JPH08239546A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject compound excellent in sliding property, flame retardancy, moldability and processability and impact resistance and useful as an electrical product part, etc., by blending an organosiloxane-based rubber- like polymer with a rubber-like polymer in a prescribed ratio. CONSTITUTION: This resin composition is obtained by adding (C) 1-50 pts.wt. bromine-based flame retardance (e.g. an oligomer of tetrabromobisphenol A) to 100 pts.wt. resin composition composed of (A) 1-99wt.% siloxane rubber- reinforced resin obtained by (co)polymerizing 90-30wt.% of (ii) an aromatic vinyl compound or the components (ii) and (iii) other vinyl monomer copolymerizable with the component (ii) in the presence of (i) 10-70wt.% organosiloxane-based rubber-like polymer and (B) 99-1wt.% rubber-reinforced resin and having 20-200wt.% graft ratio and obtained by (co)polymerizing 95-30wt.% of the component (ii) or the components (ii) and (iii) in the presence of (iv) 5-70wt.% rubber-based polymer [excluding the component (i)].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent slidability, flame retardancy, moldability and impact resistance.

2. Description of the Related Art Styrene-based resins obtained by graft-polymerizing styrene, acrylonitrile and the like on silicone rubber have a characteristic that they are more slidable than ABS resins which are typical butadiene rubber-based graft copolymers. Such sliding materials are used for gears, bearings, CDs (compact discs), laser disc tray materials, keyboard key tops, key frames and the like. Depending on these applications, there are applications where flame retardancy is required,
So far it has been insufficient. It is possible to add flame retardancy to a silicone rubber-modified resin by adding a flame retardant, but in this case, there is a problem that the impact resistance is poor.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. The organosiloxane rubbery polymer and the rubbery polymer (organosiloxane) present in the thermoplastic resin composition are present. It is intended to provide a thermoplastic resin composition having excellent slidability, flame retardancy, molding processability, and impact resistance by blending with (except system rubber) in a certain ratio.

[0002]

SUMMARY OF THE INVENTION The present invention provides (A) an aromatic vinyl compound (b) or an aromatic vinyl compound (b) in the presence of 10 to 70% by weight of an organosiloxane rubber polymer (a). And 1 to 99% by weight of a siloxane rubber-reinforced resin obtained by polymerizing 90 to 30% by weight of another vinyl monomer (c) copolymerizable with the aromatic vinyl compound (b).
And (B) rubbery polymer (excluding organosiloxane rubbery polymer) (a ') in the presence of 5 to 70% by weight of aromatic vinyl compound (b), or aromatic vinyl compound (b) and aromatic 99-1% by weight of a rubber-reinforced resin obtained by polymerizing 95-30% by weight of another vinyl monomer (c) copolymerizable with the vinyl compound (b) and having a graft ratio of 20-200% by weight. % Resin composition (A) +
(B) 100 parts by weight of (C) brominated flame retardant 1-5
The present invention provides a thermoplastic resin composition containing 0 part by weight. Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. The component (A) of the present invention will be described. Component (A) is an organosiloxane rubbery polymer (a) 10 to 70% by weight, preferably 25 to 6
The aromatic vinyl compound (b) or another vinyl monomer copolymerizable with the aromatic vinyl compound (b) and the aromatic vinyl compound (b) in the presence of 0% by weight, more preferably 30 to 55% by weight. It is a siloxane rubber-reinforced resin obtained by polymerizing 90 to 30% by weight, preferably 75 to 40% by weight, and more preferably 70 to 45% by weight of the monomer (c). The organosiloxane rubbery polymer (a) used as the component (A) of the present invention is obtained by condensing the organosiloxane (I) or (I) and the graft crossing agent (II). Here, as the organosiloxane (I), for example, the general formula R ¹ _n SiO _{(4-n) / 2} (wherein R is
¹ is a substituted or unsubstituted monovalent hydrocarbon group, and n has a structural unit represented by 0), and has a linear, branched or cyclic structure. , And preferably an organosiloxane having a cyclic structure.
Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane (I) include a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, and a substituted one thereof with a halogen atom or a cyano group. A hydrocarbon group etc. can be mentioned. Specific examples of the organosiloxane (I) include, in addition to cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane, A chain or branched organosiloxane can be mentioned. Also,
Preferred graft crossing agent (II) used in the present invention
Can include, for example: (I)

[0003]

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(In the formula, R ² is a hydrogen atom or a carbon number of 1 to
A graft crossing agent having an unsaturated group represented by 6) and an alkoxysilyl group. Specific examples of these preferable (a) graft crossing agents include p
-Vinylphenylmethyldimethoxysilane, 1- (m-
Vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, and more preferably p-vinylphenylmethyldimethoxysilane. With the use of the (a) graft crossing agent, a composition having a high graft ratio can be obtained, and therefore, a more excellent composition intended by the present invention can be obtained. (B) R ³ _p SiO _{(3-p) / 2} (In the formula, R ³ represents a vinyl group or an allyl group, and p represents an integer of 0 to 2.) Specific examples include vinylmethyldimethoxysilane and tetravinyltetra Examples thereof include methylcyclosiloxane and allylmethyldimethoxysilane. This graft crossing agent (I
The use ratio of I) is preferably 0 to 0 in the total amount of the components (I) and (II) in order to achieve the object of the present invention.
It is 50% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 5% by weight. A cross-linking agent may be added as a third component in the production of the organosiloxane rubber polymer (a) for the purpose of improving the impact resistance of the resulting resin. As this cross-linking agent,
Examples thereof include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. The amount of the crosslinking agent added is usually 10% by weight or less, preferably 5% by weight, based on the total amount of the organosiloxane (I) and the graft crossing agent (II).
It is about the following. The polystyrene-converted weight average molecular weight of the organosiloxane rubbery polymer (a) thus obtained is usually 30,000 to 1,000,
000, preferably about 50,000 to 300,000.

Next, the organosiloxane rubbery polymer (a) thus obtained is copolymerized with an aromatic vinyl compound (b) or an aromatic vinyl compound (b) and an aromatic vinyl compound (b). The siloxane rubber-reinforced resin (A) is obtained by graft-polymerizing another possible vinyl monomer (c). Examples of the aromatic vinyl compound (b) used as the component (A) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene,
Examples thereof include p-methylstyrene, p-hydroxystyrene, methyl-α-methylstyrene, dimethylstyrene, bromostyrene, dibromostyrene, chlorostyrene and sodium styrenesulfonate. Of these, styrene, p-methylstyrene and α-methylstyrene are preferred. Examples of other vinyl monomers (c) copolymerizable with the aromatic vinyl compound (b) include vinyl cyanide compounds, (meth) acrylic acid esters, acid anhydride monomers, and maleimide compounds. And a vinyl cyanide compound is preferable. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. Of these, methyl methacrylate and butyl acrylate are preferable. Maleic anhydride is preferable as the acid anhydride-based monomer. As the maleimide compound, maleimide, N-methylmaleimide, N
-Ethyl maleimide, N-propyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N
Examples include-(2-methylphenyl) maleimide and N- (4-hydroxyphenyl) maleimide. Among these, maleimide, N-phenylmaleimide, N-
Cyclohexylmaleimide is preferred. These monomer components (b) and / or (c) can be used alone or in combination of two or more.

The reasons for limiting the component (A) will be described below. When the organosiloxane rubbery polymer (a) in the component (A) is less than 10% by weight, the slidability is insufficient, while when it exceeds 70% by weight, the moldability and the appearance of the molded product are Inferior. Further, if the amount of the monomer (mixture) comprising (b) or (b) and (c) is less than 30% by weight, moldability is poor, while if it exceeds 90% by weight, slidability is poor. Also, in order to impart flame retardancy and improve molding processability,
It is preferable to use a vinyl cyanide compound as (c). The preferable blending amount is 1 to 40% by weight, and more preferably 5 to 35% by weight in the monomer mixture consisting of (b) and (c). The graft ratio of the siloxane rubber-reinforced resin (A) is preferably 10% by weight to 180% by weight, more preferably 20 to 150% by weight, and particularly preferably 35 to 130% by weight. Here, as for the graft ratio, 1 g of the material was precisely weighed, 20 cc of methyl ethyl ketone was added to it, and the mixture was shaken for 10 hours, and then the soluble content and the insoluble content were separated using a centrifugal separator at a rotation speed of 20,000 rpm. Then, the insoluble matter was dried by a vacuum dryer to obtain an insoluble matter (X). On the other hand, it is a value obtained by calculating the amount of rubber (R) in the insoluble matter (X) from the polymerization composition and the polymerization conversion rate, and obtaining the graft ratio from the following formula. Graft ratio (%) = [(X)-(R)] × 100 / (R) Furthermore, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the matrix resin in the component (A) is preferably It is 0.1 to 1.2 dl / g, more preferably 0.2 to 0.8 dl / g. The intrinsic viscosity [η] is 0.
If it is less than 1 dl / g, the impact strength is not sufficient, while
If it exceeds 1.2 dl / g, the moldability will deteriorate. Here, the matrix resin is a resin component other than the grafted rubber component in the component (A), and the intrinsic viscosity [η] is the amount of methyl ethyl ketone dissolved in the component (A) measured by a conventional method. This is the value obtained by
As the polymerization method, an ordinary method such as emulsion polymerization, solution polymerization or suspension polymerization can be used. A typical component (A) is a siloxane rubber-reinforced resin obtained by graft-polymerizing styrene and acrylonitrile onto an organosiloxane rubber polymer.

Next, the rubber-reinforced resin (B) will be described in detail. Component (B) is a rubbery polymer (excluding organosiloxane rubber) (a ') 5 to 70% by weight, preferably 10
To 65% by weight, more preferably 30 to 60% by weight, the aromatic vinyl compound (b) or another vinyl monomer copolymerizable with the aromatic vinyl compound (b) and the aromatic vinyl compound (b) in the presence thereof. 95-30% by weight of the monomer (c), preferably 90-35% by weight, more preferably 70-40
It is obtained by polymerizing wt% and has a graft ratio of 20 to 20.
The rubber-reinforced resin is 0% by weight, preferably 30 to 150% by weight, more preferably 40 to 130% by weight.
Examples of the rubbery polymer (a ') include polybutadiene, polyisoprene, butyl rubber, styrene-butadiene copolymer (styrene content is preferably 5 to 60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer. , Ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, acrylic rubber, butadiene- (meth) acrylate copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene Examples thereof include block copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated butadiene-based polymers, ethylene-based ionomers and the like. The styrene-butadiene block copolymer and the styrene-isoprene block copolymer include those having an AB type, ABA type, taper type, radial teleblock type structure and the like. Further, the hydrogenated butadiene-based polymer has, in addition to the hydride of the above block copolymer, a hydride of a block of a styrene block and a styrene-butadiene random copolymer, and a 1,2-vinyl bond content in polybutadiene of 20. Included are hydrides of polymers consisting of up to 20% by weight of blocks and polybutadiene blocks with a 1,2-vinyl bond content above 20% by weight. As the aromatic vinyl compound (b) that can be used as the component (B) and another vinyl compound (c) that can be copolymerized with the aromatic vinyl compound, the compounds listed as the component (A) can be used in the same manner. it can. The content of the rubber-like polymer (a ') in the rubber-reinforced resin (B) is 5 to 7
It is 0% by weight, preferably 10 to 65% by weight, more preferably 25 to 60% by weight. If the content of the rubbery polymer (a ') is less than 5% by weight, the impact resistance is insufficient, while if it exceeds 70% by weight, the graft ratio, the surface gloss of the resin and the moldability are deteriorated. . Further, when (b) or a monomer (mixture) composed of (b) and (c) is 30
If it is less than 100% by weight, the moldability is poor, while if it exceeds 90% by weight, the impact resistance is poor. Furthermore, in order to impart flame retardancy and improve moldability, it is preferable to use a vinyl cyanide compound as (c). As a preferable blending amount, 1 to 40 in the monomer mixture consisting of (b) and (c)
%, More preferably 5 to 35% by weight. When the graft ratio of the rubber-reinforced resin (B) is less than 20% by weight, the effect of adding the rubber component is not sufficiently exhibited, and, for example, sufficient impact resistance and good molding appearance cannot be obtained. On the other hand, if it exceeds 200% by weight, the rubber elasticity is lowered and sufficient impact resistance cannot be obtained. Furthermore, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the matrix resin in the component (B) is 0.1 to 1.2 dl / g, preferably 0.2 to 0.8 dl / g. . Intrinsic viscosity [η]
Is less than 0.1 dl / g, the impact strength is not sufficiently expressed, while if it exceeds 1.2 dl / g, moldability is deteriorated. Here, the matrix resin is a resin component other than the grafted rubber component in the component (B),
The intrinsic viscosity [η] is a value obtained by measuring the methyl ethyl ketone dissolved content in the component (B) according to a conventional method. The above-mentioned representative component (B) is an ABS resin or an AES resin. A styrene resin may be added to the component (B) if necessary. A composition consisting of the component (B) and the styrene resin is also regarded as (B). The styrene resin is obtained by polymerizing the aromatic vinyl compound (b), or the aromatic vinyl compound (b) and another vinyl monomer (c) copolymerizable with the aromatic vinyl compound (b). Aromatic vinyl compound (b) or (b)
As the other vinyl monomer (c), the same compounds as listed in the component (A) can be used. (B) component,
The proportion of the component (c) used is 50 to 100% by weight, preferably 40 to 80% by weight, and the component (c) is 50 to 0% by weight.
%, Preferably 60 to 20% by weight. (B),
When the component (c) is in the above range, a moldable product is obtained. The styrene resin preferably has an intrinsic viscosity of 0.2 to 0.9 dl / g, preferably 0.4 to
It is 0.8 dl / g. When a vinyl cyanide compound is used as one of the components (c), the thermoplastic resin composition of the present invention having excellent flame retardancy and processability can be obtained. The blending ratio of the styrene resin is preferably 0 to 80% by weight, more preferably 10 to 70% by weight based on the composition comprising the component (B) and the styrene resin. Within the above range, the thermoplastic resin composition of the present invention having excellent impact resistance and workability can be obtained. AS is a typical styrene resin
Resin, α-methylstyrene-styrene-acrylonitrile copolymer, phenylmaleimide, styrene copolymer.

The component (C) will be described in detail. The component (C) is a brominated flame retardant. Tetrabromobisphenol A, tetrabromobisphenol A as brominated flame retardants
-Bis (2-hydroxyethyl ether), tetrabromobisphenol A oligomer (terminal is epoxy group,
Tribromophenoxy group), a polycarbonate oligomer of tetrabromobisphenol A, a polycarbonate oligomer of tetrabromobisphenol S, decabromodiphenyl ether, octabromodiphenyl ether, bis (tribromophenoxy) ethane and the like. Preferred are tetrabromobisphenol A oligomers (epoxy groups, tribromophenoxy groups, etc. at the ends), and tetrabromobisphenol A polycarbonate oligomers. The preferable softening point (or melting point) of the brominated flame retardant is 80 to 350 ° C, more preferably 100 to 280 ° C. When the softening point (melting point) of the brominated flame retardant is within the above range, the thermoplastic resin composition of the present invention having good moldability can be obtained. Also, a phosphorus-based flame retardant may be used in combination as the flame retardant. Examples of the phosphorus-based flame retardant include organic phosphorus-containing compounds, red phosphorus, phosphazene-based compounds, ammonium polyphosphate and the like. Of these, organic phosphorus-containing compounds are preferred. Examples of the organic phosphorus-containing compound include phosphates typified by triphenyl phosphate and phosphites typified by triphenyl phosphite. In the present invention, as the organic phosphorus-containing compound, triphenyl phosphate, triphenyl thiophosphate, trixylenyl phosphate, trixylenyl thiophosphite, triphenyl phosphate oligomer, hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl) Phosphate) and the like are preferable, and triphenyl phosphate and hydroquinone bis (diphenyl phosphate) are particularly preferable. The content of the phosphorus compound is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). Further, an antimony compound, polytetrafluoroethylene, or the like may be added to improve flame retardancy. Examples of the antimony-based compound include antimony trioxide and antimony pentoxide. The compounding amount of the antimony-based compound is (A) component, (B)
The amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the resin composition containing the components. If the amount of the antimony compound is less than 0.1 part by weight, the effect of imparting flame retardancy is small, and if it exceeds 5 parts by weight, the slidability is poor. The particle size of the antimony compound is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less. Further, preferable polytetrafluoroethylene has an average molecular weight of 100,000 to 500.
10,000, average particle size 500-1000 μm, density 100-1
000 g / l, melting point 250-300 ° C., and specific gravity 1.
8 to 2.5. Examples of the polymerization method of polytetrafluoroethylene include emulsion polymerization and suspension polymerization, but suspension polymerization is particularly preferable. Further, the following terpolymer type fluorine-containing polymer can be used for preventing adhesion. Melting point, dropping point or softening point is 100 to 300 ° C., preferably 110.
It is a fluorine-containing polymer having a temperature of up to 230 ° C, and is inferior in thermal stability below 100 ° C or above 300 ° C. The fluorine-containing polymer is produced by copolymerization of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene or terpolymerization of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene. Particularly preferred is a terpolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene. Further, the fluorine content is preferably 50% by weight or more, and particularly preferably 68 to 76% by weight. The blending amount of polytetrafluoroethylene, or polytetrafluoroethylene and a fluorine-containing polymer is (A) component, (B)
With respect to 100 parts by weight of the resin composition comprising the components, preferably 0.01 to 10 parts by weight, more preferably 0.5 to
8 parts by weight. Within the above range, flame retardancy is improved (drip prevention) and adhesion prevention is also effective.

Next, the compounding ratios of (A), (B) and (C) of the present invention will be described in detail. The blending ratio of the component (A) and the component (B) is from 1 to 99% by weight of the component (A), preferably 10
~ 75 wt%, more preferably 15-40 wt%,
The component (B) is 99 to 1% by weight, preferably 90 to 25%.
% By weight, more preferably 85-60% by weight ((A) +
(B) = 100% by weight). 1% by weight of component (A)
If it is less than 100% by weight, the slidability is not sufficient, and if it exceeds 99% by weight, the molding appearance is poor. If the content of the component (B) is less than 1% by weight, the impact resistance is insufficient, while if it exceeds 99% by weight, the slidability is poor. The weight ratio of the organosiloxane rubbery polymer (a) to the rubbery polymer (a ') is preferably (a) / (a') = 1/20 to 20/1, more preferably 1 / 8 to 15/1, preferably 1/5 to
It is 10/1. Within the above range, the thermoplastic resin composition of the present invention having excellent slidability and impact resistance can be obtained.
The compounding amount of the component (C) is 1 to 50 parts by weight, preferably 5 to 45 parts by weight, and more preferably 10 to 40 parts by weight based on 100 parts by weight of the resin composition comprising the components (A) and (B).
Parts by weight, particularly preferably 20 to 38 parts by weight.
If the amount of component (C) is less than 1 part by weight, the effect of imparting flame retardancy is insufficient, while if it exceeds 50 parts by weight, impact resistance is poor.
The thermoplastic resin composition of the present invention contains a silicone oil, a silane coupling agent, molybdenum disulfide, nylon 6, nylon 6,6, nylon 12, nylon 4,6, and polyoxymethylene for improving slidability. , Calcium titanate, mica, carbon fiber, silicon carbide whiskers and the like may be added. Of these, silicone oil is particularly preferable. The viscosity of the silicone oil is preferably 10 to 30,000 cps (measured at 30 ° C.), and particularly preferably 50 to 20,000 cps. The preferred blending amount of these slidability improvers is (A)
0.1 to 30 parts by weight, more preferably 0.5 to 100 parts by weight of the resin composition comprising the component and the component (B).
10 parts by weight, particularly preferably 1 to 5 parts by weight. With the above blending ratio, the thermoplastic resin composition of the present invention having excellent slidability and impact resistance can be obtained. Further, other resin materials may be added to the thermoplastic resin composition of the present invention as needed. Other resin materials include polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyphenylene oxide (PP).
O), polyether ester amide, polyether imide, polyimide, polyether ether ketone (PEE)
K), polyarylate, chlorine-based polymers such as vinyl chloride resin (PVC), epoxy resins, polyurethanes, unsaturated polyesters, and at least one polymer selected from the group of thermoplastic elastomers. Among these, at least one polymer selected from the group of PBT, PET and PPO is preferable. The mixing ratio of the other resin material is preferably 30 to 90% by weight of the thermoplastic resin composition of the present invention, and 70 to 10% by weight of the other resin material.
Is. When the other resin material is in this numerical range, the effect of adding the other resin material can be obtained. In the production of the thermoplastic resin composition of the present invention or a mixture of the thermoplastic resin composition and other resin material, impact resistance and molding can be improved by using a compatibilizing agent to improve compatibility between polymers. The appearance of the product surface can be improved. The compatibilizing method includes a functional group-containing unsaturated compound having at least one functional group selected from the group consisting of an acid anhydride group, a hydroxyl group, an amino group, an epoxy group, an oxazoline group and an imide group during kneading, and If necessary, a method of allowing a peroxide to be present, a method of using another polymer having the above functional group, and the like can be used. The polymer having the functional group is a random, block or graft copolymer of the unsaturated compound having the functional group and another vinyl monomer copolymerizable therewith. Specific examples of the compatibilizer include styrene and the above functional groups such as styrene-glycidyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-methacrylic acid copolymer, styrene-acrylonitrile-methacrylic acid copolymer. Examples thereof include a copolymer obtained by copolymerizing an unsaturated compound contained and optionally one or more vinyl monomers copolymerizable therewith. In addition, ethylene-
Ethylene such as glycidyl methacrylate copolymer and ethylene-glycidyl methacrylate-vinyl acetate copolymer, and the above functional group-containing unsaturated compound and, if necessary, at least one other vinyl monomer copolymerizable therewith. Copolymerized copolymers are also included. These copolymers also include those obtained by graft-reacting other polymers on these ethylene copolymers. Other polymers to be graft-reacted include, for example, radically polymerizable vinyl monomers such as poly (meth) acrylic acid alkyl ester, polystyrene, styrene-acrylonitrile copolymer, and styrene- (meth) acrylic acid alkyl ester copolymer. The polymer polymerized using the body is mentioned. Further, in the thermoplastic resin composition of the present invention, if necessary, an antioxidant, a stabilizer such as an ultraviolet absorber, a lubricant such as low molecular weight polyethylene (including polyethylene oxide wax), calcium carbonate, talc, clay, Titanium oxide, copper oxide, zinc oxide,
Zinc borate, magnesium oxide, aluminum hydroxide,
Addition of fillers such as magnesium hydroxide, magnesium carbonate, carbon black, calcium oxide, aluminum oxide, glass beads, glass fibers, aramid fibers, glass flakes, heat-expandable graphite, metal fillers, dispersants, foaming agents, colorants, etc. Agents can be added. Of these, the shapes of glass fiber and carbon fiber are:
A fiber having a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more is preferable. The blending amount of these additives is 0.01 to 10 with respect to 100 parts by weight of the thermoplastic resin composition of the present invention.
About 0 parts by weight is preferable. The thermoplastic resin composition of the present invention can be obtained by kneading each component in various extruders, Banbury mixers, kneaders, rolls, etc., preferably in the range of 200 to 300 ° C. At the time of kneading, the respective components may be kneaded at once, or a multi-stage divided kneading method in which after kneading arbitrary components and then adding the remaining components and kneading can be adopted. A preferable kneading method is a method carried out by an extruder, and as the extruder, a biaxial rotation extruder is particularly preferable. The thermoplastic resin composition of the present invention is formed into a molded product by molding means such as extrusion molding, injection molding, and compression molding, but is excellent in slidability, flame retardancy, molding processability and impact resistance, It is extremely useful as an article such as household goods, electric equipment, office automation equipment, parts such as automobiles, or a building material. Further, it is particularly useful for applications requiring slidability and flame retardancy, for example, tray materials such as compact discs and CD-ROMs, switch parts for OA equipment, keyboards and key top materials.

[0010]

EXAMPLES The present invention will be described in more detail below with reference to examples.
The present invention will be described below, unless the gist thereof is exceeded.
The present invention is not limited to the embodiment. Example
Middle, parts and% are by weight unless otherwise specified.
It Various measurement items in the examples are as follows.Average particle size The average particle size of dispersed particles was previously synthesized in an emulsified state.
The particle size of the latex is the same as that of the dispersed particles in the resin.
Since it was confirmed with an electron microscope that it represents the diameter,
The particle size of dispersed particles in the column was measured by a light scattering method. Measurement
Equipment uses LPA-3100 made by Otsuka Electronics Co., Ltd.
Then, the particle size is calculated using the cumulant method by integrating 70 times.
did.Graft rate 1 g of the material was accurately weighed and added with 20 cc of acetone.
Yes, shake for 10 hours, then rotate at 20,000
Separate the soluble and insoluble components using a rpm centrifuge,
The insoluble matter was dried with a vacuum dryer to obtain an insoluble matter (X). one
The amount of rubber in the insoluble matter (X) based on the polymerization composition and conversion rate
(R) was calculated and the graft ratio was calculated from the following equation. Graft ratio (%) = [(X)-(R)] × 100 / (R)Intrinsic viscosity [η] The soluble matter is dried using a vacuum dryer, and the solvent
Dissolve in chill ethyl ketone, and dissolve at temperature of 30 ℃.
It was measured with a Bellows type viscometer.Izod impact strength (IMP)  According to ASTM D256, wall thickness 1/4 ", 23 ° C,
The measurement was carried out under test conditions with a notch. The unit is kg cm
/ Cm.Dynamic friction coefficient Using Suzuki type sliding tester, steel as the mating material
(S45C) was used. The test piece has an outer diameter of 25.6 mm,
Use a hollow cylinder with an inner diameter of 20.0 mm, and use the mating material
The same shape was used. The measurement conditions for the coefficient of dynamic friction are
0.5 kg load in an atmosphere of room temperature 23 ° C and humidity 50%,
Measured at a running speed of 50 cm / sec and a running distance of 3 km,
The friction coefficient and the amount of wear were measured. The dynamic friction coefficient is
Therefore, it calculates. μ = [3 × F × (r₂ ²-R₁ ²)] / [P × (r₂ ³-R₁ ³)] (Where μ is the coefficient of dynamic friction, F is the force applied to the load cell,
P is the load, R is the arm length to the load cell, r₁Is inside
Diameter, r₂Represents the outer diameter. )Flowability (melt flow rate; MFR) MFR complies with ASTM D1238, 220 ℃, load
The weight was measured at 10 kg. The unit is g / 10 minutes.Heat resistance (heat distortion temperature; HDT) Heat distortion temperature conforms to ASTM D648, wall thickness 1 /
It was measured at 2 ″ (without annealing) and a load of 18.6 kg.
The unit is ° C.Flame retardant (UL-94; V-test) It conforms to the UL-94 standard. The thickness is 1.6 mm. Production of organosiloxane rubbery polymer (a) 1.5 parts of p-vinylphenylmethyldimethoxysilane
And 98.5 parts of octamethylcyclotetrasiloxane
Mix and add 2.0 parts of dodecylbenzene sulfonic acid
Put in 300 parts of dissolved distilled water, and use a homomixer
It was emulsified and dispersed by stirring for 3 minutes. This mixed solution is
Sensor, nitrogen inlet and stirrer separable
Transfer to a flask and heat at 90 ° C for 6 hours with stirring and mixing
And complete the condensation by cooling at 5 ° C for 24 hours.
I let you. Octamethy in the obtained polyorganosiloxane
The condensation rate of rucyclotetrasiloxane was 92.8%.
Was. This polyorganosiloxane latex is
It was neutralized to pH 7 with an aqueous solution of lithium. The obtained polyorgana
The average particle size of the non-siloxane latex is 2,800
It was Ngstrom. Production of Siloxane Rubber Reinforced Resin A- (1) to (2) Glass Flask with Internal Volume of 7 L Equipped with Stirrer
100 parts of ion-exchanged water and dodecylbenzene sulfone
0.5 part of sodium acidate, 0.01 part of potassium hydroxide, t
-0.1 parts of dodecyl mercaptan and siloxane latte
Is a batch polymerization component composed of various vinyl monomers.
Was added and the temperature was raised with stirring. The temperature reached 45 ° C
At this point, 0.1 part of sodium ethylenediaminetetraacetate,
0.003 parts of ferrous sulfate, sodium formaldehyde
0.2 parts of sulfoxylate dihydrate and ion-exchanged water
15 parts activator aqueous solution and diisopropyl
Add 0.1 parts of benzene hydroperoxide and
The reaction continued for a while. After that, 50 parts of deionized water, dodeci
1 part sodium benzene sulfonate, potassium hydroxide
0.02 part, t-dodecyl mercaptan 0.1 part, di
0.2 parts of sopropylbenzene hydroperoxide and
And various vinyl-based monomers in the proportions shown in Table 1
The mixture of Clement polymer components was passed at 85 ° C. for 3 hours.
Was continuously added, and the reaction was continued. After addition is complete,
After continuing the reaction for 1 hour with stirring, 2,2-methyl
Len-bis- (4-ethylene-6-t-butylpheno
0.2 part) and the reaction product was removed from the flask.
I put it out. The product was then coagulated with 2 parts potassium chloride.
It is solidified, dehydrated, washed with water and dried to obtain powder
Sun rubber reinforced resin A- (1) to (2) was recovered. Table 1
Shows the polymerization conversion rate, graft rate, and intrinsic viscosity [η].

[0011]

[Table 1]

Production of Component (B) By emulsion polymerization with the monomer composition shown in Table 2, (B)-(1)-
(B)-(6) was obtained. The polymerization method was the same as that of the component (A), but sodium laurate was used as the emulsifier, and dilute sulfuric acid (0.5%) was used as the coagulant.

[0013]

[Table 2]

Styrenic resins that can be used in combination with component (B) Styrene resins (1) to (3) were obtained by solution polymerization with the monomer compositions shown in Table 3.

[0015]

[Table 3]

Component (c) The following compounds were used as flame retardants. (C)-(1) tetrabromobisphenol-A;
Tosoh (C)-(2) TAB oligomer (terminal epoxy group); Dainippon Ink (C)-(3) TAB oligomer (terminal tribromophenoxy group); Dainippon Ink (C)-(4) Tri Phenyl phosphate (TP
P); manufactured by Daihachi Chemical Co., Ltd. (C)-(5) triphenyl phosphate oligomer (CR-733S); manufactured by Daihachi Chemical Co., Ltd. polytetrafluoroethylene (Hostafuron TF162).
0); Sliding property improver manufactured by Hoechst Co., Ltd. The following compounds were used as sliding property improvers. Silicone oil (viscosity 100cps, 30 ° C measurement); Toray Dow polytetrafluoroethylene (Hostafuron TF-92)
05); Preparation of thermoplastic resin composition manufactured by Hoechst Co., Ltd. According to the formulation shown in Table 4, melt-kneading was performed at a temperature of 200 to 240 ° C. with an extruder having an inner diameter of 50 mm to prepare pellets. These pellets are injected into a 50z injection molding machine [Toshiba IS-8
0A] was molded at a molding temperature of 220 ° C. to prepare test pieces, and the physical properties were evaluated. As shown in Table 4, Examples 1 to 6 are excellent in slidability, flame retardancy, impact resistance and practical physical properties. Further, as shown in Example 6, the flame retardant aid (Sb ₂ O
₃ ) Flame-retardant V-0 was reached even in the non-added system. In contrast,
In Comparative Example 1, the blending amount of the component (B) exceeds the range of the present invention and the sliding temperature is poor. In Comparative Example 2, the blending amount of the component (A) exceeds the range of the present invention, and the molding appearance is poor. Comparative Example 3 is an example in which the amount of rubber in the component (B) is less than the range of the present invention, and the impact resistance is poor. In Comparative Example 4, the amount of rubber in the component (B) exceeds the range of the present invention, and the molding appearance and slidability are poor. In Comparative Example 5, the blending amount of the component (C) is outside the range of the present invention, and the flame retardancy is poor. In Comparative Example 6, the content of the component (C) exceeds the range of the present invention, and the impact resistance, slidability, and molding appearance are poor.

[0017]

[Table 4]

[0018]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is a material excellent in slidability, flame retardancy, molding processability and impact resistance, and is used for electric appliances, automobile parts and the like, various gears, rollers and bearings. Suitable for tray materials such as compact discs and CD-ROMs.

Front page continued (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. An aromatic vinyl compound (b), or an aromatic vinyl compound (b) and an aromatic vinyl compound (b) in the presence of (A) an organosiloxane rubber polymer (a) in an amount of 10 to 70% by weight. 1 to 99% by weight of a siloxane rubber-reinforced resin obtained by polymerizing 90 to 30% by weight of another vinyl monomer (c) copolymerizable with (B) a rubber polymer (organosiloxane rubber (Excluding coalescence)
(A ') Aromatic vinyl compound (b) in the presence of 5 to 70% by weight, or aromatic vinyl compound (b) and other vinyl monomer (c) copolymerizable with aromatic vinyl compound (b) Rubber-reinforced resin 99-having a graft ratio of 20-200 wt%, obtained by polymerizing 95-30 wt%
A thermoplastic resin composition comprising 1 to 50 parts by weight of a bromine-based flame retardant (C) per 100 parts by weight of a resin composition (A) + (B) consisting of 1% by weight.