl methacrylate-modified SP S, Ami Modified styrene-based polymers such as styrene-modified SP s, (styrene-maleic anhydride) polyphenylene ether-graft polymer, maleic anhydride-modified polyphenylene ether, fumanoleate-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene Modified polyphenylene ether polymers such as diene ether and amine-modified polyphenylene ether are exemplified. In particular, modified polyphenylene ether, modified SPS and the like are suitable.

The polymer of the component (B) may be used alone or in combination of two or more.

The above-mentioned 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. For example, 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.

Specific examples of the polyphenylene ether 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-Fen-Nen-Rei 1, 4-Fu-Len-Eten-No-Re), Pori (2-Methino-Len 6) , 4_ phenylene ethereol), poly (2-chloro-1,4-phenyleneethereolene), poly (2-methynolate1,4,4-phenyleneethereolole), poly (2-chloro-6-ethylethyle1,4— Phenylene ether, poly (2-chloro-6_promo-1,4-phenylene ether), poly (2,6-di-η-propyl-11,4-phenylene ether), poly (2- Methyl-1-6-isopropinoー 1,4-phenylene ether '), poly (2-chloro-1-6-methynole-1,4-phenylene ether), poly (2-methinolate 6-ethynole_1'4-phenylene ether), Poly (2,6-dipromo 1,4-phenylene ether), Poly (2,6-dichloro-1,4-phenylene ether), Poly (2,6-diethyl-1,4-phenylene ether) And poly (2,6-dimethyl-1,4-phenylene ether).

Also suitable are, for example, copolymers derived from two or more of the phenolic compounds used in the preparation of the homopolymer.

Further, for example, a graft copolymer and a block copolymer of a vinyl aromatic compound such as polystyrene and the above-mentioned polyphenylene ether may be mentioned. Among these various polyphenylene ethers, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used. Examples of modifiers used for modifying these polyphenylene ethers include compounds having an ethylenic double bond and a polar group in the same molecule. Specifically, for example, maleic anhydride, maleic acid, Estenole maleate, maleimide and its substituted product, maleic acid derivatives such as maleate, Fumaric acid derivatives such as luic 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.

Of these, maleic anhydride, fumaric acid or glycidyl methacrylate is particularly preferably used.

The above various modifiers may be used alone or in combination of two or more.

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. There is no particular limitation on the method of denaturation, 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, Banbury mixer, extruder, or the like, Alternatively, a method of performing a heat reaction in a solvent such as benzene, toluene, or xylene can be used.

Furthermore, in order to facilitate these reactions, 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.

Among these polyphenylene ethers, maleic anhydride-modified polyphenylene ether, fumaric acid-modified polyphenylene ether or glycidyl methacrylate-modified polyphenylene ether is particularly preferably used. Further, 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.

There is no particular limitation on the composition ratio of the copolymer, it 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.

It this content is difficult to denaturation is less than 3 mol%, 5 0 mole ^_0/0 When a exceeds undesirable because the compatibility is lowered with the other ingredients.

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.

One of these substituted styrenes may be used, or two or more of them may be used in combination.

As 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.

Examples of such a modifying agent 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;

The above various modifiers may be used alone or in combination of two or more.

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.

Furthermore, in order to facilitate these reactions, 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.

Among these modified SPS, 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.

If 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.

On the other hand, if it exceeds 20% by mass, the compatibility with the component (A) is lowered, 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.

In addition, these 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.

(1)

(In the formula, 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.)

A polymer composed of one or more aromatic vinyl compounds represented by the formula or a copolymer of one or more other vinyl monomers copolymerizable with one or more aromatic vinyl compounds; Coalesced hydrogenated polymers and mixtures thereof. Preferred aromatic butyl compounds include styrene, α-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.

Particularly preferred aromatic vinyl compounds include styrene, ρ-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 , Methacrylates such as feninolemethacrylate, benzinolemethacrylate, maleimide, N-methylmaleimide, N-ethylethylmalide, N-butylmaleimide, N-laurylmaleimide, N Maleimide compounds such as —cyclohexyl maleimide, N-phenylmaleimide, and N— (p-bromopheninole) maleimide;

Examples of copolymerizable rubbery polymers include polybutadienes, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, gen-based rubbers such as polyisoprene, ethylene-co-olefin copolymers, ethylene- _α- 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.

If the weight-average molecular weight is less than 100,000, thermal The properties and mechanical properties deteriorate, which is not desirable.

Further, there is no restriction on the molecular weight distribution, and various types can be applied.

As described above, 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.

Examples of preferable polyphenylene ethers 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-methinolate) Les _ 6—Feninole-1,4 -Fenyleneatenole), Poly (2-Feninole-1,4 -Funeleneatenole), Poly (2 -Chloro-1,4 -Fen-leeneatenole), Poly (2-methyl-1,4-phenylene ethere), poly (2-chloro-6-ethynole-1,1,4-phenylene ethere), poly (2-chloro-6-promo 1,4,4-phenylene ethereole), Poly (2, 6-ge n-propynole 1,4-phenylene ethereol, poly (2-methinole 6-isopropinolee 1,4-phenyleneatenole), poly (2-chloro-6-methineole 1,1,4-phenyleneatenole), poly (2-methinolate) 6-ethinole 1,4-1,6-dichloroetheneole, poly (2,6-dibutene 1,4-1-phenyleneate), poly (2,6-dichloro-1,4-phenyleneateno), poly (2 , 6-Jetinole 1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether) and the like.

For example, copolymers such as copolymers derived from two or more phenolic compounds used in the preparation of the homopolymer are also suitable. Further, for example, a graft copolymer and a block copolymer of a Bier aromatic compound such as polystyrene and the above-mentioned polyphenylene ether can be mentioned. Particularly preferably, poly (2,6-dimethyl-1,4-phenylene ether) is used.

Specific examples of 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), 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 Body (SEPS), d Len propylene rubber (E PM), ethylene pro Pilet Njengomu (E PDM), Orefin rubbers such as ethylene-Otaten copolymer Heras Tomah one, butadiene-§ click Li Roni tolyl one Suchirenko Ryo Shell rubber (ABS), methinolate methacrylate butadiene-styrene-core chelene rubber (MBS), methinolate methacrylate acrylate / reactylate-styrene-core-shell rubber (MAS), octyl acrylate-styrene-core styrene-core shell rubber (MAB S), alkyl acrylate Core-shell-type particles such as latex ptadene-acrylonitrile-to-styrene-core-shell rubber (AAB S), butadiene-styrene-to-core chenore rubber (SBR), siloxane-containing core rubber such as methionolemethacrylate-to-butyl acrylate-siloxane Elastic bodies or rubbers modified from these may be used.

Among them, SBR, SEB, SBS, SEBS, SIR, SEP, SIS, SEPS, core shell rubber, EPM, EPDM, ethylene octene copolymer elastomer or these Rubber is preferably used.

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.

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.

In addition, these 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).

If the compounding amount exceeds 5% by mass, the D component acts as a foreign substance, resulting in a decrease in strength and a decrease in thermal stability.

(E) 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).

Since reinforcement in the direction perpendicular to the length direction of the glass fiber is an important factor, it is desirable that the major axis and the minor axis be 2.5 or more.

It is more preferably at least 3.0, even more preferably at least 3.5.

If the major axis and the minor axis are less than 2.5, the desired balance between good fluidity and mechanical properties cannot be maintained, resulting in a decrease in fluidity.

The upper limit of the major axis / minor axis is about 6.

Furthermore, it is desirable that 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.

It is preferably 15 to 65% by mass, more preferably 20 to 65% by mass. 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.

Further, 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.

Among them .gamma.-aminopropyl trimethinecyanine Tokishishiran, Nyu- - (Aminoechi Le) Single _gamma - § amino propyl trimethinecyanine Tokishishiran, .gamma.-glycidoxypropyltrimethoxysilane prop Noretorime Tokishishiran, beta-such as (3, 4 one epoxycyclohexyl) Echiru trimethyl Tokishishiran Aminosilane, epoxysilane, and isoprovir tri (ト -amidoethyl, aminoethyl) titanate are preferred.

Further, 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.

In addition, these fiber reinforcements can be used alone or in combination of two or more.

(F) Organic or inorganic filler

Examples of the inorganic filler 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. In the case of a focused cut shape, the length is preferably 0.055 mm to 50 mm and the fiber diameter is 5 to 20 m.

On the other hand, 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.

Examples of the organic filler include organic synthetic fibers and natural fibers.

Examples of the organic synthetic fibers 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.

Among them, γ-aminopropyl trimethoxysilane, Ν—] 3- (aminoethyl) -1-γ-aminopropyl trimethoxysilane, γ-glycidoxypropyl pyritrimethoxysilane, β- (3,4-epoxycyclohexyl) Aminosilanes such as tinoletrimethoxysilane, epoxysilane, and isopropyl tri (Ν-amidoethyl, aminoethyl) titanate are preferred.

Further, 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.

If it exceeds 50% by mass, the strength and the moldability are reduced.

The total amount of (E) + (F) ranges from 10 to 65% by mass.

If it exceeds 65% by mass, the strength and the formability are reduced. .

The organic filler or the inorganic filler may be used alone or in combination of two or more.

(G) Other additives

The 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.

As the 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 .

Furthermore, antioxidants, plasticizers, flame retardants, flame retardant aids, pigments, antistatic agents, etc. Can be used alone or in combination of two or more.

The method for preparing the thermoplastic resin composition of the present invention is not particularly limited, and can be prepared by a known method.

For example, the 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 and kneading methods, melt kneading using a twin-screw extruder is preferably used.

In 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.

If 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.

The method for molding the 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.

In injection molding, the molding temperature is preferably equal to or higher than the melting point of the SPS used and lower than 350 ° C.

If the molding temperature is lower than the melting point of the used SPS, 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.

If 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.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples. (1) Raw materials used

(A) Styrene polymer having syndiotactic structure

① SPS: Homo syndio-tack polystyrene (manufactured in accordance with Japanese Patent Application Laid-Open No. 62-187780); 1,2,4-trichloro-open benzene as solvent at 150 ° C Weight average molecular weight in terms of polystyrene measured by GPC method Mw = 200,000 Mw / Mn = 2.20

(B) Polymer having compatibility or affinity with component (A) and having a polar group

① FAPPO: fumaric acid-modified polyphenylene ether

(Manufacture of fumaric acid-modified polyphenylene ether)

Lkg, polyphenylene ether (intrinsic viscosity 0.45 dec. 7, in chloroform at 25 ° C), 30 g of fumaric acid, 2,3-dimethyl-2,3-diphenylbutane as radical generator (Nippon Oil & Fats) (Nofmer BC) (20 g) was dry-blended and melt-kneaded using a 30 mm twin-screw extruder at a screw rotation speed of 2 rpm and a set temperature of 300 ° C.

The resin temperature at this time was about 331 ° C.

After the strand was cooled, it was pelletized to obtain fumaric acid-modified borifene diene ether.

To measure the denaturation rate, 1 g of the obtained modified polyphenylene ether was dissolved in ethyl benzene, reprecipitated with methanol, the recovered polymer was subjected to Soxhlet extraction with methanol, dried, and dried for The denaturation rate was determined by the intensity of the absorption and the titration by the total force.

The modification rate was 1.45% by weight.

(C) thermoplastic resin and / or rubber-like elastic material other than styrene-based polymer having syndiotactic structure

① P PO: poly (2,6-dimethyl-1,4-phenylene ether) [3 Ryogas Chemical Co., Ltd. YPX—100H]

(2) HH30: Homopolystyrene (Idemitsu Sekiyu styrene HH30)

③ PPS: Polyphenylene sulfide (Idemitsu Petrochemical Co., Ltd., Idemitsu PPS)

800 S8006: SEBS type elastomer (hydrogenated styrene-butadiene-styrene block copolymer) [Kuraray SEPTON 8006]

[0 0 0 1]

(1) Nuclear agent (NA3 5 manufactured by Asahi Denka)

②Nucleating agent (NA11 by Asahi Denka)

(E) Flat cross-section glass fiber (flat glass fiber manufactured according to Japanese Patent Application Laid-Open No. 2-173047)

①Flat GF1: Aminosilane / urethane surface treatment (short diameter 7 μm, long diameter / short diameter = 3/1)

② Flat GF 2: Aminosilane Z urethane ^ surface treatment (minor axis 7 μπι, major axis / minor axis = 4/1)

(3) Flat GF3: Aminosilane / urethane surface treatment (minor axis 8 μm, major axis minor axis = 5/1)

(F) Organic or inorganic filler

(1) Calcium carbonate: Heavy tankal P-30 manufactured by Shiroishi Calcium Co., Ltd.

② Circle GF: Glass fiber with a circular cross section [Asahi Fiberglass Co., Ltd. C S 03 MA F T 164 G]

3) 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 ''

① Irg. 10 10: Antioxidant ilganox 10 1 0 manufactured by Chipagaigi Co., Ltd.

② P E P 36: Antioxidant, manufactured by Asahi Denka

③ S.80 10: Flame retardant [1,2-di (pentabromophenyl) ethane] [SAYTEX 800/10 manufactured by Ethyl Corporation]

③ P ATOX: Flame retardant aid (antimony trioxide) [PATO X-M manufactured by Nippon Seiko Co., Ltd.]

④ DHT-4A: Halogen scavenger (Kyowa Chemical)

The 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.

(Mold shrinkage measurement method)

Molding a flat plate with a thickness of 2 mm and a height and width of 80 mm with a resin temperature of 290 ° C, a mold temperature of 150 ° C, a filling time of 1 second, and a cooling time of 10 seconds. The mold shrinkage was determined by comparing the mold dimensions.

Mold shrinkage = (Die size-Molded product size) / (Die size)

(Adhesion strength evaluation method)

AS TM No. 1 dumbbell cut in half. Then, the surface was degreased with ethanol and air-dried.

Two 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.

Example Comparison f system ί

1 2 3 4 5 1 2 3 4 5

SPS wt% 87 87 87 87 87 87 87 89 87 87

S8006 wt% 10 10 10 10 10 10 10 10 10 10 10

NA35 wt% 0.5 0.5 0.5 0.5 0.5 0.5 0.5 `` 0.5 0.5 0.5 0.5 0.5 0.5 0.5 irglOlO wt% 0.25 0.25 0.25 0.25 .25 0.25 0.25 0.25 0.25 0.25

PEP36 wt% 0.25 0.25 0.25 0, 25 0.25 0.25 0.25 0 0.25 0.25

FAPPO wt% 2 2 2 2 2 2 2 2 2 2 Total .100 100 100 100 100 100 100 100 100 100 100 yen GF wt% 40 30 50 Eyebrow type GF wt% 40

Flat GF1 wt% 40

Flat GF2 t% 40 30 50 40

Flat GF3 wt% 40

Total 40 40 40 30 50 40 40 40 30 50 Tensile strength MP all 9 131 115 141 ll 119 90 110 129 Flexural strength MP a 195 208 209 181 228 184 181 181 161 170 200 Molding pressure% 35 34 33 30 40 39 39 36 34 in 45 molding shrinkage X 10- ³ 2. 92 2. 91 adhesive strength kgf / cm 0. 03 0. 03 flame retardancy 1/16 'UL94 HB HB table 1, the compositions of examples 1 3 and Comparative Example 1 (Circular glass fiber). Comparative example 2 Higher tensile strength and flexural strength than the composition of (Mayu type glass fiber). The molding pressure is low (the fluidity is good).

Also, from Example 2 [addition of FAPPO (fumaric acid-modified polyphenylene ether)] and Comparative Example 3 [addition of no FAPPO], when the component (B) was not present, even when flat glass fiber was used, It can be seen that no effect is exhibited. Furthermore, from Example 4 and Comparative Example 5, and Example 5 and Comparative Example 5, even when the glass fiber content was 30% by mass and 50% by mass, respectively, the compounding amount of the glass fiber was 40% by mass. Flat glass fiber has higher tensile strength and bending strength-better flowability.

Table 2

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. In 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.

In contrast, in Example 6 and Example 7, the use of flat glass fibers improved the strength and moldability as compared with the circular glass fiber type.

Table 3

In Table 3, from Example 8 and Comparative Example 8, 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.

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. .

On the other hand, in Examples 8 to 10 using flat glass fibers, compared to the circular glass fiber system, the decrease in strength and moldability was small, and the thermoplastic resin composition having good strength and fluidity was used. It has become.

SPS is flammable (HB) when no flame retardant is added. However, flame retardancy is required for some applications such as electric and electronic parts, so it is necessary to add a flame retardant. May decrease.

In contrast to Comparative Example 11 using a circular glass fiber, Example 11 using a flat glass fiber has high tensile strength and bending strength and good fluidity. Industrial availability

According to the present invention, there is provided a 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.

The thermoplastic resin composition of the present invention can be used in the following fields.

In the field of electricity and electronics, various connectors (S LOT, PGA, D-SUB, AGP, PCI, USB, audio jack, etc.), printed circuit boards, LED components, terminal blocks, relay boxes, F terminals, motor terminals Parts, power modules, fan motor parts (frames, fans), lens parts (CD pickup lens holder, DVD pickup) In the field of automobiles, there are three types of vehicles: connectors for vehicle installation, p-unit boxes, fuse boxes, junction bottas, reflectors, extensions, canisters, various vanolebs, la jetter grinole, grinole, mark, Knottano No. ⁰ , door mirror, wheel cap, pneumatic boiler, motorcycle cow Λ ^, cylinder head force par, insnolement panel, meter hood, pillar, glove box, console box In the field of electrical equipment, housings, chassis, cassette cases, CD magazines, remote control cases, connectors, fans, refrigerator parts (lining, trays, arms, door caps, Vacuum cleaner parts (housing, handle, pipe, suction port, fan guide, etc.) Air conditioner parts (housing, fan, remote control case, etc.), pots, fans, ventilation fans, washing machines, lighting equipment Parts, tableware dryer parts, microwave oven parts (choke cover, roller ring), battery case, etc.

Other general equipment includes printers (housing, chassis, ribbon cassette, tray, ink peripheral parts, etc.), copiers, 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.

Claims

The scope of the claims

1. A thermoplastic resin composition comprising the following components (A) to (F).

(A) Styrene-based polymer mainly having syndiotactic structure

(A) + (B) + 2 5~90 mass of ^{(C) + (D) 0} /0

0.2 to 10% by mass of (A) + (B) + (C) + (D)

0 to 60% by mass of (A) + (B) + (C) + (D) (including 0) (D) A component that promotes the crystallization rate of a styrenic polymer having a syndiotactic structure

0 to 5% by mass of (A) + (B) + (C) + (D) (including 0)

10 to 65% by mass based on the thermoplastic resin composition

(F) Organic or inorganic fillers ''

(F) is 0 to 50% by mass (including 0) based on the thermoplastic resin composition, provided that (E) + (F) is 10 to 65% by mass based on the thermoplastic resin composition It is.

2. The minor axis (longest linear distance in the direction perpendicular to the major axis) of the fiber reinforcement is 3 μηι or more, and the major axis (linear distance of the longest section) / minor axis is 2.5 or more. Item 4. The thermoplastic resin composition according to Item 1.

3. The thermoplastic resin composition _c according to claim 1, wherein the fiber reinforcing agent is glass fiber.

4. A molded article comprising the thermoplastic resin composition according to claim 1.