JPH03126744A - Styrene-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, containing respective components mixed with excellent compatibility and capable of providing useful materials remarkably improved in heat and water resistance while sufficiently holding mechanical properties by blending a polyamide with a specific styrene-based polymer and polyphenylene ether. CONSTITUTION:A styrene-based resin composition obtained by blending (A) 99-1wt.% styrene-based polymer without any functional group with (B) 0.1-50wt.% polymer, composed of polyphenylene ether or a mixture thereof with a styrene-based polymer without any functional group and having polar groups, (C) 0.9-98.9wt.% polyamide and further (D) a filler having the surface treated with a silane coupling agent. A styrene-based polymer having a syndiotactic structure is used as the component (A). The polar groups of the component (B) are acid derivative and maleic anhydride group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a styrenic resin composition, and more specifically, it can be used for electrical/electronic materials (e.g., printed circuit board connectors, etc.), industrial structural materials, automobile parts (e.g., military vehicle connectors, etc.).
The present invention relates to styrene resin compositions suitable for the bottom shapes of industrial materials such as wheel camps, cylinder heads, etc.), home appliances, and various mechanical parts.

[Prior art and problems to be solved by the invention] In general, polyamide has excellent moldability and heat resistance, and has sufficient rigidity, so it is used to hold household items and electrical products.
It is used as an acid form material for various products such as parts for machinery and equipment.

However, although boriagodo has such excellent properties, it has the drawback that it cannot be said to have sufficient water resistance.

By the way, the group of the present inventors recently succeeded in developing a styrenic polymer with high syndiotacticity, and also developed a thermoplastic resin composition in which this styrenic polymer was blended with other components. (Unexamined Japanese Patent Publication No. 62-104
No. 818, No. 61-257950).

An attempt was made to improve the above-mentioned drawbacks by blending this styrene polymer into polyamide 1', but the combination of resins that are essentially incompatible with each other, such as boria and polystyrene, causes problems at the interface between the phases. Since deterioration in mechanical properties due to insufficient strength cannot be avoided, there is a limit to the modifying effect of blending.

Therefore, the present inventor solved the above-mentioned problems by improving the compatibility between a styrene polymer with a syndiotactic structure and a polyamide resin, thereby improving heat resistance without impairing the mechanical properties of the polyamide resin. conducted extensive research to develop a composition with significantly improved water resistance.

[Means to solve the problem]

As a result, polyamide is combined with a specific styrenic polymer,
It has been found that the above problem can be solved by blending a specific polyphenylene ether in a certain ratio.

The present invention was completed based on this knowledge.

That is, the present invention is a polar polymer comprising either (A) 99 to 1% by weight of a styrenic polymer having no functional group, and (B) a polyphenylene ether or a mixture of polyphenylene ether and a styrenic polymer having no functional group. 0.1 to 50% by weight of those having groups and 0.1 to 50% by weight of (C) polyamide.
A styrenic resin composition comprising 9 to 98.9% by weight is provided.

In the present invention, the styrenic polymer having no functional group used as (A) Ifi may be any of various styrenic polymers on the condition that it does not have a functional group.
- Numerical formula (wherein R represents hydrogen or an alkyl group having 1 to 4 carbon atoms,
Z represents hydrogen, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 5. ) A polymer having at least 25% by weight of a repeating structural unit derived from a vinyl aromatic compound represented by the following formula can be used.

Such styrenic polymers include, for example, homopolymers of styrene or its derivatives, as well as styrenic polymers modified with natural or synthetic elastomeric materials, such as polybutadiene, polyisoprene, butyl rubber EPDM, ethylene-propylene copolymers, natural rubber, epichlorohydrin, etc. Polymers, and further include styrene-containing copolymers, such as styrene-methylstyrene copolymers, styrene-butadiene copolymers, and the like. Among these, especially
Styrenic polymer having syndiotactic structure, active polystyrene, active polystyrene, polybutadiene-modified styrenic polymer, butadiene-styrene copolymer, isoprene-styrene copolymer 5
High impact polystyrene (HTPS) is preferred.

Here, the syndiotactic structure in a styrenic polymer having a syndiotactic structure means that the stereochemical structure is a syndiotactic structure, that is, a phenyl group that is a side chain with respect to the main chain formed from carbon-carbon bonds. It has a three-dimensional structure in which phenyl groups and substituted phenyl groups are alternately positioned in opposite directions, and its toughness is determined by nuclear magnetic resonance (C-NMR) using carbon isotopes.

Toughness measured by 13C-NMR is expressed by the proportion of consecutive constituent units, for example, diand for two units, triat for three units, and pentad for five units. However, the styrenic polymer having a syndiotactic structure referred to in the present invention is usually 75% or more in terms of racemic pentads, preferably 85% or more, or 30% or more in terms of racemic pentads, preferably 50% or more. % or more syndiotactic city
polystyrene 1 poly(al-4-rustyrene) poly(halogenated styrene), poly(halogenated alkylstyrene), poly(alkoxystyrene) poly(vinyl benzoate), hydrogenated polymers thereof and mixtures thereof, Alternatively, it refers to a copolymer containing these as main components. Note that poly(alkylstyrene) here includes poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(terjalibdelstyrene), poly(phenylstyrene), poly(vinylstyrene). Examples of poly(halogenated styrene) include poly(chlorostyrene), poly(vinyl styrene), poly(vinyl styrene), and fluorostyrene. Examples of poly(halogenated alkylstyrene) include poly(chloromethylstyrene), and examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene).

Among these, particularly preferred styrenic polymers include polystyrene, poly(p-butylstyrene), poly(n-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), and polystyrene. (
m-chlorostyrene), poly(p-fluorostyrene),
Examples include hydrogenated polystyrene and copolymers containing these structural units.

The molecular weight of this styrenic polymer is not particularly limited, but the weight average molecular weight is 10,000 or more, preferably 50,000 or more. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used. If the weight average molecular weight is less than 10,000, the thermal properties and mechanical properties of the resulting composition or molded article will deteriorate, which is undesirable.

A styrenic polymer having such a syndiotactic structure can be produced by combining a titanium compound and a condensation product of water with a trialkylaluminum with a catalyst, for example, in an inert hydrocarbon solvent or in the absence of a solvent. (monomer corresponding to the above-mentioned styrene polymer)
Publication No. 8). Further, poly(halogenated alkyl styrene) can be obtained by the method described in JP-A-1-46912, and hydrogenated polymers thereof can be obtained by the method described in JP-A-1-178,505.

The blending amount of component (A) is 1 to 99% by weight, preferably 10 to 95% by weight, and more preferably 20 to 95% by weight. If the blending amount is less than 1% by weight, no effect of improving Mi or acid water resistance can be observed. Moreover, when it exceeds 99% by weight, the mechanical strength is no different from that of the styrene polymer of component (A).

As the component (B) of the present invention, a polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group and having a polar group is used. First, as styrene polymers without functional groups, in addition to the styrene polymers shown in component (A) above, acrylonitrile, methyl methacrylate, methacrylate trile, etc. Examples include styrenic polymers into which at least one of the compounds is introduced. The amount of this styrene polymer added to polyphenylene ether is preferably 80% by weight or less.
) is not preferable because the substantial amount of polyphenylene ether blended in the component decreases.

Moreover, polyphenylene ether is a compound known per se. For this purpose, U.S. Patent No. 3.306.8
No. 74, No. 3,306,875, No. 3.257,35
Reference may be made to the specifications of No. 7 and No. 3,257,358. Polyphenylene ethers are usually prepared by oxidative coupling reactions to form homopolymers or copolymers in the presence of a copper amine complex, one or more tri- or tri-substituted phenols. Here, as the copper amine complex, a copper amine complex derived from a first, second and/or tertiary amine can be used. An example of a suitable polyphenylene ether is poly(23-dimethyl-6-edylphenylene-1,4-ether).

Poly(2-methyl-6-chloromethyl-1,4phenylene)ether poly(2-methyl-6-hydroxydidiethyl-1゜4-
phenylene) ether.

Poly(2-methyl-6-n-butyl-1,4-phenylene)ether poly(2-ethyl-6-isopropyl-1,4phenylene)ether poly(2-ethyl-6-n-propyl-1, 4 phenylene) ether.

Poly(23,6-drimethylphenylene-I4-ether) Bo1J(2-(,1'-methylphenyl)phenylene1
．． 4-ether] poly(2-bromo-6-phenylphenylene-I.

4-ether) poly(2-methyl-6-phenylphenylene-14-ether).

Poly(2-phenylphenylene-1,4-ether) Poly(2=chlorophenylene-14-ether) Poly(
2-methylphenylene-14-ether) poly(2-chloro-6-ethylphenylene-14-ether) poly(2-chloro-6-promophenylene-14-ether).

Poly(2,6-di-n-propylphenylene-14-ether).

Poly(2-methyl-6-ituprobylphenylene 1.4
-ether) Poly(2-chloro-6-methylphenylene-14-ether) 2 Poly(2-methyl-6-ethylphenylene-14-ether) Poly(2,6-dipromof5rulene-1,4-ether) Poly (2,6-cyclophenylene-1,4-ether) Poly(26-danitylphenylene-1,4-ether)
and poly(26-dimethylphenylene-1,4-ether).

Copolymers are also suitable, such as copolymers derived from two or more phenolic compounds, such as those used for the preparation of the homopolymers mentioned above.

Further examples include graft copolymers and block copolymers of vinyl aromatic compounds such as polystyrene and the aforementioned polyphenylene ethers.

In addition, the polar groups contained in this component (B) include acid halide, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfmene group, nitrile group, cyano group, isocyanate ester group, amino group, hydroxyl group,
1F group, 100-ol group, oxazoline group, epoxy group, etc. A particularly preferred polar group is an acid anhydride, and among these, a maleic anhydride group is preferred. The content of this polar group is 0.01% by weight based on the polyphenylene ether.
If it is less than 0.01% by weight, no improvement in mechanical strength can be expected.

Component (B) can be obtained by polymerizing one or more phenol compounds having polar groups, or by polymerizing one or more phenol compounds having polar groups with polar groups. Examples include a method in which a phenol compound having no group is polymerized, and a method in which a compound having both a polar group and an unsaturated group is reacted with polyphenylene ether.

The compound having both a polar group and an unsaturated group is an unsaturated group, i.e., a carbon-carbon double bond or a carbon-carbon triple bond, and a carboxylic acid group derived from carboxylic acid as a polar group. Various salts and esters, acid amides, acid anhydrides, imides, acid azides, acid halides, oxazoline nitriles, epoxy groups, amino groups, hydroxyl groups, isocyanate groups, etc., in which the hydrogen atom or hydroxyl group of a carboxyl group is substituted. It is a compound that has both in the same molecule.

As compounds having both an unsaturated group and a polar group, unsaturated carboxylic acid monounsaturated carboxylic acid derivatives, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines, and unsaturated isocyanate esters are mainly used.

Specifically, maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide.

Reactant of maleic anhydride and diamine, e.g.○
0 11] 1 (wherein R represents an aliphatic or aromatic group), etc., methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, itaconic acid, itaconic anhydride, large Bean oil tung oil, castor oil, flax oil, Asamiura, cottonseed oil.

Sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil.

Natural fatty acids such as coconut oil and sardine oil, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tebric acid, 2-pentenoic acid, 3-pentenoic acid, α-ethyl acrylic acid, β -Methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-
3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 54-decenoic acid, 9-undecenoic acid, 10-undecenoic acid , 4-dotesenoic acid, 5-totisenoic acid, 4-tetradecenoic acid, 9tetradecenoic acid, 9-hexadenoic acid, 2-octadecenoic acid,
9-octadecenoic acid, icosenoic acid, tocosenoic acid, erucic acid, tetracosenoic acid, mayelichenic acid, 24-pentadienoic acid, 2,4 hexadienoic acid, diallylacetic acid, geranic acid.

2.4-decadienoic acid, 2.4-dodecadienoic acid.

9.12-hexadecadienoic acid, 9.12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, lylunic acid, octadecatrienoic acid, icosadienoic acid, icosatrienoic acid, icosatetraenoic acid, ricinoleic acid,
Eleostearic acid oleic acid 1 icosapen citric acid, erucic acid docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapene citric acid, tetraenoic acid hexacosenic acid, hexacosenoic acid, occucosenoic acid,
Unsaturated carboxylic acids such as traaconic acid, or esters, acid acids, anhydrides or allyl alcohols of these unsaturated carboxylic acids; Crotyl alcohol; Methyl vinyl carbinol; Allyl carbinol; Methylpropenyl carbinol; 4-pentene-1- All, 10-
Undecane-1-ol; Propangyl alcohol; L
4-Hexadien-3-ol; 1,4-hexadien-3-ol; 3,5-hexadien-2ol; 24
-Hexadien-1-ol; -Alcohol represented by the formula % (where n' is a positive integer); 3-
Butene-1,2-diol; 2,5-dimethyl-3-hexene-2,5-diol; 1.5 hexadiene-3,
4-diol: unsaturated alcohols such as 45-diol 26-octadecenoate, unsaturated amines in which the OH group of such unsaturated alcohols is replaced with Nl2 groups, or low polymerizations such as butadiene and isoprene (e.g., 500 to 10,000) or polymers (for example, those with an average molecular weight of 10,000 or more) to which maleic anhydride or phenols are added, or amino groups, carboxylic acid groups, hydroxyl groups, epoxy groups, etc. are introduced. and allyl isocyanate.

Further, examples of the vinyl compound having an epoxy group include glycidyl methacrylate-1 and glycidyl methacrylate-1 vinyl glycidyl ether.

Glycidyl ether of hydroxyalkyl (meth)acrylate Glycidyl ether of polyalkylene glycol (meth)acrylate, glycidyl icconate, etc. are mentioned, and among these, glycidyl methacrylate is particularly preferred.

In the present invention, a compound having both an unsaturated group and a polar group is defined as having two or more unsaturated groups, and two or more polar groups (
Needless to say, it includes compounds containing the same type or different types, and it is also possible to use two or more types of compounds.

A specific method for obtaining component (B) is to prepare a compound having both polyphenylene ether and a polar group using a roll mill, Banbury Kisa-5 extruder, etc.
A method of melt-kneading and reacting at a temperature of 350'C, and a method of heating and reacting polyphenylene ether with a compound having both a polar group and an unsaturated group in a solvent such as Hensen, i-luene, xylene, etc. can be mentioned. Furthermore, in order to facilitate these reactions, molar peroxides such as hensyl peroxide, di-savetyl peroxide, dicumyl peroxide, 1-butyl peroxyhenzoate, and azobis isobutyroyl peroxide are added to the reaction system. It is effective to have a radical initiator represented by ab compounds such as nitrile, abbisisovaleroni, and the like. A more effective method is melt-kneading in the presence of a radical initiator.

It can also be produced by melt-kneading the styrene polymer as part of component (B), polyphenylene ether, a compound having both a polar group and an unsaturated group, and a radical initiator in coexistence. can.

The blending amount of component (B) is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, and preferably 1 to 30% by weight. In particular, when a styrene polymer having a syndiotactic structure is used as component (A), the amount is preferably 0.5 to 30% by weight, particularly preferably 1 to 25% by weight. The polyphenylene ether that is component (B) or a part thereof has very good compatibility with the styrene polymer that is component (A), but
．． The mechanical strength of the resulting resin is less than 1% by weight.
I can't hope for anything. When added in excess of 50%, heat resistance
Formability decreases.

In producing the resin composition of the present invention, this (B)
It is not necessary to prepare only the components in advance, and the styrenic polymer as a part of component (A) and (F3), and (
+3) After mixing the component polyphenylene ether, a compound having both a polar group and an unsaturated group, and additives such as fillers, the mixture is heated at 150 to 350°C using an RL-Lumil, Banbury Mixer 2 extruder, etc. It can also be produced by melt-kneading at high temperatures.

As the polyamide which is component (C) of the present invention, all known thermoplastic polyamides can be used.

Suitable polyamides are, for example, Boria 5F-4; Polyamide-6; Boria Draft 4,6; Polyamide-6,6;
Polyamide-3,4; Boriagodo I2; Polyamide-1
1; Boria polyamide purified from -610 terephthalic acid and 44'-diaminocyclohexylmethane; Boria polyamide purified from azelaic acid, adipic acid and 2,2-bis(p-aminocyclohexyl)propane: adipic acid and polyamide 1, which is purified from metaxylylene diamine; and polyamide 1, which is purified from terephthalic acid and trimethylhexamethylene diamine.

In addition, aromatic polyamide resin (hereinafter abbreviated as PA)
is a boria triglyceride containing an aromatic nucleus in the main chain and a repeating structural unit consisting of an added bond. More specifically, the aromatic polyamide resin of the present invention is produced by reacting a polymer obtained by reacting an aromatic diamine component and a dicarboxylic acid component by a conventional method and an ω''-carboxyl compound having an aromatic group by a conventional method. An appropriate polymer can be selected from among the polymers obtained by the reaction.

Here, the aromatic siane component includes 1,4 diaminohenzene: 13-diaminohenzene, 12-diaminohenzene; 2,4-diaminohenzene; 2,3-diaminohenzene; 2,3-diaminohenzene;
・Luene; 2,5-';Aminotoluene;2,6-diaminotluene; Ortho, meta or para xylylene; Ortho, meta or para 2,2'-diaminodiethylhenzene ・44 4,4'-cyanodiphenylmethane;44'-diaminodiphenylether; 44-diaminodiphenyl thioether; 4,4'-diaminodiphenyl methane;
A diamine compound having a Hensen ring, which can be typically exemplified by 44゛-cyanodiphenyl sulfone, is used, and the aromatic diamine component may be a diamine compound having a Hensen ring of -J2, even if it is alone, Other diamine compounds as long as they contain 50 mol% or more,
For example, it may be a mixture with aliphatic diamines. Of course, two or more types of diamine compounds having a Hensen ring may be used in combination.

Next, as dicarboxylic acid components, aliphatic dicarpoloxyl compounds such as glutaric acid, 3 adipic acid, pimelic acid, 1 speric acid, azelaic acid, sebacic acid, etc., and fucuric acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc. Examples thereof include aromatic dicarboxyl compounds, and acid chlorides of these dicarboxyl compounds, and these compounds may be used in combination.

Furthermore, examples of the ω-amino-ω''-carboxy compound having an aromatic nucleus include 4-aminophenylcarboxylmethane, 1-(4-aminophenyl)-2-carboxylethane, 3-(47gonophenyl)-1 -carboxylpropane para-(3-amino-3゛-hydroxy)dipropylhenzene, etc. The preferred aromatic boria resin used in the present invention is a diamine compound having a Hensen ring and an aliphatic dicarboxylic acid. A more preferred example is a polyamide derived from xylylenecyamine and adipic acid.

The most preferred example is a polyamide derived from meta-xylylene diamine and adipic acid.

The blending amount of this component (C) is 0.9 to 98.9% by weight,
Preferably 5 to 90% by weight, more preferably 5 to 65% by weight
Heavy view% weight. If the blending amount is less than 0.9% by weight, no improvement in mechanical strength is observed. Moreover, when it exceeds 98.9% by weight, the water resistance is no different from that of polyamide 1.

The citrus & Il base material of the present invention basically consists of the above (A) and (B).
) and (C), but optionally a filler surface-treated with a cambling agent may be added as component (D). The filler used in the present invention may be fibrous or granular or powdery. Examples of the fibrous filler include glass fibers, carbon fibers, organic synthetic fibers, whiskers, ceramic fibers, metal fibers, and natural vegetable fibers. Specific examples of organic synthetic fibers include fibers such as fully aromatic polyamide woven navy blue polyimide m fibers; whiskers include boron, alkali, silica, and silicon carbide; and examples of cerago ivy fibers include gypsum and potassium titanate. +Fibers of magnesium oxide, magnesium oxide, etc., and metal fibers include fibers of copper, aluminum, steel, etc., and glass fibers and carbon fibers are particularly preferred. Here, the shapes of the filling fibers include a cross shape, a mat shape, a focused cut shape, short fibers, a filament shape, and a whisker. ~20 μm is preferred. Further, as the carbon fiber, polyacrylonitrile (PAN) type carbon fiber is preferable.

On the other hand, examples of granular and powdery fillers include talc, carbon black, graphite, titanium dioxide, silica mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, and aluminum oxide. Examples include ξ, kaolin, silicon carbide metal powder, glass powder, glass flakes, glass beads, and the like. Particularly preferred are talc calcium carbonate and mica. The preferred average particle size of Kuruku is 0.3 to 20 μm, more preferably 0.6 to 10 μm.
A μm one is better. The preferred average particle size of calcium carbonate is 0.1 to 20 μm. In addition, the average particle size of mica is preferably 40 to 2507 zm, more preferably 50 to 2507 zm.
It is 150 μm.

Among the various fillers mentioned above, glass fillers such as glass powder, glass flakes, glass beads, glass filaments, glass fibers, glass lobing, and glass pine I are particularly preferred.

” = The coupling agent used in the surface treatment of the filler is used to improve the adhesion between the filler and the polyphenylene ether having a polar group, which is the component (B) above, and is a so-called coupling agent. silane coupling agent,
As the titanium-based coupling agent, any titanium-based coupling agent can be selected from among those conventionally known. Specific examples of this silane coupling agent include triethoxysilane, vinyltris(β-methoxyethoxy)silane γ
-methacryloxypropyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, β-(1,1
-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(amidoethyl)-γ-antanopropyltrimethoxysilane.

N-β-(agonoethyl)-γ-aminopropylmethyldimethoxysilane, γ-agonopropyltriethoxysilane, N-phenyl-T-aminopropyltrimethoxysilane, r-mercaptopropyltrimethoxysilane,
T-chloropropyltrimethoxysilane, γ-amitube 2-pyltrimethoxysilane, T-aminopropyl-tris(2methoxy-ethoxy)silane, N-methyl-γ
Aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-45 dihydroimidazolepropyltriethoxysilane, HeniF samethyldisilazane , N50-(bis8 trimethylsilyl)amide, N,N-bis(trimethylsilyl)urea, and the like. Among these, γ−
Agonopropyltriethoxysilane N-β-(amidoethyl)-T-aminopropyltrimethoxysilane 1 γ
-glycidoxypropyltrimethoxysilane, β-(3
, 4-epoxycyclohexyl)ethyltrimethoxysilane, and epoxysilane are preferred. In particular, it is preferable to use the above-mentioned aminosilane.

Specific examples of titanium-based coupling agents include isopropyl triisostearate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, and tetraisopropyl bis(dioctyl phosphite) titanate. Tetraoctylbis(ditridecylphosphite) titanate Te! -(1,1-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate bis(dioctylpi 1':I phosphate)oxyacetate titanate-1-.

Bis(dioctyl pyrophosphate) ethylene titanate, isobrobyl trioctanoyl titanate, isopropyl dimethacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, Isoprobyl (N-amidoethyl, aminoethyl) titanate, dicumylphenyloxyacetate chikunet
Examples include diisostearoyl ethylene titanate. Among these, isopropyltri(N-adoethyl, aminoethyl)thicnate is preferred.

The surface treatment of the filler using such a coupling agent can be carried out by a conventional method and is not particularly limited. For example, sizing treatment 1 in which an organic solvent solution or suspension of the coupling agent described above is applied to the filler as a so-called sizing agent, or a Henschel mixer;
It can be carried out by an appropriate method depending on the shape of the filling material, such as dry mixing using a super mixer, Loedige Dankisa 1 type blender, etc., spray method, integral blend method, dry concentrate method, etc., but sizing Preferably, it is carried out by processing, dry mixing, or spraying methods.

Further, a film-forming substance for glass can be used in combination with the above-mentioned coupling agent. There are no particular restrictions on this film-forming substance, such as polyester,
Examples include polymers such as urethane, epoxy, acrylic, and trivinyl acetate.

In the present invention, the surface treatment filler component as described above is blended, and the blending ratio thereof is the same as (A) above.

1 to 350 parts by weight, preferably 5 to 20 parts by weight of a surface-treated filler is added to 100 parts by weight of the composite layers of components (B) and (C).
Add 0 parts by weight. If the amount of the surface-treated filler is less than 1 part by weight, a sufficient blending effect as a filler will not be observed. On the other hand, if it exceeds 350 parts by weight, there will be problems such as poor dispersibility and difficulty in molding.

1 Furthermore, in the present invention, as the component (A) (8°
) Styrenic polymer with syndiotactic structure,
In addition, as component (B) (B') a polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group and having a maleic anhydride group, that is, a polyphenylene modified with maleic anhydride. By blending 0.1 to 50% by weight of ether, and as component (D) a filler surface-treated with an aminosilane coupling agent (D゛) and a boric acid as component (C), as described above,
A resin composition with better properties that can improve the adhesion between a styrenic polymer with a syndiotactic structure and a filler.
Acids can be obtained.

The resin composition of the present invention is composed of the above-mentioned styrene polymer and polyphenylene ether having a polar group, and further contains hyt+g which has been surface-treated with a coupling agent if necessary. However, various additives, other thermoplastic resins, and rubber-like elastic bodies may be blended as necessary, as long as they do not impede the purpose of the present invention. Here, the additives include, for example, phosphorous acid esters and phosphoric acid ester antioxidants described in JP-A-6328424tM, ultraviolet absorbers, JP-A-1201350,
Nucleating agents and mold release agents such as aliphatic carboxylic acid ester-based and paraffin-based external d'I agents, organic acid metal salts, and organic phosphorus compounds described in Japanese Patent Application No. 122587; 4
+) Antistatic agent, coloring agent, flame retardant, flame retardant aid, etc.

J-Heat-fiJ plastic citrus resins include polyphenylene ether that does not contain polar groups, polyethylene boria 1゛J pyrene, polybutene, polyolefin exclusively for polybenlane, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyphenylene sulfur. 1st class polydioether, polycarbo-1-polyarylate polysulfone, polyetheretherketone, polyethersulfone, polyimideboriatoy, polymethyl methacrylate,
Ethylene-acrylic acid copolymer, acrylonitrile-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, ethylene-hinyl acetate copolymer,
Ethylene-hinyl alcohol copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl chloride resin 2
Examples include chlorinated polyethylene, fluorinated polyethylene, polyacecool thermoplastic polyurethane elastomer, 2-polybutadiene, styrene-maleic anhydride, and the like. Preferred thermoplastic resins include thermoplastic resins that have affinity or reactivity with the polar groups of the polyphenylene ether having a polar group, which is the component (I3). Polyolefins such as polyethylene, polypropylene, polybutene, polypentene, etc., and polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, polyethylene, etc., into which a compound having both a polar group and an unsaturated group is introduced by melt reaction, solution reaction, or polymerization. Polyester such as phthalate, polycarbonate polyarylate, polysulfone,
polyetheretherketone, polyethersulfone,
Polyimide boria toy ξ-do, polymethyl methacrylate, ethylene-acrylic acid copolymer, acrylonitrile-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer Polymers, ethylene-vinyl alcohol copolymer, crylonitrile-butadiene-styrene copolymer polyacecool, styrene-maleic anhydride copolymer, and the like can be mentioned. A particularly preferred thermoplastic resin is maleic anhydride-modified polyethylene. Examples include polypropylene, styrene-maleic anhydride copolymer, polyarylate, polycarbonate epoxy group-containing polyphenylene sulfite, and amino-based polyphenylene sulfite F.

Furthermore, various rubber-like elastic bodies can be used, but the most suitable one is a rubber-like copolymer containing a styrene compound as one of its components.

For example, styrene-butadiene copolymer rubber (SBR)
, Styrene-butadiene Bronoch copolymer (SB, S
BS, BSB, etc.), styrene-hydrogenated butene block copolymer (SEBS, SEB, etc.), 2-styrene-isoprene block copolymer (Sl, SIS, ISI, etc.), styrene-hydrogenated isoprene block copolymer (S
EP, 5EPS, etc.) or patent application 1986-12170
As described in specification No. 0, alkyl acrylate,
A vinyl monomer is produced by polymerizing one or more monomers selected from the group consisting of alkyl methacrylate and a polyfunctional monomer having a conjugated diene type double bond. For example, acrylonitrile styrene grafted butadiene rubber (ABS).

Acrylonitrile - styrene graph 1 - butadiene -
Butyl acrylate copolymer rubber (AABS) Methyl methacrylate-styrene grafted butylene acrylate rubber (MAS) Styrene-grafted butadiene rubber (SB), Methyl methacrylate-styrene grafted butadiene rubber (MBS), Methyl methacrylate-styrene graph 1~ Butadiene-butyl acrylate copolymer rubber (MABS) is mentioned.

Further, one or more block or graft copolymers selected from A-B block copolymers, A-grafted B copolymers, and B-grafted A copolymers (where A is an active polymer) Tinku polystyrene acrylonitrile-styrene random copolymer, styrene-maleic anhydride random copolymer, styrene-acrylonitrile-maleimide anhydride random copolymer, styrene-methyl methacrylate random copolymer and styrene-methacrylic acid random copolymer B represents one or more styrenic polymers or styrene copolymers selected from polybutadiene 1 polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, and polycarbonate; and polyamide, polymethyl methacrylate, polyethylene terephthalate, and polybutylene terephthalate.

Furthermore, as the rubber-like elastic body, in addition to the above, natural rubber,
polybutadiene, polyisoprene polyisobutylene,
Examples include neoprene, ethylene-propylene copolymer rubber, polysulfide rubber, thiokol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and the like.

As these rubber-like elastic bodies, rubber-like elastic bodies modified by reacting with a compound having a polar group and an unsaturated group used for introducing the polar group into polyphenylene ether having a polar group may be used.

Various types of flame retardants can be used, but halogen-based flame retardants and phosphorus-based flame retardants are particularly preferred.

Examples of halogen flame retardants include tetrabromobisphenol A, tetrabromophthalic anhydride hexabromobenzene tribromophenyl allyl ether, pentabromo 1-luene, pentabromophenol, tribromophenyl-2,3-dibromopropyl ether, tris(23- dibromopropyl) phosphate, tris(
2-chloro1-3-bromopropyl)phosphate-1~,
Octabromodiphenyl ether Decabromodiphenyl ether Octabromo biphenyl, pentachloropentacyclodecane, hexabromocyclododecane, hexachlorobenzene 5bencchlorotoluene, hexabromo biphenyl, decabromo biphenyl, decabromo biphenyl oxide, tetrabromobutane, decabromo diphenyl ether hexa Bromodiphenyl ether ethylene-bis-(tetrabromobutane), tetrachlorobisphenol A, tetraprobisphenol A
, oligomers of tetrachlorobisphenol A or tetrabromobisphenol A, brominated 9 halogenated polycarbonate oligomers such as polycarbonate oligomers, halogenated epoxy compounds, halogenated polystyrenes such as polychlorostyrene, polytribromostyrene, poly(dibromophenylene oxide)
, bis(tribromophenoxy)ethane, and the like.

On the other hand, examples of phosphorus-based flame retardants include ammonium phosphate, tricresyl phosphate, triethyl phosphate, acidic phosphoric acid ester, and triphenylphosphine oxide.

Among these flame retardants, polytribromostyrene poly(dibromophenylene oxide), decabromodiphenyl ether, bis(+-ribromophenoxy)ethane, ethylene-bis-(tetrabromophthalimide), tetrabromobisphenol A, Brominated polycarbonate oligomers are preferred.

The flame retardant is blended in an amount of 3 to 40 parts by weight, preferably 5 to 35 parts by weight, based on a total of 100 parts by weight of the components (A), (B), and (C). If the blending ratio is less than 3 parts by weight, little effect will be obtained; on the other hand, if it exceeds 40 parts by weight, the flame retardance will not improve in proportion to the ratio, and on the contrary, other mechanical properties will deteriorate. It is undesirable because it damages it.

Further, in the present invention, it is preferable to use a flame retardant aid together with the above-mentioned flame retardant. There are various types of flame retardant aids, such as antimony dioxide, antimony pentoxide, monometallic antimony sodium antimonate, antimony trichloride, antimony pentachloride, antimony trisulfide, and antimony pentasulfide. Examples include auxiliary agents.

In addition to these, zinc borate, barium metaborate, zirconium oxide, etc. can be mentioned. Among these, antimony trioxide is particularly preferred. This flame retardant aid is
It is blended in an amount of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on a total of 100 parts by weight of components (A), (B), and (C). If the blending ratio of the flame retardant auxiliary agent is less than 1 part by weight, the effect as an N combustion auxiliary agent will not be sufficient. on the other hand,
Even if it exceeds 15 parts by weight, the effect as a flame retardant aid will not improve in proportion to the proportion, and on the contrary, other physical properties may be impaired, which is not preferable.

Furthermore, in the present invention, a tetrafluoroethylene polymer can be used to prevent melt dripping. Specifically, tetrafluoroethylene polymers include, in addition to tetrafluoroethylene homopolymer (polytetrafluoroethylene), copolymers of tetrafluoroethylene and hexafluoropropylene, and copolymerizable ethylenic polymers. Examples include Te1-Raful 1st coethylene copolymers containing a small amount of saturated monomers. This tetrafluoroethylene polymer has a fluorine content of 65 to 76% by weight.
, preferably 70 to 76% by weight. The above-mentioned tetrafluoroethylene polymer includes the above-mentioned (A) and (B).
) and (C) 0.00 per 100 parts by weight in total
It is blended in an amount of 3 to 10 parts by weight, preferably 0.02 to 2 parts by weight, and more preferably 0.1 to 2 parts by weight.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Reference Example 1 In a glass container with an internal volume of 500 mβ that was replaced with argon,
Copper sulfate pentahydrate (Cu S Oa ・5 Hz O) 17
．． 8 g (71 mmol), 200 rrdl of toluene and 24 m of trimethylaluminum ((250: Eritham) were added and reacted at 40°C for 8 hours. After that, from the solution obtained by removing the solid portion, further Then, toluene was distilled off under reduced pressure at room temperature to obtain 6.7 g of a contact product.The molecular weight of this product was determined by freezing point depression method (the molecular weight was 610).

Manufacturing example 1 Inner volume 2I! , purified styrene] I.

Using 7.5 mmol of the contact product obtained in the above-mentioned Reference Example 1 as an aluminum atom, 7.5 mmol of I.
The polymerization reaction was carried out at 0°C for 5 hours. After completion of the reaction, the product was hydroxylated) After decomposing the catalyst component with a methanol solution of IJum, the mixture was washed repeatedly with methanol and dried to obtain 466 g of a polymer.

The weight average molecular weight of this polymer was measured by gel permeation chromatography at 130°C using I, 2.4 trichlorohenzene as a solvent and was 290.0.
00, and the weight average molecular weight/number average molecular weight is 2.
It was 72. Furthermore, it was confirmed by melting point and 13C-NMR measurements that this polymer was polystyrene (sps) with a syndiotactic structure.

Production Example 2 In a reaction vessel having an internal volume of 2, purified styrene 11 was mixed with the contact product obtained in Reference Example 1 described above, and 5 aluminum atoms were added.
mmol 5 mmol of triisobutylalkunium,
A polymerization reaction was carried out at 90°C for 5 hours using 0.025S rimole of pentamethylcyclopentadienyl titanium trimethoxide.

After the reaction was completed, the catalyst component of the product was decomposed with a methanol solution of sodium hydroxide, washed repeatedly with methanol, and then dried to obtain 308 g of a polymer.

4 The weight average molecular weight of this polymer was measured by gel permeation chromatography at I 30 'C using 1,2.4 trichlorobenzene as a solvent and found to be 389.
,000, and the weight average molecular weight/number average molecular weight was 2.64. Furthermore, it was confirmed by melting point and -NMR measurements that this polymer C was polystyrene with a syndiotactic structure.

Production Example 3 In a reaction vessel with an internal volume of 21, 7.5 mmol of the contact product obtained in Reference Example 1 of purified styrene 11'' was added as an aluminum atom, and 7.5 mmol of triisobutyral≧nium was added.
Polymerization reaction was carried out at 70°C for 3 hours using 10.038 mmol of pentamethylcyclopentadienyl titanium trime I xy. After the reaction was completed, the catalyst component was decomposed with a methanol solution of thorium to hydroxide the product, washed repeatedly with methanol, and dried to obtain 580 g of a polymer.

The weight average molecular weight of this polymer is 1, 2. /1 As measured by gel permeation chromatography at 130°C using trichlorohenzene as a solvent, it was 592.
000, and the weight average molecular weight/number average molecular weight is 2
．． It was 81. Furthermore, it was confirmed by melting point and C-NMR measurements that this polymer was polystyrene with a syndiotactic structure.

Production Example 4 Poly(2,6-dimethyl-14-phenylene) ether (PPO) (manufactured by Al-Lynch Co., Catalog: J Ri No.
, 1817Ei-1) ] 5 parts by weight of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., S-Grade) and L-butylhydroperoxa. After mixing 0.2 parts by weight of Perbutyl H) in a Henschel mixer, the mixture was kneaded while being heated and melted in a twin-screw extruder at a temperature of 300 to 320°C to obtain maleic anhydride-modified PPO. The obtained modified PP○ was purified by dissolving it in toluene and re-precipitating it dropwise into methanol.

After press molding purified modified P I”0, infrared rays (IR)
Through measurement, a peak based on carbonyl groups was observed, and it was confirmed that the sample had been modified with maleic anhydride.

Production Example 5 1 liter of 25°C glue: Intrinsic viscosity in I volume is 0.4
Styrene grafted polyphenylene ether (P
0.5 parts by weight of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., S Gray 1.), cumene hydrobar as a peroxide, per 100 parts by weight of PE) (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Copier Ace CPX100). Okizai I- (+'1 made by Hontomari ■, product name: Parkmino 1 Kawa 1) 0. /1 part by weight was mixed in a Henschel mixer, then heated and melt-kneaded in a twin-screw extruder at a temperature of 300°C to obtain maleic anhydride-modified P.
I got PE. It was confirmed that the obtained modified PPE was modified with maleic anhydride in the same manner as in Production Example 4.

Production Example 6 Poly(2,6-dimethyl-1.4phenylene)ether (PPO) (manufactured by Aldrich, Kata [No. 1, 18
178-1) To 85 parts by weight, 15 parts by weight of SPS obtained in Production Example 1, 0.5 parts by weight of maleic anhydride 7 (manufactured by Wako Pure Chemical Industries Ltd., S grade), and t-butyl as peroxide. After mixing 0.2 parts by weight of hydroxy peroxide (manufactured by NOF ■, trade name: Perbutyl H) in a Henschel mixer, the mixture was heated and melt-kneaded in a twin-screw extruder at a temperature of 300 to 320°C to form maleic anhydride. Modified PPO was obtained. It was confirmed that the obtained modified PPO was modified with maleic anhydride in the same manner as in Production Example 4.

Production Example 7 Poly(2,6-dimethyl-1,4phenylene)ether (PPO) (manufactured by Aldrich, Catalog No. 181
78-1) For 85 parts by weight, Idemitsu polystyrene HT-
54 (HI PS) 15 parts by weight 5 Maleic anhydride (manufactured by Wako Pure Chemical, S grade) 5 parts by weight, L as peroxide
- Mix 0.2 parts by weight of butyl hydroxyver oxide (manufactured by NOF ■, trade name: Perbutyl H) in a Henschel mixer, then heat-melt knead with a twin-screw extruder at a temperature of 260 to 270°C. Then, maleic anhydride-modified PPO was obtained.

The obtained modified P1)0 was converted to anhydrous 8 in the same manner as in Production Example 4. It was confirmed that it was modified with maleic acid.

Example 1 85% by weight of polystyrene (SPS) having a syndiotactic structure obtained in Production Example 1, 5% by weight of maleic anhydride-modified PY) obtained in Production Example 4, nylon-6,
6 (manufactured by Ube Industries On, Ube Nylon 2020B) for a total of 100 parts by weight, as an antioxidant (2
, 6-diL) methyl-4-methylphenyl diphosphite (manufactured by Adeka Chigas Co., Ltd. Product name: I
) BP-36) 0.7 parts by weight. 2.6-di-butyl-4-phenol (manufactured by Sumitomo Chemical Co., Ltd., product name: Sumilizer)
BHT) 0.1 part by weight and 1 part by weight of aluminum p(L-butyl)benzoate were added, and after performing dry plaining in a Henschel mixer, melt kneading was performed in a twin-screw extruder at a cylinder temperature of 300°C. and pelletized.

Using the obtained pellet, injection molding was performed to obtain a tensile test piece, and the tensile modulus, water absorption, and retention of the tensile modulus after water absorption were measured. The results are shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 3 Example 1 except that the styrene polymer, polyphenylene ether polyamide, and additives were blended in the proportions shown in Table 1.
Do the same as and calculate the tensile modulus.

The water absorption rate and retention of tensile modulus after water absorption were measured. The results are shown in Table 1. Regarding Example 3 and Comparative Example 3, bending strength was also measured.

Example 6 85% by weight of polystyrene (SPS) having a syndiotactic structure obtained in Production Example 1. Maleic anhydride modified PP05% by weight obtained in Production Example 4, Nylon-6,6
(Made by Ube Industries, Ube Nylon 2020B) 10% by weight
As an antioxidant, (2 6 parts by weight)
-C-L-butyl-4-methylphenyl) pentaerythritor diphosphite (manufactured by Adeka Chigas. Product name:
PEP-36) 0.7 parts by weight. Te1-rakis[methylene-3-(3',5''-di-L-butyl 4-hydroxyphenyl)]propionate (manufactured by Adeka Twogas).

Product name: MARK AO60) 0.1 part by weight and p-
After adding 1 part by weight of (t-butyl)benzoic acid and performing tri-blending in a Henschel mixer, glass fiber treated with aminosilane (Asahi Glass Fiber 43 parts by weight of C303MA416 (trade name: C303MA416, manufactured by Co., Ltd.) was melt-kneaded while side-feeding to form a pellet.

Using the obtained pellets, injection molding was performed to obtain tensile test piece 1 bending test piece, and the tensile modulus was measured.

The water absorption rate, retention of tensile modulus after water absorption, and heat distortion temperature were measured. The results are shown in Table 2.

Examples 7-16 Styrenic m combination, polyphenylene ether.

The same procedure as in Example 6 was carried out except that the polyamide, filler, and additive were blended in the proportions shown in Table 3, and the tensile modulus 2 water absorption, retention of tensile modulus after water absorption, and heat distortion temperature were measured. went. The results are shown in Table 2.

Example 10. Regarding Comparative Example 4, the Izod impact value was also measured.

3 *1 Achinosilane treatment 13 μm / 3 mm Cheaped strand glass fiber *2 p-(t-butyl)benzoic acid algonilla J *3
Atactic polystyrene (Polystyrene HH30B manufactured by Idemitsu Petrochemical ■) *4 High impact polystyrene (Polystyrene HT-54 manufactured by Idemitsu Ishiyu Chemical ■) *5 Spray a toluene/water suspension of T-aminopropyltriethoxysilane. Talc *6 Styrene-butadiengo J1 (manufactured by Nippon Zeon Co., Ltd.,
ZLS-01) [Effects of the Invention] As described above, the styrenic resin & IN material of the present invention has excellent impact resistance, water resistance, and mechanical properties, and is useful for electrical/electronic materials, industrial structures, and automobile parts. It is expected to be effectively used in a variety of applications, including the bottom shape of industrial materials such as home appliances and various mechanical parts.

Procedural amendment (voluntary) September 6, 1990

Claims (6)

[Claims] (1) (A) Styrenic polymer without functional group 99~
1% by weight, (B) 0.1 to 50% by weight of polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group and having a polar group, and (C) 0.9% of polyamide. A styrenic resin composition consisting of ~98.9% by weight. (2) The styrenic resin composition according to claim 1, wherein component (A) is a styrenic polymer having a syndiotactic structure. (3) Claim 1 wherein the polar group of component (B) is an acid derivative.
The styrenic resin composition described above. (4) A styrenic resin composition comprising 100 parts by weight of the styrenic resin composition according to any one of claims 1 to 3 and (D) 1 to 350 parts by weight of a filler surface-treated with a coupling agent. . (5) The styrenic resin composition according to claim 4, wherein the coupling agent used in the surface treatment of the filler as component (D) is a silane coupling agent. (6) (A') 99 to 1% by weight of a styrenic polymer having a syndiotactic structure and (B') anhydrous polyphenylene ether or a mixture of polyphenylene ether and a styrene polymer having no functional group; Those with maleic acid group0.
(C) polyamide 0.9 to 98.9% by weight (D') The filler surface-treated with an aminosilane coupling agent was added to the filler (A'), (B') and (C). ) A styrenic resin composition blended in an amount of 1 to 350 parts by weight based on a total of 100 parts by weight of the components.