KR102070981B1 - Metal-resin composite molded body and method for manufacturing the same - Google Patents

Abstract

The present invention provides a metal resin composite molded article having a strong bonding strength between the insert metal member and the resin member, having a good external appearance, and excellent chemical resistance against acids, alkalis, and the like, and a method of manufacturing the same.
The metal resin composite molded body includes an insert metal member and a resin member formed of a resin composition and insert-molded on the insert metal member, and at least a part of the surface of the insert metal member, which is in contact with the resin member, Treatment and / or chemical treatment is carried out. The said resin composition is (A) 100 mass parts of polyarylene sulfide resins, (B) non-fibrous, the average particle diameter is 30 micrometers or less, and simultaneously the inorganic filler 10 ~ chosen from the group which consists of a spherical silica and glass beads. 250 mass parts and (C) epoxy compound 3-55 mass parts, are included.

Description

Metal resin composite molded article and its manufacturing method {METAL-RESIN COMPOSITE MOLDED BODY AND METHOD FOR MANUFACTURING THE SAME}

TECHNICAL FIELD This invention relates to a metal resin composite molded object and its manufacturing method.

BACKGROUND ART A metal resin composite molded body in which an insert metal member composed of a metal, an alloy, or the like and a resin member composed of a thermoplastic resin composition is integrated has been conventionally used as an internal component of an automobile such as a console box around an instrument panel or an engine peripheral part. In addition, it is used for parts which come into contact with external sources, such as interface parts of electronic devices, such as an interior component, a digital camera, a mobile phone, and a power supply terminal part.

As a method of integrating the insert metal member and the resin member, a method of physically and / or chemically treating the joint surface on the insert metal member side to improve the adhesion between the insert metal member and the resin member, adhesive or double-sided tape Method of bonding using a metal, a fixing member such as a bent piece or a protrusion to an insert metal member and / or a resin member, and fixing the both by using the fixing member, or joining using a screw, etc. have. Among these, the method of performing physical treatment and / or chemical treatment to the joint surface on the insert metal member side, or the method using an adhesive agent is effective from the viewpoint of freedom when designing a metal resin composite molded body.

In particular, the method of physically and / or chemically treating the bonding surface on the insert metal member side is advantageous in that no expensive adhesive is used. As a method of performing physical treatment and / or chemical treatment to the joint surface on the insert metal member side, the method described in patent document 1 is mentioned, for example. This method can form a rough surface in the desired range on the surface of the insert metal member, and it is also one of the effective methods since the work is simple. Here, the method of patent document 1 is a method of forming a rough surface on the said surface with a laser.

Japanese Unexamined Patent Application Publication No. 2010-167475

As described above, the metal resin composite molded body is also used for parts in contact with the outside world in electronic devices and the like. The metal resin composite molded body used for such a component must not only have a strong bonding strength between the insert metal member and the resin member, but also have a good external appearance and excellent chemical resistance against acids, alkalis and the like.

An object of the present invention is to provide a metal resin composite molded article having a strong bonding strength between an insert metal member and a resin member, a good external appearance of the insert, and excellent chemical resistance against acids, alkalis and the like, and a method of manufacturing the same.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to solve the said subject. As a result, by physically and / or chemically treating at least a part of the surface of the insert metal member in contact with the resin member, by using a resin member composed of a specific resin composition containing polyarylene sulfide resin, It was found out that the above problems can be solved and the present invention has been completed. More specifically, the present invention provides the following.

(1) an insert metal member and a resin member made of a resin composition and insert-molded on the insert metal member, wherein 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 a metal resin composite molded article subjected to chemical treatment, wherein the resin composition is 100 parts by mass of (A) polyarylene sulfide resin, (B) non-fibrous, has an average particle diameter of 30 µm or less, and simultaneously spherical silica and 10 to 250 parts by mass of an inorganic filler selected from the group consisting of glass beads, and 3 to 55 parts by mass of (C) an epoxy group-containing olefin copolymer, wherein the epoxy group content in the resin composition is 0.01 to 0.80% by mass of metal Resin composite molded body.

(2) To (1), wherein the (C) epoxy group-containing olefin copolymer includes a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid. The metal resin composite molded body described.

(3) The metal resin composite molded article according to (1) or (2), wherein the (C) epoxy group-containing olefin copolymer further comprises a structural unit derived from (meth) acrylic acid ester.

(4) The metal resin composite molded article according to any one of (1) to (3), further comprising (D) an epoxy group-containing compound.

(5) In the electrical / electronic device provided with a case, the metal resin composite according to any one of (1) to (4), which constitutes at least a part of the case and has a portion exposed to the outside of the electrical / electronic device. Molded body.

(6) 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 molding die, and a resin composition is injected into the injection molding die in a molten state, thereby inserting the insert metal member. A method for producing a metal resin composite molded article comprising an integration step of integrating with a resin member, wherein the resin composition is (A) 100 parts by mass of a polyarylene sulfide resin, (B) a non-fiber shape, and an average particle diameter is 30 µm. 10 to 250 parts by mass of an inorganic filler selected from the group consisting of spherical silica and glass beads at the same time, and 3 to 55 parts by mass of (C) an epoxy group-containing olefin copolymer, wherein the epoxy group content in the resin composition is The manufacturing method of a metal resin composite molded object which is 0.01-0.80 mass%.

(7) to (6), wherein the (C) epoxy group-containing olefin copolymer includes a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid. The manufacturing method of the metal resin composite molded object described.

(8) The method for producing a metal resin composite molded article according to (6) or (7), wherein the (C) epoxy group-containing olefin copolymer further includes a structural unit derived from (meth) acrylic acid ester.

(9) The manufacturing method of the metal resin composite molded object in any one of (6)-(8) containing (D) epoxy group containing compound further.

According to the present invention, it is possible to provide a metal resin composite molded article having a strong bonding strength between the insert metal member and the resin member, good surface appearance, and excellent chemical resistance against acids, alkalis, and the like, and a method of manufacturing the same.

1: is a figure which shows typically the metal resin composite molded object used by the Example and the comparative example, (a) is an exploded perspective view, (b) is a perspective view, (c) is a figure which shows only a metal part.
It is a figure which shows typically the measuring method of the bonding strength between a resin part and a metal part performed in the Example.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. However, the present invention is not limited to the following embodiment.

<Insert metal member>

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

The metal material constituting the insert metal member is not particularly limited, and examples thereof include copper, aluminum, magnesium, and the like. In addition, the insert metal member may be made of a metal alloy. As a metal alloy, a copper alloy, an aluminum alloy, a magnesium alloy, stainless steel etc. are mentioned, for example. In addition, the surface of the metal material may be subjected to surface treatment or coating such as anodizing treatment.

In this invention, the insert metal member shape | molded to the desired shape according to a use etc. is used. For example, an insert metal member of a desired shape can be obtained by injecting molten metal or the like into a frame of a desired shape. In addition, in order to shape the insert metal member into a desired shape, cutting or the like 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 at which the physical treatment and / or chemical treatment is performed and the size of the treatment range are determined in consideration of the position at which the resin member is formed.

Physical treatment and chemical treatment are not particularly limited, and known physical treatment and chemical treatment can be used. By the physical treatment, the surface of the insert metal member is roughened, and an anchor effect is caused by the resin composition constituting the resin member sticking into the hole formed in the roughened region, resulting in adhesion at the interface between the insert metal member and the resin member. This is easily improved. On the other hand, since the chemical treatment gives a chemical bonding effect such as covalent bonds, hydrogen bonds, or intermolecular forces between the insert metal member and the resin member to be insert-molded, the adhesion at the interface between the insert metal member and the resin member is easily improved. do. The chemical treatment may be accompanied by roughening of the surface of the insert metal member, in which case the same anchor effect as the physical treatment occurs, and the adhesion at the interface between the insert metal member and the resin member is more easily improved.

Examples of the physical treatment include laser treatment and sand blast (Japanese Patent Laid-Open No. 2001-225346). It is also possible to combine a plurality of physical processes. In the case of laser treatment, specifically, roughening is performed on the conditions which irradiate a laser, groove, melt, and resolidify to a metal surface.

As the chemical treatment, for example, dry treatment such as corona discharge, triazine treatment (see JP-A-2000-218935), chemical etching (JP-A-2001-225352), and anodic oxidation treatment (JP-A 2010-64496), hydrazine treatment, etc. are mentioned. Moreover, when the metal material which comprises an insert metal member is aluminum, hot water processing (Unexamined-Japanese-Patent No. 8-142110) is also mentioned. As hot water treatment, immersion for 3 to 5 minutes is mentioned in 100 degreeC water. It may also be performed by combining a plurality of chemical treatments.

<Resin member>

The resin member used for this invention consists of a resin composition, and is insert-molded on an insert metal member. The said resin composition is (A) 100 mass parts of polyarylene sulfide resins, (B) non-fibrous, the average particle diameter is 30 micrometers or less, and simultaneously the inorganic filler 10- which is chosen from the group which consists of a spherical silica and glass beads. 250 mass parts and (C) epoxy group containing olefin copolymer 3-55 mass parts, The epoxy group content in the said resin composition is 0.01-0.80 mass%. Hereinafter, each component contained in the resin composition used for this invention is demonstrated.

[(A) Polyarylene Sulfide Resin]

(A) It is not specifically limited as polyarylene sulfide resin, Conventionally well-known polyarylene sulfide resin can be used. As (A) polyarylene sulfide resin, polyphenylene sulfide (PPS) resin is used preferably. (A) Polyarylene sulfide resin can be used individually by 1 type or in combination of 2 or more types.

(A) The polyarylene sulfide resin has a melt viscosity of 8 to 300 Pa · s at a shear rate of 1216 / sec, measured at 310 ° C, in that better adhesion between the insert metal member and the resin member can be obtained. It is preferable and it is especially preferable that it is 10-200 Pa.s.

[(B) Inorganic Filler]

The inorganic filler of component (B) is not particularly limited as long as it is nonfibrous, has an average particle diameter of 30 µm or less, and is selected from the group consisting of spherical silica and glass beads. The inorganic filler of (B) component can be used individually by 1 type or in combination of 2 or more types.

The shape of the inorganic filler of (B) component will not be specifically limited if it is non-fibrous, For example, spherical shape, a granular shape, plate shape, a flaky shape, an irregular shape, etc. are mentioned. Can be. When the shape of the inorganic filler is non-fibrous, the resulting metal resin composite molded article is likely to be excellent in surface appearance and chemical resistance.

The average particle diameter of the inorganic filler of (B) component is 30 micrometers or less, Preferably it is 0.1-25 micrometers, More preferably, it is 0.1-10 micrometers, More preferably, it is 0.1 micrometer-5 micrometers. The smaller the average particle diameter is, the better the surface appearance is. On the other hand, when the said average particle diameter exceeds 30 micrometers, sufficient surface appearance may not be obtained. In this specification, the average particle diameter is the particle diameter (50% d) of 50% of the integrated value in the particle size distribution measured by the laser diffraction scattering method.

Content of the inorganic filler of (B) component is 10-250 mass parts normally with respect to 100 mass parts of (A) polyarylene sulfide resin, Preferably it is 20-200 mass parts. If the said content is less than 10 mass parts, rigidity of a material and dimensional precision will fall easily. When the content exceeds 250 parts by mass, fluidity may be easily deteriorated, and sufficient bonding strength with a metal may not be obtained.

[(C) Epoxy Group-Containing Olefin Copolymer]

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

As the (C) epoxy group-containing olefin copolymer, 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 may be mentioned. Especially, the olefin type copolymer which further contains the structural unit derived from the (meth) acrylic acid ester is preferable at the point which can obtain the especially excellent metal resin composite molded object. Hereinafter, (meth) acrylic acid ester is also called (meth) acrylate. For example, (meth) acrylic acid glycidyl ester is also called glycidyl (meth) acrylate. In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid, and "(meth) acrylate" means both acrylate and methacrylate.

 It does not specifically limit as alpha olefin, For example, ethylene, propylene, butylene, etc. are mentioned, Especially ethylene is preferable. An alpha olefin may be used individually by 1 type, and may use 2 or more types together. (C) Flexibility is easily given to a resin member because an epoxy-group containing olefin copolymer contains the structural unit derived from an alpha olefin. Softening the resin member by providing flexibility contributes to the improvement of the bonding strength between the insert metal member and the resin member, and also to the improvement of the impact resistance.

It does not specifically limit as glycidyl ester of (alpha), (beta)-unsaturated acid, For example, acrylic acid glycidyl ester, methacrylic acid glycidyl ester, ethacrylic acid glycidyl ester, etc. are mentioned, Especially Methacrylic acid glycidyl ester is preferable. The glycidyl ester of the (alpha), (beta)-unsaturated acid may be used individually by 1 type, and may use 2 or more types together. When the (C) epoxy group-containing olefin copolymer contains a structural unit derived from glycidyl ester of α, β-unsaturated acid, the effect of improving the bonding strength between the insert metal member and the resin member can be easily obtained.

It does not specifically limit as (meth) acrylic acid ester, For example, Acrylic ester, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-octyl methacrylate, etc. The methacrylic acid ester of is mentioned. Among these, methyl acrylate is especially preferable. (Meth) acrylic acid ester may be used individually by 1 type, and may use 2 or more types together. The structural unit derived from the (meth) acrylic acid ester contributes to the improvement of the bonding strength between the insert metal member and the resin member.

The olefin copolymer containing the structural unit derived from the (alpha) -olefin, and the structural unit derived from the (alpha), (beta)-unsaturated acid glycidyl ester, and the olefin copolymer further containing the structural unit derived from (meth) acrylic acid ester, It can manufacture by copolymerizing by a conventionally well-known method. For example, the said copolymer can be obtained by copolymerizing normally by the well-known radical polymerization reaction. The kind of copolymer does not have a problem in particular, For example, it may be a random copolymer and may be a block copolymer. In addition, the polyolefin, polyacrylonitrile, acrylic, polymethyl acrylate, ethyl polymethacrylate, methyl polyacrylate, ethyl polyacrylate, butyl acrylate, 2-ethylhexyl polyacrylate, polystyrene, for example, to the olefin copolymer An olefin graft copolymer in which a ronitrile styrene copolymer, a butyl acrylate styrene copolymer, or the like is chemically bonded in a branched or crosslinked structure may be used. As a kind of said copolymer, it is preferable that it is not an olefin type graft copolymer, and it is more preferable that it is a random copolymer and / or a block copolymer.

The olefin copolymer used in the present invention may contain structural units derived from other copolymerization components within a range not impairing the effects of the present invention.

More specifically, as the (C) epoxy group-containing olefin copolymer, for example, glycidyl methacrylate-modified ethylene-based copolymer, glycidyl ether-modified ethylene copolymer, etc. may be mentioned. Preference is given to cydyl methacrylate-modified ethylene copolymers.

Examples of the glycidyl methacrylate-modified ethylene copolymers include glycidyl methacrylate graft-modified ethylene polymers, ethylene-glycidyl methacrylate copolymers, and ethylene-glycidyl methacrylate-methyl acrylate copolymers. Can be mentioned. Among these, an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable at the point that a metal resin composite molding which is especially excellent can be obtained, and ethylene-glycidyl meta Particular preference is given to acrylate-methyl acrylate copolymers. Examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include "bond fast" (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

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

Content of (C) epoxy group containing olefin type copolymer is 3-55 mass parts normally with respect to 100 mass parts of (A) polyarylene sulfide resin, Preferably it is 3-30 mass parts. If the content is less than 3 parts by mass, the joint strength between the insert metal member and the resin member may not be sufficiently obtained. The difference in linear expansion between these members affects the adhesion between the insert metal member and the resin member. (C) It is thought that deformation | transformation becomes small and the said bond strength improves because an epoxy group containing olefin type copolymer implements stress relaxation. Toughness has an effect on stress relaxation, and toughness can be evaluated by tensile length. When there is little content of the (C) epoxy group containing olefin type copolymer which functions as an elastomer, it is thought that a tensile length is small and sufficient stress relaxation effect cannot be acquired. In addition, stress relaxation contributes to improvement of impact resistance. On the other hand, when the content exceeds 55 parts by mass, the viscosity rise due to the reaction between the (C) epoxy group-containing olefin copolymer and the (A) polyarylene sulfide resin tends to be large, so that the fluidity is easily deteriorated and the insert metal member and Bond strength between resin members may not be sufficiently obtained. If the said content is 3-30 mass parts, it is preferable also from a sulfuric acid resistance viewpoint, and it is easy to obtain a more excellent metal resin composite molded object.

In addition, the epoxy group content in a resin composition is 0.01-0.80 mass% normally, and it is preferable that it is 0.03-0.60 mass%. When the epoxy group content is 0.01 to 0.80% by mass, the bonding strength between the insert metal member and the resin member is easily maintained, and the releasability at the time of insert molding does not easily deteriorate, and the amount of generated gas tends to be suppressed. This is preferable in that the frequency of mold maintenance tends to be low. The epoxy group content in the said resin composition is a sum total of the epoxy group content in the (C) epoxy group containing olefin type copolymer, and the epoxy group content in the (D) epoxy group containing compound mentioned later. When the said resin composition contains only (C) epoxy group containing olefin copolymer as a component containing an epoxy group, the epoxy group content in the said resin composition is the same as the epoxy group content in the (C) epoxy group containing olefin copolymer. (C) It is preferable that it is 0.02-0.60 mass% in the whole composition, and, as for epoxy group content in an epoxy group containing olefin copolymer, it is more preferable that it is 0.02-0.50 mass%.

[(D) Epoxy Group-Containing Compound]

The resin composition used for this invention can contain the (D) epoxy group containing compound. When the (D) epoxy group-containing compound is added to the resin composition used in the present invention, the bonding strength between the insert metal member and the resin member is more easily improved in the resulting metal resin composite molded body. The epoxy group-containing compound (D) is not particularly limited as long as it is an epoxy group-containing compound other than the above (C) epoxy group-containing olefin copolymer. (D) An epoxy group containing compound can be used individually by 1 type or in combination of 2 or more types.

The epoxy group-containing compound (D) may be a compound containing one epoxy group in one molecule, or may be a compound containing two or more epoxy groups in one molecule. (D) As an epoxy-group containing compound, For example, the bisphenol-type epoxy compound obtained by making bisphenol A react with epichlorohydrin, the novolak-type epoxy resin obtained by making a novolak resin and epichlorohydrin react, and polycarboxylic acid, Polyglycidyl esters obtained by reacting epichlorohydrin, alicyclic compound type epoxy compounds obtained from alicyclic compounds, glycidyl ethers obtained by reacting aliphatic compounds having an alcoholic hydroxyl group with epichlorohydrin, epoxidized butadiene, And epoxy compounds obtained by reacting a compound having a double bond with a peroxide. Specific examples include bisphenol A epoxy compounds, methylglycidyl ether, phenylglycidyl ether, various fatty acid glycidyl esters, diethylene glycol diglycidyl ether, diglycidyl phthalate, and hexahydrophthalic acid diglycides. And diester esters, epoxidized polybutadienes, and epoxidized SBS. Among these, bisphenol-type epoxy compounds, such as a bisphenol-A epoxy compound, are preferable.

(D) Content of an epoxy-group containing compound becomes like this. Preferably it is 0.01-10 mass parts with respect to 100 mass parts of (A) polyarylene sulfide resin, More preferably, it is 0.01-5 mass parts. If the said content is 0.01-10 mass parts, the joining strength between an insert metal member and a resin member will improve more easily.

In addition, the epoxy group content in the (D) epoxy-group-containing compound is as mentioned above, and the sum total of the epoxy group content in the (C) epoxy-group-containing olefin copolymer and the epoxy group content in the (D) epoxy-group-containing compound is 0.01 in all the compositions. Although it will not specifically limit if it is -0.80 mass%, (D) It is preferable that epoxy group content in an epoxy-group containing compound is 0.5 mass% or less (for example, more than 0 mass% and 0.5 mass% or less) in all the compositions, and is 0.35 It is more preferable that it is mass% or less (for example, more than 0 mass% and 0.35 mass% or less). When the said epoxy group content is 0.5 mass% or less in the whole composition, the peeling resistance between an insert metal member and a resin member does not fall easily. In particular, at the time of insert molding, interfacial peeling is not easily generated even at the flow end of the resin composition in the molten state. Moreover, since mold release property at the time of insert molding does not deteriorate easily, it is preferable at the point that a desired molded article is easy to be obtained and productivity does not fall easily.

[Other Ingredients]

The resin composition used in the present invention, in addition to the above components, inorganic fillers, organic fillers, flame retardants, ultraviolet absorbers, heat stabilizers, other than the component (B) in order to impart desired physical properties in a range that does not significantly inhibit the effects of the present invention. Additives, such as a light stabilizer, a coloring agent, carbon black, a mold release agent, and a plasticizer, can be contained.

[Method for Producing Resin Composition]

The manufacturing method of the resin composition used by this invention will not be specifically limited if the components in this resin composition can be mixed uniformly, It can select suitably from the manufacturing method of the conventionally known resin composition. For example, after melt-kneading and extruding each component using melt-kneading apparatuses, such as a single screw or twin screw extruder, the method of processing the obtained resin composition into a desired form, such as powder, a flake, and a pellet, is mentioned.

<Metal Resin Composite Molded Body>

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 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. Since the metal resin composite molded body which concerns on this invention used the resin composition which included the (C) epoxy group containing olefin copolymer and adjusted the epoxy group content to a predetermined range, the joint strength between an insert metal member and a resin member is strong. Moreover, since the inorganic filler of (B) component is included, the external appearance of a surface is favorable and excellent chemical-resistance with respect to an acid, an alkali, etc. is carried out.

  Because of the above characteristics, the metal resin composite molded body of the present invention has not only a strong bonding strength between the insert metal member and the resin member, but also a good surface appearance and excellent chemical resistance against acids and alkalis. It can be used suitably. For example, the metal resin composite molded article of the present invention is suitable as a metal resin composite molded article having an electric / electronic component or the like that is easily affected by humidity or moisture therein. In particular, it is suitable to be used as a component for electric or electronic devices where the intrusion of moisture or moisture is expected to be used in fields requiring high level waterproofing, for example, rivers, pools, ski resorts, bathrooms, etc. . In addition, the metal resin composite molded article of the present invention is also useful as at least a part of a case for an electrical / electronic device. The said case for electrical and electronic devices can be equipped with the resin boss, the holding member, etc. inside. Here, as a case for electric and electronic equipment, in addition to a mobile phone, a case of a portable video electronic device such as a camera, a video integrated camera, a digital camera, a laptop computer, a pocket computer, a calculator, an electronic notebook, a PDC, a PHS, a mobile phone and the like The case of an information or communication terminal, the case of portable acoustic electronic devices, such as MD, a cassette headphone stereo, a radio, the case of home telephone apparatuses, such as a liquid crystal TV monitor, a telephone, a facsimile, a hand scanner, etc. are mentioned.

<Method for producing metal resin composite molded article>

The specific process of the manufacturing method of a metal resin composite molded object is not specifically limited, A resin member is made to adhere | attach an insert metal member and a resin member through the insert metal member at least part of the surface in which the physical treatment and / or chemical treatment were performed. The insert and metal member may be integrated.

For example, 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 molding die, and the resin composition used in the present invention is injected into the injection molding die in a molten state, and the resin And a method of manufacturing a metal resin composite molded body in which the member and the insert metal member are integrated. Injection molding conditions are not specifically limited, According to the physical property of polyarylene sulfide resin, etc., suitable conditions can be set suitably. In addition, a method using transfer molding, compression molding, or the like is also an effective method of forming a metal resin composite molded body in which the resin member and the insert metal 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 by a general molding method such as an injection molding method, and the insert metal member, which has been subjected to physical treatment and / or chemical treatment, is brought into contact with the resin member at a desired bonding position, and heat is applied to the contact surface. And a method of manufacturing a metal resin composite molded body in which the vicinity of the contact surface of the resin member is melted and the resin member and the insert metal member are integrated. Also in such a method, physical treatment and / or chemical treatment are performed on at least a part, preferably all, of the surface of the insert metal member in contact with the resin member.

Example

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 object used by the Example and the comparative example is shown in FIG. (a) is an exploded perspective view, (b) is a perspective view, and (c) is a figure which shows only a metal part. Such a metal resin composite molded article was produced by the following method. In the figure the dimension units are mm.

<Preparation of resin composition>

After dry blending the following raw material components, the mixture was put in a twin screw extruder having a cylinder temperature of 320 ° C., and melt-kneaded to pelletize a thermoplastic resin composition. The compounding quantity (mass part) of each component is as showing in Tables 1-3.

, Polyphenylene sulfide resin,

A-1: Creha Co., Ltd., Portron KPS W202A (product name), melt viscosity: 20 Pa.s (shear rate: 1216 sec ^-1 , temperature: 310 ° C)

A-2: Creha Co., Ltd., Portron KPS W214A (product name), melt viscosity: 130 Pa.s (shear rate: 1216 sec ^-1 , temperature: 310 ° C)

Inorganic filler

B-1: Glass Beads (manufactured by Porters Ballotini Co., Ltd., EMB-10 (average particle size: 5 µm))

B-2: Glass Beads (manufactured by Porters Ballotini Co., Ltd., GL-BS (average particle size: 20 µm))

B-3: spherical silica (manufactured by Adomatech Co., Ltd., SO-C2 (average particle size: 0.55 탆))

B-4: Spherical Silica (manufactured by Adomatech Co., Ltd., SO-C6 (average particle diameter: 2.2 탆)

B-5: calcium carbonate (Shiraishi Kogyo Co., Ltd. product, Brilliant-1500 (average particle diameter 50% d: 0.7 micrometer))

 B-6: Glass Flake (Japan Glass Co., Ltd. product, REFG-401 (average particle diameter: 300 µm, average thickness: 5 µm))

 B-7: Glass fiber (made by Owen Corning Co., Ltd., 03 DE-FT798 (fiber diameter 6㎛, fiber length 3mm))

Epoxy group-containing olefin copolymer

C-1: Ethylene glycidyl methacrylate methyl acrylate copolymer (Sumitomo Chemical Co., Ltd., bond fast 7L)

C-2: ethylene glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., bond fast E)

C-3: ethylene ethyl acrylate copolymer (manufactured by Nippon Unicar Co., NUC-6570)

Epoxy group-containing compound

D-1: Bisphenol A type epoxy resin (product of Mitsubishi Chemical Corporation, jER (formerly "Epicote", all registered trademarks) 1004K (product name)), epoxy group content: 4.6 mass%, epoxy equivalent 925, molecular weight : 1650

The measurement method of melt viscosity is as follows.

Melt Viscosity

The melt viscosity at the barrel temperature of 310 degreeC and shear rate 1216 / sec was measured using the capillary product of Toyo Seiki Co., Ltd. as a capillary, using 1 mm ( phi) * 20 mmL / flat die.

Physical or chemical treatment of insert metal parts

As the insert metal member, a plate made of copper (C-1100P, 2 mm thick) or aluminum (A5052, 2 mm thick) and subjected to physical or chemical treatment as follows was used. These plate-shaped insert metal members have a joining surface at the part shown by the diagonal line of FIG. 1 (a). In Tables 1-3, "physical", "hwa 1", and "hwa 2" refer to the following physical treatments, chemical treatment 1, and chemical treatment 2, respectively.

[Physical processing]

Alumina abrasive with a particle size of # 1000 (center particle size: 14.5-18 μm) was used for an insert metal member made of aluminum, and a concentration of 20% and a gauge pressure of 0.4 MPa. It sprayed on condition and performed the roughening process.

[Chemical Treatment 1]

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

Etching liquid 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 was immersed in an alkali degreasing solution (aqueous solution) of 5 minutes for degreasing treatment, and then immersed in an etching solution A (aqueous solution) having the following composition for 3 minutes to etch the surface of the metal part. .

Alkaline degreasing liquid (temperature 40 ℃)

AS-165F (Ebara Oily Light Products) 50ml / L

Etching liquid A (temperature 40 ℃)

OF-901 (Ebara maintenance light product) 12 g / L

Magnesium Hydroxide 25g / L

<Production of Metal Resin Composite Molded Product>

The insert metal member subjected to the physical treatment or the chemical treatment is disposed in the mold, and the insert metal member is integrated with the resin member composed of the polyphenylene sulfide resin composition prepared in any one of Examples 1 to 19 and Comparative Examples 1 to 12. An integration process was performed. Molding conditions are as follows. The shape of the metal resin composite molded body is as shown in FIG.

[Molding conditions]

Molding Machine: Sodick TR-40 VR (Vertical Injection Molding Machine)

Cylinder temperature: 320 ℃

Mold temperature: 150 ℃

Injection speed: 100mm / s

Holding pressure: 49 MPa x 5 seconds

<Evaluation of Metal Resin Composite Molded Product>

About the metal resin composite molded object produced by the said method, the joint strength of the joined part, the fractured form after peeling, and peeling resistance were evaluated. The specific evaluation method is as follows.

[Bond strength]

As shown in FIG. 2, the metal resin composite molded body having the shape shown in FIG. 1 is disposed on a support (jig), and the jig is pushed to separate the resin member from the insert metal member in the direction of the arrow at a speed of 1 mm / minute. It worked. The strength at the time when the resin member was separated from the insert metal member was measured as the bonding strength. Tenshiron UTA-50 kN (Orientech Co., Ltd.) was used as a measuring instrument. The measurement results are shown in Tables 1 to 3 (values are average values of three tests).

[Destructive form]

After the joint strength measurement, the area that was the joint was visually observed, and whether fracture occurred at the interface between the insert metal member and the resin member (interface peeling, denoted by ×), or whether it occurred in the insert metal member or the resin member (aggregate fracture, (Marked by ○) was evaluated. The results are shown in Tables 1 to 3.

[Peel resistance]

After the measurement of the joint strength, the insert metal member side of the region that was the bonded portion was visually observed to determine the ratio of the area occupied by the resin member attached to the insert metal member and the area of the entire region that was the bonded portion. Evaluated. The results are shown in Tables 1 to 3.

(Double-circle): The said ratio is 50% or more, and peeling resistance is very favorable.

(Circle): Said ratio is 20% or more and less than 50%, and peeling resistance is favorable.

(Triangle | delta): The said ratio is more than 0% and less than 20%, and peeling resistance is bad.

X: The above ratio is 0%, and the peeling resistance is extremely poor.

<Other Ratings>

[Surface appearance]

By injection molding, the dumbbell test piece of thickness 4mmt was produced at the cylinder temperature of 320 degreeC, and the mold temperature of 150 degreeC, and the surface appearance was visually observed. The result of the surface appearance evaluated by the following evaluation criteria is shown in Tables 1-3. If evaluation is any of 5-3, it can be used as a product without a problem, but when evaluation is 2 or 1, it is not a level which can be used as a product.

 5: The surface roughness resulting from the added inorganic filler was not recognized, and there is no cloudy and gloss.

 4: The surface roughness resulting from the added inorganic filler was not confirmed, but some blur was seen. Overall it is glossy.

 3: The surface roughness resulting from the added inorganic filler was not confirmed, but a slight cloudiness was seen.

 2: The surface roughness resulting from the added inorganic filler is confirmed about 1/3 of the whole surface.

 1: The surface roughness resulting from the added inorganic filler is confirmed in almost the whole surface.

[Sulfur Acid Resistance]

The dumbbell test piece produced in the same manner as used for the observation of the surface appearance was immersed in a 10 mass% sulfuric acid aqueous solution at room temperature for 1 hour, washed with water and dried, and the surface appearance was visually observed. The sulfuric acid resistance results evaluated by the following evaluation criteria are shown in Tables 1-3.

(Double-circle): There is no change before immersion.

(Circle): Although there exists cloudy on a surface slightly, there is no change in surface smoothness.

X: Whitening was seen on the surface, and surface smoothness deteriorated.

[Deformation]

The release property from the metal mold | die at the time of dumbbell test piece preparation used for the observation of surface appearance was evaluated with the following reference | standard. The results are shown in Tables 1 to 3.

(Circle): Mold release from a metal mold | die does not have a problem, and mold release property is favorable.

X: Mold release from a metal mold | die is difficult, and mold release property is bad. Surface appearance evaluation is not possible.

As shown in Table 1 and Table 2, in Examples 1 to 19 in which (B) spherical silica and / or glass beads and (C) epoxy group-containing olefin copolymers were used in combination, and the content of each component was adjusted to a predetermined range. It was confirmed that the bonding strength between the insert metal member and the resin member in the metal resin composite molded body was strong, and at the same time, the surface appearance and sulfuric acid resistance were excellent. In addition, in the metal resin composite molded body of Examples 15-18 which used together the (C) epoxy group containing olefin type copolymer and (D) epoxy group containing compound, and adjusted the epoxy group content in each of these components to a predetermined range, Bonding strength was strong between resin members, and was also excellent in peeling resistance.

In addition, when only spherical silica and / or glass beads having an average particle diameter of 10 µm or less were used, it was confirmed that the surface appearance was better.

On the other hand, as shown in Table 3, the comparative examples 1 and 6 which used calcium carbonate instead of spherical silica and / or glass beads (B) were inferior to sulfuric acid resistance compared with Examples 1-19. In addition, Comparative Examples 2-4 and 7 which used glass flakes or glass fibers instead of (B) spherical silica and / or glass beads were inferior in surface appearance compared with Examples 1-19.

In addition, although the (C) epoxy group containing olefin type copolymer and (D) epoxy group containing compound were used together, the comparative example 9 in which the sum total of the epoxy group content in each these components exceeded 0.80 mass% in all the compositions was inferior in releasability.

Claims (9)

An insert metal member and a resin member made of a resin composition and insert-molded on the insert metal member, wherein at least a part of the surface of the insert metal member in contact with the resin member is at least one of a physical treatment and a chemical treatment; As a metal resin composite molded body in which one was carried out,
The said resin composition is (A) 100 mass parts of polyarylene sulfide resins, (B) non-fibrous, the average particle diameter is 30 micrometers or less, and simultaneously the inorganic filler 10 ~ chosen from the group which consists of a spherical silica and glass beads. 250 parts by mass, and (C) an epoxy group-containing olefin copolymer 3 to 55 parts by mass,
The (C) epoxy group-containing olefin copolymer contains a structural unit derived from (meth) acrylic acid ester,
Metal resin composite molded object whose epoxy group content in the said resin composition is 0.01-0.80 mass%. The method of claim 1,
The metal resin composite molded article in which said (C) epoxy group containing olefin type copolymer is a olefin type copolymer containing the structural unit derived from the alpha-olefin, and the structural unit derived from the glycidyl ester of an alpha, (beta)-unsaturated acid. The method according to claim 1 or 2,
(D) A metal resin composite molded article further comprising an epoxy group-containing compound. The method according to claim 1 or 2,
In the electric / electronic device provided with a case, the metal resin composite molded object which comprises the part which comprises at least one part of the said case, and is exposed to the exterior of the said electric / electronic device. An insert metal member having at least a part of the surface subjected to at least one of physical treatment and chemical treatment is disposed in an injection molding die, and a resin composition is injected into the injection molding die in a molten state, thereby inserting the insert metal member into a resin member. As a manufacturing method of a metal resin composite molded object which has an integration process which integrates with,
The said resin composition is (A) 100 mass parts of polyarylene sulfide resins, (B) non-fibrous, the average particle diameter is 30 micrometers or less, and simultaneously the inorganic filler 10 ~ chosen from the group which consists of a spherical silica and glass beads. 250 parts by mass, and (C) an epoxy group-containing olefin copolymer 3 to 55 parts by mass,
The (C) epoxy group-containing olefin copolymer contains a structural unit derived from (meth) acrylic acid ester,
The epoxy group content in the said resin composition is a manufacturing method of the metal resin composite molded object which is 0.01-0.80 mass%. The method of claim 5,
Said (C) epoxy group containing olefin type copolymer is a manufacturing method of the metal resin composite molded object which is an olefin type copolymer containing the structural unit derived from the alpha-olefin, and the structural unit derived from the glycidyl ester of an alpha, (beta)-unsaturated acid. . The method according to claim 5 or 6,
(D) The manufacturing method of the metal resin composite molded object containing an epoxy group containing compound further. delete delete

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