JP2000265021A - Styrene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a syndiotactic styrene resin composition which has a high mold-release characteristic at molding, allows little bleedout onto molds and exerts little adverse effect on the appearance of a molded article. SOLUTION: This composition comprises (A) 100 to 5 wt.% syndiotactic styrene polymer, (B) 0 to 95 wt.% thermoplastic resin and/or rubber-like elastic body other than syndiotactic styrene polymers and (C) 0.01 to 0.5 pts.wt., against 100 pts.wt. total of (A)+(B), dimethyl silicone oil which contains less than 100 ppm oligomer component having 10 or less silicon atoms and has a viscosity of from 90 to 50,000 cSt. Otherwise, the composition comprises (D) 0.1 to 2.0 pts.wt. alkyl-modified silicone oil against 100 pts.wt. total of the above-mentioned (A)+(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 resin composition mainly containing a styrenic polymer having a syndiotactic structure and comprising a specific silicone oil.

[0002]

2. Description of the Related Art Styrene-based polymers having a syndiotactic structure (hereinafter sometimes referred to simply as "syndiotactic polystyrene", "syndiotactic styrene-based polymer" or "SPS") are excellent. It has chemical resistance, heat resistance, electrical characteristics, and water absorption dimensional stability, and is used for various industrial parts as an engineering plastic.

[0003] When a plastic industrial part is produced by an injection molding method, a press molding method, a vacuum / pressure molding method, or the like, a short molding cycle may be required in order to reduce production costs and mass production. . However, in syndiotactic polystyrene molding, if the molding cycle is shortened excessively, when removing the product from the mold,
In some cases, the protrusions may be deformed by pins or the like, and this difficulty in shortening the molding cycle has limited the scope of further application of SPS to the plastics industry.

In general, in order to suppress the protrusion deformation of a product in a short molding cycle, a method of improving the rigidity of the product by adding an inorganic filler to the resin composition, a method of adding a release agent, and a method of releasing the resin. There are known methods for improving the lubricity between a product and a mold at the time of molding. By the way, when a release agent is used, delicate control is required for the affinity between the base resin and the release agent. That is,
If the affinity is excessively good, the release agent is taken into the resin and is not localized on the product surface, so that the release effect cannot be expected. On the other hand, if the affinity is low, it is not taken into the resin, and although it has a releasing effect, it bleeds out to the mold and causes a poor appearance of the product.

Hitherto, it has been widely known that dimethyl silicone oil is added as a releasing agent or a sliding agent in the molding of atactic polystyrene (generally, GPPS and HIPS). However, in syndiotactic polystyrene, the kneading temperature, molding temperature, and mold temperature in injection molding are higher than that of atactic polystyrene. The use of the dimethyl silicone oil was undesirable because of the occurrence of defects such as bleed-out to the mold.

Therefore, there has been a strong demand for a high-performance release agent that can be preferably applied to the molding of syndiotactic polystyrene.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a syndiotactic styrenic resin composition having high mold release performance during molding, and having little effect on bleed-out to a mold and appearance of a product. It is intended for.

[0008]

As described above, the present inventors have conducted intensive studies to develop a styrene-based resin composition containing syndiotactic polystyrene having desirable properties. Even a dimethyl silicone oil that has been considered to be incompatible with SPS and is not suitable as a release agent even if it has a specific viscosity and a low molecular component is equal to or less than a specific amount (specific amount) (2) adding a specific amount of an alkyl-modified silicone oil, which was conventionally considered to have poor compatibility with a styrenic polymer, and found that the object can be achieved. The invention has been completed.

That is, the present invention provides the following styrene resin composition. 1. (A) 100 to 5% by weight (including 100) of a styrene polymer having a syndiotactic structure,
(B) a thermoplastic resin and / or rubber-like elastic material other than a styrene-based polymer having a syndiotactic structure, and 0 to 95% by weight (including 0); and (C) an oligomer component having 10 or less silicon atoms. Is less than 10 ppm and the viscosity at 25 ° C. is 90 to 50,000 cSt.
Dimethylsilicone oil, (A) +
A styrenic resin composition containing 0.01 to 0.5 part by weight with respect to 100 parts by weight in total of (B). 2. (A) 100 to 5% by weight (including 100) of a styrene polymer having a syndiotactic structure,
(B) A thermoplastic resin other than a styrene-based polymer having a syndiotactic structure and / or 0 to 95% by weight (including 0) of a rubber-like elastic material, and (D) an alkyl-modified silicone oil are mixed with the above (A) ) + (B) total 10
A styrenic resin composition containing 0.1 to 2.0 parts by weight with respect to 0 parts by weight.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments. 1. Contents of Respective Components of Styrene Resin Composition The styrene resin composition according to the present invention comprises, as an essential component, a syndiotactic styrene polymer, a thermoplastic resin other than the syndiotactic styrene polymer, and / or a rubber. Elastomer, having a specific dimethyl silicone oil or an alkyl-modified silicone oil, but in addition to these components, as long as the object of the present invention is not impaired, if necessary, other components may be added. Is also good. (1) Syndiotactic styrene-based polymer A syndiotactic styrene-based polymer has a syndiotactic structure in which a stereochemical structure is a syndiotactic structure, that is, a side chain with respect to a main chain formed from carbon-carbon bonds. Has a steric structure in which phenyl groups are alternately located in opposite directions, and its tacticity is quantified by nuclear magnetic resonance ( ^13C -NMR) using isotope carbon. Tacticity measured by the ¹³ C-NMR method can be represented by the proportion of a plurality of continuous constituent units, for example, a dyad in the case of two, a triad in the case of three, and a pentad in the case of five. However, the styrenic polymer having a syndiotactic structure referred to in the present invention generally means at least 75%, preferably at least 85%, or at least 30%, preferably at least 50%, of a racemic diad in a racemic pentad. Polystyrene having syndiotacticity, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated 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).

Among 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.

Such a syndiotactic styrene-based polymer is prepared, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. Monomer (
(A monomer corresponding to the above-mentioned styrenic polymer) can be produced (JP-A-62-1877).
08 publication). Further, poly (halogenated alkylstyrene) 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-1-178505.

These styrenic polymers having a predominantly syndiotactic structure can be used alone.
Alternatively, two or more kinds can be used in combination. (2) Thermoplastic resin other than syndiotactic styrene-based polymer Examples of the thermoplastic resin other than syndiotactic styrene-based polymer include 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, 4-methylpentene, polyolefin resins including cyclic polyolefin, atactic polystyrene, isotactic polystyrene, HIPS, Polystyrene resins such as ABS and AS, polyester resins such as polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide 6, polyamide 6 , 6 and other polyamide-based resins, polyphenylene ether, PPS, or modified ones thereof, and may be arbitrarily selected and used.
Among these thermoplastic resins, polyethylene, polypropylene, and polystyrene resins such as atactic polystyrene, isotactic polystyrene, HIPS, ABS, AS, polyphenylene ether, fumaric acid-modified polyphenylene ether, and maleic acid-modified polyphenylene ether are Particularly preferably used. In addition,
These thermoplastic resins can be used alone or in combination of two or more.

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

[0015]

Embedded image

Preferred aromatic vinyl compounds used herein include styrene, α-methylstyrene, methylstyrene, ethylstyrene, isopropylstyrene, tertiary butylstyrene, phenylstyrene, vinylstyrene, chlorostyrene, bromostyrene, and fluorostyrene. Styrene, chloromethylstyrene, methoxystyrene,
There are ethoxystyrene and the like, which are used alone or in combination of two or more. Of these, particularly preferred aromatic vinyl compounds include styrene, p-methylstyrene, m
-Methylstyrene, p-tert-butylstyrene,
p-chlorostyrene, m-chlorostyrene and p-fluorostyrene. Examples of other copolymerizable vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Acrylates such as, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Methacrylates such as octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, maleimide, N-methylmaleimide, N-
Maleimide compounds such as ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N- (p-bromophenyl) maleimide. Examples of the copolymerizable rubbery polymer include diene rubbers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and polyisoprene; ethylene-α-olefin copolymer; Non-diene rubber such as olefin-polyene copolymer, polyacrylate, styrene-butadiene block copolymer,
Examples include a hydrogenated styrene-butadiene block copolymer, an ethylene-propylene elastomer, a styrene-graft-ethylene-propylene elastomer, an ethylene ionomer resin, and a hydrogenated styrene-isoprene copolymer.

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

Polyphenylene ether is a known compound, and is used for this purpose.
306,874, 3,306,875, 3,2
Reference can be made to the specifications of JP-A-57,357 and JP-A-3,257,358. Polyphenylene ether is
It is usually prepared by an oxidative coupling reaction to form a homopolymer or a copolymer in the presence of a copper amine complex, one or more di- or tri-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)
Tell), 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, for example, a vinyl aromatic compound such as polystyrene and the above-mentioned polyphenylene ether
Examples include a graft copolymer and a block copolymer with ter. Of these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used. (3) Rubber-like elastic body Specific examples of the rubber-like elastic body include, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber Styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer ( SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SI
S), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), or ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPD)
M), olefin rubbers such as ethylene-octene copolymer elastomers, 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 (AAB)
S), butadiene-styrene-core-shell rubber (SB
R), a core-shell type particulate elastic material such as a siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate-siloxane, or a rubber modified from these. Of these, SBR,
SEB, SBS, SEBS, SIR, SEP, SIS,
SEPS, core-shell rubber, EPM, EPDM, ethylene / octene copolymer-based elastomer or a rubber modified from these is preferably used. These rubber-like elastic bodies can be used alone or in combination of two or more. (4) Dimethyl silicone oil The dimethyl silicone oil in the present invention mainly has a repeating unit of [(CH ₃ ) ₂ SiO] n.

Generally, dimethyl silicone oil includes:
Although viscosities of various viscosities are known, the dimethyl silicone oil of the present invention has a viscosity at 25 ° C of 90.
５50,000 cSt, 100
~ 30,000 cSt is preferred. When a material having a low viscosity of less than 90 cSt is used, even if a small amount is added, mold release performance is improved, but there is a possibility that poor product appearance such as silver may occur. In addition, when a material having a high viscosity of more than 50,000 cSt is used, appearance defects do not occur, but the effect of improving the mold release performance is reduced, and furthermore, the handling property at the time of melt-kneading production to plastic is remarkably reduced, and mass production is performed. Is not suitable. Here, the viscosity is JIS C2101-78R
It is a value measured in.

Furthermore, since dimethyl silicone oil is a polymer having a siloxane structure, the degree of polymerization has a distribution, and some have a low molecular weight component (oligomer). Dimethyl silicone oil in the present invention,
10pp oligomer component with 10 or less silicon atoms
m and less than 13 silicon atoms.
The following oligomer components are preferably less than 10 ppm. When dimethyl silicone oil having a large amount of oligomer components is used, bleeding out to a mold is not particularly problematic, but molding defects such as silver may occur depending on molding conditions of injection molding. Here, the amount of the oligomer component is determined by using tetrahydrofuran (THF) as a solvent in G
It is a value obtained by measurement with a PC (gel permeation chromatograph).

[0021] These dimethyl silicone oils can be used alone or in combination of two or more. (5) Alkyl-modified silicone oil The alkyl-modified silicone oil in the present invention has a structure in which a part or all of a side chain methyl group in dimethyl silicone oil is substituted with an alkyl group. That is, [(CH ₃ )
Any compound may be used as long as the CH ₃ — moiety in the repeating unit of ₂ SiO] n is substituted with an alkyl group, and all the CH ₃ — moieties in all the repeating units are substituted with an alkyl group (that is, the modification rate). 100 mol% of one) or, CH ₃ - portions repeating units and CH substituted with an alkyl group ₃ - the so-called random body portion of the repeating units which are not substituted by an alkyl group are linked randomly Ya And a so-called block body in which both are united and chained.

Assuming that the proportion of the CH ₃ — moiety substituted with an alkyl group is referred to as a modification rate (unit%), a modification rate of 20 mol% or more is preferable. When the amount is less than 20 mol%, bleed out may be easily caused. The type of the alkyl group is not particularly limited, and examples thereof include a linear alkyl group and a branched alkyl group. Specifically, carbon number 2
A linear or branched alkyl group or a cycloalkyl group having 3 to 20 carbon atoms, such as an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group;
Isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group,
Examples include a tetradecyl group, a hexadecyl group, an octadecyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group.

[0023] These alkyl-modified silicone oils can be used alone or in combination of two or more. (6) Other Additives The resin composition according to the present invention may contain an inorganic filler, an antioxidant, a nucleating agent, a plasticizer, a flame retardant, a flame retardant auxiliary, a pigment, and a charge as long as the object of the present invention is not impaired. Additives such as inhibitors can be blended.

Inorganic filler The inorganic filler includes a fibrous material, a granular material and a powdery material. As the fibrous filler, for example, glass fiber,
Carbon fibers, whiskers, mica and the like can be mentioned. Examples of the shape include a cross shape, a mat shape, a bundle cut shape, a short fiber, a filament shape, and a whisker. In the case of the bundle cut shape, the length is 0.05 mm to 50 mm and the fiber diameter is 5 to 20.
μm is preferred. On the other hand, as the granular or powdery filler, for example, talc, carbon black, graphite,
Titanium dioxide, silica, mica, calcium sulfate, calcium carbonate, 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, carbon fibers, mica, calcium carbonate, and glass fillers such as glass powder, glass flake, glass beads, glass filament, glass fiber, glass lobing, and glass mat are preferable. Of these, glass fillers are particularly preferred, and glass fibers are more preferred.

The above-mentioned filler is preferably a surface-treated filler. The coupling agent used for the surface treatment is used for improving the adhesiveness between the filler and the resin, and includes a so-called silane-based coupling agent, a titanium-based coupling agent, and the like. Any one can be selected and used. Among them, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-
Aminosilanes such as epoxycyclohexyl) ethyltrimethoxysilane, epoxysilane, and isopropyltri (N-amidoethyl, aminoethyl) titanate are preferred.

Further, a film-forming substance for glass can be used in combination with the above-mentioned coupling agent. The film-forming substance is not particularly limited, and examples thereof include polymers of polyester type, polyether type, urethane type, epoxy type, acrylic type, vinyl acetate type and the like. These inorganic fillers can be used alone or in combination of two or more.

Antioxidant The antioxidant can be arbitrarily selected from phosphorus, phenol, sulfur and the like. In addition, these antioxidants may be used alone, or
Two or more can be used in combination. Nucleating agents As nucleating agents, metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate) and metal salts of phosphoric acid such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate , Talc, phthalocyanine derivatives and the like can be arbitrarily selected and used. Specific product names include NA11 and NA21 manufactured by Asahi Denka, PTBBA-AL manufactured by Dainippon Ink and the like. These nucleating agents can be used alone or in combination of two or more. Plasticizers Examples of the plasticizer include polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalic acid ester, polystyrene oligomer, and the like. Any known materials such as polyethylene wax and silicone oil can be arbitrarily selected and used. These plasticizers can be used alone or in combination of two or more.

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 known compound such as a brominated aromatic compound can be 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. These flame retardants and flame retardant assistants can be used alone or in combination of two or more. 2. (1) (A) SPS 100 to 5% by weight (including 100), preferably 98 to 10% by weight, more preferably 95 to 15% by weight, and (B) thermoplastic other than SPS 0 to 95% by weight (including 0), preferably 2 to 90% by weight, more preferably 5 to 90% by weight of resin and / or rubbery elastic body
~ 85% by weight. When SPS is less than 5% by weight, S
The properties of PS may not be exhibited. In (B), when a thermoplastic resin other than SPS and a rubber-like elastic body are used together, the mixing ratio of both is not particularly limited. What is necessary is just to select a compounding ratio suitably according to the objective. (C) The addition amount of dimethyl silicone oil is 10% of the total amount of thermoplastic resin and / or rubber-like elastic material other than (A) SPS and (B) SPS.
0.01 to 0.5 part by weight, preferably 0.05 part by weight based on 0 part by weight
〜0.4 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving the releasability cannot be expected. If the amount exceeds 0.5 part by weight, the effect of improving the releasability can be expected. May cause problems such as a decrease in continuous productivity due to occurrence of bleed-out. (2) The addition amount of the (D) alkyl-modified silicone oil is from 0.1 to 100 parts by weight of the total amount of the thermoplastic resin and / or rubber-like elastic material other than (A) SPS and (B) SPS. 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight. Addition of less than 0.1 parts by weight cannot improve the releasability. Addition of more than 2.0 parts by weight can improve the releasability, but the product appearance is poor such as silver and the mold Bleed-out may cause problems such as a decrease in continuous productivity. 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 may be blended by various methods such as mixing at room temperature or melt kneading, and the method is not particularly limited. Among these mixing and kneading methods, melt kneading using a twin screw extruder is preferably used. In melt kneading using a twin-screw extruder, kneading at a temperature equal to or higher than the melting point of the SPS to be used and lower than 350 ° C. is preferable. If the kneading temperature is lower than the melting point of the SPS to be used, the viscosity of the resin is too high, and the productivity may be lowered, which is not preferable.
If the temperature exceeds 0 ° C., the resin may be thermally decomposed. 4. Molding method using the styrene-based resin composition according to the present invention The molding method is not particularly limited, and molding can be performed by a known method such as injection molding or extrusion molding. In the injection molding, the molding temperature is preferably equal to or higher than the melting point of the SPS used and lower than 350 ° C. If the molding temperature is lower than the melting point of the SPS used, it is not preferable because the fluidity may decrease.
If the temperature exceeds 350 ° C., the resin may be thermally decomposed, which is not preferable. The mold temperature is 40 ° C to 200 ° C.
C is preferable, and 50C to 180C is more preferable. If the mold temperature is lower than 40 ° C, the SPS will not crystallize sufficiently,
Is not preferable because there is a possibility that the feature of the above may not be sufficiently exhibited. If the temperature exceeds 200 ° C., the rigidity at the time of releasing the mold decreases,
Ejector cracking and deformation may occur. 5. Uses of the Styrene Resin Composition According to the Present Invention The styrenic resin composition according to the present invention can be used for various uses and is not particularly limited. In the electric and electronic fields, various connectors (SLOT, PGA, D
-SUB, AGP, PCI, USB, audio jack, etc.), printed circuit board, LED parts, terminal block, relay box, F terminal, motor insulator, power module, fan motor parts (frame, fan), lens surrounding parts (CD pickup) Lens holder, DV
D pickup lens holder), and in the field of automobiles, connectors for vehicles, control unit boxes, fuse boxes, junction boxes, reflectors, extensions, canisters,
Various valves, radiator grills, grills, marks, back panels, door mirrors, wheel caps, air spoilers, motorcycle cowls, cylinder head covers, instrument panels, meter hoods, pillars, glove boxes, console boxes, speaker boxes, lids In the field of electric appliances, housings, chassis, cassette cases, CD magazines,
Remote control case, connector, fan, refrigerator parts (lining, tray, arm, door cap, handle, fan, etc.), vacuum cleaner parts (housing, handle, pipe, suction port, fan guide, etc.), air conditioner parts (housing,
Fans, remote control cases, etc.), pots, electric fans, ventilation fans, washing machines, parts for lighting equipment, parts for tableware dryers, parts for microwave ovens (choke covers, roller rings), battery cases, and the like.

Other general equipment includes printers (housing, chassis, ribbon cassette, tray, ink peripheral parts, etc.), copying machines (personal computers (housing, floppy disk shell, keyboard, etc.)), projector parts, telephones, communication equipment. (Housing, handset, etc.), mechanical chassis, sewing machine, register, typewriter, computer, optical equipment, musical instruments and other miscellaneous goods, toys, leisure, sports equipment, remote control car, block, pachinko machine parts, surfboard, helmet, Toilet seats, toilet lids, tanks, shower parts, pump parts, water supply and drain outlets, lunch boxes, various containers, pots, building material housing parts, containers, furniture, stationery (ballpoint pens, magic, writing implement trays, etc.), stamp stands, etc. Various parts, pipes,
Industrial materials such as sheets, trays, and films are included.

[0031]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (1) Raw materials used (A) Syndiotactic styrene polymer • SPS1: 150 ° C. using homosyndiotactic polystyrene 1,2,4-trichlorobenzene as a solvent
Weight average molecular weight Mw = 200,000, Mw / Mn = 2.20 in terms of polystyrene measured by the GPC method in the above. SPS2: Syndiotactic styrene-paramethylstyrene copolymer 1,2,4-trichlorobenzene As a solvent, a weight average molecular weight Mw = 190,000 in terms of polystyrene measured by the GPC method at 150 ° C.,
Mw / Mn = 2.30 (B1) Thermoplastic resin other than syndiotactic styrene-based polymer ・ FAPPO: fumaric acid-modified polyphenylene ether produced in Production Example 1 ・ PPO1: poly (2,6-dimethyl-1, 4-phenylene ether) YPX-100 manufactured by Mitsubishi Gas Chemical Company
H PPO2: poly (2,6-dimethyl-1,4-phenylene ether) YPX-100 manufactured by Mitsubishi Gas Chemical Company
L HH30: GPPS Idemitsu Petrochemical Co., Ltd. Idemitsu Styrol HH30 640UF: High-density polyethylene Idemitsu Petrochemical Co., Ltd. IDEMISU HD 640UF (B2) Rubber elastic body M1962: Maleic acid-modified SEBS type elastomer Asahi Kasei Kogyo Co., Ltd. Tuftec M1962 G1651: Clayton G1651 manufactured by SEBS Type Elastomer Shell Co. Sep. 8006: SEBS type elastomer Septon 8006 manufactured by Kuraray Co., Ltd. Sep. 2104: SEPS type elastomer Septon 2104 manufactured by Kuraray Co., Ltd. ENG. 8150: Ethylene / octene copolymer elastomer ENGAGE 81 manufactured by Dupont Dow Elastomer Co., Ltd.
50 (C) dimethyl silicone oil SH200 100 cSt: viscosity at 25 ° C. =
100 cSt, oligomer component having 10 or less silicon atoms = 130 pp
m Toray Dow Corning Silicone Co., Ltd. SH200CV 100 cSt: Viscosity at 25 ° C. = 100 cSt, oligomer component having 10 or less silicon atoms = 0 ppm ppm Toray Dow Corning Silicone Co., Ltd. SH200 10000 cSt: Viscosity at 25 ° C. = 10000 cSt Oligomer component having 10 or less silicon atoms = 250 pp
m, manufactured by Dow Corning Toray Silicone Co., Ltd. SH200 CV 10,000 cSt: viscosity at 25 ° C. = 10000 cSt, oligomer component having 10 or less silicon atoms = 0 ppm,
SH200 10cSt: viscosity at 25 ° C = 1, manufactured by Dow Corning Toray Silicone Co., Ltd.
0 cSt, manufactured by Toray Dow Corning Silicone Co., Ltd. SH200 100,000 cSt: viscosity at 25 ° C. = 100,000 cSt manufactured by Toray Dow Corning Silicone Co., Ltd. (D) alkyl-modified silicone oil ・ SF8416: Toray Dow Corning Silicone Modification rate = 50 mol% manufactured by Toray Dow Corning Silicone Co., Ltd. SH203: Modification rate = 38 mol% manufactured by Toray Dow Corning Silicone Co., Ltd. Modification rate = 38 mol% manufactured by Toray Dow Corning Silicone Co., Ltd. (E) Silicone oil SH510: Methylphenyl silicone oil Toray Dow Corning Silicone Co., Ltd. SH550: Methylphenyl silicone oil Toray Dow Corning Silicone Co., Ltd. (F) Other components NA21: Nucleating agent, manufactured by Asahi Denka Co., Ltd. 1010: Antioxidant Irganox1010 manufactured by Ciba Geigy Co., Ltd. • PEP36: Antioxidant, manufactured by Asahi Denka Co., Ltd. 8010: Flame retardant, SAYTEX 8010 manufactured by 1,2-di (pentabromophenyl) ethane ethyl Co., Ltd. • PATOX: Flame retardant aid, antimony trioxide PATOX-M manufactured by Nippon Seiko Co., Ltd. • DHT-4A: Halogen scavenger, Kyowa * GF: glass fiber, manufactured by Asahi Fiber Glass Co., Ltd. CS 03 JA FT 1
64G (2) Evaluation method Releasability Using an injection molding machine (SH100A manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions, 97 mm as shown in FIG.
(L) x 60mm (W) x 30mm (D), thickness 1m
m of a box-shaped molded product was formed, and deformation of the product due to ejector pin protrusion at the time of product release was observed. The ejector pins are disposed so as to hit four corners of the bottom plate of the box-shaped molded body. The cooling time (molding cycle) is shortened until the ejector pin protrudes to cause a visually significant large deformation or the ejector pin breaks through the bottom plate portion of the box-shaped molded body. Were compared. That is, the shorter the shortest cooling time, the higher (good) the releasability. The molding conditions are as follows.・ Cylinder temperature: 260 ° C or 290 ° C ・ Mold temperature: 80 ° C or 140 ° C ・ Filling time: 1.0 second ・ Holding pressure time: 2.0 seconds ・ Holding pressure: 1,900 kgf / cm2 ・ Ejector ejection speed: 35% poor product appearance Visual observation of the box-shaped molded body produced at the time of the above-mentioned release property evaluation,
The presence or absence of appearance defects such as silver and gas burning was observed.

Using a bleed-out injection molding machine (SH100A manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions, 80 × 80 × 3 mm shown in FIG.
Molding was performed for 500 shots so that the flat plate of t was filled to half, and the deposit near the flow end of the mold was observed. The case where nothing was observed was evaluated as ○, and the case where oil droplets were observed was evaluated as ×.

The molding conditions are as follows.・ Cylinder temperature: 260 ° C. or 290 ° C. ・ Mold temperature: 80 ° C. or 140 ° C. [Production Example 1] Production of fumaric acid-modified polyphenylene ether Polyphenylene ether (intrinsic viscosity 0.45 dL / g,
1 kg of chloroform, 25 g of fumaric acid, 20 g of 2,3-dimethyl-2,3-diphenylbutane (NOF, BC, NOFMER BC) as a radical generator were dry-blended and screwed using a 30 mm twin screw extruder. Melt kneading was performed at a rotation speed of 200 rpm and a set temperature of 300 ° C. At this time, the resin temperature was about 331 ° C. The strand was cooled and pelletized to obtain a fumaric acid-modified polyphenylene ether. For the measurement of the modification rate, 1 g of the obtained modified polyphenylene ether was dissolved in ethylbenzene, reprecipitated in methanol, the recovered polymer was subjected to Soxhlet extraction with methanol, and after drying, the modification rate was determined by IR spectrum carbonyl absorption intensity and titration. I asked. At this time, the modification ratio was 1.45% by weight. [Example 1] 88 parts by weight of SPS1, SH200CV
0.05 parts by weight of 100 cSt, 2 parts by weight of FAPPO, 6 parts by weight of ENGAGE 8150, Septon
2104 2 parts by weight, G1651 2 parts by weight, NA2
0.6 parts by weight of 1 and 0.3 parts of Irganox 1010
Parts by weight and 0.3 parts by weight of PEP36 were dry-blended, and then the mixture was heated at a cylinder temperature of 290 ° C. using a twin-screw extruder.
Melt kneading was performed while side-feeding a glass fiber (FT164G) in parts by weight, and the resulting strand was cooled through a water tank and then pelletized. The obtained pellets were evaluated for mold release, product appearance, and bleed-out at a cylinder temperature of 290 ° C and a mold temperature of 140 ° C. Table 1 shows the results. [Examples 2 to 4 and Comparative Example 1] The same procedure as in Example 1 was carried out except that the ingredients were blended as shown in Table 1. Table 1 shows the results. [Comparative Examples 2 to 7] The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 2. Table 2 shows the results. [Examples 5 to 8 and Comparative Example 8] The same procedure as in Example 1 was carried out except that the ingredients were blended as shown in Table 3. Table 3 shows the results. [Comparative Examples 9 to 14] Example 1 except that it was blended as shown in Table 4.
The same was done. Table 4 shows the results. [Examples 9 to 12 and Comparative Example 15] Compounded as shown in Table 5, the cylinder temperature during molding was 260 ° C and the mold temperature was 8
The procedure was performed in the same manner as in Example 1 except that the temperature was set to 0 ° C. Table 5 shows the results
Shown in [Comparative Examples 16 to 21] The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 6 and the cylinder temperature during molding was set to 260 ° C and the mold temperature was set to 80 ° C. Table 6 shows the results. [Examples 13 to 16 and Comparative Example 22] The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 7 and the cylinder temperature during molding was 260 ° C and the mold temperature was 80 ° C. Table 7 shows the results. [Comparative Examples 23 to 28] The same procedures as in Example 1 were carried out except that the components were blended as shown in Table 8, the cylinder temperature during molding was 260 ° C, and the mold temperature was 80 ° C. Table 8 shows the results. [Example 17] 76 parts by weight of SPS1, SH200CV
0.05 parts by weight of 100 cSt, 4 parts by weight of PPO1, 16 parts by weight of G1651, 4 parts by weight of M1962,
After dry-blending 0.6 parts by weight of NA21, 0.3 parts by weight of Irganox 1010 and 0.3 parts by weight of PEP36, the cylinder temperature was 290 ° C. using a twin-screw extruder.
The resulting strands were cooled through a water bath and then pelletized.

The obtained pellets were evaluated for mold release, product appearance, and bleed-out at a mold temperature of 80 ° C. Table 9 shows the results. [Examples 18 to 20 and Comparative Example 29] The same procedures as in Example 17 were carried out except that the ingredients were blended as shown in Table 9. Table 9 shows the results. [Comparative Examples 30 to 35] The same procedures as in Example 17 were carried out except that the ingredients were blended as shown in Table 10. Table 10 shows the results. [Examples 21 to 23, Comparative Examples 36 to 38] The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 11. Table 11 shows the results.
Shown in Examples 24 to 26 and Comparative Examples 39 to 41 The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 12. Table 12 shows the results.
Shown in Examples 27 to 29, Comparative Examples 42 to 44 The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 13 and the cylinder temperature during molding was set to 260 ° C. and the mold temperature was set to 80 ° C. Table 13 shows the results. [Examples 30 to 32, Comparative Examples 45 to 47] The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 14 and the cylinder temperature during molding was set to 260 ° C and the mold temperature was set to 80 ° C. Table 14 shows the results. [Examples 33 to 35, Comparative examples 48 to 50] The same procedures as in Example 17 were carried out except that the ingredients were blended as shown in Table 15. Table 1 shows the results
FIG. [Examples 36 to 39, Comparative Example 51] The components were blended as shown in Table 16, and the cylinder temperature during molding was 260 ° C and the mold temperature was 8
The procedure was performed in the same manner as in Example 1 except that the temperature was set to 0 ° C. Table 1 shows the results
6 is shown. [Comparative Examples 52 to 57] The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 17 and the cylinder temperature during molding was set at 260 ° C and the mold temperature was set at 80 ° C. Table 17 shows the results. [Examples 40 to 42, Comparative Examples 58 to 60] The same procedures as in Example 1 were carried out except that the ingredients were blended as shown in Table 18 and the cylinder temperature during molding was set to 260 ° C and the mold temperature was set to 80 ° C. The results are shown in Table 18.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

[Table 9]

[0044]

[Table 10]

[0045]

[Table 11]

[0046]

[Table 12]

[0047]

[Table 13]

[0048]

[Table 14]

[0049]

[Table 15]

[0050]

[Table 16]

[0051]

[Table 17]

[0052]

[Table 18]

[0053]

According to the present invention, it is possible to obtain a syndiotactic styrene resin composition which has high mold release performance at the time of molding, and has little influence on bleed out to a mold and appearance of a product. .

[Brief description of the drawings]

FIG. 1 is a schematic drawing of a box-shaped molded product for a release property test.

[Fig. 2] Conceptual diagram of mold release by ejector pin projection

FIG. 3 is a conceptual diagram of injection molding of a bleed-out evaluation flat plate.

[Explanation of symbols]

1: Vertical length of the box-shaped molded body 97 mm 2: Horizontal length of the box-shaped molded body 60 mm 3: Depth of the box-shaped molded body 30 mm 4: Thickness of the box-shaped molded body 1 mm 5: Ejector pin mark 6: Gate direction 7 : Ejector pin 8: Box-shaped molded body 9: Die 10: Vertical length of bleed-out evaluation flat plate 80 m
m11: Horizontal length of bleed-out evaluation plate 80m
m12: Flow stop end 13: Gate direction

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83:04) F-term (Reference) 4J002 AC01X AC03X AC06X AC08X AC09X AC14X BB03X BB05X BB12X BB14X BB15X BB17X BC03W BC03X BC04X BC05 BC06X BC08W BC09W BC11W BC12W BG04X BK00X BL01X BN12X BN14X BN15X BN16X BN17X BP01X BP02X CF06X CF07X CG00X CH04X CH07X CK02X CL01X CL03X CN01X CP03X CP033 CP17X FD010 FD010 FD010 FD010 FD010 FD010 FD010 FD010 FD010 FD010 FD010FD

Claims (2)

[Claims] 1. A thermoplastic resin other than (A) 100 to 5% by weight (including 100) of a styrene-based polymer mainly having a syndiotactic structure, (B) a thermoplastic resin other than a styrene-based polymer mainly having a syndiotactic structure, and And / or 0 to 95% by weight (including 0) of a rubber-like elastic material, and (C) 10 ppm of an oligomer component having 10 or less silicon atoms.
And a viscosity at 25 ° C. of 90 to 50,000
Dimethylsilicone oil of 0 cSt was added in an amount of 0.01
A styrenic resin composition containing 0.5 parts by weight. 2. A thermoplastic resin other than (A) 100 to 5% by weight (including 100) of a styrene polymer mainly having a syndiotactic structure, (B) a thermoplastic resin other than a styrene polymer mainly having a syndiotactic structure, and And / or 0 to 95% by weight (including 0) of a rubber-like elastic body and (D) an alkyl-modified silicone oil in an amount of 0.1 to 2.0 parts by weight based on a total of 100 parts by weight of (A) + (B). A styrenic resin composition containing parts by weight.