CN1806010A - Resin moldings and conductive resin composition - Google Patents
Resin moldings and conductive resin composition Download PDFInfo
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- CN1806010A CN1806010A CN 200480016801 CN200480016801A CN1806010A CN 1806010 A CN1806010 A CN 1806010A CN 200480016801 CN200480016801 CN 200480016801 CN 200480016801 A CN200480016801 A CN 200480016801A CN 1806010 A CN1806010 A CN 1806010A
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Abstract
Resin moldings made of a composition which comprises a polyamide (A) consisting of two or more kinds of polyamide components, polyphenylene ether (B), and a partially hydrogenated block copolymer (C) obtained by partial hydrogenation of a block copolymer composed of an aromatic vinyl polymer block and a conjugated diene polymer block (which contains a copolymer (C-1) having a number-average molecular weight of 200,000 to 300,000) and in which the component (A) forms a continuous phase and the component (B) forms a dispersed phase in the continuous phase, with the component (C) being present in the continuous phase and/or the dispersed phase, characterized in that the surface areas of the component (A) appearing on the surface of the molding account for at least 80 % of the whole surface area of the molding; and a conductive resin composition comprising polyamide (A), polyphenylene ether (B), a block copolymer (C) composed of an aromatic vinyl polymer block and a conjugated diene polymer block, an electrically conducting carbonaceous material (D), and wollastonite particles (E).
Description
Background of invention
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) that contains at least two kinds of different polyamide compositions, polyphenylene oxide (B) and specific partially hydrogenated segmented copolymer (C), wherein said polymeric amide (A) exists as external phase, disperse to form disperse phase at polyphenylene oxide described in the described external phase (B), and described partially hydrogenated segmented copolymer (C) be present in the described external phase that is selected from polymeric amide (A) and polyphenylene oxide (B) described disperse phase at least one mutually in, wherein said polymeric amide (A) exposes to the open air on the surface of described molded resin product so that the total area that exposes to the open air at the lip-deep polymeric amide of described 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 forms on this molded resin product, and this coating that forms on this molded resin product 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), polyphenylene oxide (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 forms has the excellent acutance of the image that wherein mirrors on this moulded products.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.
Prior art
Polyphenylene oxide 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, polyphenylene oxide is used in the various fields.The insufficient formability of polyphenylene oxide but.In order to improve the formability of polyphenylene oxide, open (clear) 45-997 of the Japanese Patent of Shening discloses a kind of technology, in this technology polymeric amide is added in the polyphenylene oxide, 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 431508,4732938 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 Publication specification sheets (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 Publication specification sheets (putting down) 3-143571 and disclose a kind of technology, wherein handle molded resin product, improved the coating bond strength of this molded resin product thus, and needn't use this moulded products of undercoat precoating with tensio-active agent.
But, all there is a problem in above-mentioned every kind of technology, promptly uses additive to improve the coating bond strength of described alloy, and the shortcoming that causes thus is that the thermotolerance of described 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, wish 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 by 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 forms on this moulded products has relatively poor gloss.Therefore, wish 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.
Summary of the invention
In this case, 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 forms has the excellent acutance of the image that wherein mirrors on this moulded products.The result unexpectedly finds, above-mentioned purpose can realize by the molded resin product that comprises polymeric amide, polyphenylene oxide 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), polyphenylene oxide (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 forms on this moulded products has the excellent acutance of the image that wherein mirrors.In addition, described moulded products has favourable low coefficient of linear expansion.Finished 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 forms on this molded resin product 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 forms on this moulded products has the excellent acutance of the image that wherein mirrors, and this moulded products has favourable low coefficient of linear expansion.
From the following detailed description and appended claims, above-mentioned and other purposes of the present invention, feature and advantage will be apparent.
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,
Polyphenylene oxide (B) and
One or more partially hydrogenated segmented copolymers, (C), it obtains by the unhydrided segmented copolymer of partial hydrogenation independently of one another, described 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, described 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 polyphenylene oxide described in the described external phase (B), and described partially hydrogenated segmented copolymer (C) be present at least one described external phase that is selected from polymeric amide (A) and polyphenylene oxide (B) described disperse phase mutually in
Wherein said polymeric amide (A) exposes to the open air on the surface of described molded resin product so that the surface-area that exposes to the open air at the whole lip-deep polymeric amide (A) of described 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:
The polymeric amide (A) that contains at least two kinds of different polyamide compositions,
Polyphenylene oxide (B) and
One or more partially hydrogenated segmented copolymers (C),
Wherein said partially hydrogenated segmented copolymer, (C) obtain by the unhydrided segmented copolymer of partial hydrogenation independently of one another, described 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, described 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 polyphenylene oxide described in the described external phase (B), and described partially hydrogenated segmented copolymer (C) be present at least one described external phase that is selected from polymeric amide (A) and polyphenylene oxide (B) described disperse phase mutually in
Wherein said polymeric amide (A) exposes to the open air on the surface of described molded resin product so that the surface-area that exposes to the open air at the whole lip-deep polymeric amide (A) of described molded resin product is at least 80% of a molded resin product surface-area.
2. according to above 1 molded resin product, it is characterized in that described 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 and be different from polyamide 6,6 polymeric amide.
4. according to above 3 molded resin product, it is characterized in that, the described 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 described 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 described 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, described polyphenylene oxide (B) contain molecular weight be 200000 or the polyphenylene oxide molecule of higher higher molecular weight and molecular weight be 5000 or the polyphenylene oxide molecule of lower lower molecular weight, the weight ratio of the polyphenylene oxide molecule of wherein said higher molecular weight and the polyphenylene oxide molecule of described lower molecular weight is 0.35 or littler.
8. according to above 1 molded resin product, it is characterized in that, described polyphenylene oxide (B) contain molecular weight be 200000 or the polyphenylene oxide molecule of higher higher molecular weight and molecular weight be 5000 or the polyphenylene oxide molecule of lower lower molecular weight, the amount of the amount of the polyphenylene oxide molecule of wherein said lower molecular weight and the polyphenylene oxide molecule of described higher molecular weight is respectively the 5 weight % or the littler and 2 weight % or littler of described polyphenylene oxide resin (B) weight.
9. according to above 1 molded resin product, it is characterized in that described 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 described at least a partially hydrogenated segmented copolymer (C-1) and described 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 by the unhydrided segmented copolymer of partial hydrogenation, the amount that wherein said at least a aromatic vinyl polymer block exists be described 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 by the unhydrided segmented copolymer of partial hydrogenation, the amount that wherein said at least a aromatic vinyl polymer block exists be described unhydrided segmented copolymer weight 20 to less than 60 weight %, and
Wherein be present in described hydrogenant segmented copolymer (C-1) and (C-2) in the total amount of aromatic vinyl polymer block be described 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, carbon fiber and carbon nanotube, and these goods are undertaken by the composition to the described carbonaceous material (D) of the masterbatch that comprises the described polymeric amide (A) that wherein is dispersed with described carbonaceous material (D) and described polyphenylene oxide (B), described one or more partially hydrogenated segmented copolymers (C) and non-essential at least a described 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 described 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),
Polyphenylene oxide (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 is undertaken by the composition to the described carbonaceous material (D) of the masterbatch that comprises the described polymeric amide (A) that wherein is dispersed with described carbonaceous material (D) and described polyphenylene oxide (B), described segmented copolymer (C), described wollastonite particle (E) and non-essential at least a described 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, carbon fiber and carbon nanotube.
18. the conductive resin composition according to above 16 is characterized in that the average particulate diameter of described wollastonite particle (E) is 2～9 μ m.
19. conductive resin composition according to above 16, it is characterized in that, described 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 described 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, provide a kind of molded resin product, it comprises:
The polymeric amide (A) that contains at least two kinds of different polyamide compositions,
Polyphenylene oxide (B) and
The partially hydrogenated segmented copolymer (C) that one or more are specific,
Wherein said polymeric amide (A) exists as external phase, disperse to form disperse phase at polyphenylene oxide described in the described external phase (B), and described partially hydrogenated segmented copolymer (C) be present at least one described external phase that is selected from polymeric amide (A) and polyphenylene oxide (B) described disperse phase mutually in
Wherein said polymeric amide (A) exposes to the open air on the surface of described molded resin product so that the surface-area that exposes to the open air at the whole lip-deep polymeric amide (A) of described molded resin product is at least 80% of a molded resin product surface-area.
There is no particular limitation for the type of the polymeric amide that can be used for molded resin product of the present invention (A), as long as it is the polymkeric substance that has acid amides { NH-C (=O)-} key in its repeating unit.
Usually, for example the polycondensation of ring-opening polymerization, diamines and the di-carboxylic acid by 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 examples.
The example of above-mentioned diamines comprises aliphatic diamine, alicyclic diamine and aromatic diamine.Particularly, can mention butanediamine, 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 example 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 by 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 example 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 by 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 or more different polymeric amide compositions, and preferably use two or more 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 example of described 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 described polyamide compound has in the above-mentioned scope can be confirmed by the following method: wherein, to be 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 described polymeric amide composition that obtains to carry out viscosity test according to ISO307.As described below, have the combination of the polymeric amide composition of different viscosity by use, can improve the coating bond strength of this molded resin product, and can not sacrifice the mechanical properties of this molded resin product.
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 described 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:
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.
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 6,12 and/or polyamide 6,6/6, I.
When using polyamide 6,6 and be different from polyamide 6, the combination of 6 polymeric amide can be selected polyamide 6 during as polymeric amide (A) suitably, and 6 and 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, to contain at least a terminal amino group content be 1 * 10 to the polymeric amide that preferably uses in molded resin product of the present invention (A)
5～4 * 10
5The polymeric amide of mol/kg more advantageously is 2 * 10
5～3 * 10
5Mol/kg.In the case, be not particularly limited for 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 interior endgroup content of 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), as described in Japanese Patent Application Publication specification sheets (putting down) 1-163262 (corresponding to U.S. Pat 4857575) that does not examine, and can not produce any problem.
In described 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 be used singly or in combination.
With respect to the polymeric amide (A) of 100 weight parts, preferably the amount with 0.001～1 weight part adds described 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 example 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 described organic stabilizer is preferably 0.001～1 weight part.
In addition, also any other conventional additives that is used for polymeric amide can be added polymeric amide (A).With respect to the polymeric amide (A) of 100 weight parts, can be to use described additive less than the amount of 10 weight parts.
The example that can be used for the polyphenylene oxide (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 represents Sauerstoffatom, and R represents hydrogen atom, 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 polyphenylene oxide of molded resin product of the present invention comprises poly-(2,6-dimethyl-1,4-phenylene ether), poly-(2-methyl-6-ethyl-1, the 4-phenylene ether), poly-(2-methyl-6-phenyl-1, the 4-phenylene ether) and poly-(2,6-two chloro-1,4-phenylene ether).Other examples of polyphenylene oxide 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 Japanese Patent Application Publication (clear) 52-17880 (corresponding to U.S. Pat 4011200) that examines to some extent.
In above-mentioned polyphenylene oxide, preferred poly-(2,6-dimethyl-1,4-phenylene ether), 2,6-xylenol and 2,3, multipolymer of 6-pseudocuminol and composition thereof.
Method for polyphenylene oxide (B) used in the preparation molded resin product of the present invention is not particularly limited, and can use any ordinary method.For example, can mention as U.S. Pat 3306874,3306875,3257357 and 3257358, do not examine Japanese Patent Application Publication specification sheets (clear) 50-51197 (corresponding to U.S. Pat 3929930), Japanese Patent Application Publication specification sheets (clear) 52-17880 that has examined, not examine the method described in Japanese Patent Application Publication specification sheets (clear) 63-152628 (corresponding to U.S. Pat 4011200).
For the polyphenylene oxide 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, described viscosity 0.5g/dl chloroformic solution with respect to polyphenylene oxide under 30 ℃ records.
Using the mixture of two or more dissimilar polyphenylene oxide with different viscosity that reduce is favourable as polyphenylene oxide (B), and this is because can improve the fluidity of molten of polyphenylene oxide (B) and the balance of shock resistance.Example as described mixture, the mixture of the polyphenylene oxide that can mention viscosity and the polyphenylene oxide of viscosity and have 0.40dl/g or the mixture of the polyphenylene oxide of the viscosity of lower reduction and the polyphenylene oxide of viscosity with 0.50dl/g or higher reduction with 0.50dl/g or higher reduction with 0.45dl/g or lower reduction, but described polyphenylene oxide alloy is not limited to above those that exemplify.
The polyphenylene oxide (B) that the present invention uses can be modified form or can be the form of mixtures of unmodified polyphenylene oxide and Noryl.The mixture of preferred especially unmodified polyphenylene oxide of use and Noryl is as polyphenylene oxide (B).
In the present invention, " Noryl " is meant the polyphenylene oxide 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 WO 02/094936.
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 polyphenylene oxide and Noryl, be not particularly limited for the amount of Noryl; But, the amount of described Noryl is preferably 10～95 weight % of polyphenylene oxide (B) weight, and more preferably 30～90 weight % most preferably are 45～85 weight %.
For described polyphenylene oxide 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 by the part or all of polyphenylene oxide (B) that melt-polyphenylene oxide of kneading (B) obtains.By adding polyphenylene oxide (B), can improve the certainly transmission ability of polyphenylene oxide in kneading machine (for example forcing machine), thereby improve the throughput rate of molded resin product with this particulate form.In addition, use the polyphenylene oxide (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 (for example saccharoid) that obtained 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, by using polyphenylene oxide, can suppress the appearance of this crazing by melt-particulate form that the polyphenylene oxide of kneading obtains.
In addition, the polyphenylene oxide (B) that is preferred for molded resin product of the present invention has specific molecular weight.Particularly, preferred polyphenylene oxide (B) contain molecular weight be 200000 or the polyphenylene oxide of higher higher molecular weight and molecular weight be 5000 or the polyphenylene oxide of lower lower molecular weight, and satisfy following require (I) and/or (II):
(I) requiring the weight ratio of the polyphenylene oxide of the polyphenylene oxide of described higher molecular weight and described lower molecular weight is 0.35 or littler; And/or
(II) require the amount of the polyphenylene oxide of the polyphenylene oxide of described lower molecular weight and described higher molecular weight to be respectively the 5 weight % or the littler and 2 weight % or littler of described polyphenylene oxide resin (B) weight.
More preferably above-mentioned two requirements (I) and (II) be met simultaneously.Molecular weight by regulating polyphenylene oxide (B) is to meet the demands (I) and/or (II), can further improve the coating bond strength of this molded resin product.
Can be by may further comprise the steps 1)-3) method measure the molecular weight of the polyphenylene oxide of the polyphenylene oxide of above-mentioned lower molecular weight and higher molecular weight.
1) molded resin product that its amount enough is used for the molecular weight test is pulverized.Then, the pulverized molded resin product of gained is immersed in the chloroform, by supersound washing device etc. its solvable composition is dissolved in the chloroform, thereby obtains solution.
2) solution that in step 1), obtains by 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 by being purchased the GPC process software) in the molecular weight data of acquisition, to determine 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 described segmented copolymer, operate the UV spectrum detector, thereby do not detect the segmented copolymer of following polyphenylene oxide 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 polyphenylene oxide (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 polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin) and the vinylbenzene-rubber polymer-acrylonitrile copolymer (ABS resin) of polystyrene (homopolymer), modified rubber.
In addition, any conventional stablizer that is used for polyphenylene oxide can use at preparation molded resin product of the present invention.The example 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 polyphenylene oxide (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 polyphenylene oxide can use at preparation molded resin product of the present invention, and with respect to the polyphenylene oxide (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 described partially hydrogenated segmented copolymer (C) that can use in molded resin product of the present invention is to obtain by the unhydrided segmented copolymer of partial hydrogenation, and described 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 mainly aromatic vinyl polymer block of 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 described 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 mainly conjugated diolefin polymer block of 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 described 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 described 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 described aromatic vinyl monomer comprises vinylbenzene, alpha-methyl styrene and Vinyl toluene.These compounds can be used singly or in combination.In the compound that more than exemplifies, vinylbenzene is particularly preferred.
The specific examples that is used to form the conjugated diolefine of described conjugated diene monomeric unit comprises divinyl, isoprene, piperylene and 1,3-pentadiene.These compounds can be used singly or in combination.In the compound that more than exemplifies, 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 described segmented copolymer that uses in the present invention must be partially hydrogenated segmented copolymer.
" partially hydrogenated segmented copolymer " is meant the multipolymer that obtains by 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 described 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, by gel permeation chromatography (GPC) equipment (GPC SYSTEM 21, by Japanese Showa Denko company's production and sale), use UV spectrum detector (UV-41, 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 correct molecular weight distribution of calculating (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).By using partially hydrogenated segmented copolymer (C-1) and mixture (C-2), can improve the coating bond strength of this molded resin product and be used to prepare the shock resistance of resin combination of this molded resin product and the balance of fluidity of molten.
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 described at least a partially hydrogenated segmented copolymer (C-1) and described 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 by the unhydrided segmented copolymer of partial hydrogenation, the amount that wherein said at least a aromatic vinyl polymer block exists be described 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 by the unhydrided segmented copolymer of partial hydrogenation, the amount that wherein said at least a aromatic vinyl polymer block exists be described unhydrided segmented copolymer weight 20 to less than 60 weight %
Wherein be present in described hydrogenant segmented copolymer (C-1) and (C-2) in the total amount of aromatic vinyl polymer block be described hydrogenant segmented copolymer (C-1) and (C-2) 30～40 weight % of gross weight.
By using at least a partially hydrogenated segmented copolymer and at least a this mixture, can obtain at high temperature hardness and the molded resin product that all is improved of shock resistance aspect 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 by the unhydrided segmented copolymer of partial hydrogenation, and the amount that wherein said aromatic vinyl polymer block exists is 60 to 90 weight % of described 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 described 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 represents 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 represents 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, the mixture of the segmented copolymer of 4-vinyl bonds total content, the mixture of segmented copolymer and mixture with segmented copolymer of different hydrogenation degrees with different aromatic vinyl monomers unit content.
Can prepare above-mentioned unhydrided segmented copolymer by any ordinary method.Also can carry out above-mentioned hydrogenation to unhydrided segmented copolymer by 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 WO 02/094936.
Molded resin product of the present invention can also comprise carbonaceous material (D).By adding carbonaceous material (D), this molded resin product can 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 by its adding.
In described carbonaceous material, preferred especially graphitized carbon black, carbon fiber and carbon nanotube.These carbonaceous materials can be used singly or in combination.As being used for graphitized carbon black of the present invention, can mention the graphitized carbon black of describing among the WO 01/081473.The example of commercial graphitized carbon black comprises KetjenBlack EC and Ketjen Black EC600JD (produced and sold by Japanese Ketjen BlackInternational Company respectively).As the example that can be used for carbon fiber of the present invention, can mention the very fine carbon fiber of describing among the WO 94/023433.Broadly, carbon nanotube is included in the carbon fiber; 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 carbon fiber of 75nm Fibre diameter etc., as described in 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 relatively large branch, hollow structure and 75nm or bigger Fibre diameter.As the example of the carbon nanotube that is obtained commercially, 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 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), polyphenylene oxide (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.There is no particular limitation for the method for preparing above-mentioned masterbatch; But, most preferred a kind of method is that wherein masterbatch is undertaken by 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) infeeds the forcing machine from described first inlet, thereby described resin is carried out melt-knead in the upstream portion of forcing machine, and carbonaceous material (D) is infeeded forcing machine, thereby described resin and carbonaceous material (D) are carried out melt-knead in the downstream part of forcing machine from described second inlet.In the method, the preferred resin temperature is lower than 340 ℃.The amount of the carbonaceous material that comprises in the described masterbatch (D) is preferably 5～30 weight % of master batch weight, more preferably 8～25 weight %.
There is no particular limitation for the form of the above-mentioned masterbatch that contains at least a portion carbonaceous material (D), 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 example that is purchased masterbatch, can mention polyamide 66/carbon fiber 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 passing through Sedigraph particle size analyzer (model 5100 by the solution that the supersound washing device obtains the wollastonite particles dispersed satisfactorily therein by 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 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 two or more types wollastonite particulate mixture with different length-to-diameter ratios.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 % or more of the contained wollastonite particle of described mixture gross weight (that is the gross weight of wollastonite particle (E)).
As the example 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 polyphenylene oxide (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 polyphenylene oxide (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 by obtaining the wollastonite particles dispersed at least a portion polymeric amide (A) and/or at least a portion hydrogenant segmented copolymer (C).
Example 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 carries out melt-knead in certain temperature range 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, first inlet that provides in the forcing machine upstream portion and second inlet that provides in the forcing machine downstream part are provided this forcing machine, 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, compatibilizing agent can be added in the molded resin product.
There is no particular limitation 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 polyphenylene oxide 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 example 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 describing in these patent documents may be used among the present invention, and this compatibilizing agent may be used singly or in combin.
In numerous conventional compatibilizing agents, preferred especially maleic anhydride and derivative, toxilic acid and derivative thereof, citric acid and derivative thereof, fumaric acid and derivative thereof and with the compound modified polyphenylene oxide saccharoid of any of these.
With respect to polymeric amide of 100 weight parts (A) and polyphenylene oxide (B) altogether, the consumption of compatibilizing agent is preferably 0.01～25 weight part in the present invention.
There is no particular limitation 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, the compatibilizing agent that has a pungency peculiar smell when use (for example, maleic anhydride) time, 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 polyphenylene oxide (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 polyphenylene oxide (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.There is no particular limitation for the dispersion state of partially hydrogenated segmented copolymer (C) in the disperse phase of polyphenylene oxide (B), and partially hydrogenated segmented copolymer (C) can have the described micro phase separation structure as 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 this polymeric amide area ratio of following measurement.
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, wash with water then and drying from the described 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, wherein under the acceleration voltage of 5kV, operate microscope, 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 by the painted polymeric amide of tungsten, the part that is not colored is black.Therefore, in the gained image, exposing the polymeric amide part that belongs on the molded resin product surface 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, determine the binary-state threshold of image in the following manner.From the histogram of the tone of back-scattered electron image, determine to belong to white the peak intensity and belong to the intensity at the peak of black, and with the mean value of these two intensity as binary-state threshold.)
Determine this polymeric amide area ratio by at least 10 different pieces of observing the molded resin product surface, and the mean value of each polymeric amide area ratio of observed part 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 (such surface portion is hereinafter referred to as " flow end part ") 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 prepare this molded resin product situation by injection molding, select to be observed being used to measure the above-mentioned part of polymeric amide area ratio in the following manner.When a part of molded resin product (such part is hereinafter referred to as " inlet 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 by the cross section 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 cross section.
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 requirement, 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 polyphenylene oxide.
Molded resin product of the present invention be characterised in that form disperse phase resin (hereinafter referred to as " disperse phase resin ") (promptly, polyphenylene oxide (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 described recessed-convex portion is coated with polymeric amide (A).Because this feature, this molded resin product shows aforesaid excellent effect.For recessed-convex portion, must increase the melt viscosity of this disperse phase resin by this disperse phase resin formation appropriateness.On the other hand, in order to form desirable polymeric amide (A) coating on recessed-convex portion, 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) by 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 or more types of polymeric amide.
In the present invention, preferably the melt viscosity of this disperse phase resin (that is, polyphenylene oxide (B) and non-essential partially hydrogenated segmented copolymer (C)) (290 ℃ and shearing rate is 1000sec
-1Following measurement) be 800Pas or higher, 1000Pas or higher more preferably.
On the other hand, (290 ℃ and shearing rate is 1000sec to be preferably formed the melt viscosity of the resin (that is polymeric amide (A)) (hereinafter referred to as " 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 following measurement disperse phase resin and the melt viscosity of external phase resin.For example, can measure the melt viscosity of disperse phase resin by the following method: wherein the material extrusion moulding that will have a same composition with the disperse phase resin to be obtaining saccharoid, and measures the melt viscosity of gained saccharoid by capillary rheometer etc.Can measure the melt viscosity of external phase resin by method same as described above.
In measuring disperse phase resin and external phase resin melt viscosity separately, even when 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 described additive, carry out the measurement of the melt viscosity of described resin.
By 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 feature 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 polyphenylene oxide (B), the amount of polyphenylene oxide (B) was 50～90 weight % of disperse phase gross weight in the preferred disperse phase.When the amount of polyphenylene oxide in the disperse phase is big, can reduce the gloss of molded resin product.Particularly, the amount of preferred polyamide (A), polyphenylene oxide (B) and partially hydrogenated segmented copolymer (C) is respectively 50～70 weight %, 25～45 weight % and 5～25 weight % of polymeric amide (A), polyphenylene oxide (B) and partially hydrogenated segmented copolymer (C) gross weight.More preferably the amount of polymeric amide (A), polyphenylene oxide (B) and partially hydrogenated segmented copolymer (C) is respectively 50～60 weight %, 35～45 weight % and 5～15 weight % of polymeric amide (A), polyphenylene oxide (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 feature 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 example at least 80% method; And the method that wherein polymeric amide (A) and the amount of the reaction product (graftomer) of polyphenylene oxide (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 polyphenylene oxide the polymerization degree so that with the molecular-weight adjusting of polyphenylene oxide (being used for this molded resin product) to the method that falls in the above-mentioned scope; And wherein mix the method that two or more have the polyphenylene oxide of different molecular weight.
The specific examples that the amount of the reaction product (graftomer) of polymeric amide (A) and polyphenylene oxide (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 polyphenylene oxide) by polyphenylene oxide with modification.
In the present invention, regulate the polymeric amide area and be not limited to above those that exemplify than method at least 80%.In addition, multiple different methods can be used in combination 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 in the following manner.ISO15103-2:1997 defined terms (melt temperature: 290 ℃, mould temperature: 90 ℃) down preparation thickness be the D2 type flat board of 2mm (stipulating among the ISO294-3:1996).Then, downcut one section from the center of D2 type flat board, it is of a size of 10mm (length, in mould, record on the resin flows direction) * 3mm (width, in perpendicular to mould, record on the direction of resin flows direction) * 2mm (thickness), 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), polyphenylene oxide (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 example 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 dioxide, potassium titanate, carbon fiber and glass fibre); Strengthen the conventional silane coupling agent of affinity between mineral filler and the resin; Fire retardant (for example, halogenated resin, siloxanes fire retardant, magnesium hydroxide, aluminium hydroxide, 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 carbon fiber and graphitized carbon black; Static inhibitor; Multiple superoxide; Antioxidant; UV light absorber; And photostabilizer.
In the present invention, with respect to the polymeric amide of 100 weight parts (A), polyphenylene oxide (B), partially hydrogenated segmented copolymer (A) 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 example 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, polyphenylene oxide and compatibilizing agent are infeeded in the forcing machine by different loaders, thereby with polymeric amide, polyphenylene oxide and compatibilizing agent melt together-knead.
Particularly working as used compatibilizing agent is the larger particles form; and when used polyphenylene oxide is the powder type that is formed by fine granular; it is favourable using different loaders to infeed compatibilizing agent and infeed polyphenylene oxide; because this can prevent granular mixture (promptly; the mixture of the larger particles of compatibilizing agent and the fine granular of polyphenylene oxide) classification takes place in forcing machine, the ratio that this classification meeting causes compatibilizing agent and polyphenylene oxide is along with in the position of the loader that is used to infeed compatibilizing agent and polyphenylene oxide and the shortcoming that changes.When causing such shortcoming, the ratio that infeeds polyphenylene oxide in the forcing machine and compatibilizing agent 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 may 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.By using screw type gravity supply device, can improve the feed stability of compatibilizing agent, thereby suppress the quality fluctuation of final molding resin.
For the preparation this resin combination used melt-there is no particular limitation for the temperature of kneading.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 examples.
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, (1) by the following method～(3) prepare this resin combination: (1) a kind of method, wherein infeed the forcing machine from first inlet by the mixture of belt gravity supply device with segmented copolymer and polyphenylene oxide, and compatibilizing agent is infeeded in the forcing machine by first inlet by screw type gravity supply device, thereby in the upstream portion of forcing machine with said mixture 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; (2) a kind of method, wherein polyphenylene oxide is infeeded the forcing machine from first inlet by belt gravity supply device, and infeed in the forcing machine by first inlet by the mixture of screw type gravity supply device with compatibilizing agent and segmented copolymer, thereby with polyphenylene oxide 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 by the polyphenylene oxide of belt gravity supply device with powder type, and infeed in the forcing machine by first inlet by the polyphenylene oxide of screw type gravity supply device with compatibilizing agent and particulate form, thereby with polyphenylene oxide 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 by 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 by 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 by 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),
Polyphenylene oxide (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).
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 or more dissimilar polymeric amide, only one type polymeric amide can be used as polymeric amide (A).However, preferably use two or more dissimilar polymeric amide, as the situation of molded resin product of the present invention.
For the polyphenylene oxide that is used for conductive resin composition of the present invention (B), can use the above any polyphenylene oxide 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 does not need to 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 example 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, 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 computers and the peripherals that is used for this computer; 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 that more than exemplifies, 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 limited to scope of the present invention.
Preparation embodiment 1: prepare with maleic anhydride modified polyphenylene oxide (hereinafter referred to as " MPPE ")
Be prepared as follows MPPE.It is mixed that the viscosity that the maleic anhydride of 3 weight parts and 100 weight parts are reduced is that the polyphenylene oxide of 0.42dl/g is done, melt-knead then, subsequently under 320 ℃ tube temperature at forcing machine " ZSK-40 " (by German Coperion Werner ﹠amp; Pfleiderer GmbH ﹠amp; Co.KG produces and sells; 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, its polymers 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 atmosphere in the autoclave with nitrogen.Subsequently, under agitation, the temperature with autoclave in about l 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 discharge nozzle 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 (hereinafter referred to as " PA-MB ")
(ZSK-58MC is by German Coperion Werner ﹠amp to use twin screw extruder; Pfleiderer GmbH ﹠amp; Co.KG produces and sells) preparation PA-MB, this forcing machine part at its upstream has an inlet (hereinafter referred to as " upstream inlet "), and another inlet (hereinafter referred to as " downstream inlet ") is arranged, wherein L/D (ratio of the diameter (D) of length of extruder screw (L) and extruder screw)=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 by the upstream inlet of forcing machine and the downstream inlet of forcing machine respectively.Make the content of forcing machine carry out melt-knead under the following conditions: wherein the tube temperature of part is 280 ℃ between forcing machine upstream 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 " (by German Coperion Werner ﹠amp; Pfleiderer GmbH ﹠amp; Co.KG produces and sells, L/D=46) saccharoid of preparation resin combination, this forcing machine has 12 tube unit and (extrudes direction from forcing machine, they are called as " the 1st unit ", " the 2nd unit " respectively ... " the 12nd unit ") and mould, the unitary temperature separately of tube wherein can be regulated independently.This forcing machine has inlet (hereinafter referred to as " upstream inlet ") at the 1st place, unit, another inlet (hereinafter referred to as " the 1st downstream inlet ") is arranged at the 6th place, unit, also have an inlet (hereinafter referred to as " the 2nd downstream inlet ") at the 8th place, unit, and at place, the 5th and 11 unit two air outlets arranged (thus can vacuum suction).Inlet is installed belt gravity supply device and two screw type gravity supply devices in the upstream of forcing machine, and at the 1st downstream of forcing machine inlet other screw type gravity supply device is installed.
Particularly, use above-mentioned forcing machine, be prepared as follows the saccharoid of resin combination.At first, following raw material with resin combination infeeds in the above-mentioned forcing machine.By being installed in a screw type gravity supply device (hereinafter referred to as " loader 1 ") of forcing machine upstream inlet, the polyphenylene oxide powder (hereinafter referred to as " PPE1 ") that will have the viscosity 0.52dl/g (under 30 ℃, being that the chloroformic solution of 0.5g/dl records with respect to polyphenylene oxide concentration) of reduction infeeds in the forcing machine.By being installed in the other screw type gravity supply device (hereinafter referred to as " loader 2 ") of forcing machine upstream inlet, (sheet, each diameter are that 4～5mm) (produced and sold by Japanese Mitsubishi Chemical Corporation) (hereinafter referred to as " MAH ") infeed 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 (hereinafter referred to as " SEBS1 ") and 8 weight parts is that (styrene content: 29%) (hereinafter referred to as " SEBS2 ") does mixed for polystyrene/polyvinylidene/polystyrene block copolymer of 98500 for polystyrene/polyvinylidene/polystyrene block copolymer of 246000.By being installed in the belt gravity supply device (hereinafter referred to as " loader 3 ") of forcing machine upstream inlet, the gained mixture is infeeded in the forcing machine.Using rotating cylinder, is that 120ml/g, terminal amino group content are 2.5 * 10 by 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 (hereinafter referred to as " 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 (hereinafter referred to as " PA66-b ") are done and are mixed, the preparation polyamide compound.By being installed in the screw type gravity supply device (hereinafter referred to as " loader 4 ") of forcing machine the 1st downstream inlet, the gained polyamide compound is infeeded in the forcing machine.
Temperature condition in the forcing machine is as follows: 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 polyphenylene oxide molecular weight)
By 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 by the GPC (gel permeation chromatography) that uses the UV spectrum detector gained the section saccharoid chloroformic solution (wherein, main solute is polyphenylene oxide and segmented copolymer), and use is with respect to the molecular weight of the calibrating curve determining polyphenylene oxide of polystyrene standard sample acquisition.This UV spectrum detector is to operate under the 283nm at the UV wavelength, thereby does not detect the segmented copolymer of following the polyphenylene oxide wash-out to go out in the gpc analysis process.
Thus obtained molecular weight data is analyzed.Found that to have molecular weight 200000 or higher polyphenylene oxide molecule independently of one another and have molecular weight 5000 independently of one another or the amount of lower polyphenylene oxide molecule is respectively the 1.45 weight % and the 4.78 weight % of polyphenylene oxide molecule gross weight.Find that also having molecular weight 200000 or higher polyphenylene oxide molecule independently of one another is 0.30. with the weight ratio that has molecular weight 5000 or lower polyphenylene oxide 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 exposes 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 is 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, wash with water then and drying.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 to operate 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, the binary-state threshold of following definite image.From the histogram of the tone of back-scattered electron image, determine to belong to white the peak intensity and belong to the intensity at the peak of black, and with the mean value 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 as follows: injection rate (by 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.Found 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 finished, toast coated flat board down at 80 ℃ and reach 30 minutes.
Then, make coated flat board 23 ℃ down and humidity be to leave standstill 24 hours for 50% time.(be of a size of 2cm * 2cm) with respect to certain area on the coated surface of this flat board, cut coated surface with cutting machine, (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, wherein cellophane tape is sticked on the coated surface portion with the cutting pattern that is verified, peel off rapidly then.Measure and stay the quantity of coated lip-deep square coating layer portion after cellophane tape is peeled off, thereby estimate the coating bond strength.Found that 95 square coating layer portions (in 100 square coating layer portions) are stayed on the dull and stereotyped surface.
The results are shown in the table 1.
(acutance of the image that in coated surface, reflects)
The outward appearance of the above-mentioned coated flat board of following observation.At first, examine the coated surface of this coated flat board, to watch whether any unfairness is arranged on the surface.Then, estimate the acutance of the image that reflects on coated surface by the image (being arranged in about 1.5m place, coated dull and stereotyped top) of observing the luminescent lamp that in the coated surface of this flat board, reflects.Judgement criteria is as follows.
The A level: the profile of the luminescent lamp image of coated surface reflection is obviously clearly.
The B level: the profile of the luminescent lamp image of coated surface reflection is unintelligible, but can distinguish out.
The C level: the profile of the luminescent lamp image of coated surface reflection is unintelligible, and almost can not pick out.
D level: less unfairness is arranged on the coated surface.
In addition, in order to measure the melt viscosity (hereinafter referred to as " disperse phase resinous principle ") of the resinous principle that forms the molded resin product disperse phase, 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 by the 4th loader feed (that is, only carrying out feed by the 1st to the 3rd loader).On the other hand, in order to measure the melt viscosity (hereinafter referred to as " external phase resinous principle ") of the resinous principle that forms molded resin product external phase, 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 by the 1st to the 3rd loader feed (that is, only carrying out feed by 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.Found that the melt viscosity of this disperse phase resinous principle (η d) is about 1570Pasec, 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 prepare the saccharoid of resin combination in the mode identical substantially with embodiment 1, 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, estimates these character in the mode identical substantially with embodiment 1 subsequently.
Particularly, for used raw material among embodiment 2～4 and the comparative example 1, it is as follows to be different from raw material used among those embodiment 1:
The viscosity that reduces is the polyphenylene oxide powder (hereinafter referred to as " 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 (hereinafter referred to as " PA66-c "); With
The PA66/6I that in embodiment 2, makes.
Table 1
| Ex. 1 | Ex. 2 | Ex. 3 | Ex. 4 | Com.Ex. 1 | |||
| The upstream inlet | |||||||
| Loader 1 | PPE-1 (weight part) PPE-2 (weight part) | *1 *2 | 38 | 38 | 38 | 30 | 38 |
| Loader 2 | MPPE (weight part) MAH (weight part) | *3 *4 | 0.2 | 0.3 | 0.3 | 8 | 0.3 |
| Loader 3 | SEBS1 (weight part) SEBS2 (weight part) | *5 *6 | 4 8 | 4 8 | 4 8 | 4 8 | 4 8 |
| First downstream inlet | |||||||
| Loader 4 | PA66-a (weight part) PA66-b (weight part) PA66-c (weight part) PA66/6I (weight part) | *7 *8 *9 *10 | 40 10 | 40 10 | 40 10 | 40 10 | 50 |
| Polymeric amide area ratio | ％ | 84 | 94 | 90 | 87 | 67 | |
| Molal weight is 5000 or littler PPE | ％ | 4.78 | - | 7.18 | 3.67 | - | |
| Molal weight is 200000 or bigger PPE | ％ | 1.45 | - | 0.82 | 3.4 | - | |
| Molal weight be 200000 or bigger PPE/ molal weight be 50000 or littler PPE | - | 0.30 | - | 0.11 | 0.93 | - | |
| The no photosensitiveness on the coated surface of acutance of the image that reflects in the coated surface of coating bond strength (in 100 square coating layer portions, staying the amount of the lip-deep square coating layer portion of molded resin product) | - - | 95 A III | 100 A II | 60 A II | 100 A III | 5 A I | |
*1) viscosity of Jiang Diing is the PPE powder of 0.52dl/g
*2) viscosity of Jiang Diing is the PPE powder of 0.42dl/g
*3) PPE of MAH modification is that the PPE of 0.42dl/g and MAH melt are kneaded and obtained by the viscosity that makes reduction
*4) maleic anhydride (sheet)
*5) SEBS segmented copolymer (styrene content: 33%; Mn:246000)
*6) SEBS segmented copolymer (styrene content: 29%; Mn:98500)
*7) PA6,6, viscosity number is 120ml/g; [NH
2]=2.5 * 10
5Mol/g; [COOH]=11.6 * 10
5Mol/g
*8) PA6,6, viscosity number is 130ml/g; [NH
2]=4.2 * 10
5Mol/g; [COOH]=9.1 * 10
5Mol/g
*9) PA6,6, viscosity number is 230ml/g; [NH
2]=2.4 * 10
5Mol/g; [COOH]=4.8 * 10
5Mol/g
*10) PA6,6/6, I contains 19 moles of % polyamide 6 I; [NH
2]=3.9 * 10
5Mol/g; [COOH]=10.2 * 10
5Mol/g
Embodiment 5～7 and comparative example 2
Next the saccharoid for preparing resin combination in the mode identical substantially with embodiment 1, different the following stated raw materials that are to use.For the saccharoid of gained, estimate its different properties in the mode identical substantially subsequently with embodiment 1.The results are shown in the table 2, also have the composition of this saccharoid.
Number-average molecular weight (Mn) is polystyrene/polyvinylidene/polystyrene block copolymer (styrene content: 60%) (hereinafter referred to as " SEBS3 ") of 105000;
Ketjen black " EC-600JD " (trade name; Produce and sell by Japanese Ketjen BlackInternational Company Ltd.) (hereinafter referred to as " KB "); With
Polymeric amide/carbon the masterbatch (hereinafter referred to as " PA-MB ") that makes among the preparation embodiment 3.
Table 2
| The upstream inlet | Ex.5 | Com.Ex.2 | Ex.6 | Ex.7 | ||
| Loader 1 | PPE-1 (weight part) | 38 | 38 | 38 | 22 | |
| Loader 2 | MPPE (weight part) MAH (weight part) | 0.3 | 0.3 | 0.3 | 16 | |
| Loader 3 | SEBS1 (weight part) | 12 | 12 | 3 | ||
| SEBS2 (weight part) | 12 | 5 | ||||
| SEBS3 (weight part) | *11 | 4 | ||||
| First downstream inlet | ||||||
| Loader 4 | PA66-a (weight part) PA66-b (weight part) PA66-c (weight part) PA-MB (weight part) KB (weight part) | *12 *13 | 30 20 | 30 20 | 50 2 | 20 10 20 |
| Polymeric amide area ratio | ％ | 81 | 75 | 96 | 97 | |
| Molal weight is 5000 or littler PPE | ％ | - | - | - | 3.12 | |
| Molal weight is 200000 or bigger PPE | ％ | - | - | - | 0.92 | |
| Molal weight be 200000 or bigger PPE/ molal weight be 50000 or littler PPE | - | - | - | - | 0.29 | |
| The no photosensitiveness on the coated surface of acutance of the image that reflects in the coated surface of coating bond strength (in 100 square coating layer portions, staying the amount of molded resin product surface square coating layer portion up and down) | - - | 83 B III | 45 A II | 70 B IV | 100 A IV | |
*11) SEBS segmented copolymer (styrene content: 60%; Mn:105000)
*12) electrically conductive polyamide/carbon masterbatch (carbon content: 10 weight %)
*13) conductive carbon (ketjen blace EC600JD)
Embodiment 8～10 and comparative example 3
Next the saccharoid for preparing resin combination in the mode identical substantially with embodiment 1, different is that the forcing machine that uses among embodiment 8～10 and the comparative example 3 also has the other screw type gravity supply device (hereinafter referred to as " loader 5 ") that is installed in 2 downstreams inlet, by this loader wollastonite is infeeded in the forcing machine, thereby obtain saccharoid.For the saccharoid of gained, estimate its different properties in the mode identical substantially subsequently with embodiment 1.The results are shown in the table 3, also have the composition of this saccharoid.Particularly, for used raw material among embodiment 8～10 and the comparative example 3, it is as follows to be different among those embodiment 1 raw material used or that do not use in embodiment 1:
Polyamide 6 " 1013B " (trade name; Produce and sell by Japanese Ube Industries Ltd.)) (hereinafter referred to as " 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.
Table 3
| The upstream inlet | Ex.8 | Ex.9 | Com.Ex.3 | Ex.10 | ||
| Loader 1 | PPE-1 (weight part) | 38 | 38 | 38 | 38 | |
| Loader 2 | MAH (weight part) | 0.3 | 0.3 | 0.3 | 0.3 | |
| Loader 3 | SEBS1 (weight part) SEBS2 (weight part) | 12 | 12 | 12 | 12 | |
| First downstream inlet | ||||||
| Loader 4 | PA66-a (weight part) PA6 (weight part) PA66/6I (weight part) | 30 20 | 30 20 | 30 20 | 30 20 | |
| Second downstream inlet | ||||||
| Loader 5 | Wollastonite 1 (weight part) wollastonite 2 (weight part) wollastonite 3 (weight parts) | *14 *15 *16 | 20 | 20 | 20 | 15 5 |
| Polymeric amide area ratio | ％ | 87 | 83 | 82 | 88 | |
| The no photosensitiveness on the coated surface of acutance of the image that reflects in the coated surface of coating bond strength (in 100 square coating layer portions, staying the amount of molded resin product surface square coating layer portion up and down) | - - | 100 A III | 100 A III | 32 D I | 100 A IV | |
*14) wollastonite (average particulate diameter: 5 μ m, length-to-diameter ratio: 13)
*15) wollastonite (average particulate diameter: 5 μ m, length-to-diameter ratio: 3)
*16) wollastonite (average particulate diameter: 10 μ m, length-to-diameter ratio: 13)
Embodiment 11
Next prepare the saccharoid of resin combination in the mode identical substantially with embodiment 1, different is to use raw material with the ratio shown in the table 4.For the saccharoid of gained, estimate its different properties in the mode identical substantially subsequently with embodiment 1.The results are shown in the table 4, also have the composition of this saccharoid.
Table 4
| The upstream inlet | Ex.11 | ||
| Loader 1 | PPE-1 (weight part) | 38 | |
| Loader 2 | MAH (weight part) | 0.3 | |
| Loader 3 | SEBS1 (weight part) SEBS2 (weight part) SEBS2 (weight part) | 3 5 4 | |
| First downstream inlet | |||
| PA66-a (weight part) PA66-b (weight part) PA-MB (weight part) | 20 10 20 | ||
| Second downstream inlet | |||
| Wollastonite 1 (weight part) wollastonite 2 (weight part) wollastonite 3 (weight parts) | 15 5 | ||
| Polymeric amide area ratio | ％ | 92 | |
| The no photosensitiveness on the coated surface of acutance of the image that reflects in the coated surface of coating bond strength (in 100 square coating layer portions, staying the amount of the lip-deep square coating layer portion of molded resin product) | - - | 100 A IV | |
Industrial applicibility
The advantage of molded resin product of the present invention is that not only this molded resin product has excellent matt surface, and be that this molded resin product has excellent bonding strength (namely for the coating that forms at this molded resin product, " coating adhesion intensity "), and the acutance (that is, this coating has excellent gloss) that has the excellent image that wherein reflects in this coating that this molded resin product forms. 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 matt surface, and be that this moulded products has excellent coating adhesion intensity, and has the acutance of the excellent image that reflects in the coating that this moulded products forms. In addition, prepared moulded products has gratifying low linear expansion coefficient, 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 the field of parts can be used for using in Electrical and Electronic parts, office automated machine parts, mechanical part and motorcycle and the automobile.
Claims (19)
1. molded resin product is characterized in that, it comprises:
The polymeric amide (A) that contains at least two kinds of different polyamide compositions,
Polyphenylene oxide (B) and
One or more partially hydrogenated segmented copolymers (C),
Wherein said partially hydrogenated segmented copolymer, (C) obtain by the unhydrided segmented copolymer of partial hydrogenation independently of one another, described 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, described 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 polyphenylene oxide described in the described external phase (B), and described partially hydrogenated segmented copolymer (C) be present at least one described external phase that is selected from polymeric amide (A) and polyphenylene oxide (B) described disperse phase mutually in
Wherein said polymeric amide (A) exposes to the open air on the surface of described molded resin product so that the surface-area that exposes to the open air at the whole lip-deep polymeric amide (A) of described molded resin product is at least 80% of a molded resin product surface-area.
2. according to the molded resin product of claim 1, it is characterized in that described polymeric amide (A) contains at least two kinds and different has its polymeric amide composition of different viscosity separately.
3. according to the molded resin product of claim 1, it is characterized in that described polymeric amide (A) contains polyamide 6,6 and be different from polyamide 6,6 polymeric amide.
4. according to the molded resin product of claim 3, it is characterized in that, the described polyamide 6 that is different from, 6 polymeric amide is a polyamide 6.
5. according to the molded resin product of claim 3, it is characterized in that the described 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 the molded resin product of claim 1, it is characterized in that it is 1 * 10 that described 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 the molded resin product of claim 1, it is characterized in that, described polyphenylene oxide (B) contain molecular weight be 200000 or the polyphenylene oxide molecule of higher higher molecular weight and molecular weight be 5000 or the polyphenylene oxide molecule of lower lower molecular weight, the weight ratio of the polyphenylene oxide molecule of wherein said higher molecular weight and the polyphenylene oxide molecule of described lower molecular weight is 0.35 or littler.
8. according to the molded resin product of claim 1, it is characterized in that, described polyphenylene oxide (B) contain molecular weight be 200000 or the polyphenylene oxide molecule of higher higher molecular weight and molecular weight be 5000 or the polyphenylene oxide molecule of lower lower molecular weight, the amount of the amount of the polyphenylene oxide molecule of wherein said lower molecular weight and the polyphenylene oxide molecule of described higher molecular weight is respectively the 5 weight % or the littler and 2 weight % or littler of described polyphenylene oxide resin (B) weight.
9. according to the molded resin product of claim 1, it is characterized in that described 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 the molded resin product of claim 9, it is characterized in that described at least a partially hydrogenated segmented copolymer (C-1) and described 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 by the unhydrided segmented copolymer of partial hydrogenation, the amount that wherein said at least a aromatic vinyl polymer block exists be described 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 by the unhydrided segmented copolymer of partial hydrogenation, the amount that wherein said at least a aromatic vinyl polymer block exists be described unhydrided segmented copolymer weight 20 to less than 60 weight %, and
Wherein be present in described hydrogenant segmented copolymer (C-1) and (C-2) in the total amount of aromatic vinyl polymer block be described hydrogenant segmented copolymer (C-1) and (C-2) 30～40 weight % of gross weight.
11. molded resin product according to claim 1, wherein these goods also comprise at least a carbonaceous material (D) that is selected from graphitized carbon black, carbon fiber and carbon nanotube, and these goods are undertaken by the composition to the described carbonaceous material (D) of the masterbatch that comprises the described polymeric amide (A) that wherein is dispersed with described carbonaceous material (D) and described polyphenylene oxide (B), described one or more partially hydrogenated segmented copolymers (C) and non-essential at least a described polymeric amide (A) that is selected from additional content and additional content, and melt-kneading makes.
12. the molded resin product according to claim 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 claim 12 is characterized in that, described wollastonite particle (E) has at least two kinds of different length-to-diameter ratios.
14. the molded resin product according to claim 1 is characterized in that, these goods are saccharoids.
15. the molded resin product according to claim 1 is characterized in that, these goods are automobile external-use parts.
16. conductive resin composition, it comprises:
Polymeric amide (A),
Polyphenylene oxide (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 claim 16, it is characterized in that, said composition is undertaken by the composition to the described carbonaceous material (D) of the masterbatch that comprises the described polymeric amide (A) that wherein is dispersed with described carbonaceous material (D) and described polyphenylene oxide (B), described segmented copolymer (C), described wollastonite particle (E) and non-essential at least a described 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, carbon fiber and carbon nanotube.
18. the conductive resin composition according to claim 16 is characterized in that, the average particulate diameter of described wollastonite particle (E) is 2～9 μ m.
19. conductive resin composition according to claim 16, it is characterized in that, described 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 described wollastonite particle (E) be 50 weight % or bigger of wollastonite particle (E) gross weight.
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|---|---|---|---|
| JP2003113589 | 2003-04-18 | ||
| JP113589/2003 | 2003-04-18 | ||
| JP119814/2003 | 2003-04-24 |
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|---|---|---|---|
| CN 200910142578 Division CN101585965B (en) | 2003-04-18 | 2004-04-16 | Resin moldings and conductive resin composition |
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|---|---|
| CN1806010A true CN1806010A (en) | 2006-07-19 |
| CN100528964C CN100528964C (en) | 2009-08-19 |
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| CN 200480016801 Expired - Fee Related CN100528964C (en) | 2003-04-18 | 2004-04-16 | Resin moldings and conductive resin composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056989A (en) * | 2008-04-09 | 2011-05-11 | 沙伯基础创新塑料知识产权有限公司 | Filled compositions and a method of making |
| CN103154085A (en) * | 2010-10-13 | 2013-06-12 | 旭化成化学株式会社 | Polyphenylene ether as well as resin composition and molding thereof |
| CN103619952A (en) * | 2011-06-17 | 2014-03-05 | 旭化成化学株式会社 | Resin composition and molded article thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6334842B2 (en) * | 2012-12-20 | 2018-05-30 | 旭化成株式会社 | Conductive polyacetal resin composition pellets and method for producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665500A (en) * | 1992-08-21 | 1994-03-08 | Mitsubishi Gas Chem Co Inc | Polyamide resin composition |
| US6984678B2 (en) * | 2001-05-24 | 2006-01-10 | Asahi Kasei Kabushiki Kaisha | Thermoplastic resin composition and molded articles |
-
2004
- 2004-04-16 CN CN 200910142578 patent/CN101585965B/en not_active Expired - Fee Related
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056989A (en) * | 2008-04-09 | 2011-05-11 | 沙伯基础创新塑料知识产权有限公司 | Filled compositions and a method of making |
| US8257613B2 (en) | 2008-04-09 | 2012-09-04 | Sabic Innovative Plastics Ip B.V. | Filled compositions and a method of making |
| CN103154085A (en) * | 2010-10-13 | 2013-06-12 | 旭化成化学株式会社 | Polyphenylene ether as well as resin composition and molding thereof |
| US8901222B2 (en) | 2010-10-13 | 2014-12-02 | Asahi Kasei Chemicals Corporation | Polyphenylene ether, resin composition, and molded body of resin composition |
| CN103154085B (en) * | 2010-10-13 | 2015-07-08 | 旭化成化学株式会社 | Polyphenylene ether as well as resin composition and molding thereof |
| CN103619952A (en) * | 2011-06-17 | 2014-03-05 | 旭化成化学株式会社 | Resin composition and molded article thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101585965B (en) | 2012-04-18 |
| CN101585965A (en) | 2009-11-25 |
| CN100528964C (en) | 2009-08-19 |
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