CN104098898B - Insert-molding resin combination, metal-resin composite shaped body and its manufacture method using it - Google Patents
Insert-molding resin combination, metal-resin composite shaped body and its manufacture method using it Download PDFInfo
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- CN104098898B CN104098898B CN201410137387.5A CN201410137387A CN104098898B CN 104098898 B CN104098898 B CN 104098898B CN 201410137387 A CN201410137387 A CN 201410137387A CN 104098898 B CN104098898 B CN 104098898B
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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
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
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Abstract
The present invention provides insert-molding resin combination, metal-resin composite shaped body and its manufacture method using it, the insert-molding resin combination can realize the strong metal-resin composite shaped body of the bond strength between inserts hardware and resin component element, and impact resistance and low dielectric property（Low-k and low-dielectric loss angle tangent）It is excellent, and then whiteness is high.The present invention provides a kind of resin combination, and it is the resin combination for carrying out insert-molding on physical treatment and/or chemically treated inserts hardware is implemented, and aforementioned resin includes（A）The mass parts of polyarylene sulfide resin 100,（B）Mass parts of olefin copolymer 3~55 containing epoxy radicals and（C）The mass parts of polystyrene resin 5~60, it is foregoing（B）The content of olefin copolymer containing epoxy radicals is relative to foregoing（C）The ratio of the content of polystyrene resin（（B）/（C））For 0.3~5.0.
Description
Technical field
The present invention relates to insert-molding with resin combination, possess the gold of the resin component element formed by above-mentioned resin combination
Belong to the manufacture method of resin molding compound body and above-mentioned metal-resin composite shaped body, the resin component element insert-molding exists
Implement on physical treatment and/or chemically treated inserts hardware.
Background technology
The inserts hardware formed by metal, alloy etc. and the resin component element one formed by thermoplastic resin composition
Change decorative trim member, the hair of the automobiles such as the console box that the metal-resin composite shaped body formed is used for around instrument board all the time
The interface connecting portion of the electronic equipments such as part, interior decoration parts, digital camera, mobile phone around motivation, power end sub-portion
Deng the part contacted with the external world.
As by the inserts hardware method integrated with resin component element, there is following method：To inserts hardware
Physical treatment and/or chemical treatment are implemented in the composition surface of side, the method for improving the adaptation of inserts hardware and resin component element；
The method that bonding is brought using bonding agent, double faced adhesive tape；Turn back piece, pawl etc. are set in inserts hardware and/or resin component element
Fixing component, the method for being fixed both using the fixing component；Method engaged using screw etc. etc..In these methods
In, free degree aspect when metal-resin composite shaped body is designed, the composition surface of inserts hardware side is implemented
Physical treatment and/or chemically treated method, the use of the method for bonding agent is effective.
Especially, in terms of without using the bonding agent of costliness, physical treatment is implemented to the composition surface of inserts hardware side
And/or chemically treated method is favourable.Implement physical treatment and/or chemistry as the composition surface to inserts hardware side
The method of processing, such as the method described in patent document 1 can be included.This method is the phase on the surface of inserts hardware
The method that the scope of prestige forms mat surface with laser.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-167475 publications
The content of the invention
Problems to be solved by the invention
For metal-resin composite shaped body, in practical application, in the base of the excellent impact resistance of resin component element
On plinth, it is also necessary to which inserts hardware is integrated with resin component element fully.Therefore, in metal-resin composite shaped body
Ask the bond strength of inserts hardware and resin component element strong.In addition, metal-resin composite shaped body is applied to such as high frequency
The demand of part is improving, and it is expected the dielectric constant and dielectric loss angle tangent of the resin component element in metal-resin composite shaped body
It is low.It is special and then the demand that metal-resin composite shaped body is applied to such as electric/electronic device housing is also improving
When not being using metal-resin composite shaped body as the white component exposed in outside, it is expected in metal-resin composite shaped body
Resin component element whiteness it is high.
It is combined into it is an object of the present invention to provide a kind of insert-molding with resin combination, using its metal-resin
Type body and its manufacture method, the insert-molding resin combination can realize connecing between inserts hardware and resin component element
Close the strong metal-resin composite shaped body of intensity, and impact resistance and low dielectric property（Low-k and low-dielectric loss angle
Tangent）It is excellent, and then whiteness is high.
The solution used to solve the problem
The present inventor etc. are furtherd investigate repeatedly in order to solve the above problems.Its result is found, is made using combination
The resin of prescribed limit is adjusted to the olefin copolymer containing epoxy radicals and polystyrene resin and by the content of each composition
Composition can solve the above problems, so as to complete the present invention.More specifically, the present invention provides following technical scheme.
（1）A kind of resin combination, it is for implementing physical treatment and/or chemically treated inserts hardware
The upper resin combination for carrying out insert-molding,
Aforementioned resin includes（A）The mass parts of polyarylene sulfide resin 100,（B）Olefin copolymer 3 containing epoxy radicals
~55 mass parts and（C）The mass parts of polystyrene resin 5~60,
It is foregoing（B）The content of olefin copolymer containing epoxy radicals is relative to foregoing（C）The content of polystyrene resin
Ratio（（B）/（C））For 0.3~5.0.
（2）According to（1）Described resin combination, wherein, it is foregoing（B）Olefin copolymer containing epoxy radicals is comprising next
From the olefin copolymer of the construction unit of ethylene oxidic ester of the construction unit from alpha, beta-unsaturated acid of alpha-olefin.
（3）According to（1）Or（2）Described resin combination, wherein, it is foregoing（B）Olefin copolymer containing epoxy radicals is
Also include and come from（Methyl）The olefin copolymer of the construction unit of acrylate.
（4）According to（1）~（3）Any one of resin combination, wherein, it is foregoing（B）Olefin-based containing epoxy radicals
0.05~0.20 mass % that epoxy group content in copolymer is accounted in all compositions.
（5）According to（1）~（4）Any one of resin combination, its relative to（A）The matter of polyarylene sulfide resin 100
Amount part also includes（D）The mass parts of inorganic filling material 5~80,（E）Containing the mass parts of epoxy compounds 0.01~10 and（F）No
The mass parts of alkene based compound 0.01~25 containing epoxy radicals it is at least one kind of.
（6）According to（5）Described resin combination, wherein, it is foregoing（E）It is epoxy resin containing epoxy compounds.
（7）According to（5）Or（6）Described resin combination, wherein, it is foregoing（E）It is bis-phenol type ring containing epoxy compounds
Oxygen tree fat.
（8）According to（5）~（7）Any one of resin combination, wherein, it is foregoing（E）Containing in epoxy compounds
Below the 0.2 mass % that accounts in all compositions of epoxy group content.
（9）According to（1）~（8）Any one of resin combination, it is also included（G）Selected from by titanium oxide, vulcanization
At least one kind of Chinese white in the group of zinc, magnesia and barium sulfate composition.
（10）A kind of metal-resin composite shaped body, it possess inserts hardware and by（1）~（9）Any one of
Resin combination formed and resin component element of the insert-molding on foregoing inserts hardware, foregoing inserts hardware with
At least a portion on the surface that aforementioned resin component is in contact implements physical treatment and/or chemical treatment.
（11）A kind of manufacture method of metal-resin composite shaped body, it includes integrated process as described below：By table
At least a portion in face implements physical treatment and/or the configuration of chemically treated inserts hardware in die injection moulding
It is interior, will（1）~（9）Any one of resin combination be expelled to molten condition in foregoing die injection moulding, will
Foregoing inserts hardware is integrated with resin component element.
The effect of invention
In accordance with the invention it is possible to provide a kind of insert-molding resin combination, the metal-resin composite molding using it
Body and its manufacture method, the insert-molding resin combination can realize the engagement between inserts hardware and resin component element
The strong metal-resin composite shaped body of intensity, and impact resistance and low dielectric property（Low-k and low-dielectric loss angle are just
Cut）It is excellent, and then whiteness is high.
Brief description of the drawings
Fig. 1 is the figure for schematically showing the metal-resin composite shaped body used in embodiment and comparative example,（a）To decompose
Stereogram,（b）For stereogram,（c）Only to show the figure of metal portion.
Fig. 2 is the method for measuring for schematically showing the bond strength between the resin portion and metal portion carried out in embodiment
Figure.
Embodiment
Hereinafter, embodiments of the present invention are illustrated.It should be noted that the present invention is not limited to following implementation
Mode.
Resin combination
The resin combination of the present invention is used to implement physical treatment and/or chemically treated inserts hardware is enterprising
Row insert-molding, it is included（A）The mass parts of polyarylene sulfide resin 100,（B）The mass of olefin copolymer 3~55 containing epoxy radicals
Part and（C）The mass parts of polystyrene resin 5~60.Hereinafter, each composition contained in the resin combination is illustrated.
（A）Polyarylene sulfide resin
As（A）Polyarylene sulfide resin, it is not particularly limited, known polyarylene sulfide resin can be used.As
（A）Polyarylene sulfide resin, preferably using polyphenylene sulfide（PPS）Resin.（A）Polyarylene sulfide resin can be used alone or group
Conjunction uses two or more.
In order to obtain the better adaptation of inserts hardware and resin component element,（A）Polyarylene sulfide resin preferably exists
Melt viscosity determined at 310 DEG C, that shear rate is under 1216/ second is 8~300Pas, particularly preferably 10~200Pa
s。
（B）Olefin copolymer containing epoxy radicals
It is right（B）Olefin copolymer containing epoxy radicals is not particularly limited.（B）Olefin copolymer containing epoxy radicals can be with
It is used alone or in combination of two or more.
As（B）Olefin copolymer containing epoxy radicals, such as can include：Comprising the construction unit from alpha-olefin and
From α, the olefin copolymer of the construction unit of the ethylene oxidic ester of beta-unsaturated acid, wherein, especially from can obtain especially
From the viewpoint of excellent metal-resin composite shaped body, preferably also include and come from（Methyl）The alkene of the construction unit of acrylate
Hydrocarbon system copolymer.It should be noted that it is following,（Methyl）Acrylate（(meth)acrylic acid ester）Also referred to as
（Methyl）Acrylate（(meth)acrylate）.For example,（Methyl）Glycidyl acrylate is also referred to as glycidyl（First
Base）Acrylate.In addition, in this manual, "（Methyl）Acrylic acid " refers to both acrylic acid and methacrylic acid, "（First
Base）Acrylate " refers to both acrylate and methacrylate.
As alpha-olefin, it is not particularly limited, such as can includes：Ethene, propylene, butylene etc., particularly preferably ethene.
Alpha-olefin can be used singly or in combination of two or more.Due to（B）Olefin copolymer containing epoxy radicals includes
Construction unit from alpha-olefin, therefore easily resin component element is assigned flexible.Resin component element is set to soften by assigning flexibility,
Help to improve the bond strength between inserts hardware and resin component element, in addition, it helps improve impact resistance.
As α, the ethylene oxidic ester of beta-unsaturated acid, it is not particularly limited, such as can includes：Glycidyl
Ester, GMA, glycidyl ethacrylate（ethacrylic acid glycidyl ester）
Deng particularly preferably GMA.α, the ethylene oxidic ester of beta-unsaturated acid can be used alone,
Two or more can be applied in combination.Due to（B）It is sweet that olefin copolymer containing epoxy radicals includes the shrink from alpha, beta-unsaturated acid
The construction unit of grease, therefore the effect that the bond strength being readily obtained between inserts hardware and resin component element improves.
As（Methyl）Acrylate, it is not particularly limited, such as can includes：Methyl acrylate, ethyl acrylate, third
The acrylate such as olefin(e) acid n-propyl, isopropyl acrylate, n-butyl acrylate, the just own ester of acrylic acid, n-octyl；Methyl
Methyl acrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA,
The methacrylates such as Isobutyl methacrylate, n-amylmethacrylate, n octyl methacrylate.Wherein, it is especially excellent
Select methyl acrylate.（Methyl）Acrylate can be used singly or in combination of two or more.Come from（Methyl）Third
The construction unit of olefin(e) acid ester is favorably improved the bond strength between inserts hardware and resin component element.
Comprising the construction unit from alpha-olefin and from α, the alkene of the construction unit of the ethylene oxidic ester of beta-unsaturated acid
Hydrocarbon system copolymer and also comprising coming from（Methyl）The olefin copolymer of the construction unit of acrylate can by using with
It is copolymerized toward known method to manufacture.For example, can be copolymerized using generally known Raolical polymerizable, from
And obtain above-mentioned copolymer.The species of copolymer is had no particular limits, such as can be random copolymer, or be embedding
Section copolymer.Alternatively, it is also possible to being following copolymer：Make such as polymethyl methacrylate, polyethyl methacrylate, gather
Methyl acrylate, polyethyl acrylate, butyl polyacrylate, polyacrylic acid -2- ethylhexyls, polystyrene, polyacrylonitrile, third
Alkene nitrile-styrol copolymer, n butyl acrylate styrene etc. is chemically bound in above-mentioned alkene with branched or cross-linked structure
Olefin-based graft copolymer obtained from hydrocarbon system copolymer.As the species of above-mentioned copolymer, preferably it is not grafted for olefin-based
Copolymer, more preferably random copolymer and/or block copolymer.
Olefin copolymer for the present invention can contain in the range of the effect of the present invention is not damaged comes from other
Copolymer composition construction unit.
More specifically, as（B）Olefin copolymer containing epoxy radicals, such as can include：Glycidyl methacrylate
The ethene improved based copolymer of glyceride, glycidyl ether modified ethylene copolymer etc., wherein, preferably Glycidyl methacrylate is sweet
The ethene improved based copolymer of grease.
As the ethene improved based copolymer of GMA, can include：Methyl propenoic acid glycidyl
Ester graft modification ethene polymers, ethylene-methyl methacrylate glycidyl ester copolymer, ethylene-methyl methacrylate glycidol
Ester-methyl acrylate copolymer.Wherein, it is excellent especially from the viewpoint of it can obtain excellent metal-resin composite shaped body
Select ethylene-methyl methacrylate glycidyl ester copolymer and ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate copoly
Thing, particularly preferably ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate copolymer.Contracted as ethylene-methyl methacrylate
The concrete example of water glycerine ester copolymer and ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate copolymer, can be included
“BONDFAST”（Sumitomo Chemical Co manufactures）Deng.
As glycidyl ether modified ethylene copolymer, such as can include：Glycidol ether graft modification ethene is copolymerized
Thing, glycidol ether-ethylene copolymer.
Relative to（A）The mass parts of polyarylene sulfide resin 100,（B）The content of olefin copolymer containing epoxy radicals is usually 3
~55 mass parts, preferably 15~40 mass parts.If above-mentioned content is less than 3 mass parts, inserts hardware and resin component element
Between bond strength be easily reduced or the impact resistance of resin combination is easily reduced or dielectric constant easily uprises.
It should be noted that line differential expansion of the adaptation between inserts hardware and resin component element between by these components is influenceed.Can
Think（B）Olefin copolymer containing epoxy radicals is strained and reduced by realizing stress relaxation, thus above-mentioned bond strength
Improved.For stress relaxation, toughness is effective, and toughness can be evaluated by tensile elongation.As elasticity
What body played a role（B）When the content of olefin copolymer containing epoxy radicals is few, it is believed that tensile elongation is small, can not obtain fully
Stress relaxation effect.In addition, stress relaxation also contributes to improve impact resistance.On the other hand, if above-mentioned content is more than 55 matter
Part is measured, then the dielectric loss angle tangent of resin combination is easily uprised, or mobility during insert-molding is easily reduced.
In addition,（B）Epoxy group content in olefin copolymer containing epoxy radicals is preferably 0.05 in all compositions
~0.20 mass %, more preferably 0.08~0.18 mass %.If above-mentioned epoxy group content account in all compositions 0.05~
0.20 mass %, then the bond strength between inserts hardware and resin component element easily maintain well, in addition, from inserts into
Release property during type does not allow corruptible aspect and the frequency for having the tendency of to be inhibited, mould is safeguarded from the amount for producing gas
It is preferable that the aspect that rate is easily reduced, which is set out,.
（B）The content of olefin copolymer containing epoxy radicals is adjusted to（B）The content of olefin copolymer containing epoxy radicals
（Unit：Mass parts）Relative to described later（C）The content of polystyrene resin（Unit：Mass parts）Ratio（（B）/（C））
For 0.3~5.0.Passing through will（B）/（C）The scope is adjusted to, the resin combination by being compounded with these compositions can be improved together
The impact resistance of obtained formed body and low dielectric property（Low-k and low-dielectric loss angle tangent）.（B）/（C）It is if low
In 0.3, then the poor impact resistance of the formed body obtained by resin combination.（B）/（C）If more than 5.0 surpassing, by resin combination
The low dielectric property for the formed body that thing obtains is poor.
（C）Polystyrene resin
It is right（C）Polystyrene resin is not particularly limited.（C）Polystyrene resin can be used alone, and also may be used
So that two or more is applied in combination.
As（C）Polystyrene resin, such as can include：Polystyrene；It is poly-（Ring-alkylated styrenes）；It is poly-（Benzene halide
Ethene）；It is poly-（Alkoxystyrene）；It is poly-（Vinyl benzoic acid ester）；Selected from by styrene, ring-alkylated styrenes, halogenated styrenes,
At least two kinds of copolymers in alkoxystyrene and the group of vinyl benzoic acid ester composition.
It is poly-（Ring-alkylated styrenes）Can be that homopolymer can also be copolymer.As ring-alkylated styrenes, such as can include：
Methyl styrene, ethyl styrene, isopropyl styrene and t-butyl styrene etc..Thus, as poly-（Ring-alkylated styrenes）,
Such as it can include：It is poly-（Methyl styrene）；It is poly-（Ethyl styrene）；It is poly-（Isopropyl styrene）；It is poly-（T-butyl styrene）；
It is at least two kinds of in the group being made up of methyl styrene, ethyl styrene, isopropyl styrene and t-butyl styrene
Copolymer etc..
It is poly-（Halogenated styrenes）Can be that homopolymer can also be copolymer.As halogenated styrenes, such as can include：
Chlorostyrene, bromstyrol, fluorobenzene ethene etc..Thus, as poly-（Halogenated styrenes）, such as can include：It is poly-（Chlorobenzene second
Alkene）；It is poly-（Bromstyrol）；It is poly-（Fluorobenzene ethene）；In the group being made up of chlorostyrene, bromstyrol and fluorobenzene ethene
At least two kinds of copolymer etc..
It is poly-（Alkoxystyrene）Can be that homopolymer can also be copolymer.As alkoxystyrene, such as can arrange
Enumerate：Methoxy styrene, ethoxystyrene etc..Thus, as poly-（Alkoxystyrene）, such as can include：It is poly-（First
Epoxide styrene）, it is poly-（Ethoxystyrene）, methoxy styrene-ethoxystyrene copolymer etc..
Among these, preferred polystyrene, poly-（P-methylstyrene）, it is poly-（Between methyl styrene）, it is poly-（To tert-butyl benzene
Ethene）, it is poly-（P-chlorostyrene）, it is poly-（M-chlorostyrene）, it is poly-（Pfluorostyrene）, styrene and p-methylstyrene copolymerization
Thing, particularly preferred polystyrene.
It is right（C）There is no particular limitation for the structure of polystyrene resin, can be random（atactic）Structure, isotactic
（isotactic）Structure and a rule（syndiotactic）Any of structure.Polystyrene with disordered structure
Resin refers to：With the phenyl as side chain, substituted-phenyl random position is in relative to by the main chain of carbon-carbon bond formation
The polystyrene resin of stereochemical structure.Polystyrene resin with isotactic structure refers to：With the phenyl as side chain,
Substituted-phenyl is relative to the polystyrene resin that unidirectional stereochemical structure is entirely located in by the main chain of carbon-carbon bond formation.
Polystyrene resin with syndiotactic structure（Hereinafter also referred to " SPS resins ".）Refer to：With the phenyl as side chain, take
Polystyrene resin for phenyl relative to the stereochemical structure that opposite direction is alternately positioned in by the main chain of carbon-carbon bond formation.
SPS resins such as fusing point is 180~310 DEG C, and heat resistance is especially excellent compared with the polystyrene resin with disordered structure.
Therefore, from the viewpoint of the heat resistance of the resin component element of gained, the preferred polystyrene resin with syndiotactic structure.
（C）Polystyrene resin can be manufactured using known method.Especially, SPS resins can by with
Lower method manufactures：For example, in nonactive hydrocarbon solvent or under conditions of in the absence of solvent, by titanium compound and water and trialkyl
The condensation product of aluminium is as catalyst, by styrenic monomers（The monomer corresponding with the construction unit contained by SPS resins）
Polymerization（For example, referring to Japanese Unexamined Patent Application 62-187708）.
Relative to（A）The mass parts of polyarylene sulfide resin 100,（C）The content of polystyrene resin is usually 5~60 mass
Part, preferably 5~40 mass parts.If above-mentioned content is less than 5 mass parts, the dielectric constant of resin combination easily uprises.On
If state content to be easily reduced more than 60 mass parts, the impact resistance of resin combination.
（D）Inorganic filling material
The resin combination of the present invention can include（D）Inorganic filling material.If add in the resin combination of the present invention
Add（D）Inorganic filling material, then the mechanical strength of resin component element of gained easily improve.It is right（D）Inorganic filling material is without spy
Do not limit, known inorganic filling material can be included.It is right（D）The shape of inorganic filling material is not particularly limited, can
To be the Non-fibrous such as fibrous or spherical, granular, tabular, Scales sheets, indefinite shape, but it is preferably threadiness.
As（D）Inorganic filling material, such as can include：Glass fibre, spherical silicon dioxide, glass microballoon etc., wherein being preferably
Glass fibre.（D）Inorganic filling material can be used alone or two or more is applied in combination.
Relative to（A）The mass parts of polyarylene sulfide resin 100,（D）The content of inorganic filling material is preferably 5~80 mass
Part, more preferably 20~50 mass parts.Above-mentioned content is if 5~80 mass parts, then easily to maintain inserts metal structure well
The state of mobility when bond strength between part and resin component element, insert-molding obtains by the resin group in the present invention
Added in compound（D）Inorganic filling material and the effect brought, are preferable in this aspect.In addition, the resin combination of gained
Easily become with excellent low dielectric property（Low-k and low-dielectric loss angle tangent）Resin combination.
（E）Containing epoxy compounds
The resin combination of the present invention can also include（E）Containing epoxy compounds.If in the resin combination of the present invention
Middle addition（E）Containing epoxy compounds, then in the metal-resin composite shaped body of gained, inserts hardware and resin component element
Between bond strength can be more prone to improve.（E）As long as containing epoxy compounds except above-mentioned（B）Olefin-based containing epoxy radicals
Being just not particularly limited containing epoxy compounds beyond copolymer.（E）It can be used alone containing epoxy compounds or group
Conjunction uses two or more.
（E）Can be that compound that 1 intramolecular contains 1 epoxy radicals or 1 intramolecular contain containing epoxy compounds
There is the compound of more than 2 epoxy radicals.As（E）Containing epoxy compounds, epoxy resin and in addition can be roughly divided into
Containing epoxy compounds, such as can include：Make bisphenol-A and epichlorohydrin react obtained from bisphenol-type epoxy resin, make phenolic aldehyde
Phenolic resin varnish type epoxy resin obtained from the reaction of varnish gum and epichlorohydrin, make polycarboxylic acid poly- obtained from being reacted with epichlorohydrin
Glycidol esters, the alicyclic compound type epoxy resin obtained by alicyclic compound, make the aliphatic with alcohol hydroxyl group
Glycidol ethers, epoxidized butadiene obtained from the reaction of compound and epichlorohydrin and make the compound and mistake with double bond
Epoxide obtained from oxide reaction.As concrete example, can include：Bisphenol A type epoxy resin, methyl glycidyl
Ether, phenyl glycidyl ether, various fatty acid glycidyl esters, diethylene glycol diglycidyl glycerin ether, phthalic acid two shrink
Glyceride, hexahydrophthalic acid 2-glycidyl ester, epoxidized polybutadiene, epoxidized SBS etc..Wherein, from stay in grade
Property（With the stability of the reaction of polyarylene sulfide resin）, good treatability, environmental sanitation（There is no mutagenicity）Go out etc. viewpoint
Hair, preferably epoxy resin, the particularly preferably bisphenol-type epoxy resin such as bisphenol A type epoxy resin.
Relative to（A）The mass parts of polyarylene sulfide resin 100,（E）Content containing epoxy compounds is preferably 0.01~10
Mass parts, more preferably 0.01~5 mass parts.Above-mentioned content is if 0.01~10 mass parts, then inserts hardware and resin
Bond strength between component can be more prone to improve.
In addition,（E）Below the 0.2 mass % preferably accounted in all compositions containing the epoxy group content in epoxy compounds
（For example, more than 0 mass % and it is below 0.2 mass %）, more preferably below 0.1 mass %（For example, more than 0 mass % and it is 0.1
Below quality %）.If below the 0.2 mass % that above-mentioned epoxy group content is accounted in all compositions, inserts hardware and resin
Peel resistance between component is difficult to reduce.Especially in insert-molding, even in the resin combination in molten condition
Flow end be also difficult to produce interface peel.In addition, release property during insert-molding is difficult to deteriorate, therefore from being readily obtained mesh
It is preferable to mark the aspect that the aspect of products formed and productivity ratio are difficult to reduce and set out.
（F）Alkene based compound without epoxy radicals
The resin combination of the present invention can also include（F）Alkene based compound without epoxy radicals.If the present invention's
Added in resin combination（F）Alkene based compound without epoxy radicals, then easily improved from the impact resistance of resin combination,
It is preferable that the aspect that other dielectric constant is easily reduced, which is set out,.（F）As long as the alkene based compound without epoxy radicals is free of
The olefin polymer of epoxy radicals is just not particularly limited.（F）Alkene based compound without epoxy radicals can be used alone
Or two or more is applied in combination.
（F）Alkene based compound without epoxy radicals can also be by the halogen atoms such as chlorine atom, bromine atoms, hydroxyl, amino, carboxylic
Base, alkoxy carbonyl etc. include functional group's substitution of the atom beyond carbon atom and hydrogen atom, but from low dielectric property（Low Jie
Electric constant and low-dielectric loss angle tangent）From the viewpoint of, the material that is preferably only made up of carbon atom and hydrogen atom.
As the olefin polymer without epoxy radicals, such as can include：The α such as ethene, propylene, 1- butylene, 1- octenes-
Alkene；The alkene in addition to alpha-olefin such as 2- butylene, 2- amylenes；Butadiene, isoprene, 2,3- dimethyl -1,3- butadiene,
The diene such as 1,3- pentadienes, 1,3- hexadienes；Polyenoid the, homopolymer and copolymer in addition to diene such as toluene, tetraene.As
Above-mentioned homopolymer, such as can include：Polyethylene, polybutene etc..As above-mentioned copolymer, such as can include：Ethylene-octene
Copolymer, ethylene-ethyl acrylate copolymer etc., particularly preferably ethylene-octene copolymer.
Relative to（A）The mass parts of polyarylene sulfide resin 100,（F）The content of alkene based compound without epoxy radicals is preferred
For 0.01~25 mass parts.Above-mentioned content then easily maintains inserts hardware and tree well if 0.01~25 mass parts
Mobility during bond strength and insert-molding between fat component.
（G）Chinese white
The resin combination of the present invention can also include（G）Selected from by titanium oxide, zinc sulphide, magnesia and barium sulfate group
Into group at least one kind of Chinese white.Even if the resin combination of the present invention does not include（G）Composition whiteness is also high（Form and aspect L
It is worth for more than 80）, but by comprising（G）Composition, form and aspect b values diminish, and yellow chromaticity is suppressed, and whiteness further improves.From
Low dielectric property（Low-k and low-dielectric loss angle tangent）From the viewpoint of, preferably titanium oxide and zinc sulphide, wherein special
Not preferred zinc sulphide.
Other compositions
The resin combination of the present invention is in addition to mentioned component, in the scope for the effect that will not significantly damage the present invention
It is interior, in order to assign desired physical property, organic filler material, fire retardant, ultra-violet absorber, heat stabilizer, light can also be contained
The additives such as stabilizer, colouring agent, carbon black, releasing agent, plasticizer.
The manufacture method of resin combination
On the manufacture method of the resin combination of the present invention, as long as the composition in the resin combination can be mixed equal
It is even to be just not particularly limited, can suitably it be selected from the manufacture method of previously known resin combination.Such as it can include：
Each components fuse is kneaded and extruded using the melting mixing such as single screw rod or double screw extruder device, then by the resin of gained
Composition is processed into powder, fragment（flake）, the desired form such as particle method.
Metal-resin composite shaped body
The metal-resin composite shaped body of the present invention possesses inserts hardware and formed by the resin combination of the present invention
And resin component element of the insert-molding on above-mentioned inserts hardware.Above-mentioned inserts hardware connects with above-mentioned resin component element
At least a portion on tactile surface implements physical treatment and/or chemical treatment.The metal-resin composite shaped body of the present invention makes
With being applied in combination（B）Olefin copolymer containing epoxy radicals and（C）Polystyrene resin is simultaneously adjusted the content of each composition
For the resin combination of defined scope, therefore the bond strength between inserts hardware and resin component element is strong, and resin structure
The impact resistance of part and low dielectric property（Low-k and low-dielectric loss angle tangent）It is excellent, and then whiteness is high.
Due to characteristic as described above, therefore the metal-resin composite shaped body of the present invention can be applied to engaging
The excellent adhesion of inserts hardware and resin component element is required in terms of intensity and requires the impact resistance of resin component element and low
The purposes that dielectric property is excellent, whiteness is high.Internally possess for example, the metal-resin composite shaped body of the present invention is suitably used as
Easily because humidity, moisture and by the metal-resin composite shaped body of dysgenic electrical and electronic parts etc..Particularly suitable work
For the use being expected in requiring the field of high-caliber waterproof such as rivers and creeks, swimming pool, skifield, bathroom and moisture,
The intrusion of moisture can cause the part of the electrically or electronically equipment of failure to use.In addition, the metal-resin of the present invention is combined into
Type body is as being also useful such as the hub for internally possessing resin-made, the electric/electronic device holding member with housing.
Herein, as electric/electronic device housing, in addition to mobile phone, it can also include camera, shoot with video-corder integrated camera, number
The housing of the carryings such as camera image electronic equipment, notebook computer, palm PC, calculator, electronic notebook, individual digital
Cellular system（PDC）, personal handhold telephone system（PHS）, the carrying information such as mobile phone or communication terminal housing, miniature light
Disk（MD）, the carrying acoustic electronic equipment such as tape-earphone stereo sound equipment, radio housing, lcd tv display,
Housing of the household electrical appliance such as phone, facsimile machine, hand held scanner etc..
Inserts hardware
For the inserts hardware used in the present invention, at least one of its surface being in contact with resin component element
Divide and implemented physical treatment and/or chemical treatment, preferably physical treatment was all implemented on its surface being in contact with resin component element
And/or chemical treatment.
The metal material for forming inserts hardware is not particularly limited, as its example, can include selected from by copper,
Copper alloy, aluminium, aluminium alloy and group of magnesium alloys into group at least one kind of metal material.
In the present invention, it is molded the inserts hardware for scheduling to last the shape hoped using according to purposes etc..For example, pass through to
Metal of melting etc. is injected in the mould of desired shape, the inserts hardware of desired shape can be obtained.In addition, in order to
Inserts hardware is shaped to desired shape, can also use and utilize machining of lathe etc. etc..
Implement physical treatment and/or chemical treatment in the surface of inserts hardware to obtaining in the manner described above.Implement
Physical treatment and/or chemically treated position, the size of process range can consider to be formed position of resin component element etc. to determine
It is fixed.
Physical treatment and chemical treatment are not particularly limited, known physical treatment and chemical treatment can be used.It is logical
Physical treatment is crossed, by mat surface, the resin combination for forming resin component element is entered coarse on the surface of inserts hardware
The adaptation of the interface of the Kong Zhonghui generation anchoring effects formed in the region of face, inserts hardware and resin component element becomes
Easily improve.On the other hand, by chemical treatment, can be assigned between the resin component element of inserts hardware and wanted insert-molding
The chemical adhesive effect such as covalent bond, hydrogen bond or molecular separating force is given, therefore the interface of inserts hardware and resin component element is close
Conjunction property becomes easily to improve.Chemical treatment can also with the mat surface on the surface of inserts hardware, now, can produce with
The adaptation of the interface of the same anchoring effect of physical treatment, inserts hardware and resin component element becomes to be more prone to carry
It is high.
As physical treatment, such as can include：Laser treatment, sandblasting（Japanese Unexamined Patent Publication 2001-225346 publications）Deng.
It can also combine and implement a variety of physical treatments.
As chemical treatment, such as can include：The dry process such as corona discharge, triazine processing（Referring to Japanese Unexamined Patent Publication
2000-218935 publications）, chemical etching（Japanese Unexamined Patent Publication 2001-225352 publications）, anodized（Japanese Unexamined Patent Publication
2010-64496）, hydrazine processing etc..In addition, when the metal material for forming inserts hardware is aluminium, warm water processing can be also included
（Japanese Unexamined Patent Publication 8-142110 publications）.As warm water processing, it can include and be impregnated 3~5 minutes in 100 DEG C of water.
It can combine and implement a variety of chemical treatments.
Resin component element
The resin component element used in the present invention is made up of polyarylene sulfide resin composition and insert-molding is in inserts metal structure
On part.
The manufacture method of metal-resin composite shaped body
The specific process of the manufacture method of metal-resin composite shaped body is not particularly limited, is by above-mentioned inserts gold
At least a portion for implementing physical treatment and/or chemically treated surface of metal elements makes inserts hardware and resin structure
Part is closely sealed, so that the manufacture method that inserts hardware is integrated with resin component element.
Such as following method can be included：At least a portion on surface is implemented into physical treatment and/or chemically treated
Inserts hardware is configured in die injection moulding, and the resin combination of the present invention is expelled into above-mentioned note with molten condition
Mould in mold for forming, the manufacture inserts hardware metal-resin composite shaped body integrated with resin component element.To being molded into
The condition of type is not particularly limited, can according to settings such as the physical property of polyarylene sulfide resin appropriate, preferable condition.In addition, make
Method with transfer molding, compression forming etc. is also that to form the inserts hardware metal-resin integrated with resin component element compound
The effective ways of formed body.In these methods, the surface being in contact with above-mentioned resin component element of above-mentioned inserts hardware
At least a portion implements physical treatment and/or chemical treatment, and the whole on the surface being preferably in contact with above-mentioned resin component element is real
Physical treatment and/or chemical treatment are applied.
As other examples, following method can be included：Beforehand through the common forming method system such as injection molding method
Molding resins component, physical treatment and/or chemically treated inserts hardware will be implemented with above-mentioned resin component element desired
Bonding station abuts, and the bearing surface of resin component element is nearby melted by being heated to bearing surface, so as to manufacture inserts metal structure
The part metal-resin composite shaped body integrated with resin component element.In the method, and above-mentioned inserts hardware with it is upper
At least a portion for stating the surface that resin component element is in contact implements physical treatment and/or chemical treatment, preferably with above-mentioned resin
The whole on the surface that component is in contact implements physical treatment and/or chemical treatment.
Embodiment
The present invention is specifically described for embodiment described below and comparative example, but the present invention is not limited by these embodiments
It is fixed.
By the schematic diagram of the metal-resin composite shaped body used in embodiment and comparative example in Fig. 1.（a）It is vertical to decompose
Body figure,（b）For stereogram,（c）It is the figure for only showing metal portion.The metal-resin composite shaped body is made using the following method.Need
It is noted that the unit of the size in figure is mm.
The preparation of resin combination
By following material compositions it is dry-mixed after, put into 320 DEG C of barrel zone temperature double screw extruder and melting mixing, obtain
The thermoplastic resin composition of granulating.The compounding amount of each composition（Mass parts）As shown in 1~table of table 5.
Polyphenylene sulfide
A-1：FORTRON KPS W214A（Product name）, melt viscosity：130Pa·s（Shear rate：1216/ second, temperature
Degree：310℃）, Kureha Corporation manufacture
A-2：FORTRON KPS W205AH（Product name）, melt viscosity：55Pa·s（Shear rate：1216/ second, temperature
Degree：310℃）, Kureha Corporation manufacture
Olefin copolymer containing epoxy radicals
B-1：Ethylene-methyl methacrylate ethylene oxidic ester-methyl acrylate copolymer, BONDFAST7L（Product name）, ring
Epoxide content：3 mass %, Sumitomo Chemical Co's manufacture
B-2：Ethylene-methyl methacrylate glycidyl ester copolymer, BONDFAST E（Product name）, epoxy group content：12
Quality %, Sumitomo Chemical Co's manufacture
Polystyrene resin
C-1：Syndiotactic polystyrene resin, XAREC130ZC（Product name）, Idemitsu Kosen Co., Ltd. manufacture
Inorganic filling material
D-1：Glass fibre（Chopped strand）、CS GL-HF（Product name）, Owens Corning Corporation manufacture
D-2：Glass fibre（Chopped strand）、T-747（Product name）, Nippon Electric Glass Co., Ltd manufacture
Containing epoxy compounds
E-1：Bisphenol A type epoxy resin（Solid-state）、jER（Old " EPICOAT ", is registration mark）1004K（Product name）、
Epoxy group content：4.6 quality %, epoxide equivalent 925, molecular weight：1650th, Mitsubishi chemical Co., Ltd manufactures
Alkene based compound without epoxy radicals
F-1：Ethylene-octene copolymer, Engage8003（Product name）, Dow Chemical Japan Co., Ltd. systems
Make
F-2：Ethylene-octene copolymer, Engage8440（Product name）, Dow Chemical Japan Co., Ltd. systems
Make
Chinese white
G-1：Titanium oxide, TITONE SR-1（Product name）, Sakai Chemical Industry Co., Ltd. manufacture
G-2：Zinc sulphide
Wherein, the assay method of melt viscosity is as described below.
Melt viscosity
The CAPIROGRAPH manufactured using Toyo Seiki Co., Ltd., capillary is used as using 1mm φ × 20mmL/ flat-dies
Pipe, the melt viscosity of measure 310 DEG C of barrel temperature, shear rate under 1216/ second.
The evaluation of impact resistance
For the resin combination prepared by any one of embodiment 1~14 and comparative example 1~10, using being molded into
Type, Charpy-type test piece is made at 320 DEG C of barrel zone temperature, 150 DEG C of mold temperature, is commented according to specified in ISO179/1eA
Valency benchmark, evaluated under conditions of 23 DEG C.As a result it is shown in 1~table of table 5.
The evaluation of dielectric property
For the resin combination prepared by any one of embodiment 1~14 and comparative example 1~10, using being molded into
Type, 1.8mm × 1.8mm × 80mm test film is shaped at 320 DEG C of barrel zone temperature, 150 DEG C of mold temperature, in air conditioning chamber room
Temperature（23℃±2℃、50%RH±5%RH）Placed more than 2 hours under environment, then with Agilent Technologies, Inc.
Network Analyzer8757D, Synthesized Sweeper83650L and the Northeast applying electronic exploitation strain of manufacture
The 2GHz cavity resonators of formula commercial firm manufacture, the relative dielectric constant under 2GHz is determined by cavity resonance method of perturbation（εr）With
Dielectric loss angle tangent（tanδ）.As a result it is shown in 1~table of table 5.
The physical treatment or chemical treatment of inserts hardware
As inserts hardware, using by copper（C-1100P, thickness 2mm）Or aluminium（A5052, thickness 2mm）Form and such as
Under implement physical treatment or chemically treated plate object describedly.The inserts hardware of these tabulars is Fig. 1's（a）It is oblique
Part shown in line has composition surface.It should be noted that in 1~table of table 5, " physics ", " chemistry 1 " and " difference of chemistry 2 "
Refer to following physical treatments, chemical treatment 1 and chemical treatment 2.
Physical treatment
Using commercially available liquid honing device, with concentration 20%, gauge pressure 0.4Mpa bar on the inserts hardware of aluminum
It is #1000 that part, which blows granularity,（Medium particle diameter：14.5~18 μm）Alumina abrasive, be roughened.
Chemical treatment 1
By the surface of inserts hardware made of copper following compositions etching solution A（The aqueous solution）Middle dipping 1 minute, is carried out
The removal of antirust epithelium, then in the etching solution B of following compositions（The aqueous solution）Middle dipping 5 minutes, etches metal part surface.
Chemical treatment 2
By the surface of the inserts hardware of aluminum following compositions alkali degreasing liquid（The aqueous solution）Middle dipping 5 minutes, enters
Row ungrease treatment, then in the etching solution C of following compositions（The aqueous solution）Middle dipping 3 minutes, etches metal part surface.
The making of metal-resin composite shaped body
Physical treatment or the configuration of chemically treated inserts hardware will be implemented in a mold, enter to be about to the inserts metal
Component and the resin component element one formed as the resin combination prepared by any one of embodiment 1~14 and comparative example 1~10
The integrated process of body.Condition of molding is as described below.The shape of metal-resin composite shaped body is as shown in Figure 1.
Condition of molding
The evaluation of metal-resin composite shaped body
For the metal-resin composite shaped body made with the aforedescribed process, evaluate resin component element from inserts hardware
Failure mode and peel resistance after stripping.As a result it is shown in 1~table of table 5.Specific evaluation method is as described below.
Failure mode and peel resistance
Metal-resin composite shaped body with the shape shown in Fig. 1 is configured in pedestal as shown in Figure 2（Folder
Tool）On, with the speed movable clamp of 1mm/ minutes, so that in the direction of the arrow by resin component element from inserts hardware
Pressing is peeled off.The region of bonding part is originally used for visual observation, evaluation is the boundary only in inserts hardware and resin component element
Face generates destruction（Interface peel, with × represent）Still destruction is at least generated in resin component element（Cohesional failure, with ◎ tables
Show）.
In addition, with the visual inserts hardware side for observing the region for being originally used for bonding part, obtain and be attached to inserts gold
The area ratio of region entirety of the area shared by resin component element with being originally used for bonding part on metal elements, according to following benchmark
Evaluated.
◎：Above-mentioned ratio is more than 50%, and peel resistance is very good.
○：For above-mentioned ratio for 20% less than 50%, peel resistance is good.
△：Above-mentioned ratio is that peel resistance is bad more than 0% and less than 20%.
×：Above-mentioned ratio is 0%, and peel resistance is extremely bad.
The evaluation of form and aspect
For the resin combination prepared by any one of embodiment 15~17, using injection molding, in barrel zone temperature
320 DEG C, thickness 4mm dumbbell shaped test film is made at 150 DEG C of mold temperature, made using electricity Se Industrial Co., Ltd of Japan system
Colour difference meter, by 0 ° of-d mode colour examining of the defineds of JIS Z 8722, based on the result, pass through the henry of the defineds of JIS Z 8730
It is special（Hunter）Aberration formula obtains form and aspect L（Brightness）, form and aspect b（Yellow chromaticity）And form and aspect a（Red degree）.As a result it is shown in table 6.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
As shown in 1~table of table 5, for 3~55 mass parts are applied in combination（B）Olefin copolymer containing epoxy radicals and 5
~60 mass parts（C）Polystyrene resin simultaneously will（B）The content of olefin copolymer containing epoxy radicals relative to（C）Polyphenyl
The ratio of the content of vinylite（（B）/（C））Be adjusted to 0.3~5.0, the content of each composition is adjusted to defined model
For the embodiment 1~14 enclosed, the engagement between inserts hardware and resin component element in metal-resin composite shaped body is strong
Degree is strong, and the impact resistance of resin component element and low dielectric property are excellent.
On the other hand, for（C）For the content of polystyrene resin is less than the comparative example 1~3 of 5 mass parts, with reality
Apply example 1~14 to compare, low dielectric property is poor（Relative dielectric constant is high）.
For（C）The content of polystyrene resin less than 5 mass parts and（F）Alkene based compound without epoxy radicals
Content more than the comparative example 4 and 5 of 25 mass parts for, compared with embodiment 1~14, peel resistance is poor.
For（C）For the content of polystyrene resin is more than the comparative example 6 of 60 mass parts, with the phase of embodiment 1~14
Than poor impact resistance.
For（B）For the content of olefin copolymer containing epoxy radicals is less than the comparative example 7 of 3 mass parts, with embodiment 1
~14 compare, and impact resistance, low dielectric property are poor（Relative dielectric constant is high）, and then, it is embedding in metal-resin composite shaped body
Bond strength between part hardware and resin component element is also poor.
For（B）For the content of olefin copolymer containing epoxy radicals is more than the comparative example 8 of 55 mass parts, with embodiment
1~14 compares, and low dielectric property is poor（Dielectric loss angle tangent is high）.
（B）/（C）Comparative example 9 less than 0.3 poor impact resistance compared with embodiment 1~14.
（B）/（C）Comparative example 10 more than the 5.0 low dielectric property compared with embodiment 1~14 is poor（Dielectric loss angle tangent
It is high）.
As shown in table 6, even if the resin combination of embodiment 15 is free of（G）The Chinese white of composition, whiteness are also high（Color
Phase L values are more than 80）.
On the other hand, comprising（G）The resin combination of the embodiment 16 and 17 of the Chinese white of composition and embodiment 15
Resin combination is compared, and form and aspect b values are small, and yellow chromaticity is inhibited, and whiteness further improves.
Claims (11)
1. a kind of resin combination, it is for implementing physical treatment and/or chemically treated inserts hardware is enterprising
The resin combination of row insert-molding,
The resin combination includes the mass parts of (A) polyarylene sulfide resin 100, the olefin copolymer 3~55 of (B) containing epoxy radicals
Mass parts and the mass parts of (C) polystyrene resin 5~60,
The content of the olefin copolymer of (B) containing epoxy radicals relative to the content of (C) polystyrene resin ratio
Example ((B)/(C)) is 0.3~5.0,
(C) polystyrene resin is selected from polystyrene, poly- (ring-alkylated styrenes), poly- (halogenated styrenes), poly- (alkoxy
Styrene), poly- (vinyl benzoic acid ester), selected from by styrene, ring-alkylated styrenes, halogenated styrenes, alkoxystyrene with
It is and one kind or two or more at least two kinds of copolymers in the group of vinyl benzoic acid ester composition.
2. resin combination according to claim 1, wherein, the olefin copolymer of (B) containing epoxy radicals be comprising
The olefin copolymer of the construction unit of ethylene oxidic ester of the construction unit from alpha-olefin from alpha, beta-unsaturated acid.
3. resin combination according to claim 1 or 2, wherein, the olefin copolymer of (B) containing epoxy radicals is also
Include the olefin copolymer of the construction unit from (methyl) acrylate.
4. resin combination according to claim 1 or 2, wherein, in the olefin copolymer of (B) containing epoxy radicals
0.05~0.20 mass % that epoxy group content is accounted in all compositions.
5. resin combination according to claim 1 or 2, it is also included relative to the mass parts of (A) polyarylene sulfide resin 100
(D) mass parts of inorganic filling material 5~80, (E) are free of epoxy radicals containing the mass parts of epoxy compounds 0.01~10 and (F)
The mass parts of alkene based compound 0.01~25 it is at least one kind of.
6. resin combination according to claim 5, wherein, (E) is epoxy resin containing epoxy compounds.
7. resin combination according to claim 6, wherein, (E) is biphenol type epoxy tree containing epoxy compounds
Fat.
8. resin combination according to claim 5, wherein, (E) is containing the epoxy group content in epoxy compounds
Below the 0.2 mass % accounted in all compositions.
9. resin combination according to claim 1 or 2, it is also selected from by titanium oxide, zinc sulphide, magnesia comprising (G)
And at least one kind of Chinese white in the group of barium sulfate composition.
10. a kind of metal-resin composite shaped body, it possesses inserts hardware and as any one of claim 1~9
Resin combination formed and resin component element of the insert-molding on the inserts hardware, the inserts hardware with
At least a portion on the surface that the resin component element is in contact implements physical treatment and/or chemical treatment.
11. a kind of manufacture method of metal-resin composite shaped body, it includes integrated process as described below：By surface extremely
A few part implements physical treatment and/or the configuration of chemically treated inserts hardware in die injection moulding, will weigh
Profit requires that the resin combination any one of 1~9 is expelled in the die injection moulding with molten condition, by described in
Inserts hardware is integrated with resin component element.
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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 |
| JP6167011B2 (en) * | 2013-10-25 | 2017-07-19 | ポリプラスチックス株式会社 | Electrically insulating high thermal conductive resin composition |
| CN105566909A (en) * | 2014-12-26 | 2016-05-11 | 比亚迪股份有限公司 | Resin composition, metal-resin complex and preparation method and application thereof, and electronic product shell |
| 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 |
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| JP7143713B2 (en) * | 2018-10-02 | 2022-09-29 | 東ソー株式会社 | Metal member-polyarylene sulfide resin member composite manufacturing method |
| CN110951177A (en) * | 2019-12-13 | 2020-04-03 | Oppo广东移动通信有限公司 | Nano injection molding composite material, preparation method thereof, shell assembly and electronic equipment |
| 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 |
| CN118703040A (en) * | 2024-06-27 | 2024-09-27 | 江苏欧瑞达新材料科技有限公司 | A kind of durable polyphenylene sulfide and preparation method thereof |
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| JP2010167475A (en) * | 2009-01-26 | 2010-08-05 | Yamase Denki Kk | Metallic material joined with different kind of material and having airtightness in boundary therebetween, and method of manufacturing the same |
| JP5234011B2 (en) * | 2010-01-07 | 2013-07-10 | 豊田合成株式会社 | Method for producing composite of metal and resin |
| JP2012135884A (en) * | 2010-12-24 | 2012-07-19 | Toray Ind Inc | Method of manufacturing composite molding |
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- 2014-03-13 JP JP2014049777A patent/JP6325295B2/en active Active
- 2014-03-20 TW TW103110428A patent/TWI638010B/en not_active IP Right Cessation
- 2014-03-31 KR KR20140038042A patent/KR20140122180A/en not_active Application Discontinuation
- 2014-04-04 CN CN201410137387.5A patent/CN104098898B/en not_active Expired - Fee Related
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| CN1134960A (en) * | 1995-03-17 | 1996-11-06 | 通用电气公司 | Epoxy-functional polyphenylene ether/polyarylene sulfide, epoxy-functional alpha-olefin elastomer, elastomeric block copolymer composition |
| CN1564850A (en) * | 2001-10-05 | 2005-01-12 | 汎塑料株式会社 | Insert-molded article |
| CN1488675A (en) * | 2002-08-28 | 2004-04-14 | 宝理塑料株式会社 | Polyarylene sulfide resin composition and molded product thereof |
| CN1798807A (en) * | 2003-06-05 | 2006-07-05 | 汎塑料株式会社 | Polyarylene sulfide resin composition and coated molding |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI638010B (en) | 2018-10-11 |
| KR20140122180A (en) | 2014-10-17 |
| TW201504347A (en) | 2015-02-01 |
| JP6325295B2 (en) | 2018-05-16 |
| JP2014218076A (en) | 2014-11-20 |
| CN104098898A (en) | 2014-10-15 |
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