CN1644612A - Anti-static thermoplastic resin composition and shaped products therefrom - Google Patents

Abstract

The present invention provides a thermoplastic resin composition that gives a molded article excellent in antistatic properties and sliding properties and to provide a molded article produced by using the thermoplastic resin composition. The antistatic thermoplastic resin composition is produced by blending 100 pts.mass of [A] a rubber-reinforced resin which comprises a rubber-reinforced copolymer resin produced by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and the like in the presence of a butadiene rubbery polymer and/or an acrylic rubbery polymer and has a content of the rubbery polymer of 3-40 mass%, 0.2-20 pts.mass of [B] an alkyl sulfonate, 0.1-10 pts.mass of [C] a polyolefin having a weight-average molecular weight of 500-40,000 and 0.1-20 pts.mass of [D] a combined product of (d) an olefin-based polymer and a (co)polymer of (b-2) a vinyl monomer including an aromatic vinyl compound. Additionally, the composition may contain an aromatic polycarbonate resin or a flame-retardant.

Description

Anti-static thermoplastic resin composition and the moulding product that use said composition

Technical field

The present invention relates to a kind of thermoplastic resin composition that can prepare the moulding product of anti-charging property and excellent in sliding property, and the moulding product that use this thermoplastic resin composition to make.

Background technology

Styrene resins such as ABS resin are because forming process, physical properties and mechanical property excellence are widely used in electric electronic applications, field of household appliances and automotive field etc.Yet this styrene resin is an electrical insulator, is effectively as insulating material, but because its entrained electricity can not leak, makes the surface can adhere to dust, and in relevant electronics, charged electricity can produce harm.As the method that overcomes this shortcoming, the method for static inhibitor is sneaked in known common employing.

On the other hand, if above-mentioned ester moulding is used for the basket etc. of electronics, except that competent anti-electrical property, owing to contact with metal parts, can produce friction or wearing and tearing during assembling, therefore requirement has sliding.As the method that improves the ABS resin sliding, known method of when melting mixing, sneaking into polyolefins wax usually.

By above-mentioned method, can improve the anti-charging property and the sliding of styrene resin to a great extent, yet, be accompanied by increasing of use field this year, need better anti-charging property and sliding, particularly high anti-charging property.

[patent documentation 1] spy opens clear 61-261359 communique

Summary of the invention

The purpose of this invention is to provide a kind of thermoplastic resin composition that can prepare the moulding product of anti-charging property and excellent in sliding property, and use the resulting moulding product of the thin compound of this thermoplastic resin.

The inventor has carried out meticulous research for above-mentioned purpose, found that, by in being mixed with the specific styrene resin that low-molecular-weight polyolefin forms, sneak into the alkylsulfonate of specified quantitative as static inhibitor, sneak into specified quantitative modified polyolefin base polymer simultaneously, can greatly improve the anti-charging property and the sliding of this styrene resin, also can improve plasticity and shock-resistance simultaneously, thereby finish the present invention.

Therefore, according to the present invention, a kind of anti-static thermoplastic resin composition is provided, it is characterized in that, this anti-static thermoplastic resin composition contains following compositions [A]-[D], with respect to the composition [A] of 100 mass parts, is mixed with the composition [B] of 0.2-20 mass parts, 0.1-10 the composition of mass parts [C], and the composition of 0.1-20 mass parts [D].

Composition [A] is a kind of rubber-reinforced resin, it is in the presence of by the rubber polymer (a) of butadiene type rubber polymer and/or acrylic rubber matter polymer formation, the rubber-reinforced copolymer resin (A-1) that obtains by the vinyl monomer that contains aromatic ethylene compound and acrylonitrile compound (b-1) polymerization, or by the mixture formation of this rubber-reinforced copolymer resin (A-1) with (being total to) polymkeric substance (A-2) of vinyl monomer, and the content of above-mentioned rubber polymer (a) is 3-40 quality %.

Composition [B] is an alkylsulfonate.

Composition [C] is that weight average molecular weight is the low-molecular-weight polyolefin of 500-40000.

Composition [D] is olefin polymer (d) and (being total to) mixture of polymers that contains the vinyl monomer (b-2) of aromatic ethylene compound.

Among this thermoplastic resin composition,, can also further contain 1-30 mass parts aromatic polycarbonate resin as composition [E] with respect to the composition [A] of 100 mass parts.

Among this thermoplastic resin composition,, can also further contain 1-30 mass parts fire retardant as composition [F] with respect to the composition [A] of 100 mass parts.

In addition,, provide a kind of moulding product, it is characterized in that using this thermoplastic resin composition to make according to the present invention.

The inventor thinks, be not bound by any theory, according to the present invention, by using composition [C] and composition [D], because the passage (channel) of composition [C] and composition [D] effect, make composition [B] be easy to come across the surface of moulding product, therefore not only can significantly improve sliding, can also significantly improve anti-charging property (surperficial intrinsic resistance) with anti-charging property.

In addition, in this manual, " (being total to) polymerization " is meant equal polymerization and/or copolymerization, and " (methyl) vinylformic acid) " is meant vinylformic acid or methacrylic acid.

Embodiment

Below, elaborate the present invention.

The rubber-reinforced resin [A] that the present invention relates to is in the presence of the rubber polymer (a) that is made of butadiene type rubber polymer and/or acrylic rubber matter polymkeric substance, the rubber-reinforced copolymer resins (A-1) that obtains by the vinyl monomer that contains aromatic ethylene compound and acrylonitrile compound (b-1) polymerization, or the mixture of (being total to) polymkeric substance (A-2) of this rubber-reinforced copolymer resins (A-1) and vinyl monomer, and the content of above-mentioned rubber polymer (a) is 3-40 quality %.

Rubber polymer (a) is made of as main component butadiene type rubber polymer or acrylic rubber matter polymkeric substance or both, but as required, can also contain other rubber polymer.

As the butadiene type rubber polymer, remove polybutadiene rubber, polyisoprene rubber, (co) polychloroprene rubber, styrene butadiene random copolymerization rubber (optimization styrene content is 5-60 weight %), the divinyl acrylate copolymer, styrene-isoprene random copolymerization rubber, acrylonitrile-butadiene random copolymerization rubber, isobutylene-isoprene random copolymerization rubber (isoprene-isobutylene rubber), styrene butadiene block copolymerization rubber, styrene-isoprene block copolymerization rubber, vinylbenzene-isopentene-styrene block copolymer rubber, outside the butadiene type rubber such as isobutylene-isoprene copolymer rubber, can also enumerate the resulting rubber of above-mentioned butadiene type rubber hydrogenation such as SEBS.

As acrylic rubber matter polymkeric substance, can enumerate acrylic elastomer, acrylate-aromatic vinyl copolymer rubber, acrylate-conjugated diene compound copolymer rubber, acrylic compound-conjugated diene compound-aromatic ethylene compound copolymer rubber etc.

Gel content ratio in the above-mentioned rubber polymer (a) is generally 98 quality % or following, is preferably 40-98 quality %, more preferably 50-95 quality %, especially preferably 60-90 quality %.In this scope, the thermoplastic resin composition of excellent in flame retardance in the time of can obtaining making shock-resistance, appearance, the use fire retardant of moulding product.

In addition, above-mentioned gel content ratio can be tried to achieve by following method.That is, in 100ml toluene, add the 1g rubber polymer, at room temperature leave standstill 48 hours after, (quality is as W with 100 purpose wire nettings ₁G) filter, with the insoluble composition of toluene and wire netting 80 ℃ of following vacuum-dryings after 6 hours weighing (quality is as W ₂G), calculate by following formula.

Gel content ratio (%)=[{ W ₂(g)-W ₁(g) }/1 (g)] * 100

The gel content ratio can be when rubber polymer prepares, and kind by suitable setting molecular weight regulator and amount, polymerization time, polymerization temperature, polymerisation conversion etc. are adjusted.

Vinyl monomer (b-1) contains as necessary monomer component aromatic ethylene compound and acrylonitrile compound, as required, can also contain can with other monomer component of its copolymerization.

As aromatic ethylene compound, can enumerate vinylbenzene, alpha-methyl styrene, o-vinyl toluene, p-vinyl toluene, Vinyl toluene, methyl-alpha-methyl styrene, bromostyrene and hydroxy styrenes etc., they can a kind of independent use, or it is used in combination.In addition, wherein optimization styrene and alpha-methyl styrene.

As acrylonitrile compound, can enumerate vinyl cyanide and methacrylonitrile etc., they can a kind of independent use, or it is used in combination.In addition, wherein preferred vinyl cyanide.

Aromatic ethylene compound and acrylonitrile compound preferably account for 30 whole quality % of vinyl monomer (b-1) or more than, more preferably 50 quality % or more than, preferred especially 60 quality or more than.In addition, the usage rate of aromatic ethylene compound and acrylonitrile compound, if they add up to 100 quality %, optimization aromatic vinyl compound/acrylonitrile compound=95-60 quality %/5-40 quality %, more preferably 90-65 quality %/10-35 quality %.

As can with other monomer component of above-mentioned aromatic ethylene compound or acrylonitrile compound copolymerization, can enumerate (methyl) acrylate, maleimide compound, hydroxyl unsaturated compound, contain the carboxyl unsaturated compound, contain the acid anhydrides unsaturated compound, contain the unsaturated compound etc. of the unsaturated compound, Han oxazolinyl of epoxy group(ing), their respectively can a kind of independent use, or it is used in combination.

As (methyl) acrylate, can enumerate methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc., they can a kind of independent use, or it is used in combination.

As maleimide compound, can enumerate maleimide, N-methyl maleimide, N-butyl maleimide, N-phenylmaleimide, N-cyclohexyl maleimide etc.They can a kind of independent use, or it is used in combination.In addition, for importing the maleimide amine unit, can also make maleic anhydride (being total to) polymerization, again the method for imidization.

Unsaturated compound as hydroxyl, can enumerate 3-hydroxyl-1-propylene, 4-hydroxyl-1-butylene, suitable-4-hydroxyl-2-butylene, anti--4-hydroxyl-2-butylene, 3-hydroxy-2-methyl-1-propylene, 2-hydroxyethyl methacrylic ester, N-(4-hydroxy phenyl) maleimide etc., they can a kind of independent use, or it is used in combination.

As carboxylic and unsaturated compound, can enumerate vinylformic acid, methacrylic acid etc.They can a kind of independent use, or it is used in combination.

As the unsaturated compound that contains acid anhydrides, can enumerate maleic anhydride, itaconic anhydride, citraconic anhydride etc., they can a kind of independent use, or it is used in combination.

As the unsaturated compound that contains epoxy group(ing), can enumerate epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester, glycidyl allyl ether etc., they can a kind of independent use, or it is used in combination.

As the unsaturated compound of Han oxazolinyl, can enumerate Yi Xi oxazoline etc., they can a kind of independent use, or it is used in combination.

When using above-mentioned other monomer, employed amount when vinyl monomer (b-1) adds up to 100 quality %, is preferably 70 quality % or following, and more preferably 50 quality % or following are preferably 40 quality % and following especially.

The rubber-reinforced copolymer resin [below, abbreviate " copolymer resin " as] that constitutes the rubber-reinforced resin (A) that the present invention relates to (A-1) can a kind of independent use, or it is used in combination.For example, above-mentioned copolymer resin (A-1) can also be in the presence of the rubber polymer that is formed by the butadiene type rubber polymer (a), the rubber-reinforced copolymer resin (A-1-a) that vinyl monomer (b-1) polymerization is obtained, perhaps, can also be in the presence of rubber polymer (a) that acrylic rubber matter polymkeric substance is formed, the rubber-reinforced copolymer resin (A-1-b) that vinyl monomer (b-1) polymerization is obtained, in addition, it can also be the mixture of this rubber-reinforced copolymer resin (A-1-a) and this rubber-reinforced copolymer resin (A-1-b), in addition, can also be this rubber-reinforced copolymer resin (A-1-a) or (A-1-b) and the mixture of other rubber-reinforced copolymer resin.

Above-mentioned copolymer resin can use known polymerization process, for example emulsion polymerization, mass polymerization, solution polymerization, suspension polymerization and it is made up resulting polymerization process be prepared.Wherein, preferred especially emulsion polymerization.

If, use polymerization starter, chain-transfer agent, emulsifying agent etc. by the emulsion polymerization preparation.These can use known material.

As polymerization starter, can enumerate cumene hydroperoxide, di-isopropylbenzene hydroperoxide, Potassium Persulphate, Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide laurate, tert-butyl hydroperoxide monocarbonate etc.

As chain-transfer agent, can enumerate octyl mercaptan, n-lauryl mercaptan, t-lauryl mercaptan, n-hexyl mercaptans, sulphur tetrem base thiuram, propenal, Methylacrylaldehyde, vinyl carbinol, 2-ethylhexyl sulphur glycol etc.

As emulsifying agent, the anionic species tensio-active agents such as aliphatic sulfonates such as alkylbenzene sulfonate, sodium lauryl sulphate, senior aliphatic carbonate, resinate, phosphoric acid salt such as sulfuric ester, Sodium dodecylbenzene sulfonate of higher alcohols can be used, and known nonionic class tensio-active agent can also be used.

In addition, in emulsion polymerization, the using method of rubber polymer (a) and vinyl monomer (b-1) can also be: in the presence of whole rubber polymers (a), vinyl monomer (b-1) added in the lump carry out polymerization, perhaps polymerization is carried out in interpolation in batches or continuously.In addition, can also be in the presence of a part of rubber polymer (a), vinyl monomer (b-1) can be added in the lump and carry out polymerization, in polymerization process, with remaining rubber polymer (a) adding carrying out polymerization, also vinyl monomer (b-1) can be added in batches or continuously and carry out polymerization, in polymerization process, add remaining rubber polymer (a) and carry out polymerization.

Behind the emulsion polymerization, usually by with the gained emulsion with condensing agent condense, washing, drying, obtain the copolymer resins powder.As condensing agent herein, can use inorganic salt such as calcium chloride, sal epsom, magnesium chloride, perhaps acid such as sulfuric acid, hydrochloric acid, acetic acid.Wherein, preferably sulfuric acid.

In addition, pass through emulsion polymerization, in the presence of rubber polymer (a), in the copolymer resin (A-1) that polymerising ethylene class monomer (b-1) obtains, usually contain above-mentioned vinyl monomer (b-1) is grafted to the not grafting composition (that is to say above-mentioned vinyl monomer (b-1) (being total to) polymkeric substance each other) that the resulting co-polymer of rubber polymer (a) and above-mentioned vinyl monomer (b-1) are not grafted to rubber polymer (a).

If by the solution polymerization copolymer resin, operable solvent is the inertia polymer solvent that uses in common radical polymerization, for example can enumerate aromatic hydrocarbon such as ethylbenzene, toluene, halohydrocarbon such as ketone such as methylethylketone, acetone, methylene dichloride, tetracol phenixin, acetonitrile, dimethyl formamide, N-Methyl pyrrolidone etc.Polymerization temperature is preferably 80-140 ℃, more preferably 85-130 ℃, is preferably 90-120 ℃ especially.

In polymerization, can also use polymerization starter, when not using polymerization starter, also can carry out polymerization by thermopolymerization.As polymerization starter, preferably use organo-peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, hydrogen peroxide etc.

In addition, if use chain-transfer agent, for example, can use thio-alcohol and α-Jia Jibenyixierjuwu etc.

In addition, if be prepared, can use at polymerization starter described in the solution polymerization and chain-transfer agent etc. by mass polymerization.

The rubber-reinforced resin [A] that the present invention relates to can also be by the mixture of this copolymer resin (A-1) with the resulting polymkeric substance of at least a kind of vinyl monomer of (being total to) polymerization (A-2) except that above-mentioned copolymer resin (A-1) itself.And above-mentioned copolymer resin (A-1) does not contain following composition [D].

Form the vinyl monomer of above-mentioned (being total to) polymkeric substance (A-2), can use independent a kind that forms in the illustrated monomer of above-mentioned copolymer resin (A-1) separately, also it can be used in combination more than 2 kinds.Preferred monomer is at least 2 kinds that are selected from aromatic ethylene compound, acrylonitrile compound, (methyl) acrylate and the maleimide compound, more preferably aromatic ethylene compound and acrylonitrile compound must be arranged.In addition, the importing of maleimide compound can be used by first polymerizable maleimide acid anhydrides, again the material that obtains of the method for imidization.

As above-mentioned vinyl monomer, if must use aromatic ethylene compound and acrylonitrile compound, with respect to used whole vinyl monomers, the usage rate of ratio, aromatic ethylene compound and the acrylonitrile compound of the total of their use total amount the same with described in the above-mentioned copolymer resin (A-1).

In addition, above-mentioned (being total to) polymkeric substance (A-2) can also be (being total to) polymkeric substance of one-component, also can be (being total to) mixture of polymers of different components more than 2 kinds.

Preparation method as above-mentioned (being total to) polymkeric substance can enumerate solution polymerization, mass polymerization and suspension polymerization etc., the same with described in the above-mentioned copolymer resin of solution polymerization and mass polymerization.

After obtaining copolymer resin (A-1) and/or (being total to) polymkeric substance (A-2) by above-mentioned various polymerization processs, the final residue amount of monomer is preferably 10000ppm or following in rubber-reinforced resin [A], more preferably 5000ppm or following.

The content of contained rubber polymer (a) is 3-40 quality % with respect to all resins in the rubber-reinforced resin [A] that the present invention relates to, and is preferably 5-35 quality %, more preferably 5-30 quality %.If rubber polymer (a) contain quantity not sufficient 3 quality %, the shock-resistance of moulding product is good inadequately, on the other hand, in case surpass 40 quality %, appearance is understood poor.

In addition, if above-mentioned rubber-reinforced resin [A] is the mixture of copolymer resin (A-1) and (being total to) polymkeric substance (A-2), usually use the copolymer resin (A-1) of rubber polymer content as 10-80 quality %, selection to the usage rate of copolymer resin (A-1) and (being total to) polymkeric substance (A-2) should make the rubber polymer (a) in the mixture fall into above-mentioned scope.

The percentage of grafting of above-mentioned rubber-reinforced resin [A] is preferably 20-200 quality %, and more preferably 30-150 quality % is preferably 40-120 quality % especially.Wherein, percentage of grafting (quality %) is tried to achieve by following formula.

Percentage of grafting (quality %)=(T-S)/S} * 100

In the following formula, T is defined as: the rubber-reinforced resin of 1g [A] is dropped into 20ml acetone (still, when rubber polymer (a) is acrylic rubber matter polymkeric substance, be acetonitrile) in, vibration is 2 hours in vibrator, (rotating speed: 23000rpm) centrifugation is 60 minutes with separating centrifuge, with insoluble composition and solvable component separating, the quality of resulting insoluble composition (g), S is the quality (g) of the rubber polymer that contains in the rubber-reinforced resin of 1g [A].

In addition, the peak viscosity [η] of the solvable composition of acetone of the rubber-reinforced resin [A] that the present invention relates to (using methylethylketone as solvent, 30 ℃ of mensuration) is preferably 0.2-1.2dl/g, and more preferably 0.2-1dl/g is preferably 0.3-0.8dl/g especially.

The median size of dispersive rubber constituent is preferably 500 -30000 in the rubber-reinforced resin [A] that the present invention relates to, and more preferably 1000 -20000 is preferably 1500 -8000 especially.Median size can be measured by the such known method of electron microscope method.

As the alkylsulfonate that the present invention relates to [B], for example, can enumerate general formula (R-SO ₃) _nM (in the formula, R is the alkyl of straight or branched, M be metal ion etc. to ion, n be 1 or above integer) shown in alkylsulfonate and metal-salt thereof.As above-mentioned alkyl, the saturated alkyl of preferred straight chain.The average carbon atom number of abovementioned alkyl is preferably 8-23, and more preferably 12-20 is preferably 12-18 especially.Alkylsulfonate [B] is preferably metal-salt, and more preferably basic metal and alkaline earth salt are preferably sodium salt, lithium salts, sylvite, most preferably sodium salt especially.

With respect to 100 mass parts composition of the present invention [A], the addition of alkylsulfonate [B] is the 0.2-20 mass parts, is preferably the 0.2-5 mass parts, more preferably the 0.5-3 mass parts.If less than 0.2 mass parts, the anti-charging property of the moulding product that obtain is not high enough.Surpass 20 mass parts if add, the appearance and the shock-resistance of moulding product are poor, are not preferred.

As the weight-average molecular weight that the present invention relates to is the low-molecular-weight polyolefine [C] of 500-40000, can enumerate the low-molecular-weight polyolefin of so-called polyolefin-wax, specifically, can enumerate polyethylene wax, Poly Propylene Wax etc.The weight-average molecular weight of this composition [C] is preferably 1000-20000, and more preferably 2000-8000 is preferably 4000-7000 especially.If molecular weight in above-mentioned scope, when making thin molded article with composition of the present invention, can obtain sufficient mould separation property, and can make the moulding product have sufficient sliding.

In low-molecular-weight polyolefine, the polyolefine that contain the polyolefine that uses Z-type catalyst etc. to make, makes by high-pressure process and decompose resulting degraded polyolefine by the high molecular polyolefine that makes by above-mentioned low-pressure process or high-pressure process by the low-pressure polymerization method.In addition, in low-molecular-weight polyolefin, also contain material and modifier by the partial oxidation that imports functional group, but common preferred unmodified material.In addition, in low-molecular-weight polyolefin, contain a straight catenate and a catenate polyolefine, but the polyolefine of usually preferred side chain.

With respect to 100 mass parts composition of the present invention [A], the addition of composition [C] is the 0.1-10 mass parts, is preferably the 0.1-5 mass parts, and more preferably the 0.5-4 mass parts is preferably the 0.5-3 mass parts especially, most preferably is the 1-2 mass parts.If less than 0.1 mass parts, the anti-charging property of gained moulding product and sliding are good inadequately.If surpass 10 mass parts, shock-resistance is poor, and, owing to can produce the bad phenomenon of peeling off, be not preferred therefore at the near surface of moulding product.

The composition that the present invention relates to [D] is the mixture of (being total to) polymers of olefin polymer [d] and the vinyl monomer (b-2) that contains aromatic ethylene compound.

As olefin polymer (d), for example, can use to be selected from following compositions (d-1), (d-2) and (d-3) polymkeric substance in.

(d-1): olefin resin,

(d-2): ethene-alpha-olefin class rubber polymer,

(d-3): the hydrogenation thing of diolefinic polymer.

As olefin resin (d-1), for example, can enumerate polyethylene, polypropylene etc.This olefin resin (d-1) preferably at room temperature can demonstrate the material of degree of crystallinity by X-ray diffraction, be more preferably degree of crystallinity and be 20% or more than, fusing point is 40 ℃ or above material.In addition, the resin of using as moulding at normal temperatures, this olefin resin (d-1) must have enough molecular weight, and for example, olefin resin has to be measured melt flow according to JIS K-6758 and be preferably 0.01-500g/10 branch, the suitable molecular weight of 0.05-100g/10 branch more preferably.In addition, olefin resin (d-1) can also be the material by modifications such as acid anhydrides, carboxyls.

Ethene-alpha-olefin class rubber polymer (d-2) is that main body constitutes with ethene-alpha-olefin class rubber polymer, as required, can also contain other rubber polymer.

As ethene-alpha-olefin class rubber polymer, can enumerate ethene-alpha-olefin copolymerization rubber, ethylene-alpha-olefin-nonconjugated diene copolymerization rubber etc.

As the object lesson of ethene-alpha-olefin class rubber polymer, for example can enumerate the resulting copolymerization rubber of forming by the ratio of mixture of the alpha-olefin/nonconjugated diene that by ethene/carbonatoms is 3-20=5-95/95-5/0-30 weight % (these three kinds of compositions add up to 100 weight %) of monomer copolymerizable.As carbon number described herein is the alpha-olefin of 3-20, can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-laurylene etc.Be preferably propylene, 1-butylene, 1-octene, more preferably propylene and 1-butylene.This alpha-olefin can a kind of independent use, or it is used in combination.The carbonatoms of alpha-olefin is 3-20, is preferably 3-12, more preferably 3-8.If carbonatoms is too much, copolymerization can descend greatly.The ratio of ethene and alpha-olefin (ethylene/alpha-olefin) is preferably 5-95/95-5, and more preferably 40-90/60-10 is preferably 50-90/50-10 especially, most preferably is 50-85/50-15.

In addition, and the non-conjugated diene of usefulness, can enumerate alkenyl norbornylene class, cyclodienes, aliphatics dienes etc., preferred Dicyclopentadiene (DCPD) and 5-vinyl-2-norbornylene.These non-conjugated dienes can a kind of independent use, or with its two or more groups uses.The content of non-conjugated diene is 0-30 weight % in the ethene-alpha-olefin class rubber polymer, is preferably 0-15 weight %.In addition, the unsaturated amount of this copolymerization rubber converts by iodine number and is preferably 0-40.If unsaturated amount is too high, weather (light) property, color will be improper.

For obtaining these ethene-alpha-olefin class rubber polymers, can also use single-phase, heterogeneous any catalyzer.As the single phase catalysis agent, can enumerate the class of metallocenes catalyzer.As heterogeneous catalyst, for example, can enumerate the vanadium class catalyzer that vanadium compound and organo-aluminium compound are formed.

In addition, the mooney viscosity (ML of ethene-alpha-olefin class rubber polymer ₁₊₄, 100 ℃) be preferably 60 or below, more preferably 50 or below, be preferably 5-40 especially.The second-order transition temperature of ethene-alpha-olefin class rubber polymer is preferably-110 ℃--and 40 ℃, more preferably-70 ℃--45 ℃.

Hydrogenation thing (d-3) as diolefinic polymer, can enumerate conjugated diolefine hydrogenation of polymer thing (d-3-1), conjugated diolefine and vinyl monomer (for example, vinylbenzene, vinyl cyanide etc.) random copolymers hydrogenation thing (d-3-2), have with the aromatic ethylene compound and be the main polymer blocks (PST-1) that constitutes and be the block polymer hydrogenation thing (d-3-3) etc. of the main polymer blocks (PBD-2) that constitutes with the conjugated diene compound.Preferred diolefinic polymer hydrogenation thing (d-3) is mentioned component (d-3-3).

Aromatic ethylene compound as the polymer blocks (PST-1) of mentioned component (d-3-3) uses can all use the represented compound of composition [A], is preferably vinylbenzene and alpha-methyl styrene, is preferably vinylbenzene especially.In addition, as the conjugated diene compound that polymer blocks (PBD-2) uses, can enumerate divinyl, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene etc. are preferably divinyl and isoprene.They can a kind of independent use, or it is used in combination.And polymer blocks (PBD-2) can use the conjugated diene compound more than 2 kinds, and it can also be with any form bonded block in random shape, block-wise, the tapered block shape.In addition, polymer blocks (PBD-2) can contain 1-10 the tapered block that aromatic ethylene compound is cumulative, suitably copolymerizations such as conjugated diolefin polymer block that can also the ethylenic linkage content of conjugated diene compound origin is different.

The preferred structure of mentioned component (d-3-3) is the hydrogenation of polymer thing of following formula ()～(three) expression.

(A-B) _Y... (one)

(A-B) _Y-X ... (two)

A-(B-A) _Z... (three)

(among structural formula ()～(three), A is the polymer blocks based on aromatic ethylene compound, as long as it is the polymer blocks of being made up of aromatic ethylene compound basically, can also contain some conjugated diene compound.A be the content of wherein aromatic ethylene compound be preferably 90 quality % or more than, more preferably 99 quality % or above polymer blocks.B be single polymers of conjugated diolefine or aromatic ethylene compound etc. other monomer and the multipolymer of conjugated diene compound.X is the coupler residue, and Y represents the integer of 1-5, and Z represents the integer of 1-5

In the mentioned component (d-3), the usage rate of aromatic ethylene compound and conjugated diene compound is preferably aromatic ethylene compound/conjugated diolefine=10-70/90-30 quality %, more preferably 15-65/85-35 quality % is preferably 20-60/80-40 quality % especially.

The segmented copolymer that is formed by aromatic ethylene compound and conjugated diene compound is known in the anionic polymerization field, for example, open in the public clear 47-28915 communique of spy, special public clear 47-3252 communique, special public clear 48-2423 communique, special public clear 48-20038 communique etc.In addition, the preparation method with polymer blocks of tapered block opens in the clear 60-81217 communique etc. open the spy.

Content from the ethylenic linkage (1,2-and 3,4-key) of the conjugated diene compound of mentioned component (d-3), be preferably 5-80%, more preferably 5-75% is preferably 5-70% especially, if drop in this scope,, be preferred therefore because it is more excellent to produce anti-charging property effect.The number-average molecular weight of mentioned component (d-3) is preferably 10000-1000000, more preferably 20000-500000, especially preferably 20000-200000.Wherein, the number-average molecular weight of the A part of preferred above-mentioned formula ()～(three) expression is 3000-150000, and the number-average molecular weight of preferred B part is 5000-200000.

The adjusting of the ethylenic linkage content of conjugated diene compound can be undertaken by using following compound: N, N, N ', N '-Tetramethyl Ethylene Diamine, Trimethylamine, triethylamine, two azo rings (2,2,2) amine such as octane, the alkoxide of ethers such as tetrahydrofuran (THF), diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, thioether class, phosphine class, phosphoramide types, alkyl benzene sulfonate, potassium and sodium etc.

Mentioned component (d-3) can also be after obtaining polymkeric substance as stated above, uses coupler, makes the resultant product of polymer molecule chain extension or branch by the coupler residue.As coupler as used herein, can enumerate diethylene adipate, Vinylstyrene, dimethyl dichlorosilane (DMCS), silicon tetrachloride, butyl trichlorosilicane, tin tetrachloride, butyl tin trichloride, dimethyl chlorination silicon, germanium tetrachloride, 1,2-ethylene dibromide, 1,4-chloromethylbenzene, two (trichloromethane is silica-based) ethane, epoxidized linseed, benzylidene vulcabond, 1,2,4-benzene triisocyanate etc.

Mentioned component (d-3) is with the carbon-to-carbon double bond of the conjugated diolefine part of above-mentioned segmented copolymer etc. partially or completely hydrogenation and the material that obtains.Hydrogenation rate is preferably 30-100%, more preferably 50-100%.If hydrogenation rate is low, can cause producing the relatively poor tendency of effect of anti-charging property.

The hydrogenation reaction of above-mentioned block copolymer etc. can be undertaken by known method, and the adjustment of hydrogenation rate also can be undertaken by known method.There are special public clear 42-8704 communique, special public clear 43-6636 communique, special public clear 63-4841 communique, special public clear 63-5401 communique, spy to open flat 2-133406 communique, spy as concrete method and open disclosed method in the flat 1-297413 communique etc.

The usage quantity of olefin polymer (d) in the composition [D] of 100 quality %, is preferably 10-90 quality %, more preferably 20-80 quality %.

The vinyl monomer (b-2) that uses in the composition [D] contains as aromatic ethylene compound that must composition, as required, can also contain other can with the monomer of this aromatics copolymerization.As can with the monomer of this aromatics copolymerization, can enumerate acrylonitrile compound, (methyl) acrylate, maleimide, contain functional group unsaturated compound (for example the unsaturated compound of hydroxyl, carboxylic unsaturated compound, contain acid anhydrides unsaturated compound, contain the unsaturated compound etc. of the unsaturated compound, Han oxazolinyl of epoxy group(ing)) etc.They can distinguish a kind of independent use, or it is used in combination.

As the unsaturated compound of unsaturated compound, the carboxylic unsaturated compound of above-mentioned aromatics, acrylonitrile compound, (methyl) acrylate, maleimide, hydroxyl, the unsaturated compound that contains acid anhydrides, the unsaturated compound that contains epoxy group(ing) and Han oxazolinyl, can enumerate compound separately shown in [A] composition and preferred compound.

The usage quantity of the aromatic ethenyl compound that uses in the composition [D], in the vinyl monomer (b-2) of 100 quality %, be preferably 5 quality % or more than, more preferably 10 quality % or more than.

If composition [D] uses acrylonitrile compound, in the vinyl monomer (b-2) of 100 quality %, its usage quantity is preferably 3-60 quality %, more preferably 5-50 quality %.

If composition [D] uses (methyl) acrylate, in the vinyl monomer (b-2) of 100 quality %, its usage quantity is preferably 3-95 quality %, more preferably 5-85 quality %.

If composition [D] uses maleimide, in the vinyl monomer (b-2) of 100 quality %, its usage quantity is preferably 3-60 quality %, more preferably 5-50 quality %.

If composition [D] uses the unsaturated compound that contains functional group, in the vinyl monomer (b-2) of 100 quality %, its usage quantity is preferably 0.05-30 quality %, more preferably 0.1-20 quality %.

If the usage quantity of above-claimed cpd is littler than above-mentioned scope, just can't obtain the positive effect of compound, on the other hand,, can cause significant counter productive if surpass above-mentioned scope, any situation is not preferred.

The preferably combination of vinyl monomer (b-2) is a kind or 2 kinds of monomer combination that are selected from aromatic ethylene compound and acrylonitrile compound, (methyl) acrylate and the maleimide compound.

In the composition [D] of 100 quality %, the usage quantity of vinyl monomer (b-2) is preferably 10-90 quality %, more preferably 20-80 quality %.

As composition [D], for example, can enumerate following graft copolymer (D1), addition copolymer (D2) etc.

(D1): in the presence of olefin polymer (d), the so-called graft copolymer that vinyl monomer (b-2) polymerization is obtained.

(D2): (being total to) polymers of olefin polymer (d) and vinyl monomer (b-2) is mixed the product that obtains, so-called addition copolymer.

Graft copolymer (D1) can for example adopt free radical catalyst by known polymerization, makes by emulsion polymerization, mass polymerization, solution polymerization, suspension polymerization and polymerization mix method thereof.Wherein, preferred mass polymerization, solution polymerization.In addition, the preparation method of mentioned component [A] is described, also is applicable in the preparation of graft copolymer (D1).

In the graft copolymer (D1), as olefin polymer (d), preferred above-mentioned ethene-alpha-olefin class rubber polymer (d-2) and/or the above-mentioned diolefinic polymer hydrogenation thing (d-3) of using, at this moment, graft copolymer (D1) becomes so-called rubber-reinforced resin.By the microscopical known measuring method of applying electronic, the number average bead diameter of dispersive rubber constituent in the rubber-reinforced resin of this that records is preferably 500 -100000 , and more preferably 1000 -5000 is preferably 1500 -50000 especially.The composition (d-2) and the content (d-3) that contain in this rubber-reinforced resin with respect to total mass, are preferably 3-40 quality %, and more preferably 5-35 quality % is preferably 5-30 quality % especially.When this contains quantity not sufficient 3 quality %, owing to prevent charging property, sliding meeting variation, and produce the bad phenomenon that comes off, be not preferred therefore.On the other hand, if surpass 40 quality %, show that outward appearance can variation.

The olefin polymer (d) that addition copolymer (D2) can obtain by the unsaturated compound copolymerization that will contain functional group with contain the co-polymer of the unsaturated compound of functional group as the vinyl monomer (b-2) of copolymerization composition, carry out high molecular weight reactive by methods such as for example hot-melt mixtures and be prepared.Here, with respect to the olefin polymer (d) or the vinyl monomer (b-2) of 100 mass parts, the usage quantity that contains the unsaturated compound of functional group is preferably the 0.01-20 mass parts, more preferably the 0.1-10 mass parts.

In the addition copolymer (D2),, preferably use above-mentioned olefin resin (d-1) as olefin polymer (d).

Graft copolymer (D1) can also only be made of the graftomer to olefin polymer (d) grafted ethene class monomer (b-2) polymkeric substance gained, perhaps, can also be this graftomer and the mixture of the polymkeric substance that is not grafted to the vinyl monomer (b-2) of olefin polymer (d) (promptly not graftomer), be generally the form of latter's mixture.

The percentage of grafting of graft copolymer (D1) by trying to achieve with the same method of mentioned component [A], is preferably 20-200 quality %, and more preferably 30-150 quality % is preferably 40-120 quality % especially.

In addition, the limiting viscosity [η] of the solvable composition of acetone of graft copolymer (D1) (use methylethylketone as solvent, measure down at 30 ℃) is preferably 0.2-1.2dl/g, and more preferably 0.2-1dl/g is preferably 0.3-0.8dl/g especially.

In the graft copolymer (D1), olefin polymer (d) can also perhaps, can also be made of by mixing more than 2 kinds any formation in composition (d-1), composition (d-2) and the composition (d-3).In addition, graft copolymer (D1) can also be the mixture that has the different graft copolymers that constitute more than 2 kinds.

Addition copolymer (D2) can also be only by constituting to the resulting addition polymer of olefin polymer (d) addition vinyl monomer (b-2), perhaps, can also be this addition polymer and the mixture of the polymkeric substance that does not add to the vinyl monomer (b-2) of olefin polymer (d) (promptly not addition polymer), the normally form of latter's mixture.In the addition copolymerization compound (D2), the markup percentage of the polymkeric substance of vinyl monomer (b-2) is preferably 20-200 quality %, and more preferably 30-150 quality % is preferably 30-120 quality % especially.The limiting viscosity [η] of the solvable composition that the mensuration by markup percentage obtains (use methylethylketone as solvent, measure down at 30 ℃) is preferably 0.2-1.2dl/g, and more preferably 0.2-1dl/g is preferably 0.3-0.8dl/g especially.

Can in the measuring method of above-mentioned percentage of grafting, use vinyl monomer (b-2) to dissolve, and the undissolvable solvent of addition copolymer replace acetone, and markup percentage is measured.

In the addition copolymer (D2), olefin polymer (d) can perhaps, can also be made of by mixing more than 2 kinds any formation in composition (d-1), composition (d-2) and the composition (d-3).In addition, addition copolymer (D2) can also be the mixture that has the different addition copolymers that constitute more than 2 kinds.

After obtaining mentioned component [D] by above-mentioned various polymerization processs, the monomer content of final residue is preferably 10000ppm or following, more preferably 5000ppm or following in this composition [D].

The addition of composition of the present invention [D] with respect to 100 mass parts composition of the present invention [A], is the 0.1-20 mass parts, is preferably the 1-20 mass parts, and more preferably the 2-15 mass parts is preferably the 2-10 mass parts especially, most preferably is the 3-8 mass parts.If less than 0.1 mass parts then can not fully improve the anti-charging property and the sliding of gained moulding product.If surpass 20 mass parts, owing to can reduce the intensity of machinery, therefore surface hardness etc. are not preferred.

The preferred material that is rich in the alkene composition identical that uses of composition [D] with alkene kind in the composition [C].For example, if use polyethylene wax as composition [C], then preferably use the olefin polymer (d) of polyvinyl paraffin wax polymkeric substance,, then preferably use the olefin polymer (d) of Poly Propylene Wax polymkeric substance as composition [D] if use Poly Propylene Wax as composition [C] as composition [D].

In addition, composition [C] and composition [D] addition separately, the 0.5-5 that is preferably composition [B] addition is doubly.By using these compositions of this ratio, it is contemplated that the composition [B] with charging preventive property is easy to arrive the surface of moulding product owing to the channelling effect of composition [C] with composition [D].

For as the aromatic copolycarbonate [E] that the present invention relates to, there is no particular limitation, for example, can use various hydroxy aryl compounds and phosgene by the resulting material of surperficial polycondensation, perhaps the material that obtains by known polymerization process by resulting material of transesterification reaction (melt-polycondensation) etc. of carbonic ether such as dihydroxyl aryl compound and hexichol carbonic ether.

Dihydroxyl aryl compound as the raw material that forms aromatic copolycarbonate, can enumerate two (4-hydroxy phenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 2,2-two (4-hydroxy phenyl) propane, 2,2-two (4-hydroxy phenyl) butane, 2,2-two (4-hydroxy phenyl) octane, two (4-hydroxy phenyl) phenylmethane, 2,2-two (4-hydroxy-3-methyl phenyl) propane, 2,2-two (4-hydroxyl-3-tert-butyl-phenyl) propane, 2,2-two (4-hydroxyl-3-bromophenyl) propane, 2,2-two (4-hydroxyl-3, the 5-dichlorophenyl) propane, 1,1-two (4-hydroxy phenyl) pentamethylene, 1,1-two (4-hydroxy phenyl) hexanaphthene, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxyl-3,3 '-dimethyl phenyl ether, 4, the basic thioether of 4 '-dihydroxy, 4,4 '-dihydroxyl-3,3 '-dimethyl benzene thioether, 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxyl-3,3 '-dimethyl thionyl benzene, 4,4 '-dihydroxy phenyl sulfone, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfone, quinhydrones, Resorcinol etc.Wherein, preferred 2,2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane).In addition, these can a kind of independent use, or it is used in combination.In addition, as the composition that the present invention relates to [E], can a kind of independent use, or it is used in combination.

The viscosity-average molecular weight of the aromatic copolycarbonate that the present invention relates to [E] is preferably 13000-32000, and more preferably 17000-31000 is preferably 18000-30000 especially.If viscosity-average molecular weight less than 13000, moulding product shock-resistance has the tendency of reduction.On the other hand, if viscosity-average molecular weight surpasses 31000, formability has the tendency of variation.

If use the different aromatic polycarbonate resin of viscosity-average molecular weight more than 2 kinds, the viscosity-average molecular weight during mixing also can drop in the above-mentioned scope.When using the different aromatic polycarbonate resin of viscosity-average molecular weight more than 2 kinds, if with viscosity-average molecular weight is the resin of 13000-19000 (E1) and the resin of 20000-32000 (E2), (still, it adds up to 100 quality % in the ratio of (E1)/(E2)=10-50 quality %/90-50 quality %.) share, can obtain shock-resistance and mobile harmonious excellent moulding product.In addition, above-mentioned (E1) and (E2) both can be identical separately aromatic polycarbonate resin, also can be different separately resins.

Above-mentioned viscosity-average molecular weight can calculate by following method: be solvent with the methylene dichloride, record specific viscosity (η sp) 20 ℃ of concentration with [0.7g/100ml (methylene dichloride)], calculated by this specific viscosity by following formula.

Viscosity-average molecular weight=([η] * 8130) 1.205

(in the formula, [η]=[(η sp * 1.12+1) ^1/2-1]/and 0.56C, C is the concentration (g/100ml) of polymers soln.)

If the aromatic copolycarbonate that the present invention relates to [E] is the material that obtains by surperficial condensation, it contains various muriates.Because this muriate can produce bad influence to thermoplastic resin composition's of the present invention thermostability, so the chloride content of aromatic copolycarbonate, the amount of pressing chlorine converts, and is preferably 300ppm or following, more preferably 100ppm or following.

With respect to 100 mass parts composition of the present invention [A], the addition of aromatic copolycarbonate [E] is the 1-30 mass parts, is preferably the 5-25 mass parts.If less than 1 mass parts, the thermotolerance of the moulding product that obtain can be good inadequately, if surpass 30 mass parts, then can not fully improve the anti-charging property and the sliding of gained moulding product.

Among the present invention,, can obtain not only anti-charging property owing to contain the thermoplastic resin composition of fire retardant [F], sliding is good, and also excellent moulding product of flame retardant resistance.

As above-mentioned fire retardant [F], there is no particular limitation to it, can enumerate organic based flame retardants such as inorganic phosphorus such as mineral-type fire retardant, red phosphorus such as magnesium hydroxide, aluminum oxide, potassium borate, low melting glass, organic halogen based flame retardant, organic phosphates fire retardant, silicone compounds, organometallic compound, hindered amines fire retardant etc.These materials can a kind of independent use, or it is used in combination.

In addition, wherein organic halogen based flame retardant and more than one the combination that is selected from weisspiessglanz, zinc borate, zinc, the ferric oxide etc. are arranged as the example that is used in combination, the combination of organic phosphates fire retardant and silicone compounds, the combination of organopolysiloxane and organometallic compound etc.

As above-mentioned organic halogen based flame retardant, preferred brominated and/or chloride compound, especially preferably as the halid halogenated bisphenol compound of bis-phenol, as halogenated bisphenol compound and epihalohydrins, or the halogenated epoxide of the reaction product of halogenated bisphenol compound and halogenated bisphenol diglycidylether and halo triaizine compounds etc.

As above-mentioned halogenated bisphenol compound, can enumerate tetrabromo-bisphenol, dibromo dihydroxyphenyl propane, tetrachlorobisphenol A, dichloro dihydroxyphenyl propane, tetrabromobisphenol F, dibromo Bisphenol F, tetrachlorobisphenol F, dichloro Bisphenol F, tetrabromo-bisphenol s, dibromo bisphenol S, tetrachlorobisphenol S, dichloro bisphenol S etc.These materials can a kind of independent use, or it is used in combination.

As above-mentioned halogenated epoxide, can enumerate material with structure shown in the following general formula (1):

[in the formula, R ¹Expression isopropylidene, methylene radical or sulfuryl, R ², R ³Represent 2 respectively, the 3-epoxypropyl or-CH ₂CH (OH) CH ₂OR base (R is the alkyl or aryl that can replace with bromine or chlorine), X represents bromine or chlorine, a, b, c and d represent the integer of 1-4, n represents 0 or above integer.]

The n of the compound shown in the above-mentioned general formula (1) be preferably 15 or below.In addition, the end of above-claimed cpd both can be an epoxy group(ing), also can epoxy group(ing) be sealed with aryl or alkyl etc.The aryl of closed end and alkyl as required, can also use halogen atoms such as chlorine, bromine to modify.As the object lesson of end closure base, can enumerate phenyl, naphthyl etc. and not have the aryl that replaces, halogenated aryls such as tribromo phenyl, penta-bromophenyl, trichlorophenyl, five chlorophenyl, the alkyl of stearyl-etc.In addition, a terminal end can be identical with the other end, or inequality.These materials can a kind of independent use, or it is used in combination.

As above-mentioned halo triaizine compounds, so long as contain the compound of triazine skeleton, there is no particular limitation to it, for example, can enumerate the compound with structure shown in the following general formula (2).

(in the formula, R ⁴Aryl and/or alkyl or the hydrogen of representing bromo or chloro respectively, Y represents-O-or-NH-.)

Such compound normally contains in the compound of triazine skeleton at cyanuric acid or trimeric cyanamide etc., and the reaction of hydroxy-containing compounds such as the phenol by bromo or chloro, alcohols or amine compound obtains.These materials can a kind of independent use, or it is used in combination.

In addition, as above-mentioned organic phosphates fire retardant,, so be preferred owing to phosphate compound, phosphazene compound can improve the flame retardant resistance of moulding product.

As above-mentioned phosphate compound, for example, can enumerate compound with structure shown in following formula (3) and (4).

(in the formula, R ⁵, R ⁶, R ⁷And R ⁸Being alkyl, phenyl or xylyl, can be identical separately, also can be different.X is Resorcinol residue, quinhydrones residue or the dihydroxyphenyl propane residue of divalent.N mean value is 0-5.)

(in the formula, R ⁹And R ¹⁰Be hydrogen atom, halogen atom or low alkyl group, R ¹¹Be the group that hydrogen atom, phenyl or following formula are represented,

Above-mentioned phenyl can also be selected from least a replacement in halogen atom, hydroxyl or the low alkyl group.Y and z are the integers of 1-4, and they both can be identical, also can be different.In addition, R ⁹And R ¹⁰Both can be identical, also can be different.)

As the fire retardant shown in the above-mentioned general formula (4), can enumerate the compound shown in following (5)-(8).

Above shown in compound in, the compound shown in preferred formula (5) and (6).

In addition, as above-mentioned phosphazene compound, can enumerate with phosphorus and nitrogen is the compound that constitutes element, contains two keys, on phosphorus atom in conjunction with the compound of propoxy-, amino etc. etc.Its concrete structure is shown in following general formula (9) and (10).

(in the formula, R ¹²-R ²⁰Be alkyl, aryl, alkoxyl group, aryloxy, amino or hydroxyl, it can be respectively identical, also can be different.N ' is the integer of 0-15, is preferably 1-10.In addition, above-mentioned functional group can also further be selected from least a kind of replacement in alkyl, aryl, alkoxyl group, aryloxy, amino and the hydroxyl.)

(in the formula, R ²¹-R ²⁶Be alkyl, aryl, alkoxyl group, aryloxy, amino or hydroxyl, it can be respectively identical, also can be different.N " be the integer of 0-15, be preferably 1-10.In addition, above-mentioned functional group can also further be selected from least a kind of replacement in alkyl, aryl, alkoxyl group, aryloxy, amino and the hydroxyl.)

As above-mentioned phosphazene compound, can enumerate for example propoxy-phosphonitrile, phenoxy phosphazene, methylphenoxy phosphonitrile, amino phosphonitrile, fluoro-alkyl phosphonitrile etc.Wherein, preferred phenoxy phosphazene.

With respect to the composition of the present invention [A] of 100 mass parts, the addition of fire retardant [F] is the 1-30 mass parts, is preferably the 3-25 mass parts, more preferably the 5-20 mass parts.If less than 1 mass parts, the flame retardant resistance of the moulding product that obtain is good inadequately, if surpass 30 mass parts, can not fully improve the anti-charging property and the sliding of gained moulding product.

If use above-mentioned fire retardant among the thermoplastic resin composition of the present invention, can also further mix flame retardant.As above-mentioned flame retardant, can enumerate antimony compounds, zinc borate, zinc, ferric oxide, polytetrafluoroethylene (PTFE)s etc. such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, four weisspiessglanzs, antimony pentaoxide.If use the halogen fire retardant, flame retardant is preferably antimony compounds, if use phosphorus type flame retardant, flame retardant is preferably PTFE.

Dripping when above-mentioned PTFE can prevent to burn (only for fused solution) has and makes the effect more fully of burning.The weight-average molecular weight of PTFE be generally 500,000 or more than, be preferably 1,000,000 or more than.When mixing with other component of polymer etc., the median size of PTFE is generally 90-600 μ m, is preferably 100-500 μ m, more preferably 120-400 μ m.After other component of polymer mixed, PTFE can be dispersed into granular substance that median size is 0.1-100 μ m or finer fibrous material.The proportion of PTFE is generally 1.5-2.5, is preferably 2.1-2.3.In addition, apparent density is generally 0.5-1g/ml, is preferably 0.6-0.9g/ml.As PTFE, can also use in the water equal solvent with lubricant dispersive decentralized PTFE.

According to the kind of fire retardant, the combined amount of above-mentioned flame retardant is generally the 0.1-50 mass parts with respect to the fire retardant of 100 mass parts, is preferably the 1-40 mass parts.

Among the thermoplastic resin composition of the present invention, can be further suitably mixed polyamide, polyamide elastomer, polyester elastomer, polyethylene, polypropylene, polyphenylene oxide, POM, phenolic resin, Resins, epoxy, LCP, PPS, HIPS, polystyrene, thermoplastic polyurethane etc. as other component of polymer.

Among the thermoplastic resin composition of the present invention,, can mix various additives according to purpose, purposes.As the example of additive, can enumerate weighting agent, weather (light) agent, antistatic agent, oxidation inhibitor, lubricant, softening agent, tinting material, antiseptic-germicide, silicone oil, coupler etc.

There is no particular limitation to the blending means of each composition of [A] of the present invention-[D].Especially,, re-use after can also being blended in (A-2) composition in (A-1) composition in advance, re-use after perhaps it can also being blended in advance in (D) composition if use (A-2) composition.

Thermoplastic resin composition of the present invention can pass through various forcing machines, Banbury, stirrer, Rolled machine, feeder rod (Off イ one ダ one Le one ダ one) etc., and each composition is mixed with and gets.Preferred manufacturing procedure is for using the method for forcing machine or Banbury.

In addition, when mixing various composition, these compositions can be mixed together.Can also use forcing machine or Banbury coal mixer to carry out segmentation, batch mixing.

In addition, after mixing, can also carry out granulating by forcing machine with Banbury, stirrer etc.

Thermoplastic resin composition of the present invention can make the moulding product by known forming methods such as injection molding, extrusion forming, thin slice extrusion moulding, vacuum forming, special-shaped extrusion moulding, foamings.Various moulding product by above-mentioned forming method obtains utilize its excellent character, can be used for various parts and shell, the groceries etc. of various shells, electric and electronic field or the automotive field of household appliances.

[embodiment]

Below, by way of example, the present invention will be described in detail, and the present invention is not subjected to any restriction of following examples.In addition, among the embodiment, portion and % are meant quality criteria when not specifying.

1. evaluation method

The various evaluation methods of using in the present embodiment are as follows.

(1) median size of rubber polymer

The rubber polymer particulate median size of using in the formation of rubber-reinforced resin [A] obtains by the discrete particles in the light scattering determining latex." LPA-3100 type " (trade(brand)name) that metering equipment Shi Yong Da mound electronics society produces used accumulative accumulation 70 times.In addition, the particle diameter of the discrete particles in the rubber-reinforced resin [A] is confirmed by electron microscope, and is basic identical with the particle diameter of latex.

(2) percentage of grafting of rubber-reinforced resin [A] and [D]

As implied above.

(3) limiting viscosity [η] of the solvable composition of acetone of rubber-reinforced resin [A] and [D]

As implied above.

(5) viscosity-average molecular weight of polycarbonate [E]

As implied above.

(6) anti-charging property

Make diameter 100mm, the plectane of thick 2mm is under 50% the condition 23 ℃ and relative temperature, carry out 7 days status adjustment after, use the 4329A type superinsulation ohmer that Yokogawa ヒ ユ-レ Star ト パ Star カ-De society produces, measure surperficial intrinsic resistance.

(7) sliding (kinetic friction coefficient)

Use Suzuki formula sliding test machine (ring type on the ring, ring on ring), use steel (S45C) as respective material.Test film uses external diameter to be 25.4mm, and internal diameter is the extrusion molding product of the hollow cylindrical of 20.0mm, and respective material is also used same shape.Kinetic friction coefficient be determined at 23 ℃ of room temperatures, temperature is under the atmosphere of 50%RH, is 0.5kgf with the load, circumferential speed is 500mm/s, miles of relative movement is that the condition of 10km is carried out.Kinetic friction coefficient calculates according to following formula.

μ＝[3×F×R×(r ₂ ²-r ₁ ²)]/[P×(r ₂ ³-r ₁ ³)]…(3)

(in the formula, μ is a kinetic friction coefficient, and F is the power that is added on the load cell, and P is load, and R is long for the wall to load cell, r ₁The expression internal diameter, r ₂The expression external diameter.)

(8) flame retardant resistance of moulding product

By the method for formulating in the UL94 standard, be 5 to length ", wide is 13mm, thick is 1/16 " test film carry out testing vertical flammability.

(9) formability

The surface of the injection molding test film of visual observation is judged by following standard.

Zero: do not peel off, have uniform outward appearance,

*: find to peel off and weld seam, present pearliness.

(10) shock resistance

Measure (1/4 foot has recess) based on ASTM D256, judge by following standard.

Zero: 7KJ/m ²Or more than,

*: not enough 7KJ/m ²

2. composition [A] (rubber-reinforced resin)

Preparation example 1 (preparation of rubber-reinforced copolymer resin A-1-a)

Under stream of nitrogen gas, internal volume to the dress stirrer is in 7 liters the glass flask, add 75 parts of ion exchanged waters, 0.5 part of resinous acid potassium, 0.1 part of t-dodecyl mercaptans, 40 parts of polyhutadiene latex (median sizes: 3500 , gel content ratio: 85%) (solids component), 15 parts of vinylbenzene, 5 parts of vinyl cyanide, stir, heat up simultaneously.When internal temperature reached 45 ℃, adding was dissolved in 0.2 part of trisodium phosphate of 20 parts of ion exchanged waters, 0.01 part of ferrous sulfate 7 hydrate and 0.2 part of glucose solution.Afterwards, add 0.07 part of cumene hydroperoxide, the beginning polymerization, after the polymerization 1 hour, added 50 parts of ion exchanged waters, 0.7 part of resinous acid potassium, 30 parts of vinylbenzene, 10 parts of vinyl cyanide, 0.05 part of t-dodecyl mercaptans and 0.01 part of cumene hydroperoxide more continuously through 3 hours, repolymerization 1 hour adds 0.2 part 2, and 2 '-methylene radical-two (4-ethylidene-6-tert.-butyl phenol) finishes polyreaction.The emulsion of reaction product is condensed in aqueous sulfuric acid, after the washing, obtain the rubber-reinforced Resin A-1-a of exsiccant.The percentage of grafting of this rubber-reinforced copolymer resin A-1-a is 72%, and the limiting viscosity of the solvable composition of acetone [η] is 0.47dl/g.

Preparation example 2 (preparation of rubber-reinforced copolymer resin A-1-b)

With 50 parts (converting) by frozen composition by 99 parts of n-butyl acrylates and the 1 part of resulting acrylic rubber matter of aryl methacrylate emulsion polymerization polymer emulsion (median size: 1200 , gel content 85%), 200 parts of water (total amount), 1 part of Sodium dodecylbenzene sulfonate add in the reactor, stir, under stream of nitrogen gas, be warming up to 60 ℃ simultaneously.When reaching 60 ℃, in reactor, add the aqueous solution that is dissolved with 0.2 part of formaldehyde sodium sulfoxylate, liquid is held in the mixing that added 38 parts of vinylbenzene, 12 parts of vinyl cyanide and 0.6 part of tertbutyl peroxide through 3 hours continuously afterwards, carries out polymerization, obtains the emulsion of rubber-reinforced copolymer resin A-1-b.This moment, polymerisation conversion was 96%.Use calcium chloride this rubber-reinforced copolymer resin A-1-b emulsion of condensing, cleaning, drying then obtain pulverous rubber-reinforced copolymer resin A-1-b.Percentage of grafting is 55%.

Preparation example 3 (preparation of co-polymer A-2)

Connect 2 internal volumes and be 30 liters the strap clamp cover polymerization reactor that banded oar is housed, after the nitrogen ventilation, in the 1st reaction vessel, add 75 parts of vinylbenzene, 25 parts of vinyl cyanide, 20 parts of toluene continuously.Supply with continuously as the solvent of 0.1 part of t-lauryl mercaptan of molecular weight regulator and 5 parts of toluene with as 0.1 part 1 of polymerization starter, the solution of 1 '-azo two (cyclohexyl-1-nitrile) and 5 parts of toluene.Polymerization temperature in the 1st container is controlled to be 110 ℃, and mean residence time is 2.0 hours, and polymerisation conversion is 60%.The polymers soln that obtains by being contained in the pump of the 1st reaction vessel outside, to take out continuously with the same amount of vinylbenzene, vinyl cyanide, toluene, molecular weight regulator, the polymerization starter supplied with, is fed in the 2nd reaction vessel.The polymerization temperature of the 2nd reaction vessel is 130 ℃, and mean residence time is 2.0 hours, and polymerisation conversion is 80%.The copolymer solution that obtains in the 2nd reaction vessel uses the 23 sections forcing machines (3 sections ベ Application of 2 Shaft ト pay I Ya Chu Machine) of taking the hole out of, directly sloughs unreacted monomer and solvent, obtains co-polymer A-2.The limiting viscosity of the solvable composition of acetone [η] is 0.48dl/g.

Preparation example 4 (preparation of rubber-reinforced resin [A])

With above-mentioned rubber-reinforced copolymer resin (A-1-a) and (A-1-b) and co-polymer (A-2) press the mixed shown in the table 1, obtain rubber-reinforced resin [A].

3. composition [B] (static inhibitor)

B-1: alkylsulfonate

The use average carbon atom number is 14 straight chain saturated alkyl sulfonate sodium (trade(brand)name " エ レ Network ト ロ ス ト Star パ-PC-3 ", flower king (strain) produces).

B-2: glyceryl monostearate

Used commodity are called " リ ケ マ-Le S-100 ", and reason is ground PVC ミ Application (strain) and produced.

4. composition [C] (low-molecular-weight polyolefin)

C-1: the use molecular weight is 6000 unmodified polyethylene wax (trade(brand)name " サ Application ワ Star Network ス 171-P ", Sanyo changes into industry (strain) and produces).

C-2: the use molecular weight is 900 poly-combustion chloroflo (trade(brand)name " Mitsui Ha イ ワ Star Network ス 100P ", Mitsui petrochemical industry (strain) is produced).

C-3: use the High molecular weight polyethylene that melt flow (MFR) divides as 22g/10 (trade(brand)name " ノ バ テ Star Network LJ803 ", Japanese polyethylene society produces).

C-4: the use molecular weight is 15000 Poly Propylene Wax (trade(brand)name: " PVC ス コ-Le 550-P ", Sanyo change into industry (strain) and produce).

5. composition [D] (olefin polymer of modification)

(5-1.D-1 AES resin)

In the volume that is equipped with banded stirring rake, the continuous adding set of auxiliary agent, thermometer etc. is 20 liters stainless steel autoclave, add 20 parts of ethylene, propylene acids rubber polymers (ethylene/propene=78/22 (%), mooney viscosity (ML ₁₊₄, 100 ℃) be 20 ethylene-propylene analog copolymer), 56 parts of vinylbenzene, 24 parts of vinyl cyanide, 110 parts of toluene, internal temperature is risen to 75 ℃, the content of agitated autoclave 1 hour makes it to become homogeneous solution.Afterwards, add 0.45 part of BPIC (t butyl peroxy isopropyl carbonate), the internal temperature that further raises, reach 100 ℃ after, keep this temperature, simultaneously the mixing speed with 100rpm carries out polyreaction.Began the back the 4th hour from polyreaction, internal temperature is risen to 120 ℃, keep this temperature, further reaction finished reaction in 2 hours simultaneously.The percentage of grafting of the AES resin that obtains is 55%.

After internal temperature is cooled to 100 ℃; add 0.2 part of octadecyl-3-(3; 5-two-tertiary butyl-4-hydroxy phenol)-propionic ester; then reaction mixture is taken out from autoclave, the distillation of unreacted reactant and solvent is removed, in having the forcing machine that 40mm Ф portals by wet distillation; regulating temperature cylinder is 220 ℃; vacuum tightness is 770mmHg, sloughs volatile component basically, with the AES resin particleization.

5-2.?D-2

Employing adds to styrene acrylonitrile copolymer (AS) resulting co-polymer on the main chain of low molecular weight polyethylene (LDEP), and (trade(brand)name " モ デ イ パ-A1401 ", Japanese grease (strain) produces, LDEP/AS=50/50).

5-3.?D-3

Employing adds to styrene acrylonitrile copolymer (AS) resulting co-polymer on the main chain of low-molecular-weight polypropylene (PP), and (trade(brand)name " モ デ イ パ-A3400 ", Japanese grease (strain) produces, PP/AS=70/30).

5-4. D-4 (graft copolymer of diolefinic polymer hydrogen affixture)

5-4-1. the preparation of composition (d-3) (styrene-butadiene block copolymer of hydrogen addition fully)

With stirrer and the autoclave drying that has chuck,, drop into the cyclohexane solution that contains 20 parts of divinyl with the nitrogen ventilation.Then, add 0.025 part of n-Butyl Lithium, under 50 ℃, carry out the constant temperature polymerization.Transformation efficiency reaches at 100% o'clock, adds 0.75 part of tetrahydrofuran (THF), 65 parts of divinyl, is warming up to 80 ℃ from 50 ℃ and carries out polymerization.Transformation efficiency reaches at 100% o'clock, adds 15 parts of vinylbenzene, carries out polyreaction again, obtains hydrogen addition A-B1-B2 triblock copolymer before.The content ratio of the styrene block of this A-B1-B2 triblock copolymer (A) is 15%, and the content ratio of butadiene block (B1) is 65%, and the content ratio of butadiene block (B2) is 20%.In addition, 1 in the B1 block, 2-alkene content is 35%, 1 in the B2 block, 2-alkene content is 10%.The number-average molecular weight of A-B1-B2 triblock copolymer is 200000.

The hydrogen addition of A-B1-B2 triblock copolymer is undertaken by following step.That is, in other container, 1 part of titanocene dichloride is dispersed in the hexanaphthene, at room temperature, itself and 0.5 part of triethyl aluminum is reacted.The homogeneous solution that obtains is added in the above-mentioned A-B1-B2 triblock copolymer solution, at 50 ℃, 50kgf/cm ²Hydrogen-pressure under, carry out 2 hours hydrogenation.Add 2, behind 6-two-tert-butyl catechol, remove and desolvate, obtain the hydrogen markup percentage and be approximately 100% hydrogen affixture (d-3).In addition, vinylbenzene key amount, ethylenic linkage amount, number-average molecular weight and hydrogen markup percentage are measured as follows.

Vinylbenzene key amount:

Polymkeric substance before the hydrogen addition is measured.By infrared method, based on 699cm ^-1Phenyl absorb the drawing standard curve, try to achieve vinylbenzene key amount by this typical curve.

Number-average molecular weight:

Polymkeric substance before the hydrogen addition is measured.(GPC) tries to achieve by gel permeation chromatography.

The ethylenic linkage amount:

Polymkeric substance before the hydrogen addition is measured.Try to achieve by infrared method (モ レ ロ method).

The hydrogen markup percentage

Polymkeric substance after the hydrogen addition is measured.With zellon as solvent, under 15% concentration, the 100MHz's that records ¹H-NMR spectrum is calculated by unsaturated double-bond compound spectrum reduction.

5-4-2. the preparation of graft copolymer (D-4)

With nitrogen to be equipped with banded stirring rake, volume is after 10 liters stainless steel autoclave is taken a breath, under stream of nitrogen gas, add in advance with toluene as the uniform 28 parts of above-mentioned hydrogen affixtures of solvent (d-3), 7 parts of vinylbenzene, 10 parts of vinyl cyanide, 55 parts of methyl methacrylates, 120 parts of toluene and 0.1 part of uncle-lauryl mercaptan, when stirring, heat up.When internal temperature reaches 50 ℃, add 0.5 part of benzoyl peroxide, 0.1 part of dicumyl peroxide, further heat up, reach 80 ℃ after, control stabilization is carried out polyreaction simultaneously at 80 ℃.Began the back the 6th hour from reaction, must be warming up to 120 ℃, further react and finish reaction after 2 hours through 1 hour.Transformation efficiency is 97%.

After being cooled to 100 ℃, add 0.2 part 2,2-methylene radical-two-4-methyl-6-tert butyl phenol takes out reaction mixture then from autoclave, by wet distillation unreacted reactant and solvent distillation is removed, and makes the polymer particles granulation simultaneously, obtains polymkeric substance D-4.The percentage of grafting of this polymkeric substance is 45%, and the limiting viscosity of the solvable composition of acetone [η] is 0.45dl/g.

6. composition [E] (polycarbonate resin E-1)

The use viscosity-average molecular weight is 22000 aromatic copolycarbonate (trade(brand)name " ノ バ レ Star Network ス 7022PJ ", the エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ Star Network ス society produces).

7. composition [F] (fire retardant)

F-1: phosphorus type flame retardant

Use 1,3-phenylene-two (two xylyl phosphoric acid ester) (trade(brand)name " PX-200 ", big eight chemical industry produce).

F-2: bromo epoxy oligomer

Used commodity are called " プ ラ サ-system EPC-15F " (big Japanese ink chemical industry produces).

8. embodiment 1-15 and comparative example 1-10

Use mentioned component [A]-[F], press the blending ratio shown in the table 1, after mixing by Henschel mixer, with biaxial extruder (the machine barrel design temperature is 280 ℃) mixing, granulating.Use the removal moisture drying device, be dried to moisture and be 0.02% or below, will estimate the test film machine-shaping that various physical propertiess are used by injection molding (design temperature is 260 ℃).And, use the test film that obtains, estimate as stated above.With flame retardant resistance embodiment 2-5 and comparative example 4-5 are estimated.Above evaluation result is listed in the table 1.

Table 1

		Blending ratio														Evaluation result
																					The rubber-reinforced resin of composition (A)				Composition (B) static inhibitor		Composition (C) low molecular weight olefins		Composition (D) modified olefin base polymer		Composition (E) aromatic polycarbonate resin		Composition (F) fire retardant		Surface intrinsic resistance (Ω)	Sliding	Flame retardant resistance	Formability	Shock-resistance
		Kind	Part	Kind	Part	Kind	Part	Kind	Part	Kind	Part	Kind	Part	Kind	Part
																Embodiment	??1	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????1	??D-1	????6	????-	??-	????-	????-	??1×10 11	????○	????-						????○	??○
??2	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????1	??D-1	????6	????-	??-	????F-1	????12	??1×10 11																				????○	????V-2	????○	??○
																	??3	A-1-a	?30	????A-2	????70	????B-1	????2	????C-1	????3	??D-1	????6	????-	??-	????F-1	????12	??1×10 10	????○	????V-2					????○	??○
??4	A-1-a	?30	????A-2	????70	????B-1	????2	????C-1	????1	??D-1	????12	????-	??-	????F-1	????7	??1×10 10																				????○	????V-2	????○	??○
																	??5	A-1-a	?30	????A-2	????70	????B-1	????2	????C-1	????2	??D-1	????12	????E-1	??20	????F-1	????8	??1×10 12	????○	????V-2					????○	??○
??6	A-1-a	?30	????A-2	????70	????B-1	????1	????C-2	????1	??D-1	????6	????-	??-	????-	????-	??1×10 11																				????○	????-	????○	??○
																	??7	A-1-a	?30	????A-2	????70	????B-1	????1	????C-4	????1	??D-1	????6	????-	??-	????-	????-	??1×10 12	????○	????-					????○	??○
??8	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????1	??D-2	????6	????-	??-	????-	????-	??1×10 12																				????○	????-	????○	??○
																	??9	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????1	??D-3	????6	????-	??-	????-	????-	??1×10 12	????○	????-					????○	??○
??10	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????1	??D-4	????6	????-	??-	????-	????-	??1×10 12																				????○	????-	????○	??○
																	??11	A-1-a	?30	????A-2	????70	????B-1	????8	????C-1	????1	??D-1	????6	????-	??-	????-	????-	??1×10 20	????○	????-					????○	??○
??12	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????8	??D-1	????6	????-	??-	????-	????-	??1×10 11																				????○	????-	????○	??○
																	??13	A-1-b	?24	????A-2	????76	????B-1	????1	????C-1	????1	??D-1	????6	????-	??-	????-	????-	??1×10 11	????○	????-					????○	??○
??14	A-1-b	?24	????A-2	????76	????B-1	????1	????C-1	????1	??D-2	????6	????-	??-	????-	????-	??1×10 11																				????○	????-	????○	??○
																	??15	A-1-a A-1-b	?12 ?15	????A-2	????73	????B-1	????1	????C-1	????1	??D-1	????6	????-	??-	????-	????-	??1×10 11	????○	????-					????○	??○
Comparative example	??1	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????1	??D-1	????0	????-	??-	????-	????-																				??1×10 14		????-	????○			??○
																??2	A-1-a	?30	????A-2	????70	????B-1	????0.1	????C-1	????3	??D-1	????6	????-	??-	????-	????-	??1×10 15	????○	????-	????○					??○
	??3	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????0	??D-1	????6	????-	??-	????-	????-																				??1×10 15		????-	????○		??○
																??4	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????0	??D-1	????6	????-	??-	????F-1	????12	??1×10 15		????V-2	????○					??○
	??5	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????0	??D-1	????6	????E-1	??20	????F-1	????12																				??1×10 15		????V-2	????○		??○
																??6	A-1-a	?30	????A-2	????70	????B-2	????2	????C-1	????2	??D-1	????6	????-	??-	????-	????-	??1×10 14		????-	????○					??○
	??7	A-1-a	?30	????A-2	????70	????B-1	????22	????C-1	????2	??D-1	????6	????-	??-	????-	????-																				??1×10 12		????-
																??8	A-1-a	?30	????A-2	????70	????B-1	????1	????C-3	????2	??D-1	????6	????-	??-	????-	????-	??1×10 15		????-						??○
	??9	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????12	??D-1	????6	????-	??-	????-	????-																				??1×10 13	????○	????-
																??10	A-1-a	?30	????A-2	????70	????B-1	????1	????C-1	????2	??D-1	????22	????-	??-	????-	????-	??1×10 14	????○	????-	????○					??○

9. the effect of embodiment

As shown in table 1, comparative example 1 is the scope of the invention example in addition that does not contain composition [D], and its anti-charging property and sliding are relatively poor.Comparative example 2 is the less scope of the invention examples in addition that drop on of composition [B] content, and its anti-charging property is relatively poor.Comparative example 3-5 is the scope of the invention example in addition that does not contain composition [C], and its anti-charging property and sliding are relatively poor.In addition, comparative example 6 is to use glyceryl monostearate to replace the scope of the invention example in addition of composition [B], and its anti-charging property and sliding are relatively poor.Comparative example 7 is examples that the content of composition [B] is Duoed than the scope of the invention, and its sliding, formability and shock-resistance are relatively poor.Comparative example 8 is high examples of the molecular weight ratio scope of the invention of composition [C], and its anti-charging property, sliding and formability are relatively poor.Comparative example 9 is the addition of composition [C] examples higher than the scope of the invention, and its formability and shock-resistance are relatively poor.Comparative example 10 is the addition of composition [D] examples higher than the scope of the invention, and its anti-charging property is relatively poor.

On the other hand, as shown in table 1, embodiment 1-15 is the example in the scope of the invention of dropping on of the composition [A] that contains the regulation ratio, [B], [C] and [D], and having reached surperficial intrinsic resistance is 1 * 10 ¹³(Ω) or following fabulous anti-charging property, simultaneously, obtained good sliding, though contain composition [E] and/or [F], also obtain same result.

According to the present invention, a kind of styrene resin is provided, owing to be mixed with in the specific styrene resin that low-molecular-weight polyolefin forms at this, be mixed with alkylsulfonate as the specified amount of static inhibitor, be mixed with the modified polyolefin base polymer of specified amount simultaneously, so its anti-charging property and sliding are very excellent, and formability and shock-resistance are also very excellent.At the high styrene resin of the thermotolerance that is mixed with aromatic copolycarbonate be mixed with in the high styrene resin of the flame retardant resistance of fire retardant, also reached same effect.Because anti-static thermoplastic resin composition of the present invention can machine-shaping be the various moulding product that use in field of household appliances, electric electronic applications, automotive field and the groceries field etc., is useful therefore.

Claims (9)

1. anti-static thermoplastic resin composition, it is characterized in that, this anti-static thermoplastic resin composition contains following compositions [A]-[D], composition [A] with respect to 100 mass parts, be mixed with the composition [B] of 0.2-20 mass parts, 0.1-10 the composition of mass parts [C], and the composition of 0.1-20 mass parts [D]

Composition [A] is in the presence of by the rubber polymer (a) of butadiene type rubber polymer and/or acrylic rubber matter polymer formation, the rubber-reinforced copolymer resin (A-1) that obtains by the vinyl monomer that contains aromatic ethylene compound and acrylonitrile compound (b-1) polymerization, or by the mixture formation of this rubber-reinforced copolymer resin (A-1) with vinyl monomer (being total to) polymkeric substance (A-2), and the content of above-mentioned rubber polymer (a) is 3-40 quality %.

Composition [B] is an alkylsulfonate,

Composition [C] is that weight average molecular weight is the low-molecular-weight polyolefin of 500-40000,

Composition [D] is olefin polymer (d) and vinyl monomer (b-2) (being total to) mixture of polymers that contains aromatic ethylene compound.

2. the described anti-static thermoplastic resin composition of claim 1 is characterized in that, composition [D] is in the presence of olefin polymer (d), with the resulting material of vinyl monomer (b-2) polymerization.

3, the described anti-static thermoplastic resin composition of claim 1 is characterized in that, composition [D] is with olefin polymer (d) and the resulting material of vinyl monomer (b-2) (being total to) mixed with polymers.

4. claim 2 or 3 described anti-static thermoplastic resin compositions is characterized in that, the olefin polymer (d) of composition [D] is selected from following compositions (d-1), at least a in (d-2) and (d-3),

(d-1): olefin resin,

(d-2): ethene-alpha-olefin class rubber polymer,

(d-3): the hydrogen affixture of diolefinic polymer.

5. the described anti-static thermoplastic resin composition of claim 2 is characterized in that, the olefin polymer (d) of composition [D] is the hydrogen affixture (d-3) of ethene-alpha-olefin class rubber polymer (d-2) and/or diolefinic polymer.

6. the described anti-static thermoplastic resin composition of claim 3 is characterized in that, the olefin polymer (d) of composition [D] is olefin resin (d-1).

7. the described anti-static thermoplastic resin composition of claim 1 is characterized in that, with respect to the composition [A] of 100 mass parts, further contains 1-30 mass parts aromatic copolycarbonate as composition [E].

8, claim 1 or 7 described anti-static thermoplastic resin compositions is characterized in that, with respect to the composition [A] of 100 mass parts, further contain 1-30 mass parts fire retardant as composition [F].

9. moulding product is characterized in that using that each described anti-static thermoplastic resin composition makes among the claim 1-8.