JP2014208444A - Resin composition for insert molding, metal resin composite molding using the same, and production method thereof - Google Patents

Abstract

A resin composition for insert molding that gives a metal resin composite molded body having high bonding strength and excellent peel resistance between an insert metal member and a resin member, and a metal resin composite molded body using the same And a method for manufacturing the same. A resin composition for insert molding on an insert metal member subjected to physical treatment and / or chemical treatment, the resin composition comprising: (A) a polyarylene sulfide resin; (B) an epoxy group-containing compound and (C) an epoxy group-containing olefin-based copolymer, and the epoxy group content in the (B) epoxy group-containing compound is 0.01-0. The epoxy group content in the (C) epoxy group-containing olefin copolymer is 0.01 to 0.3% by mass in the total composition, and the total of the epoxy group contents is all The resin composition which is 0.02-0.40 mass% in a composition. [Selection figure] None

Description

  The present invention provides a resin composition for insert molding, a metal resin composite molded body comprising a resin member made of the above resin composition insert-molded on an insert metal member subjected to physical treatment and / or chemical treatment, The present invention also relates to a method for producing the metal resin composite molded body.

  Conventionally, a metal-resin composite molded body in which an insert metal member made of metal, an alloy, etc. and a resin member made of a thermoplastic resin composition are integrated has been conventionally used for automobiles such as console boxes around instrument panels. It is used for parts that come into contact with the outside world, such as interior parts, parts around the engine, interior parts, interface connection parts of electronic devices such as digital cameras and mobile phones, and power terminal parts.

  As a method of 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 performing physical treatment and / or chemical treatment on the joint surface on the insert metal member side. , A method of adhering using an adhesive or a double-sided tape, a method of providing a fixing member such as a folded piece or a nail on an insert metal member and / or a resin member, and fixing both using the fixing member, using a screw or the like There is a method of joining. Among these, the method of performing physical treatment and / or chemical treatment on the joint surface on the insert metal member side and the method of using an adhesive are effective in terms of the degree of freedom when designing the metal resin composite molded body. .

  In particular, the method of performing physical treatment and / or chemical treatment on the joint surface on the insert metal member side is advantageous in that an expensive adhesive is not used. As a method for performing physical treatment and / or chemical treatment on the joint surface on the insert metal member side, for example, a method described in Patent Document 1 can be mentioned. This method is a method of forming a rough surface with a laser in a desired range on the surface of the insert metal member.

JP 2010-167475 A

  In the metal-resin composite molded body, it is practically necessary that the insert metal member and the resin member are sufficiently integrated. Therefore, the metal-resin composite molded body is required not only to have a strong bonding strength between the insert metal member and the resin member, but also to hardly cause peeling between the insert metal member and the resin member.

  An object of the present invention is to provide a resin composition for insert molding that provides a metal resin composite molded body having high bonding strength and excellent peel resistance between an insert metal member and a resin member, and a metal resin composite using the same It is providing the molded object and its manufacturing method.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, the above problem is solved by a resin composition in which an epoxy group-containing compound and an epoxy group-containing olefin copolymer are used in combination, and the epoxy group content in each of these components is adjusted to a predetermined range. The headline and the present invention were completed. More specifically, the present invention provides the following.

  (1) A resin composition for insert molding on an insert metal member that has been subjected to physical treatment and / or chemical treatment, wherein the resin composition comprises (A) polyarylene sulfide resin, B) an epoxy group-containing compound and (C) an epoxy group-containing olefin copolymer, and the epoxy group content in the (B) epoxy group-containing compound is 0.01 to 0.25 in the total composition. The epoxy group content in the (C) epoxy group-containing olefin copolymer is 0.01 to 0.30% by mass in the total composition, and the (B) epoxy group-containing compound The resin composition whose sum total of epoxy group content and the epoxy group content in said (C) epoxy group containing olefin type copolymer is 0.02-0.40 mass% in all the compositions.

  (2) The resin composition according to (1), wherein the (B) epoxy group-containing compound is an epoxy resin.

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

  (4) The (C) epoxy group-containing olefin copolymer is an olefin 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 ( The resin composition according to any one of 1) to (3).

  (5) The (C) epoxy group-containing olefin copolymer is an olefin copolymer further comprising a structural unit derived from a (meth) acrylic acid ester, according to any one of (1) to (4). Resin composition.

  (6) The resin composition according to any one of (1) to (5), further including 1 to 300 parts by mass of (D) an inorganic filler with respect to 100 parts by mass of (A) polyarylene sulfide resin.

  (7) An insert metal member and a resin member made of the resin composition according to any one of (1) to (6), and insert-molded on the insert metal member, A metal resin composite molded body in which at least a part of a surface in contact with the resin member is subjected to physical treatment and / or chemical treatment.

  (8) An insert metal member having at least a part of the surface subjected to physical treatment and / or chemical treatment is disposed in an injection mold, and the resin according to any one of (1) to (6) A method for producing a metal-resin composite molded body, comprising an integration step of injecting the composition into a mold for injection molding in a molten state and integrating the insert metal member with a resin member.

  ADVANTAGE OF THE INVENTION According to this invention, between the insert metal member and the resin member, the resin composition for insert molding which gives the metal resin composite molded object which is strong in joining strength and is excellent in peeling resistance, and metal resin composite using the same A molded body can be provided.

FIG. 1 is a diagram schematically 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. It is a figure which shows only a part. FIG. 2 is a diagram schematically illustrating a method for measuring the bonding strength between the resin portion and the metal portion, performed in the example.

  Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.

<Resin composition>
The resin composition according to the present invention is for insert molding on an insert metal member that has been subjected to physical treatment and / or chemical treatment. (A) Polyarylene sulfide resin and (B) Epoxy A group-containing compound, and (C) an epoxy group-containing olefin copolymer. Hereinafter, each component contained in the resin composition will be described.

[(A) Polyarylene sulfide resin]
(A) It does not specifically limit as polyarylene sulfide resin, A conventionally well-known polyarylene sulfide resin can be used. As (A) polyarylene sulfide resin, 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) Since polyarylene sulfide resin provides better adhesion between the insert metal member and the resin member, the melt viscosity at a shear rate of 1216 / sec, measured at 310 ° C., is 8 to 300 Pa · s. Is preferable, and 10 to 200 Pa · s is particularly preferable.

[(B) Epoxy group-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 (C) epoxy group-containing olefin copolymer 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 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. (B) Epoxy group-containing compounds can be broadly classified into epoxy resins and other epoxy group-containing compounds. For example, bisphenol-type epoxy resins obtained by reacting bisphenol A and epichlorohydrin, novolak resins and epichlorohydrins Novolak type epoxy resin obtained by reacting polycarboxylic acid and polyglycidyl esters obtained by reacting epichlorohydrin, alicyclic compound type epoxy resin obtained from alicyclic compound, aliphatic compound having alcoholic hydroxyl group and Examples thereof include glycidyl ethers obtained by reacting with epichlorohydrin, epoxidized butadiene, and epoxy compounds obtained by reacting a compound having a double bond with a peroxide. Specific examples include bisphenol A type epoxy resins, methyl glycidyl ether, phenyl glycidyl ether, various fatty acid glycidyl esters, diethylene glycol diglycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, epoxidized polybutadiene, epoxidation SBS etc. are mentioned. Of these, epoxy resins are preferred from the viewpoints of quality stability (stability of reaction with polyarylene sulfide resin), good handling properties, environmental hygiene (no mutagenicity), and in particular, bisphenol A type. Bisphenol type epoxy resins such as epoxy resins are preferred.

  The content of the (B) epoxy group-containing compound is such that the epoxy group content in the (B) epoxy group-containing compound is usually 0.01 to 0.25% by mass in the entire composition, preferably 0.01 to The amount is 0.20% by mass. When the epoxy group content is less than 0.01% by mass in the total composition, the peel resistance between the insert metal member and the resin member tends to be lowered. In particular, interfacial peeling is likely to occur at the flow end of the resin composition in a molten state during insert molding. On the other hand, if the epoxy group content is more than 0.25% by mass in the total composition, the releasability at the time of insert molding is likely to deteriorate, so that it is difficult to obtain the desired molded product, or the productivity tends to decrease. It is not preferable in terms.

[(C) Epoxy group-containing olefin copolymer]
(C) The epoxy group-containing olefin copolymer is not particularly limited. (C) Epoxy group containing olefin type copolymer can be used individually by 1 type or in combination of 2 or more types.

  Examples of the (C) epoxy group-containing olefin copolymer include an olefin copolymer including a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid. Among them, an olefin copolymer containing a structural unit derived from (meth) acrylic acid ester is more preferable because a particularly excellent metal resin composite molded body can be obtained. Hereinafter, (meth) acrylic acid ester is also referred to as (meth) acrylate. For example, glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate. In this specification, “(meth) acrylic acid” means both acrylic 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 ethylene is particularly preferable. The α-olefin can be used alone or in combination of two or more. (C) Since the epoxy group-containing olefin copolymer contains a structural unit derived from α-olefin, flexibility is easily imparted to the resin member. The softening of the resin member due to the provision of flexibility contributes to the improvement of the bonding strength between the insert metal member and the resin member.

  The glycidyl ester of 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. The glycidyl ester of α, β-unsaturated acid can be used alone or in combination of two or more. (C) When the epoxy group-containing olefin copolymer contains a glycidyl ester of α, β-unsaturated acid, an effect of improving the bonding strength between the insert metal member and the resin member is easily obtained.

  The (meth) acrylic acid ester is not particularly limited. For example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid-n-hexyl, acrylic Acrylic acid esters such as acid-n-octyl; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid-n-amyl, methacrylic acid And methacrylates such as -n-octyl. Of these, methyl acrylate is particularly preferable. The (meth) acrylic acid ester can be used alone or in combination of two or more. The structural unit derived from (meth) acrylic acid ester contributes to the improvement of the joining strength between the insert metal member and the resin member.

  Olefin copolymer containing a structural unit derived from α-olefin and a structural unit derived from a glycidyl ester of α, β-unsaturated acid, and an olefin copolymer containing a structural unit derived from (meth) acrylic acid ester The coalescence can be produced by performing copolymerization by a conventionally known method. For example, the copolymer can be obtained by performing copolymerization by a generally well-known radical polymerization reaction. The type of copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer. Examples of the olefin copolymer include polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyacrylate-2-ethylhexyl, polystyrene, polyacrylonitrile. An olefin-based graft copolymer in which acrylonitrile / styrene copolymer, butyl acrylate / styrene copolymer, or the like is chemically bonded in a branched or cross-linked structure may be used.

  The olefin-based copolymer used in the present invention can contain structural units derived from other copolymerization components as long as the effects of the present invention are not impaired.

  More specifically, examples of the (C) epoxy group-containing olefin copolymer include glycidyl methacrylate-modified ethylene copolymer, glycidyl ether-modified ethylene copolymer, and the like. A copolymer is preferred.

  Examples of the glycidyl methacrylate-modified ethylene copolymer include glycidyl methacrylate graft-modified ethylene polymer, ethylene-glycidyl methacrylate copolymer, and ethylene-glycidyl methacrylate-methyl acrylate copolymer. Among them, an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable, and an ethylene-glycidyl methacrylate-methyl acrylate copolymer is preferable because a particularly excellent metal resin composite molded body can be obtained. Particularly preferred. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include “Bond First” (manufactured by Sumitomo Chemical Co., Ltd.).

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

  The content of the (C) epoxy group-containing olefin copolymer is usually 0.01 to 0.30% by mass in the total composition of the epoxy group content in the (C) epoxy group-containing olefin copolymer. The amount is preferably 0.03 to 0.25% by 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 tends to be lowered. The adhesion between the insert metal member and the resin member is affected by the difference in linear expansion between these members. (C) It is considered that the epoxy group-containing olefin copolymer realizes stress relaxation, thereby reducing the strain and improving the bonding strength. Toughness is effective for stress relaxation, and toughness can be evaluated by tensile elongation. If the content of the (C) epoxy group-containing olefin copolymer that functions as an elastomer is small, it is considered that the tensile elongation is small and a sufficient stress relaxation effect cannot be obtained. On the other hand, if the epoxy group content is more than 0.3% by mass in the total composition, the mold releasability at the time of insert molding tends to deteriorate, or the generated gas tends to increase, and the frequency of mold maintenance is high. It is not preferable because it tends to be high.

  Moreover, the sum total 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 usually 0.02 to 0 in the entire composition. .40% by mass, preferably 0.03 to 0.30% by mass, and more preferably 0.035 to 0.25. When the total is more than 0.40% by mass, it is not preferable in that the mold release property of the obtained molded body tends to deteriorate. The lower limit of the total is the sum of (B) the lower limit of the epoxy group content in the epoxy group-containing compound and (C) the lower limit of the epoxy group content in the epoxy group-containing olefin copolymer. is there.

[(D) Inorganic filler]
The resin composition according to the present invention may include (D) an inorganic filler. When (D) inorganic filler is added to the resin composition according to the present invention, the mechanical strength of the resulting resin member is likely to be improved. (D) An inorganic filler is not specifically limited, A conventionally well-known thing is mentioned. (D) The shape of the inorganic filler is not particularly limited, and may be fibrous or non-fibrous, such as spherical, powdery, plate-like, scale-like, or irregular, but is fibrous. Preferably there is. (D) As an inorganic filler, glass fiber, spherical silica, a glass bead etc. are mentioned, for example, Among these, glass fiber is preferable. (D) An inorganic filler can be used individually by 1 type or in combination of 2 or more types.

  (D) Content of an inorganic filler is 1-300 mass parts normally with respect to 100 mass parts of (A) polyarylene sulfide resin, Preferably it is 25-250 mass parts. The effect by adding (D) inorganic filler to the resin composition which concerns on this invention as the said content is less than 1 mass part is hard to appear. When the content exceeds 300 parts by mass, the joining strength between the insert metal member and the resin member is likely to be lowered, or the fluidity during insert molding is liable to be lowered.

[Other ingredients]
In addition to the above components, the resin composition according to the present invention is provided with an organic filler, a flame retardant, an ultraviolet absorber, a heat stabilizer, light, and the like in order to impart desired physical properties within a range that does not greatly impair the effects of the present invention. It may contain additives such as a stabilizer, a colorant, carbon black, a release agent, and a plasticizer.

[Method for Producing Resin Composition]
The method for producing the resin composition according to the present invention is not particularly limited as long as the components in the resin composition can be mixed uniformly, and can be appropriately selected from conventionally known methods for producing resin compositions. For example, after melt-kneading and extruding each component using a melt-kneading apparatus such as a single-screw or twin-screw extruder, the resulting resin composition is processed into a desired form such as powder, flakes, pellets, etc. Is mentioned.

<Metal resin composite molding>
The metal resin composite molded body according to the present invention includes an insert metal member and a resin member made of the resin composition according to the present invention and insert-molded on the insert metal member. At least a part of the surface of the insert metal member in contact with the resin member is subjected to physical treatment and / or chemical treatment. The metal resin composite molded body according to the present invention uses (B) an epoxy group-containing compound and (C) an epoxy group-containing olefin copolymer, and adjusts the epoxy group content in each of these components to a predetermined range. Since the resin composition is used, the bonding strength between the insert metal member and the resin member is strong and the peel resistance is excellent.

  Because of the above properties, the metal-resin composite molded article of the present invention is suitable for applications that require excellent adhesion between the insert metal member and the resin member on both the bonding strength and peel resistance sides. Can be used. For example, the metal-resin composite molded body according to the present invention is suitable as a metal-resin composite molded body having therein an electric / electronic component that is easily affected by humidity and moisture. In particular, it should be used as a part for electrical or electronic equipment that is expected to be used in fields requiring high level waterproofing, for example, rivers, pools, ski resorts, baths, etc., and intrusion of moisture and moisture leads to failure. Is preferred. In addition, the metal resin composite molded body of the present invention is also useful as, for example, a housing for an electric / electronic device provided with a resin boss, a holding member, and the like. Here, as a case for electric / electronic devices, in addition to mobile phones, cases for portable video electronic devices such as cameras, video integrated cameras, digital cameras, notebook computers, pocket computers, calculators, electronic notebooks , Portable information such as PDC, PHS, mobile phone, etc., housing of communication terminals, MD, cassette headphone stereo, housing of portable acoustic electronic equipment such as radio, LCD TV / monitor, telephone, facsimile, hand scanner, etc. A housing of household appliances and the like can be given.

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

  The metal material which comprises an insert metal member is not specifically limited, As an example, at least 1 sort (s) selected from the group which consists of copper, a copper alloy, aluminum, an aluminum alloy, and a magnesium alloy is mentioned.

  In this invention, the insert metal member shape | molded in the desired shape according to a use etc. is used. For example, an insert metal member having a desired shape can be obtained by pouring molten metal or the like into a mold having a desired shape. Further, in order to form the insert metal member into a desired shape, cutting by a machine tool 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 and the size of the treatment range are determined in consideration of the position where the resin member is formed.

  Physical treatment and chemical treatment are not particularly limited, and known physical treatment and chemical treatment can be used. The surface of the insert metal member is roughened by physical treatment, and the anchor effect is generated by the resin composition constituting the resin member entering the hole formed in the roughened region, and the insert metal member and the resin member It becomes easy to improve the adhesiveness at the interface. On the other hand, since chemical treatment effects such as covalent bonding, hydrogen bonding, or intermolecular force are imparted between the insert metal member and the insert molded resin member by the chemical treatment, the insert metal member and the resin member It becomes easy to improve the adhesiveness at the interface. The chemical treatment may involve a roughening of the surface of the insert metal member, and in this case, an anchor effect similar to that of the physical treatment occurs, and at the interface between the insert metal member and the resin member. Adhesion can be further improved.

Examples of the physical treatment include laser treatment and sandblasting (Japanese Patent Laid-Open No. 2001-225346). A plurality of physical treatments may be combined.
Examples of the chemical treatment include dry treatment such as corona discharge, triazine treatment (see JP-A No. 2000-218935), chemical etching (JP-A No. 2001-225352), and anodization treatment (JP-A 2010-64496). And hydrazine treatment. Moreover, when the metal material which comprises an insert metal member is aluminum, warm water processing (Unexamined-Japanese-Patent No. 8-142110) is also mentioned. Examples of the hot water treatment include immersion in water at 100 ° C. for 3 to 5 minutes. A plurality of chemical treatments may be combined.

[Resin member]
The resin member used in the present invention is composed of a polyarylene sulfide resin composition and is insert-molded on an insert metal member.

[Method for producing metal resin composite molded body]
The specific steps of the method for producing a metal resin composite molded body are not particularly limited, and the insert metal member is inserted through at least a part of the surface of the insert metal member subjected to physical treatment and / or chemical treatment. What is necessary is just to integrate an insert metal member and a resin member by making it closely_contact | adhere with a resin member.

  For example, an insert metal member having at least a part of the surface subjected to physical treatment and / or chemical treatment is placed in an injection mold, and the resin composition according to the present invention is used for the above injection molding in a molten state. A method for producing a metal-resin composite molded body in which an insert metal member and a resin member are integrated by injection into a mold is mentioned. The conditions for injection molding are not particularly limited, and preferable conditions can be appropriately set according to the physical properties of the polyarylene sulfide resin. A method using transfer molding, compression molding, or the like 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, preferably all, of the surface of the insert metal member in contact with the resin member is subjected to physical treatment and / or chemical treatment.

  As another example, a resin member is manufactured in advance by a general molding method such as an injection molding method, and an insert metal member that has been subjected to physical treatment and / or chemical treatment and the resin member are obtained in a desired manner. A method of manufacturing a metal-resin composite molded body in which an insert metal member and a resin member are integrated by abutting at a joining position and applying heat to the abutment surface to melt the vicinity of the abutment surface of the resin member. Can be mentioned. Also in this method, at least a part, preferably all, of the surface of the insert metal member in contact with the resin member is subjected to physical treatment and / or chemical treatment.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these Examples.

  The schematic diagram of the metal resin composite molded body used in Examples and Comparative Examples is shown in FIG. (A) is an exploded perspective view, (b) is a perspective view, (c) is a figure which shows only a metal part. This metal resin composite molded body was produced by the following method. In addition, the unit of the dimension in a figure is mm.

<Preparation of resin composition>
After dry blending the following raw material components, the mixture was put into a twin screw extruder having a cylinder temperature of 320 ° C. and melt-kneaded to obtain a pelletized thermoplastic resin composition. The amount (parts by mass) of each component is as shown in Tables 1 to 4.
Polyphenylene sulfide resin A-1: Fortron KPS W214A (product name), melt viscosity: 130 Pa · s (shear rate: 1216 / second, temperature: 310 ° C.), manufactured by Kureha Co., Ltd. • Epoxy group-containing compound B-1 : Bisphenol A type epoxy resin, jER (formerly “Epicoat”, both registered trademarks) 1004K (product name), epoxy group content: 4.6 mass%, epoxy equivalent 925, molecular weight: 1650, manufactured by Mitsubishi Chemical Corporation -Epoxy group-containing olefin copolymer C-1: ethylene-glycidyl methacrylate-methyl acrylate copolymer, Bond First 7L (product name), epoxy group content: 3 mass%, manufactured by Sumitomo Chemical Co., Ltd. C- 2: Ethylene-glycidyl methacrylate-methyl acrylate copolymer, Bond First 7M (product name), D Xyl group content: 6% by mass, manufactured by Sumitomo Chemical Co., Ltd. C-3: Ethylene-glycidyl methacrylate copolymer, Bond First E (product name), Epoxy group content: 12% by mass, manufactured by Sumitomo Chemical Co., Ltd. -Epoxy group-free polymer C'-1: ethylene octene copolymer, Engage 8440 (product name), manufactured by Dow Chemical Japan Co., Ltd. C'-2: ethylene ethyl acrylate copolymer, NUC-6570 (product) Name), Nippon Unicar Co., Ltd. C'-3: Silicone elastomer, DY33-315 (product name), Toray Dow Corning Co., Ltd., inorganic filler D-1: Glass fiber, ECS03T747 (product name), Manufactured by Nippon Electric Glass Co., Ltd. The method for measuring the melt viscosity is as follows.

[Melt viscosity]
Using a Capillograph manufactured by Toyo Seiki Co., Ltd., a melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1216 / sec was measured using a 1 mmφ × 20 mmL / flat die as a capillary.

<Physical treatment or chemical treatment of insert metal member>
As the insert metal member, a plate-like material made of copper (C-1100P, thickness 2 mm) or aluminum (A5052, thickness 2 mm) and subjected to physical treatment or chemical treatment as follows was used. These plate-like insert metal members have a joining surface at a portion indicated by hatching in FIG. In Tables 1 to 4, “Physics”, “Chemical 1”, and “Chemical 2” refer to the following physical treatment, chemical treatment 1, and chemical treatment 2, respectively.

[Physical processing]
A commercially available liquid honing apparatus is used for an insert metal member made of aluminum, and an alumina abrasive having a particle size of # 1000 (center particle size: 14.5 to 18 μm) is used at a concentration of 20% and a gauge pressure of 0.4 MPa. Spraying and roughening were performed.

[Chemical treatment 1]
The surface of the copper insert metal member is immersed in an etching solution A (aqueous solution) having the following composition for 1 minute to remove the rust preventive film, and then immersed in an etching solution B (aqueous solution) having the following composition for 5 minutes to obtain a metal part. The surface was etched.
・ Etching solution A (temperature 20 ℃)
Hydrogen peroxide 26g / L
Sulfuric acid 90g / L
・ Etching solution B (Temperature 25 ℃)
Hydrogen peroxide 80g / L
Sulfuric acid 90g / L
Benzotriazole 5g / L
Sodium chloride 0.2g / L

[Chemical treatment 2]
The surface of the insert metal member made of aluminum is degreased by immersing it in an alkaline degreasing solution (aqueous solution) having the following composition for 5 minutes, and then immersed in an etching solution C (aqueous solution) having the following composition for 3 minutes. Was etched.
・ Alkaline degreasing liquid (temperature 40 ℃)
AS-165F (manufactured by Ebara Eugelite) 50ml / L
・ Etching solution C (temperature 40 ℃)
OF-901 (Made in Ebara Eugelite) 12g / L
Magnesium hydroxide 25g / L

<Production of metal resin composite molded body>
An insert metal member subjected to physical treatment or chemical treatment is placed in a mold, and the insert metal member is made of a resin composition prepared in any one of Examples 1 to 10 and Comparative Examples 1 to 12, and The integration process to integrate was performed. The molding conditions are as follows. The shape of the metal resin composite molded body is as shown in FIG.
[Molding condition]
Molding machine: Sodick TR-40VR (vertical injection molding machine)
Cylinder temperature: 320 ° C
Mold temperature: 150 ° C
Injection speed: 70mm / s
Holding pressure: 80 MPa x 5 seconds

<Evaluation of metal resin composite molded body>
About the metal resin composite molded object produced by said method, the joint strength of a junction part, the fracture | rupture form after peeling, and peeling resistance were evaluated. The specific evaluation method is as follows.
[Joint strength]
As shown in FIG. 2, the metal-resin composite molded body having the shape shown in FIG. 1 is placed on a pedestal (jig), and the resin member is pushed away from the insert metal member in the direction of the arrow at a speed of 1 mm / min. I moved the jig. The strength at the time when the resin member was peeled from the insert metal member was measured as the bonding strength. In addition, Tensilon UTA-50kN (made by Orientec Co., Ltd.) was used as a measuring instrument. The measurement results are shown in Tables 1 to 4 (values are average values in three tests).

[Destruction mode]
After the joint strength measurement, the region that was the joint portion was visually observed, and whether the fracture occurred only at the interface between the insert metal member and the resin member (interface peeling, indicated by x), or at least in the resin member ( Cohesive fracture, indicated by ◎, was evaluated. The results are shown in Tables 1 to 4.

[Peeling resistance]
After the bonding strength measurement, the insert metal member side of the region that was the bonded portion was visually observed, and the ratio of the area occupied by the resin member adhering to the insert metal member to the entire area that was the bonded portion Was evaluated according to the following criteria. The results are shown in Tables 1 to 4.
○: The above ratio is 50% or more, and the peel resistance is good.
X: The above ratio is 20% or more and less than 50%, and the peel resistance is poor.
XX: The above ratio is less than 20%, and the peel resistance is extremely poor.

<Other evaluations>
[Releasability]
The releasability from the mold was evaluated according to the following criteria when the metal resin composite molded body was produced. The results are shown in Tables 1 to 4.
○: Release from the mold can be performed without any problem, and the release property is good.
X: It is difficult to release from the mold, and the releasability is poor. It is impossible to evaluate the bonding strength of the bonded portion, the fracture mode after peeling, and the peeling resistance.

[Tensile fracture strain]
About the resin composition prepared in any of Examples 1-10 and Comparative Examples 1-12, tensile fracture strain was measured 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 copolymer were used in combination, and the epoxy group content in each of these components was adjusted to a predetermined range. In the metal resin composite molded bodies of Examples 1 to 10, the bonding strength was strong and the peel resistance was excellent between the insert metal member and the resin member.
As shown in Table 3, in the metal resin composite molded body of Comparative Example 2 in which neither (B) an epoxy group-containing compound nor (C) an epoxy group-containing olefin copolymer was used, the bonding strength was higher than in Examples 1-10. In addition, the peel resistance was poor.
As shown in Tables 3 and 4, the metal resin composite molded articles of Comparative Examples 1, 3, 6, and 7 using (C) an epoxy group-containing olefin copolymer and (B) not using an epoxy group-containing compound. Then, compared with Examples 1-10, it was inferior to peeling resistance.
As shown in Tables 3 and 4, the metal resin composite molded articles of Comparative Examples 4, 5, and 8 to 11 using (B) an epoxy group-containing compound and (C) not using an epoxy group-containing olefin copolymer. Then, compared with Examples 1-10, it was inferior to joint strength and peeling resistance.
In addition, as shown in Table 4, although (B) the epoxy group-containing compound and (C) the epoxy group-containing olefin copolymer were used in combination, the total of the epoxy group content in these components was in the total composition. The metal resin composite molded body of Comparative Example 12 exceeding 0.4% by mass was inferior in releasability.

Claims (8)

A resin composition for insert molding on an insert metal member subjected to physical treatment and / or chemical treatment,
The resin composition includes (A) a polyarylene sulfide resin, (B) an epoxy group-containing compound, and (C) an epoxy group-containing olefin copolymer,
The epoxy group content in the (B) epoxy group-containing compound is 0.01 to 0.25% by mass in the total composition,
The epoxy group content in the (C) epoxy group-containing olefin copolymer is 0.01 to 0.30% by mass in the total composition,
The total 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 0.02 to 0.40% by mass in the total composition. A resin composition.   The resin composition according to claim 1, wherein the (B) epoxy group-containing compound is an epoxy resin.   The resin composition according to claim 1 or 2, wherein the (B) epoxy group-containing compound is a bisphenol-type epoxy resin.   The (C) epoxy group-containing olefin copolymer is an olefin 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. 4. The resin composition according to any one of 3.   The resin composition according to any one of claims 1 to 4, wherein the (C) epoxy group-containing olefin copolymer is an olefin copolymer further containing a structural unit derived from a (meth) acrylic acid ester.   Furthermore, the resin composition in any one of Claim 1 to 5 containing 1-300 mass parts (D) inorganic filler with respect to 100 mass parts of (A) polyarylene sulfide resin.   An insert metal member and a resin member made of the resin composition according to any one of claims 1 to 6 and insert-molded on the insert metal member, wherein the insert metal member is in contact with the resin member. A metal resin composite molded body in which at least a part of the surface is subjected to physical treatment and / or chemical treatment.   An insert metal member having at least a part of the surface subjected to physical treatment and / or chemical treatment is placed in an injection mold, and the resin composition according to any one of claims 1 to 6 is melted. The method for producing a metal-resin composite molded body comprising an integration step in which the insert metal member is integrated with the resin member by being injected into the injection mold.

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