JPH11279349A - Styrenic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an APS resin compsn. which is improved in solvent resistance without using a special compatibilizer and has good heat resistance and stability during staying in a molding machine. SOLUTION: This compsn. comprises (A) 30-95 wt.% atactic polystyrene, or atactic polystyrene and a rubbery elastomer and (B) 70-5 wt.% syndiotactic polystyrene having a wt. average mol.wt.(Mw) of 200,000 or lower and a mol.wt. distribution [wt. average mol.wt.(Mw)/number average mol. wt. (Mn)] of 1.7 or lower. If necessary, the compsn. further contains (C) polyphebylene ether having an intrinsic viscosity (in chloroform at 25 deg.C) of 0.5 dl/g or lower, (D) an inorg. filler, and (E) a polar polymer compatible with or affinitive to ingredients A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrenic resin composition, and more particularly, to a styrenic polymer having an atactic structure (hereinafter referred to as "atactic polystyrene").
It may be called. It may also be abbreviated as APS. ) Or a mixture of APS and a rubber-like elastic material, and a specific styrene-based polymer having a predominantly syndiotactic structure (hereinafter sometimes referred to as “syndiotactic polystyrene”, and may be abbreviated as SPS). ,
Further, the present invention relates to a styrene-based resin composition containing a specific polyphenylene ether (hereinafter sometimes abbreviated as PPE) or an inorganic filler, if necessary.

[0002]

2. Description of the Related Art Conventionally, APS resins produced by a radical polymerization method are inexpensive and have been used for various applications. However, since their tertiary structure is atactic, they are amorphous resins and are resistant to solvents. Regarding the properties, it was not always satisfactory, so that the applicable range as a material was limited.

In order to improve such solvent resistance, it has been practiced to copolymerize styrene with polar monomers such as acrylonitrile, methacrylate, acrylate, maleic anhydride, and maleimide, but these copolymers are randomly copolymerized. There are problems such as a limited ratio, low productivity, poor color tone, odor, and difficulty in mixing and recycling with other polystyrene resins.

On the other hand, a syndiotactic polystyrene resin having crystallinity has been developed, and a composition in which a syndiotactic polystyrene resin is blended with its resin component has been proposed for the purpose of improving the heat resistance of a certain thermoplastic resin. (Japanese Patent Laid-Open No. 62-104818, Japanese Patent Laid-Open No. 62-2
57948, JP-A-62-257950,
JP-A-1-182344). However, when syndiotactic polystyrene resin is blended with atactic polystyrene resin, the heat resistance is improved, but the solvent resistance and impact resistance of the molded product are not sufficiently satisfactory.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made from the above viewpoint, and has improved solvent resistance without using a special compatibilizer and has good heat resistance and impact resistance. It is an object to provide an APS-based resin composition having the same.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that simply blending SPS having a specific molecular weight and a specific molecular weight distribution with an APS-based resin, It has been found that by adding a polyphenylene ether having the following formula, the solvent resistance can be improved and also the impact resistance can be improved. Further, it has been found that the heat resistance and the elastic modulus can be further improved by blending the inorganic filler in a predetermined ratio.

The present invention has been completed based on such findings. That is, the present invention provides the following resin composition. (1) A styrene resin composition comprising the following components (A) and (B). (A) Styrene-based polymer 30 having an atactic structure
~ 95% by weight, (B) weight average molecular weight (Mw) is 20
70 to 5% by weight of a styrene polymer mainly having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of not more than 0.00 and not more than 2.7. (2) A styrene resin composition comprising the following components (A) and (B). (A) the total amount of the styrenic polymer having an atactic structure and the rubber-like elastic body is 30 to 95% by weight, (B) the weight average molecular weight (Mw) is 200,000 or less, and the molecular weight distribution (weight average molecular weight (Mw) Mw) / number average molecular weight (M
70 to 5% by weight of a styrenic polymer having a predominantly syndiotactic structure wherein n)) is 2.7 or less. (3) A styrene resin composition containing the following components (A), (B) and (C). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). (4) A styrenic resin composition containing the following components (A), (B) and (D). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (D) 1 to 70% by weight of the total weight of the inorganic filler, including the components (A), (B), (D) and other components. (5) A styrene resin composition containing the following components (A), (B), (D) and (E). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (D) The inorganic filler is mixed with the components (A), (B), (D) and (E).
1 to 70% by weight based on the total weight of the components and other components, (E) a polymer having compatibility or affinity with the components (A) and (B) and having a polar group, 0.1 to 10 parts by weight based on 100 parts by weight of the total of the component and the component (B). (6) A styrene resin composition containing the following components (A), (B), (C) and (D). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). (D) The inorganic filler is used in an amount of 1 to 70% by weight based on the total weight of the components (A), (B), (C), (D) and other components. A) component, (B) component, (C) component,
A styrene-based resin composition containing the component (D) and the component (E). (A) a styrene polymer having an atactic structure, or a total amount of a styrene polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). (D) The inorganic filler is used as the component (A), the component (B), the component (C), the component (D),
(E) 1 to 7 of the total weight including the components and other components
0% by weight, (E) A polymer having compatibility or affinity with the components (A) and (B) and having a polar group is the sum of the components (A), (B) and (C). 0.1 to 10 parts by weight based on 100 parts by weight.

[0008]

Embodiments of the present invention will be described below. 1. (1) Styrene-based polymer having atactic structure (A) The styrene-based polymer having an atactic three-dimensional structure used in the present invention includes solution polymerization, bulk polymerization, and suspension polymerization. A polymer composed of one or more aromatic vinyl compounds represented by the following general formula, or copolymerizable with one or more aromatic vinyl compounds, obtained by a polymerization method such as suspension polymerization or bulk-suspension polymerization. Copolymers of one or more other vinyl monomers, hydrogenated polymers of these polymers, and mixtures thereof.

[0009]

Embedded image

(Wherein R is any 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)
It represents a substituent containing at least one kind, and m represents an integer of 1 to 3. However, when m is plural, each R may be the same or different. The preferred aromatic vinyl compound used herein includes styrene, α-methylstyrene, methylstyrene,
Ethyl styrene, isopropyl styrene, tertiary butyl styrene, phenyl styrene, vinyl styrene,
Chlorostyrene, bromostyrene, fluorostyrene,
There are chloromethylstyrene, methoxystyrene, ethoxystyrene and the like, and these are used alone or in combination of two or more. Of these, particularly preferred aromatic vinyl compounds are styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, m-chlorostyrene and p-fluorostyrene.

Other copolymerizable vinyl monomers include:
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate,
Acrylates such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylates such as benzyl methacrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butyl Rumareimido, N- lauryl maleimide, N- cyclohexyl maleimide, N- phenylmaleimide, there are maleimide compounds such as N-(p-bromophenyl) maleimide.

The copolymerizable rubbery polymer includes polybutadiene, styrene-butadiene copolymer,
Diene rubbers such as acrylonitrile-butadiene copolymer and polyisoprene, non-diene rubbers such as ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer and polyacrylate, styrene-
Butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene elastomer, styrene-graft-ethylene-propylene elastomer, ethylene-based ionomer resin, hydrogenated styrene-isoprene copolymer, and the like.

The molecular weight of this atactic polystyrene is not particularly limited, but generally has a weight average molecular weight of 10,000 or more, preferably 50,000 or more. Here, if the weight average molecular weight is less than 10,000, the thermal properties and mechanical properties of the obtained molded article are undesirably reduced. Furthermore, there is no restriction on the molecular weight distribution, and various types can be applied.

Further, in order to improve the impact resistance,
As a part of the component (A), a rubber-like elastic body can be used in combination depending on the purpose. Specific examples of the rubber-like elastic body include, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer (SB
S), 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 (SEP)
S) or ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate -Styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene-core shell rubber (ABS), butadiene-styrene-core shell rubber (SBR), methyl methacrylate- Core-shell type particulate elastic material such as siloxane-containing core-shell rubber such as butyl acrylate-siloxane, Like rubber, and the like. Among them, SBR, SEB, SBS, SEBS, SI
R, SEP, SIS, SEPS, core shell rubber, EP
M, EPDM, or rubber modified from these is preferably used. These rubber-like elastic bodies can be used alone or in combination of two or more.

The mixing ratio of the rubber-like elastic body is as follows:
80% by weight or less in the components, preferably 60% by weight or less,
More preferably, it is at most 50% by weight. If it exceeds 80% by weight, the solvent resistance and the elastic modulus may be reduced. (2) Styrene-based polymer mainly having a syndiotactic structure (B) In the styrene-based polymer mainly having a syndiotactic polystyrene structure which is a component (B), a syndiotactic structure means a stereochemical structure having a syndiotactic structure. Has a steric 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 determined by nuclear magnetic resonance Quantified by the method (13C-NMR). The tacticity measured by the 13C-NMR method is determined by the proportion of a plurality of continuous structural units, for example, 2
The styrene polymer having a syndiotactic structure referred to in the present invention is usually a racemic dyad. Polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated halogenated) having a syndiotacticity of 75% or more, preferably 85% or more, or 30% or more, preferably 50% or more in racemic pentad Alkylstyrene), poly (alkoxystyrene),
Poly (vinyl benzoate), hydrogenated polymers thereof, mixtures thereof, or copolymers containing these as a main component. Here, poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiarybutylstyrene), poly (phenylstyrene), poly (vinylnaphthalene) , Poly (vinylstyrene), and the like, and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like. Examples of the poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of the poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

Of these, particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), and poly (p-chlorostyrene). Styrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units.

As a method for producing such a styrenic polymer having a predominantly syndiotactic structure, known methods may be used. For example, a titanium compound and an inert hydrocarbon solvent may be used in the presence or absence of a solvent. A method of polymerizing a styrene-based monomer (a monomer corresponding to the above-mentioned styrene-based polymer) using a condensation product of water and a trialkylaluminum as a catalyst (Japanese Patent Application Laid-Open No. 62-18 / 1987)
No. 7708). Poly (halogenated alkylstyrene) and hydrogenated polymers thereof can also be obtained by known methods, for example, methods described in JP-A-1-46912 and JP-A-1-178505. .

In the present invention, these styrenic polymers mainly having a syndiotactic structure have a weight average molecular weight (Mw) of 200,000 or less, preferably 190,000 or less.
00 or less, more preferably 180,000 or less,
In addition, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) must be 2.7 or less, preferably 2.6 or less, more preferably 2.5 or less. The lower limits are not particularly limited. Weight average molecular weight 200,00
If it exceeds 0 or if Mw / Mn exceeds 2.7,
The dispersibility may deteriorate, and the impact resistance may decrease.

These styrenic polymers having a predominantly syndiotactic structure alone may be used alone.
Alternatively, two or more kinds can be used in combination. (3) Polyphenylene ether (C) The polyphenylene ether as the component (C) is a known compound and is used for this purpose.
Nos. 6874, 3306875, 3257357 and 3257358 can be referred to. Polyphenylene ether is usually a copper amine complex,
It is prepared by an oxidative coupling reaction to form a homopolymer or a copolymer in the presence of one or more two- or three-substituted phenols. Here, the copper amine complex may be a copper amine complex derived from primary, secondary and / or tertiary amines. Examples of suitable polyphenylene ethers include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1,4-phenylene ether) ), Poly (2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly (2-methyl-
6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1,4-phenylene ether), poly (2-ethyl-6-n-propyl-)
1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly (2-
(4′-methylphenyl) -1,4-phenylene ether), poly (2-bromo-6-phenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-)
1,4-phenylene ether), poly (2-phenyl-
1,4-phenylene ether), poly (2-chloro-
1,4-phenylene ether), poly (2-methyl-
1,4-phenylene ether), poly (2-chloro-6)
-Ethyl-1,4-phenylene ether), poly (2-
Chloro-6-bromo-1,4-phenylene ether),
Poly (2,6-di-n-propyl-1,4-phenylene ether), poly (2-methyl-6-isopropyl-)
1,4-phenylene ether), poly (2-chloro-6)
-Methyl-1,4-phenylene ether), poly (2-
Methyl-6-ethyl-1,4-phenylene ether),
Poly (2,6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether) And poly (2,6-dimethyl-1,4-phenylene ether). Copolymers such as, for example, copolymers derived from two or more of the phenolic compounds used in the preparation of the homopolymers are also suitable. Further, those modified with a modifying agent such as maleic anhydride, fumaric acid or the like are also preferably used. Further, for example, a graft copolymer and a block copolymer of a vinyl aromatic compound such as polystyrene and the above-mentioned polyphenylene ether are also exemplified.

Of these, poly (2,6) is particularly preferred.
-Dimethyl-1,4-phenylene ether) is used. The molecular weight of the polyphenylene ether used as the component (C) is such that the intrinsic viscosity measured at 25 ° C. in chloroform is not more than 0.5 deciliter / g, preferably not more than 0.45.
It must be less than deciliter / g. There is no particular lower limit. If the content exceeds 0.5 deciliter / g, the effect of the component (B) as a dispersant is reduced, and the effect of improving impact resistance may be reduced, which is not preferable. (4) Inorganic Filler (D) Regarding the inorganic filler of the component (D), it does not matter whether it is fibrous, granular or powdery. Examples of the fibrous filler include glass fiber, carbon fiber, and whisker. Cloth, mat,
There are bundle cut, short fiber, filament, whisker, etc., but in the case of bundle cut, the length is 0.05 mm to 50 mm.
mm and a fiber diameter of 5 to 20 μm are preferred.

On the other hand, as the granular or powdery filler, for example, talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, Oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, glass beads and the like can be mentioned.

Among the various fillers described above, glass fillers such as glass powder, glass flake,
Glass beads, glass filaments, glass fibers, glass lobing, and glass mats are preferred. Also,
These fillers are preferably surface-treated.
The coupling agent used for the surface treatment is used for improving the adhesiveness between the filler and the resin,
Any one of conventionally known ones such as a so-called silane coupling agent and a titanium coupling agent can be selected and used. Among them, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And aminosilane, epoxysilane and isopropyl tri (N-amidoethyl, aminoethyl) titanate.

As the film former, conventionally known ones can be used, and among them, urethane type, epoxy type, polyether type and the like are preferably used. In addition, these inorganic fillers can be used alone or in combination of two or more. (5) A polymer having compatibility or affinity with the components (A) and (B) and having a polar group (E) In order to improve the adhesion between the inorganic filler of the component (D) and the resin. As the component (E), a polymer having compatibility or affinity with the components (A) and (B) and having a polar group is preferably blended.

Here, the polymer having compatibility or affinity with the components (A) and (B) is defined as a polymer having compatibility or affinity with the components (A) and (B) in a polymer chain. To contain. Examples of the polymer exhibiting these compatibility or affinity include, for example, syndiotactic polystyrene,
Atactic polystyrene, isotactic polystyrene, styrene copolymer, polyphenylene ether,
Those having polyvinyl methyl ether or the like as a main chain, a block or a graft chain are exemplified.

The polar group referred to herein may be any group which improves the adhesiveness with the inorganic filler as the component (D), and specifically includes an acid anhydride group, a carboxylic acid group and a carboxylic acid group. Acid ester group, carboxylic acid chloride group, carboxylic acid amide group, 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, imide And oxazoline groups.

The component (E) is obtained by reacting a polymer having compatibility or affinity with the components (A) and (B) with a modifier described below in the presence or absence of a solvent or other resin. Can be obtained by As a denaturing agent, for example,
A compound containing an ethylenic double bond and a polar group in the same molecule can be used. Specifically, maleic anhydride, maleic acid, maleic ester, maleimide and its N-substituted product, maleic acid derivatives such as maleic acid salt, fumaric acid, fumaric acid ester, and fumaric acid such as fumaric acid salt Derivatives, itaconic anhydride, itaconic acid, itaconic acid esters, itaconic acid and other itaconic acid derivatives, acrylic acid, acrylic acid esters, acrylamide, acrylic acid derivatives including acrylates, methacrylic acid, methacrylic acid And methacrylic acid derivatives such as acid esters, methacrylamide, methacrylate, and glycidyl methacrylate. Among them, maleic anhydride, fumaric acid and glycidyl methacrylate are particularly preferably used.

A known method is used for the modification.
150 using a mill, Banbury mixer, extruder, etc.
A method of melt-kneading and reacting at a temperature of from 0 to 350 ° C, and a method of heating and reacting in a solvent such as benzene, toluene, and xylene can be exemplified. In order to further facilitate these reactions, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, azobisisovaleronitrile, It is effective to use a radical generator such as 2,3-diphenyl-2,3-dimethylbutane. Of these, 2,3-diphenyl-2,3-dimethylbutane is particularly preferably used.

A preferred modification method is a method of melt-kneading in the presence of a radical generator. Further, at the time of modification, another resin may be added. Specific examples of the component (E) include a styrene-maleic anhydride copolymer (SM
A), a styrene-glycidyl methacrylate copolymer,
Carboxylic acid-modified polystyrene, epoxy-modified polystyrene, oxazoline-modified polystyrene, amine-modified polystyrene, sulfonated polystyrene, styrene ionomer, styrene-methyl methacrylate
To-graft polymer, (styrene-glycidyl methacrylate) -methyl methacrylate-graft copolymer, acid-modified acryl-styrene-graft polymer,
(Styrene-glycidyl methacrylate) -styrene-
Graft polymer, polybutylene terephthalate-polystyrene-graft polymer, maleic anhydride-modified P
S, fumaric acid-modified PS, glycidyl methacrylate-modified PS, amine-modified PS and other modified styrenic polymers,
Modified polyphenylene ethers such as (styrene-maleic anhydride) -polyphenylene ether-grafted polymer, maleic anhydride-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, and amine-modified polyphenylene ether And the like.

Of these, modified PS and modified polyphenylene ether are particularly preferably used. Further, two or more of the above polymers can be used in combination. (E)
The polar group content in the component is preferably in the range of 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, based on 100% by weight of the component (E). If the content is less than 0.01% by weight, it is necessary to add a large amount of the component (E) in order to exert an adhesive effect with the inorganic filler, which may reduce the mechanical properties, heat resistance, and moldability of the composition. Not preferred. On the other hand, if it exceeds 20% by weight, the compatibility with the components (A) and (B) may be reduced, which is not preferable. (5) Other Additives In the resin composition of the present invention, a nucleating agent, a plasticizer, a release agent, and an antioxidant, in addition to the components (A) to (E), unless the object of the present invention is inhibited. , A flame retardant, a flame retardant auxiliary, a thermoplastic resin, and additives such as a dye, a pigment, and an antistatic agent. Each of these can be used alone or in combination of two or more.

Nucleating agent A nucleating agent can be added to promote crystallization of SPS and to further enhance solvent resistance. Examples of the nucleating agent include metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate), metal salts of phosphoric acid such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate, and talc. And phthalocyanine derivatives and the like can be arbitrarily selected and used.

Plasticizer The plasticizer is arbitrarily selected from known ones such as polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalic acid ester, polystyrene oligomer, polyethylene wax, mineral oil and silicone oil. Can be used.

Release Agent The release agent can be arbitrarily selected from known materials such as polyethylene wax, silicone oil, long-chain carboxylic acid, and metal salt of long-chain carboxylic acid. Antioxidant As the antioxidant, any known antioxidant such as phosphorus-based, phenol-based, and sulfur-based can be used.

Flame retardants and flame retardant assistants Examples of flame retardants include brominated polymers such as brominated polystyrene, brominated syndiotactic polystyrene, and brominated polyphenylene ether, brominated diphenylalkane, and brominated diphenyl ether. Any of known brominated aromatic compounds, phosphorus-based flame retardants such as tricresyl phosphate, triphenyl phosphate, tris-3-chloropropyl phosphate and the like can be arbitrarily selected and used. Further, as the flame retardant auxiliary, any one of antimony compounds such as antimony trioxide and other known ones can be arbitrarily selected and used. The anti-drip agent may be arbitrarily selected from known materials such as Teflon.

Thermoplastic resin As the thermoplastic resin, linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene,
Isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene,
Cyclic polyolefin, polyolefin resin including poly-4-methylpentene, polystyrene, HIP
Polystyrene resins such as S, ABS, AS, and SMA; polyester resins such as polycarbonate, polyethylene terephthalate and polybutylene terephthalate; polyamide resins such as polyamide 6, polyamide 6,6; and polyarylene sulfide resins Any known ones can be used. 2. Mixing ratio of each component constituting the styrene-based resin composition (1) Regarding the mixing ratio of the components (A) and (B), the component (A) (that is, atactic polystyrene (APS), or APS and rubber) (When the rubber-like elastic body is used in combination), the total amount is 30 to 95% by weight, preferably 50 to 95% by weight.
90% by weight, more preferably 60-85% by weight,
(B) Syndiotactic polystyrene (SPS) is 7
It is 0 to 5% by weight, preferably 50 to 10% by weight, more preferably 40 to 15% by weight. If the component (B) is less than 5% by weight, the effect of solvent resistance may not be exhibited. If it exceeds 70% by weight, the properties of the APS may be lost and the impact resistance may be reduced. (2) The component (C) is used in an amount of 1 to 100 parts by weight, preferably 3 to 80 parts by weight, per 100 parts by weight of the total of the components (A) and (B). Furthermore, the range of 1 to 20 parts by weight is also suitable.

When the amount is less than 1 part by weight, the effect of improving the impact resistance is small, and when it is more than 100 parts by weight, there is a possibility that the fluidity of the composition may be lowered or a gel component may be generated. (3) Regarding the compounding ratio of the (D) inorganic filler, in the styrene resin composition according to the present invention, the (A) component, the (B) component, the (C) component, the (D) inorganic filler, Of the total weight including the component (E) and other components,
(D) 1 to 70% by weight of inorganic filler, preferably 5 to 5%
0% by weight. When the amount is less than 1% by weight, the effect of blending the inorganic filler is not exhibited. (4) About the compounding ratio of the component (E), the component (A) and the component (B) may be added to the total of 100 parts by weight or (A).
The amount is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the components (B) and (C). If the amount is less than 0.1 part by weight, the adhesive effect of the component (D) with the inorganic filler is small, and the adhesiveness between the resin and the inorganic filler is insufficient. No improvement is observed, and this is economically disadvantageous. 3. Method for Preparing Styrenic Resin Composition According to the Present Invention The method for preparing the styrenic resin composition according to the present invention is not particularly limited, and can be prepared by a known method. For example, the above components and various additives are melt-kneaded using a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single screw extruder, twin screw extruder, co-kneader, multi-screw extruder, etc. The resin composition of the present invention can be obtained.

The resin temperature at the time of melt-kneading is from the melting point of SPS to 300 ° C., preferably from the melting point of SPS to 290 ° C., and more preferably from the melting point of SPS to 285 ° C. When the melting point is lower than the melting point of SPS, the dispersion state of SPS is deteriorated, and the effect of improving the solvent resistance may be lowered, and the impact resistance may be lowered, which is not preferable. If the temperature exceeds 300 ° C, APS, PP
In some cases, impact resistance may be reduced due to deterioration of E. 4. Molding method using the styrene-based resin composition according to the present invention.
It can be formed by a known method such as extrusion. The resin temperature during molding is not particularly limited, but is preferably 200
To 300 ° C, more preferably 220 to 280 ° C. If the temperature is lower than 200 ° C., the fluidity may be inferior.
If the temperature exceeds 0 ° C., the APS may deteriorate, which is not preferable. Mold temperature (actual temperature) during molding is 30 to 100 ° C
Is preferably used. If the temperature is lower than 30 ° C., the surface appearance of the molded product may be inferior. 5. Uses of the Styrene Resin Composition According to the Present Invention The styrene resin composition according to the present invention can be used for various uses, and is not particularly limited. Applications for automobile parts include radiator grills, grills, marks, back panels, door mirrors, wheel caps, air spoilers, and cowls for motorcycles as exterior parts.
Instrument panels, meter hoods, pillars, glove boxes, console boxes,
Speaker box, lid, and the like. Examples of the electric appliance use include a housing, a chassis, a cassette case, a CD magazine, and a remote control case for an AV device, and a lining, a tray, an arm, a door cap, a handle, etc. for an electric refrigerator, and a vacuum cleaner. Housing, handle, pipe, suction port, etc.
Housings, fans, remote control cases, etc. are listed for air conditioners, and fans, ventilation fans, washing machines, etc.
Lighting equipment parts, battery cases, and the like. General equipment applications include housings, chassis, ribbon cassettes, trays and the like for printers and copiers, and housings, floppy disk shells and k-boards for personal computers. In addition, a housing, a receiver, a mechanical chassis, and the like are used for telephones and communication devices. Other devices include sewing machines, registers, typewriters, calculators, optical devices, musical instruments, and the like. Furthermore, it is used for toys such as miscellaneous goods, remote control cars, blocks, pachinko machine parts, surfboards, helmets, etc., leisure and sporting goods. It is also used for toilet articles such as toilet seats, toilet lids, tanks, showers, etc., lunch boxes, various containers, household goods such as pots, building material housing parts, furniture, stationery and the like. As applications for industrial structural materials, it is also suitably used for applications such as pipes, containers, trays, uniaxially and biaxially stretched films and sheets by extrusion and stretching, and fibrous molded products by spinning.

[0037]

〔Evaluation methods〕

-Impact strength (with notch): JIS K 7110
Sought in accordance with. -Solvent resistance (1) Stress cracking property As a solvent, a surfactant (manufactured by Kao Corporation, trade name: Bass Magic Lin), soybean oil, and MCT oil (manufactured by RIKEN Vitamin Co., trade name: Actor M1) are used. It was measured. The specific method is as follows. Using a 0.8% bending strain jig, the test piece is fixed to the curved portion, and the solvent is dripped so that the solvent is soaked in the entire gauze spread on the upper surface of the curved portion of the test piece. C. in an oven at room temperature for 1 hour and at room temperature for 1 hour. Thereafter, the change in appearance was visually determined. The case where no change in appearance was observed was evaluated as ◎, the case where almost no change was observed was evaluated as ○, the case where slight craze occurred was evaluated as Δ, and the case where cracks occurred or fractured was evaluated as x. (2) Immersion test The appearance change when immersed in Freon 141B at room temperature for 1 hour was visually judged. The determination of the appearance change is the same as above. [Raw materials used] (A) Component (APS) High impact polystyrene (HIPS) Idemitsu Petrochemical Co., Ltd., trade name: HT52 General-purpose polystyrene (GPPS) Idemitsu Petrochemical Co., Ltd., trade name: HH30E rubber-like elastic body G1651: SEBS type rubber-like elastic material (manufactured by Shell Co., trade name: Clayton G1651) D1101: SBS type rubber-like elastic material (manufactured by Shell Co., trade name: Clayton D1101) (B) component The weight average molecular weight and the molecular weight distribution below. Is 1,
The measurement was performed by gel permeation (GPC) at 130 ° C. using 2,4-trichlorobenzene as a solvent. The melting point was determined from the peak position at a heating rate of 20 ° C./min by differential thermal analysis (DSC). Each SPS is manufactured by a known method described in JP-A Nos. 62-104818 and 62-187708. SPS1: Styrene homopolymer Weight average molecular weight Mw = 180,000, Mw / Mn = 2.6 Melting point 270 ° C. SPS2: Styrene-p-methylstyrene copolymer (p-methylstyrene content: 12 mol%) weight Average molecular weight Mw = 180,000, Mw / Mn = 2.6 Melting point 240 ° C. SPS3: Styrene homopolymer Weight average molecular weight Mw = 180,000, Mw / Mn = 2.9 Melting point 270 ° C. SPS4: Styrene single weight Coupling Weight average molecular weight Mw = 300,000, Mw / Mn = 2.6 Melting point 270 ° C. (C) Polyphenylene ether In the following, the intrinsic viscosity is a value measured at 25 ° C. in chloroform. Each PPE is described in US Pat.
Nos. 6874 and 3308875 and 3257
It is manufactured by a known method described in JP-A-357-357 and the like. PPE1: poly (2,6-dimethyl-1,4-phenylene ether) intrinsic viscosity 0.41 deciliter / g PPE2: poly (2,6-dimethyl-1,4-phenylene ether) intrinsic viscosity 0.45 deciliter / G ・ PPE3: poly (2,6-dimethyl-1,4-phenylene ether) intrinsic viscosity 0.51 deciliter / g (D) component ・ GF: glass fiber (manufactured by Asahi Fiberglass Co., trade name: FT164) ( E) Component polyphenylene ether (intrinsic viscosity 0.45 dl / g,
1 kg in chloroform, 25 ° C.), fumaric acid 30
Gram, 2,3-dimethyl-2,
3-diphenylbutane (NOF, NOFMA-BC) 20
Grams were dry blended and melt kneaded at a screw rotation speed of 200 rpm and a set temperature of 300 ° C. using a 30 mm twin screw extruder. The strand was cooled and pelletized to obtain a maleic anhydride-modified polyphenylene ether. To measure the denaturation rate, 1 gram of the obtained modified polyphenylene ether was dissolved in ethylbenzene and then reprecipitated in methanol.
The recovered polymer is soxhlet-extracted with methanol,
After drying, the denaturation rate was determined by carbonyl absorption intensity and titration in the IR spectrum. At this time, the modification rate was 1.6% by weight.
Met. Example 1 As component (A), high impact polystyrene (HIPS) (trade name: HT, manufactured by Idemitsu Petrochemical Co., Ltd.)
52) 90% by weight, 10% by weight of syndiotactic polystyrene of SPS-1 as the component (B), and (A)
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (PEP manufactured by Asahi Denka Co., Ltd.) as an antioxidant with respect to 100 parts by weight of the total of the component and the component (B). -36) 0.1 parts by weight, tetrakis (methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl)) propionate (MARKAO60 manufactured by ADEKA ARGUS CO., LTD.) 1 part by weight was added, and dry blending was performed with a Henschel mixer, followed by melt kneading with a twin screw extruder to form pellets. At this time, the resin temperature is 2
80 ° C. Using the obtained pellets, resin temperature 2
Injection molding was performed at 80 ° C. and a mold temperature of 60 ° C. to obtain Izod test pieces and bending test pieces. Using the obtained test pieces, Izod impact strength and solvent resistance were measured. The results are shown in Table 1.

[0038]

[Table 1]

Examples 2 to 10 and Comparative Examples 1 to 17
As shown in Table 1, the components (A) and (B) were used in the same manner as in Example 1 except that the composition and the composition ratio were changed. The results are shown in Table 1. [Examples 11 to 51, Comparative Examples 18 to 43, Reference Examples 1 and 2] Tables 1 to 3 as components (A), (B), (C), (D), (E) and other components As shown in the table,
The same procedure was performed as in Example 1 except that the composition and the composition ratio were changed. For the introduction of glass fiber,
Melt kneading was performed while side-feeding with a twin-screw extruder. The component (D) indicates the weight% based on the total weight of the composition, and the component (E) indicates parts by weight based on 100 parts by weight of the total of the components (A) and (B), or the component (A) , The sum of components (B) and (C) 100
The values of parts by weight relative to parts by weight are shown. The results are shown in Tables 2 to 5.

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

According to the present invention, the solvent resistance is high, the heat resistance and the impact resistance are excellent, and the solvent resistance is improved without using a special compatibilizer. A molded article having excellent physical properties could be obtained without any restriction. The styrene-based resin composition of the present invention includes, for example, various molded articles by injection molding, sheets and films by extrusion molding, containers and trays by extrusion and thermoforming, uniaxial and biaxially stretched films by extrusion and stretching, It is effectively used for manufacturing fibrous molded articles by spinning, such as sheets.

Claims (10)

[Claims] 1. A styrenic resin composition comprising the following components (A) and (B). (A) Styrene-based polymer 30 having an atactic structure
~ 95% by weight, (B) weight average molecular weight (Mw) is 20
70 to 5% by weight of a styrene polymer mainly having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of not more than 0.00 and not more than 2.7. 2. A styrenic resin composition comprising the following components (A) and (B). (A) the total amount of the styrenic polymer having an atactic structure and the rubber-like elastic body is 30 to 95% by weight, (B) the weight average molecular weight (Mw) is 200,000 or less, and the molecular weight distribution (weight average molecular weight (Mw) Mw) / number average molecular weight (M
70 to 5% by weight of a styrenic polymer having a predominantly syndiotactic structure wherein n)) is 2.7 or less. 3. A styrenic resin composition comprising the following components (A), (B) and (C). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total of the components (A) and (B). 4. A styrenic resin composition comprising the following components (A), (B) and (C). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). 5. A styrenic resin composition comprising the following components (A), (B) and (D). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (D) 1 to 70% by weight of the total weight of the inorganic filler, including the components (A), (B), (D) and other components. 6. A styrenic resin composition comprising the following components (A), (B), (D) and (E).
(A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 9;
5% by weight, (B) a weight average molecular weight (Mw) of 200,000
0 or less and the molecular weight distribution (weight average molecular weight (M
w) / styrenic polymer 7 mainly having a syndiotactic structure and having a number average molecular weight (Mn) of 2.7 or less
0-5% by weight. (D) The inorganic filler is the component (A),
1 to 70% by weight based on the total weight of component (B), component (D), component (E) and other components, having compatibility or affinity with component (E), component (A) and component (B). And a polymer having a polar group, and the total of the components (A) and (B) is 100
0.1 to 10 parts by weight with respect to parts by weight. 7. A styrenic resin composition comprising the following components (A), (B), (C) and (D). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total of the components (A) and (B). (D) 1 to 70% by weight of the total weight including the components (A), (B), (C), (D) and other components, 8. A styrenic resin composition comprising the following components (A), (B), (C) and (D). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
(D) The inorganic filler is the component (A), the component (B),
1 to 70% by weight of the total weight including the components (C), (D) and other components, 9. A styrenic resin composition comprising the following components (A), (B), (C), (D) and (E). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the total of the components (A) and (B). (D) 1 to 70% by weight of the total weight of the inorganic filler containing the components (A), (B), (C), (D), (E) and other components, E) (A)
The polymer having compatibility or affinity with the component and the component (B) and having a polar group is used in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). 10 parts by weight. 10. A styrenic resin composition comprising the following components (A), (B), (C), (D) and (E). (A) a styrene-based polymer having an atactic structure, or a total amount of a styrene-based polymer having an atactic structure and a rubber-like elastic material of 30 to 95% by weight, and (B) a weight-average molecular weight (Mw) of 200,000 or less. 70 to 5% by weight of a styrene polymer having a syndiotactic structure and having a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.7 or less. (C) an intrinsic viscosity of 0.5 deciliter / g measured in chloroform at 25 ° C.
The following polyphenylene ether is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
(D) The inorganic filler is the component (A), the component (B),
1 to 70% by weight based on the total weight of components (C), (D), (E) and other components, having compatibility or affinity with components (E), (A) and (B). And a polymer having a polar group in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C).