CN1984957A - Thermoplastic resin composition - Google Patents

Abstract

The present invention is a thermoplastic resin composition which is obtained by adding a specific modified vinyl copolymer having a specific intrinsic viscosity to a composition comprising a styrene -based resin and a polyamide resin. The thermoplastic resin composition has excellent flowability and has a far better surface appearance than conventional ones while satisfactorily retaining rigidity, heat resistance, chemical resistance, and impact resistance at room and low temperatures.

Description

The thermoplastic resin composition

Technical field

The present invention relates to a kind of thermoplastic resin composition that specific ethene improved based copolymer forms that in phenylethylene resin series and polyamide resin, adds.

Background technology

Phenylethylene resin series is owing to the feature that has high rigidity and outward appearance is good, dimensional stability is good, water-absorbent is low, so be widely used as the interchangeable heat plastic resin.But the chemical resistant properties of phenylethylene resin series, wear resistant and thermotolerance are insufficient, and the use under severe condition is restricted.In addition, for crystalline thermoplastic resin combination, particularly polyamide resin, because of its chemical resistant properties, wear resistant and excellent heat resistance, thus be widely used as engineering plastics, but its water-absorbent height, rigidity and dimensional stability are insufficient.

Therefore,, the resin combination of the advantage separately that has phenylethylene resin series and polyamide resin concurrently is studied all the time, for example, proposed as the ABS resin of representational phenylethylene resin series and the blend composition of polyamide resin.But, under the situation of the simple adulterant of ABS resin and polyamide resin, have both consistencies poor, the also significantly reduced problem of mechanical properties.

Therefore, method as the consistency that improves ABS resin and polyamide resin, studied to have and the monomer-grafted copolymerization of functional group of affinity has been arranged on rubbery polymer with polyamide resin, and with the method for itself and polyamide resin fusion, as a kind of method wherein, proposed the blend composition of graft copolymer and polyamide resin, described graft copolymer is with α, and the beta-unsaturated carboxylic acid acid anhydride is combined in other monomer graft copolymerizations and forms on the rubbery polymer.But,, the problem of appearance, flowability and thermostability deficiency etc. is arranged for the resin combination that obtains like this.

In addition, also proposed the blend composition of following graft copolymer and polyamide resin, described graft copolymer is combined in the unsaturated carboxylic acid acid amides on the rubbery polymer with other polymkeric substance graft copolymerizations and forms.But the shock-resistance of this resin combination is insufficient, in addition existing problems aspect the mechanical characteristics when appearance and suction.

Therefore, the improvement of the mechanical characteristics during with suction is as purpose, a kind of resin combination has been proposed, it uses by aromatic vinyl system and α, the multipolymer that the beta-unsaturated carboxylic acid acid anhydride forms is as the compatilizer of phenylethylene resin series and polyamide resin, thereby contain this three kinds of compositions (for example, referring to Patent Document 1).But, for this resin combination, when the case member periphery material that is considered as automobile inside/outside decorative material or electric/electronic apparatus is expanded the purposes of this resin combination, insufficient as shock-resistance, flowability and appearance under the low temperature of the characteristic of its requirement.

To improve shock-resistance is purpose, a kind of resin combination has for example been proposed, it is in phenylethylene resin series and polyamide resin, added by aromatic vinyl system and α, beta-unsaturated carboxylic acid and/or α, (for example, the referring to Patent Document 2) that the low-molecular-weight multipolymer that the beta-unsaturated carboxylic acid acid anhydride forms forms.But, be monomeric this resin combination in above-mentioned multipolymer, not containing vinyl cyanide, shock-resistance and appearance under its low temperature are insufficient.

In addition, a kind of resin combination has been proposed, it is about styrene-acrylonitrile-copolymer-maleic anhydride of 40,000～about 200,000 by add the maleic anhydride, the weight-average molecular weight that contain 0.3～1.5 mole of % in ABS resin and polyamide resin, make shock-resistance further improve (for example, referring to Patent Document 3).But, owing to added the styrene-acrylonitrile-copolymer-maleic anhydride of this molecular weight ranges, thereby cause obtaining the abundant equilibrated resin combination of shock-resistance, flowability and appearance under the low temperature.

In addition, in order to improve the shock-resistance under the low temperature, a kind of resin combination is proposed, it is the styrene-acrylonitrile-copolymer-maleic anhydride of 160,000～230,000 scopes by add weight-average molecular weight in ABS resin and polyamide resin, make shock-resistance further improve (for example, referring to Patent Document 4).But, for this resin combination, because added the styrene-acrylonitrile-copolymer-maleic anhydride of this molecular weight ranges, thus for such use, flowability and appearance, especially surface gloss is insufficient.

With the resin combination that obtains shock-resistance and mobile balance excellence is purpose, a kind of resin combination has been proposed, it has used by cooperation and has contained the α with specific reduced viscosity, the multipolymer of beta-unsaturated carboxylic acid, styrene-acrylonitrile-Sipacril 2739OF for example, and make the small-particle rubber of specified particle diameter assemble the gathering enlarged rubber (for example, referring to Patent Document 5) that forms.But though the flowability of this resin combination improves, shock-resistance and appearance, especially surface gloss still are inadequate level for such use.

Disclose a kind of resin combination, it is to have added polyamide resin and contain α, (for example, the referring to Patent Document 6) that beta-unsaturated carboxylic acid or α, the multipolymer of beta-unsaturated carboxylic acid acid anhydride form in containing the phenylethylene resin series of rubber.But, because the purpose of this invention is to obtain the excellent resin combination of the transparency, so it is that amount of monomer is controlled as amount seldom that rubber strengthens the aromatic vinyl that contains in the phenylethylene resin series, the poor impact resistance of the resin combination of this invention under normal temperature, low temperature.

Patent documentation 1: the spy opens clear 60-195157 communique

Patent documentation 2: european patent application discloses specification sheets No. 0068132

Patent documentation 3: No. 4713415 specification sheets of United States Patent (USP)

Patent documentation 4: No. 5756576 specification sheets of United States Patent (USP)

Patent documentation 5: the spy opens the 2000-17170 communique

Patent documentation 6: the spy opens the 2004-300354 communique

Summary of the invention

Problem of the present invention is, when obtaining the resin combination that forms by phenylethylene resin series and polyamide resin, a kind of thermoplastic resin composition is provided, it can keep rigidity, thermotolerance, chemical resistant properties and the shock-resistance under normal temperature, low temperature well, mobile simultaneously excellent, and then have more excellent appearance, especially surface gloss with comparing at present.

Present inventors are in order to solve above-mentioned problem, further investigate, found that by by containing in the composition that phenylethylene resin series that specific ethene system (being total to) polymkeric substance forms and polyamide resin form, add and compared with prior art to have lower molecular weight scope more, contain α, beta-unsaturated carboxylic acid acid anhydride unit and vinyl cyanide are the ethene improved based copolymer of monomeric unit, can solve described problem, can access a kind of thermoplastic resin composition, it can keep rigidity well, thermotolerance, chemical resistant properties and at normal temperature, shock-resistance under the low temperature, simultaneously mobile excellent, and then have more excellent appearance with comparing at present.

Promptly, the present invention is a kind of thermoplastic resin composition, it is characterized in that, be the thermoplastic resin composition who forms by 1～99 weight % phenylethylene resin series (A) and 99～1 weight % polyamide resins (B) with respect to 100 weight parts, and then the thermoplastic resin composition that forms of the ethene improved based copolymer (C) that contains 0.5～80 weight part, described phenylethylene resin series (A) cooperates grafting (being total to) polymkeric substance (A-1) and ethene system (being total to) polymkeric substance (A-2) to form, described grafting (being total to) polymkeric substance (A-1) is that graft polymerization is that the monomeric unit that other at least a kind of monomer of monomer and 0～60 weight % form forms by the aromatic vinyl of 100～40 weight % on rubber polymer, described ethene system (being total to) polymkeric substance (A-2) is that other at least a kind of monomer of monomer and 0～50 weight % form by the aromatic vinyl of 100～50 weight %, described ethene improved based copolymer (C) is the α that contains 1.5～10 weight %, the vinyl cyanide of beta-unsaturated carboxylic acid acid anhydride unit and 0.5～60 weight % is that monomeric unit forms

And ethene improved based copolymer (C) dissolves the back in the scope of the limiting viscosity of measuring under 30 ℃ the temperature at 0.15～0.41dl/g in the methylethyl ketone solvent.

According to the present invention, can obtain a kind of thermoplastic resin polymer, it can keep rigidity, thermotolerance, chemical resistant properties and the shock-resistance under normal temperature, low temperature, and is simultaneously mobile excellent, and has more excellent appearance with comparing at present.The thermoplastic resin composition of the application of the invention, can obtain having the thin formed body of good appearance, large-scale formed body, complicated shape formed body, therefore thermoplastic resin composition of the present invention is useful as the case member periphery material of automobile inside/outside decorative material purposes or electric/electronic apparatus.

Description of drawings

[Fig. 1] is the general view of 1/4 oval anchor clamps of use in the chemical resistant properties test.

[Fig. 2] is the mode chart that is presented at an example of the preferred phase structure that thermoplastic resin composition's of the present invention formed body central part forms.

The explanation of symbol

1 test film

21/4 oval anchor clamps

The major axis of a anchor clamps

The minor axis of b anchor clamps

The thickness of t test film

The length of the length direction of X crack origination point

3 polyamide resins (B) form the part of external phase

4 ethene system (being total to) polymkeric substance (A-2) form the part of disperse phase

5 grafting (being total to) polymkeric substance (A-1) form the part of disperse phase

Embodiment

Below, the best mode that is used to implement thermoplastic resin composition of the present invention is described.

The phenylethylene resin series that uses among the present invention (A) cooperates grafting (being total to) polymkeric substance (A-1) and ethene system (being total to) polymkeric substance (A-2) to form.

Grafting of the present invention (being total to) polymkeric substance (A-1) is that graft polymerization is that the monomeric unit that other at least a kind of monomer of monomer and 0～60 weight % form forms by the aromatic vinyl of 100～40 weight % on rubber polymer, that is be to be monomer or to contain aromatic vinyl be more than the monomer 40 weight % and at least a kind of monomeric monomer mixture except that aromatic vinyl is monomer forms, at graft polymerization aromatic vinyl on the rubber polymer.

Object lesson as grafting (being total to) polymkeric substance (A-1), can enumerate impact resistant polystyrene, with the aromatic vinyl that contains more than the 40 weight % is that monomer is the graft copolymer of feature, for example ABS, AAS (vinyl cyanide-acrylic rubber-styrol copolymer), AES (vinyl cyanide-ethylene-propylene rubber-styrene-alkene copolymer) and MBS (methyl methacrylate butadiene rubber-styrol copolymer) etc.

As the rubber polymer that constitutes grafting (being total to) polymkeric substance (A-1), the preferred glass transition temperature is the polymkeric substance below 0 ℃.Particularly, can list, polyhutadiene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, the diene series rubber of the diolefin series segmented copolymer that the segmented copolymer of styrene butadiene is such and butyl acrylate-butadienecopolymer etc., butyl polyacrylate, the acrylic rubber of alkyl acrylate-vinylformic acid allyl ester etc., polyisoprene, ethylene-propylene-diolefin series terpolymer, the ethene-alpha-olefin of ethylene-propylene copolymer and ethylene-propylene-(non-conjugated diene) multipolymer etc. is a copolymerization rubber, the silicon rubber of poly organo methane series rubber polymer latex etc., the hydride of butadiene-based polymkeric substance, hydrorubber of the hydride of the segmented copolymer of conjugated diolefin polymer block and aromatic vinyl based compound polymer blocks and segmented copolymer that they have been made up etc. etc., wherein, the preferred diene series rubber that uses, ethylene-propylene-(non-conjugated diene) multipolymer, hydrogenated diene polymer, silicon rubber or acrylic rubber, preferred especially polyhutadiene or butadienecopolymer.These polymkeric substance can be used alone, or with a combination of two or more.As the non-conjugated diene composition, can preferably use 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl norbornene and dicyclopentadiene etc.

There is no particular limitation to the rubber size of described rubber polymer, but the weight average particle diameter of preferred rubber particle be 0.05～0.7 μ m, in particular for 0.10～0.55 μ m, because shock-resistance excellence like this.In addition, with 90: 10～60: 40 weight ratios and to have used weight average particle diameter be that rubber and the weight average particle diameter of 0.20～0.25 μ m is the rubber polymer of the rubber of 0.50～0.65 μ m, because its shock-resistance and the drop impact that carries out with thin moulding product are significantly excellent, so preferred use.In addition, as rubber polymer, also can use and assemble the loose polymkeric substance of having changed.

In addition, the weight average particle diameter of rubber particles can be measured by the sodiun alginate method of " Rubber Age Vol.88 is (1960) by E.Schmidt p.484～490; P.H.Biddison " record, promptly, utilize sodiun alginate concentration difference and make the polyhutadiene particle diameter difference of emulsifiable pasteization, according to the emulsifiable paste change part by weight and the accumulating weight of sodiun alginate concentration divide rate, obtain accumulating weight branch rate and be the method for 50% particle diameter.

The aromatic vinyl that uses as the monomeric unit of graft polymerization in grafting (being total to) polymkeric substance (A-1) is a monomer, can list, vinylbenzene, alpha-methyl styrene, Vinyl toluene, adjacent ethyl styrene, to t-butyl styrene, p-methylstyrene, chloro-styrene, with bromstyrol etc., special optimization styrene, these monomers can use separately, also can use more than 2 kinds.

To improve chemical resistant properties is purpose, other monomers of at least a kind that in grafting (being total to) polymkeric substance (A-1), use as the monomeric unit of graft polymerization, and especially preferably using vinyl cyanide is monomer.As vinyl cyanide is monomer, can enumerate vinyl cyanide, methacrylonitrile and ethyl acrylonitrile etc., preferred especially vinyl cyanide.In addition, also preferably use (methyl) acrylic ester monomer.As (methyl) acrylic ester monomer, can enumerate carboxylate that vinylformic acid and methacrylic acid form by methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., special preferable methyl methyl acrylate.In addition; as the monomer beyond them; also can use unsaturated carboxylic acid monomer unit and these monomeric metal-salts of (methyl) vinylformic acid etc.; (methyl) glycidyl acrylate; glycidyl itoconate; glycidyl allyl ether; vinylbenzene-to glycidyl ether; to glycidyl vinylbenzene; toxilic acid; maleic anhydride; monomethyl maleate; ethyl maleate; methylene-succinic acid; itaconic anhydride; fumaric acid; 1, the 2-dimethyl maleic anhydride; the phenyl maleic anhydride; N-methyl maleimide; the N-ethyl maleimide; N-cyclohexyl maleimide; N-phenylmaleimide; acrylamide; Methacrylamide; N methacrylamide; the butoxymethyl acrylamide; N-propyl methyl acid amides; (methyl) acrylic-amino ethyl ester; (methyl) vinylformic acid propyl group amino ethyl ester; (methyl) vinylformic acid-2-dimethylamino ethyl ester; (methyl) vinylformic acid-2-diethylamino ethyl ester; (methyl) vinylformic acid-2-dibutylamino ethyl ester; (methyl) vinylformic acid-3-dimethylamino propyl ester; (methyl) vinylformic acid-3-diethylamino propyl ester; (methyl) vinylformic acid phenyl amino ethyl ester; (methyl) vinylformic acid cyclohexyl amino ethyl ester; N-vinyl diethylamide; N-ethanoyl vinyl amine; allyl amine; methallyl amine; N-methacrylic amine; p-aminophenyl ethene; 2-Yi Bing Xi oxazolin; 2-Yi Xi oxazolin; 2-acryl-oxazolines; 2-Ben Yi Xi oxazolin; 3-hydroxyl-1-propylene; 4-hydroxyl-1-butylene; cis 4-hydroxyl-2-butylene; trans 4-hydroxyl-2-butylene; 3-hydroxy-2-methyl-1-propylene; cis 5-hydroxyl-2-amylene; trans 5-hydroxyl-2-amylene; 4-dihydroxyl-2-butylene; ethene; propylene; vinylchlorid; vinyl acetate; isopropenyl acetate; vinyl benzoate; polyoxyethylene glycol (methyl) acrylate; polypropylene glycol (methyl) acrylate or polytetramethylene glycol methacrylic ester etc.These monomers may be used alone, two or more kinds can also be used.

Grafting among the present invention (being total to) polymkeric substance (A-1), by preferred 10～80 weight parts, more preferably 40～80 weight parts and then preferred 50～80 weight parts rubber polymer in the presence of, preferred 90～20 weight parts of graft copolymerization, more preferably the monomeric unit of 60～20 weight parts and then preferred 50～20 weight parts obtains, and described monomeric unit is that other at least a kind of monomer of monomer and 0～60 weight % form by the aromatic vinyl of 100～40 weight %.Ratio to rubber polymer is not particularly limited, if but less than 10 weight parts, the tendency that has shock strength to reduce, if greater than 80 weight parts, the tendency that has appearance to descend.

The aromatic vinyl that uses in grafting of the present invention (being total to) polymkeric substance (A-1) is monomeric amount, preferably in the scope of 40～95 weight %, more preferably in the scope of 50～80 weight %, and then preferably in the scope of 60 weight %～75 weight %.

In addition, other at least a kind monomeric amount of using in grafting (being total to) polymkeric substance (A-1) is preferably in the scope of 60～5 weight %, more preferably in the scope of 50 weight %～20 weight %, and then preferably in the scope of 40 weight %～25 weight %.

Grafting (being total to) polymkeric substance (A-1) also can contain (being total to) polymkeric substance that does not have grafting that generates when being aggregated in following substances grafting (being total to) on the rubber polymer, described material is, the aromatic vinyl of 100～40 weight % be monomer and 0～60 weight % by the monomer component that can form with this aromatic vinyl other monomer that is monomer copolymerizable.That is, it also can contain (being total to) polymkeric substance that bonded between the monomer of monomer mixture does not have grafting, can use the material that obtains with the form with (being total to) mixture of polymers that does not have grafting usually.In grafting of the present invention (being total to) polymkeric substance (A-1), also comprise with this material that does not have the form of the monomeric mixture of grafting to obtain.Here, limit especially, but from the viewpoint of shock strength, percentage of grafting is preferably 10～150% for percentage of grafting.Percentage of grafting calculates according to following formula.

Percentage of grafting (%)=[amount of ethene system (being total to) polymkeric substance of graft polymerization on rubber polymer]/[rubber content of grafting (being total to) polymkeric substance] * 100

Grafting (being total to) polymkeric substance (A-1) is dissolved in the limiting viscosities of measuring in the methylethyl ketone solvent under 30 ℃ be not particularly limited, but equilibrated viewpoint from shock-resistance and forming process, be preferably the scope of 0.10～1.0dl/g, the more preferably scope of 0.15～0.70dl/g, the scope of preferred especially 0.15～0.48dl/g.

Manufacture method about grafting (being total to) polymkeric substance (A-1) is not particularly limited, and can use the combination of these such polymerization processs of mass polymerization, solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization or body suspension polymerization.In addition, also can with more than 2 kinds respectively (grafting) copolymerization grafting (being total to) polymkeric substance (A-1) fusion use.

Ethene system of the present invention (being total to) polymkeric substance (A-2) is that other at least a kind of monomer of monomer and 0～50 weight % form by the aromatic vinyl of 100～50 weight %, promptly, by aromatic vinyl is that monomer or monomer mixture form, and described monomer mixture is more than the monomer 50 weight % by aromatic vinyl and aromatic vinyl is that monomer at least a kind of monomer in addition forms.

Object lesson as ethene system (being total to) polymkeric substance (A-2), can list polystyrene, be that monomer is the following vinyl copolymer of feature: AS (acrylonitritrile-styrene resin), MS resin (copolymer of methyl methacrylatestyrene), MAS resin (methyl methacrylate-acrylonitritrile-styrene resin) etc. with the aromatic vinyl that contains more than the 50 weight %.

As the aromatic vinyl that uses in ethene system (being total to) polymkeric substance (A-2) is monomer, can enumerate vinylbenzene, alpha-methyl styrene, Vinyl toluene, adjacent ethyl styrene, to t-butyl styrene, p-methylstyrene, chloro-styrene and bromstyrol etc., special optimization styrene.They can use separately, perhaps also use more than 2 kinds.

As other monomers of at least a kind that in ethene system (being total to) polymkeric substance (A-2), use, from improving the chemical-resistant aspect, especially preferably using the vinyl cyanide of vinyl cyanide, methacrylonitrile and ethyl acrylonitrile etc. is monomer, wherein vinyl cyanide most preferably.In addition, because the maleimide of also preferred N-phenylmaleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide and N-cyclohexyl maleimide etc. is a monomer, because it can improve thermotolerance and flame retardant resistance, especially preferred N-phenylmaleimide.As the monomer beyond them; also can use vinylformic acid and methacrylic acid to pass through methyl; ethyl; propyl group; normal-butyl; (methyl) acrylic ester monomer of the carboxylate that isobutyl-forms etc.; unsaturated carboxylic acid monomer of (methyl) vinylformic acid etc. and their metal-salt; (methyl) glycidyl acrylate; glycidyl itoconate; glycidyl allyl ether; vinylbenzene-to glycidyl ether; to glycidyl vinylbenzene; toxilic acid; maleic anhydride; monomethyl maleate; ethyl maleate; methylene-succinic acid; itaconic anhydride; fumaric acid; 1, the 2-dimethyl maleic anhydride; the phenyl maleic anhydride; acrylamide; Methacrylamide; N methacrylamide; the butoxymethyl acrylamide; N-propyl methyl acid amides; (methyl) acrylic-amino ethyl ester; (methyl) vinylformic acid propyl group amino ethyl ester; (methyl) vinylformic acid-2-dimethylamino ethyl ester; (methyl) vinylformic acid-2-diethylamino ethyl ester; (methyl) vinylformic acid-2-dibutylamino ethyl ester; (methyl) vinylformic acid-3-dimethylamino propyl ester; (methyl) vinylformic acid-3-diethylamino propyl ester; (methyl) vinylformic acid phenyl amino ethyl ester; (methyl) vinylformic acid cyclohexyl amino ethyl ester; N-vinyl diethylamide; N-ethanoyl vinyl amine; allyl amine; methallyl amine; N-methacrylic amine; to basic amino-benzene ethene; 2-Yi Bing Xi oxazolin; 2-Yi Xi oxazolin; 2-acryloyl oxazolin; 2-Ben Yi Xi oxazolin; 3-hydroxyl-1-propylene; 4-hydroxyl-1-butylene; cis 4-hydroxyl-2-butylene; trans 4-hydroxyl-2-butylene; 3-hydroxy-2-methyl-1-propylene; cis 5-hydroxyl-2-amylene; trans 5-hydroxyl-2-amylene; 4-hydroxyl-2-butylene; ethene; propylene; vinylchlorid; vinyl acetate; isopropenyl acetate; vinyl benzoate; polyoxyethylene glycol (methyl) acrylate; polypropylene glycol (methyl) acrylate or polytetramethylene glycol methacrylic ester etc.They can use separately, perhaps also use more than 2 kinds.

The aromatic vinyl that uses in ethene system (being total to) polymkeric substance (A-2) is monomeric amount, sets out from the viewpoint of shock-resistance and appearance, the especially surface gloss of resin combination of the present invention, needs 50 weight % at least.Be preferably 50～95 weight %, more preferably 50～80 weight %, and then preferred 60～75 weight %.

In addition, other at least a kind monomeric amount of using in ethene system (being total to) polymkeric substance (A-2) is preferably 5～50 weight %, more preferably 20～50 weight %, and then preferred 25～40 weight %.

Ethene system of the present invention (being total to) polymkeric substance (A-2) is dissolved in the limiting viscosities of measuring in the methylethyl ketone solvent under 30 ℃ be not particularly limited, but equilibrated viewpoint from shock-resistance and forming process, the scope of the preferred 0.10～1.2dl/g of limiting viscosity, the more preferably scope of 0.15～0.70dl/g, when considering appearance, especially during surface gloss, so the scope of preferred 0.15～0.55dl/g, the scope of preferred especially 0.15～0.50dl/g.

Manufacture method about ethene system (being total to) polymkeric substance (A-2), be not particularly limited, preferred especially the use for example is that monomer or the aromatic vinyl that contains more than the 50 weight % are that monomeric monomer mixture carries out (being total to) polymeric method with aromatic vinyl, can list in addition, make ethene system (being total to) polymkeric substance that polymerization obtains and then in reactor, carry out suitable reaction, obtain the method for ethene system (being total to) polymkeric substance (A-2) that needs etc.For the manufacturing of ethene system (being total to) polymkeric substance (A-2), can use mass polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization, perhaps the usual methods such as combination of these polymerization processs such as body suspension polymerization.Also be not particularly limited about monomeric charging method, can add together in the starting stage, in addition, the generation that distributes for the composition that prevents multipolymer, part or all the monomer that is housed to of also can packing into continuously or in batches on one side is Yi Bian carry out polymerization.In addition, preferably with more than 2 kinds respectively polymerization ethene system (being total to) polymkeric substance (A-2) fusion use.

In the present invention, by with ethene system (being total to) polymkeric substance (A-2) and multipolymer (C) and usefulness, can improve flowability and appearance, the especially surface gloss of the resin combination that obtains greatly.From appearance, especially the viewpoint of surface gloss is set out, and the content of ethene system (being total to) polymkeric substance (A-2) preferably contains more than the 5 weight % in phenylethylene resin series (A).Grafting (being total to) polymkeric substance (A-1) and the more preferred ratio of mixture of ethene system (being total to) polymkeric substance (A-2), be grafting (being total to) polymkeric substance (A-1) of 5～95 weight % and ethene system (being total to) polymkeric substance (A-2) of 5～95 weight %, and then ethene system (being total to) polymkeric substance (A-2) of the grafting of preferred 5～80 weight % (being total to) polymkeric substance (A-1) and 20～95 weight %, ethene system (being total to) polymkeric substance (A-2) of the grafting of preferred especially 40～80 weight % (being total to) polymkeric substance (A-1) and 20～60 weight %.

The polyamide resin of Shi Yonging (B) is meant with aminocarboxylic acid, lactan or diamines and the dicarboxylic acid polymkeric substance as main raw material in the present invention.Representation example as the polyamide resin that uses among the present invention (B) raw material, can list 6-aminocaprolc acid, the amino undecanoic acid of 11-, the aminocarboxylic acid of 12 amino dodecanoic acid etc., ε-Ji Neixianan, the lactan of omega-lauric lactam etc., perhaps tetramethylene-diamine, hexamethylene-diamine, 1, the 2-quadrol, 1, the 3-propylene diamine, 1, the 5-pentamethylene diamine, the 2-methyl isophthalic acid, the 5-pentamethylene diamine, 11 methylene diamines, dodecamethylene diamine, 2,2,4-trimethylammonium 1, the 6-hexanediamine, 2,4,4-trimethylammonium 1, the 6-hexanediamine, 1, the 9-nonamethylene diamine, 5-methyl 1, the 9-nonamethylene diamine, m-xylene diamine, the p-Xylol diamines, 1, two (aminomethyl) hexanaphthenes of 3-, 1, two (aminomethyl) hexanaphthenes of 4-, 1-amino-3-aminomethyl-3,5, the 5-trimethyl-cyclohexane, two (4-aminocyclohexyl) methane, two (3-methyl-4-aminocyclohexyl) methane, 2, two (4-aminocyclohexyl) propane of 2-, two (aminopropyl) piperazine, aliphatics such as aminoethyl piperazine, alicyclic, aromatic diamines, with hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, 1, the 3-cyclohexane cyclohexanedimethanodibasic, 1,4 cyclohexanedicarboxylic acid, terephthalic acid, m-phthalic acid, 2-chlorine terephthalic acid, 2-methyl terephthalic acid, the oreinol dioctyl phthalate, m-phthalic acid 5-sodium sulfonate, hexahydroterephthalic acid, aliphatics such as hexahydro-m-phthalic acid, alicyclic, the combination arbitrarily of aromatic dicarboxylic acid.

Polyamide resin (B) in the present invention, can will be used with the form of independent or mixture respectively by these raw material deutero-polyamide homopolymers or multipolymer by incompatible the obtaining of the generally well-known polycondensation of these prepared usings.

Example as preferred polyamide resin (B), can list, polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), nylon 11 (Ni Long11), poly-lauramide (nylon 12), polyhexamethylene sebacamide (NYLON610), nylon 6/66 copolymer, nylon 6/66/610 multipolymer, nylon 6/12 multipolymer, nylon 66/ isophthaloyl hexanediamine (hexamethyleneisophthalamide) is multipolymer (6I)/6, multipolymer with nylon 6/66/610/12 multipolymer etc., preferred nylon 6, nylon 66 and be the multipolymer of principal constituent with them, preferred especially nylon 6 and be the multipolymer of principal constituent with nylon 6, most preferably nylon 6.

Molecular weight to these polyamide resins (B) is not particularly limited, but in 98% vitriol oil relative viscosity of the solution during with the dissolving of the concentration of 1g/dl in 25 ℃ of preferred down scopes 1.8～7.5.From the viewpoint of the flowability of the resin combination that obtains, more preferably in 1.8～4.0 scope, so that preferred in 1.8～2.8 scope, in 1.8～2.4 scope, most preferably in 1.8～2.3 scope.When relative viscosity surpassed 7.5, the flowability of resin combination of the present invention had the tendency of reduction.In addition, when relative viscosity less than 1.8 the time, the mechanical characteristics of resin combination of the present invention has the tendency of reduction.The fusing point of polyamide resin (B) can be by using differential scanning calorimeter (the system DSC-7 of パ one キ Application エ Le マ one (Perkin Elmer) society type), be determined at the crystallization fusion peak value of measuring down with the heat-up rate of 20 ℃/min in the nitrogen gas stream and try to achieve, preferably this fusing point is 150～280 ℃.In addition, the melt viscosity of the polyamide resin that uses among the present invention (B), the temperature when melt-processed, velocity of shear are 1000 seconds ^-1Condition under, be preferably 15～600Pas, more preferably 15～250Pas, and then preferred 15～200Pas, preferred especially 15～150Pas, most preferably 15～100Pas.

Ethene improved based copolymer C among the present invention (below, simply be called multipolymer (C) sometimes), be to contain 1.5～10 weight % α, beta-unsaturated carboxylic acid acid anhydride unit and 0-5～60 weight % vinyl cyanides are that monomeric unit forms.

The α that contains in the multipolymer (C), the unitary amount of beta-unsaturated carboxylic acid acid anhydride is in the scope of 1.5～10 weight %, preferably in the scope of 2～10 weight %, more preferably in the scope of 2.5～10 weight %.Work as α, beta-unsaturated carboxylic acid acid anhydride unit is during less than 1.5 weight %, owing to reduce with the reactivity of polyamide resin (B) or reactivity and affinity, so the shock-resistance of the resin combination that obtains has the tendency of reduction.If α, beta-unsaturated carboxylic acid acid anhydride unit or its derivative unit surpass 10 weight %, and then the forming process of final composition and shock-resistance have the tendency of reduction.

Vinyl cyanide in the multipolymer (C) is that the amount of monomeric unit is 0.5～60 weight %, preferred 0.5～50 weight %, more preferably 2～50 weight %.The shock-resistance and the chemical-resistant viewpoint of the resin combination that obtains from adding multipolymer (C), vinyl cyanide is that the lower limit of amount of monomeric unit is more preferably more than the 20 weight %, if consider the moulding processibility in addition, then its upper limit is more preferably below the 50 weight %, particularly below the 40 weight %.Therefore, when considering these factors, vinyl cyanide is the scope that the amount of monomeric unit is preferably 20～50 weight %, the scope of preferred especially 20～40 weight %.

To the α that contains in the multipolymer (C), the unitary kind of beta-unsaturated carboxylic acid acid anhydride does not limit especially, if for example, then can list maleic anhydride, fumaric acid anhydride, itaconic anhydride, crotonic anhydride, methyl maleic anhydride, the methylfumaric acid acid anhydride, the methylfumaric acid acid anhydride, citraconic anhydride, glutaconic anhydride, tetrahydronaphthalic anhydride, 1, the 2-dimethyl maleic anhydride, the phenyl maleic anhydride, bridge dicyclo-(2,2,1)-5-heptene-2, the 3-dicarboxylic anhydride, methyl isophthalic acid, 2,3, the 6-tetrahydronaphthalic anhydride, 5-norbornylene-2, the 3-dicarboxylic anhydride, methyl-5-norbornylene-2,3-dicarboxylic anhydride etc., preferred especially maleic anhydride.These compounds can use separately, perhaps also use more than 2 kinds.

Multipolymer (C) also can contain the α that contains, the α that the beta-unsaturated carboxylic acid acid anhydride is transformed into by reactions such as for example hydrolysis, the derivative unit of beta-unsaturated carboxylic acid acid anhydride in multipolymer (C).These derivative unit have and can change α again into by suitable vacuum drying treatment or thermal treatment, the chemical structure of beta-unsaturated carboxylic acid acid anhydride.As α, the derivative unit of beta-unsaturated carboxylic acid acid anhydride, can list toxilic acid, fumaric acid, methylene-succinic acid, Ba Dousuan, methyl-maleic acid, methylfumaric acid, methylfumaric acid, citraconic acid, propene dicarboxylic acid, tetrahydrophthalic acid, bridge dicyclo-(2,2,1)-5-heptene-2, the 3-dicarboxylic acid, methyl isophthalic acid, 2,3, the 6-tetrahydrophthalic acid, 5-norbornylene-2, the 3-dicarboxylic acid, methyl-5-norbornylene-2, the α of 3-dicarboxylic acid etc., β-unsaturated dicarboxylic acid, these α, the metal-salt of β-unsaturated dicarboxylic acid, monomethyl maleate, ethyl maleate, monomethyl fumarate, monomethyl ester, monomethyl itaconate, the methylene-succinic acid mono ethyl ester, the Ba Dousuan mono-methyl, the Ba Dousuan mono ethyl ester, the methyl-maleic acid mono-methyl, the methylfumaric acid mono-methyl, the methylfumaric acid mono-methyl, the citraconic acid mono-methyl, the propene dicarboxylic acid mono-methyl, the α of tetrahydrophthalic acid mono-methyl etc., β-unsaturated dicarboxylic acid mono alkyl ester or their metal-salt, α, β-unsaturated dicarboxylic acid mono-alkenyl ester or their metal-salt, α, β-unsaturated dicarboxylic acid list aryl ester or their metal-salt, α, β-unsaturated dicarboxylic acid dialkyl etc.

As the vinyl cyanide in the multipolymer (C) is monomeric unit, can list vinyl cyanide, methacrylonitrile, ethyl acrylonitrile etc., preferred vinyl cyanide.

It is monomeric unit that multipolymer (C) also can contain aromatic vinyl.When in multipolymer (C), containing aromatic vinyl and be monomeric unit, its content is preferably the scope of 30～98 weight %, more preferably 30～97.5 weight %, more preferably 30～97 weight %, and then preferred 50～97 weight %, the scope of preferred especially 50～78.5 weight %, the most preferably scope of 50～78 weight %, and then the scope of 50～77.5 weight %.

As the preferred as required aromatic vinyl that uses in multipolymer (C) is monomeric unit, can list vinylbenzene, alpha-methyl styrene, Vinyl toluene, adjacent ethyl styrene, to t-butyl styrene, p-methylstyrene, chloro-styrene, bromstyrol etc., optimization styrene and alpha-methyl styrene, more preferably vinylbenzene.These monomers can use separately, perhaps also use more than 2 kinds.

In addition, also can to contain to be other monomers of at least a kind of monomeric unit and usefulness with vinyl cyanide to multipolymer (C).Particularly; can list (methyl) vinylformic acid; (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) vinylformic acid n-propyl; (methyl) n-butyl acrylate; the just own ester of (methyl) vinylformic acid; (methyl) cyclohexyl acrylate; (methyl) vinylformic acid chloromethyl ester; (methyl) vinylformic acid-2-chloroethene ester; (methyl) 2-Hydroxy ethyl acrylate; (methyl) vinylformic acid-3-hydroxy propyl ester; (methyl) vinylformic acid-2; 3; 4; 5; the own ester of 6-penta hydroxy group and (methyl) vinylformic acid-2; 3; 4,5-tetrahydroxy pentyl ester; vinylformic acid or its metal-salt; methacrylic acid or its metal-salt; (methyl) vinylformic acid tertiary butyl ester; (methyl) acrylic amino ethyl ester; (methyl) vinylformic acid propyl group amino ethyl ester; (methyl) vinylformic acid-2-dimethylamino ethyl ester; (methyl) vinylformic acid-2-diethylamino ethyl ester; (methyl) vinylformic acid-2-dibutylamino ethyl ester; (methyl) vinylformic acid-3-dimethylamino propyl ester; (methyl) vinylformic acid-3-diethylamino propyl ester; (methyl) vinylformic acid phenyl amino ethyl ester; (methyl) vinylformic acid cyclohexyl amino ethyl ester; glycidyl allyl ether; vinylbenzene-to glycidyl ether; ethyl maleate; N-methyl maleimide; the N-ethyl maleimide; N-cyclohexyl maleimide; N-phenylmaleimide; acrylamide; Methacrylamide; N methacrylamide; the butoxymethyl acrylamide; N-propyl methyl acid amides; N-vinyl diethylamide; N-ethanoyl vinyl amine; allylamine; methallyl amine; N-methyl allylamine; p-aminophenyl ethene; 2-Yi Bing Xi oxazolin; 2-Yi Xi oxazolin; 2-acryloyl oxazolin and 2-Ben Yi Xi oxazolin etc.In these monomers, preferably use methacrylic acid, methyl methacrylate, N-methyl maleimide, N-phenylmaleimide, more preferably methyl methacrylate, N-phenylmaleimide.These monomers can use separately, perhaps also use more than 2 kinds.

Making multipolymer of the present invention (C) be dissolved in the limiting viscosity of measuring in the methylethyl ketone solvent under 30 ℃ temperature is the scope of 0.15～0.41dl/g.The scope of preferred 0.15～0.40dl/g, the scope of the more preferably scope of 0.15～0.36dl/g, and then preferred 0.15～0.30dl/g, the scope of preferred especially 0.15～0.25dl/g, the most preferably scope of 0.15～0.20dl/g.When limiting viscosity surpassed 0.41dl/g, the flowability of resin combination and appearance descended.On the other hand, when limiting viscosity was lower than 0.15dl/g, the shock-resistance of resin combination and appearance descended.Here, limiting viscosity and intrinsic viscosity synonym are the ultimate value of reduced viscosity under infinite dilution, can calculate by the reduced viscosity that is determined under a plurality of any concentration.So-called reduced viscosity is meant the ratio η r/c of the increase part η r of relative viscosity with respect to the mass concentration c of polymer material.

Usually, the limiting viscosity of known polymer material and molecular weight have certain dependency, and dropping in the above-mentioned scope with limiting viscosity is that the multipolymer of the present invention (C) of feature can be set up feature by molecular weight ranges.As molecular weight, can represent that the both is dissolved in multipolymer (C) in the tetrahydrofuran (THF) with number-average molecular weight or weight-average molecular weight, use gel permeation chromatography (GPC) to measure, obtain with the form of the value of vinylbenzene calibration.

Particularly, the limiting viscosity in methyl ethyl ketone solution, under 30 ℃ is that the number-average molecular weight of multipolymer 0.15～0.41dl/g, of the present invention (C) is 4000～20000, and weight-average molecular weight is 12000～39000.With limiting viscosity under the condition is that the number-average molecular weight of multipolymer of the present invention (C) 0.15～0.40dl/g, preferred is 4000～19000, and weight-average molecular weight is 12000～38000.With limiting viscosity under the condition is that the number-average molecular weight of multipolymer of the present invention 0.15～0.36dl/g, preferred (C) is 4000～17000, and weight-average molecular weight is 12000～36000.With limiting viscosity under the condition is that 0.15～0.30dl/g's and then preferred multipolymer of the present invention (C) number-average molecular weight is 4000～16000, and weight-average molecular weight is 12000～34000.With limiting viscosity under the condition is that the number-average molecular weight of multipolymer of the present invention 0.15～0.25dl/g, particularly preferred (C) is 4000～14000, and weight-average molecular weight is 12000～31000.With limiting viscosity under the condition is that the number-average molecular weight of multipolymer of the present invention 0.15～0.20dl/g, most preferred (C) is 4000～9000, and weight-average molecular weight is 12000～19000.

For making the method with multipolymer (C) of desired limiting viscosity scope of the present invention, do not limit especially, by using known method, can obtain having the multipolymer (C) of desired characteristic range of viscosities, described known method is included in and controls azo-compound in the polymerization, the decomposition temperature of radical polymerization initiators such as superoxide and addition, alkyl sulfhydryl, tetracol phenixin, carbon tetrabromide, N,N-DIMETHYLACETAMIDE, dimethyl formamide, the addition of chain-transfer agents such as triethylamine, perhaps when in polymerization, using solvent, control the method for its quantity of solvent etc.Wherein, from keeping the viewpoint of polymeric stability and polymerization velocity, more preferably use the method for the addition of Quality Initiative transfer agent, the chain-transfer agent as this moment especially preferably uses alkyl sulfhydryl.As alkyl sulfhydryl used herein, for example can list, n-octyl mercaptan, uncle's lauryl mercaptan, n-dodecyl mercaptan, n-tetradecane base mercaptan or Octadecane base mercaptan etc., more preferably n-octyl mercaptan, uncle's lauryl mercaptan, n-dodecyl mercaptan.

The addition of the alkyl sulfhydryl when making multipolymer of the present invention (C) can be according to the desired characteristics viscosity of multipolymer (C), and the kind of the decomposition temperature of cooperation radical polymerization initiator and addition, alkyl sulfhydryl, polymerization temperature, monomer concentration etc. carry out suitable setting.

For example, when making multipolymer (C) by solution polymerization, the monomer mixture that is encased in reaction system with respect to total amount 100 weight parts, use the methyl ethyl ketone of 120 weight parts, use 2 of 0.3 weight part as initiator, the 2'-Diisopropyl azodicarboxylate, implementing under 80 ℃ under the polymeric situation, when the limiting viscosity in being manufactured on methyl ethyl ketone under 30 ℃ is the multipolymer (C) of 0.15～0.4dl/g scope, the addition of uncle's lauryl mercaptan is controlled in the scope of 0.1～0.8 weight part with respect to the monomer mixture that is encased in reaction system of total amount 100 weight parts.In addition, when the manufacturing limiting viscosity is the multipolymer (C) of 0.15～0.36dl/g scope, uncle's lauryl mercaptan is controlled in the scope of 0.15～0.8 weight part.And then, when making the multipolymer that limiting viscosity is 0.15～0.3dl/g scope (C) by same solution polymerization, uncle's lauryl mercaptan is controlled in the scope of 0.2～0.8 weight part.

In addition, for example, using 2 of 0.3 weight part, the 2'-Diisopropyl azodicarboxylate is as initiator, make under the situation of multipolymer (C) carrying out mass polymerization under 80 ℃, when the limiting viscosity in being manufactured on methyl ethyl ketone under 30 ℃ was the multipolymer (C) of 0.15～0.40dl/g scope, the addition of uncle's lauryl mercaptan was controlled at the scope of 0.35～2.5 weight part with respect to the monomer mixture that is encased in reaction system of total amount 100 weight parts.In addition, when the manufacturing limiting viscosity is the multipolymer (C) of 0.15～0.36dl/g scope, uncle's lauryl mercaptan is controlled in the scope of 0.5～2.5 weight part.And then, when the manufacturing limiting viscosity is the multipolymer (C) of 0.15～0.30dl/g scope, uncle's lauryl mercaptan is controlled in the scope of 0.75～2.5 weight part.

α in the multipolymer (C), beta-unsaturated carboxylic acid acid anhydride unit and vinyl cyanide are monomeric unit, preferably are incorporated in the main chain of multipolymer by random polymerization.Polymerization process for this situation, can use and for example utilize combination radical polymerization, polymerization process such as mass polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization or body suspension polymerization, more preferably use mass polymerization, solution polymerization, body suspension polymerization or precipitation polymerization.In addition, can preferably use any mode of batch-type, continous way.According to polymerization process, multipolymer (C) also can be the form that contains the mixture of the multipolymer with unsaturated carboxylic acid anhydrides monomeric unit.For the granularity and the shape of the polymkeric substance that utilizes body suspension polymerization or precipitation polymerization to obtain, do not limit especially, the granularity of the polymkeric substance that preferably obtains is in the scope of 0.1 μ m～8mm, more preferably in the scope of 1 μ m～5mm.When granularity during less than 0.1 μ m, have for example in filtering operation, produce stop up or the processing after polymerizations such as drying process in operation become the tendency of difficulty.On the other hand, when granularity surpasses 8mm, there be the drying efficiency of polymkeric substance in drying process to reduce or tendency that the detersive efficiency when washing also reduces.And, so-called here granularity, expression utilizes the mean diameter of the polymer particle that precipitation polymerization obtains itself.

In addition, each monomeric charging method during about polymerization, there is no particular limitation, can add together in the starting stage, in addition, the generation that distributes for the composition that prevents multipolymer, part or all the monomer that is housed to of also can packing into continuously or in batches on one side is Yi Bian carry out polymerization.For example, (C) passes through α when multipolymer, beta-unsaturated carboxylic acid acid anhydride, vinyl cyanide be monomer and aromatic vinyl be monomer copolymerizable form multipolymer the time, if in this polymerization, the monomer mixture that is housed to was added together in the starting stage, the multipolymer that half stage generated before percent polymerization for example is less than 30% such polymerization then is with the variant very big tendency of composition separately that at for example percent polymerization is the multipolymer of polymerization rear half stage generation such 60% or more.For the generation that prevents that this composition from distributing, preferably appending aromatic vinyl in polymerization is monomer and α, the beta-unsaturated carboxylic acid acid anhydride.In addition, as the multipolymer (C) that cooperates, also can be with polymeric multipolymer (C) fusion use respectively more than 2 kinds.

Unitary quantitatively for each composition in the multipolymer of the present invention (C), can use infrared spectrophotometer or proton magnetic resonance (PMR) instrument (1H-NMR), gas chromatograph etc.α in the multipolymer (C), the beta-unsaturated carboxylic acid acid anhydride is unitary quantitatively can to carry out as following.

(i) pass through α, beta-unsaturated carboxylic acid acid anhydride and vinyl cyanide are that monomer is with various mixed in molar ratio, carry out infrared absorption spectrometry and make following infrared absorption spectrum typical curve, promptly, about α, beta-unsaturated carboxylic acid acid anhydride and vinyl cyanide are the typical curve of the strength ratio and their mol ratio of monomeric charateristic avsorption band.

(ii) then by carrying out the infrared absorption spectrometry of multipolymer (C), use the typical curve of making, calculate the α reaction addition, that contain in the multipolymer (C), beta-unsaturated carboxylic acid acid anhydride unit and vinyl cyanide are monomeric mol ratio.

(iii) follow, also make for other one-tenth subdivision of multipolymer (C) to use the same method, calculate with vinyl cyanide be monomeric mol ratio, calculate α based on these results, the unitary content of beta-unsaturated carboxylic acid acid anhydride.

Here, when making the infrared absorption spectrum typical curve, α, the beta-unsaturated carboxylic acid acid anhydride can use the charateristic avsorption band by the stretching vibration generation of carbonyl, for vinyl cyanide is monomeric unit, can use the charateristic avsorption band that produces by the stretching vibration of CN base, when containing aromatic vinyl and be monomer, use the charateristic avsorption band that produces by aromatic C=C in plane vibration.

In the present invention, with respect to the phenylethylene resin series (A), polyamide resin (B) and the multipolymer (C) that add up to 100 weight parts, can contain the packing material (D) of 0.1～150 weight part.The preferred content of packing material (D) is in the scope of 1～100 weight part.By containing packing material (D), can increase substantially rigidity, thermotolerance of the resin combination that obtains etc.The thermoplastic resin composition of the present invention of containing packing material (D) has excellent coating by containing multipolymer (C).

Packing material (D) can be fibrous, also can be the non-fibrous of granular grade.

As fibrous packing material, can list the steel fiber of glass fibre, carbon fiber, Stainless Steel Fibre or aluminum fiber etc., the organic fibre of aromatic polyamide fibre, polyphenylene sulfide fibre, liquid crystalline polyester fiber etc., the whisker of potassium titanate crystal whisker, aluminium borate whisker, silicon nitride crystal whisker etc., the fibrous mineral of wollastonite, asbestos, sepiolite etc., these packing materials also can be hollow.Wherein preferably use the glass fibre of chopped strand type or carbon fiber etc.Carbon fiber can list PAN system, pitch system and cellulose-based etc., in addition, also can use the carbon fiber of having implemented metallic coating.The PAN based carbon fiber that wherein the preferred mechanical characteristic is high.

When using carbon fiber as packing material (D), preferred number average Fibre diameter is the carbon fiber of 1～20 mu m range.For the staple length of carbon fiber, there is no particular limitation, and preferred weight average fiber length is 0.2～10mm, more preferably 3～8mm.If weight average fiber length surpasses 10mm, the tendency of formability variation is arranged then.

In addition, when using glass fibre, can use generally well-known glass fibre arbitrarily, preferred E glass fibre as packing material (D).There is no particular limitation to the Fibre diameter of glass fibre, is preferably 5～15 μ m, and length also is not particularly limited, and is preferably 1.5～5mm, especially preferably handles with known coupler, sizing agent etc.From obtaining the viewpoint of more excellent physical strength, preferably these fibrous packing materials are carried out pre-treatment with known coupler and use.

As non-fibrous packing material, can list the silicate of zeolite, sericite, kaolin, mica, pyrophyllite, wilkinite, talcum, pure aluminium silicate etc., the metallic compound of aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide etc., the carbonate of lime carbonate, magnesiumcarbonate, rhombspar etc., the vitriol of calcium sulfate, Tai-Ace S 150, barium sulfate etc., the oxyhydroxide of magnesium hydroxide, calcium hydroxide, aluminium hydroxide etc., granulated glass sphere, ceramic bead, boron nitride, silicon carbide, zinc oxide, graphite, magnesia, wollastonite or silicon-dioxide etc.Also can and use these the non-fibrous packing materials more than 2 kinds.In these packing materials, preferably talc, kaolin and mica, special preferably talc.The steatitic median size is not particularly limited preferred 0.5～8 μ m.In addition, the mean aspect ratio of preferably talc is more than 4, more preferably 5～100.In addition, the SiO in the composition after more preferably when having removed burning, losing partly ₂With the ratio of MgO be talcum more than the 92 weight %.In addition, in the present invention, use, can make more High Level such as thermoplastic resin composition's of the present invention rerum natura balance or injection molding processibility by non-fibrous packing material being carried out surface treatment with coupler and/or other surface treatment agent.There is no particular limitation to coupler and/or other surface treatment agent, can preferably use present known surface treatment agent.

In thermoplastic resin composition of the present invention, packing material (D) is dispersed in phenylethylene resin series (A) and/or the polyamide resin (B), in addition, preferred packing material (D) is dispersed in the polyamide resin (B) at least.And then the dispersion state of preferred packing material (D) is a homodisperse.This state can be confirmed from the section that the thermoplastic resin composition cuts down by using electron microscope observation.

As adding packing material (D), make it be dispersed in method among the thermoplastic resin composition of the present invention, there is no particular limitation, and packing material (D) is dispersed in the polyamide resin (B) in advance.

In thermoplastic resin composition of the present invention, can contain layered silicate (E).By containing layered silicate (E), can improve the rigidity and the thermotolerance of the resin combination that obtains.The thermoplastic resin composition of the present invention of containing layered silicate (E) has excellent coating by containing multipolymer (C).

As the layered silicate that uses among the present invention (E), preferred swelling property layered silicate.So-called swelling property layered silicate, has following such structure, promptly, formed 1 layer the structure plate crystal layer, 2: 1 types at 4 body sheets of the overlapping silicic acid in the top and the bottom of 8 body sheets that contain metals such as aluminium, magnesium, lithium, usually, the interlayer of this plate crystal layer has the positively charged ion of exchangeability.This 1 laminate shape crystalline size is generally width 0.05～0.5 μ m, thickness is 6～15 dusts.In addition, the cation exchange capacity of this exchangeable cation can be enumerated 0.2～3meq/g.

Object lesson as layered silicate (E), the montmorillonite that can list montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite etc. is a clay mineral, the various clay minerals of vermiculite, halloysite, hydraulic rankinite (Kanemite), ケ ニ ヤ イ ト (kenyait), zirconium phosphate, titanium phosphate etc., the swelling property mica of Li type fluorine taincolite, Na type fluorine taincolite, Na type tetrasiuicic fluoromica, Li type tetrasiuicic fluoromica etc. etc., these layered silicates can be natural, also can be synthetic.Wherein, the montmorillonite of preferred montmorillonite, hectorite etc. is the swelling property mica of clay mineral or Na type tetrasiuicic fluoromica, Li type fluorine taincolite etc., more preferably montmorillonite.

In addition, as layered silicate of the present invention (E), the preferred layered silicate that exchanged by organic ion of the exchange cation that exists at interlayer.As organic ion, can list ammonium ion Huo Phosphonium ion, sulfonium cation etc.Wherein, preferably use ammonium ion with the Phosphonium ion especially preferably uses ammonium ion.As ammonium ion, any one of uncle ammonium, secondary ammonium, tertiary amine, quaternary ammonium all can.In these ammonium ions, preferred especially quaternary ammonium, particularly, preferred tricaprylmethylammonium, trimethylammonium octadecyl ammonium, benzyl dimethyl octadecyl ammonium, preferred especially tricaprylmethylammonium, benzyl dimethyl octadecyl ammonium.

In the present invention, the layered silicate (E) that the exchangeable cation that interlayer exists has been exchanged by organic ion can react and makes by using known method to make to have the layered silicate of exchangeable cation and organic ion at interlayer.In the present invention, organic ion is with respect to the amount of layered silicate, with respect to the cation exchange capacity of layered silicate, usually preferably in 0.4～2.0 normal scope.

In addition, to these layered silicates, the coupler that adds above-mentioned organic salt and then responding property of apparatus functional group carries out pre-treatment to be used, and can obtain more excellent physical strength, is preferred therefore.As described coupler, can preferably use present known coupler, preferred especially organosilane based compound.As the method for handling layered silicates with these couplers, can preferably use present known method, also can be by the layered silicate of having handled with such coupler be heat-treated, and then promote to react.

When making the thermoplastic resin composition of containing layered silicate (E) of the present invention, as making layered silicate (E) be dispersed in method among the thermoplastic resin composition, be not particularly limited, layered silicate (E) is dispersed in the polyamide resin (B) in advance.Be dispersed in method in the polyamide resin (B) as such layered silicate (E) that makes, be not particularly limited, can preferably use present known method, preferred use make layered silicate (E) be dispersed in as the monomer of polyamide resin (B) raw material in after, carry out the polymeric method, the layered silicate (E) that the exchangeable cation that perhaps will be in advance exists at the interlayer of layered silicate with the organic ion exchange forms and polyamide resin (B) carry out the method for melting mixing.For layered silicate (E) and polyamide resin (B) are carried out the method that melting mixing is made, can use following such method: the exchangeable cation that will exist at the interlayer of layered silicate does not in advance exchange with organic ion yet, but with layered silicate and polyamide resin (B) melting mixing the time, handle with these organic ions.

When using coupler,, after preferably at first handling, carry out coupler again and handle with organic ion to utilizing organic ion to the processing of layered silicate with utilize coupler that the order of its processing also is not particularly limited.

In the present invention, the content of layered silicate (E), with respect to the thermoplastic resin composition that the polyamide resin (B) of the phenylethylene resin series by 1～99 weight % (A) of 100 weight parts and 1～99 weight % forms, be 0.05～40 weight part, be preferably 0.05～20 weight part.When the content of layered silicate (E) during less than 0.05 weight part, rigidity and stable on heating improved effect are little, and when the content of layered silicate (E) surpassed 40 weight parts, appearance descended.

In the present invention, from the shock-resistance of keeping the thermoplastic resin composition who obtains and the state of appearance, improve rigidity simultaneously and stable on heating viewpoint is set out, preferred layered silicate (E) in phenylethylene resin series (A) and/or polyamide resin (B) with the horizontal homodisperse below 10 layers, more preferably with the horizontal homodisperse below 6 layers, and then preferably with the horizontal homodisperse of individual layer.In addition, preferred layered silicate (E) homodisperse in polyamide resin (B) at least.In the present invention, so-called with the homodisperse state of the level of individual layer, be meant that layered silicate under the state about individual layer～5 layer secondary does not take place and is not dispersed in the resin with assembling.This state can be confirmed from the section that resin combination cuts down by using electron microscope observation.

Thermoplastic resin composition of the present invention, can add in following addition scope as required and not damage effect of the present invention, particularly do not damage the resin of rigidity, thermotolerance, flowability and appearance, described addition scope is the scope of the amount of not damaging these characteristics.Object lesson as such resin, can list, the vibrin of polymethylmethacrylate, polycarbonate, polyethylene terephthalate or polybutylene terephthalate and polyarylester etc., polyphenylene oxide, polyphenylene sulfide, polyethersulfone, polyoxymethylene, tetrafluoroethylene, poly(lactic acid), the linear novolac resin of epoxy phenol, polysulfones, polyimide, polyetherimide, polyether-ether-ketone, polyetheramides or polyamidoimide etc.

In addition, in order to give its electroconductibility, in thermoplastic resin composition of the present invention, can contain electroconductive stuffing and/or electric conductive polymer.Electroconductive stuffing is so long as be generally used for the electrochemical electroconductive stuffing of leading of resin and get final product, just do not limit especially, as its concrete example, can list mineral filler, carbon dust, graphite, carbon fiber, carbon thin slice, flakey carbon, carbon fibrils and the carbon nanotube etc. of metal powder, sheet metal, metal strip, steel fiber, metal oxide, the conductive material that has been covered, these fillers also can be the hollow form things.As the object lesson of electric conductive polymer, can list, polyaniline, polypyrrole, polyacetylene, p-poly-phenyl, Polythiophene, and polyphenylene ethylene (polyphenylene vinylene) etc.These electroconductive stuffings and/or electric conductive polymer also can more than 2 kinds and be used for using.In described electroconductive stuffing and electric conductive polymer, consider that from the aspect of intensity and economy carbon black is preferred especially the use.

The electroconductive stuffing that uses among the present invention and/or the content of electric conductive polymer, according to the kind of electroconductive stuffing that uses and/or electric conductive polymer and suitable regulation, from electroconductibility and flowability, set out with the equilibrated viewpoint of physical strength etc., the thermoplastic resin composition who forms by phenylethylene resin series (A) and polyamide resin (B) with respect to 100 weight parts, preferably in the scope of 0.1～250 weight part, in the scope particularly preferably in 1～100 weight part.

In addition, thermoplastic resin composition of the present invention, under the scope of not damaging effect of the present invention, also can and then add other composition, for example the antioxidant or the heat-resisting stabilizing agent of metal salt stabilizers such as sulfocompound system, acrylic ester, phosphorus series organic compound, cupric chloride, cuprous iodide, neutralized verdigris or cerium stearate etc.

In addition, as other compositions that can add, can add weather agent or UV light absorber, photostabilizer, releasing agent, slipping agent, pigment, high-visibility pigment, dyestuff, fluorescence dye, the anti-coloring agent, softening agent, antistatic agent (ionization series antistatic agent, the such nonionic of polyoxyethylene sorbitan monostearate is an antistatic agent, trimethyl-glycine is the both sexes antistatic agents, polyether ester amides, polyamide ether, random or the block polymer of polyamide elastomers such as ethylene series ether-ether acid amides or ethylene series ether-ether acid amides etc.), fire retardant (red phosphorus, the metal hydroxides flame retardant, phosphorus flame retardant, the silicone-based fire retardant, the halogen flame retardant, perhaps combination of these halogen flame retardants and ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.), lime carbonate, granulated glass sphere, wood powder, powdered rice hulls, walnut powder, waste paper, light-storing paint, tungsten powder or tungsten alloy powder, the antiseptic-germicide of borate glass or silver-series antibacterial agent etc. or mould resistant etc.

In thermoplastic resin composition of the present invention, as long as the content of multipolymer (C), the resin combination that forms by phenylethylene resin series (A) and polyamide resin (B) with respect to 100 weight parts, the scope that is 0.5～80 weight part gets final product, do not limit especially, be preferably the scope of 0.5～30 weight part, more preferably the scope of 0.5～15 weight part, and then the scope of preferred 0.5～10 weight part, the scope of preferred especially 1～7 weight part.When multipolymer (C) during less than 0.5 weight part, the tendency that the shock-resistance of the composition that additive effect shortcoming as compatilizer is arranged, obtains reduces when surpassing 80 weight parts, has the tendency of the forming process reduction of final composition.

In thermoplastic resin composition of the present invention, the blending ratio of phenylethylene resin series (A) and polyamide resin (B), need only scope at phenylethylene resin series (A) with the polyamide resin (B) of 99～1 weight % of 1～99 weight %, there is no particular limitation, and optimization styrene is that resin (A) is that 45～90 weight % and polyamide resin (B) are 55～10 weight %.Appearance from further raising resin combination of the present invention, especially the viewpoint of surface gloss is set out, more preferably phenylethylene resin series (A) is that 55～85 weight % and polyamide resin (B) are 45～15 weight %, and then optimization styrene is that resin (A) is that 60～80 weight % and polyamide resin (B) are 40～20 weight %, special optimization styrene is that resin (A) is that 65～80 weight % and polyamide resin (B) are 35～20 weight %, and most preferably phenylethylene resin series (A) is that 67～80 weight % and polyamide resin (B) are 33～20 weight %.

The shape of the formed body that obtains for resin combination of the present invention is carried out melt molding and the phase structure of formed body, there is no particular limitation, but from so improve the shock-resistance of resin combination and the equilibrated viewpoint of flowability and appearance, preferred resin combination of the present invention is as follows, the formed body central part that obtains it being carried out melt molding processing, promptly, will be perpendicular to the direction on the surface of formed body during as thickness, to the zone with respect to the degree of depth of full depth 40～60%, polyamide resin (B) forms external phase from the surface.Particularly, in the phase structure of formed body central part, the part that polyamide resin (B) is external phase is preferably formed more than the 10 volume %, and then is preferably formed more than the 20 volume %, most preferably forms more than the 30 volume %.

Resin combination of the present invention when forming external phase as polyamide resin (B), optimization styrene is that resin (A) is that 55～85 weight % and polyamide resin (B) are 45～15 weight %, more preferably phenylethylene resin series (A) is that 60～80 weight % and polyamide resin (B) are 40～20 weight %, and then optimization styrene is that resin (A) is that 65～80 weight % and polyamide resin (B) are 35～20 weight %, special optimization styrene is that resin (A) is that 67～80 weight % and polyamide resin (B) are 33～20 weight %, and most preferably phenylethylene resin series (A) is that 70～80 weight % and polyamide resin (B) are 30～20 weight %.

In addition, preferred resin combination of the present invention is as follows, the formed body central part that obtains it being carried out melt molding processing, promptly, when will be perpendicular to the direction on the surface of formed body during as thickness, to the zone with respect to the degree of depth of full depth 40～60%, grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) form disperse phase from the surface.Particularly, in the phase structure of formed body central part, the part that grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) are disperse phase is preferably formed more than the 5 volume %, more preferably form more than the 10 volume %, and then be preferably formed more than the 30 volume %, be preferably formed especially more than the 50 volume %, most preferably form more than the 60 volume %.

Fig. 2 has represented the formed body central part at resin combination of the present invention, and polyamide resin (B) forms external phase, other grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) have formed the phase structure of disperse phase with respect to polyamide resin (B) electron micrograph mode chart.

In Fig. 2, the part of symbol 3 expressions is the polyamide resins (B) that form external phase.The part of symbol 4 expressions is ethene system (being total to) polymkeric substance (A-2) that form disperse phase.The part of symbol 5 expressions is grafting (being total to) polymkeric substance (A-1) that form disperse phase.When being contained in ethene system (being total to) polymkeric substance (A-2) in grafting (being total to) polymkeric substance (A-1) quilt, both are disperse phase for grafting (being total to) polymkeric substance (A-1) and ethene system (being total to) polymkeric substance (A-2).The disperse phase that so-called grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) form, be meant that grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) are in the phase that is enclosed in the state in the polyamide resin (B) when observed under specific scope, especially, in the present invention, be meant in the electron micrograph of the formed body central part of resin combination, be in the phase that is enclosed in the state in the polyamide resin (B) when under the scope of 10 μ m * 10 μ m, observing.

In the observed preferred phase structure of thermoplastic resin composition's of the present invention formed body central part, be not limited to the form of Fig. 2, form non-circular that the shape of grafting (being total to) polymkeric substance (A-1) of disperse phase and/or ethene system (being total to) polymkeric substance (A-2) can be for strip, polygon, ellipse etc.In addition, to the qualification especially of dispersion state of multipolymer (C), mainly be present in the interface of polyamide resin (B) and grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2).In addition, when at least a portion of formed body central part, forming the such phase structure of Fig. 2, form grafting (being total to) polymkeric substance (A-1) of disperse phase and/or ethene system (being total to) polymkeric substance (A-2) is not assembled in the external phase of polyamide resin (B) and dispersive one side more equably, the shock-resistance of formed body has the tendency of raising.

The phase structure of resin combination of the present invention can use electron microscope to observe.As electron microscope, can enumerate TEM (transmission electron microscope) or SEM (scanning electronic microscope).The part of polyamide resin (B) formation external phase or grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) form the volume ratio of the part of disperse phase, can form the part of external phase or the part of grafting (be total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) formation disperse phase with polyamide resin (B), calculate with respect to the form of the area ratio of all areas of electron micrograph.

In order in resin combination of the present invention, to form so special phase structure, for phenylethylene resin series (A) and polyamide resin (B) at 1000 seconds ^-1Velocity of shear under separately melt viscosity, preferably add under the temperature in man-hour＜melt viscosity of phenylethylene resin series (A) at melt molding 〉/＜melt viscosity of polyamide resin (B) the melt viscosity ratio of definition is more than 1.5.More preferably the melt viscosity ratio is more than 2.2, and then preferred more than 3.2.

Even in phenylethylene resin series (A) and polyamide resin (B), do not adding under the situation of multipolymer (C), by being that 65～80 weight %, polyamide resin (B) they are the melt viscosities of 35～20 weight % as ratio of mixture, general＜phenylethylene resin series (A) with phenylethylene resin series (A) 〉/＜melt viscosity of polyamide resin (B)〉the melt viscosity ratio of definition is controlled at more than 2.3, also can obtain at the formed body central part, the external phase that polyamide resin (B) forms is the above resin combinations of 10 volume %.By in such resin combination, add comprise following monomeric unit with the different multipolymer of multipolymer of the present invention (C), can obtain comparing with present known resin combination, shock-resistance and mobile excellent resin combination, described monomeric unit and polyamide resin (B) have the vinyl monomer unit of reactivity or affinity (methyl) vinylformic acid, maleic anhydride, (methyl) glycidyl acrylate etc.But they are compared with resin combination of the present invention, and flowability and appearance are poor.

Manufacture method as thermoplastic resin composition of the present invention, can adopt for example following method, promptly, use homogenizers etc. are with phenylethylene resin series (A), polyamide resin (B), multipolymer (C) and the packing material (D) that adds as required, layered silicate (E) and/or other additives, with particle, powder, perhaps behind the state uniform mixing of shred etc., use possesses the single screw rod or the multiscrew of abundant mixing ability, and have the method that forcing machine that temperature is warming up to 210～330 ℃ port carries out melting mixing, perhaps use Banbury or rubber rollers to carry out method of melting mixing etc.Screw rod to forcing machine arranges that also there is no particular limitation.In addition, to the order by merging of phenylethylene resin series (A), polyamide resin (B), multipolymer (C) and the packing material (D), layered silicate (E) and/or other the additive that add as required with and state, without any qualification, can list with these compositions together simultaneously the blended method or specific two or more composition carried out premix after, the method for mixing all the other compositions.In addition, as required, packing material (D) also can and with the packing material more than a kind, to they order by merging with and state also without any qualification.

Thermoplastic resin composition of the present invention is carried out the formed body that melt molding processes, can obtain by adopting present known forming methods such as injection molding, extrusion moulding, blow molding, compression moulding, compressed moulding or gas assistant formation.For the mold temperature under this situation, from 210～330 ℃ temperature range, select usually.

Thermoplastic resin composition of the present invention, owing to can keep rigidity, thermotolerance, chemical resistant properties and the shock-resistance under normal temperature, low temperature, mobile simultaneously excellent, and then has more excellent appearance with comparing at present, so can be used to bring into play the various moulding product of these character, particularly can be used for the moulding product of the case member periphery of automobile inside/outside decorative material or electric/electronic apparatus.

Embodiment

Below, further specify formation of the present invention, effect according to embodiment.But the present invention is not limited to following embodiment.Before each embodiment of narration, the measuring method of the various rerum naturas that adopt is in an embodiment described.

Cantilever-type impact strength

Utilizing thickness is 1/8 inch injection-molded article, measures nicked cantilever-type impact strength according to ASTM D256.Shock strength is measured and is carried out under normal temperature (23 ℃) and low temperature (30 ℃) respectively.

Modulus in flexure

Measure according to ASTM D-790.

Thermotolerance

According to ASTM D-648, used thickness is 1/4 inch a injection-molded article, at 4.6kgf/cm ²Load measure down heat-drawn wire (HDT).

Mobile

According to JIS K7210 B method, be under the condition of 10kgf at load, measure melt flow rate (MFR).It is as described below to survey periodic melt temperature.Nylon 6 in using polyamide resin (B) and when using the multipolymer of nylon 6 compositions and nylon 66 compositions, melt temperature is 250 ℃, when the use Nylon 66, melt temperature is 280 ℃.

Chemical resistant properties

With injection molding shown in Figure 1 rectangular test film 1 (129mm * 12.6mm; Thickness t=1.5mm), along shown in Figure 1 1/4 oval anchor clamps 2 fixing after, at test film surface coated soup, after placing 24 hours under 23 ℃ of environment, confirm to have or not minute crack and fissured generation,, calculate critical strain ε (%) according to formula 1 according to a shown in Figure 1, b, t and X.Soup uses methyl alcohol and gasoline.And a, b, t and X among Fig. 1 and the Shi 1 represent the following meaning respectively.Anchor clamps use the anchor clamps of major axis a=123mm, minor axis b=47mm.

ε: critical strain (%)

A: the major axis of anchor clamps (mm)

B: the minor axis of anchor clamps (mm)

T: the thickness of test film (mm)

X: the crack produces the length (mm) of the length direction in site

$\mathrm{\ϵ}(\%)=\frac{b\·t}{2a^2}{(1-\frac{X^2(a^2-b^2)}{a^4})}^{-3/2}\×100...\left(1\right)$

Appearance 1

Inject and carry out injection molding 50 times, obtain the sample of the square plate of 50 vertical 80mm * horizontal 80mm * thickness 3mm.Judge the appearance of these square plates by range estimation.Criterion is according to the number that has produced the sample that is selected from the defective more than a kind in ripple, crazing, the little scratch in 50 injections on the square plate surface, to be divided into 5 ranks (5 for best) of 1～5 minute.5 minutes standard is that having produced the sample number that is selected from the defective more than a kind in ripple, crazing, the little scratch is 0 in 50 injections; 4 minutes standard is that 50 these sample numbers in the injection are 1～10; 3 minutes standard is that 50 these sample numbers in the injection are 11～40; 2 minutes standard is that 50 these sample numbers in the injection are 41～49; 1 minute standard is that 50 these sample numbers in the injection are 50.Under the situation of polyamide resin (B), when using Nylon 6 and using the multipolymer of nylon 6 compositions and nylon 66 compositions, at mold temperature is that 250 ℃, die temperature are to carry out injection molding under 70 ℃ the condition, when using Nylon 66, be that 280 ℃, die temperature are to carry out injection molding under 80 ℃ the condition at injecting forming temperature.

Surface gloss

To the square plate of 80mm * thickness 3mm of vertical 80mm of obtaining by above-mentioned injection molding * laterally, use digital goniophotometer (ス ガ trier society system model: UGV-5D), be to measure surface gloss under 60 degree in input angle according to ASTM D256A.The numerical value of surface gloss (%) is high more, and the gloss of minute surface is excellent more, in the present invention, means that appearance is excellent more.

Appearance 2

Inject and carry out injection molding 50 times, obtain the sample of the square plate of 50 vertical 80mm * horizontal 80mm * thickness 3mm.Judge the appearance of these square plates by range estimation.Criterion is according to the number that has produced the sample that is selected from the defective more than a kind in ripple, crazing, the little scratch in 50 injections, on the square plate surface, to be divided into 5 ranks (5 for best) of 1～5 minute.5 minutes standard is that producing the sample number that is selected from the defective more than a kind in ripple, crazing, the little scratch is 0 in 50 injections; 4 minutes standard is that 50 these sample numbers in the injection are 1～5; 3 minutes standard is that 50 these sample numbers in the injection are 6～30; 2 minutes standard is that 50 these sample numbers in the injection are 31～49; 1 minute standard is that 50 these sample numbers in the injection are 50.Injection molding is that 250 ℃, die temperature are to carry out under 70 ℃ the condition at mold temperature.

Coating

On the square plate of vertical 80mm * horizontal 80mm * thickness 3mm, behind the coating acrylic acid-polyurethane two-component coating (ウ レ Application PG60/ Ha one De Na Yi ， Seki west ペ イ Application ト (strain) system), under 80 ℃, 2 hours condition, carry out drying.Then,, mark 1mm quadrate checker (10 * 10), carry out the cellophane tape stripping test,, estimate its coating according to the residual number of filming according to the checker adhesive tape method of JIS K5400-1990 specification specifies.Judgement criteria is as described below.The residual number of filming is that 95 above time notes do zero, and the residual number of filming is that 80～94 o'clock notes are △, the residual number of filming be 79 remember when following do *.

The melt viscosity ratio

Use plunger tpe capillary rheometer (the smart mechanism of Japan is made made キ ヤ ピ ロ グ ラ Off type 1C), being determined under the temperature that melt molding adds man-hour in velocity of shear is 1000 seconds ^-1Phenylethylene resin series (A) and the melt viscosity separately (Pas) of polyamide resin (B), calculate＜phenylethylene resin series the melt viscosity of (A) 〉/＜melt viscosity of polyamide resin (B) the melt viscosity ratio of definition.

Phase structure 1 (polyamide resin (B) external phase)

Use phospho-wolframic acid that the part (central part) from surface 1.2～1.8mm on the thickness direction of No. 1 dumbbell of ASTM (thickness is 3mm) is dyeed, polyamide resin (B) is dyeed.Then, use TEM (the system H-7100 of Hitachi type transmission electron microscope) to observe the central part of formed body.On the electron micrograph (the thickness homogeneous of photo) of the central part of the formed body that obtains like this, extract any 3 places (scopes of 10 μ m * 10 μ m), cut the part that is colored and forms external phase in each place (scopes of 10 μ m * 10 μ m) of being extracted, measure its gross weight, calculate with respect to the ratio that cuts all (scopes of the 10 μ m * 10 μ m) weight before this part.Because the thickness of this electron micrograph is homogeneous, so it is the ratio of volume that the ratio of this weight can be used as, therefore, can will carry out in any 3 places the mean value that obtains of this operation, adopt as ratio (volume %) at the volume of the central part of formed body, part that polyamide resin (B) forms external phase.The part that is external phase when polyamide resin (B) in the phase structure at central part forms 30 volume % when above, evaluation score is 4, when this external phase is during more than or equal to 20 volume %, less than 30 volume %, evaluation score is 3, and when this external phase during more than or equal to 10 volume %, less than 20 volume %, evaluation score is 2, when this external phase during less than 10 volume %, evaluation score is 1, and when this external phase can not form fully, evaluation score was 0.Phase structure 2 (ethene system (being total to) polymkeric substance (A-2) disperse phase)

With the analysis of phase structure 1 in the same electron micrograph of used photo, 3 places of arbitrary extracting cut and are not dyeed by phospho-wolframic acid in each place (scopes of 10 μ m * 10 μ m) of being extracted and grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) form the part of disperse phase.Here, under grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) stretch to situation outside 10 μ m * 10 mu m ranges that extracted, in the time of in being included in arbitrarily 10 μ m * 10 mu m ranges, it as disperse phase, is cut the part that exists in this scope.Measure the gross weight that these cut part, calculate with respect to the ratio that cuts all (scopes of the 10 μ m * 10 μ m) weight before this part.Because the thickness of this electron micrograph is homogeneous, so the ratio of this weight can be regarded as the ratio of volume, therefore, can will carry out the mean value that this operation obtained in any 3 places, the ratio (volume %) of the volume of the part that is disperse phase as central part grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) at formed body adopts.The part that is disperse phase when grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) is that 50 volume % are when above, evaluation score is 4, when this disperse phase is during more than or equal to 30 volume %, less than 50 volume %, evaluation score is 3, and when this disperse phase during more than or equal to 10 volume %, less than 30 volume %, evaluation score is 2, when this disperse phase during less than 10 volume %, evaluation score is 1, and when this disperse phase can not form fully, evaluation score was 0.

The α of multipolymer (C), the beta-unsaturated carboxylic acid acid anhydride is unitary quantitatively

By with α, beta-unsaturated carboxylic acid acid anhydride and vinyl cyanide are that monomer is with various mixed in molar ratio, and carry out infrared absorption spectrometry, and to make about α, beta-unsaturated carboxylic acid acid anhydride and vinyl cyanide are the infrared absorption spectrum typical curve of the strength ratio and the mol ratio of monomeric charateristic avsorption band.Then, carry out the infrared absorption spectrometry of multipolymer (C), by the typical curve that use is made, calculate reaction α addition, that contain in multipolymer (C), beta-unsaturated carboxylic acid acid anhydride unit and vinyl cyanide are monomeric mol ratio.Then, other one-tenth subdivision of multipolymer (C) also made use the same method, calculate with vinyl cyanide be monomeric mol ratio, calculate α based on these results, the unitary content of beta-unsaturated carboxylic acid acid anhydride.In addition, when making the infrared absorption spectrum typical curve, α, beta-unsaturated carboxylic acid acid anhydride use the charateristic avsorption band by the stretching vibration generation of carbonyl (to be about 1780cm ^-1), be monomeric unit for vinyl cyanide, use (is about 2228cm by the charateristic avsorption band of the stretching vibration generation of CN base ^-1), when containing aromatic vinyl and be monomer, use the charateristic avsorption band that produces by aromatic C=C in plane vibration (to be about 1495cm ^-1).With regard to these charateristic avsorption bands, in multipolymer (C), for α, about 1780cm is confirmed as in beta-unsaturated carboxylic acid acid anhydride unit ^-1, be that monomeric unit is confirmed as about 2238cm for vinyl cyanide ^-1, be that monomer is confirmed as about 1495cm for aromatic vinyl ^-1

Weight-average molecular weight

20mg multipolymer (C) is dissolved in the solvents tetrahydrofurane of 10ml, use gel permeation chromatography (pump: 515 types, Waters society system, chromatographic column: TSKgel GMHHR-H (30) directly is connected with TSKgel Multipore HXL-M, eastern ソ one society's system) measure.Column temperature is 40 ℃, and detector uses UV-detector.Weight-average molecular weight is tried to achieve with the polystyrene calibration.

＜phenylethylene resin series (A) 〉

(reference example 1) grafting (being total to) polymkeric substance (A-1) modulation (a-1)

With the following material aggregation container of packing into, be warming up to 65 ℃ while stir.The moment that reaches 65 ℃ in interior temperature begins polymerization, the mixture that forms with uncle's lauryl mercaptan of the vinyl cyanide of the vinylbenzene by 71 weight parts that dripped 40 weight parts in 5 hours continuously, 29 weight parts and 0.3 weight part.

Polyhutadiene latex (the weight average particle directly is 0.2 μ m): 60 weight parts (dividing calibration) Gu form

Potassium oleate: 0.5 weight part

Glucose: 0.5 weight part

Trisodium phosphate: 0.5 weight part

Ferrous sulfate: 0.005 weight part

Deionized water: 120 weight parts

Simultaneously, with the aqueous solution that the pure water that dripped continuously in 7 hours by the potassium oleate of the cumene hydroperoxide of 0.25 weight part, 2.5 weight parts and 25 weight parts forms, finish reaction.With sulfuric acid the graft copolymer latex that obtains is solidified, with in the caustic soda and after, wash, filter, drying, obtain graft copolymer (a-1).

In this graft copolymer (a-1) of specified amount (m), add acetone, refluxed 4 hours, this solution after carrying out 40 minutes centrifugation under the 8800rpm (centrifugal force 10000G), is filtered insoluble composition.Should insoluble composition at 70 ℃ of following drying under reduced pressure after 5 hours, gravimetry (n), the percentage of grafting that utilizes the calculating formula of percentage of grafting=[(n)-(m) * L]/[(m) * L] * 100 to calculate is 37%.Here, L is the rubber containing ratio of graft copolymer.

The filtrate of above-mentioned acetone soln is concentrated with rotary evaporator, obtain precipitate (acetone-insoluble composition).Should after 5 hours, be modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃) at 70 ℃ of following drying under reduced pressure by solvable composition, its limiting viscosity of using Ubbelohde (Ubbelodhe) viscometer to determine under 30 ℃ was 0.39dl/g.

(reference example 2) grafting (being total to) polymkeric substance (A-1) modulation (a-2)

With the following material aggregation container of packing into, be warming up to 65 ℃ while stir.The moment that reaches 65 ℃ in interior temperature begins polymerization, the mixture that forms with uncle's lauryl mercaptan of the vinyl cyanide of the vinylbenzene by 71 weight parts of 5 hours continuous Dropwise 58 weight parts, 29 weight parts and 0.3 weight part.

Polyhutadiene latex (the weight average particle directly is 0.2 μ m): 42 weight parts (dividing calibration) Gu form

Potassium oleate: 0.5 weight part

Glucose: 0.5 weight part

Trisodium phosphate: 0.5 weight part

Ferrous sulfate: 0.005 weight part

Deionized water: 120 weight parts

Simultaneously, with the aqueous solution that the pure water that dripped continuously in 7 hours by the potassium oleate of the cumene hydroperoxide of 0.25 weight part, 2.5 weight parts and 25 weight parts forms, finish reaction.With sulfuric acid the graft copolymer latex that obtains is solidified, with in the caustic soda and after, wash, filter, drying, obtain graft copolymer (a-2).For the graft copolymer that obtains (a-2), the percentage of grafting that the same method of utilization and graft copolymer (a-1) is calculated is 48%, and limiting viscosity is 0.43dl/g.

(reference example 3) grafting (being total to) polymkeric substance (A-1) modulation (a-3)

Except the monomer of will packing into became the vinyl cyanide of vinylbenzene, 33 weight parts of 67 weight parts, other manufacture method with graft copolymer (a-1) were the same, modulate pulverous graft copolymer (a-3).

For the graft copolymer that obtains (a-3), the percentage of grafting that the same method of utilization and graft copolymer (a-1) is calculated is 37%, and limiting viscosity is 0.39dl/g.

(reference example 4) vinyl copolymer (A-2) modulation (a-4)

The acrylamide of 80 weight parts, the methyl methacrylate of 20 weight parts, the Potassium Persulphate of 0.3 weight part, the ion exchanged water of 1500 weight parts are encased in the reactor, also fully mix with the gas phase in the nitrogen replacement reactor on one side, Yi Bian maintain 70 ℃.Reaction lasts till that monomer is converted into till the polymkeric substance fully, obtains the aqueous solution of acrylamide and methyl methacrylate copolymer.Dilute with ion exchanged water, obtain in 165 parts of ion exchanged waters, having dissolved the solution of 0.05 part of methyl methacrylate/acrylamide copolymer.

Be 20 liters at volume, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, the resulting solution that has dissolved 0.05 part of methyl methacrylate/acrylamide copolymer in 165 parts of ion exchanged waters is stirred with 400rpm, with the system nitrogen replacement.Then, on one side the stirring reaction system add following compounding substances on one side, be warming up to 60 ℃, beginning suspension polymerization.

Vinylbenzene: 71 weight parts

Vinyl cyanide: 29 weight parts

Uncle's lauryl mercaptan: 0.2 weight part

2,2 '-Diisopropyl azodicarboxylate: 0.4 weight part

After with 15 minutes temperature of reaction being warming up to 65 ℃, be warming up to 90 ℃ with 2 hours, kept 2 hours down, stop polymerization at 90 ℃.Carry out cooling, the separation of polymkeric substance, washing, the drying of reaction system, thereby obtain containing the vinyl copolymer (a-4) of the pearl of 71 weight % styrene units, 29 weight % acrylonitrile unit.The yield of polymkeric substance is 96%.This multipolymer is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), and the limiting viscosity of using determination of ubbelohde viscometer to go out is 0.51dl/g.

(reference example 5) vinyl copolymer (A-2) modulation (a-5)

Be 20 liters at volume, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, stir solution the same with the solution that in the modulation of vinyl copolymer (a-4), uses, that in 165 parts of ion exchanged waters, dissolved 0.05 part of methyl methacrylate/acrylamide copolymer with 400rpm, with the system nitrogen replacement.Then, on one side the stirring reaction system, add following compounding substances on one side, be warming up to 60 ℃, beginning suspension polymerization.

Vinylbenzene: 67 weight parts

Vinyl cyanide: 33 weight parts

Uncle's lauryl mercaptan: 0.34 weight part

2,2 '-Diisopropyl azodicarboxylate: 0.4 weight part

After with 15 minutes temperature of reaction being warming up to 65 ℃, be warming up to 90 ℃ with 3 hours, kept 3 hours down, stop polymerization at 90 ℃.Carry out cooling, the separation of polymkeric substance, washing, the drying of reaction system, thereby obtain containing the vinyl copolymer (a-5) of the pearl of 67 weight % styrene units, 33 weight % acrylonitrile unit.The yield of polymkeric substance is 97%.This multipolymer is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), and the limiting viscosity of using determination of ubbelohde viscometer to go out is 0.34dl/g.

The modulation of (reference example 6) vinyl copolymer (a-6) (comparative example is used)

Be 20 liters at volume, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, stir solution the same with the solution that in the modulation of vinyl copolymer (a-4), uses, that in 165 parts of ion exchanged waters, dissolved 0.05 part of methyl methacrylate/acrylamide copolymer with 400rpm, with the system nitrogen replacement.Then, on one side the stirring reaction system add following compounding substances on one side, be warming up to 60 ℃, beginning suspension polymerization.

Vinylbenzene: 30 weight parts

Methyl methacrylate: 40 weight parts

Vinyl cyanide: 30 weight parts

Uncle's lauryl mercaptan: 0.34 weight part

2,2 '-Diisopropyl azodicarboxylate: 0.4 weight part

After with 15 minutes temperature of reaction being warming up to 65 ℃, be warming up to 90 ℃ with 3 hours, kept 5 hours down, stop polymerization at 90 ℃.Carry out cooling, the separation of polymkeric substance, washing, the drying of reaction system, thereby obtain containing the vinyl copolymer (a-6) of the pearl of 30 weight % vinylbenzene, 40 weight % methyl methacrylates, 30 weight % vinyl cyanide.The yield of polymkeric substance is 97%.This multipolymer is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), and the limiting viscosity of using determination of ubbelohde viscometer to go out is 0.35dl/g.

＜multipolymer (C) 〉

(reference example 7) multipolymer (C) modulation (c-1)

In the stainless steel autoclave with baffle plate and pfaudler type agitating vane of the methyl ethyl ketone that has added 60 weight parts, pack into 30 weight parts vinylbenzene, 32.9 weight parts vinyl cyanide, 0.2 weight part maleic anhydride, 0.3 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, on one side temperature is warming up to 80 ℃.Then, add continuously following solution with 5 hours, that is, with 2 of the maleic anhydride of the vinylbenzene of 34.6 weight parts and 2.3 weight parts, 0.2 weight part, 2 '-Diisopropyl azodicarboxylate is dissolved in the solution that forms in the methyl ethyl ketone of 60 weight parts.Add the back and then kept 3 hours the termination polymerization at 80 ℃ down.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-1) by drying.The yield of polymkeric substance is 93%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 64.8 weight %, the acrylonitrile unit of 32.7 weight %, the maleic anhydride unit of 2.5 weight %.In addition, multipolymer (C) (c-1) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.30dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 34000.

(reference example 8) multipolymer (C) modulation (c-2)

At the methyl ethyl ketone that has added 80 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 70.0 weight parts vinylbenzene, 28.5 weight parts vinyl cyanide, 1.5 weight parts maleic anhydride, 0.35 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, after temperature being warming up to 80 ℃ on one side, kept 5 hours down at 80 ℃, stop polymerization.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-2) by drying.The yield of polymkeric substance is 94%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 70.7 weight %, the acrylonitrile unit of 27.8 weight %, the maleic anhydride unit of 1.5 weight %.In addition, multipolymer (C) (c-2) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.34dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 35000.

(reference example 9) multipolymer (C) modulation (c-3)

At the methyl ethyl ketone that has added 140 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 66.0 weight parts vinylbenzene, 32.4 weight parts vinyl cyanide, 1.6 weight parts maleic anhydride, 0.16 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, after temperature being warming up to 80 ℃ on one side, kept 5 hours down at 80 ℃, stop polymerization.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-3) by drying.The yield of polymkeric substance is 87%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 68.8 weight %, the acrylonitrile unit of 29.7 weight %, the maleic anhydride unit of 1.5 weight %.In addition, multipolymer (C) (c-3) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.41dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 39000.

(reference example 10) multipolymer (C) modulation (c-4)

At the methyl ethyl ketone that has added 60 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 30 weight parts vinylbenzene, 30 weight parts vinyl cyanide, 0.3 weight part maleic anhydride, 0.6 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, on one side temperature is warming up to 80 ℃.Then, with the 5 hours following solution of continuous interpolation, that is, 2 of the maleic anhydride of the vinylbenzene of 37 weight parts and 2.7 weight parts, 0.2 weight part, 2 '-Diisopropyl azodicarboxylate is dissolved in the solution that forms in the methyl ethyl ketone of 60 weight parts.Add the back and then under 80 ℃ temperature, kept 4 hours the termination polymerization.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, under 80 ℃, carry out 15 hours vacuum-drying, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-4).The yield of polymkeric substance is 93%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 67.0 weight %, the acrylonitrile unit of 30.0 weight %, the maleic anhydride unit of 3.0 weight %.In addition, multipolymer (C) (c-4) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ temperature is 0.25dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 31000.(reference example 11) multipolymer (C) modulation (c-5)

At the methyl ethyl ketone that has added 80 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 56 weight parts vinylbenzene, 27.5 weight parts vinyl cyanide, 15 weight parts methyl methacrylate, 1.5 weight parts maleic anhydride, 0.26 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, after temperature being warming up to 80 ℃ on one side, kept 7 hours down at 80 ℃, stop polymerization.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-5) by drying.The yield of polymkeric substance is 98%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 56.5 weight %, the acrylonitrile unit of 26.6 weight %, the methyl methacrylate units of 15.4 weight %, the maleic anhydride unit of 1.5 weight %.In addition, multipolymer (C) (c-5) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.34dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 35000.(reference example 12) multipolymer (C) modulation (c-6)

At the methyl ethyl ketone that has added 60 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 38.5 weight parts vinylbenzene, 28.0 weight parts vinyl cyanide, 1.0 weight parts maleic anhydride, 0.7 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, on one side temperature is warming up to 80 ℃.Then, with the 5 hours following solution of continuous interpolation, that is, 2 of the maleic anhydride of the vinylbenzene of 30 weight parts and 2.5 weight parts, 0.2 weight part, 2 '-Diisopropyl azodicarboxylate is dissolved in the solution that forms in the methyl ethyl ketone of 60 weight parts.Kept 9 hours down at 80 ℃, stop polymerization.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, under 80 ℃, carry out 12 hours vacuum-drying, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-6).The yield of polymkeric substance is 87%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 68.5 weight %, the acrylonitrile unit of 28.0 weight %, the maleic anhydride unit of 3.5 weight %.In addition, multipolymer (C) (c-6) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.20dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 19000.

(reference example 13) multipolymer (C) modulation (c-7)

At the methyl ethyl ketone that has added 60 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 38 weight parts vinylbenzene, 29 weight parts vinyl cyanide, 0.5 weight part maleic anhydride, 0.65 weight part uncle's lauryl mercaptan, 0.1 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, on one side temperature is warming up to 80 ℃.Then, with the 6 hours following solution of continuous interpolation, that is, 2 of the maleic anhydride of the vinylbenzene of 30 weight parts and 2.5 weight parts, 0.3 weight part, 2 '-Diisopropyl azodicarboxylate is dissolved in the solution that forms in the methyl ethyl ketone of 60 weight parts.Add the back and then kept 3 hours the termination polymerization at 80 ℃ down.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-7) by drying.The yield of polymkeric substance is 91%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 68.1 weight %, the acrylonitrile unit of 28.9 weight %, the maleic anhydride unit of 3.0 weight %.In addition, multipolymer (C) (c-7) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.23dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 27000.

(reference example 14) multipolymer (C) modulation (c-8)

At the methyl ethyl ketone that has added 60 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 30 weight parts vinylbenzene, 33.5 weight parts vinyl cyanide, 0.3 weight part maleic anhydride, 0.28 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, on one side temperature is warming up to 80 ℃.Then, with the 5 hours following solution of continuous interpolation, that is, 2 of the maleic anhydride of the vinylbenzene of 33.5 weight parts and 2.5 weight parts, 0.2 weight part, 2 '-Diisopropyl azodicarboxylate is dissolved in the solution that forms in the methyl ethyl ketone of 60 weight parts.Add the back and then kept 3 hours the termination polymerization at 80 ℃ down.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (C) (c-8) by drying.The yield of polymkeric substance is 93%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 63.4 weight %, the acrylonitrile unit of 33.6 weight %, the maleic anhydride unit of 2.8 weight %.In addition, multipolymer (C) (c-8) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.30dl/g.In addition, the weight-average molecular weight of using gel permeation chromatography to go out is 34000.

The modulation of (reference example 15) multipolymer (c-9) (comparative example is used)

At the methyl ethyl ketone that has added 120 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 66.9 weight parts vinylbenzene, 31.9 weight parts vinyl cyanide, 1.2 weight parts maleic anhydride, 0.02 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, after temperature being warming up to 80 ℃ on one side, kept 8 hours down at 80 ℃, stop polymerization.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (c-9) by drying.The yield of polymkeric substance is 94%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 69.9 weight %, the acrylonitrile unit of 28.9 weight %, the maleic anhydride unit of 1.2 weight %.In addition, multipolymer (c-9) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.58dl/g.Multipolymer (c-9), its limiting viscosity and α, the unitary content of beta-unsaturated carboxylic acid acid anhydride is different with multipolymer of the present invention (C).

The modulation of (reference example 16) multipolymer (c-10) (comparative example is used)

At the methyl ethyl ketone that has added 80 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 70.0 weight parts vinylbenzene, 28.8 weight parts vinyl cyanide, 1.2 weight parts maleic anhydride, 0.02 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, on one side temperature is warming up to 80 ℃.Kept 9 hours down at 80 ℃ with such state, stop polymerization.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (c-10) by drying.The yield of polymkeric substance is 97%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 70.7 weight %, the acrylonitrile unit of 28.1 weight %, the maleic anhydride unit of 1.2 weight %.In addition, multipolymer (c-10) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.69dl/g.For multipolymer (c-10), its limiting viscosity and α, the unitary content of beta-unsaturated carboxylic acid acid anhydride is different with multipolymer of the present invention (C).

The modulation of (reference example 17) multipolymer (c-11) (comparative example is used)

At the methyl ethyl ketone that has added 60 weight parts, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, pack into 30 weight parts vinylbenzene, 31.3 weight parts vinyl cyanide, 0.2 weight part maleic anhydride, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate, stir this solution with 300rpm on one side, on one side temperature is warming up to 80 ℃.Then, with the 5 hours following solution of continuous interpolation, that is, 2 of the maleic anhydride of the vinylbenzene of 37.5 weight parts and 1.0 weight parts, 0.2 weight part, 2 '-Diisopropyl azodicarboxylate is dissolved in the solution that forms in the methyl ethyl ketone of 60 weight parts.Add the back and then kept 3 hours the termination polymerization at 80 ℃ down.After the cooling, solution is injected 5 times of normal methyl alcohol, utilize redeposition to make with extra care, solvent is heated up in a steamer fully, obtain multipolymer (c-11) by drying.The yield of polymkeric substance is 93%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 67.9 weight %, the acrylonitrile unit of 30.8 weight %, the maleic anhydride unit of 1.3 weight %.In addition, multipolymer (c-11) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.84dl/g.For multipolymer (c-11), its limiting viscosity and α, the unitary content of beta-unsaturated carboxylic acid acid anhydride is different with multipolymer of the present invention (C).

The modulation of (reference example 18) multipolymer (c-12) (comparative example is used)

The acrylamide of 80 weight parts, the methyl methacrylate of 20 weight parts, the Potassium Persulphate of 0.3 weight part, the ion exchanged water of 1500 weight parts are encased in the reactor, also fully mix with the gas phase in the nitrogen replacement reactor on one side, Yi Bian maintain 70 ℃.Reaction lasts till that monomer is converted into till the polymkeric substance fully, obtains the aqueous solution of acrylamide and methyl methacrylate copolymer.Dilute with ion exchanged water, obtain in 165 parts of ion exchanged waters, having dissolved the solution of 0.05 part of methyl methacrylate/acrylamide copolymer.

Be 20 liters at volume, have in the stainless steel autoclave of baffle plate and pfaudler type agitating vane, stir the resulting solution that in 165 parts of ion exchanged waters, has dissolved 0.05 part of methyl methacrylate/acrylamide copolymer with 400rpm, with the system nitrogen replacement.Then, on one side the stirring reaction system add following compounding substances on one side, be warming up to 60 ℃, beginning suspension polymerization.

Vinylbenzene: 70 weight parts

Vinyl cyanide: 25 weight parts

Methyl methacrylate: 5 weight parts

Uncle's lauryl mercaptan: 0.4 weight part

2,2 '-Diisopropyl azodicarboxylate: 0.2 weight part

After with 15 minutes temperature of reaction being warming up to 65 ℃, be warming up to 90 ℃ with 2 hours, kept 2 hours down, stop polymerization at 90 ℃.Carry out cooling, the separation of polymkeric substance, washing, the drying of reaction system, thereby obtain the multipolymer (c-12) of pearl.The yield of polymkeric substance is 96%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 70 weight %, the acrylonitrile unit of 25 weight %, the methacrylic acid unit of 5 weight %.In addition, multipolymer (c-12) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.59dl/g.Multipolymer (c-12) does not contain α, beta-unsaturated carboxylic acid acid anhydride unit, and this point is different with multipolymer of the present invention (C), and its limiting viscosity is also different with multipolymer of the present invention (C) in addition.

The modulation of (reference example 19) multipolymer (c-13) (comparative example is used)

Pack in aggregation container 120 parts pure water and 0.3 part Potassium Persulphate are warming up to 65 ℃ while stir.The moment that reaches 65 ℃ in interior temperature begins polymerization, the mixture that forms with the uncle's lauryl mercaptan that added continuously in 5 hours by the methacrylic acid of the vinyl cyanide of the vinylbenzene of 67 weight parts, 30 weight parts, 3 weight parts and 1.5 weight parts, and 30 parts of emulsifier aqueous solutions that contain 2 parts of Sodium dodecylbenzene sulfonatees respectively.Then polymerization system is warming up to 70 ℃, carries out 3 hours polymerization, stop polymerization.Afterwards, dehydrate, obtain multipolymer (c-13) by using calcium chloride to saltout.This moment, the yield of polymkeric substance was 95%.By infrared absorption spectrometry and use consisting of that the infrared absorption spectrum typical curve tries to achieve, contain the styrene units of 67 weight %, the acrylonitrile unit of 30 weight %, the methacrylic acid unit of 5 weight %.In addition, multipolymer (c-13) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using Ubbelohde viscometer to determine under 30 ℃ is 0.31dl/g.Multipolymer (c-13) does not contain α, beta-unsaturated carboxylic acid acid anhydride unit, and this point is different with multipolymer of the present invention (C).

The modulation of (reference example 20) multipolymer (c-14) (comparative example is used)

The methyl methacrylate of 90 weight parts, the vinylbenzene of 8 weight parts, the maleic anhydride of 2 weight parts are dissolved in the methyl ethyl ketone of 150 weight parts, and add 0.14 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate carries out 6 hours solution polymerization under 80 ℃.After the cooling, be injected in 5 times of normal methyl alcohol, carry out redeposition and obtain multipolymer.This multipolymer is carried out 12 hours warm air drying under 80 ℃, obtain multipolymer (c-14), it contains the methyl methacrylate units of 90 weight %, the styrene units of 8 weight %, the maleic anhydride unit of 2 weight %.In addition, multipolymer (c-14) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using determination of ubbelohde viscometer to go out is 0.38dl/g.It is monomeric unit that multipolymer (c-14) does not contain vinyl cyanide, and this point is different with multipolymer of the present invention (C).

The modulation of (reference example 21) multipolymer (c-15) (comparative example is used)

The vinylbenzene of 92 weight parts, the maleic anhydride of 8 weight parts are dissolved in the methyl ethyl ketone of 130 weight parts, and add 0.8 weight part uncle's lauryl mercaptan, 0.3 weight part 2,2 '-Diisopropyl azodicarboxylate carries out 6 hours solution polymerization under 80 ℃.After the cooling, be injected in 5 times of normal methyl alcohol, carry out redeposition and obtain multipolymer.This multipolymer is carried out 12 hours warm air drying under 80 ℃, obtain multipolymer (c-15), it contains the styrene units of 92 weight %, the maleic anhydride unit of 8 weight %.In addition, multipolymer (c-15) is modulated into 0.4g/100ml (methyl ethyl ketone, 30 ℃), the limiting viscosity of using determination of ubbelohde viscometer to go out is 0.15dl/g.It is monomeric unit that multipolymer (c-15) does not contain vinyl cyanide, and this point is different with multipolymer of the present invention (C).

＜polyamide resin (B) 〉

(reference example 22) polyamide resin (B) is (b-1): used nylon 6, the relative viscosity of this nylon 6 solution during with the concentration dissolving of 1g/dl in 98% vitriol oil is 2.3 under 25 ℃.

(reference example 23) polyamide resin (B) is (b-2): used nylon 6, the relative viscosity of this nylon 6 solution during with the concentration dissolving of 1g/dl in 98% vitriol oil is 2.9 under 25 ℃.

(reference example 24) polyamide resin (B) is (b-3): used nylon 6, the relative viscosity of this nylon 6 solution during with the concentration dissolving of 1g/dl in 98% vitriol oil is 3.8 under 25 ℃.

(reference example 25) polyamide resin (B) is (b-4): the relative viscosity of the multipolymer that has used nylon 6 compositions and nylon 66 compositions to form, this multipolymer solution during with the concentration dissolving of 1g/dl in 98% vitriol oil is 2.5 under 25 ℃.

(reference example 26) polyamide resin (B) is (b-5): used nylon 66, the relative viscosity of this nylon 66 solution during with the concentration dissolving of 1g/dl in 98% vitriol oil is 2.4 under 25 ℃.

＜packing material (D) 〉

(reference example 27) packing material (D) is (d-1): having used weight average fiber length is the carbon fiber of 10 μ m as 6mm, number average Fibre diameter.

(reference example 28) packing material (D) is (d-2): having used Fibre diameter is chopped strand (NEG society system, the trade(brand)name: ECS03T-351) of the glass fibre of 13 μ m.

(reference example 29) packing material (D) is (d-3): having used median size is 4.5 μ m, SiO ₂Be 98% with the ratio of MgO, whiteness is 95% talcum ( of Fuji Le Network industry society system, trade(brand)name: LMS300).

＜layered silicate (E) 〉

(reference example 30) swelling property layered silicate (E) modulation (e-1)

(the Network ニ ミ ネ industry: Network ニ ピ ア F of the Na type montmorillonite of dispersed with stirring 100g in 10 liters warm water, cation exchange capacity 120m equivalent/100g), to wherein adding the warm water that 2L has dissolved 51g (with cation exchange capacity equivalent) benzyl dimethyl octadecyl ammonium chloride, stirred 1 hour.Behind the sedimentation and filtration that generates, wash with warm water.Carry out 3 such washings and filter operation, the solid that obtains is carried out vacuum-drying under 80 ℃, obtain exsiccant swelling property layered silicate (e-1).Inorganic ash component to the swelling property layered silicate (e-1) that obtains is measured, and the result is 68 weight %.And the mensuration of inorganic ash component is with 600 ℃ electric furnace 0.1g swelling property layered silicate to be carried out the value that ashing in 3 hours is tried to achieve.

(reference example 31) contains the modulation of the polyamide resin (b-6) of layered silicate

At above-mentioned polyamide resin (b-1) with respect to 100 weight parts, after mixing the above-mentioned swelling property layered silicate (e-1) of 8 weight parts, from screw diameter is that 30mm, L/D are the opening for feed input of the upstream side of 44.5 equidirectional rotation twin screw extruder (the system TEX-30 of JSW), under the condition of 250 ℃ of resin temperatures, screw rod rotation number 150rpm, carry out melting mixing, obtain containing the polyamide resin (b-6) of layered silicate thus.After resulting polyamide resin (b-6) granulation that contains layered silicate, under 80 ℃, carry out 10 hours vacuum-drying.

(reference example 32) contains the modulation of the polyamide resin (b-7) of layered silicate

At above-mentioned polyamide resin (b-1) with respect to 100 weight parts, after mixing the above-mentioned swelling property layered silicate (e-1) of 3 weight parts, from screw diameter is that 30mm, L/D are the opening for feed input of the upstream side of 44.5 equidirectional rotation twin screw extruder (the system TEX-30 of JSW), under the condition of 250 ℃ of resin temperatures, screw rod rotation number 150rpm, carry out melting mixing, obtain containing the polyamide resin (b-7) of layered silicate thus.After resulting polyamide resin (b-7) granulation that contains layered silicate, under 80 ℃, carry out 10 hours vacuum-drying.

(embodiment 1～5)

To in reference example, synthetic phenylethylene resin series (A), polyamide resin (B) and multipolymer (C) mix by the proportioning shown in the table 1, using screw diameter is 25 equidirectional rotation twin screw extruder (pond shellfish ironworker makes PCM-30) as 30mm, L/D, under the condition of 250 ℃ of resin temperatures, screw rod rotation number 150rpm, carry out melting mixing, extrude, make particle thus.For each particle, with its mold temperature be 250 ℃, die temperature be under 70 ℃ the condition in injection molding, make each test film, it is carried out the evaluation of rerum natura.It the results are shown in table 1.

(comparative example 1～4)

Multipolymer that will synthetic phenylethylene resin series (A), polyamide resin (B) and comparative example are used in reference example mixes by the proportioning shown in the table 1, uses with the same manufacture method of embodiment 1～5 and makes each test film, and it is carried out the evaluation of rerum natura.It the results are shown in table 1.

(comparative example 5,6)

To in reference example, synthetic graft copolymer (A-1), vinyl copolymer (a-6), polyamide resin (B) and multipolymer (C) mix by the proportioning shown in the table 1, with making each test film, it is carried out the evaluation of rerum natura with the same manufacture method of embodiment 1～5.It the results are shown in table 1.Comparative example 5,6 does not contain ethene system (being total to) polymkeric substance (A-2), and this point is different with resin combination of the present invention.

Table 1

			Embodiment					Comparative example
														1	2	3	4	5	1	2	3	4	5	6
			(a-1)	Reference example 1		35	35	-	35	35	35	35	35												35	-	35
(a-2)	Reference example 2													-	-	45	-	-	-	-	-	-	55	-
			(a-4)	Reference example 4		15	-	-	-	-	15	-	15												15	-	-
(a-5)	Reference example 5													-	20	10	20	15	-	20	-	-	-	-
			(a-6)	Reference example 6		-	-	-	-	-	-	-	-												-	-	20
(b-1)	Reference example 22													50	45	45	45	50	50	45	50	50	45	45
			(c-1)	Reference example 7		5	-	-	-	-	-	-	-												-	-	-
(c-3)	Reference example 9													-	5	-	-	-	-	-	-	-	-	-
			(c-4)	Reference example 10		-	-	5	-	-	-	-	-												-	5	5
(c-6)	Reference example 12													-	-	-	5	-	-	-	-	-	-	-
			(c-7)	Reference example 13		-	-	-	-	8	-	-	-												-	-	-
(c-9)	Reference example 15													-	-	-	-	-	5	-	-	-	-	-
			(c-10)	Reference example 16		-	-	-	-	-	-	5	-												-	-	-
(c-14)	Reference example 20													-	-	-	-	-	-	-	5	-	-	-
			(c-15)	Reference example 21		-	-	-	-	-	-	-	-												2	-	-
Cantilever-type impact strength	23℃	J/m												874	799	904	910	936	708	673	197	552	780	570
			-30℃	J/m	290	251	310	314	340	204	189	70	85												240	130
	Modulus in flexure													GPa	2.2	2.2	2.2	2.2	2.2	2.1	2.1	1.9	1.9	2.1			2.1
Heat-drawn wire			℃	110	110	110	110	110	109	109	108	109	109												109
		Melt flow rate (MFR)												G/10 minute	63	58	65	72	66	33	29	30	33	53		38
Critical strain	Methyl alcohol			％	*	*	*	*	*	1.3	1.3	0.85	1.3												*		1.1
		Gasoline	％											*	*	*	*	*	1.3	1.2	0.9	1.3	*	1
	Appearance 1			5	5	5	5	5	3	3	3	2	4												4
Surface gloss														％	91	91	92	93	92	79	73	76	75	83		84

*: the expression critical strain is greater than 1.4%

(embodiment 6～8)

To in reference example, synthetic phenylethylene resin series (A), polyamide resin (B) and multipolymer (C) mix, and use with the same manufacture method of embodiment 1～5 and make each test film, it will be carried out the evaluation of rerum natura by the proportioning shown in the table 2.It the results are shown in table 2.

(comparative example 7～10)

Multipolymer that will synthetic phenylethylene resin series (A), polyamide resin (B) and comparative example are used in reference example mixes by the proportioning shown in the table 2, uses with the same manufacture method of embodiment 1～5 and makes each test film, and it is carried out the evaluation of rerum natura.It the results are shown in table 2.

(embodiment 9, comparative example 11)

Will be in reference example the multipolymer used of synthetic phenylethylene resin series (A), polyamide resin (B) and multipolymer (C) or comparative example mix by the proportioning shown in the table 2, using screw diameter is 25 equidirectional rotation twin screw extruder (pond shellfish ironworker makes PCM-30) as 30mm, L/D, under the condition of 280 ℃ of resin temperatures, screw rod rotation number 150rpm, carry out melting mixing, extrude, make particle thus.For each particle, with its mold temperature be 280 ℃, die temperature be under 80 ℃ the condition in injection molding, make each test film, it is carried out the evaluation of rerum natura.It the results are shown in table 2.

Table 2

			Embodiment				Comparative example
												6	7	8	9	7	8	9	10	11
			(a-1)	Reference example 1		-	35	35	35	-	35										35	30	35
(a-2)	Reference example 2											-	-	-	-	55	-	-	-	-
			(a-3)	Reference example 3		35	-	-	-	-	-										-	-	-
(a-4)	Reference example 4											-	20	20	20	-	20	20	10	20
			(a-5)	Reference example 5		20	-	-	-	-	-										-	-	-
(b-1)	Reference example 22											-	-	-	-	-	-	-	-	-
			(b-2)	Reference example 23		45	-	-	-	45	-										-	60	-
(b-3)	Reference example 24											-	45	-	-	-	45	-	-	-
			(b-4)	Reference example 25		-	-	45	-	-	-										45	-	-
(b-5)	Reference example 26											-	-	-	45	-	-	-	-	45
			(c-1)	Reference example 7		-	5	5	5	-	-										-	-	-
(c-5)	Reference example 11											5	-	-	-	-	-	-	-	-
			(c-9)	Reference example 15		-	-	-	-	5	-										-	-	-
(c-10)	Reference example 16											-	-	-	-	-	5	5	-	5
			(c-11)	Reference example 17		-	-	-	-	-	-										-	8	-
Cantilever-type impact strength	23℃	J/m										764	756	776	665	700	293	476	695	384
			-30℃	J/m	235	224	230	159	194	78	116										166	80
	Modulus in flexure											GPa	2.3	2.3	2.2	2.2	2.1	2.2	2.2	2.2			2.2
Heat-drawn wire			℃	109	110	110	118	109	109	109	109										116
		Melt flow rate (MFR)										G/10 minute	56	39	54	57	21	7	27	10		25
Critical strain	Methyl alcohol			％	*	*	*	*	1.05	0.55	0.6										1.3		1.1
		Gasoline	％									*	*	*	*	1.0	0.4	0.55	1.3	1.1
	Appearance 1			5	5	5	5	3	1	3	2										1
Surface gloss												％	90	90	89	88	67	66	74	66		68

*: the expression critical strain is greater than 1.4%

(embodiment 10～12)

To in reference example, synthetic phenylethylene resin series (A), polyamide resin (B) and multipolymer (C) mix by the proportioning shown in the table 3, from screw diameter is that 30mm, L/D are the opening for feed input of the upstream side of 44.5 equidirectional rotation twin screw extruder (the system TEX-30 of JSW), opening for feed drops into the packing material (D) of reference example 27～29 from the side, at resin temperature is that 250 ℃, screw rod rotation number are to carry out melting mixing under the condition of 150rpm, extrude, and makes particle thus.For each particle, with its mold temperature be 250 ℃, die temperature be under 70 ℃ the condition in injection molding, make each test film, it is carried out the evaluation of rerum natura.It the results are shown in table 3.

(comparative example 12,13)

Will be in reference example synthetic phenylethylene resin series (A), polyamide resin (B) and relatively the multipolymer of usefulness mix by the proportioning shown in the table 3, from screw diameter is that 30mm, L/D are the opening for feed input of the upstream side of 44.5 equidirectional rotation twin screw extruder (the system TEX-30 of JSW), opening for feed drops into the packing material (D) of reference example 27,28 from the side, at resin temperature is that 250 ℃, screw rod rotation number are to carry out melting mixing under the condition of 150rpm, extrude, and makes particle thus.For each particle, with its mold temperature be 250 ℃, die temperature be under 70 ℃ the condition in injection molding, make each test film, it is carried out the evaluation of rerum natura.It the results are shown in table 3.

Table 3

			Embodiment			Comparative example
								10	11	12	12	13
			(a-1)	Reference example 1		28	28						28	28	28
(a-4)	Reference example 4							14	14	14	14	14
			(b-1)	Reference example 22		50	50						50	50	50
(c-4)	Reference example 10							8	-	-	-	-
			(c-6)	Reference example 12		-	-						8	-	-
(c-8)	Reference example 14							-	8	-	-	-
			(c-12)	Reference example 18		-	-						-	8	-
(c-13)	Reference example 19							-	-	-	-	8
			(d-1)	Reference example 27		5	-						-	5	-
(d-2)	Reference example 28							-	10	-	-	10
			(d-3)	Reference example 29		-	-						12	-	-
Cantilever-type impact strength	23℃	J/m						101	96	172	57	78
			-30	J/m	60	54	90						27	37
	Modulus in flexure							GPa	4.4	3.6	2.7	4.2			3.5
Heat-drawn wire			℃	210	190	127	199						185
		Melt flow rate (MFR)						G/10 minute	28	32	43	14		18
Appearance 2				5	5	5	2						3
			Coating					○	○	○	×	△
Surface gloss		％				87	87						88	64	66

(embodiment 13～16)

To in reference example, synthetic phenylethylene resin series (A), polyamide resin (B), the polyamide resin that contains layered silicate, multipolymer (C), layered silicate (E) mix by the proportioning shown in the table 4, using screw diameter is 25 equidirectional rotation twin screw extruder (pond shellfish ironworker makes PCM-30) as 30mm, L/D, under the condition of 250 ℃ of resin temperatures, screw rod rotation number 150rpm, carry out melting mixing, extrude, make particle thus.For each particle, with its mold temperature be 250 ℃, die temperature be under 70 ℃ the condition in injection molding, make each test film, it is carried out the evaluation of rerum natura.It the results are shown in table 4.

(comparative example 14～16)

Multipolymer that will synthetic phenylethylene resin series (A), the polyamide resin that contains layered silicate and comparative example are used in reference example mixes by the proportioning shown in the table 4, with making each test film, it is carried out the evaluation of rerum natura with the same manufacture method of embodiment 13～16.It the results are shown in table 4.

Table 4

			Embodiment				Comparative example
										13	14	15	16	14	15	16
			(a-1)	Reference example 1		35	30	27	27								35	35	35
(a-4)	Reference example 4									10	25	23	23	15	10	10
			(b-1)	Reference example 22		-	15	-	50								-	-	-
(b-6)	Reference example 31									59.4	32.4	-	-	54	59.4	59.4
			(b-7)	Reference example 32		-	-	51.5	-								-	-	-
(c-6)	Reference example 12									-	-	6	6	-	-	-
			(c-8)	Reference example 14		6	4	-	-								-	-	-
(c-12)	Reference example 18									-	-	-	-	7	-	-
			(c-13)	Reference example 19		-	-	-	-								-	6	15
(e-1)	Reference example 30									-	-	-	1.5	-	-	-
			Cantilever-type impact strength	23℃	J/m	221	220	197	180								168	100	164
-30℃	J/m	104								110	103	88	77	55	71
				Modulus in flexure		GPa	2.8	2.7	2.7							2.7	2.6	2.5	2.6
Heat-drawn wire		℃	140							135	138	138	128	126	132
				Melt flow rate (MFR)		G/10 minute	43	44	47							45	15	27	15
Appearance 2			5							5	5	5	2	3	2
				Coating			○	○	○							○	△	△	△
Surface gloss		％	87							87	88	87	64	66	64

(embodiment 17～23)

To in reference example, synthetic phenylethylene resin series (A), polyamide resin (B) and multipolymer (C) mix by the proportioning shown in the table 5, using screw diameter is 25 equidirectional rotation twin screw extruder (pond shellfish ironworker makes PCM-30) as 30mm, L/D, revolve at 250 ℃ of resin temperatures, screw rod under the condition of several 150rpm and carry out melting mixing, extrude, make particle thus.For each particle, with its mold temperature be 250 ℃, die temperature be under 70 ℃ the condition in injection molding, make each test film, it is carried out the evaluation of rerum natura.It the results are shown in table 5.

(comparative example 17～19)

Multipolymer that will synthetic phenylethylene resin series (A), polyamide resin (B) and comparative example are used in reference example mixes by the proportioning shown in the table 5, uses with the same manufacture method of embodiment 17～23 and makes each test film, and it is carried out the evaluation of rerum natura.It the results are shown in table 5.

Table 5

			Embodiment							Comparative example
													17	18	19	20	21	22	23	17	18	19
			(a-1)	Reference example 1		35	30	30	35	33	40	35											30	30	35
(a-4)	Reference example 4												28	45	39	-	32	-	32	45	39	25
			(a-5)	Reference example 5		-	-	-	35	-	35	-											-	-	-
(b-1)	Reference example 22												37	25	16	30	35	25	-	25	16	-
			(b-2)	Reference example 23		-	-	15	-	-	-	33											-	15	-
(b-3)	Reference example 24												-	-	-	-	-	-	-	-	-	40
			(c-1)	Reference example 7		-	-	-	-	4	-	4											-	-	-
(c-2)	Reference example 8												4	-	-	-	-	-	-	-	-	-
			(c-6)	Reference example 12		-	-	4	3	-	3	-											-	-	-
(c-7)	Reference example 13												-	3	-	-	-	-	-	-	-	-
			(c-9)	Reference example 15		-	-	-	-	-	-	-											3	4	5
Cantilever-type impact strength	23℃	J/m											763	821	851	835	758	800	755	157	175	186
			-30℃	J/m	263	310	335	337	241	321	250	53											63	70
	Modulus in flexure												GPa	2.3	2.3	2.3	2.2	2.3	2.2	2.2	2.1	2.1			2.1
Heat-drawn wire			℃	110	109	111	110	110	108	110	104	103											106
		Melt flow rate (MFR)											G/10 minute	61	75	62	75	62	56	45	33	17		13
Critical strain	Methyl alcohol			％	*	*	*	*	*	*	*	0.2											0.3		0.45
		Gasoline	％										*	*	*	*	*	*	*	0.2	0.3	0.3
	Appearance 1			5	5	5	5	5	5	5	3	2											1
Surface gloss													％	96	96	96	97	96	97	95	72	75		66
		The melt viscosity ratio			4.0	2.3	2.1	3.2	3.3	3.6	2.3	2.3											2.1		1.5
Phase structure 1													4	3	3	3	4	3	4	0	0	0
			Phase structure 2			3	4	4	4	3	4	3											0	0	0

*: the expression critical strain is greater than 1.4%

By embodiment and comparative example, can the clear and definite fact as described below.

By table 1 and table 2 as can be known, added the resin combination of the embodiment 1～9 of specific copolymer (C) with specific limiting viscosity, compare with the resin combination of comparative example 1～4,7～11, have equal above rigidity, thermotolerance and chemical resistant properties, while shock-resistance, mobile excellent, and then have excellent especially appearance.In addition, from embodiment 1～5 and comparative example 5 and 6 more as can be known, by with multipolymer (C) and specific ethene system (being total to) polymkeric substance (A-2) and usefulness, can access shock-resistance and mobile excellent and appearance, the especially resin combination of surface gloss excellence.

As shown in Table 3, the resin combination that has added the embodiment 10～12 of specific multipolymer (C) of the present invention, compare with the resin combination of comparative example 12,13, have excellent in impact resistance, thermotolerance and coating, and excellent especially in flowability and appearance.

As shown in Table 4, the resin combination that has added the embodiment 13～16 of specific multipolymer (C) of the present invention, compare with the resin combination of comparative example 14～16, have excellent in impact resistance, rigidity, thermotolerance and coating, particularly excellence aspect mobile and appearance.

As shown in Table 5, the specific multipolymer (C) that added of the present invention, and has following special phase structure like that, promptly, although polyamide resin (B) is in a ratio of minor constituent with phenylethylene resin series (A), but form the resin combination of the present invention of embodiment 17～23 of phase structure that polyamide resin (B) is the part of external phase at the central part of formed body, not forming the resin combination of comparative example 17～19 that polyamide resin (B) is the part of external phase with central part at molding compares, has superior stiffness, thermotolerance and chemical resistant properties, particularly shock-resistance and flowability are excellent, and at appearance, especially the surface luster aspect is very excellent.

The industry utilizability

Thermoplastic resin composition of the present invention can be as the case member periphery material of having brought into play the material of above-mentioned excellent specific property, particularly automobile inside/outside decorative material or electric/electronic apparatus.

Claims (9)

1. thermoplastic resin composition, it is characterized in that, be the thermoplastic resin composition who forms by 1～99 weight % phenylethylene resin series (A) and 99～1 weight % polyamide resins (B) with respect to 100 weight parts, and then the thermoplastic resin composition that forms of the ethene improved based copolymer (C) that contains 0.5～80 weight part, described phenylethylene resin series (A) cooperates grafting (being total to) polymkeric substance (A-1) and ethene system (being total to) polymkeric substance (A-2) to form, described grafting (being total to) polymkeric substance (A-1) is that graft polymerization is that the monomeric unit that other at least a kind of monomer of monomer and 0～60 weight % form forms by the aromatic vinyl of 100～40 weight % on rubber polymer, described ethene system (being total to) polymkeric substance (A-2) is that other at least a kind of monomer of monomer and 0～50 weight % form by the aromatic vinyl of 100～50 weight %, described ethene improved based copolymer (C) is the α that contains 1.5～10 weight %, the vinyl cyanide of beta-unsaturated carboxylic acid acid anhydride unit and 0.5～60 weight % is that monomeric unit forms

And ethene improved based copolymer (C) is dissolved in the methylethyl ketone solvent, in the scope of limiting viscosity that determines under 30 ℃ of temperature at 0.15～0.41dl/g.

2. thermoplastic resin composition as claimed in claim 1, ethene improved based copolymer (C) is dissolved in the methylethyl ketone solvent, in the scope of limiting viscosity at 0.15～0.30dl/g that determines under 30 ℃ of temperature.

3. thermoplastic resin composition as claimed in claim 1 is with respect to the phenylethylene resin series (A), polyamide resin (B) and the ethene improved based copolymer (C) that add up to 100 weight parts, and then contains that the packing material (D) of 0.1～150 weight part forms.

4. thermoplastic resin composition as claimed in claim 1 is with respect to the phenylethylene resin series (A), the polyamide resin (B) that add up to 100 weight parts, and then contains that the layered silicate (E) of 0.05～40 weight part forms.

5. thermoplastic resin composition as claimed in claim 4 is characterized in that, layered silicate (E) in phenylethylene resin series (A) and/or polyamide resin (B) with the horizontal homodisperse below 10 layers.

6. thermoplastic resin composition as claimed in claim 1, it is characterized in that, in the formed body that obtains this resin combination being carried out melt molding processing, when will be perpendicular to the direction on the surface of formed body during as thickness, from the surface to zone with respect to the degree of depth of full depth 40～60%, as using the observed phase structure of electron microscope, the part that polyamide resin (B) is external phase forms more than the 10 volume %.

7. thermoplastic resin composition as claimed in claim 6 is characterized in that, the part that polyamide resin (B) is external phase forms more than the 30 volume %.

8. thermoplastic resin composition as claimed in claim 1, it is characterized in that, in the formed body that obtains this resin combination being carried out melt molding processing, when will be perpendicular to the direction on the surface of formed body during as thickness, from the surface to zone with respect to the degree of depth of full depth 40～60%, as using the observed phase structure of electron microscope, the part that grafting (being total to) polymkeric substance (A-1) and/or ethene system (being total to) polymkeric substance (A-2) are disperse phase forms more than the 5 volume %.

9. formed body, it carries out melt molding with the described thermoplastic resin composition of claim 1 and processes.