CN104098898A - Resin composition used for insert molding, metal resin composite molding body using resin composition, and manufacturing method of metal resin composite molding body - Google Patents
Resin composition used for insert molding, metal resin composite molding body using resin composition, and manufacturing method of metal resin composite molding body Download PDFInfo
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- CN104098898A CN104098898A CN201410137387.5A CN201410137387A CN104098898A CN 104098898 A CN104098898 A CN 104098898A CN 201410137387 A CN201410137387 A CN 201410137387A CN 104098898 A CN104098898 A CN 104098898A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
The present invention provides a resin composition used for insert molding, a metal resin composite molding body using the resin composition, and a manufacturing method of the metal resin composite molding body. The resin composition used for insert molding can realize the metal resin composite molding body in which joint strength between an insert metal member and a resin member is strong, and can realize excellent impact resistance and low dielectric property (low dielectric constant and low dielectric loss angle tangent), and further realizes high whiteness. The present invention provides a resin composition used for performing insert molding for an insert metal member on which physical treatment and/or chemical treatment are implemented. The resin composition contains 100 parts by mass of (A) polyarylene sulfide resin, 3-55 parts by mass of (B) olefine copolymer containing an epoxy group, and 5-60 parts by mass of (C) polystyrene resin, wherein the ratio ((B)/(C)) between the content of the (B) olefine copolymer containing an epoxy group and the content of the (C) polystyrene resin is within the range from 0.3 to 5.0.
Description
Technical field
The present invention relates to resin combination for insert moulding, possess the manufacture method of metal-resin composite shaped body and the above-mentioned metal-resin composite shaped body of the resin component element being formed by above-mentioned resin combination, described resin component element insert moulding is being implemented on physical treatment and/or chemically treated inserts hardware.
Background technology
The parts that the inserts hardware being formed by metal, alloy etc. and the integrated metal-resin composite shaped body forming of the resin component element being formed by thermoplastic resin composition contact with the external world for the interface connection section of the electronicss such as parts around of the interior trim member of the dashboard automobiles such as console box around, engine, upholstery parts, digital camera, mobile phone, power supply terminal portion etc. all the time.
As by inserts hardware and the integrated method of resin component element, there is following method: physical treatment and/or chemical treatment are implemented in the junction surface of inserts hardware side, improve the method for the adaptation of inserts hardware and resin component element; Use caking agent, double faced adhesive tape to bring bonding method; The stationary members such as sheet, pawl that turn back are set in inserts hardware and/or resin component element, use this stationary member by both fixing methods; The method that use screw etc. engages etc.In these methods, the aspect of the degree of freedom during from design metal-resin composite shaped body, the junction surface of inserts hardware side is implemented physical treatment and/or chemically treated method, used the method for caking agent is effective.
Especially, do not use expensive caking agent aspect, to the junction surface of inserts hardware side implementing physical treatment and/or chemically treated method is favourable.As the junction surface to inserts hardware side, implement physical treatment and/or chemically treated method, for example, can list the method for recording in patent documentation 1.The method is in the scope of the surperficial expectation of inserts hardware, with laser, to form the method for uneven surface.
prior art document
patent documentation
Patent documentation 1: TOHKEMY 2010-167475 communique
Summary of the invention
the problem that invention will solve
For metal-resin composite shaped body, in practical application, on the basis of the shock-resistance excellence of resin component element, also need inserts hardware and resin component element integrated fully.Therefore,, in metal-resin composite shaped body, require the bond strength of inserts hardware and resin component element strong.In addition, metal-resin composite shaped body is applied to for example demand of high-frequency unit and is improving, specific inductivity and the tangent of the dielectric loss angle of the resin component element in expectation metal-resin composite shaped body are all low.And then, metal-resin composite shaped body is applied to for example electric/electronic device also to be improved by the demand of housing, particularly use metal-resin composite shaped body as externally expose white member time, the whiteness of the resin component element in expectation metal-resin composite shaped body is high.
The object of the invention is to, a kind of resin combination for insert moulding is provided, uses its metal-resin composite shaped body and manufacture method thereof, described insert moulding can be realized the strong metal-resin composite shaped body of bond strength between inserts hardware and resin component element with resin combination, and shock-resistance and low dielectric characteristics (low-k and low-dielectric loss angle tangent) excellence, and then whiteness is high.
for the scheme of dealing with problems
The inventor etc. have carried out further investigation repeatedly in order to address the above problem.It found that, utilizes and is used in combination containing the olefin copolymer of epoxy group(ing) and polystyrene resin and by the resin combination that the content of each composition is adjusted to specialized range and can addresses the above problem, thereby completed the present invention.More specifically, the invention provides following technical scheme.
(1) resin combination, it is for the resin combination having implemented to carry out on physical treatment and/or chemically treated inserts hardware insert moulding,
Aforementioned resin comprises (A) polyarylene sulfide resin 100 mass parts, (B) containing olefin copolymer 3～55 mass parts of epoxy group(ing) and (C) polystyrene resin 5～60 mass parts,
Aforementioned (B) is 0.3～5.0 containing the content of the olefin copolymer of epoxy group(ing) with respect to the ratio of the content of aforementioned (C) polystyrene resin ((B)/(C)).
(2) resin combination according to (1), wherein, aforementioned (B) is to comprise structural unit from alpha-olefin from α, the olefin copolymer of the structural unit of the glycidyl ester of beta-unsaturated acid containing the olefin copolymer of epoxy group(ing).
(3), according to the resin combination (1) or (2) described, wherein, aforementioned (B) is also to comprise the olefin copolymer from the structural unit of (methyl) acrylate containing the olefin copolymer of epoxy group(ing).
(4), according to the resin combination described in any one in (1)～(3), wherein, aforementioned (B) accounts for 0.05～0.20 quality % in whole compositions containing the epoxy group content in the olefin copolymer of epoxy group(ing).
(5), according to the resin combination described in any one in (1)～(4), it also comprises (D) inorganic filling material 5～80 mass parts, (E) containing epoxy compounds 0.01～10 mass parts and (F) not containing at least a kind of ethylene series compound 0.01～25 mass parts of epoxy group(ing) with respect to (A) polyarylene sulfide resin 100 mass parts.
(6), according to the resin combination (5) described, wherein, aforementioned (E) is epoxy resin containing epoxy compounds.
(7), according to the resin combination (5) or (6) described, wherein, aforementioned (E) is bisphenol-type epoxy resin containing epoxy compounds.
(8), according to the resin combination described in any one in (5)～(7), wherein, aforementioned (E) accounts for below 0.2 quality % in whole compositions containing the epoxy group content in epoxy compounds.
(9), according to the resin combination described in any one in (1)～(8), it also comprises (G) and selects at least a kind of white pigment in the group that free titanium oxide, zinc sulphide, magnesium oxide and barium sulfate forms.
(10) a kind of metal-resin composite shaped body, it possess inserts hardware and in (1)～(9) resin combination described in any one form and the resin component element of insert moulding on aforementioned inserts hardware, surperficial at least a portion contacting with aforementioned resin member of aforementioned inserts hardware has been implemented physical treatment and/or chemical treatment.
(11) a kind of manufacture method of metal-resin composite shaped body, it comprises integrated operation as described below: surperficial at least a portion has been implemented to physical treatment and/or chemically treated inserts hardware is configured in die injection moulding, resin combination described in any one in (1)～(9) is expelled in aforementioned die injection moulding with molten state, aforementioned inserts hardware and resin component element is integrated.
the effect of invention
According to the present invention, a kind of resin combination for insert moulding can be provided, use its metal-resin composite shaped body and manufacture method thereof, described insert moulding can be realized the strong metal-resin composite shaped body of bond strength between inserts hardware and resin component element with resin combination, and shock-resistance and low dielectric characteristics (low-k and low-dielectric loss angle tangent) excellence, and then whiteness is high.
Accompanying drawing explanation
Fig. 1 is the figure that schematically shows the metal-resin composite shaped body using in embodiment and comparative example, (a) is exploded perspective view, is (b) stereographic map, (c) for the figure of metal portion is only shown.
Fig. 2 is the figure that schematically shows the method for measuring of the resin portion of carrying out in embodiment and the bond strength between metal portion.
Embodiment
Below, embodiments of the present invention are described.It should be noted that, the present invention is not limited to following embodiment.
resin combination
Resin combination of the present invention is being for implementing to carry out insert moulding on physical treatment and/or chemically treated inserts hardware, and it comprises (A) polyarylene sulfide resin 100 mass parts, (B) containing olefin copolymer 3～55 mass parts of epoxy group(ing) and (C) polystyrene resin 5～60 mass parts.Below, each composition contained in this resin combination is described.
(A) polyarylene sulfide resin
As (A) polyarylene sulfide resin, be not particularly limited, can use known polyarylene sulfide resin in the past.As (A) polyarylene sulfide resin, preferably use polyphenylene sulfide (PPS) resin.(A) polyarylene sulfide resin can be used separately a kind or be used in combination two or more.
In order to obtain the better adaptation of inserts hardware and resin component element, (A) polyarylene sulfide resin melt viscosity that preferably measure at 310 ℃, under velocity of shear 1216/ second is 8～300Pas, is particularly preferably 10～200Pas.
(B) contain the olefin copolymer of epoxy group(ing)
(B) is not particularly limited containing the olefin copolymer of epoxy group(ing).(B) containing the olefin copolymer of epoxy group(ing), can use separately a kind or be used in combination two or more.
Olefin copolymer as (B) containing epoxy group(ing), for example can list: comprise from the structural unit of alpha-olefin with from α, the olefin copolymer of the structural unit of the glycidyl ester of beta-unsaturated acid, wherein, especially from obtaining the viewpoint of excellent especially metal-resin composite shaped body, preferably also comprise the olefin copolymer from the structural unit of (methyl) acrylate.It should be noted that, below, (methyl) acrylate ((meth) acrylic acid ester) is also referred to as (methyl) acrylate ((meth) acrylate).For example, (methyl) glycidyl acrylate is also referred to as glycidyl (methyl) acrylate.In addition, in this manual, " (methyl) vinylformic acid " refers to vinylformic acid and methacrylic acid, and " (methyl) acrylate " refers to acrylate and methacrylic ester.
As alpha-olefin, be not particularly limited, such as listing: ethene, propylene, butylene etc., be particularly preferably ethene.Alpha-olefin can be used singly or in combination of two or more.The olefin copolymer that contains epoxy group(ing) due to (B) comprises the structural unit from alpha-olefin, therefore easily resin component element is given flexible.By giving the flexible resin component element deliquescing that makes, contribute to improve the bond strength between inserts hardware and resin component element, in addition, also contribute to improve shock-resistance.
As α, the glycidyl ester of beta-unsaturated acid, be not particularly limited, such as listing: glycidyl acrylate, glycidyl methacrylate, ethyl propylene acid glycidyl ester (ethacrylic acid glycidyl ester) etc., be particularly preferably glycidyl methacrylate.α, the glycidyl ester of beta-unsaturated acid can be used singly or in combination of two or more.Because (B) comprises from α containing the olefin copolymer of epoxy group(ing), the structural unit of the glycidyl ester of beta-unsaturated acid, therefore easily obtains the effect that the bond strength between inserts hardware and resin component element improves.
As (methyl) acrylate, be not particularly limited, such as listing: acrylate such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, the just own ester of vinylformic acid, vinylformic acid n-octyls; The methacrylic esters such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid n-pentyl ester, n octyl methacrylate.Wherein, methyl acrylate particularly preferably.(methyl) acrylate can be used singly or in combination of two or more.Structural unit from (methyl) acrylate contributes to improve the bond strength between inserts hardware and resin component element.
Comprise from the structural unit of alpha-olefin with from α the olefin copolymer of the structural unit of the glycidyl ester of beta-unsaturated acid and also comprise from the olefin copolymer of the structural unit of (methyl) acrylate and can manufacture by utilizing in the past known method to carry out copolymerization.For example, can utilize known Raolical polymerizable conventionally to carry out copolymerization, thereby obtain above-mentioned multipolymer.Kind to multipolymer has no particular limits, for example, can be random copolymers, can be also segmented copolymer.In addition, can be also following multipolymer: make to be chemically bound in above-mentioned olefin copolymer and the ethylene series graft copolymer obtaining with chain or crosslinking structure such as polymethylmethacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, polyacrylic acid-2-ethylhexyl, polystyrene, polyacrylonitrile, acrylonitritrile-styrene resin, n butyl acrylate styrene etc.As the kind of above-mentioned multipolymer, be not preferably ethylene series graft copolymer, more preferably random copolymers and/or segmented copolymer.
For olefin copolymer of the present invention, in the scope of not damaging effect of the present invention, can contain the structural unit from other copolymer composition.
More specifically, olefin copolymer as (B) containing epoxy group(ing), such as listing: the ethene improved based copolymer of glycidyl methacrylate, glycidyl ether modified ethylene copolymer etc., wherein, be preferably the ethene improved based copolymer of glycidyl methacrylate.
As the ethene improved based copolymer of glycidyl methacrylate, can list: the ethene improved polymkeric substance of glycidyl methacrylate graft, ethylene-methyl methacrylate glycidyl ester copolymer, ethylene-methyl methacrylate glycidyl ester-methyl acrylate copolymer.Wherein, especially from obtaining the viewpoint of excellent metal-resin composite shaped body, optimal ethylene-glycidyl methacrylate copolymer and ethylene-methyl methacrylate glycidyl ester-methyl acrylate copolymer, be particularly preferably ethylene-methyl methacrylate glycidyl ester-methyl acrylate copolymer.As the concrete example of ethylene-methyl methacrylate glycidyl ester copolymer and ethylene-methyl methacrylate glycidyl ester-methyl acrylate copolymer, can list " BONDFAST " (Sumitomo Chemical Co's manufacture) etc.
As glycidyl ether modified ethylene copolymer, for example, can list: glycidyl ether graft modification ethylene copolymer, glycidyl ether-ethylene copolymer.
With respect to (A) polyarylene sulfide resin 100 mass parts, the content that (B) contains the olefin copolymer of epoxy group(ing) is generally 3～55 mass parts, is preferably 15～40 mass parts.If above-mentioned content is lower than 3 mass parts, the bond strength between inserts hardware and resin component element easily reduces or the shock-resistance of resin combination easily reduces or specific inductivity easily uprises.It should be noted that, the adaptation between inserts hardware and resin component element is subject to that the polar expansion between these members is poor to be affected.Can think that (B) reduces strain containing the olefin copolymer of epoxy group(ing) by realizing stress relaxation, above-mentioned bond strength improves thus.For stress relaxation, toughness is that effectively toughness can be evaluated by tensile elongation.When (B) playing a role as elastomerics is few containing the content of the olefin copolymer of epoxy group(ing), think that tensile elongation is little, cannot obtain sufficient stress relaxation effect.In addition, stress relaxation also contributes to improve shock-resistance.On the other hand, if above-mentioned content surpasses 55 mass parts, the tangent of the dielectric loss angle of resin combination easily uprises, or mobility during insert moulding easily reduces.
In addition, (B) containing the epoxy group content in the olefin copolymer of epoxy group(ing), all in composition, be preferably 0.05～0.20 quality %, more preferably 0.08～0.18 quality %.If above-mentioned epoxy group content accounts for 0.05～0.20 quality % in whole compositions, the bond strength between inserts hardware and resin component element easily maintains well, release property during in addition, from insert moulding is not allowed corruptible aspect and is preferred from the aspect that produces the amount of gas and have the tendency that is inhibited, frequency that mould is safeguarded easily to reduce.
(B) containing the content of the olefin copolymer of epoxy group(ing), be adjusted to (B) containing the content of the olefin copolymer of epoxy group(ing) (unit: mass parts) with respect to the content of (C) described later polystyrene resin (unit: ratio mass parts) ((B)/(C)) is 0.3～5.0.By by (B)/(C) be adjusted to this scope, can improve together by compounding shock-resistance and the low dielectric characteristics (low-k and low-dielectric loss angle tangent) of the formed body that the resin combination of these compositions obtains.(B) if/(C) lower than 0.3, the poor impact resistance of the formed body being obtained by resin combination.(B) if/(C) surpass and 5.0 to surpass, the low dielectric characteristics of the formed body being obtained by resin combination is poor.
(C) polystyrene resin
(C) polystyrene resin is not particularly limited.(C) polystyrene resin can be used singly or in combination of two or more.
As (C) polystyrene resin, for example, can list: polystyrene; Poly-(ring-alkylated styrenes); Poly-(halogenated styrenes); Poly-(alkoxystyrene); Poly-(vinyl benzoic acid ester); Select the multipolymer of at least 2 kinds in the group that free vinylbenzene, ring-alkylated styrenes, halogenated styrenes, alkoxystyrene and vinyl benzoic acid ester form.
Poly-(ring-alkylated styrenes) can be that homopolymer can be also multipolymer.As ring-alkylated styrenes, such as listing: vinyl toluene, ethyl styrene, isopropyl benzene ethene and t-butyl styrene etc.Thus, as poly-(ring-alkylated styrenes), for example, can list: poly-(vinyl toluene); Poly-(ethyl styrene); Poly-(isopropyl benzene ethene); Poly-(t-butyl styrene); Select the multipolymer of at least 2 kinds in the group that free vinyl toluene, ethyl styrene, isopropyl benzene ethene and t-butyl styrene form etc.
Poly-(halogenated styrenes) can be that homopolymer can be also multipolymer.As halogenated styrenes, such as listing: chloro-styrene, bromstyrol, fluorobenzene ethene etc.Thus, as poly-(halogenated styrenes), for example, can list: poly-(chloro-styrene); Poly-(bromstyrol); Poly-(fluorobenzene ethene); Select the multipolymer of at least 2 kinds in the group that free chloro-styrene, bromstyrol and fluorobenzene ethene forms etc.
Poly-(alkoxystyrene) can be that homopolymer can be also multipolymer.As alkoxystyrene, such as listing: methoxy styrene, phenetole ethene etc.Thus, as poly-(alkoxystyrene), such as listing: poly-(methoxy styrene), poly-(phenetole ethene), methoxy styrene-phenetole ethylene copolymer etc.
In the middle of these, the preferably multipolymer of polystyrene, poly-(p-methylstyrene), poly-(vinyl toluene), poly-(p-tert-butylstyrene), poly-(to chloro-styrene), poly-(m-chlorostyrene), poly-(pfluorostyrene), vinylbenzene and p-methylstyrene, particularly preferably polystyrene.
To the structure of (C) polystyrene resin, there is no particular limitation, can be any in random (atactic) structure, isotactic (isotactic) structure and rule (syndiotactic) structure.The polystyrene resin with random structure refers to: have the phenyl as side chain, the polystyrene resin of substituted-phenyl three-dimensional arrangement in random position with respect to the main chain being formed by C-C.The polystyrene resin with isotactic structure refers to: the phenyl, the substituted-phenyl that have as side chain are all positioned at the polystyrene resin of unidirectional three-dimensional arrangement with respect to the main chain being formed by C-C.There is the polystyrene resin of syndiotactic structure (below also referred to as " SPS resin ".) referring to: the phenyl, the substituted-phenyl that have as side chain are alternately positioned at the polystyrene resin of rightabout three-dimensional arrangement with respect to the main chain being formed by C-C.SPS resin for example fusing point is 180～310 ℃, compares thermotolerance especially excellent with the polystyrene resin with random structure.Therefore,, from the stable on heating viewpoint of the resin component element of gained, preferably there is the polystyrene resin of syndiotactic structure.
(C) polystyrene resin can utilize known method in the past to manufacture.Especially, SPS resin can be manufactured by the following method: for example, in nonactive hydrocarbon solvent or do not exist under the condition of solvent, using the condensation resultant of titanium compound and water and trialkylaluminium as catalyzer, by styrenic monomers (monomer that the structural unit contained with SPS resin is corresponding) polymerization (for example,, with reference to Japanese kokai publication sho 62-187708).
With respect to (A) polyarylene sulfide resin 100 mass parts, (C) content of polystyrene resin is generally 5～60 mass parts, is preferably 5～40 mass parts.If above-mentioned content is lower than 5 mass parts, the specific inductivity of resin combination easily uprises.If above-mentioned content surpasses 60 mass parts, the shock-resistance of resin combination easily reduces.
(D) inorganic filling material
Resin combination of the present invention can comprise (D) inorganic filling material.If add (D) inorganic filling material in resin combination of the present invention, the physical strength of the resin component element of gained easily improves.(D) inorganic filling material is not particularly limited, can lists known inorganic filling material in the past.Shape to (D) inorganic filling material is not particularly limited, and can be fibrous, can be also that spherical, granular, tabular, Scales sheet, indefinite shape etc. are non-fibrous, but be preferably fibrous.As (D) inorganic filling material, such as listing: glass fibre, spherical silicon dioxide, glass microballon etc., be wherein preferably glass fibre.(D) inorganic filling material can be used separately a kind or be used in combination two or more.
With respect to (A) polyarylene sulfide resin 100 mass parts, (D) content of inorganic filling material is preferably 5～80 mass parts, more preferably 20～50 mass parts.If above-mentioned content 5～80 mass parts, easily the state of the mobility when maintaining well bond strength between inserts hardware and resin component element, insert moulding obtains by add the effect that (D) inorganic filling material brings in resin combination of the present invention, is being preferred aspect this.In addition, the resin combination of gained easily becomes the resin combination with excellent low dielectric characteristics (low-k and low-dielectric loss angle tangent).
(E) containing epoxy compounds
Resin combination of the present invention also can comprise (E) containing epoxy compounds.If add (E) containing epoxy compounds in resin combination of the present invention,, in the metal-resin composite shaped body of gained, the bond strength between inserts hardware and resin component element can be more prone to improve.(E) containing epoxy compounds so long as except above-mentioned (B) is containing being just not particularly limited containing epoxy compounds the olefin copolymer of epoxy group(ing).(E) containing epoxy compounds, can use separately a kind or be used in combination two or more.
(E) containing epoxy compounds, can be the compound that 1 molecule contains 1 epoxy group(ing), can be also the compound that 1 molecule contains 2 above epoxy group(ing).As (E), contain epoxy compounds, can roughly be divided into epoxy resin and in addition containing epoxy compounds, for example can list: dihydroxyphenyl propane is reacted and the bisphenol-type epoxy resin that obtains with Epicholorohydrin, the phenolic resin varnish type epoxy resin that novolac resin is reacted with Epicholorohydrin and obtain, the poly glycidyl ester class that poly carboxylic acid is reacted with Epicholorohydrin and obtain, the alicyclic compound type epoxy resin being obtained by alicyclic compound, the fatty compounds that makes to have alcohol hydroxyl group reacts with Epicholorohydrin and the Racemic glycidol ethers that obtains, epoxidation divinyl, and make to have the compound of two keys and peroxide reactions and the epoxy compounds that obtains.As concrete example, can list: bisphenol A type epoxy resin, methyl glycidyl ether, phenyl glycidyl ether, various fatty acid glycidyl ester, Diethylene Glycol diglycidylether, o-phthalic acid diglycidyl ester, hexahydrophthalic acid 2-glycidyl ester, epoxidized polybutadiene, epoxidized SBS etc.Wherein, from viewpoints such as quality stability (with the stability of reacting of polyarylene sulfide resin), good treatability, environmental healths (there is no mutagenicity), be preferably epoxy resin, be particularly preferably the bisphenol-type epoxy resins such as bisphenol A type epoxy resin.
With respect to (A) polyarylene sulfide resin 100 mass parts, (E) content containing epoxy compounds is preferably 0.01～10 mass parts, more preferably 0.01～5 mass parts.If above-mentioned content 0.01～10 mass parts, the bond strength between inserts hardware and resin component element can be more prone to improve.
In addition, (E) the 0.2 quality % preferably accounting in whole compositions containing the epoxy group content in epoxy compounds is following (for example, surpass 0 quality % and be that 0.2 quality % is following), 0.1 quality % following (for example, surpass 0 quality % and be that 0.1 quality % is following) more preferably.If above-mentioned epoxy group content accounts for below 0.2 quality % in whole compositions, the resistance to separability between inserts hardware and resin component element is difficult to reduce.Especially when insert moulding, even be also difficult to produce interface peel in the flow end of the resin combination in molten state.In addition, release property during insert moulding is difficult to worsen, and it is preferred setting out in the aspect that the aspect of the target products formed that is therefore easy to get calmly and productivity are difficult to reduce.
(F) do not contain the ethylene series compound of epoxy group(ing)
Resin combination of the present invention also can comprise (F) and not contain the ethylene series compound of epoxy group(ing).If add (F) not containing the ethylene series compound of epoxy group(ing) in resin combination of the present invention, from the aspect that the shock-resistance of resin combination easily improves, specific inductivity easily reduces in addition, be preferred.(F) not containing the ethylene series compound of epoxy group(ing) so long as be not just not particularly limited containing the olefin polymer of epoxy group(ing).(F) containing the ethylene series compound of epoxy group(ing), can not use separately a kind or be used in combination two or more.
(F) functional group that also can not comprised the atom except carbon atom and hydrogen atom by the halogen atoms such as chlorine atom, bromine atoms, hydroxyl, amino, carboxyl, alkoxy carbonyl etc. containing the ethylene series compound of epoxy group(ing) replaces, but the viewpoint from low dielectric characteristics (low-k and low-dielectric loss angle tangent), is preferably the material only consisting of carbon atom and hydrogen atom.
As not containing the olefin polymer of epoxy group(ing), such as listing: alpha-olefins such as ethene, propylene, 1-butylene, 1-octenes; The alkene except alpha-olefin such as 2-butylene, 2-amylene; Divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1, the diene such as 3-hexadiene; The polyenoid except diene such as toluene, tetraene, homopolymer and multipolymer.As above-mentioned homopolymer, such as listing: polyethylene, polybutene etc.As above-mentioned multipolymer, such as listing: ethylene-octene copolymer, ethylene-ethyl acrylate copolymer etc., be particularly preferably ethylene-octene copolymer.
With respect to (A) polyarylene sulfide resin 100 mass parts, the content that (F) does not contain the ethylene series compound of epoxy group(ing) is preferably 0.01～25 mass parts.If above-mentioned content 0.01～25 mass parts, the mobility while easily maintaining well bond strength between inserts hardware and resin component element and insert moulding.
(G) white pigment
Resin combination of the present invention can also comprise (G) and select at least a kind of white pigment in the group that free titanium oxide, zinc sulphide, magnesium oxide and barium sulfate forms.Even if resin combination of the present invention does not comprise (G) composition whiteness yet high (form and aspect L value is more than 80), but by comprising (G) composition, form and aspect b value diminishes, yellow chromaticity is suppressed, and whiteness further improves.From the viewpoint of low dielectric characteristics (low-k and low-dielectric loss angle tangent), preferential oxidation titanium and zinc sulphide, wherein zinc sulphide particularly preferably.
other compositions
Resin combination of the present invention is except mentioned component, can significantly not damage in the scope of effect of the present invention, in order to give the physical property of expectation, also can contain the additives such as organic filler material, fire retardant, UV light absorber, thermo-stabilizer, photostabilizer, tinting material, carbon black, releasing agent, softening agent.
the manufacture method of resin combination
About the manufacture method of resin combination of the present invention, as long as the composition in this resin combination just can be mixed and is not particularly limited, can from the manufacture method of in the past known resin combination, suitably select.Such as listing: use the melting mixing devices such as single screw rod or twin screw extruder by each composition melting mixing and extrude, then the resin combination of gained being processed into the method for the form of the expectations such as powder, fragment (flake), particle.
metal-resin composite shaped body
Metal-resin composite shaped body of the present invention possesses inserts hardware and is formed and the resin component element of insert moulding on above-mentioned inserts hardware by resin combination of the present invention.Surperficial at least a portion contacting with above-mentioned resin component element of above-mentioned inserts hardware has been implemented physical treatment and/or chemical treatment.Metal-resin composite shaped body of the present invention has been used and has been used in combination (B) containing the olefin copolymer of epoxy group(ing) and (C) polystyrene resin the content of each composition is adjusted to the resin combination of the scope of regulation, therefore the bond strength between inserts hardware and resin component element is strong, and the shock-resistance of resin component element and low dielectric characteristics (low-k and low-dielectric loss angle tangent) excellence, and then whiteness is high.
Owing to having characteristic as above, therefore metal-resin composite shaped body of the present invention can be applicable to require the adaptation excellence of inserts hardware and resin component element aspect bond strength and require the shock-resistance of resin component element and the purposes that low dielectric characteristics is excellent, whiteness is high.For example, the suitable conduct of metal-resin composite shaped body of the present invention possesses easily the metal-resin composite shaped body that is subject to dysgenic electrical and electronic parts etc. because of humidity, moisture in inside.It is suitable especially that as expectation meeting, the intrusion of the use in field such as the rivers and creeks that requires high-caliber waterproof, swimming pool, skifield, bathroom etc. and moisture, moisture can cause the electric of fault or parts that electronics is used to use.In addition, metal-resin composite shaped body of the present invention is also useful as the electric/electronic device such as possess resinous hub, retaining member etc. in inside with housing.Herein, as electric/electronic device housing, except mobile phone, also can list camera, shoot with video-corder integrated camera, digital cameras etc. carry the housing with image electronics, notebook computer, palm PC, counter, electronic notebook, personal digital cellular system (PDC), personal handhold telephone system (PHS), mobile phones etc. carry the housing with information or communication terminal, Mini Disk (MD), tape-earphone stero set, receiving sets etc. carry the housing with acoustic electronic equipment, lcd tv display, phone, facsimile recorder, the housing of the household electrical appliance such as hand held scanner etc.
inserts hardware
For the inserts hardware using in the present invention, its surperficial at least a portion contacting with resin component element was implemented physical treatment and/or chemical treatment, and preferably physical treatment and/or chemical treatment were all implemented in its surface contacting with resin component element.
To forming the metallic substance of inserts hardware, be not particularly limited, as its example, can list at least a kind of metallic substance in the group of selecting free copper, copper alloy, aluminium, aluminium alloy and magnesium alloy composition.
In the present invention, use according to purposes etc. and moulding schedules to last the inserts hardware of the shape of hoping.For example, in the mould by the shape to expectation, inject the metal of melting etc., can access the inserts hardware of the shape of expectation.In addition, in order inserts hardware to be shaped to the shape of expectation, also can to adopt machining of utilizing by lathe etc. etc.
Physical treatment and/or chemical treatment are implemented in the surface of the inserts hardware obtaining in the manner described above.The size of implementing physical treatment and/or chemically treated position, process range can be considered to form the position of resin component element etc. and decide.
Physical treatment and chemical treatment are not particularly limited, can adopt known physical treatment and chemical treatment.By physical treatment, the surface of inserts hardware is by uneven surface, the resin combination that forms resin component element enters into the Kong Zhonghui forming in uneven surface region and produces anchoring effect, and the adaptation of the interface of inserts hardware and resin component element becomes and easily improves.On the other hand, by chemical treatment, between inserts hardware and the resin component element of the insert moulding of wanting, can give the chemical adhesive effects such as covalent linkage, hydrogen bond or intermolecular forces, so the adaptation of the interface of inserts hardware and resin component element becomes and easily improves.Chemical treatment also can now, can produce the anchoring effect same with physical treatment with the surperficial uneven surface of inserts hardware, and the adaptation of the interface of inserts hardware and resin component element becomes and is more prone to improve.
As physical treatment, such as listing: laser treatment, sandblast (TOHKEMY 2001-225346 communique) etc.Also can combine and implement multiple physical treatment.
As chemical treatment, such as listing: the dry process such as corona discharge, triazine are processed (referring to TOHKEMY 2000-218935 communique), chemical milling (TOHKEMY 2001-225352 communique), anodic oxidation treatment (TOHKEMY 2010-64496), hydrazine processing etc.In addition, when the metallic substance of formation inserts hardware is aluminium, also can lists warm water and process (Japanese kokai publication hei 8-142110 communique).As warm water, process, can list and in the water of 100 ℃, flood 3～5 minutes.Also can combine and implement number of chemical processing.
resin component element
The resin component element using in the present invention by polyarylene sulfide resin composition form and insert moulding on inserts hardware.
the manufacture method of metal-resin composite shaped body
Concrete operation to the manufacture method of metal-resin composite shaped body is not particularly limited, for the enforcement by above-mentioned inserts hardware at least a portion on physical treatment and/or chemically treated surface make inserts hardware and resin component element closely sealed, thereby make inserts hardware and the integrated manufacture method of resin component element.
For example can list following method: surperficial at least a portion has been implemented to physical treatment and/or chemically treated inserts hardware is configured in die injection moulding, resin combination of the present invention is expelled in above-mentioned die injection moulding with molten state, manufactures inserts hardware and the integrated metal-resin composite shaped body of resin component element.Condition to injection moulding is not particularly limited, can be according to suitable, the preferred condition of the settings such as the physical property of polyarylene sulfide resin.In addition, using the method for transfer molding, compressed moulding etc. is also the effective ways that form inserts hardware and the integrated metal-resin composite shaped body of resin component element.In these methods, surperficial at least a portion contacting with above-mentioned resin component element of above-mentioned inserts hardware has been implemented physical treatment and/or chemical treatment, and what preferably contact with above-mentioned resin component element surperficial has all implemented physical treatment and/or chemical treatment.
As other example, can list following method: by common forming methods such as injection molding methods, manufacture resin component element in advance, physical treatment and/or chemically treated inserts hardware and the above-mentioned resin component element bonding station butt in expectation will have been implemented, by bearing surface heating being made near the melting bearing surface of resin component element, thereby manufacture inserts hardware and the integrated metal-resin composite shaped body of resin component element.In the method, also the surperficial at least a portion contacting with above-mentioned resin component element that is above-mentioned inserts hardware has been implemented physical treatment and/or chemical treatment, and what preferably contact with above-mentioned resin component element surperficial has all implemented physical treatment and/or chemical treatment.
embodiment
Below embodiment is shown and comparative example is specifically described the present invention, but the present invention is not limited to the examples.
By illustrating in Fig. 1 of the metal-resin composite shaped body using in embodiment and comparative example.(a) being exploded perspective view, is (b) stereographic map, is (c) figure that metal portion is only shown.In order to below method, make this metal-resin composite shaped body.It should be noted that, the unit of the size in figure is mm.
the preparation of resin combination
After following material composition is dry mixed, drop into twin screw extruder the melting mixing of 320 ℃ of barrel zone temperatures, obtain granular thermoplastic resin composition.The compounding amount (mass parts) of each composition is as shown in table 1～table 5.
Polyphenylene sulfide
130Pas(velocity of shear: 1216/ second, temperature: 310 ℃), Kureha Corporation manufactures A-1:FORTRON KPS W214A(goods name), melt viscosity:
55Pas(velocity of shear: 1216/ second, temperature: 310 ℃), Kureha Corporation manufactures A-2:FORTRON KPS W205AH(goods name), melt viscosity:
Olefin copolymer containing epoxy group(ing)
B-1: ethylene-methyl methacrylate glycidyl ester-methyl acrylate copolymer, BONDFAST7L(goods name), epoxy group content: 3 quality %, Sumitomo Chemical Co manufacture
B-2: ethylene-methyl methacrylate glycidyl ester copolymer, BONDFAST E(goods name), epoxy group content: 12 quality %, Sumitomo Chemical Co manufacture
Polystyrene resin
C-1: syndiotactic polystyrene resin, XAREC130ZC(goods name), Idemitsu Kosen Co., Ltd. manufactures
Inorganic filling material
D-1: glass fibre (chopped strand), CS GL-HF(goods name), Owens Corning Corporation manufactures
D-2: glass fibre (chopped strand), T-747(goods name), Nippon Electric Glass Co., Ltd manufactures
Containing epoxy compounds
E-1: bisphenol A type epoxy resin (solid-state), jER(old " EPICOAT ", be registered trademark) 1004K(goods name), epoxy group content: 4.6 quality %, epoxy equivalent (weight) 925, molecular weight: 1650, Mitsubishi chemical Co., Ltd manufactures
Do not contain the ethylene series compound of epoxy group(ing)
F-1: ethylene-octene copolymer, Engage8003(goods name), Dow Chemical Japan Co., Ltd. manufactures
F-2: ethylene-octene copolymer, Engage8440(goods name), Dow Chemical Japan Co., Ltd. manufactures
White pigment
G-1: titanium oxide, TITONE SR-1(goods name), Sakai Chemical Industry Co., Ltd. manufactures
G-2: zinc sulphide
Wherein, the measuring method of melt viscosity as described below.
melt viscosity
The CAPIROGRAPH that uses Japan Jing Ji Co., Ltd. to manufacture, is used 1mm φ * 20mmL/ flat-die as kapillary, measures the melt viscosity under 310 ℃ of barrel temperatures, velocity of shear 1216/ second.
the evaluation of shock-resistance
For any one the prepared resin combination in embodiment 1～14 and comparative example 1～10, utilize injection moulding, at 150 ℃ of 320 ℃ of barrel zone temperatures, die temperature, make Charpy impact test sheet, according to the metewand of stipulating in ISO179/1eA, under the condition of 23 ℃, evaluate.The results are shown in table 1～table 5.
the evaluation of dielectric characteristics
For any one the prepared resin combination in embodiment 1～14 and comparative example 1～10, utilize injection moulding, 320 ℃ of barrel zone temperatures, the test film that 150 ℃ of compacted unders of die temperature are 1.8mm * 1.8mm * 80mm, (23 ℃ ± 2 ℃ of air-conditioning room's room temperatures, 50%RH ± 5%RH) under environment, place more than 2 hours, then use Agilent Technologies, Inc. the Network Analyzer8757D manufacturing, Synthesized Sweeper83650L, and the 2GHz rhumbatron of Northeast applying electronic exploitation Co., Ltd. manufacture, by cavity resonance method of perturbation, measure relative permittivity (ε r) and the tangent of the dielectric loss angle (tan δ) under 2GHz.The results are shown in table 1～table 5.
the physical treatment of inserts hardware or chemical treatment
As inserts hardware, use by copper (C-1100P, thickness 2mm) or aluminium (A5052, thickness 2mm) and form and also implemented as described below physical treatment or chemically treated plate object.These tabular inserts hardwares have junction surface in the part shown in the oblique line of Fig. 1 (a).It should be noted that, in table 1～table 5, " physics ", " chemistry 1 " and " chemistry 2 " refer to respectively following physical treatment, chemical treatment 1 and chemical treatment 2.
physical treatment
Use commercially available liquid honing device, the condition of concentration 20%, gauge pressure 0.4Mpa of take on the inserts hardware of aluminum blows granularity as #1000(medium particle diameter: alumina abrasive 14.5～18 μ m), carry out roughened.
chemical treatment 1
By the surface of inserts hardware made of copper at the etching solution A(of the following composition aqueous solution) in dipping 1 minute, carry out the removal of antirust epithelium, then at the etching solution B(of the following composition aqueous solution) in flood 5 minutes, etching metal parts surface.
chemical treatment 2
The surface of the inserts hardware of aluminum is flooded 5 minutes in the alkali degreasing liquid (aqueous solution) of following composition, is carried out skimming treatment, then at the etching solution C(of the following composition aqueous solution) in flood 3 minutes, etching metal parts surface.
the making of metal-resin composite shaped body
To implement physical treatment or chemically treated inserts hardware is configured in mould, carried out the integrated integrated operation of resin component element that this inserts hardware and any one prepared resin combination in embodiment 1～14 and comparative example 1～10 are formed.Condition of molding as described below.The shape of metal-resin composite shaped body as shown in Figure 1.
condition of molding
The evaluation of metal-resin composite shaped body
The metal-resin composite shaped body of making for the method for above-mentioned, evaluates by resin component element the failure mode from inserts hardware is peeled off and resistance to separability.The results are shown in table 1～table 5.Concrete evaluation method as described below.
failure mode and resistance to separability
The metal-resin composite shaped body with the shape shown in Fig. 1 is configured in to pedestal (fixture) as shown in Figure 2 upper, with the speed movable clamp of 1mm/ minute, thereby makes in the direction of arrow, resin component element to be pressed and peeled off from inserts hardware.The visual observation of take is the region of bonding part originally, evaluation be only at the generation of interfaces of inserts hardware and resin component element destruction (interface peel, use * expression) or at least produced destruction (cohesive failure, represent with ◎) in resin component element.
In addition, the visual observation of take is the inserts hardware side in the region of bonding part originally, obtain the shared area of the resin component element that is attached on inserts hardware with originally for the ratio of the area of the regional integration of bonding part, according to following benchmark, evaluate.
◎: above-mentioned ratio is more than 50%, and resistance to separability is very good.
Zero: above-mentioned ratio is more than 20% and lower than 50%, and resistance to separability is good.
△: above-mentioned ratio is over 0% and lower than 20%, resistance to separability is bad.
*: above-mentioned ratio is 0%, and resistance to separability is extremely bad.
the evaluation of form and aspect
For any one the prepared resin combination in embodiment 15～17, utilize injection moulding, at 150 ℃ of 320 ℃ of barrel zone temperatures, die temperature, make the dumbbell shaped test film of thickness 4mm, the colour-difference meter that uses Japanese electricity Se Industrial Co., Ltd to manufacture, by the 0 °-d mode colour examining of JIS Z 8722 defineds, based on this result, by Hunter (Hunter) the aberration formula of JIS Z 8730 defineds, obtain form and aspect L(brightness), form and aspect b(yellow chromaticity) and form and aspect a(redness degree).The results are shown in table 6.
table 1
table 2
table 3
table 4
table 5
table 6
As shown in table 1～table 5, for (B) that be used in combination 3～55 mass parts, containing the olefin copolymer of epoxy group(ing) and (C) polystyrene resin of 5～60 mass parts the content that will (B) contains the olefin copolymer of epoxy group(ing), with respect to the ratio of the content of (C) polystyrene resin ((B)/(C)), be adjusted to 0.3～5.0, the content of each composition is adjusted to the embodiment 1～14 of the scope of regulation, inserts hardware and the bond strength between resin component element in metal-resin composite shaped body are strong, and the shock-resistance of resin component element and low dielectric characteristics are excellent.
On the other hand, for the content of (C) polystyrene resin, lower than for the comparative example 1～3 of 5 mass parts, compare low dielectric characteristics poor (relative permittivity is high) with embodiment 1～14.
For the content of (C) polystyrene resin, lower than 5 mass parts and (F), containing the content of the ethylene series compound of epoxy group(ing), do not surpass for the comparative example 4 and 5 of 25 mass parts, compare with embodiment 1～14, resistance to separability is poor.
For the content of (C) polystyrene resin surpasses the comparative example 6 of 60 mass parts, compare poor impact resistance with embodiment 1～14.
For (B) containing the content of the olefin copolymer of epoxy group(ing) lower than for the comparative example 7 of 3 mass parts, compare with embodiment 1～14, shock-resistance, low dielectric characteristics poor (relative permittivity is high), and then inserts hardware and the bond strength between resin component element in metal-resin composite shaped body are also poor.
For (B), containing the content of the olefin copolymer of epoxy group(ing), surpass for the comparative example 8 of 55 mass parts, compare low dielectric characteristics poor (tangent of the dielectric loss angle is high) with embodiment 1～14.
(B)/(C) lower than 0.3 comparative example 9, compare poor impact resistance with embodiment 1～14.
(B)/(C) over 5.0 comparative example 10, compare low dielectric characteristics poor (tangent of the dielectric loss angle is high) with embodiment 1～14.
As shown in table 6, even if the resin combination of embodiment 15 does not contain the white pigment of (G) composition, whiteness is high (form and aspect L value is more than 80) also.
On the other hand, the embodiment 16 of the white pigment that comprises (G) composition compares with the resin combination of embodiment 15 with 17 resin combination, and form and aspect b value is little, and yellow chromaticity is inhibited, and whiteness further improves.
Claims (11)
1. a resin combination, it is for for the resin combination having implemented to carry out on physical treatment and/or chemically treated inserts hardware insert moulding,
Described resin combination comprises (A) polyarylene sulfide resin 100 mass parts, (B) containing olefin copolymer 3～55 mass parts of epoxy group(ing) and (C) polystyrene resin 5～60 mass parts,
Described (B) is 0.3～5.0 containing the content of the olefin copolymer of epoxy group(ing) with respect to the ratio of the content of described (C) polystyrene resin ((B)/(C)).
2. resin combination according to claim 1, wherein, described (B) is to comprise structural unit from alpha-olefin from α, the olefin copolymer of the structural unit of the glycidyl ester of beta-unsaturated acid containing the olefin copolymer of epoxy group(ing).
3. resin combination according to claim 1 and 2, wherein, described (B) containing the olefin copolymer of epoxy group(ing) for also comprising the olefin copolymer from the structural unit of (methyl) acrylate.
4. according to the resin combination described in any one in claim 1～3, wherein, described (B) accounts for 0.05～0.20 quality % in whole compositions containing the epoxy group content in the olefin copolymer of epoxy group(ing).
5. according to the resin combination described in any one in claim 1～4, it also comprises (D) inorganic filling material 5～80 mass parts, (E) containing epoxy compounds 0.01～10 mass parts and (F) not containing at least a kind of ethylene series compound 0.01～25 mass parts of epoxy group(ing) with respect to (A) polyarylene sulfide resin 100 mass parts.
6. resin combination according to claim 5, wherein, described (E) is epoxy resin containing epoxy compounds.
7. according to the resin combination described in claim 5 or 6, wherein, described (E) is bisphenol-type epoxy resin containing epoxy compounds.
8. according to the resin combination described in any one in claim 5～7, wherein, described (E) accounts for below 0.2 quality % in whole compositions containing the epoxy group content in epoxy compounds.
9. according to the resin combination described in any one in claim 1～8, it also comprises (G) and selects at least a kind of white pigment in the group that free titanium oxide, zinc sulphide, magnesium oxide and barium sulfate forms.
10. a metal-resin composite shaped body, it possesses inserts hardware and is formed and the resin component element of insert moulding on described inserts hardware by the resin combination described in any one in claim 1～9, and surperficial at least a portion contacting with described resin component element of described inserts hardware has been implemented physical treatment and/or chemical treatment.
The manufacture method of 11. 1 kinds of metal-resin composite shaped bodies, it comprises integrated operation as described below: surperficial at least a portion has been implemented to physical treatment and/or chemically treated inserts hardware is configured in die injection moulding, resin combination described in any one in claim 1～9 is expelled in described die injection moulding with molten state, described inserts hardware and resin component element is integrated.
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| JP2013-081679 | 2013-04-09 | ||
| JP2013081679 | 2013-04-09 |
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| Country | Link |
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| JP (1) | JP6325295B2 (en) |
| KR (1) | KR20140122180A (en) |
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| TW (1) | TWI638010B (en) |
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| CN108034249A (en) * | 2017-12-28 | 2018-05-15 | 四川中物材料股份有限公司 | A kind of high whiteness polyphenyl thioether alloy and preparation method thereof |
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| CN112368122A (en) * | 2018-06-29 | 2021-02-12 | 出光兴产株式会社 | Resin-metal composite and method for producing same |
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| CN113150457A (en) * | 2021-01-05 | 2021-07-23 | 广州辰东新材料有限公司 | Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate |
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| JP6186898B2 (en) * | 2013-06-03 | 2017-08-30 | 東ソー株式会社 | Polyarylene sulfide resin composition |
| JP6132669B2 (en) * | 2013-06-11 | 2017-05-24 | ポリプラスチックス株式会社 | Metal resin composite molded body and method for producing the same |
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| JP2017039280A (en) * | 2015-08-20 | 2017-02-23 | 大成プラス株式会社 | Composite of metal and polystyrene resin |
| JP6766340B2 (en) * | 2015-11-06 | 2020-10-14 | 東ソー株式会社 | Polyarylene sulfide-based composition |
| JP6886586B2 (en) * | 2017-06-30 | 2021-06-16 | Dic株式会社 | Polyarylene sulfide resin composition, molded article, metal / resin composite structure and manufacturing method |
| JP6823005B2 (en) * | 2018-04-17 | 2021-01-27 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition, extruded product, manufacturing method of extruded product, and transport aircraft or generator |
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| CN108034249A (en) * | 2017-12-28 | 2018-05-15 | 四川中物材料股份有限公司 | A kind of high whiteness polyphenyl thioether alloy and preparation method thereof |
| CN108219460A (en) * | 2018-02-07 | 2018-06-29 | 深圳华力兴新材料股份有限公司 | A kind of NMT technologies PPS/SPS engineering plastics and preparation method |
| CN112368122A (en) * | 2018-06-29 | 2021-02-12 | 出光兴产株式会社 | Resin-metal composite and method for producing same |
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| CN113150457A (en) * | 2021-01-05 | 2021-07-23 | 广州辰东新材料有限公司 | Modified hydrocarbon-modified syndiotactic polystyrene composite material, copper-clad plate containing modified hydrocarbon-modified syndiotactic polystyrene composite material and preparation method of copper-clad plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014218076A (en) | 2014-11-20 |
| TWI638010B (en) | 2018-10-11 |
| CN104098898B (en) | 2018-03-13 |
| JP6325295B2 (en) | 2018-05-16 |
| TW201504347A (en) | 2015-02-01 |
| KR20140122180A (en) | 2014-10-17 |
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