CN101585965B

CN101585965B - Resin moldings and conductive resin composition

Info

Publication number: CN101585965B
Application number: CN 200910142578
Authority: CN
Inventors: 三好贵章; 野田和弥; 堀尾光宏; 吉永勇二
Original assignee: Asahi Kasei Chemicals Corp
Current assignee: Asahi Kasei Corp
Priority date: 2003-04-18
Filing date: 2004-04-16
Publication date: 2012-04-18
Anticipated expiration: 2024-04-16
Also published as: CN1806010A; CN100528964C; CN101585965A

Abstract

A shaped resin article comprising a polyamide (A) (comprising at least two different polyamide components), a polyphenylene ether (B) and a partially hydrogenated block copolymer (C) (obtained by partially hydrogenating a block copolymer comprising an aromatic vinyl polymer block and a conjugated diene polymer block) including a block copolymer (C-1) having a number average molecular weight of from 200,000 to 300,000, wherein (A) is present as a continuous phase in which (B) is dispersed to form a dispersed phase, and (C) is present in the continuous phase of (A) and/or the dispersed phase of (B), wherein the surface area of the polyamide (A) exposed on the overall surface of the shaped resin article is at least 80 %, based on the surface area of the shaped resin article. A conductive resin composition comprising a polyamide (A), a polyphenylene ether (B), a partially hydrogenated block copolymer (C) comprising an aromatic vinyl polymer block and a conjugated diene polymer block, a conductive carbonaceous material (D) and wollastonite particles (E).

Description

Molded resin product and conductive resin composition

The application is that application number is dividing an application of 200480016801.1 application for a patent for invention, and the applying date of original application is on April 16th, 2004, and denomination of invention is " molded resin product and a conductive resin composition ".

Background of invention

Prior art

Ppe not only has the electrical properties (for example specific inductivity and dielectric loss factor) and the excellent thermotolerance of excellent mechanical properties, excellence, and has excellent size stability.Therefore, ppe is used in the various fields.The insufficient formability of ppe but.In order to improve the formability of ppe, open (clear) 45-997 of the Japanese Patent of having examined discloses a kind of technology, in this technology polymeric amide is added in the ppe, obtains the polyamide-polyphenylene ether alloy thus.The new technology of multiple relevant polyamide-polyphenylene ether alloy has for example also been proposed in US 4315086,4732938 and 4659760 in addition.Now, the polyamide-polyphenylene ether alloy is used to very in the extensive fields, for example the automobile external-use parts.

A lot of automobile external-use parts normally apply.Therefore, when selecting the material of automobile external-use parts, the bond strength of material and coating (this bond strength is designated hereinafter simply as " coating bond strength ") is an important factor.

Usually, proposed multiple technologies and be used to give the polyamide-polyphenylene ether alloy with the coating bond strength.For example, do not examine Japanese patent application prospectus (putting down) 8-109324 (corresponding to US 5554693) and disclose a kind of technology, wherein specific terpene phenolic resin is added in the polyamide-polyphenylene ether alloy, to improve the coating bond strength of this alloy.In addition; Do not examine Japanese patent application prospectus (putting down) 3-143571 and disclose a kind of technology; Wherein use the surfactant treatment molded resin product, improved the coating bond strength of this molded resin product thus, and needn't use this moulded products of undercoat precoating.

But, all there is a problem in above-mentioned every kind of technology, promptly uses additive to improve the coating bond strength of said alloy, and the shortcoming that causes thus is that the thermotolerance of said alloy reduces and the coating molding goods of this alloy can absorb wet the branch.Therefore, but market demands are a kind of in the technology of not using under the additive situation coating that improves molded resin product.

In addition, as one of needed character of large-scale moulded products (for example automobile guard plate and automobile back door), can also mention low coefficient of linear expansion.In automobile, between automobile guard plate and door, provide the switch door necessary gap.When automobile guard plate was made by the material with high coefficient of linear expansion, the shortcoming of bringing was that the size in above-mentioned gap can change with envrionment temperature.Therefore, hope to improve the coefficient of linear expansion of producing above-mentioned large-scale moulded products material therefor.

Usually, can improve the coefficient of linear expansion of material through adding organic or mineral filler.But; When organic or mineral filler add in the material; The shortcoming of the moulded products that is made by this material is that not only this organic or inorganic filler may be present in to deviation the near surface of this moulded products; But also make the coating bond strength descend, and the coating that on this moulded products, forms has relatively poor gloss.Therefore, hope to improve simultaneously the coefficient of linear expansion and the coating bond strength of moulded products, and the gloss of the coating that on this moulded products, forms.

Invention field

The present invention relates to molded resin product.More particularly; The present invention relates to comprise the molded resin product of following material: the polymeric amide (A), ppe (B) and the specific partially hydrogenated segmented copolymer (C) that contain at least two kinds of different polyamide compositions; Wherein said polymeric amide (A) exists as external phase; Disperse to form disperse phase at ppe described in the said external phase (B); And said partially hydrogenated segmented copolymer (C) be present in the said external phase that is selected from polymeric amide (A) and ppe (B) said disperse phase at least one mutually in, wherein said polymeric amide (A) exposes to the open air on the surface of said molded resin product so that the total area that exposes to the open air at the lip-deep polymeric amide of said molded resin product (A) is 80% of a molded resin product surface-area at least.The favourable part of molded resin product of the present invention is that not only this molded resin product has excellent matting; Be that also this molded resin product has excellent adhesion strength (this bond strength is designated hereinafter simply as " coating bond strength ") to the coating that on this molded resin product, forms; And this coating that on this molded resin product, forms has the excellent acutance (that is, this coating has excellent gloss) of the image that wherein mirrors.The invention still further relates to the conductive resin composition that comprises following material: polymeric amide (A), ppe (B), specific segmented copolymer (C), conduction carbonaceous material (D) and wollastonite particle (E).The conductive resin composition of the application of the invention can prepare moulded products; The favourable part of this moulded products is that not only this moulded products has excellent matting; Be that also this moulded products has excellent coating bond strength, and the coating that on this moulded products, forms has the excellent acutance of the image that wherein mirrors.In addition, prepared moulded products has gratifying low coefficient of linear expansion, and this is particularly advantageous in the large-scale moulded products field of for example automobile guard plate and automobile back door.Molded resin product of the present invention and can be advantageously used in various fields by the moulded products that conductive resin composition of the present invention makes; For example; Not only the automobile external-use field of components can be used for, and the electric and interior field of Electrical and Electronic parts, office automated machine parts, mechanical part, motorcycle and automobile can be used for parts.

Summary of the invention

Under this situation; The inventor has carried out extensive research; Purpose is a kind of polyamide-polyphenylene ether alloy that can be used to prepare moulded products of exploitation under the condition of not using any above-mentioned additive; Its favourable part is that not only this moulded products has excellent matting, be that also this moulded products has excellent adhesion strength, and the coating that on this moulded products, forms has the excellent acutance of the image that wherein mirrors.The result unexpectedly finds; Above-mentioned purpose can realize through the molded resin product that comprises polymeric amide, ppe and partially hydrogenated aromatic vinyl/conjugated diene block copolymer, wherein makes to expose to the open air at the area of the lip-deep polymeric amide of this molded resin product and brings up to certain level.In addition, the inventor finds under the condition of not using additive can to make from the conductive resin composition that comprises polymeric amide (A), ppe (B), specific segmented copolymer (C), conduction carbonaceous material (D) and wollastonite particle (E) moulded products of excellence.Particularly; The advantage of the moulded products that makes from this conductive resin composition is that not only this moulded products has excellent matting; But also be that this moulded products has excellent coating bond strength, and the coating that on this moulded products, forms has the excellent acutance of the image that wherein mirrors.In addition, said moulded products has favourable low coefficient of linear expansion.Accomplished the present invention based on these discoveries.

Therefore; An object of the present invention is to provide a kind of molded resin product; Its advantage is that not only this molded resin product has excellent matting; But also be that this molded resin product has excellent coating bond strength, and the coating that on this molded resin product, forms has the excellent acutance of the image that wherein mirrors.

Another object of the present invention provides a kind of conductive resin composition that can prepare molded resin product; The advantage of this molded resin product is that this moulded products has excellent matting; And be that this moulded products has excellent coating bond strength; And the coating that on this moulded products, forms has the excellent acutance of the image that wherein mirrors, and this moulded products has favourable low coefficient of linear expansion.

From following detailed description and appended claims, above-mentioned and other purposes of the present invention, feature and advantage will be obvious.

Detailed Description Of The Invention

According to the present invention, molded resin product is provided, it comprises:

The polymeric amide (A) that contains at least two kinds of different polyamide compositions,

Ppe (B) and

One or more partially hydrogenated segmented copolymers; (C); It obtains through the unhydrided segmented copolymer of partially hydrogenated independently of one another; Said unhydrided segmented copolymer comprises at least a aromatic vinyl polymer block and at least a conjugated diolefin polymer block of mainly being made up of the aromatic vinyl monomer unit of mainly being made up of conjugated diene monomeric unit; Said partially hydrogenated segmented copolymer; (C) comprise that at least a number-average molecular weight is 200000～300000 partially hydrogenated segmented copolymer; (C-1)

Wherein said polymeric amide (A) exists as external phase; Disperse to form disperse phase at ppe described in the said external phase (B); And said partially hydrogenated segmented copolymer (C) be present at least one said external phase that is selected from polymeric amide (A) and ppe (B) said disperse phase mutually in

Wherein said polymeric amide (A) exposes to the open air on the surface of said molded resin product so that the surface-area that exposes to the open air at the whole lip-deep polymeric amide (A) of said molded resin product is at least 80% of a molded resin product surface-area.

In order more easily to understand the present invention, below enumerate essential characteristic of the present invention and multiple preferred embodiment.

1. molded resin product, it comprises:

Ppe (B) and

One or more partially hydrogenated segmented copolymers (C),

Wherein said partially hydrogenated segmented copolymer; (C) obtain through the unhydrided segmented copolymer of partially hydrogenated independently of one another; Said unhydrided segmented copolymer comprises at least a aromatic vinyl polymer block and at least a conjugated diolefin polymer block of mainly being made up of the aromatic vinyl monomer unit of mainly being made up of conjugated diene monomeric unit; Said partially hydrogenated segmented copolymer; (C) comprise that at least a number-average molecular weight is 200000～300000 partially hydrogenated segmented copolymer; (C-1)

2. according to above 1 molded resin product, it is characterized in that said polymeric amide (A) contains at least two kinds and different has its polymeric amide composition of different viscosity separately.

3. according to above 1 molded resin product, it is characterized in that composition (A) contains polyamide 6,6 be different from polyamide 6,6 polymeric amide.

4. according to above 3 molded resin product, it is characterized in that, the said polyamide 6 that is different from, 6 polymeric amide is a polyamide 6.

5. according to above 3 molded resin product, it is characterized in that the said polyamide 6 that is different from, 6 polymeric amide are the polymeric amide that contains independently of one another with the repeating unit of following formula (1) expression:

R wherein ¹And R ²Represent C independently of one another ₃-C ₁₄Alkylidene group or C ₆-C ₉Arylidene, condition are R ¹And R ²Be not C simultaneously ₆Alkylidene group or C ₆Arylidene.

6. according to above 1 molded resin product, it is characterized in that it is 1 * 10 that said polymeric amide (A) contains at least a terminal amino group content ⁵Mol/g～4 * 10 ⁵The polymeric amide composition of mol/g.

7. according to above 1 molded resin product; It is characterized in that; Said ppe (B) contain molecular weight be 200000 or the ppe molecule of higher higher molecular weight and molecular weight be 5000 or the ppe molecule of lower lower molecular weight, the weight ratio of the ppe molecule of wherein said higher molecular weight and the ppe molecule of said lower molecular weight is 0.35 or littler.

8. according to above 1 molded resin product; It is characterized in that; Said ppe (B) contain molecular weight be 200000 or the ppe molecule of higher higher molecular weight and molecular weight be 5000 or the ppe molecule of lower lower molecular weight, the amount of the amount of the ppe molecule of wherein said lower molecular weight and the ppe molecule of said higher molecular weight is respectively the 5 weight % or the littler and 2 weight % or littler of said polyphenylene oxide resin (B) weight.

9. according to above 1 molded resin product, it is characterized in that said one or more partially hydrogenated segmented copolymers (C) comprise that also at least a number-average molecular weight is 50000～150000 partially hydrogenated segmented copolymer (C-2).

10. according to above 9 molded resin product, it is characterized in that said at least a partially hydrogenated segmented copolymer (C-1) and said at least a partially hydrogenated segmented copolymer (C-2) all comprise:

At least a partially hydrogenated segmented copolymer with high aromatic vinyl monomer unit content; It obtains through the unhydrided segmented copolymer of partially hydrogenated; The amount that wherein said at least a aromatic vinyl polymer block exists be said unhydrided segmented copolymer weight 60 to 90 weight % and

At least a partially hydrogenated segmented copolymer with low aromatic vinyl monomer unit content; It obtains through the unhydrided segmented copolymer of partially hydrogenated; The amount that wherein said at least a aromatic vinyl polymer block exists be said unhydrided segmented copolymer weight 20 to less than 60 weight %, and

Wherein be present in said hydrogenant segmented copolymer (C-1) and (C-2) in the total amount of aromatic vinyl polymer block be said hydrogenant segmented copolymer (C-1) and (C-2) 30～40 weight % of gross weight.

11. molded resin product according to above 1; Wherein these goods also comprise at least a carbonaceous material (D) that is selected from graphitized carbon black, thomel and carbon nanotube, and these goods carry out through the composition to the said carbonaceous material (D) of the masterbatch that comprises the said polymeric amide (A) that wherein is dispersed with said carbonaceous material (D) and said ppe (B), said one or more partially hydrogenated segmented copolymers (C) and non-essential at least a said polymeric amide (A) that is selected from additional content and additional content, and melt-kneading makes.

12. the molded resin product according to above 1 is characterized in that these goods also comprise (E) wollastonite particle that average particulate diameter is 2～9 μ m.

13. the molded resin product according to above 12 is characterized in that said wollastonite particle (E) has at least two kinds of different length-to-diameter ratios.

14. the molded resin product according to above 1 is characterized in that these goods are saccharoids.

15. the molded resin product according to above 1 is characterized in that these goods are automobile external-use parts.

16. conductive resin composition, it comprises:

Polymeric amide (A),

Ppe (B),

Segmented copolymer (C), it contains at least a aromatic vinyl polymer block and at least a conjugated diolefin polymer block of mainly being made up of the aromatic vinyl monomer unit of mainly being made up of conjugated diene monomeric unit,

The conduction carbonaceous material (D) and

Wollastonite particle (E).

17. conductive resin composition according to above 16; It is characterized in that; Said composition carries out through the composition to the said carbonaceous material (D) of the masterbatch that comprises the said polymeric amide (A) that wherein is dispersed with said carbonaceous material (D) and said ppe (B), said segmented copolymer (C), said wollastonite particle (E) and non-essential at least a said polymeric amide (A) that is selected from additional content and additional content that melt-kneading makes, and wherein said carbonaceous material (D) is at least a composition that is selected from graphitized carbon black, thomel and carbon nanotube.

18. the conductive resin composition according to above 16 is characterized in that the average particulate diameter of said wollastonite particle (E) is 2～9 μ m.

19. conductive resin composition according to above 16; It is characterized in that; Said wollastonite particle (E) comprise length-to-diameter ratio be 5 or bigger particle and length-to-diameter ratio less than 5 particle, wherein length-to-diameter ratio be 5 or the amount of bigger said wollastonite particle (E) be 50 weight % or bigger of wollastonite particle (E) gross weight.

Below will describe the present invention in detail.

In one embodiment of the invention, a kind of molded resin product is provided, it comprises:

Ppe (B) and

The partially hydrogenated segmented copolymer (C) that one or more are specific,

Type for the polymeric amide that can be used for molded resin product of the present invention (A) does not have special qualification, as long as it is the polymkeric substance that in its repeating unit, has acid amides { NH-C (=O)-} key.

Usually, for example the polycondensation of ring-opening polymerization, diamines and the di-carboxylic acid through lactan or the polycondensation of omega-amino-carboxylic acid obtain polymeric amide.But in the present invention, the method for acquisition polymeric amide is not limited to these instances.

The instance of above-mentioned diamines comprises aliphatic diamine, alicyclic diamine and aromatic diamine.Particularly; Can mention tetramethylenediamine, hexanediamine, 11 carbon diamines, 12 carbon diamines, 13 carbon diamines, 2,2,4-trimethylammonium hexanediamine, 2; 4; 4-trimethylammonium hexanediamine, 5-methyl-nonamethylene diamine, 1,3-diamino-methylcyclohexane, 1,4-diamino-methylcyclohexane, mphenylenediamine, Ursol D, m-xylylenediamine and right-benzene dimethylamine.

The instance of di-carboxylic acid comprises aliphatic dicarboxylic acid, alicyclic di-carboxylic acid and aromatic dicarboxylate.Particularly, can mention hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, 1,1,3-hendecane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, terephthalic acid, m-phthalic acid, naphthalic acid and dimeracid.

The specific examples of lactan comprises ε-Ji Neixianan, oenantholactam and omega-lauric lactam.

In addition, the specific examples of omega-amino-carboxylic acid comprises epsilon-amino caproic acid, 7-aminoheptylic acid, 8-aminocaprylic acid, 9 aminononanoic acid, the amino hendecoic acid of 11-, the amino lauric acid of 12-and the amino ficocerylic acid of 13-.

In the present invention; This polymeric amide can be from any above-claimed cpd (promptly; Lactan, diamines, di-carboxylic acid and omega-amino-carboxylic acid) homopolymer that obtains, or carry out the multipolymer that polycondensation obtains through the mixture that makes at least two types of above-claimed cpds.

In the present invention; The also preferred polymeric amide that obtains by following method that uses: wherein one or more above-claimed cpds (that is, lactan, diamines, di-carboxylic acid and omega-amino-carboxylic acid) in polymerization reactor polymerization with obtain thus a kind of low-molecular-weight oligopolymer and with the oligopolymer of gained in forcing machine etc. further polymerization to obtain high molecular weight polymers thus.

The instance that can be advantageously used in polymeric amide of the present invention comprises polyamide 6, polyamide 6,6, polymeric amide 4,6, polymeric amide 11, polymeric amide 12, polyamide 6,10, polyamide 6,12, polyamide 6/6,6, polyamide 6/6; 12, polymeric amide MXD (m-xylylenediamine), 6, polyamide 6, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6; 6/6, T, polyamide 6,6/6, I, polyamide 6/6, T/6; I, polyamide 6,6/6, T/6, I, polyamide 6/12/6, T, polyamide 6; 6/12/6, T, polyamide 6/12/6, I and polyamide 6,6/12/6, I.In addition, can also use polyamide article through utilizing forcing machine etc. that multiple different polymeric amide mixing or copolymerization are obtained.

In molded resin product of the present invention,, must use two kinds or more kinds of different polymeric amide composition, and preferably use two kinds or more kinds of dissimilar polymeric amide mixture of ingredients with different viscosity as polymeric amide (A).Can mention the polyamide compound that contains polymeric amide composition that viscosity is 80ml/g and viscosity and be the polymeric amide composition of 150ml/g, contain polymeric amide composition and the viscosity that viscosity is 120ml/g to be the polyamide compound of the polymeric amide composition of 115ml/g as the instance of said polyamide compound, wherein the viscosity of polymeric amide composition records according to ISO307 in 96% sulfuric acid respectively.The polyamide compound of polymeric amide composition that contains different viscosity when use is during as polymeric amide (A), and preferably the viscosity of this polyamide compound is in 90～130ml/g scope, more advantageously in 100～125ml/g scope.The viscosity whether said polyamide compound has in the above-mentioned scope can be confirmed through following method: wherein; With being ready to use in polymeric amide composition in the polyamide compound to be dissolved in 96% sulfuric acid with weight ratio identical in polyamide compound to be prepared; Obtain the solution of this polymeric amide composition thus, use the solution of the said polymeric amide composition that obtains to carry out viscosity test according to ISO307.Be described below, have the combination of the polymeric amide composition of different viscosity, can improve the coating bond strength of this molded resin product, and can not sacrifice the mechanical properties of this molded resin product through use.

In addition, in the present invention, preferred at least a polymeric amide composition is a polyamide 6,6.Use polyamide 6,6 is favourable as at least a said polymeric amide composition, and for example, its reason is that the thermotolerance that can suppress this molded resin product reduces.

As being different from polyamide 6,6 polymeric amide, preferably use polyamide 6 and/or with the polymeric amide of following formula (1) expression:

In these polymeric amide, preferably use at least a following polymeric amide that is selected from: polymeric amide 4,6, polyamide 6,12, polyamide 6,6/6, I, polyamide 6; 6/6, T, polyamide 6,6/6, I/6, T, polymeric amide 9, T and polymeric amide 12; T more preferably uses at least a following polymeric amide that is selected from: polyamide 6,12, polyamide 6,6/6, I and polyamide 6,6/6; T most preferably uses polyamide 6, and 12 and/or polyamide 6,6/6, I.

When using polyamide 6,6 be different from polyamide 6, the combination of 6 polymeric amide can be selected polyamide 6 during as polymeric amide (A) suitably, 6 be different from polyamide 6, the amount of 6 polymeric amide; But, polyamide 6,6 amount is preferably 99～30 weight % of polymeric amide (A) weight, and more preferably 90～45 weight % most preferably are 80～50 weight %.

In addition, it is 1 * 10 that the polymeric amide that preferably in molded resin product of the present invention, uses (A) contains at least a terminal amino group content ⁵～4 * 10 ⁵The polymeric amide of mol/kg more advantageously is 2 * 10 ⁵～3 * 10 ⁵Mol/kg.In the case, for the not special restriction of content of carboxyl end group; But, preferred content of carboxyl end group is at least 5 * 10 ⁵Mol/g or more more advantageously is 6 * 10 ⁵～13 * 10 ⁵Mol/kg.

For above-mentioned endgroup content, polymeric amide (A) can contain the polymeric amide composition of endgroup content outside above-mentioned scope, as long as have the endgroup content in the above-mentioned scope as at least a polymeric amide composition of polymeric amide (A).In addition, the preferred polyamide 6 with the endgroup content in the above-mentioned scope, 6 of using.

For the method for the endgroup content that is used to regulate polymeric amide, can use any ordinary method well known in the art.For example, can mention following method: wherein be selected from diamines, monoamine, di-carboxylic acid and monocarboxylic compound adds the polymerization reaction system that is used for preparing polymeric amide, to obtain polymeric amide with desirable endgroup content with at least a.

In addition; In molded resin product of the present invention; Can use common metallic stablizer (being used to improve the thermostability of polymeric amide), of Japanese patent application prospectus (putting down) 1-163262 (corresponding to U.S. Pat 4857575) that not examining, and can not produce any problem.

In said common metallic stablizer, preferred especially CuI, CuCl ₂, venus crystals and cerium stearate.The also halide salt of preferred as alkali, for example potassiumiodide and Potassium Bromide.These metallic stablizers can use or make up use separately.

With respect to the polymeric amide (A) of 100 weight parts, preferably the amount with 0.001～1 weight part adds said metallic stablizer in the polymeric amide (A).

In addition, in molded resin product of the present invention,, can use common organic stabilizer, and can not produce any problem as the stablizer that is different from above-mentioned containing metal stablizer.The instance of organic stabilizer comprises for example Irganox 1098 of hindered phenol antioxidant; Phosphorus stablizer is the anti-processing warm of Irgafos168 for example; The lactone stablizer is the anti-processing warm of HP-136 for example; The sulphur type thermal stabilizing agent; And hindered amine as light stabilizer.

In above-mentioned organic stabilizer, Phosphorus stablizer of preferred hindered phenol antioxidant, anti-processing heat and composition thereof.With respect to the polymeric amide (A) of 100 weight parts, the amount of said organic stabilizer is preferably 0.001～1 weight part.

In addition, also can any other conventional additives that be used for polymeric amide be added polymeric amide (A).With respect to the polymeric amide (A) of 100 weight parts, can be to use said additive less than the amount of 10 weight parts.

The instance that can be used for the ppe (B) of molded resin product of the present invention comprises homopolymer and multipolymer, contains the structural unit of representing with following formula independently of one another:

Wherein O representes Sauerstoffatom, and R representes Wasserstoffatoms, halogen atom, uncle or secondary C independently of one another ₁-C ₃Low alkyl group, C ₆-C ₉Aryl, C ₁-C ₃Haloalkyl, C ₁-C ₃Aminoalkyl group, C ₁-C ₃Hydroxyl acyloxy (the plain オキ of charing water シ yl) or C ₁-C ₃Halogenated hydroxyl acyloxy (the plain オキ of Ha ロ charing water シ yl) (wherein, at least two carbon atoms are present between halogen atom and the Sauerstoffatom).

The specific examples that can be used for the ppe of molded resin product of the present invention comprises and gathers (2,6-dimethyl--1,4-phenylene ether), gathers (2-methyl-6-ethyl-1; The 4-phenylene ether), gather (2-methyl-6-phenyl-1; The 4-phenylene ether) and gather (2,6-two chloro-1,4-phenylene ether).Other instances of ppe comprise 2; The multipolymer of 6-xylenol and other phenol (for example 2; 6-xylenol and 2,3, the multipolymer of 6-pseudocuminol and 2; The multipolymer of 6-xylenol and 2-methyl-6-butylphenol, it is discussed in open (clear) 52-17880 (corresponding to U.S. Pat 4011200) of the Japanese patent application of having examined to some extent.

In above-mentioned ppe, preferably gather (2,6-dimethyl--1,4-phenylene ether), 2,6-xylenol and 2,3, multipolymer of 6-pseudocuminol and composition thereof.

For the not special restriction of the method for ppe (B) used in the preparation molded resin product of the present invention, can use any ordinary method.For example, can mention like U.S. Pat 3306874,3306875,3257357 and 3257358, do not examine Japanese patent application prospectus (clear) 50-51197 (corresponding to U.S. Pat 3929930), Japanese patent application prospectus (clear) 52-17880 that has examined, not examine the method described in Japanese patent application prospectus (clear) 63-152628 (corresponding to U.S. Pat 4011200).

For the ppe that can be used for molded resin product of the present invention (B), the viscosity (η of its reduction _Sp/c) be preferably 0.15～0.70dl/g, 0.20～0.60dl/g more preferably, even 0.40～0.55dl/g more preferably, said viscosity 0.5g/dl chloroformic solution with respect to ppe under 30 ℃ records.

Using two kinds or more kinds of dissimilar mixture with ppe of the different viscosity that reduce is favourable as ppe (B), and this is because can improve the fluidity of molten of ppe (B) and the balance of shock resistance.Instance as said mixture; The mixture of the ppe that can mention viscosity and the ppe of viscosity and have 0.40dl/g or the mixture of the ppe of the viscosity of lower reduction and the ppe of viscosity with 0.50dl/g or higher reduction with 0.50dl/g or higher reduction with 0.45dl/g or lower reduction, but said polyphenylene oxide alloy is not limited to above those of giving an example.

The ppe (B) that the present invention uses can be modified form or can be the form of mixtures of unmodified ppe and Noryl.The preferred especially mixture that uses unmodified ppe and Noryl is as ppe (B).

In the present invention; " Noryl " is meant the ppe that carries out modification with at least a modifier compound; This compound has at least one and is selected from the unsaturated link(age) of carbon-to-carbon double bond and carbon-to-carbon triple bond and has the functional group that at least one is selected from hydroxy-acid group, anhydride group, amino, hydroxyl and glycidyl, and can use any Noryl of describing among the WO02/094936.

The Noryl that is used to prepare molded resin product of the present invention can be powder or saccharoid; But, preferably this Noryl is a saccharoid.

When using the mixture of unmodified ppe and Noryl, for the not special restriction of the amount of Noryl; But, the amount of said Noryl is preferably 10～95 weight % of ppe (B) weight, and more preferably 30～90 weight % most preferably are 45～85 weight %.

For said ppe for the adding of preparation in the molded resin product of the present invention; Preferably will add in the kneading machine (for example forcing machine) with particulate form, and resulting product is added in the reaction mixture through the part or all of ppe (B) that melt-ppe of kneading (B) obtains.Through adding ppe (B), can improve the certainly transmission ability of ppe in kneading machine (for example forcing machine), thereby improve the throughput rate of molded resin product with this particulate form.In addition, use the ppe (B) of above-mentioned particulate form to have the following advantages.Generally speaking, when attempting to improve the throughput rate of molded resin product, the volatilization efficient in the production process can descend.Therefore; When using shaper with the moulded products that is obtained (for example saccharoid) when being used to prepare final moulded product; Because the stop of melt molding goods (for example saccharoid) in shaper, crazing can appear in the moulded product of gained, yet; Through using ppe, can suppress the appearance of this crazing by melt-particulate form that the ppe of kneading obtains.

In addition, the ppe (B) that is preferred for molded resin product of the present invention has particular molecular weight.Particularly, preferred ppe (B) contain molecular weight be 200000 or the ppe of higher higher molecular weight and molecular weight be 5000 or the ppe of lower lower molecular weight, and requirement (I) below satisfying and/or (II):

(I) requiring the weight ratio of ppe of ppe and the said lower molecular weight of said higher molecular weight is 0.35 or littler; And/or

(II) require the amount of ppe of ppe and the said higher molecular weight of said lower molecular weight to be respectively the 5 weight % or the littler and 2 weight % or littler of said polyphenylene oxide resin (B) weight.

More preferably above-mentioned two requirements (I) and (II) be met simultaneously.Molecular weight through regulating ppe (B) is to meet the demands (I) and/or (II), can further improve the coating bond strength of this molded resin product.

Can be through may further comprise the steps 1)-3) method measure the molecular weight of ppe of ppe and the higher molecular weight of above-mentioned lower molecular weight.

1) its amount enough is used for the molded resin product pulverizing that molecular weight is tested.Then, the pulverized molded resin product of gained is immersed in the chloroform, through supersound washing device etc. its solvable composition is dissolved in the chloroform, thereby obtains solution.

2) solution that obtains in step 1) through gel permeation chromatography (GPC) equipment and the analysis of UV spectrum detector.From the gained data, use the working curve that obtains according to the polystyrene standard sample to obtain molecular weight data.

3) handle in step 2 through being purchased the GPC process software) in the molecular weight data of acquisition, to confirm to have the amount of the molecule of molecular weight in the specified range.

In this is measured, importantly under the wavelength that does not observe the absorption that belongs to said segmented copolymer, operate the UV spectrum detector, thereby do not detect the segmented copolymer of following ppe to go out from this eluant solution.

(measuring condition: GPC equipment: GPC SYSTEM 21 is by Japanese Showa Denko company's production and sale; Detector: UV-41 is by Japanese Showa Denko company's production and sale; Solvent: chloroform; Temperature: 40 ℃; Post: sample column (K-G, K-800RL and K-800R) and reference column (K-805L, 2 posts); Flow velocity: 10ml/min; The wavelength that is used to detect: 283nm; And pressure: 15～17kg/cm ²)

Molded resin product of the present invention can comprise and contain cinnamic thermoplastic resin, and with respect to polymeric amide of 100 weight parts (A) and ppe (B) altogether, it is measured less than 50 weight parts.

At this, contain cinnamic thermoplastic resin and be meant at least a resin that is selected from PS (HIPS), styrene-acrylonitrile copolymer (AS resin) and the vinylbenzene-rubber polymer-acrylonitrile copolymer (ABS resin) of PS (homopolymer), modified rubber.

In addition, any conventional stablizer that is used for ppe can use at preparation molded resin product of the present invention.The instance of conventional stablizer comprises the stablizer that contains metal, for example zinc oxide and zinc sulphide; And organic stabilizer, for example hindered phenol type stablizer, Phosphorus stablizer and hindered amines stablizer.With respect to the ppe (B) of 100 weight parts, the amount of stablizer is preferably less than 5 weight parts.

In addition, any conventional additives that is used for ppe can use at preparation molded resin product of the present invention, and with respect to the ppe (B) of 100 weight parts, it is measured less than 10 weight parts.

Next, the explanation partially hydrogenated segmented copolymer (C) that can in molded resin product of the present invention, use.

The said partially hydrogenated segmented copolymer (C) that can in molded resin product of the present invention, use is to obtain through the unhydrided segmented copolymer of partially hydrogenated, and said unhydrided segmented copolymer contains at least a aromatic vinyl polymer block and at least a conjugated diolefin polymer block of mainly being made up of the aromatic vinyl monomer unit of mainly being made up of conjugated diene monomeric unit.

This partially hydrogenated segmented copolymer (C) comprises that at least a number-average molecular weight is 200000～300000 partially hydrogenated segmented copolymer (C-1).

In the present invention, " the aromatic vinyl polymer block of mainly being made up of the aromatic vinyl monomer unit " is meant and contains the aromatic vinyl monomer unitary aromatic vinyl polymer block of its amount at least 50 weight % of this aromatic vinyl polymer block weight.Preferred said aromatic vinyl polymer block contains its amount and is 70 weight % of this aromatic vinyl polymer block weight or more, more preferably 80 weight % or more, most preferably 90 weight % or more aromatic vinyl monomer unit.

Similarly, " the conjugated diolefin polymer block of mainly forming " by conjugated diene monomeric unit be meant contain its amount at least 50 weight % of this conjugated diolefin polymer block weight, be preferably 70 weight % or more, more preferably 80 weight % or more, the most preferably 90 weight % or the more conjugated diolefin polymer block of conjugated diene monomeric unit.

Above-mentioned aromatic vinyl polymer block for example can be the copolymer block between the wherein a small amount of said aromatic vinyl polymer of the random insertion of conjugated diene monomeric unit unit.

Similarly, above-mentioned conjugated diolefin polymer block for example can be the copolymer block between wherein a small amount of said conjugated diene monomeric unit of the random insertion in aromatic vinyl monomer unit.

The particular instance that is used to form the unitary aromatic vinyl compound of said aromatic vinyl monomer comprises vinylbenzene, alpha-methyl styrene and Vinyl toluene.These compounds can use or make up use separately.In the compound of more than giving an example, vinylbenzene is preferred especially.

The specific examples that is used to form the conjugated diolefine of said conjugated diene monomeric unit comprises divinyl, isoprene, piperylene and 1,3-pentadiene.These compounds can use or make up use separately.In the compound of more than giving an example, divinyl, isoprene and composition thereof are preferred.

For the microtexture of the conjugated diolefin polymer block of partially hydrogenated segmented copolymer (C), preferred 1,2-vinyl bonds content or 1,2-vinyl bonds and 3,4-vinyl bonds total content is 5～80%, more preferably 10～50%, most preferably be 15～40%.

For the unhydrided segmented copolymer that is used to prepare partially hydrogenated segmented copolymer (C), preferred aromatic vinyl polymer block (a) and conjugated diolefin polymer block (b) have the block structure that is selected from a-b, a-b-a and a-b-a-b.This segmented copolymer can be the mixture with different segmented copolymers of above-mentioned block structure.In the above-mentioned block structure, more preferably a-b-a and a-b-a-b, most preferably a-b-a.

In addition, the said segmented copolymer that uses in the present invention must be partially hydrogenated segmented copolymer.

" partially hydrogenated segmented copolymer " is meant the multipolymer that obtains through any above-mentioned unhydrided segmented copolymer of hydrogenation at this, and the hydrogenation degree of aliphatic double bond is greater than 0% and less than 100% in the wherein said conjugated diolefin polymer block.The hydrogenation degree of said partially hydrogenated segmented copolymer is preferably 50% or higher and less than 100%, and more preferably 80% or higher and less than 100%, most preferably be 98% or higher and less than 100%.

In addition, contained partially hydrogenated segmented copolymer must comprise that number-average molecular weight is 200000～300000 partially hydrogenated segmented copolymer (C-1) in the molded resin product of the present invention.When only using number-average molecular weight less than 200000 partially hydrogenated segmented copolymer, its shortcoming is that the coating bond strength of this molded resin product reduces.On the other hand, when only using number-average molecular weight greater than 300000 partially hydrogenated segmented copolymer, the fluidity of molten that its shortcoming is to be used to prepare the resin combination of this molded resin product reduces.

In the present invention; Through gel permeation chromatography (GPC) equipment (GPC SYSTEM 21; By Japanese Showa Denko company's production and sale); Use UV spectrum detector (UV-41 is by Japanese Showa Denko company's production and sale) and, measure number-average molecular weight according to the working curve that the polystyrene standard sample obtains.(measuring condition: solvent: chloroform; Temperature: 40 ℃; Post: sample column (K-G, K-800RL and K-800R) and reference column (K-805L, 2 posts); Flow rate: 10ml/min; The wavelength that is used to detect: 254nm; And pressure: 15～17kg/cm ²) when measuring number-average molecular weight, can detect the low molecular weight compositions that forms owing to the polymerizing catalyst inactivation sometimes, but when calculating molecular weight, ignore such low molecular weight compositions.Usually, the MWD of correct calculation (weight-average molecular weight/number-average molecular weight ratio) is in 1.0～1.1 scopes.

In molded resin product of the present invention; As above-mentioned partially hydrogenated segmented copolymer (C), can use at least a number-average molecular weight is that 200000～300000 partially hydrogenated segmented copolymer (C-1) and at least a number-average molecular weight are the mixture of 50000～150000 partially hydrogenated segmented copolymer (C-2).Through using partially hydrogenated segmented copolymer (C-1) and mixture (C-2), shock resistance and the balance of fluidity of molten that can improve the coating bond strength of this molded resin product and be used to prepare the resin combination of this molded resin product.

When the mixture that uses at least a partially hydrogenated segmented copolymer (C-1) and at least a partially hydrogenated segmented copolymer (C-2) during as partially hydrogenated segmented copolymer (C), preferably said at least a partially hydrogenated segmented copolymer (C-1) and said at least a partially hydrogenated segmented copolymer (C-2) all comprise:

At least a partially hydrogenated segmented copolymer with low aromatic vinyl monomer unit content; It obtains through the unhydrided segmented copolymer of partially hydrogenated; The amount that wherein said at least a aromatic vinyl polymer block exists be said unhydrided segmented copolymer weight 20 to less than 60 weight %

Through using at least a partially hydrogenated segmented copolymer and at least a this mixture, can obtain the molded resin product that at high temperature hardness and shock resistance aspect all are improved with partially hydrogenated segmented copolymer of low aromatic vinyl monomer unit content with high aromatic vinyl monomer unit content.

In the case; The preferred especially partially hydrogenated segmented copolymer (C-2) (having 50000～150000 number-average molecular weight) that uses; It has high aromatic vinyl monomer unit content and obtains through the unhydrided segmented copolymer of partially hydrogenated, and the amount that wherein said aromatic vinyl polymer block exists is 60 to 90 weight % of said unhydrided segmented copolymer weight.In addition; For the partially hydrogenated segmented copolymer with above-mentioned certain number average molecular weight and above-mentioned particular aromatic vinyl polymer block content, the preferred segmented copolymer with certain number-average molecular weight and certain aromatic vinyl polymer block content that uses is so that the number-average molecular weight of said aromatic vinyl polymer block is 20000 or more.

The number-average molecular weight of the aromatic vinyl polymer block of segmented copolymer can calculate according to the number-average molecular weight of following formula from above-mentioned segmented copolymer:

Mn _(a)＝{Mn×a/(a+b)}/N

Mn wherein _(a)The number-average molecular weight of representing this aromatic vinyl polymer block; Mn representes the number-average molecular weight of this segmented copolymer; The whole aromatic vinyl polymer blocks of " a " expression account for the weight % of this segmented copolymer weight; The whole conjugated diolefin polymer blocks of " b " expression account for the weight % of this segmented copolymer weight; And N representes the quantity of aromatic vinyl polymer block in this segmented copolymer.

Above-mentioned partially hydrogenated segmented copolymer can be the mixture of different segmented copolymers, needs only the character that every kind of segmented copolymer can not influence molded resin product of the present invention negatively.For example; This segmented copolymer can be mixture, the mixture that contains the unitary segmented copolymer of different aromatic vinyl monomers, the mixture that contains the segmented copolymer of different conjugated diene monomeric units with segmented copolymer of different block structures, have different 1; 2-contents of ethylene or different 1; 2-vinyl bonds and 3, has mixture and the mixture with segmented copolymer of different hydrogenation degrees of the segmented copolymer of different aromatic vinyl monomers unit content at the mixture of the segmented copolymer of 4-vinyl bonds total content.

Can prepare above-mentioned unhydrided segmented copolymer through any ordinary method.Also can carry out above-mentioned hydrogenation to unhydrided segmented copolymer through any ordinary method.

In the present invention, also preferred use modification or partially modified segmented copolymer or with the segmented copolymer of oily premix, it is stated in WO02/094936.

Molded resin product of the present invention can also comprise carbonaceous material (D).Through adding carbonaceous material (D), can this molded resin product be used for the Application Areas that the requirement molded resin product has electroconductibility.

The carbonaceous material (D) that can be used for molded resin product of the present invention is the carbonaceous feedstock that can improve the electroconductibility (that is, reducing volume specific resistance) of this molded resin product through its adding.

In said carbonaceous material, special preferred conduction carbon black, thomel and carbon nanotube.These carbonaceous materials can use or make up use separately.As being used for graphitized carbon black of the present invention, can mention the graphitized carbon black of describing among the WO01/081473.The instance of commercial graphitized carbon black comprises KetjenBlack EC and Ketjen Black EC600JD (produced and sold by Japanese Ketjen BlackInternational Company respectively).As the instance that can be used for thomel of the present invention, can mention the very fine thomel of describing among the WO94/023433.Broadly, carbon nanotube is included in the thomel; But common, the carbonaceous material that will have specific tubular structure is called " carbon nanotube ".In the present invention; Term " carbon nanotube " be meant have hollow structure, a small amount of branch and less than the thomel of 75nm Fibre diameter etc., of US 4663230, US 5165909, US5171560, US 5578543, US 5589152, US 5650370 and US 6235674.In addition, carbon nanotube can be that volume (coil) spacing is 1 μ m or littler web-like.In the present invention, carbon nanotube can have single layer structure or multilayered structure.In addition, carbon nanotube comprises that also those have the carbon nanotube of a large amount of branches, hollow structure and 75nm or bigger Fibre diameter.As the instance that is purchased the carbon nanotube that can get, can mention BN FIBRIL (produce and sell) by U.S. Hyperion CatalysisInternational.

In molded resin product of the present invention, the amount of preferred carbonaceous material (D) is 0.5～2.5 weight % of this molded resin product weight, more preferably 1.0～2.0 weight %.

As a kind of carbonaceous material (D) is added the preferred method in the molded resin product of the present invention; Can mention following method: wherein at least a portion carbonaceous material (D) is dispersed at least a portion of at least a composition that is selected from polymeric amide (A), ppe (B) and partially hydrogenated segmented copolymer (C) obtaining masterbatch, and thus obtained masterbatch (having the carbonaceous material (D) that is scattered in wherein) is used to prepare this molded resin product.Preferred a kind of method is wherein at least a portion carbonaceous material (D) to be dispersed at least a portion polymeric amide (A) obtaining masterbatch, and thus obtained masterbatch is used to prepare this molded resin product.Method for the above-mentioned masterbatch of preparation does not have special qualification; But, most preferred a kind of method is that wherein masterbatch carries out through using forcing machine that melt-kneading makes.Particularly; Can mention a kind of method; This method is used the twin screw extruder of common rotation; It has respectively at least one first inlet and at least one second inlet that upstream portion (one or more such part) and downstream part (one or more such part) at forcing machine provide; Wherein the inside of forcing machine is preheated to 250～300 ℃, and wherein for example the resinous principle of polymeric amide (A) infeed the forcing machine from said first inlet, thereby in the upstream portion of forcing machine said resin is carried out melt-knead; And carbonaceous material (D) is infeeded forcing machine, thereby said resin and carbonaceous material (D) are carried out melt-knead in the downstream part of forcing machine from said second inlet.In the method, the preferred resin temperature is lower than 340 ℃.The amount of the carbonaceous material that comprises in the said masterbatch (D) is preferably 5～30 weight % of master batch weight, more preferably 8～25 weight %.

Form for the above-mentioned masterbatch that contains at least a portion carbonaceous material (D) does not have special qualification, and this masterbatch can be any form, for example powder, saccharoid, flap, bar or block with uncertain shape; But, preferred carbonaceous material (D) is a saccharoid.

As above-mentioned masterbatch, can use to be purchased masterbatch.As the instance that is purchased masterbatch, can mention polyamide 66/thomel masterbatch, it is produced and is sold (trade name: have Fibril by U.S. Hyperion Catalysis International ^TMThe polyamide 66 of Nanotubes RMB4620-00; Carbon fiber content: 20 weight %).

Molded resin product of the present invention can also comprise wollastonite particle (E).As wollastonite particle (E), preferably using average particulate diameter is that 2～9 μ m and length-to-diameter ratio are 5 or bigger wollastonite particle.(at this, term " average particulate diameter " is meant for also satisfactorily the solution that the wollastonite particles dispersed obtains therein being passed through Sedigraph particle size analyzer (model 5100 through the supersound washing device through the 0.05%Calgon solution that 0.75g wollastonite particle is added 45ml; Produce and sell by U.S. Micromeritics Instrument Corporation) spherical diameter of the equivalence measuring and calculate; Term " length-to-diameter ratio " is meant, the length-to-diameter ratio that the mean diameter that at least 500 wollastonite particles on the Photomicrograph of taking at scanning electron microscope are recorded and average length computation obtain.)

As the wollastonite particle, more preferably use the wollastonite particulate mixture with different length-to-diameter ratios of two kinds or more kinds of types.Particularly, can use length-to-diameter ratio be 5 or bigger wollastonite particle and length-to-diameter ratio less than 5 wollastonite particulate mixture.

For this mixture of wollastonite particulate with different length-to-diameter ratios, most preferably length-to-diameter ratio be 5 or bigger wollastonite particle be 50 weight % of the contained wollastonite particle of said mixture gross weight (that is the gross weight of wollastonite particle (E)) or more.

As the instance that wollastonite particle (E) is added the preferred method in the molded resin product of the present invention; Can mention a kind of method; Wherein wollastonite particle (E) is added the other materials be used for preparing molded resin product and the gained mixture is carried out melt-knead with ppe (B), thereby obtain molded resin product; A kind of method wherein adds wollastonite particle (E) other materials be used for preparing molded resin product and the gained mixture is carried out melt-knead with polymeric amide (A), thereby obtains molded resin product; And a kind of method, it carries out melt-knead together with ppe (B) and polymeric amide (A), then to wherein adding wollastonite particle (E), and further the gained mixture is carried out melt-knead, thereby obtains molded resin product.In above-mentioned three kinds of methods, the third method is most preferred.

In addition; From the dispersiveness of raising wollastonite particle (E) and the angle of handling properties; Can add wollastonite particle (E) with the master batch form that contains wollastonite, this masterbatch is through obtaining the wollastonite particles dispersed at least a portion polymeric amide (A) and/or at least a portion hydrogenant segmented copolymer (C).

Instance as the concrete grammar of the above-mentioned masterbatch that contains wollastonite of preparation; Can mention following method (1)～(3): (1) a kind of method; Wherein in preparation polymeric amide (A); The starting monomer that will be used to prepare polymeric amide (A) carries out polymerization in the presence of wollastonite, thereby obtains to contain the masterbatch of wollastonite; (2) a kind of method of using forcing machine; Wherein do mixed with wollastonite polymeric amide (A) and/or partially hydrogenated segmented copolymer (C); The gained mixture in certain temperature range, carries out melt-knead so that polymeric amide (A) and/or partially hydrogenated segmented copolymer (C) fusion satisfactorily, and the thermolysis of polymkeric substance does not take place; (3) a kind of method of using twin screw extruder; This forcing machine has first inlet that provides in the forcing machine upstream portion and second inlet that provides in the forcing machine downstream part; Wherein polymeric amide (A) and/or partially hydrogenated segmented copolymer (C) infeed the forcing machine from first inlet, and from second inlet wollastonite are infeeded forcing machine.In these methods, method (3) is most preferred.

In addition, in the present invention, in preparation molded resin product process, can compatibilizing agent be added in the molded resin product.

There is not special qualification for being used for compatibilizing agent of the present invention, as long as it is the reagent that can improve the physical properties of polyamide-polyphenylene ether alloy.Particularly, can be used for compatibilizing agent of the present invention is and one of ppe and polymeric amide or both interactional polyfunctional compounds.This interaction can be chemical interaction (for example, grafting) or physics interaction (for example, the variation of the surface properties of disperse phase).

The instance that can be used for preparing the compatibilizing agent of molded resin product of the present invention is included in those that examine Japanese Patent prospectus (put down) 8-8869 (corresponding to EP 201416) and (putting down) 9-124926 (corresponding to EP 747439) detailed description.All conventional compatibilizing agents of in these patent documents, describing may be used among the present invention, and this compatibilizing agent can use or make up use separately.

In numerous conventional compatibilizing agents, preferred especially maleic anhydride and verivate, toxilic acid and verivate thereof, Hydrocerol A and verivate thereof, fumaric acid and verivate thereof and with the compound modified ppe saccharoid of any of these.

With respect to polymeric amide of 100 weight parts (A) and ppe (B) altogether, the consumption of compatibilizing agent is preferably 0.01～25 weight part in the present invention.

There is not special qualification for the shape that can be used for compatibilizing agent of the present invention.But, from the easy to handle angle, preferably use the larger particles form rather than the compatibilizing agent of the powder type that forms by fine granular.Particularly; For example, when use has the compatibilizing agent (for example, maleic anhydride) of pungency peculiar smell; Preferred compatibilizing agent is the larger particles form; Because with compatibilizing agent wherein is that the situation of the powder type that formed by fine granular is compared, its pungency peculiar smell is reduced, and can not destroy operating environment thus.

For the compatibilizing agent of larger particles form, its particle diameter is preferably 1mm or bigger, and more preferably 1mm～10mm most preferably is 3mm～8mm.When particle diameter is 10mm or more hour, for infeeding this particle in the forcing machine, there is not the danger that any trouble occurs.

In molded resin product of the present invention; Polymeric amide (A) exists as external phase; Wherein ppe (B) disperse to form disperse phase, and partially hydrogenated segmented copolymer (C) be present at least one external phase that is selected from polymeric amide (A) and ppe (B) disperse phase mutually in.When the composition of this molded resin product made that polymeric amide (A) can not form external phase, the coating bond strength of this molded resin product can reduce unfriendly.Do not have special qualification for the dispersion state of partially hydrogenated segmented copolymer (C) in the disperse phase of ppe (B), and partially hydrogenated segmented copolymer (C) can have the described micro phase separation structure like US5109052, perhaps can be the agglomerate form.

In molded resin product of the present invention, require polymeric amide (A) to expose to the open air on the surface of molded resin product so that the surface-area that exposes to the open air at the whole lip-deep polymeric amide (A) of this molded resin product is at least 80% of a molded resin product surface-area.It is preferred that above-mentioned to expose surface-area at the whole lip-deep polymeric amide (A) of molded resin product (hereinafter, the surface-area of above-mentioned polymeric amide (A) often abbreviates " polymeric amide area than " as) to the open air be 90% or more.

When above-mentioned polymeric amide area than less than 80% the time, the coating bond strength of this molded resin product can reduce unfriendly.

Can measure this polymeric amide area ratio as follows.

Downcut the flat board that is of a size of about 1cm～about 1cm from molded resin product, as the sample of measuring polymeric amide area ratio.(when this molded resin product was saccharoid, this saccharoid itself was as sample).Under 20～80 ℃ of temperature, the gained sample is immersed in 10% phosphotungstic acid aqueous solution is no more than 24 hours, thereby optionally partly locate this sample dyeing at its polymeric amide.

After the sample dyeing, reclaim the sample that dyeed, then with water washing and dry from the said aqueous solution.Use field emission scanning electron microscope (FE-SEM) (model " S-4700 "; By Japanese Hitachi; Ltd. produce and sell) Photomicrograph (the back-scattered electron image) (magnification: * 2500) of taking this stained specimens surface; Operation microscope under the acceleration voltage of 5kV wherein, and with sample surfaces part (examining under a microscope this part) vertical angle shot Photomicrograph.

In the gained image, because the electron reflection of tungsten partly is white in color the part black in color that is not colored by the painted polymeric amide of tungsten.Therefore, in the gained image, exposing the polymeric amide part that on the molded resin product surface, belongs to the open air can distinguish with other parts.

For thus obtained Photomicrograph (back-scattered electron image), use image analysis apparatus (model name: Image-Pro PLUS ver.4.0; The U.S. Media Cybernetics Inc.) measures the total area of its white portion, and the total area that obtains white portion and the ratio of the whole area of sample Photomicrograph are as polymeric amide area ratio.(in measuring back-scattered electron image, in the total area of white portion, confirm the binary-state threshold of image according to following mode.From the histogram of the tone of back-scattered electron image, confirm to belong to the intensity and the intensity that belongs to the peak of black at the peak of white, and with the MV of these two intensity as binary-state threshold.)

At least 10 different pieces through observing the molded resin product surface are confirmed this polymeric amide area ratio, and the MV that will be observed each polymeric amide area ratio partly is defined as the polymeric amide area ratio of molded resin product.Select above-mentioned at least 10 parts to be observed from part near this molded resin product center; Rather than from any surface portion (for example near surface portion or its; This surface portion is selected corresponding to the mobile stopping place (being called " flow end part " below such surface portion) of molten resin in the mould, estimates that comparing this surface portion with other parts has a spot of polymeric amide.Particularly, for example, in through this molded resin product situation of injection molding preparation, select to be observed being used to measure the above-mentioned part of polymeric amide area ratio according to following mode.When a part of molded resin product (being called " inlet part " below such part) corresponding to die entrance is defined as starting point; And the distance of part was defined as 1 o'clock from the door section to the flow end, measured polymeric amide area ratio with respect to the interior part of measuring from starting point of 0～0.8 distance.

In addition; When the moulding resin be flushing cutting saccharoid (promptly; Saccharoid by the method acquisition that wherein will water-bath, cool off and cut then) time, is not regarded as the surface portion of the measurement polymeric amide area ratio of this molded resin product through the xsect of cutting flushing acquisition from the flushing that forcing machine is extruded.That is to say, under the saccharoid situation of flushing cutting, measure polymeric amide area ratio with respect to the surface portion of the saccharoid except the surface portion that passes through cutting flushing gained xsect.

In the present invention, with respect to the polymeric amide area of the whole surface measurement of molded resin product than must be high, thereby obtain the coating bond strength of excellent molded resin product.When satisfying such requiring, the coating bond strength of this molded resin product improves with only comparing greatly from the coating bond strength of polymeric amide or the moulded products that only forms from ppe.

Molded resin product of the present invention is characterised in that the resin that forms disperse phase (below be called " disperse phase resin ") (promptly; Ppe (B) and optional part hydrogenant multipolymer (C)) existing way make this disperse phase resin form the recessed-convex portion of appropriateness on the surface of molded resin product, and said recessed-convex portion is coated with polymeric amide (A).Because this characteristic, this molded resin product shows aforesaid excellent effect.For recessed-convex portion, must increase the melt viscosity of this disperse phase resin through this disperse phase resin formation appropriateness.On the other hand, in order on recessed-convex portion, to form desirable polymeric amide (A) coating, the melt viscosity of preferred polyamide (A) is low.

For the melt viscosity that increases this disperse phase resin fully on this molded resin product surface, to form the recessed-convex portion of appropriateness, the molecular weight of partially hydrogenated segmented copolymer (C) must be high.Particularly, be 200000～300000 partially hydrogenated segmented copolymer (C-1) through using above-mentioned number-average molecular weight, can on this molded resin product surface, form the recessed-convex portion of appropriateness.

When the polymeric amide of independent use low melt viscosity during, can obtain high polymeric amide area ratio as polymeric amide (A); But, shortcoming is mechanical properties (for example, the shock strength) decline of this molded resin product.On the other hand, when the polymeric amide of independent use high melt viscosity during as polymeric amide (A), the mechanical properties of this molded resin product is improved; But, shortcoming is that the polymeric amide area ratio of the surface measurement of this molded resin product relatively reduces, so the coating bond strength descends.Therefore, in order to obtain excellent mechanical properties and excellent coating bond strength, must use the mixture of aforesaid two kinds or more kinds of type polymeric amide.

In the present invention, preferably the melt viscosity of this disperse phase resin (that is, ppe (B) and non-essential partially hydrogenated segmented copolymer (C)) (290 ℃ with shearing rate is 1000sec ^-1Following measurement) be 800Pas or higher, 1000Pas or higher more preferably.

On the other hand, (is 1000sec at 290 ℃ with shearing rate to be preferably formed the melt viscosity of resin (that is polymeric amide (A)) (below be called " external phase resin ") of external phase ^-1Following measurement) less than 200Pas, is more preferably less than 100Pas.

In addition, the ratio of the melt viscosity of preferred disperse phase resin and the melt viscosity of external phase resin is 10 or bigger, more preferably 20 or bigger.

Can measure the melt viscosity of disperse phase resin and external phase resin as follows.For example, can measure the melt viscosity of disperse phase resin through following method: the material extrusion moulding that wherein will have a same composition with the disperse phase resin to be obtaining saccharoid, and measures the melt viscosity of gained saccharoids through capillary rheometer etc.Can measure the melt viscosity of external phase resin through method same as described above.

In measuring disperse phase resin and external phase resin melt viscosity separately; When even plan is used for the resin of molded resin product with additive (for example wollastonite) adding, under the situation that in this resin, does not add said additive, carry out the measurement of the melt viscosity of said resin.

Through the melt viscosity of the melt viscosity of disperse phase resin, external phase resin and disperse phase resin/external phase resin melt viscosity ratio are adjusted to respectively 800Pas or higher, less than 200Pas and 10 or higher; Be easy to improve above-mentioned polymeric amide area ratio, and be easy to keep high coating bond strength (it is one of characteristic of molded resin product of the present invention).

In the present invention, the weight ratio of preferred disperse phase resin and external phase resin is less than 1.0, and more preferably 0.9 or littler.When the weight ratio of disperse phase resin and external phase resin is controlled in less than 1.0 the time, can stably improve above-mentioned polymeric amide area ratio.In addition, when partially hydrogenated segmented copolymer (C) was present in the disperse phase of ppe (B), the amount of ppe (B) was 50～90 weight % of disperse phase gross weight in the preferred disperse phase.When the amount of ppe in the disperse phase is big, can reduce the gloss of molded resin product.Particularly, the amount of preferred polyamide (A), ppe (B) and partially hydrogenated segmented copolymer (C) is respectively 50～70 weight %, 25～45 weight % and 5～25 weight % of polymeric amide (A), ppe (B) and partially hydrogenated segmented copolymer (C) gross weight.More preferably the amount of polymeric amide (A), ppe (B) and partially hydrogenated segmented copolymer (C) is respectively 50～60 weight %, 35～45 weight % and 5～15 weight % of polymeric amide (A), ppe (B) and partially hydrogenated segmented copolymer (C) gross weight.

Molded resin product of the present invention is characterised in that, even when the polymeric amide content of this molded resin product during less than 80 weight %, the polymeric amide area is than also being at least 80%.(this means expose to the open air the ratio of the whole lip-deep polymeric amide of this molded resin product not necessarily be present in this molded resin product generally in the ratio of polymeric amide identical.) because this characteristic can obtain high coating bond strength.Regulate the polymeric amide area and comprise the method that wherein melt viscosity of external phase resin is suppressed to the level of the melt viscosity that is lower than the disperse phase resin than instance at least 80% method; And the method that wherein polymeric amide (A) and the amount of the reaction product (graftomer) of ppe (B) is adjusted to proper level.

The specific examples of method that the melt viscosity of external phase resin is suppressed to the level of the melt viscosity that is lower than the disperse phase resin comprises the aforesaid method of the viscosity of wherein regulating polymeric amide (A); Wherein regulate ppe the polymerization degree so that with the molecular-weight adjusting of ppe (being used for this molded resin product) to the method that falls in the above-mentioned scope; And wherein mix two kinds or more kinds of method with ppe of different molecular weight.

The specific examples that the amount of the reaction product (graftomer) of polymeric amide (A) and ppe (B) is adjusted to the method for proper level comprises and wherein uses above-mentioned method with polymeric amide of specific amino content; And wherein regulate the The Modification of Polyphenylene Oxide degree method of (for example, mixing with unmodified ppe) through ppe with modification.

In the present invention, regulate the polymeric amide area and be not limited to above those of giving an example than method at least 80%.In addition, multiple different methods can make up use to regulate polymeric amide area ratio.

For molded resin product of the present invention.When using wollastonite, the amount of preferred wollastonite makes that the average coefficient of linear expansion of this molded resin product is 4.5 * 10 ^-5℃ ^-1～6.5 * 10 ^-5℃ ^-1, wherein measure the average coefficient of linear expansion of this molded resin product according to following mode.ISO15103-2:1997 defined terms (melt temperature: 290 ℃, mould temperature: 90 ℃) down preparation thickness be that the D2 type of 2mm (stipulating among the ISO294-3:1996) is dull and stereotyped.Then; Downcut one section from the center that the D2 type is dull and stereotyped; It is of a size of 10mm (length records on the resin flows direction) * 3mm (width records on the direction of resin flows direction) * 2mm (thickness) in perpendicular to mould in mould; The gained flat board was left standstill 48 hours under 100 ℃ at least, thereby obtain test sample book.Use the test sample book of gained, according to JIS K7197-1991 under-30～80 ℃ the temperature under the temperature rise rate of 5 ℃/min the measure linear coefficient of expansion.

Particularly, with respect to the polymeric amide of 100 weight parts (A), ppe (B) and partially hydrogenated segmented copolymer (C) altogether, the amount of wollastonite is preferably 10～50 weight parts, more preferably 15～35 weight parts.

This supplementary component in the present invention,, if desired, can in this molded resin product, add supplementary component, as long as can not influence the excellent properties of molded resin product of the present invention negatively except the mentioned component of molded resin product.

The instance of supplementary component comprises and is different from thermoplastic resin mentioned above, for example polyester and polyolefine; Mineral filler (for example, talcum, kaolinite, xonotlite, titanium oxide, potassium titanate, thomel and spun glass); The conventional silane coupling agent of affinity between reinforcing inorganic and the resin; Fire retardant (for example, halogenated resin, siloxanes fire retardant, Marinco H, white lake, organophosphorus ester compound, ammonium polyphosphate and red phosphorus), has the fluoro-resin that prevents the burning particles drip effect; Softening agent (for example, the polyolefine of oils, small molecular weight, polyoxyethylene glycol and fatty ester class); Flame retardant, for example, ANTIMONY TRIOXIDE SB 203 99.8 PCT; Carbon black as pigment; Electroconductibility is given reagent, for example thomel and graphitized carbon black; Static inhibitor; Multiple superoxide; Inhibitor; UV light absorber; And photostabilizer.

In the present invention, with respect to the polymeric amide of 100 weight parts (A), ppe (B), partially hydrogenated segmented copolymer (C) and compatibilizing agent altogether, the amount that adds the supplementary component in this molded resin product is no more than 100 weight parts.

Next, just the preparation method that can be used for preparing the resin combination of molded resin product of the present invention provides following explanation.

As the special instance of the processing units that can be used to prepare the invention described above resin combination, can mention single screw extrusion machine, twin screw extruder, roller mill, kneading machine, BrabenderPlastograph and Banbury mixing machine.In these equipment, preferred twin screw extruder, and especially preferably have the twin screw extruder of first inlet and at least one second inlet (being formed at the upstream portion and the downstream part of this forcing machine respectively).

Especially preferably use screw diameter as 50mm and be equipped with the forcing machine of 3 or more a plurality of loaders; Wherein respectively polymeric amide, ppe and compatibilizing agent are infeeded in the forcing machine through different loaders, thereby with polymeric amide, ppe and compatibilizing agent melt together-knead.

Particularly working as used compatibilizing agent is the larger particles form; And when used ppe is the powder type that is formed by fine granular; It is favourable using different loaders to infeed compatibilizing agent and infeed ppe; Because this can prevent particulate mixture (promptly; The mixture of the larger particles of compatibilizing agent and the fine granular of ppe) classification takes place in forcing machine, the ratio that this classification meeting causes compatibilizing agent and ppe is along with in the position of the loader that is used to infeed compatibilizing agent and ppe and the shortcoming that changes.When causing such shortcoming, the ratio that infeeds ppe and compatibilizing agent in the forcing machine can fluctuate in this extruder-processed of operation, thereby causes the viscosity of disperse phase resin and particle diameter to fluctuate.The problem that this fluctuation of the viscosity of disperse phase resin and particle diameter possibly cause is that the gloss of final molding resin and coating bond strength change along with the position in this molded resin product.

In addition, as the loader of compatibilizing agent, especially preferably use screw type gravity supply device.Through using screw type gravity supply device, can improve the feed stability of compatibilizing agent, thereby suppress the quality fluctuation of final molding resin.

There is not special qualification for the used melt-temperature of kneading of this resin combination of preparation.Usually, the suitable temp that obtains desirable resin combination is selected from 240～360 ℃ scope.Resin temperature in the melt-process of kneading is preferably 310～340 ℃.

The specific examples of the method be used to prepare above-mentioned resin combination is below described.Yet needless to say, the method for preparing above-mentioned resin combination should not be limited to these instances.

As the equipment that is used to prepare resin combination; Can mention the twin screw extruder that provides first inlet and at least one second inlet in the upstream and downstream part of forcing machine respectively; Wherein first inlet is equipped with screw type gravity supply device and belt gravity supply device, and second inlet is equipped with other screw type gravity supply device.Use such twin screw extruder; Can prepare this resin combination through following method (1)～(3): (1) a kind of method; Wherein infeed the forcing machine from first inlet through the mixture of belt gravity supply device with segmented copolymer and ppe; And compatibilizing agent is infeeded in the forcing machine through first inlet through screw type gravity supply device; Thereby, and polymeric amide is infeeded the forcing machine said mixture and compatibilizing agent melt together-knead in the upstream portion of forcing machine, thereby the gained mixture is carried out melt-knead in the downstream part of forcing machine from second inlet; (2) a kind of method; Wherein ppe is infeeded the forcing machine from first inlet through belt gravity supply device; And infeed in the forcing machine through first inlet through the mixture of screw type gravity supply device with compatibilizing agent and segmented copolymer; Thereby with ppe and said mixture melt together-knead, and polymeric amide is infeeded the forcing machine, thereby the gained mixture is carried out melt-knead in the downstream part of forcing machine from second inlet; (3) a kind of method; Wherein infeed the forcing machine from first inlet through the ppe of belt gravity supply device with powder type; And infeed in the forcing machine through first inlet through the ppe of screw type gravity supply device with compatibilizing agent and particulate form; Thereby with ppe and compatibilizing agent melt together-knead, and polymeric amide is infeeded the forcing machine, thereby the gained mixture is carried out melt-knead in the downstream part of forcing machine from second inlet.

Make the resin combination moulding that makes thus through desirable method, thereby obtain molded resin product of the present invention.This molded resin product not only comprises injection molding goods, and comprises the goods of extrusion moulding, for example flap, membranoid substance and saccharoid, and the moulded products that carries out the secondary processing that injection molding etc. obtains through the goods with above-mentioned extrusion moulding.The preferred embodiment of this molded resin product form comprises that diameter separately is less than 3mm and the length cylindrical saccharoid less than 3mm; Diameter is less than the spherical saccharoid of 3mm separately; Diameter is less than the dish type saccharoid of 4mm separately; And through any above-mentioned saccharoid is carried out the injection molded article that injection molding obtains.

The present invention provides conductive resin composition on the other hand, and it comprises:

Polymeric amide (A),

Ppe (B),

The conduction carbonaceous material (D) and

Wollastonite particle (E).

For the polymeric amide that is used for conductive resin composition of the present invention (A), can use the above any polymeric amide relevant with molded resin product of the present invention.But, in conductive resin composition of the present invention, needn't use two kinds or more kinds of dissimilar polymeric amide, only one type polymeric amide can be used as polymeric amide (A).However, preferably use two kinds or more kinds of dissimilar polymeric amide, like the situation of molded resin product of the present invention.

For the ppe that is used for conductive resin composition of the present invention (B), can use the above any ppe relevant with molded resin product of the present invention.

In addition, for the segmented copolymer that is used for conductive resin composition of the present invention (C), can use the above any segmented copolymer relevant with molded resin product of the present invention.But, the segmented copolymer (C) that is used for conductive resin composition of the present invention need not be hydrogenated.

The number-average molecular weight that is preferred for the segmented copolymer (C) in the conductive resin composition of the present invention is in 50000 arrive less than 150000 scopes.

In addition, for conduction carbonaceous material (D) and wollastonite particle (E), can use the above any conduction carbonaceous material and wollastonite particle relevant with molded resin product of the present invention.

For the method for preparing conductive resin composition of the present invention, can use the above and the relevant any method of resin combination that can be used to prepare molded resin product of the present invention.

Can comprise the electrical equipment that is used for motorcycle and automobile from the instance of the molded resin product of the present invention and the different moulded products of conductive resin composition preparation, for example the relay1 box material; The parts that are used for electrical means or electronic installation, the for example underframe and the box of IC seat, different disc type players; The parts and the mechanical part that are used for office automated machine, for example different computingmachines and the peripherals that is used for this computingmachine; The parts of motorcycle, for example jacket; Automobile external-use parts, for example vibroshock, backplate, door-plate, automobile-used not isolabeling and badge, outer door handle, peephole shell, wheel cover, top cover handrail and its immobilization material and turbulence generator; With use parts in the automobile, for example panel board, operation box and fringing are decorated.

In the moulded products of more than giving an example, molded resin product of the present invention and conductive resin composition are suitable for preparing the automobile external-use parts.

Preferred forms

Below, describe the present invention in detail with reference to following preparation embodiment, embodiment and comparative example, but these embodiment should not limit to scope of the present invention.

Preparation embodiment 1: preparation is with maleic anhydride modified ppe (below be called " MPPE ")

Be prepared as follows MPPE.The viscosity that the maleic anhydride of 3 weight parts and 100 weight parts are reduced is that the ppe of 0.42dl/g is done mixed; Melt-knead (is produced and sale by German Coperion Werner&Pfleiderer GmbH&Co.KG at forcing machine " ZSK-40 " down 320 ℃ tube temperature subsequently then; L/D (ratio of the diameter (D) of length of extruder screw (L) and extruder screw)=42) granulation in, thereby the MPPE of acquisition particulate form.

Preparation embodiment 2: preparation polyamide 6,6 and polyamide 6, the multipolymer of I (below be abbreviated as " PA66/6I ")

In volume is 50 liters autoclave, pack into 20.0kg hexanodioic acid and hexanediamine etc. molar salt, 5.0kg m-phthalic acid and hexanediamine etc. molar salt, 1.0kg hexanodioic acid and 25kg pure water.The abundant content of agitated autoclave, and fully purge the atmosphere in the autoclave with nitrogen.Subsequently, under agitation, the temperature with autoclave in about 1 hour is elevated to 220 ℃ from room temperature.

During the temperature of rising autoclave,, make internal pressure increase because the natural pressure that the autoclave inner vapor causes increases; But, remove heating high-pressure still when anhydrating in the reaction system from autoclave, surpass 18kg/cm with the internal pressure that prevents autoclave ²-G.After the temperature of autoclave reaches 220 ℃, continued the heating high-pressure still 2 hours, temperature is elevated to 260 ℃, so stop heating.Subsequently, close the extraction line of autoclave, and made the autoclave cool to room temperature at about 8 hours.Open autoclave then, and from autoclave, take out the polymkeric substance of 20kg.This polymkeric substance is pulverized, thus the polymkeric substance that acquisition is pulverized.

Under nitrogen gas stream, under 200 ℃, make thus obtained pulverizing polymkeric substance carry out solid state polymerization 10 hours, obtain polymeric amide.

Thus obtained polymeric amide is about 19 moles of % in the unitary content of hexa-methylene isophthaloyl amine monomers of every kg polymeric amide, and the amino content of end is 3.9 * 10 ⁵Mol/g, and the content of end carboxyl is 10.2 * 10 ⁵Mol/g.

Preparation embodiment 3: preparation polymeric amide/carbon masterbatch (below be called " PA-MB ")

Use twin screw extruder (ZSK-58MC; Produce and sell by German Coperion Werner&Pfleiderer GmbH&Co.KG) preparation PA-MB; This forcing machine is swum part above that has an inlet (below be called " upper reaches inlet "); And another inlet (below be called " downstream inlet ") is arranged, wherein the L/D ratio of the diameter (D) of extruder screw (length of extruder screw (L) with)=46 in its downstream part.Particularly, in this twin screw extruder, introduce the PA66-1 of 90 weight parts and the KB (that is Ketjen black) of 10 weight parts through the upper reaches inlet of forcing machine and the downstream inlet of forcing machine respectively.Carry out melt-knead at the content that makes forcing machine under the following condition: wherein the tube temperature of part is 280 ℃ between forcing machine upper reaches inlet and downstream inlet; And part is 300 ℃ between downstream inlet and mould; Screw speed is 400rpm; And discharging speed is 300kg/h, thereby makes PA-MB.

Embodiment 1

Use co-rotational intermeshing twin screw extruder " ZSK-70MC " (to produce and sell by German Coperion Werner&Pfleiderer GmbH&Co.KG; L/D=46) saccharoid of preparation resin combination; This forcing machine has 12 tube unit, and (extruding direction from forcing machine sees; They are called as " the 1st unit ", " the 2nd unit " respectively .... " the 12nd unit ") and mould, wherein can regulate the unitary temperature separately of tube independently.This forcing machine has inlet (below be called " upper reaches inlet "), another inlet (below be called " the 1st downstream inlet ") is arranged at the 6th place, unit, also has an inlet (below be called " the 2nd downstream inlet ") at the 8th place, unit at the 1st place, unit, and at place, the 5th and 11 unit two air outlets is arranged (thus can vacuum suction).Inlet is installed belt gravity supply device and two screw type gravity supply devices at the upper reaches of forcing machine, and inlet is installed other screw type gravity supply device in the 1st downstream of forcing machine.

Particularly, use above-mentioned forcing machine, be prepared as follows the saccharoid of resin combination.Raw material with resin combination infeeds in the above-mentioned forcing machine at first, as follows.A screw type gravity supply device through being installed in forcing machine upper reaches inlets (below be called " loader 1 "); The ppe powder (below be called " PPE1 ") that will have the viscosity 0.52dl/g (under 30 ℃, being that the chloroformic solution of 0.5g/dl records with respect to ppe concentration) of reduction infeeds in the forcing machine.Other screw type gravity supply device through being installed in forcing machine upper reaches inlets (below be called " loader 2 "); (sheet, each diameter are 4～5mm), and (produced and sold by Japanese Mitsubishi Chemical Corporation) (below be called " MAH ") infeeds in the forcing machine as compatilizer with maleic anhydride.Using the Henschel mixing tank to make the number-average molecular weight (Mn) of 4 weight parts is that (styrene content: 33%) number-average molecular weight (Mn) of (below be called " SEBS1 ") and 8 weight parts is that (styrene content: 29%) (below be called " SEBS2 ") does mixed for PS/polyvinylidene/polystyrene block copolymer of 98500 for PS/polyvinylidene/polystyrene block copolymer of 246000.Belt gravity supply device through being installed in forcing machine upper reaches inlets (below be called " loader 3 ") infeeds the gained mixture in the forcing machine.Using rotating cylinder, is that 120ml/g, terminal amino group content are 2.5 * 10 through the viscosity number that makes 40 weight parts ⁵Mol/g and content of carboxyl end group are 11.6 * 10 ⁵The polyamide 6 of mol/g, 6 (below be called " PA66-a ") are that 130ml/g, terminal amino group content are 4.2 * 10 with the viscosity number of 10 weight parts ⁵Mol/g and content of carboxyl end group are 9.1 * 10 ⁵The polyamide 6 of mol/g, 6 (below be called " PA66-b ") do and mix, the preparation polyamide compound.Screw type gravity supply device through being installed in forcing machine the 1st downstream inlets (below be called " loader 4 ") infeeds the gained polyamide compound in the forcing machine.

Temperature condition in the forcing machine is following: with the 1st unit of water cooling, the 2nd and 3 cell temperature respectively is 250 ℃, and the 4th～7 cell temperature respectively is 320 ℃, and the 8th～12 cell temperature respectively is 280 ℃, and the temperature of the mould of forcing machine is 320 ℃.

Make the above-mentioned raw materials melt-also granulation of kneading together with above-mentioned forcing machine; Regulate the feeding rate of raw material simultaneously; Make the raw mix in the forcing machine have composition as shown in table 1, and the discharging speed of gained resin combination is 909kg/h, thereby obtains the saccharoid of this resin combination.

In the above-mentioned melt-process of kneading, screw speed is 500rpm.

(measurement of ppe molecular weight)

Through the saccharoid of the above-mentioned gained of the slicing machine about 10g of cutting, to obtain the section that thickness is respectively the saccharoid of about 20 μ m.Use apparatus,Soxhlet's,, obtain the chloroformic solution of section saccharoid thus with the section of 50ml chloroform extraction gained.Analyze through the GPC (gel permeation chromatography) that uses the UV spectrum detector gained the section saccharoid chloroformic solution (wherein; Main solute is ppe and segmented copolymer), and use molecular weight with respect to the calibrating curve determining ppe of polystyrene standard sample acquisition.This UV spectrum detector is operation under the 283nm at the UV wavelength, thereby does not detect the segmented copolymer of in the gpc analysis process, following the ppe wash-out to go out.

Thus obtained molecular weight data is analyzed.The result finds, has molecular weight 200000 or higher ppe molecule independently of one another and has molecular weight 5000 independently of one another or the amount of lower ppe molecule is respectively the 1.45 weight % and the 4.78 weight % of ppe molecule gross weight.Find that also having molecular weight 200000 or higher ppe molecule independently of one another is 0.30. with the weight ratio that has molecular weight 5000 or lower ppe molecule independently of one another

(mensuration exposes to the open air at the lip-deep polymeric amide area of saccharoid (polymeric amide area ratio))

Following mensuration exposed to the open air at the surface-area of the lip-deep polymeric amide of above-mentioned saccharoid and the ratio of the whole surface-area of this saccharoid (that is polymeric amide area ratio).Under 40 ℃, saccharoid immersed in the phosphotungstic acid aqueous solution of 10 weight % and reach 8 hours, thereby partly be this saccharoid dyeing optionally at its polymeric amide.Then, from the aqueous solution, reclaim the saccharoid that is colored, then with water washing and dry.Use field emission scanning electron microscope (FE-SEM) (model " S-4700 "; By Japanese Hitachi; Ltd. produce and sell) Photomicrograph (the back-scattered electron image) (magnification: * 2500) of taking this dyeing saccharoid surface; Wherein, At acceleration voltage is operation microscope under the 5kV, and with the vertical angle shot Photomicrograph of saccharoid surface portion (examining under a microscope this part).For thus obtained Photomicrograph (back-scattered electron image), use image analysis apparatus (model name: Image-Pro PLUS ver.4.0; The U.S. Media Cybernetics Inc.) measures the total area of its white portion, and the total area that obtains white portion likens to exposing to the open air at the lip-deep polymeric amide area ratio of saccharoid with the whole area of saccharoid Photomicrograph.The result is illustrated in the table 1.(in measuring back-scattered electron image, during the total area of white portion, confirm the binary-state threshold of image as follows.From the histogram of the tone of back-scattered electron image, confirm to belong to the intensity and the intensity that belongs to the peak of black at the peak of white, and with the MV of these two intensity threshold value as binaryzation.)

(the no photosensitiveness on the surface of molded resin product)

Use injection moulding machine " IS80EPN " (tube temperature: 280 ℃; Mould temperature: 80 ℃), above-mentioned saccharoid is shaped to the flat molded resin product of long 90mm of wide 50mm and thick 2.5mm.Injecting condition is following: injection rate (through the mean rate according to the molten resin of the critical cross-section of ISO294-1 defined) is 200mm/s; Injection pressure is to pack arborescens into this injection moulding machine required minimum pressure (promptly; Prevent that molded resin product from the sinking vestige occurring or preventing that mould from not having fully to fill required minimum pressure); Be 20sec inject time, and be 25sec cooling time.

The surface of the molded resin product of the above gained of visual observations.The result finds that the almost whole surface of this molded resin product (except the part corresponding to die entrance) is unglazed.In the present invention, unglazed according to following standard evaluation molded resin product surface.

I: the whole surface of this molded resin product is glossy, and the surface of this molded resin product does not almost have unglazed part.

II: this molded resin product only in corresponding to mould the flow surface portion of stopping place of molten resin unglazed part is arranged.

III: except the part corresponding to die entrance, the almost whole surface of this molded resin product all is unglazed.

IV: the almost whole surface of this molded resin product all is unglazed.

In order to be easy to that coating composition is uniformly coated on the molded resin product surface, have the coating of uniform thickness with formation, preferably the area of unglazed part is big as far as possible in this molded resin product surface.

(average coating bond strength)

In order to estimate the bond strength of coating for molded resin product, making the gained coat-thickness therein is under the 20 μ m conditions, uses automatic coating machine to apply above-mentioned flat board.As coating composition, use Z-NY (trade name; By Japanese Origin Electric Co., Ltd. produces and sells).After spraying is accomplished, toast the flat board that is coated down at 80 ℃ and reach 30 minutes.

Then, make the flat board that is coated 23 ℃ down and humidity be to leave standstill 24 hours for 50% time.The certain area that is coated the surface with respect to this flat board (is of a size of 2cm * 2cm); Be coated the surface with the cutting machine cutting; (each is of a size of the cutting pattern that is verified of 2cm * 2cm) form by 100 square coating layer portions in formation; And peel off experiment, and wherein cellophane tape is sticked to and have being coated on the surface portion of the pattern that is verified, peel off rapidly then.Measure and stay the quantity that is coated lip-deep square coating layer portion after cellophane tape is peeled off, thereby estimate the coating bond strength.The result finds that 95 square coating layer portions (in 100 square coating layer portions) are stayed on the dull and stereotyped surface.

The result is shown in Table 1.

(acutance of the image that in being coated the surface, reflects)

Following outward appearance of observing the above-mentioned flat board that is coated.At first, examine this and be coated the dull and stereotyped surface that is coated, to watch whether any unfairness is arranged on the surface.Then, estimate the acutance that is coated the image that reflects on the surface through the image (be arranged in and be coated about 1.5m place, dull and stereotyped top) of observing the luminescent lamp that reflects in the surface being coated of this flat board.Judgement criteria is following.

The A level: the profile that is coated the luminescent lamp image of surface reflection is obviously clearly.

The B level: the profile of luminescent lamp image that is coated surface reflection is unintelligible, but can distinguish out.

The C level: the profile of luminescent lamp image that is coated surface reflection is unintelligible, and almost can not pick out.

The D level: being coated has less unfairness on the surface.

In addition; For the melt viscosity of measuring the resinous principle that forms the molded resin product disperse phase (below be called " disperse phase resinous principle "); Next with above-mentioned with the preparation resin combination the relevant cardinal principle same way as of saccharoid; The saccharoid that preparation is only formed by the disperse phase resinous principle, different is not carry out through the 4th loader feed (that is, only carrying out feed through the 1st to the 3rd loader).On the other hand; For the melt viscosity of measuring the resinous principle that forms molded resin product external phase (below be called " external phase resinous principle "); Next with above-mentioned with the preparation resin combination the relevant cardinal principle same way as of saccharoid; The saccharoid that preparation is only formed by the external phase resinous principle, different is not carry out through the 1st to the 3rd loader feed (that is, only carrying out feed through the 4th loader).

Use thus obtained saccharoid, use capillary rheometer to measure and be 1000sec down and at flow velocity at 290 ℃ ^-1The melt viscosity (η d) of following this disperse phase resinous principle and the melt viscosity (η m) of external phase resinous principle.The result finds that the melt viscosity of this disperse phase resinous principle (η d) is about 1570Pasec, and the melt viscosity of external phase resinous principle (η m) is about 50Pasec.((η d)/(η m) is about 31 to ratio between the above-mentioned viscosity number.

Embodiment 2～4 and comparative example 1

Next with embodiment 1 substantially identical mode prepare the saccharoid of resin combination, different is the type and the consumption of change raw material as shown in table 1.Table 1 also shows the different properties of gained saccharoid, subsequently to estimate these character with the identical mode of embodiment 1 cardinal principle.

Particularly, for used raw material among embodiment 2～4 and the comparative example 1, it is following to be different from raw material used among those embodiment 1:

The viscosity that reduces is the ppe powder (below be called " PPE2 ") of 0.42dl/g;

The MPPE that in embodiment 1, makes;

Viscosity number is that 230ml/g, terminal amino group content are 2.4 * 10 ⁵Mol/g and content of carboxyl end group are 4.8 * 10 ⁵The polyamide 6 of mol/g, 6 (below be called " PA66-c "); With

The PA66/6I that in embodiment 2, makes.

Embodiment 5～7 and comparative example 2

Next with embodiment 1 substantially identical mode prepare the saccharoid of resin combination, different the following stated raw materials that are to use.For the saccharoid of gained, subsequently to estimate its different properties with the identical mode of embodiment 1 cardinal principle.The result is shown in Table 2, and also has the composition of this saccharoid.

Number-average molecular weight (Mn) is PS/polyvinylidene/polystyrene block copolymer of 105000 (styrene content: 60%) (below be called " SEBS3 ");

Ketjen black " EC-600JD " (trade name; Produce and sell by Japanese Ketjen BlackInternational Company Ltd.) (below be called " KB "); With

Polymeric amide/carbon masterbatch that preparation makes among the embodiment 3 (below be called " PA-MB ").

Embodiment 8～10 and comparative example 3

Next with embodiment 1 substantially identical mode prepare the saccharoid of resin combination; The forcing machine that uses among different is embodiment 8～10 and the comparative example 3 also has the other screw type gravity supply device that is installed in 2 downstream inlet (below be called " loader 5 "); Through this loader wollastonite is infeeded in the forcing machine, thereby obtain saccharoid.For the saccharoid of gained, subsequently to estimate its different properties with the identical mode of embodiment 1 cardinal principle.The result is shown in Table 3, and also has the composition of this saccharoid.Particularly, for used raw material among embodiment 8～10 and the comparative example 3, it is following to be different among those embodiment 1 raw material used or that in embodiment 1, do not use:

Polyamide 6 " 1013B " (trade name; Produce and sell by Japanese Ube Industries Ltd.)) (below be called " PA6 "); With

Following wollastonite, all produce and sell for every kind by U.S. Nyco minerals Inc.:

[wollastonite 1] (average particulate diameter: 5 μ m, length-to-diameter ratio: 13),

[wollastonite 2] (average particulate diameter: 5 μ m, length-to-diameter ratio: 3) and

[wollastonite 3] (average particulate diameter: 10 μ m, length-to-diameter ratio: 13) (handle) with 0.5 weight % amino silane compounds.

Embodiment 11

Next with embodiment 1 substantially identical mode prepare the saccharoid of resin combination, different is to use raw material with the ratio shown in the table 4.For the saccharoid of gained, subsequently to estimate its different properties with the identical mode of embodiment 1 cardinal principle.The result is shown in Table 4, and also has the composition of this saccharoid.

Table 4

Industrial applicibility

The advantage of molded resin product of the present invention is that not only this molded resin product has excellent matting; And be that this molded resin product has excellent adhesion strength (promptly for the coating that on this molded resin product, forms; " coating bond strength "); And this coating that on this molded resin product, forms has the acutance (that is, this coating has excellent gloss) of the excellent image that is wherein reflected.In addition; The conductive resin composition of the application of the invention; Can make such moulded products; The advantage of these goods is that not only this moulded products has excellent matting, and is that this moulded products has excellent coating bond strength, and the coating that on this moulded products, forms has the acutance of the excellent image that is reflected.In addition, prepared moulded products has gratifying low coefficient of linear expansion, and this large-scale moulded products field at for example automobile guard plate and automobile back door is particularly advantageous.Molded resin product of the present invention and can advantageously various fields, use from the moulded products that conductive resin composition of the present invention makes; For example; Not only the automobile external-use field of components can be used for, and Electrical and Electronic parts, office automated machine parts, mechanical part and motorcycle and the interior field of automobile can be used for parts.

Claims

1. conductive resin composition, it comprises:

Polymeric amide (A),

Ppe (B),

One or more segmented copolymers (C) contain at least a aromatic vinyl polymer block and at least a conjugated diolefin polymer block of mainly being made up of the aromatic vinyl monomer unit of mainly being made up of conjugated diene monomeric unit independently of one another,

The conduction carbonaceous material (D) and

Wollastonite particle (E), its average particulate diameter are 2～9 μ m and comprise that length-to-diameter ratio is 5 or bigger particle.

2. according to the conductive resin composition of claim 1; It is characterized in that; Said composition carries out through the composition to the said carbonaceous material (D) of the masterbatch that comprises the said polymeric amide (A) that wherein is dispersed with said carbonaceous material (D) and said ppe (B), said one or more segmented copolymers (C), said wollastonite particle (E) and non-essential at least a said polymeric amide (A) that is selected from additional content and additional content that melt-kneading makes, and wherein said carbonaceous material (D) is at least a composition that is selected from graphitized carbon black, thomel and carbon nanotube.

3. according to the conductive resin composition of claim 1; It is characterized in that; Said wollastonite particle (E) also comprises length-to-diameter ratio less than 5 particle, wherein length-to-diameter ratio be 5 or the amount of bigger said wollastonite particle (E) be 50 weight % or bigger of wollastonite particle (E) gross weight.

4. according to the conductive resin composition of claim 1, it is characterized in that said one or more segmented copolymers (C) comprise that at least a number-average molecular weight is 200000～300000 segmented copolymer (C-1).