TW201500468A - Molding resin composition for insertion member, metal resin composite molding body using same, and its manufacturing method - Google Patents

Abstract

To provide a molding resin composition for insertion member having a strong bonding strength between a metal member and a resin member, and able to impart an excellent peeling resistance to a metal resin composite molding body, a metal resin composite molding body using same, and its manufacturing method. A resin composition, which is the molding resin composition for the insertion member on the metal member of the insertion member subjected to a physical treatment and/or a chemical treatment. The aforementioned resin composition comprises (A) a polyarylene thioether, (B) a compound containing the epoxy group, and (C) an alkene copolymer containing the epoxy group. The epoxy group content in the aforementioned (B) compound containing the epoxy group is 0.01 to 0.25 mass% in the entire composition, and the epoxy group content of the aforementioned (C) the epoxy-group content in the epoxy-containing alkene-based copolymer is 0.01 to 0.3 mass% in the entire composition, wherein the abovementioned epoxy group content in the entire composition is 0.02 to 0.4 mass% in total.

Description

Resin composition for insert molding, metal resin composite molded body using the same, and a method for producing the same

The present invention relates to a resin composition for insert molding, comprising a metal resin composite molded body of a resin member which is contained in a molded insert member which is subjected to physical treatment and/or chemical treatment. A resin composition and a method for producing the above-described metal resin composite molded body.

The insert metal member composed of a metal or an alloy and the resin member composed of the thermoplastic resin composition are integrated into a metal resin composite molded body, and conventionally used as a console box around the instrument panel (console box) ) A component such as a built-in member of an automobile or a part around an engine, or an interface of an electronic device such as a built-in component, a digital camera, or a mobile phone, or a component such as a power supply end that comes into contact with the outside.

The method of integrating the insert metal member and the resin member is a method of physically and chemically treating the joint surface on the insert metal member side to improve the adhesion between the insert metal member and the resin member. A method of using an adhesive or a double-sided tape is to provide a fixing member such as a reverse flap or a gripper to the insert metal member and/or the resin member, and a method of fixing the both by using the fixing member, a method of joining using a screw or the like. Among them, the method of using physical treatment and/or chemical treatment on the joint surface of the insert metal member and the use thereof The method of the subsequent agent is effective in terms of designing the degree of freedom in the case where the metal resin is attached to the composite body.

In particular, the method of applying physical treatment and/or chemical treatment to the joint surface on the side of the insert metal member is advantageous in terms of not using an expensive adhesive. As a method of applying physical treatment and/or chemical treatment to the joint surface on the side of the insert metal member, for example, the method disclosed in Patent Document 1 can be cited. The method is a method of forming a rough surface using a laser in a desired range on the surface of the insert metal member.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-167475

In the metal-resin composite molded body, it is practically necessary to sufficiently integrate the insert metal member and the resin member. Therefore, in the metal resin-attached composite body, the joint strength between the insert metal member and the resin member is not only strong, but also it is difficult to cause peeling between the insert metal member and the resin member.

An object of the present invention is to provide a resin composition for an insert of a metal-resin composite molded article having excellent joint strength between the insert metal member and the resin member, and to form a metal resin composite using the composition. Body, and its method of manufacture.

The inventors of the present invention have repeatedly made efforts to solve the above problems. As a result, it was found that by using a compound containing an epoxy group in combination with an epoxy group The olefin-based copolymer is a resin composition in which the epoxy group content in each component is adjusted to a predetermined range, and the above problems are solved, and the present invention has been completed. More specifically, the present invention provides the following.

(1) A resin composition for insert molding on an insert metal member to which physical treatment and/or chemical treatment is applied, the resin composition comprising (A) a poly(arylene sulfide) resin, (B) The epoxy group-containing compound, (C) the epoxy group-containing olefin-based copolymer, and the epoxy group-containing compound (B) have an epoxy group content of 0.01 to 0.25 mass% in the total composition, as described above ( C) The epoxy group content in the epoxy group-containing olefin-based copolymer is 0.01 to 0.3% by mass in the total composition, and the epoxy group content (C) in the above (B) epoxy group-containing compound is contained. The epoxy group content in the epoxy group-containing olefin-based copolymer is 0.02 to 0.40% by mass in the total composition.

(2) The epoxy group-containing compound (B) is the resin composition described in (1) of the epoxy resin.

(3) The epoxy group-containing compound (B) is a resin composition according to (1) or (2) of the bisphenol type epoxy resin.

(4) The (C) epoxy group-containing olefin-based copolymer is an olefin-based copolymer comprising a constituent unit derived from an α-olefin and a constituent unit derived from a glycidyl ester derived from an α,β-unsaturated acid ( The resin composition described in any one of (1).

(5) The (C) epoxy group-containing olefin-based copolymer further contains any one of (1) to (4) of the olefin-based copolymer derived from the (meth) acrylate. Resin composition.

(6) Further, with respect to the more (A) poly(arylene sulfide) resin 100 The resin composition as described in any one of (1) to (5) of (D) inorganic filler is contained in the mass part.

(7) comprising an insert metal member, and a resin member comprising the resin composition according to any one of (1) to (6), wherein the insert member has been molded on the insert metal member, the insert metal member and At least a part of the surface where the resin member is in contact with each other is subjected to a physical treatment and/or chemical treatment of the metal resin composite molded body.

(8) An insert metal member having at least a part of the surface subjected to physical treatment and/or chemical treatment, and is provided in the injection molding mold, and is described in any one of (1) to (6). A method of producing a metal-resin composite molded body in which the resin composition is injected in the injection molding mold in a molten state and integrated with the insert metal member and the resin member.

According to the present invention, it is possible to provide a resin composition for insert molding of a metal-resin composite molded article having a high joint strength between the insert metal member and the resin member and having excellent peeling resistance, and a metal resin using the composition. Composite formed body.

Fig. 1 is a schematic view showing a metal-resin composite molded body used in Examples and Comparative Examples, (a) is an exploded perspective view, (b) is a perspective view, and (c) is a metal only portion. Figure.

Fig. 2 is a schematic view showing a method of measuring the joint strength between the resin portion and the metal portion performed in the embodiment.

Hereinafter, embodiments of the present invention will be described. Further, the present invention is not limited to the following embodiments.

<Resin composition>

The resin composition of the present invention is used for insert molding of a metal member to be subjected to physical treatment and/or chemical treatment, which comprises (A) a poly(arylene sulfide) resin and (B) An epoxy group-containing compound and (C) an epoxy group-containing olefin-based copolymer. Hereinafter, each component contained in the resin composition will be described.

[(A) Poly(aryl thioether resin)]

The (A) poly(arylene sulfide) resin is not particularly limited, and a conventionally known poly(arylene sulfide) resin can be used. As the (A) poly(arylene sulfide) resin, a polyphenylene sulfide (PPS) resin is preferably used. (A) The poly(aryl) sulfide resin may be used alone or in combination of two or more.

(A) Poly(arylene sulfide) resin, in order to obtain better adhesion between the insert metal member and the resin member, the melt viscosity at a cutting speed of 1216 / sec measured at 310 ° C is preferably 8 to 300 Pa‧ s, especially good for 10 to 200Pa‧s.

[(B) Compound containing an epoxy group]

(B) The epoxy group-containing compound is not particularly limited as long as it is an epoxy group-containing compound other than the (C) epoxy group-containing olefin copolymer described later. (B) The epoxy group-containing compound may be used alone or in combination of two or more.

(B) The epoxy group-containing compound may be a compound containing one epoxy group in one molecule, or a compound containing two or more epoxy groups in one molecule. The (B) epoxy group-containing compound can be classified into an epoxy resin and other epoxy group-containing compounds, and examples thereof include bisphenol A and a ring. a bisphenol epoxy resin obtained by an epichlorohydrin reaction, a phenolic epoxy resin obtained by reacting a phenol resin with epichlorohydrin, a polyglycidyl ester obtained by reacting a polycarboxylic acid with epichlorohydrin, An alicyclic compound-type epoxy resin obtained from an alicyclic compound, a glycidyl ether obtained by reacting an aliphatic compound having an alcoholic hydroxyl group with epichlorohydrin, an epoxidized butadiene, and a compound having a double bond and a fruit oxide The resulting epoxy compound is reacted. Specific examples include bisphenol A epoxy resin, methyl glycidyl ether, phenyl glycidyl ether, glycidyl esters of various fatty acids, diethylene glycol diglycidyl ether, diglycidyl citrate, and the like. Hydroxypeptide diglycidyl ester, epoxidized polybutadiene, epoxidized SBS, and the like. Among them, an epoxy resin is preferable from the viewpoints of quality stability (reaction stability with a poly(arylene sulfide) resin), excellent handleability, environmental sanitation (no mutagenicity), and the like, and particularly preferably Bisphenol type epoxy resin such as bisphenol A type epoxy resin.

(B) The content of the epoxy group-containing compound, wherein the epoxy group content in the (B) epoxy group-containing compound is usually from 0.01 to 0.25% by mass, preferably from 0.01 to 0.20% by mass in the total composition. The amount. When the epoxy group content is less than 0.01% by mass in the total composition, the peeling resistance between the insert metal member and the resin member is liable to lower. In particular, when the insert is molded, interfacial peeling is likely to occur at the flow end of the resin composition in a molten state. On the other hand, when the epoxy content is more than 0.25 mass% of the total composition, the mold release property at the time of molding the insert is likely to be deteriorated, and it is difficult to obtain the intended molded article, or the productivity is liable to be lowered. .

[(C) Olefin-containing olefin-based copolymer]

(C) The epoxy group-containing olefin-based copolymer is not particularly limited. (C) contains The olefin-based copolymer of the epoxy group may be used alone or in combination of two or more.

Examples of the (C) epoxy group-containing olefin-based copolymer include an olefin-based copolymer comprising a constituent unit derived from an α-olefin and a constituent unit derived from a glycidyl ester derived from an α,β-unsaturated acid. In particular, it is preferable to further contain an olefin-based copolymer derived from a constituent unit of (meth) acrylate, since an excellent metal-resin composite molded body can be obtained. Further, in the following, the (meth) acrylate may be referred to as an ester of (meth) acrylate. For example, glycidyl (meth)acrylate is also known as glycidyl (meth) acrylate. In the present specification, "(meth)acrylic acid" means both propyl acid and methacrylic acid, and "(meth)acrylate" means both acrylate and methacrylate.

The α-olefin is not particularly limited, and examples thereof include ethylene, propylene, butylene, and the like, and ethylene is particularly preferable. The α-olefin may be used alone or in combination of two or more. (C) The epoxy group-containing olefin-based copolymer contains a constituent unit of a source α-olefin, and it is easy to impart flexibility to the resin member, and the resin member is softened by flexibility, thereby contributing to the insert metal member and Improvement in joint strength between resin members.

The glycidyl ester of the α,β-unsaturated acid is not particularly limited, and examples thereof include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and particularly preferably methacrylic acid shrinkage. Glyceride. The glycidyl ester of the α,β-unsaturated acid may be used alone or in combination of two or more. Since the (C) epoxy group-containing olefin-based copolymer contains a glycidyl ester of an α,β-unsaturated acid, the effect of improving the bonding strength between the insert metal member and the resin member can be easily obtained.

The (meth) acrylate is not particularly limited, and for example, it can be listed. Examples of acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate; methyl methacrylate, ethyl methacrylate, methyl A methacrylate such as n-propyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate or n-octyl methacrylate. Among them, methyl acrylate is particularly preferred. The (meth) acrylate may be used alone or in combination of two or more. The constituent unit derived from (meth) acrylate contributes to an improvement in the joint strength between the insert metal member and the resin member.

An olefin-based copolymer comprising a constituent unit derived from an α-olefin and a constituent unit derived from a glycidyl ester of an α,β-unsaturated acid, and an olefin-based copolymer further comprising a constituent unit derived from (meth) acrylate The copolymer can be produced by copolymerization by a conventional method. For example, the above copolymer can be obtained by carrying out a generally known radical polymerization reaction. The type of the copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer. Further, the above olefin-based copolymer, for example, polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyethyl acrylate 2-ethylhexyl ester, poly A styrene, a polyacrylonitrile, an acrylonitrile ‧ styrene copolymer, a butyl acrylate styrene copolymer, or the like may be a chemically bonded olefin-based random copolymer having a branched or crosslinked structure.

The olefin-based copolymer used in the present invention may contain a constituent unit derived from another copolymerization component insofar as the effects of the present invention are not impaired.

More specifically, examples of the (C) epoxy group-containing olefin-based copolymer include a glycidyl methacrylate-modified vinyl copolymer and a glycidyl ether-modified vinyl copolymer. Preferred for glycidol A methacrylate modified ethylene copolymer.

Examples of the glycidyl methacrylate-modified vinyl copolymer include a shrink-drying-based methacrylic acid graft-modified ethylene polymer, an ethylene-glycidyl methacrylate copolymer, and an ethylene-glycidyl group. Methacrylate-methyl acrylate copolymer. Among them, in particular, since an excellent metal resin composite molded body can be obtained, an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable, and particularly preferably ethylene- Glycidyl methacrylate-methyl acrylate copolymer. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include "BONDFAST" (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the glycidyl ether-modified ethylene-based copolymer include a glycidyl ether graft-modified ethylene copolymer and a glycidyl ether-ethylene copolymer.

(C) The content of the epoxy group-containing olefin-based copolymer, and (C) the epoxy group-containing olefin-based copolymer has an epoxy group content of usually 0.01 to 0.30% by mass in the total composition, preferably An amount of 0.03 to 0.25 mass%. When the epoxy group content is less than 0.01% by mass in the total composition, the bonding strength between the insert metal member and the resin member is liable to lower. The adhesion of the insert metal member to the resin member is affected by the difference in linear expansion between the members. The (C) epoxy group-containing olefin-based copolymer is stress-relieved and has small deformation, and the bonding strength is improved. Stress relaxation is effective for toughness, while toughness can be evaluated by stretching. When the content of the (C) epoxy group-containing olefin-based copolymer as the elastomer function is small, the stretching is small, and a sufficient stress relieving effect cannot be obtained. On the other hand, when the above epoxy group content exceeds 0.3% by mass in the total composition, the insert is formed into The mold release property at the time of molding tends to be deteriorated, or there is a tendency that gas generation tends to increase, and the frequency of mold maintenance tends to be high, which is not preferable.

Further, the total content of the epoxy group in the (B) epoxy group-containing compound and the (C) epoxy group-containing olefin-based copolymer in the total composition are usually 0.02 to 0.40% by mass, preferably 0.03 to 0.30% by mass, more preferably 0.035 to 0.25. When the total amount is more than 0.40% by mass, the release property of the obtained multiplying body is likely to be deteriorated. In addition, the lower limit of the total is the sum of the lower limit of the epoxy group content in the (B) epoxy group-containing compound and the lower limit of the epoxy group content in the (C) epoxy group-containing olefin copolymer.

[(D) Inorganic filler]

The resin composition of the present invention may further comprise (D) an inorganic filler. The (D) inorganic filler is added to the resin composition of the present invention, and the mechanical strength of the obtained resin composition is easily improved. (D) The inorganic filler is not particularly limited, and those conventionally known can be mentioned. (D) The shape of the inorganic filler is not particularly limited, and may be fibrous, or may be a non-fibrous shape such as a spherical shape, a granular shape, a plate shape, a scaly shape, or an indefinite shape, and is preferably a fibrous shape. Examples of the (D) inorganic filler include glass fibers, spherical cerium oxide, glass beads, and the like. Among them, glass fibers are preferred. (D) The inorganic filler may be used alone or in combination of two or more.

The content of the inorganic filler (D) is usually from 1 to 300 parts by mass, preferably from 25 to 250 parts by mass, per 100 parts by mass of the (A) poly(arylene sulfide) resin. When the above content is less than 1 part by mass, the resin composition of the present invention cannot be exhibited by the effect of adding (D) an inorganic filler. When the content is more than 300 parts by mass, the joint strength between the insert metal member and the resin member is liable to be lowered, or the fluidity at the time of molding of the insert is liable to be lowered.

[Other ingredients]

The resin composition of the present invention may contain an organic filler, a flame retardant, an ultraviolet absorber, a heat stabilizer, or light in order to impart desired physical properties, in addition to the above-described components, without impairing the effects of the present invention. Additives such as stabilizers, colorants, carbon black, mold release agents, and plasticizers.

[Method for Producing Resin Composition]

The method for producing the resin composition of the present invention is not particularly limited as long as the components in the resin composition can be uniformly mixed, and can be suitably selected from a conventional method for producing a resin composition. For example, a method in which a melt-kneading device such as a uniaxial or biaxial extruding base is used, and each component is melted and kneaded and then extruded, and the obtained resin composition is processed into a desired form such as a powder, a small piece, or a small particle.

<Metal resin composite molded body>

The metal resin composite molding system of the present invention comprises an insert metal member, and a resin member comprising the resin composition of the present invention and inserted into the insert metal member. At least a part of the surface of the insert metal member that is in contact with the resin member is subjected to physical treatment and/or chemical treatment. In the metal-resin composite molded article of the present invention, the (b) epoxy group-containing compound and (C) epoxy group-containing olefin copolymer are used in combination, and the epoxy group content in each of the components is adjusted to In the resin composition of a predetermined range, the joint metal member and the resin member have strong joint strength and excellent peeling resistance.

By the above-mentioned characteristics, the metal-resin composite molded article of the present invention can be suitably used for applications in which both the joint strength and the peeling resistance are required, and the adhesion between the insert metal member and the resin member is excellent. For example, the metal resin composite molded body of the present invention is suitable as a susceptible to being adversely affected by humidity or moisture. The electrical and electronic parts are equal to the metal resin composite formed body included therein. In particular, it is presumed to be used in fields requiring high degree of waterproofing, for example, in rivers, swimming pools, ski resorts, bathhouses, etc., and is suitable as a component for electric or electronic equipment related to failure of moisture or moisture intrusion. In addition, the metal-resin composite molded body of the present invention is also used as a casing for electric and electronic equipment, for example, as a bushing or a holding member made of resin. In this case, as a housing for electric and electronic equipment, in addition to a mobile phone, a casing for a portable imaging electronic device such as a camera, a photographic camera, or a digital camera, a notebook computer, a pocket computer, a computer, and an electronic device can be cited. Notepad, PDC, PHS, mobile phone, etc. The frame for carrying information or communication intermediate machine, MD, cassette stereo Walkman, radio, etc. The frame of portable audio electronic equipment, LCD TV, LCD screen, telephone, fax A casing of a home telephone device such as a machine or a handheld scanner.

[insert metal member]

The insert metal member used in the present invention, preferably at least a part of the surface in contact with the resin member, is subjected to physical treatment and/or chemical treatment.

The metal material constituting the insert metal member is not particularly limited, and examples thereof include at least one selected from the group consisting of copper, a copper alloy, aluminum, an aluminum alloy, and a magnesium alloy.

In the present invention, an insert metal member formed into a desired shape is used depending on the application. For example, by inserting a molten metal or the like into a mold of a desired shape, an insert metal member of a desired shape can be obtained. Further, in order to shape the insert metal member into a desired shape, cutting by a working machine or the like may be used.

The surface of the insert metal member obtained in the above manner is subjected to physical treatment and/or chemical treatment. The position of the physical treatment and/or chemical treatment, or the size of the treatment range, is determined in consideration of the position at which the resin member is formed.

The physical treatment and the chemical treatment are not particularly limited, and conventional physical treatment and chemical treatment can be used. By physical treatment, the surface of the insert metal member is roughened, pores are formed in the roughened region, and the anchoring effect of the resin composition constituting the resin member is formed, and the interface between the insert metal member and the resin member is easy. Improve adhesion. On the other hand, by chemical treatment, between the insert metal member and the insert-molded resin member, the metal member and the resin member are interposed by a chemical bonding effect such as a covalent bond, a hydrogen bond, or an intermolecular force. The interface is easy to improve the adhesion. The chemical treatment may be a roughening of the surface of the metal member of the insert, in which case the same anchoring effect as the physical treatment occurs, and the interface between the metal member of the insert and the resin member is more easily lifted. Sexuality.

Examples of the physical treatment include laser treatment, sandblasting (Japanese Patent Laid-Open Publication No. 2001-225346), and the like. A plurality of physical treatments may also be combined.

For the chemical treatment, for example, dry treatment such as corona discharge, triazine treatment (refer to Japanese Laid-Open Patent Publication No. 2000-218935), chemical etching (refer to Japanese Patent Laid-Open Publication No. 2001-225352), and anodizing treatment (Japanese special open 2010-64496), hydrazine treatment, and the like. In the case where the metal material constituting the insert metal member is aluminum, a warm water treatment (Japanese Patent Laid-Open No. Hei 8-142110) is also known. As warm water treatment, it can be exemplified by water impregnation at 100 ° C. 3 to 5 minutes. A plurality of chemical treatments may also be applied in combination.

[Resin member]

The resin member used in the present invention is composed of a poly(arylene sulfide) resin composition, and the insert is molded on the insert metal member.

[Method of Manufacturing Metal Resin Composite Molded Body]

The specific steps of the method for producing the metal-resin composite molded body are not particularly limited as long as at least a part of the surface of the insert metal member subjected to physical treatment and/or chemical treatment is passed through the insert metal member and the resin member. Adhesively, the insert metal member and the resin member may be integrated.

For example, an insert metal member in which at least a part of the surface is subjected to physical treatment and/or chemical treatment is disposed in a mold for injection molding, and the resin composition of the present invention is emitted in a molten state to the mold for injection molding. In the inside, a method of manufacturing a metal resin composite molded body in which an insert metal member and a resin member are integrated is manufactured. The conditions for the injection molding are not particularly limited, and appropriate preferable conditions can be set depending on the physical properties of the poly(arylene sulfide) resin and the like. Further, a method such as transfer molding or compression molding is also an effective method for forming a metal resin composite molded body in which an insert metal member and a resin member are integrated. In these methods, at least a part of the surface of the insert metal member that is in contact with the resin member is preferably all physically and/or chemically treated.

As another example, a resin member is produced by a general molding method such as a pre-extrusion molding method, and a physical member and/or a chemically treated insert metal member and the resin member are brought into contact with each other at a desired joint position. Heat is applied to the contact surface to melt the vicinity of the contact surface of the resin member, and the metal resin composite molded body in which the insert metal member and the resin member are integrated is produced. law. In this method, at least a part of the surface of the insert metal member that is in contact with the resin member is preferably all subjected to physical treatment and/or chemical treatment.

[Examples]

Hereinafter, the present invention will be specifically described by showing the examples and comparative examples, but the present invention is not limited to the examples.

A schematic diagram of the metal-resin composite molded body used in the examples and the comparative examples is shown in Fig. 1 . (a) is an exploded perspective view, (b) is an oblique view, and (c) is a view showing only a metal portion. This metal resin composite molding system was produced by the following method. Also, the unit of size on the way is mm.

<Modulation of Resin Composition>

The raw material components described below were dry-blended, and then placed in a biaxial extruder of a cylinder temperature of 320 ° C, and kneaded and kneaded to obtain a pelletized thermoplastic resin composition. The blending amount (parts by mass) of each component is shown in Tables 1 to 4.

‧Polyphenylene sulfide resin

A-1: FORTRON KPS W214A (product name), melt viscosity: 130Pa‧s (cutting speed: 1216 / sec, temperature: 310 ° C), manufactured by KUREHA

‧Epoxy-containing compounds

B-1: bisphenol A type epoxy resin, jER (former name "Epicoat", any of which is a registered trademark) 1004K (product name), epoxy group content: 4.6% by mass, epoxy equivalent 925, molecular weight: 1650, manufactured by Mitsubishi Chemical Corporation

‧Olefin-containing olefin copolymer

C-1: ethylene-glycidyl methacrylate-methyl acrylate copolymer, BOMDFAST 7L (product name), epoxy group content: 3% by mass, Sumitomo Chemical Corporation System

C-2: ethylene-glycidyl methacrylate-methyl acrylate copolymer, BONDFAST 7M (product name), epoxy group content: 6 mass%, manufactured by Sumitomo Chemical Co., Ltd.

C-3: ethylene-glycidyl methacrylate copolymer, BONDFAST E (product name), epoxy group content: 12% by mass, manufactured by Sumitomo Chemical Co., Ltd.

‧Polymer-free polymer recombination

C'-1: ethylene octene copolymer, Engage 8440 (product name), manufactured by DOW CHEMICAL Japan

C'-2: ethylene ethyl acrylate copolymer, NUC-6570 (product name), manufactured by Japan UNICAR Co., Ltd.

C'-3: Silicone elastomer, DY33-315 (product name), manufactured by TORAY‧DOW CORNING

‧Inorganic filler

D-1: Glass fiber, ECS 03T747 (product name), manufactured by Nippon Electric Glass Co., Ltd.

Further, the method for measuring the melt viscosity is as follows.

[melting viscosity]

A capillary rheometer manufactured by Toyo Seiki Co., Ltd. was used as a capillary tube, and 1 mm was used. ×20 mmL/flat fie, the melt viscosity of the crucible temperature of 310 ° C and the shear rate of 1216 / sec was measured.

<Physical treatment or chemical treatment of the insert metal member>

As the insert metal member, it is composed of copper (C-1100P, thickness 2 mm) or aluminum (A5052, thickness 2 mm), and is subjected to physical treatment as described below. A chemically treated plate. The plate-shaped insert metal members have a part of the joint faces shown by oblique lines in Fig. 1(a). In addition, in Tables 1 to 4, "physical", "chemical 1", and "chemical 2" refer to the following physical properties, chemical treatment 1 and chemical treatment 2, respectively.

[Physical processing]

For the insert metal member placed on the aluminum, a alumina honing machine having a particle size of #1000 (central particle diameter: 14.5 to 18 μm) was used at a concentration of 20% and a gauge pressure of 0.4 using a commercially available liquid honing machine. The condition of MPa is sprayed and roughened.

[Chemical treatment 1]

The surface of the copper insert member metal member was immersed in the etching liquid A (aqueous solution) having the following composition for 1 minute to remove the rust preventive film, and then etched with the etching liquid B (aqueous solution) having the following composition for 5 minutes to etch the surface of the metal member.

‧etching solution A (temperature 20 ° C)

‧ etching solution B (temperature 25 ° C)

[Chemical treatment 2]

The surface of the aluminum insert metal member was immersed in an alkali degreasing liquid (aqueous solution) having the following composition for 5 minutes to carry out degreasing treatment, followed by an etching liquid having the following composition C (aqueous solution) was immersed for 3 minutes to etch the surface of the metal part.

‧ Alkaline degreasing solution (temperature 40 ° C)

AS-165F (made by UD UDYLITE Co., Ltd.) 50ml/L

‧ etching solution C (temperature 40 ° C)

<Production of Metal Resin Composite Molded Body>

The insert metal member subjected to physical treatment and/or chemical treatment is disposed in a mold, and the insert metal member and the resin composition prepared by any of Examples 1 to 10 and Comparative Examples 1 to 12 are used. The resin member is subjected to an integrated integration step. The molding conditions are as follows. The shape of the metal resin composite molded body is as shown in FIG.

[forming conditions]

Forming machine: SODICK TR-40VR (longitudinal injection molding machine)

Barrel temperature: 320 ° C

Mold temperature: 150 ° C

Injection speed: 70mm/s

Pressure: 80MPa × 5 seconds

<Evaluation of Metal Resin Composite Shaped Body>

The metal-resin composite molded article produced by the above method was evaluated for the joint strength of the joined portion, the fracture form after peeling, and the peeling resistance. The specific evaluation method is as follows.

[joint strength]

A metal-resin composite molded body having the shape shown in Fig. 1, as shown in Fig. 2 The mold was placed on a pedestal (mold), and the mold was moved in such a manner that the insert metal member was pushed into the peeling resin member at a speed of 1 mm/min in the direction of the arrow. The strength at the time of peeling off the resin member from the insert metal member was measured as the joint strength. Further, as a measuring device, TENSILON UTA-50kN (manufactured by ORIENTEC Co., Ltd.) was used. The results of the measurements are shown in Tables 1 to 4 (the values are the average of 3 tests).

[destructive form]

After the joint strength was measured, the area of the joint portion was visually observed, and it was evaluated that only the interface between the insert metal member and the resin member was broken (interfacial peeling, indicated by ×), and it was generated at least in the resin member (aggregation failure, ◎ Express). The results are shown in Tables 1 to 4.

[Release resistance]

After the measurement of the joint strength, the side of the insert metal member in the region of the joint portion was visually observed, and the ratio of the area occupied by the resin member adhered to the insert metal member to the area of the entire joint portion was determined by the following criteria. Evaluation. The results are shown in Tables 1 to 4.

○: The above ratio was 50% or more, and the peeling resistance was good.

X: The above ratio is 20% or more and less than 50%, and the peeling resistance is not good.

××: The above ratio is less than 20%, and the peeling resistance is extremely poor.

<Other evaluation> [release]

In the production of the above-mentioned metal-resin composite molded article, the mold release property of the mold was evaluated on the basis of the following criteria. The results are shown in Tables 1 to 4.

○: The mold can be released without any problem, and the mold release property is good.

×: It is difficult to release the mold from the mold, and the mold release property is not good. Unable to engage the joint Evaluation of strength, fracture morphology after peeling, and peeling resistance.

[Stretching Deformation]

The resin composition prepared in any of Examples 1 to 10 and Comparative Examples 1 to 12 was measured for tensile fracture deformation based on ISO 527-1,2. The results are shown in Tables 1 to 4.

As shown in Table 1 and Table 2, (B) an epoxy group-containing compound and (C) an epoxy group-containing olefin-based copolymer were used in combination, and the epoxy group content in each of the components was adjusted to a predetermined range. In the metal-resin composite molded articles of Examples 1 to 10, the joint metal member and the resin member have strong joint strength and excellent peeling resistance.

As shown in Table 3, the metal-resin composite molded article of Comparative Example 2 in which (B) the epoxy group-containing compound was used instead of (C) the epoxy group-containing olefin-based copolymer was compared with Examples 1 to 10. The joint strength and peeling resistance are poor.

As shown in Tables 3 and 4, the metal-resin composite molded articles of Comparative Examples 1, 3, 6 and 7 in which (C) an epoxy group-containing olefin-based copolymer was used without using (B) an epoxy group-containing compound Compared with Examples 1 to 10, the joint strength and the peeling resistance were inferior.

As shown in Tables 3 and 4, the (B) epoxy group-containing compound was used instead of (C) the epoxy group-containing olefin copolymer, and the metal resin composites of Comparative Examples 4, 5, and 8 to 11 were used. The molded body was inferior in bonding strength and peeling resistance as compared with Examples 1 to 10.

Further, as shown in Table 4, even if (B) the epoxy group-containing compound and (C) the epoxy group-containing olefin copolymer are used in combination, the total epoxy group content in each of the components is in the total composition. The metal-resin composite molded article of Comparative Example 12, which was more than 0.4% by mass, was inferior in mold release property.

Claims (8)

A resin composition for a resin composition for insert molding on an insert metal member to which physical treatment and/or chemical treatment is applied, wherein the resin composition contains (A) polyarylene sulfide An ether resin, (B) an epoxy group-containing compound, and (C) an epoxy group-containing olefin-based copolymer, wherein the epoxy group-containing compound (B) has an epoxy group content of 0.01 to 0.1% in the total composition. 0.25 mass%, the epoxy group content of the (C) epoxy group-containing olefin-based copolymer is from 0.01 to 0.30% by mass in the total composition, and the epoxy group in the above (B) epoxy group-containing compound The content of the epoxy group in the epoxy group-containing olefin-based copolymer of the above (C) is 0.02 to 0.40% by mass in the total composition. The resin composition according to the first aspect of the invention, wherein the (B) epoxy group-containing compound is an epoxy resin. The resin composition according to the first aspect of the invention, wherein the (B) epoxy group-containing compound is a bisphenol type epoxy resin. The resin composition according to the first aspect of the invention, wherein the (C) epoxy group-containing olefin-based copolymer comprises a constituent unit derived from an α-olefin and a glycidyl ester derived from α,β-unsaturated acid. An olefin-based copolymer constituting a unit. According to the resin composition of the first aspect of the invention, the (C) epoxy group-containing olefin-based copolymer is an olefin-based copolymer further comprising a constituent unit derived from (meth) acrylate. The resin composition according to the first aspect of the invention, which further comprises 1 to 300 parts by mass of 100 parts by mass of the (A) poly(arylene sulfide) resin. (D) Inorganic filler. A metal resin composite molded body comprising an insert metal member, comprising the resin composition of any one of claims 1 to 6 and inserted into a resin member formed on the insert metal member, the insert At least a portion of the surface of the metal member that is in contact with the resin member is subjected to physical treatment and/or chemical treatment. A method for producing a metal resin composite molded body, wherein an insert metal member having at least a part of a reduced surface subjected to physical treatment and/or chemical treatment is prepared in a mold for forming and forming, and the patent application scope is first The resin composition according to any one of the above-mentioned items, wherein the resin composition is injected into the injection molding mold in a molten state, and the insert metal member and the resin member are integrated.