TWI634159B - Resin composition for insert molding, metal-resin composite molded body using the same, and manufacturing method thereof - Google Patents

Abstract

Provided are a resin composition for insert molding, which has strong bonding strength between a metal member and a resin member and imparts excellent peel resistance to a metal-resin composite molded article, a metal-resin composite molded article using the same, and a method for producing the same.

A resin composition, which is a resin composition for insert molding on a metal member of an insert subjected to physical treatment and / or chemical treatment, and the resin composition includes (A) a polyarylene sulfide resin. (B) an epoxy group-containing compound, (C) an epoxy group-containing olefin-based copolymer, and the epoxy group content in the (B) epoxy group-containing compound is 0.01 to 0.25 mass in the entire composition %, The epoxy group content in the epoxy group-containing olefin copolymer (C) is 0.01 to 0.3% by mass in the entire composition, and the total epoxy group content is 0.02 to 0.40 mass in the entire composition % Of resin composition.

Description

Resin composition for insert molding, metal-resin composite molded body using the same, and manufacturing method thereof

The present invention relates to a resin composition for insert molding, including a metal-resin composite molded body including a resin member, the resin member including the insert molded into the insert metal member subjected to physical treatment and / or chemical treatment. A resin composition, and a method for producing the metal-resin composite molded body.

The insert metal member made of metal or alloy and the resin member made of thermoplastic resin composition are integrated into a metal-resin composite molded body. Conventionally, it has been used as a console box around a dashboard. ) And other automotive interior components or parts around the engine, or parts that come into contact with the outside world, such as interior parts, interface connections of electronic devices such as digital cameras or mobile phones, and power terminals.

As a method for integrating the insert metal member and the resin member, a method of improving the adhesion between the insert metal member and the resin member by physically and / or chemically treating the joint surface on the insert metal member side, A method using an adhesive or a double-sided tape is to provide a fixing member such as a reverse folding piece or a gripper on the insert metal member and / or the resin member, a method of fixing the two using the fixing member, a method of joining using a screw, or the like. Among them, a method and application of applying a physical treatment and / or a chemical treatment to the joint surface of the insert metal member The method of the adhesive agent is effective in terms of designing the degree of freedom when the metal resin is attached to the composite body.

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

[Previous Technical Literature] [Patent Literature]

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

In the metal-resin composite molded body, full integration of the insert metal member and the resin member is practically necessary. Therefore, in the metal-resin-attached composite body, not only the bonding strength between the insert metal member and the resin member must be strong, but also the peeling between the insert metal member and the resin member is hard to occur.

An object of the present invention is to provide a resin composition for an insert between a metal member of a insert and a resin member, which has a strong bonding strength and imparts a peel resistance to a metal-resin composite molded article, and a metal-resin composite molding using the same Body, and its manufacturing method.

The present inventors have repeatedly researched in order to solve the above problems. As a result, it was found that by using an epoxy group-containing compound and an epoxy group-containing compound in combination The olefin-based copolymer is a resin composition in which the epoxy group content in each component is adjusted to a predetermined range, the above-mentioned problem is 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 subjected to a physical treatment and / or a chemical treatment, wherein the resin composition includes (A) a polyarylene sulfide resin, and (B) The epoxy group-containing compound and (C) the epoxy group-containing olefin-based copolymer, the epoxy group content in the (B) epoxy group-containing compound is 0.01 to 0.25% by mass in the entire composition, and the aforementioned ( C) The epoxy group content in the epoxy-containing olefin-based copolymer is 0.01 to 0.3% by mass in the entire composition, and the epoxy group content in the (B) epoxy group-containing compound and (C) The total amount of epoxy groups in the epoxy-based olefin-based copolymer is 0.02 to 0.40% by mass of the resin composition in the entire composition.

(2) The epoxy group-containing compound (B) is a resin composition according to (1) of an epoxy resin.

(3) The said (B) epoxy group containing compound is the resin composition as described in (1) or (2) of a bisphenol epoxy resin.

(4) The (C) epoxy group-containing olefin-based copolymer is one of olefin-based copolymers containing a constituent unit derived from an α-olefin and a constituent unit derived from a glycidyl ester of an α, β-unsaturated acid ( 1) The resin composition according to any one of (3).

(5) The epoxy group-containing olefin-based copolymer (C) described in any one of (1) to (4), further comprising an olefin-based copolymer derived from a (meth) acrylate-containing constituent unit Resin composition.

(6) Further, with respect to (A) the polyarylene sulfide resin 100 The mass part contains 1 to 300 mass parts of the resin composition described in any one of (1) to (5) of the (D) inorganic filler.

(7) A metal member including an insert metal member and a resin member including the resin composition described in any one of (1) to (6) and having an insert formed on the insert metal member, wherein the insert metal member and At least a part of the surfaces where the resin members are in contact with each other is a metal-resin composite formed body that is subjected to physical treatment and / or chemical treatment.

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

According to the present invention, a resin composition for insert molding and a metal-resin composite using the same can be provided between the insert metal member and the resin member, the metal resin composite molded body having strong bonding strength and excellent peel resistance is provided. Shaped body.

[Fig. 1] Fig. 1 is a schematic diagram showing a metal-resin composite molded body used in Examples and Comparative Examples, (a) is an exploded perspective view, (b) is an oblique view, and (c) is a view showing only a metal part. Illustration.

[Fig. 2] Fig. 2 is a schematic diagram showing a method for measuring a joint strength between a resin portion and a metal portion performed in an example.

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

<Resin composition>

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

[(A) Polyarylene sulfide resin]

The (A) polyarylene sulfide resin is not particularly limited, and a conventionally known polyarylene sulfide resin can be used. As (A) the polyarylene sulfide resin, a polyphenylene sulfide (PPS) resin is preferably used. (A) Polyarylene sulfide resin can be used individually by 1 type or in combination of 2 or more types.

(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, particularly preferred is 10 to 200Pa‧s.

[(B) Epoxy-containing compound]

The (B) epoxy group-containing compound is not particularly limited as long as it is an epoxy group-containing compound other than the epoxy group-containing olefin copolymer (C) described later. (B) An epoxy group-containing compound can be used individually by 1 type or in combination of 2 or more types.

(B) The compound containing an epoxy group may be a compound containing one epoxy group in one molecule, or a compound containing two or more epoxy groups in one molecule. (B) The epoxy group-containing compound can be classified into epoxy resins and other epoxy group-containing compounds. For example, bisphenol A and cyclic Bisphenol-type epoxy resin obtained by epichlorohydrin reaction, phenol-type epoxy resin obtained by reaction of phenol resin with epichlorohydrin, polyglycidyl esters obtained by reaction of polycarboxylic acid with epichlorohydrin, Alicyclic compound type epoxy resin obtained from alicyclic compounds, glycidyl ethers obtained by reacting aliphatic compounds having alcoholic hydroxyl groups with epichlorohydrin, epoxidized butadiene, compounds having double bonds and fruit oxides The epoxy compound obtained by the reaction. Specific examples include bisphenol A epoxy resin, methyl glycidyl ether, phenyl glycidyl ether, glycidyl esters of various fatty acids, diethylene glycol diglycidyl ether, phthalic acid diglycidyl ester, and Diglycidyl hydropeptide, epoxidized polybutadiene, epoxidized SBS, etc. Among these, from the viewpoints of quality stability (reaction stability with polyarylene sulfide resin), excellent operability, and environmental sanitation (non-mutagenicity), epoxy resins are preferred, and particularly, Bisphenol A epoxy resin such as bisphenol A epoxy resin.

(B) The content of the epoxy group-containing compound is generally 0.01 to 0.25% by mass, preferably 0.01 to 0.20% by mass, based on the content of the epoxy group in the (B) epoxy group-containing compound. The amount. When the epoxy group content is less than 0.01% by mass in the entire composition, the peel resistance between the insert metal member and the resin member is liable to decrease. In particular, when the insert is molded, interfacial peeling tends to occur at the flowing end of the resin composition in a molten state. On the other hand, when the epoxy content is more than 0.25% by mass in the entire composition, the mold release property during insert molding tends to be deteriorated, it is difficult to obtain the intended molded product, or it is not good in terms of easy productivity reduction. .

[(C) Epoxy-based olefin-based copolymer]

(C) The olefin-based copolymer containing an epoxy group is not particularly limited. (C) Contains The epoxy-based olefin copolymer may be used singly or in combination of two or more kinds.

Examples of the (C) epoxy-containing olefin-based copolymer include an olefin-based copolymer including a constituent unit derived from an α-olefin and a constituent unit derived from a glycidyl ester of an α, β-unsaturated acid. Among these, since an excellent metal-resin composite molded body can be obtained, an olefin-based copolymer further containing a constituent unit derived from (meth) acrylate is preferable. In addition, hereinafter, a (meth) acrylic acid ester may be called an (meth) acrylic acid ester. For example, glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate. In addition, 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, and butene, and ethylene is particularly preferable. The α-olefin may be used singly or in combination of two or more kinds. (C) The epoxy-containing olefin-based copolymer contains a constituent unit of the source α-olefin, and is easy to impart flexibility to the resin member. The flexibility imparts to the resin member to be softened, and contributes to the insert metal member and the Improvement of bonding strength between resin members.

The glycidyl ester of an α, β-unsaturated acid is not particularly limited, and examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferable. Glyceride. The glycidyl ester of an α, β-unsaturated acid may be used alone or in combination of two or more. Since (C) the olefin-based copolymer containing an epoxy group 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 is easily obtained.

It does not specifically limit as (meth) acrylate, For example, it is listed For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate and other acrylates; methyl methacrylate, ethyl methacrylate, methyl Methacrylates such as n-propyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, and n-octyl methacrylate. Among them, methyl acrylate is particularly preferred. (Meth) acrylic acid esters may be used individually by 1 type, and may use 2 or more types together. The (meth) acrylic acid-derived constituent unit contributes to improvement in the bonding strength between the insert metal member and the resin member.

An olefin-based copolymer containing a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid, and an olefin-based copolymer further containing a structural unit derived from a (meth) acrylate The copolymer can be produced by copolymerization by a conventionally known method. For example, the above-mentioned copolymer can be obtained by performing 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. The olefin-based copolymer is, for example, polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly 2-ethylhexyl acrylate, poly Styrene, polyacrylonitrile, acrylonitrile · styrene copolymer, butyl acrylate · styrene copolymer, etc. may also be chemically bonded olefin-based random copolymers with branched or crosslinked structures.

The olefin-based copolymer used in the present invention may contain constituent units derived from other copolymerization components within a range that does not impair the effects of the present invention.

More specifically, as (C) an epoxy-group-containing olefin copolymer, a glycidyl methacrylate modified ethylene copolymer, a glycidyl ether modified ethylene copolymer, etc. are mentioned, for example, Glycidol Methacrylate modified vinyl copolymer.

Examples of the glycidyl methacrylate-modified ethylene-based copolymer include a glycidyl water-based methacrylate graft-modified ethylene polymer, an ethylene-glycidyl methacrylate copolymer, and an ethylene-glycidyl group. Methacrylate-methyl acrylate copolymer. Among them, especially since an excellent metal resin composite molded body can be obtained, ethylene-glycidyl methacrylate copolymer and ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable, and 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.) and the like.

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, (C) The epoxy group content of the epoxy-group-containing olefin-based copolymer in the entire composition, usually 0.01 to 0.30% by mass, preferably Amount from 0.03 to 0.25% by mass. When the above-mentioned epoxy group content is less than 0.01% by mass in the entire composition, the bonding strength between the insert metal member and the resin member is liable to decrease. The adhesion between the insert metal member and the resin member is affected by the difference in linear expansion between these members. (C) The epoxy group-containing olefin-based copolymer can achieve stress relaxation and small deformation. It is believed that the above-mentioned bonding strength is improved. Stress relaxation is effective for toughness, and toughness can be evaluated by stretching. When the content of the epoxy group-containing olefin-based copolymer (C) as an elastomer function is small, the stretching is small, and a sufficient stress relaxation effect cannot be obtained. On the other hand, when the epoxy group content exceeds 0.3% by mass in the entire composition, the insert becomes The demoldability at the time of forming tends to be poor, or there is a tendency to generate more gas, and the frequency of mold maintenance tends to increase, which is not good.

The total content of the epoxy group content in the (B) epoxy group-containing compound and the epoxy group content in the (C) epoxy group-containing olefin copolymer is generally 0.02 to 10,000 in the entire composition. 0.40 mass%, preferably 0.03 to 0.30 mass%, and more preferably 0.035 to 0.25% by mass. When the total is more than 0.40% by mass, it is not preferable from the point that the mold release of the obtained molded body is likely to deteriorate. The lower limit of the total is the sum of the lower limit of the epoxy group content in the epoxy group-containing compound (B) and the lower limit of the epoxy group content in the epoxy group-containing olefin copolymer (C).

[(D) Inorganic filler]

The resin composition of the present invention may contain (D) an inorganic filler. By adding the (D) inorganic filler to the resin composition of the present invention, the mechanical strength of the obtained resin composition is easily improved. (D) The inorganic filler is not particularly limited, and examples thereof include conventionally known ones. (D) The shape of the inorganic filler is not particularly limited, and may be fibrous, or non-fibrous, such as spherical, powdery, plate-like, scaly, or irregular, preferably fibrous. Examples of the (D) inorganic filler include glass fibers, spherical silica, and glass beads. Among these, glass fiber is preferred. (D) An inorganic filler can be used individually by 1 type or in combination of 2 or more types.

The content of the (D) inorganic filler is usually 1 to 300 parts by mass, and preferably 25 to 250 parts by mass, with respect to 100 parts by mass of the (A) polyarylene sulfide resin. When the content is less than 1 part by mass, the effect of the resin composition of the present invention by adding the (D) inorganic filler cannot be exhibited. When the content is more than 300 parts by mass, it is not preferable from the point that the joint strength between the insert metal member and the resin member is likely to decrease, or the fluidity during insert molding is liable to decrease.

[Other ingredients]

In addition to the above components, the resin composition of the present invention may contain an organic filler, a flame retardant, an ultraviolet absorber, a heat stabilizer, and light in order to impart desired physical properties in a range that does not impair the effects of the present invention. Stabilizer, colorant, carbon black, release agent, plasticizer and other additives.

[Manufacturing method of 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 appropriately selected from conventionally known methods for producing resin compositions. For example, a method of melt-kneading each component using a single-axis or dual-axis extruder, etc., and extruding, and then processing the obtained resin composition into a desired form such as a powder, a tablet, or a pellet, can be mentioned.

<Metal Resin Composite Molded Body>

The metal-resin composite molding system of the present invention includes an insert metal member and a resin member including the resin composition of the present invention and insert-molded on the above-mentioned insert metal member. At least a part of a surface where the insert metal member is in contact with the resin member is subjected to physical treatment and / or chemical treatment. Since the metal-resin composite molded article of the present invention is a combination of (B) an epoxy group-containing compound and (C) an olefin-based copolymer containing an epoxy group, the epoxy group content in each of these components is adjusted to be A resin composition in a predetermined range has strong bonding strength between the insert metal member and the resin member, and has excellent peel resistance.

Due to the above-mentioned characteristics, the metal-resin composite molded article of the present invention can be suitably used in applications requiring both bonding strength and peel resistance, and having excellent adhesion between the insert metal member and the resin member. For example, the metal-resin composite molded article of the present invention is suitable for being easily affected by the influence of humidity or moisture. The electrical and electronic parts are equal to the metal-resin composite formed body. In particular, it is estimated to be used in a field requiring a high degree of waterproofing, for example, in rivers, swimming pools, ski resorts, bathhouses, etc., and it is suitable as a component for electric or electronic equipment related to failure due to intrusion of moisture or moisture. In addition, the metal-resin composite molded article of the present invention is also used, for example, as a housing for electric and electronic equipment including a resin-made shaft sleeve or a holding member. In this article, as the housing for electrical and electronic equipment, in addition to mobile phones, the housings of portable imaging electronic equipment such as cameras, photo-integrated cameras, and digital cameras can be cited, including notebook computers, pocket computers, computers, and electronics. Notepad, PDC, PHS, mobile phone and other portable information or communication mid-range housings, MD, cassette stereo Walkman, radio and other portable audio electronic equipment housings, LCD TV, LCD screen, telephone, fax Housings for home telephones such as mobile phones and handheld scanners.

[Insert metal member]

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

The metal material constituting the metal member of the insert is not particularly limited, and examples thereof include at least one selected from the group consisting of copper, copper alloy, aluminum, aluminum alloy, and 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 having a desired shape, an insert metal member having a desired shape can be obtained. In addition, in order to shape the insert metal member into a desired shape, a cutting process using a work machine or the like may be used.

The surface of the insert metal member obtained as described above is subjected to physical treatment and / or chemical treatment. The position where the physical treatment and / or chemical treatment is performed, or the size of the treatment range, is determined in consideration of the position where the resin member is formed, and the like.

The physical treatment and chemical treatment are not particularly limited, and conventional physical treatments and chemical treatments can be used. By physical treatment, the surface of the insert metal member is roughened, and holes are formed in the roughened area. An anchoring effect of the resin composition constituting the resin member occurs, and the interface between the insert metal member and the resin member is easy. Improve adhesion. On the other hand, due to the chemical treatment, a chemical bonding effect such as covalent bond, hydrogen bond, or intermolecular force is imparted between the insert metal member and the insert-molded resin member. The interface is easy to improve adhesion. Chemical treatment can also be accompanied by roughening of the surface of the insert metal member. In this case, the same anchoring effect as physical treatment occurs, and the interface between the insert metal member and the resin member is more likely to improve the density.着 性。 Sex.

Examples of the physical treatment include laser treatment, sandblasting (Japanese Patent Laid-Open No. 2001-225346), and the like. Multiple physical treatments may be applied in combination.

Examples of the chemical treatment include dry treatment such as corona discharge, triazine treatment (see Japanese Patent Laid-Open No. 2000-218935), chemical etching (see Japanese Patent Laid-Open No. 2001-225352), and anodizing (Japanese Patent Laid-Open No. 2010-64496), hydrazine treatment, etc. When the metal material constituting the metal member of the insert is aluminum, warm water treatment (Japanese Patent Application Laid-Open No. 8-142110) can also be cited. Examples of the warm water treatment include immersion in water at 100 ° C. 3 to 5 minutes. A plurality of chemical treatments may be applied in combination.

[Resin member]

The resin member used in the present invention is composed of a polyarylene sulfide resin composition, and the insert is formed on the insert metal member.

[Manufacturing method of metal resin composite molded article]

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

For example, an insert metal member having at least a part of its surface subjected to physical treatment and / or chemical treatment is arranged in a mold for injection molding, and the resin composition of the present invention is injected in a molten state into the mold for injection molding. Method of manufacturing a metal-resin composite molded body in which the insert metal member and the resin member are integrated. The conditions for the injection molding are not particularly limited, and suitable preferable conditions can be set according to the physical properties of the polyarylene sulfide resin and the like. Furthermore, methods such as transfer molding and compression molding are also effective methods for forming a metal-resin composite formed body in which the insert metal member and the resin member are integrated. In these methods, at least a part, preferably all, of a surface where the insert metal member and the resin member are in contact with each other is subjected to physical and / or chemical treatment.

As another example, a resin member may be manufactured by a general molding method such as a pre-injection molding method, and the insert metal member subjected to physical treatment and / or chemical treatment and the resin member may be connected at a desired joining position. Apply heat to the contact surface to melt the vicinity of the contact surface of the resin member to produce a metal-resin composite molded body in which the insert metal member and the resin member are integrated. law. In this method, at least a part, and preferably all, of a surface where the insert metal member and the resin member are in contact with each other is subjected to a physical treatment and / or a chemical treatment.

[Example]

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

A schematic diagram of a metal-resin composite molded body used in Examples and 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. The unit of dimension in the figure is mm.

<Preparation of resin composition>

The following raw material ingredients were dry-blended, and then charged into a biaxial extruder with a barrel temperature of 320 ° C. and melt-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 (shear speed: 1216 / sec, temperature: 310 ° C), manufactured by KUREHA

‧Epoxy-containing compounds

B-1: Bisphenol A epoxy resin, jER (formerly known as "Epicoat", either of which is a registered trademark) 1004K (product name), epoxy content: 4.6% by mass, epoxy equivalent 925, molecular weight: 1650, manufactured by Mitsubishi Chemical Corporation

‧Epoxy-based olefin copolymer

C-1: ethylene-glycidyl methacrylate-methyl acrylate copolymer, BOMDFAST 7L (product name), glycidyl methacrylate content: 3 mass %, Made by Sumitomo Chemical Co., Ltd.

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

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

‧ Non-epoxy-containing polymer

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

C’-2: ethylene ethyl acrylate copolymer, NUC-6570 (product name), made by UNICAR Japan

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.

The method for measuring the melt viscosity is as follows.

[Melting viscosity]

A capillary rheometer (capillograph) manufactured by Toyo Seiki Co., Ltd. was used, and a capillary was used at 1 mm. × 20 mmL / flat die, melt viscosity at a temperature of 310 ° C. and a shear rate of 1216 / sec.

<Physical or chemical treatment of insert metal member>

As the insert metal member, copper (C-1100P, thickness 2mm) or aluminum (A5052, thickness 2mm) is used, and is subjected to physical treatment as described below. Biochemically treated plate. These plate-shaped insert metal members have a part of joint surfaces shown by diagonal lines in FIG. 1 (a). In Tables 1 to 4, "Physics", "Chemistry 1", and "Chemistry 2" refer to the following physical properties, chemical properties 1, and chemical properties 2, respectively.

[Physical treatment]

A commercially available liquid honing machine was used for the metal member of the insert on the aluminum, and an alumina abrasive having a particle size of # 1000 (center particle size: 14.5 to 18 μm) was used at a concentration of 20% and a gauge pressure of 0.4 Spray at MPa and roughen it.

[Chemical treatment 1]

The surface of the copper insert metal member was immersed in the etching solution A (aqueous solution) of the following composition for 1 minute to remove the rust-proof film, and the etching solution B (aqueous solution) of the following composition was immersed for 5 minutes to etch the surface of the metal part.

‧Etching solution A (temperature 20 ℃)

‧Etching solution B (temperature 25 ℃)

[Chemical treatment 2]

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

‧Alkali degreasing solution (temperature 40 ℃)

AS-165F (manufactured by EBARA UDYLITE) 50ml / L

‧Etching solution C (temperature 40 ℃)

<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 one of Examples 1 to 10 and Comparative Examples 1 to 12 are prepared. The resin member is integrated into the integration step. The molding conditions are as follows. The shape of the metal-resin composite molded body is shown in FIG. 1.

[Forming conditions]

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

Barrel temperature: 320 ℃

Mold temperature: 150 ℃

Injection speed: 70mm / s

Holding pressure: 80MPa × 5 seconds

<Evaluation of Metal Resin Composite Molded Body>

In the metal-resin composite molded article produced by the above method, the joint strength of the joint portion, the fracture form after peeling, and peel resistance were evaluated. The specific evaluation method is described below.

[Joint Strength]

A metal-resin composite formed body having the shape shown in FIG. 1 is shown in FIG. 2. Type, it is arranged on a pedestal (mold), and the mold is moved so that the peeling resin member is pushed in by the insert metal member at a speed of 1 mm / minute in the direction of the arrow. The strength when the resin member was peeled from the insert metal member was measured as the joint strength. As a measuring device, TENSILON UTA-50kN (manufactured by ORIENTEC) was used. The measurement results are shown in Tables 1 to 4 (values are the average of 3 tests).

[Destruction pattern]

After the joint strength was measured, the area of the joint was visually observed, and only the interface between the insert metal member and the resin member was damaged (interface peeling, indicated by ×), and whether a small amount of resin adhered to the insert metal member (aggregation) Destruction, indicated by ◎). The results are shown in Tables 1 to 4.

[Peel resistance]

After measuring the joint strength, the side of the insert metal member in the area of the joint is visually observed, and the ratio of the area occupied by the resin member attached to the insert metal member to the area of the entire area of the joint is determined, based on the following criteria Evaluation. The results are shown in Tables 1 to 4.

(Circle): The said ratio is 50% or more, and peeling resistance is favorable.

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

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

<Other evaluations>

[Releasability]

When the metal-resin composite molded article was produced, 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 from the mold without any problem, and the mold release property is good.

×: It was difficult to release the mold from the mold, and the release property was poor. Inability to join Evaluation of strength, morphology after peeling, and peel resistance.

[Tensile failure deformation]

The resin compositions prepared in any of Examples 1 to 10 and Comparative Examples 1 to 12 were measured for tensile fracture deformation in accordance with ISO 527-1,2. The results are shown in Tables 1 to 4.

As shown in Tables 1 and 2, when (B) an epoxy group-containing compound and (C) an olefin-based copolymer containing an epoxy group are used in combination, the epoxy group content in each of these components is adjusted to a predetermined range. In the metal-resin composite molded bodies of Examples 1 to 10, the insert metal member and the resin member have strong bonding strength and excellent peel resistance.

As shown in Table 3, the metal-resin composite molded article of Comparative Example 2 using (B) an epoxy-containing compound instead of (C) an olefin-based copolymer is compared with Examples 1 to 10 , Poor bonding strength and peel resistance.

As shown in Tables 3 and 4, the metal-resin composite moldings of Comparative Examples 1, 3, 6, and 7 using (C) an epoxy-group-containing olefin-based copolymer and not (B) an epoxy-group-containing compound are used. Compared with Examples 1 to 10, the bonding strength and peel resistance were poor.

As shown in Tables 3 and 4, the metal resin composites of Comparative Examples 4, 5, and 8 to 11 in which (B) an epoxy group-containing compound was used instead of (C) an epoxy-group-containing olefin-based copolymer were used. Compared with Examples 1 to 10, the molded body had lower bonding strength and peel resistance.

As shown in Table 4, even if (B) an epoxy-group-containing compound and (C) an epoxy-group-containing olefin copolymer are used in combination, the total epoxy group content in each of these components is included in the total composition. The metal-resin composite molded article of Comparative Example 12 exceeding 0.4% by mass had poor releasability.

Claims (6)

A resin composition which is a resin composition for insert molding on an insert metal member subjected to physical treatment and / or chemical treatment, wherein the resin composition includes (A) polyarylene sulfide Ether resin, (B) an epoxy group-containing compound, and (C) a constituent unit derived from α-olefin, a constituent unit derived from α, β-unsaturated glycidyl ester, and (meth) acrylic acid derived The olefin-based copolymer of the constituent unit of the ester, the constituent unit derived from the (meth) acrylate is selected from methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate. 1 or 2 or more of the group consisting of N-butyl methacrylate, iso-butyl methacrylate, n-hexyl methacrylate, n-pentyl methacrylate, and n-octyl methacrylate are derived from ( (Meth) acrylic acid ester constituting unit, wherein the epoxy group content in the epoxy group-containing compound (B) is 0.092 to 0.25% by mass in the entire composition, and the (C) includes a α-olefin-derived unit , Derived from the structural units of α, β-unsaturated glycidyl esters, and The epoxy group content in the olefin-based copolymer derived from the (meth) acrylate constituting unit is 0.01 to 0.30% by mass in the entire composition, and the epoxy group content in the (B) epoxy group-containing compound is The total of the epoxy group content in the epoxy group-containing olefin copolymer (C) is 0.102 to 0.40% by mass in the entire composition. The resin composition according to item 1 of the patent application range, wherein the (B) epoxy group-containing compound is an epoxy resin. The resin composition according to item 1 of the scope of patent application, wherein the compound (B) containing an epoxy group is a bisphenol epoxy resin. The resin composition according to item 1 of the patent application scope, further comprising (D) an inorganic filler in an amount of 1 to 300 parts by mass with respect to 100 parts by mass of the (A) polyarylene sulfide resin. A metal-resin composite formed body comprising an insert metal member and a resin member composed of the resin composition according to any one of claims 1 to 4 and insert-molded on the insert metal member, At least a part of a surface of the insert metal member that is in contact with the resin member is subjected to a physical treatment and / or a chemical treatment. A method for manufacturing a metal-resin composite formed body, comprising insert metal members having at least a part of a surface subjected to physical treatment and / or chemical treatment in a mold for injection molding. The integration step of injecting the resin composition of any one of 4 items into the injection molding mold in a molten state, and integrating the insert metal member and the resin member.