KR20140145071A - Metal-resin composite molded body and method for manufacturing the same - Google Patents

Abstract

Provided in the present invention are a metal-resin composite molded body which includes excellent flame retardancy even with thin thickness and has high bonding strength between an insert metal member and a resin member, and a method for manufacturing the same. The metal-resin composite molded body according to the present invention includes an insert metal member; and a resin member which contains a resin composition and insert-molded on the insert metal member, wherein at least one part of the surface of the insert metal member coming in contact with the resin member is physically and/or chemically treated. The resin composition includes (A) 100 parts by mass of polyarylene sulfide resin, (B) 3-15 parts by mass of epoxy group-containing olefin-based copolymers, and (C) 0.3-5 parts by mass of silicon compounds.

Description

Technical Field [0001] The present invention relates to a metal-resin composite molded article,

The present invention relates to a metal-resin composite formed article and a method of manufacturing the same.

BACKGROUND ART A metal-resin composite formed article in which an insert metal member made of a metal or an alloy and a resin member made of a thermoplastic resin composition are integrally formed has been conventionally used for a built-in member of an automobile such as a console box around an instrument panel, And is used for parts that come into contact with the outside world such as interior parts, interface connecting parts of electronic devices such as digital cameras and cellular phones, and power source terminal parts.

As a method for integrating the insert metal member and the resin member, there are a method for 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 in which a fixing member such as a bending piece or a projection is formed on an insert metal member and / or a resin member, a method of fixing them using such fixing member, a method of bonding using a screw or the like . Among these methods, a method of applying a physical treatment and / or a chemical treatment to the joint surface on the insert metal member side or a method of using an adhesive is effective from the viewpoint of freedom in designing the metal resin composite formed article.

Particularly, a method of performing physical treatment and / or chemical treatment on the joint surface of the insert metal member side is advantageous in that an expensive adhesive is not used. As a method of performing physical treatment and / or chemical treatment on the joint surface of the insert metal member side, for example, the method described in Patent Document 1 can be mentioned. This method can form a roughened surface in a desired range on the surface of the insert metal member, and is one of the effective methods because of its simple operation. The method described in Patent Document 1 is a method of forming a roughened surface on the surface with a laser.

Japanese Patent Application Laid-Open No. 2010-167475

In the metal-resin composite formed article, it is practically required that the insert metal member and the resin member should be integrated sufficiently. Therefore, the metal-resin composite formed article must have a strong bonding strength between the insert metal member and the resin member. In addition, along with the compactness and high integration of various kinds of equipment, it has been required to reduce the thickness of the resin member in the metal-resin composite molded article. At the same time, the resin member must have excellent flame retardancy from the viewpoint of safety and the like. However, as a result of the inventors' study, it has been found that the resin member in the metal-resin composite molded article has a flame retardancy of the grade V-0 in the UL-94 standard vertical burning test of UL (Underwriters Laboratories Inc.) , And the flame retardancy in the above vertical burning test was in the range of V-2 in the case of a thin thickness of about 0.8 mm, and the flame retardancy was poor.

It is an object of the present invention to provide a metal-resin composite molded article having a resin member excellent in flame resistance even at a thin thickness and having high bonding strength between the insert metal member and the resin member, and a method for producing the same.

 DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies in order to solve the above problems. As a result, a specific resin composition containing a predetermined amount of an epoxy group-containing olefin-based copolymer and a silicon compound is subjected to physical treatment and / or chemical treatment on at least part of the surface of the insert metal member in contact with the resin member To form a resin member, the above problems can be solved, and the present invention has been accomplished. 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 / (A) 100 parts by mass of a polyarylene sulfide resin, (B) 3 to 15 parts by mass of an epoxy group-containing olefin-based copolymer, (C) And 0.3 to 5 parts by mass of a compound.

(2) The metal-organic composite molded article according to (1), wherein the silicone compound (C) is a silicone rubber and the melt viscosity of the polyarylene sulfide resin (A) measured at a temperature of 310 ° C and a shear rate of 1216 / .

(1) or (2) wherein the silicone compound (C) is a silicone rubber and the content of the epoxy group-containing olefin copolymer (B) is from 3 to 9 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A) And the metal-resin composite formed article.

(4) The metal-resin composite formed article according to (1), wherein the (C) silicon compound is a silicone oil.

(5) The epoxy resin composition according to any one of the above items (1) to (4), wherein the epoxy group-containing olefin-based copolymer (B) is an olefin-based copolymer comprising a constituent unit derived from an- And the metal-resin composite formed article according to any one of < 1 >

(6) The positive resist composition as described in any one of (1) to (6) above, which further comprises at least one kind of (E) 1 to 250 parts by mass of an inorganic filler (D) and 0.01 to 10 parts by mass of an epoxy group- (5). ≪ / RTI >

(7) An insert metal member subjected to physical treatment and / or chemical treatment at least a part of its surface is placed in a mold for injection molding, and the resin composition is injected into the injection molding mold in a molten state, (A) 100 parts by mass of a polyarylene sulfide resin, and (B) 3 to 15 parts by mass of an epoxy group-containing olefin-based copolymer And (C) 0.3 to 5 parts by mass of a silicon compound.

(8) The metal-organic composite molded article according to (7), wherein the silicone compound (C) is a silicone rubber and the melt viscosity of the polyarylene sulfide resin (A) is 90 Pa · s or more as measured at a temperature of 310 ° C. and a shear rate of 1216 / ≪ / RTI >

(9) The rubber composition according to any one of (7) to (8), wherein the silicon compound (C) is a silicone rubber and the content of the epoxy group-containing olefin copolymer (B) is from 3 to 9 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A) Wherein the metal-resin-composite molded article is produced by a method comprising the steps of:

(10) A process for producing a metal-resin composite molded article according to (7), wherein the (C) silicon compound is a silicone oil.

(11) The epoxy resin composition according to any one of (7) to (10), wherein the epoxy group-containing olefin-based copolymer (B) is an olefin-based copolymer comprising a constituent unit derived from an -olefin and a constituent unit derived from a glycidyl ester of an? Wherein the metal-resin-composite molded article is produced by a method comprising the steps of:

(12) The positive resist composition as described in any one of (7) to (7), wherein the positive resist composition comprises (A) 1 to 250 parts by mass of an inorganic filler (D) and 0.01 to 10 parts by mass of an epoxy group- 11. The method of producing a metal-resin composite formed article according to any one of claims 1 to 11.

According to the present invention, it is possible to provide a metal-resin composite formed article having a resin member having excellent flame retardancy even at a thin thickness and having high bonding strength between the insert metal member and the resin member, and a method of manufacturing the same.

Fig. 1 is a schematic perspective view of a metal-resin composite molded article used in Examples and Comparative Examples, wherein Fig. 1 (a) is an exploded perspective view, Fig. 2 (b) is a perspective view, and Fig.
Fig. 2 is a diagram schematically showing a method of measuring a bonding strength between a resin part and a metal part, which is performed in the embodiment. Fig.

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

<Insert metal member>

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

In the present invention, an insert metal member molded into a desired shape is used according to applications and the like. For example, molten metal or the like is injected into a frame having a desired shape to obtain an insert metal member having a desired shape. Further, in order to mold the insert metal member into a desired shape, a cutting process with a machine tool or the like can be used.

The surface of the insert metal member thus obtained is subjected to a physical treatment and / or a chemical treatment. The position at which the physical treatment and / or the chemical treatment is performed and the size of the treatment range are determined in consideration of the position where the resin member is formed and the like.

The physical treatment and the 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 the physical treatment, and the resin composition constituting the resin member enters the hole formed in the roughened surface area, so that an anchor effect is generated, and the adhesion property at the interface between the insert metal member and the resin member This is easily improved. On the other hand, since the chemical treatment imparts a chemical bonding effect such as covalent bonding, hydrogen bonding, or intermolecular force between the insert metal member and the resin member to be insert-molded, adhesion at the interface between the insert metal member and the resin member is facilitated . The chemical treatment may be accompanied by roughening of the surface of the insert metal member, and in this case, the same anchor effect as the physical treatment is obtained, so that the adhesion at the interface between the insert metal member and the resin member is more easily improved.

As the physical treatment, for example, laser treatment, sandblasting (Japanese Patent Application Laid-Open No. 2001-225346), and the like can be given. Or a combination of a plurality of physical processes.

Examples of the chemical treatment include dry treatment such as corona discharge and the like, triazine treatment (see Japanese Patent Application Laid-Open No. 2000-218935), chemical etching (Japanese Patent Application Laid-Open No. 2001-225352) (Japanese Patent Application Laid-Open No. 2010-64496), hydrazine treatment, and the like. Further, when the metal material constituting the insert metal member is aluminum, hot water treatment (Japanese Unexamined Patent Application, First Publication No. Hei 8-142110) can be used. As the hot water treatment, immersion in water at 100 ° C for 3 to 5 minutes can be mentioned. Or a combination of a plurality of chemical treatments.

&Lt; Resin member &

The resin member used in the present invention is formed of a resin composition and is insert-molded on an insert metal member. The resin composition comprises (A) 100 parts by mass of a polyarylene sulfide resin, (B) 3 to 15 parts by mass of an epoxy group-containing olefin-based copolymer, and (C) 0.3 to 5 parts by mass of a silicon compound. Hereinafter, each component contained in the resin composition used in the present invention will be described.

[(A) Polyarylene sulfide resin]

The polyarylene sulfide resin (A) is not particularly limited, and conventionally known polyarylene sulfide resins can be used. As the polyarylene sulfide resin (A), polyphenylene sulfide (PPS) resin is preferably used. The polyarylene sulfide resin (A) may be used singly or in combination of two or more.

(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 view of obtaining better adhesion between the insert metal member and the resin member And particularly preferably from 10 to 200 Pa · s.

In addition, when the silicone compound (C) to be described later is a silicone rubber, the melt viscosity is preferably 90 Pa · s or more because the flame retardancy of the resin member is easily improved. The melt viscosity is more preferably 90 to 300 Pa · s, further preferably 100 to 200 Pa · s, and particularly preferably 110 to 150 Pa · s.

[(B) Epoxy group-containing olefin-based copolymer]

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

Examples of the epoxy group-containing olefin-based copolymer (B) include an olefin-based copolymer containing a constituent unit derived from an -olefin and a constituent unit derived from a glycidyl ester of an?,? - unsaturated acid, Of these, an olefin-based copolymer containing a structural unit derived from a (meth) acrylate ester is preferable in that a particularly excellent metal-resin composite molded article can be obtained. Hereinafter, the (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 the present specification, "(meth) acrylic acid" means both of acrylic acid and methacrylic acid, and "(meth) acrylate" means both of acrylate and methacrylate.

The? -olefin is not particularly limited and includes, for example, ethylene, propylene and butylene, with ethylene being particularly preferred. The? -olefin may be used singly or in combination of two or more. When the epoxy group-containing olefin-based copolymer (B) contains a constituent unit derived from an -olefin, flexibility is easily imparted to the resin member. The softening of the resin member by imparting the flexibility contributes to the improvement of the joint strength between the insert metal member and the resin member and also contributes to the improvement of the impact resistance.

The glycidyl ester of an alpha, beta -unsaturated acid is not particularly limited and includes, for example, glycidyl acrylate ester, glycidyl methacrylate ester, glycidyl ethacrylate ester and the like, Methacrylic acid glycidyl esters are preferable. The glycidyl esters of?,? - unsaturated acids may be used singly or in combination of two or more. (B) the epoxy group-containing olefin-based copolymer contains the constituent unit derived from the glycidyl ester of the?,? - unsaturated acid, the effect of improving the bonding strength between the insert metal member and the resin member can be easily obtained.

The (meth) acrylic acid ester is not particularly limited, and examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate and n-octyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-octyl methacrylate Of methacrylic acid esters. Of these, methyl acrylate is particularly preferable. The (meth) acrylic acid esters may be used singly or in combination of two or more kinds. The constituent 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-based copolymer further comprising the constituent unit derived from the -olefin and the constituent unit derived from the glycidyl ester of the?,? - unsaturated acid and the constituent unit derived from the (meth) acrylate ester is , Followed by copolymerization by a conventionally known method. For example, the copolymer can be obtained by copolymerization by a commonly known radical polymerization reaction. The kind of the copolymer is not particularly limited and may be, for example, a random copolymer or a block copolymer. Examples of the olefin-based copolymer include polyolefins such as polymethyl methacrylate, polymethyl acrylate, methyl polyacrylate, ethyl polyacrylate, butyl polyacrylate, 2-ethylhexyl polyacrylate, polystyrene, polyacrylonitrile, Rhenitrile-styrene copolymer, acrylic acid-butyl styrene copolymer, or the like may be an olefin-based graft copolymer which is chemically bonded in a branched or crosslinked structure. As the kind of the copolymer, it is preferable that it is not an olefin-based graft copolymer, and it is more preferable that it is a random copolymer and / or a block copolymer.

The epoxy group-containing olefin-based copolymer may contain constituent units derived from other copolymerizable components within the range not impairing the effect of the present invention.

More specifically, examples of the epoxy group-containing olefin-based copolymer (B) include glycidyl methacrylate-modified ethylenic copolymers and glycidyl ether-modified ethylene copolymers. Of these, The syndiomethacrylate-modified ethylenic copolymer is preferred.

Examples of the glycidyl methacrylate-modified ethylenic copolymer include glycidyl methacrylate graft-modified ethylene polymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer . Of these, an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable in that a particularly excellent metal-resin composite molded article can be obtained, and ethylene- glycidyl methacrylate Acrylate-methyl acrylate copolymer is particularly preferable. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include "bondfast" (manufactured by Sumitomo Chemical Co., Ltd.).

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

The content of the epoxy group-containing olefin-based copolymer (B) is usually 3 to 15 parts by mass, preferably 3 to 12 parts by mass, per 100 parts by mass of the polyarylene sulfide resin (A). If the content is less than 3 parts by mass, the bond strength between the insert metal member and the resin member may not be sufficiently obtained. If the content is more than 15 parts by mass, the flame retardancy is lowered. In addition, since the viscosity of the epoxy group-containing olefin copolymer (B) and the polyarylene sulfide resin (A) The bonding strength between the insert metal member and the resin member may not be sufficiently obtained.

When the silicone compound (C) to be described later is a silicone rubber, the content of the epoxy group-containing olefin-based copolymer (A) in 100 parts by mass of the polyarylene sulfide resin (A) Is preferably 3 to 9 parts by mass, more preferably 3 to 8 parts by mass.

The content of the epoxy group in the epoxy group-containing olefin copolymer (B) is preferably 0.01 to 0.30% by mass, more preferably 0.03 to 0.25% by mass in the total composition. If the content of the epoxy group is 0.01 to 0.30 mass% in the total composition, the bonding strength between the insert metal member and the resin member is easily maintained and the releasability at the time of insert molding is not easily deteriorated, So that the frequency of the mold maintenance tends to be low.

[(C) Silicon compound]

The (C) silicon compound is not particularly limited as long as it is a compound having a silicon atom. In the resin composition used in the present invention, the (C) silicon compound functions as a flame retardant. That is, the resin member obtained from the resin composition tends to have excellent flame retardancy even at a thin thickness, because the resin composition used in the present invention contains (C) a silicon compound. (C) silicon compounds may be used singly or in combination of two or more.

Examples of the silicone compound (C) include silicone rubber and silicone oil. Among them, in the case where the addition amount of the epoxy group-containing olefin copolymer (B) is decreased, the bonding strength between the insert metal member and the resin member is lowered The silicone rubber is preferable. A mechanism capable of further suppressing the decrease of the bonding strength when the silicone rubber is used is presumed as follows. As described above, since the epoxy group-containing olefin-based copolymer (B) contributes to the improvement of the above bonding strength, the use of the epoxy group-containing olefin-based copolymer (B) within the above- The bonding strength can be sufficiently maintained. On the other hand, even if the amount is within the above range, the bonding strength is lowered by the amount of the epoxy group-containing olefin-based copolymer (B) added. In the case of using silicone oil as the (C) silicon compound, the influence when the amount of the epoxy group-containing olefin-based copolymer (B) added is reduced within the above-mentioned predetermined range tends to easily occur (that is, Value is sufficient, but the width of the strength drop is liable to become large). This is believed to be due to the effect that a trace amount of silicone oil bleeds out to the surface of the molded article. On the other hand, when silicone rubber is used as the silicone compound (C), bleeding-out does not occur. Therefore, even if the addition amount of the epoxy group-containing olefin copolymer (B) is reduced within the above- Can be obtained.

· Silicone rubber

Silicone rubber, R ^A ₂ SiO _2/2, and comprises a crosslinked product of a cross-linked polymer of the alignment control structures (線狀) having the unit represented by (wherein, R ^A is an organic group (有機基) are shown.) , Rubber elasticity, and the molecular structure of the organic group bonded to the silicon atom and the crosslinked product is not particularly limited.

The property of the silicone rubber is not particularly limited, but it is, for example, silicone rubber fine particles and added to the resin composition used in the present invention. The shape of the silicon rubber fine particles is not particularly limited and may be, for example, a spherical shape. The average particle diameter of the silicone rubber fine particles is preferably 1 to 40 占 퐉, and more preferably 2 to 20 占 퐉. In the present specification, as the average particle diameter, a stereomicroscopic image is taken in a PC from a CCD camera, and a value measured by an image processing method is adopted by an image measuring instrument.

· Silicone oil

The silicone oil is not particularly limited, and examples thereof include silicone oils represented by the following general formulas.

(Wherein R is the same or different and is an alkyl group of 1 to 3 carbon atoms and R 'is the same or different and represents an unsubstituted or substituted alkyl group or phenyl group, R "represents an alkyl group or alkoxy group of 1 to 3 carbon atoms, m is independently an integer of 0 to 10000, and not simultaneously 0).

In the above general formula, examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

In the above general formula, the alkyl group represented by R 'is the same as that described as the alkyl group represented by R. Examples of the substituted alkyl group include a halogenated alkyl group such as a 3,3,3-trifluoropropyl group substituted with a halogen atom. Examples of the substituted phenyl group include a chlorophenyl group substituted with a halogen atom.

The alkyl group represented by R "in the above general formula is the same as those described as the alkyl group represented by R. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, .

N is preferably an integer of 0 to 5,000, m is preferably an integer of 0 to 5,000, and it is particularly preferable that n and m satisfy this preferable range at the same time.

Specific examples of the silicone oil represented by the above general formula include dimethylsilicone oil, methylphenylsilicone oil, alkylmethyl silicone oil in which a part of the methyl group and phenyl group is substituted with an ethyl group, a propyl group and the like. Of these, Oil is preferred.

The content of the (C) silicon compound is usually 0.3 to 5 parts by mass, preferably 0.4 to 4 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A). If the content is less than 0.3 part by mass, the flame retardancy of the resin member may be lowered in the case of a thin thickness. When the content exceeds 5 parts by mass, the bonding strength between the insert metal member and the resin member may be lowered.

[(D) inorganic filler]

The resin composition used in the present invention may contain (D) an inorganic filler. When the inorganic filler (D) is added to the resin composition used in the present invention, the mechanical strength of the resulting resin member tends to be improved. (D) The inorganic filler is not particularly limited, and conventionally known ones can be mentioned. The shape of the inorganic filler (D) is not particularly limited, and may be a fibrous form, a non-fibrous form such as a spherical form, a powder form, a plate form, a scaly form, , And it is preferably fibrous. As the inorganic filler (D), for example, glass fiber, spherical silica, glass beads and the like can be mentioned, and among them, glass fiber is preferable. The inorganic fillers (D) can be used singly or in combination of two or more kinds.

The content of the inorganic filler (D) is preferably 1 to 250 parts by mass, more preferably 5 to 120 parts by mass, still more preferably 40 to 80 parts by mass, per 100 parts by mass of the polyarylene sulfide resin (A) 80 parts by mass. If the content is 1 to 250 parts by mass, it is preferable that (D) the inorganic filler is added to the resin composition used in the present invention, while maintaining the bond strength between the insert metal member and the resin member and the fluidity at the time of insert molding, It is preferable in that it is easy to obtain an effect.

[(E) epoxy group-containing compound]

The resin composition used in the present invention may contain (E) an epoxy group-containing compound. When the epoxy group-containing compound (E) is added to the resin composition used in the present invention, the bond strength between the insert metal member and the resin member tends to be further improved in the resulting metal-resin composite article. The epoxy group-containing compound (E) is not particularly limited as long as it is an epoxy group-containing compound other than the epoxy group-containing olefin-based copolymer (B). (E) epoxy group-containing compounds may be used singly or in combination of two or more.

The epoxy group-containing compound (E) may be a compound containing one epoxy group in one molecule, or a compound containing two or more epoxy groups in one molecule. (E) epoxy group-containing compounds include, for example, bisphenol-type epoxy compounds obtained by reacting bisphenol A with epichlorohydrin, novolak-type epoxy resins obtained by reacting novolak resin with epichlorohydrin, 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 an epoxy compound obtained by reacting a compound having a double bond with a peroxide. Specific examples include bisphenol A type epoxy compounds, methyl glycidyl ether, phenyl glycidyl ether, various fatty acid glycidyl esters, diethylene glycol diglycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl Epoxidized polybutadiene, epoxidized SBS, and the like. Among them, a bisphenol-type epoxy compound such as a bisphenol A type epoxy compound is preferable.

The content of the epoxy group-containing compound (E) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 7 parts by mass, per 100 parts by mass of the (A) polyarylene sulfide resin. When the content is 0.01 to 10 parts by mass, the bonding strength between the insert metal member and the resin member is likely to be further improved.

The epoxy group content in the epoxy group-containing compound (E) is preferably 0.5 mass% or less (for example, 0 mass% or more and 0.5 mass% or less) and 0.35 mass% or less (for example, More than 0 mass% and not more than 0.35 mass%). If the epoxy group content is 0.5 mass% or less in the total composition, the peel resistance between the insert metal member and the resin member is not easily deteriorated. Particularly, at the time of insert molding, the interface peeling at the flow end of the resin composition in the molten state is not easily caused. In addition, since the releasability at the time of insert molding is not easily deteriorated, it is preferable from the viewpoint that a desired molded article can be easily obtained and productivity is not easily deteriorated.

[Other ingredients]

The resin composition used in the present invention may contain, in addition to the above components, an organic filler, a flame retardant other than the component (C), an ultraviolet absorber, a heat stabilizer, a light stabilizer, A colorant, carbon black, a releasing agent, a plasticizer and the like.

[Production method of resin composition]

The method for producing the resin composition used in 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 in a conventionally known method for producing a resin composition. For example, there may be mentioned a method of melt-kneading and extruding each component using a melt-kneading apparatus such as a single-screw extruder or a twin-screw extruder, and then processing the obtained resin composition into a desired form such as powder, flakes or pellets.

&Lt; Metal-metal composite molded article &

The metal-resin composite formed article according to the present invention comprises an insert metal member and a resin member made of a 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. The metal-resin composite formed article according to the present invention comprises the resin member having excellent flame retardancy even at a thin thickness because (C) the resin composition has a silicon compound content within a specific range. Further, in the metal-resin composite formed article according to the present invention, at least a part of the surface of the insert metal member which is in contact with the resin member is subjected to physical treatment and / or chemical treatment, and at the same time, the content of the epoxy group-containing olefin- , The bonding strength between the insert metal member and the resin member is strong.

The metal-resin composite formed article of the present invention has the above-described characteristics and can be suitably used for applications where the bonding strength between the insert metal member and the resin member is high and the resin member is required to have a thin thickness and excellent flame retardancy . For example, the metal-resin composite formed article of the present invention is suitable as a metal-resin composite article having therein electric or electronic parts or the like which are easily affected by humidity or moisture. Particularly, it is suitable to be used as a component for an electric or electronic device in which penetration of moisture or moisture is connected to a fault, which is expected to be used in a field requiring waterproofing at a high level, for example, steel, grass, . Further, the metal-resin composite molded article of the present invention is also useful, for example, as at least a part of a case for an electric or electronic device. The case for the electric / electronic device may be provided with a resin boss or a holding member inside. Examples of the case for the electric / electronic device include portable electronic devices such as cameras, video-integrated cameras and digital cameras, portable computers such as a notebook computer, a pocket computer, a calculator, an electronic notebook, a PDC, a PHS, A casing of an information or communication terminal, a case of a portable acoustic electronic device such as an MD, a cassette headphone stereo or a radio, a case of a household electric telephone such as a liquid crystal TV monitor, a telephone, a facsimile, and a hand scanner.

&Lt; Method for producing a metal-resin composite molded article >

The specific process of the method for producing the metal-resin composite molded article is not particularly limited and the insert metal member and the resin member are brought into close contact with each other through at least a part of the surface subjected to the physical treatment and / The member and the resin member may be integrated.

For example, an insert metal member subjected to physical treatment and / or chemical treatment at least a part of its surface is placed in a mold for injection molding, and the resin composition used in the present invention is injected into the injection molding mold in a molten state , And a method of producing a metal-resin composite molded article in which the insert metal member and the resin member are integrated. The conditions for the injection molding are not particularly limited, and suitable conditions can be appropriately set depending on the physical properties of the resin composition and the like. A method using transfer molding, compression molding or the like is also an effective method for forming a metal-resin composite molded article 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 by a general molding method such as an injection molding method in advance, and an insert metal member subjected to physical treatment and / or chemical treatment is brought into contact with the resin member at a desired bonding position, , And a method of producing a metal-resin composite formed article in which the insert metal member and the resin member are integrated by melting the vicinity of the contact surface of the resin member. 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.

Example

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Fig. 1 shows a schematic diagram of a metal-resin composite molded article used in Examples and Comparative Examples. (a) is an exploded perspective view, (b) is a perspective view, and (c) is a view showing only a metal part. Such a metal-resin composite formed article was produced by the following method. Dimensions in the drawing are in mm.

&Lt; Preparation of Resin Composition >

The following raw material components were dry-blended and then charged into a twin-screw extruder having a cylinder temperature of 320 DEG C and melt-kneaded to obtain a pelletized thermoplastic resin composition. The blending amounts (parts by mass) of each component are as shown in Tables 1 to 3.

· Polyphenylene sulfide resin

A-1: Fractron KPS W205A (product name), melt viscosity: 55 Pa · s (shear rate: 1216 sec ^-1 , temperature: 310 ° C)

A-2: Melt viscosity: 130 Pa · s (shear rate: 1216 sec ^-1 , temperature: 310 ° C), Kureha product, Fortron KPS W214A

· Epoxy group-containing olefin-based copolymer

B-1: Ethylene-glycidyl methacrylate-methyl acrylate copolymer (Bond Fast 7L, manufactured by Sumitomo Chemical Co., Ltd.), epoxy group content: 3 mass%

· Silicon compound

C-1: Silicone oil (SH200-5000 CS, manufactured by Toray Dow Corning Silicone Co., Ltd.)

C-2: Silicone elastomer (DY33-315 (silicone rubber fine particles, average particle diameter: 10 탆 or less) manufactured by Toray Dow Corning Silicone Co., Ltd.)

· Inorganic filler

D-1: glass fiber (ECS03T-747 (fiber diameter: 13 mu m, fiber length: 3 mm), product of Nippon Electric Glass Co.,

· Epoxy group-containing compound

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

The method of measuring the melt viscosity is as follows.

[Melting point]

The melt viscosity was measured at a barrel temperature of 310 占 폚 and a shear rate of 1216 / sec using a capillary of 1 mm ? X 20 mmL / flat die as a capillary using a product of Toyo Seiki Co., Ltd.

&Lt; Physical treatment or chemical treatment of insert metal member &

A plate-like material composed of copper (C-1100 P, thickness 2 mm) or aluminum (A5052, thickness 2 mm) as the insert metal member and subjected to physical treatment or chemical treatment was used as follows. These plate-like insert metal members have a joint surface in a part indicated by oblique lines in Fig. 1 (a). In Table 1 to Table 3, "physical", "chemical 1", and "chemical 2" refer to the following physical treatments, chemical treatments 1 and chemical treatments 2, respectively.

[Physical treatment]

An alumina abrasive having a grain size of # 1000 (center diameter: 14.5 to 18 탆) was applied to an aluminum insert metal member using a commercially available liquid honing apparatus at a concentration of 20% and a gauge pressure of 0.4 MPa And subjected to roughening treatment.

[Chemical Treatment 1]

The surface of the insert metal member made of copper was immersed in the etching solution A (aqueous solution) having the following composition for one minute to remove the rust-preventive film, and then immersed in the following etching solution B (aqueous solution) for 5 minutes to etch the surface of the metal component Respectively.

Etching solution A (temperature: 20 DEG C)

Hydrogen peroxide 26g / L

Sulfuric acid 90 g / L

Etching solution B (temperature: 25 DEG C)

Hydrogen peroxide 80 g / L

Sulfuric acid 90 g / L

Benzotriazole 5 g / L

Sodium chloride 0.2 g / L

[Chemical Treatment 2]

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

· Alkaline degreasing solution (temperature 40 ℃)

AS-165 F (Ebara Yushin Light Product) 50ml / L

Etching solution C (temperature: 40 DEG C)

OF-901 (Ebara Yushin Light Product) 12 g / L

Magnesium hydroxide 25 g / L

&Lt; Fabrication of Metal Resin Composite Molded Body &

An insert metal member subjected to physical treatment or chemical treatment was placed in a metal mold and an integration step of integrating the insert metal member with a resin member made of the resin composition prepared as described above was carried out. Molding conditions are as follows. The shape of the metal-resin composite molded article is as shown in Fig.

[Molding conditions]

Molding machine: Sodick TR-40 VR (Vertical injection molding machine)

Cylinder temperature: 320 ° C

Mold temperature: 150 ℃

Injection speed: 70mm / s

Boom pressure: 80MPa × 5 seconds

&Lt; Evaluation of metallic resin composite molded article >

The bonding strength of the bonding portion, the fracture form after peeling, and the peeling resistance were evaluated for the metal-resin composite formed article produced by the above method. The concrete evaluation method is as follows.

[Bond strength]

As shown in Fig. 2, a metal-resin composite molded article having the shape shown in Fig. 1 was placed on a support (jig), and the jig was pushed to separate the resin member from the insert metal member in the direction of the arrow at a speed of 1 mm / Lt; / RTI &gt; The strength at the time when the resin member was separated from the insert metal member was measured as the bonding strength. Here, Tensilon UTA-50 kN (manufactured by Orientec Co., Ltd.) was used as a measuring instrument. The results are shown in Tables 1 to 3 (the values are the average values of the trials). Tables 1 to 3 show the results of the relative bonding strength based on the bonding strength of Comparative Example 1 (i.e., the difference between the actual bonding strength in each of the Examples and the Comparative Examples and the bonding strength of Comparative Example 1) . The bonding strength of Comparative Example 1 was about 30 MPa.

In addition, the adhesive strength was evaluated by the following evaluation criteria. The results are shown in Tables 1 to 3.

?: Relative bonding strength is -8 MPa or more, and bonding strength is strong.

X: Relative bonding strength is less than -8 MPa, bonding strength is weak.

[Destruction type]

After the bonding strength measurement, the region which was the bonding portion was visually observed and whether or not the fracture occurred in the interface between the insert metal member and the resin member (interface separation, indicated by x), whether it occurred in the insert metal member or the resin member Quot; o &quot;). The results are shown in Tables 1 to 3.

[Removability]

After the bonding strength measurement, the side of the insert metal member in the region where the bonding portion was located was visually observed to determine the ratio of the area occupied by the resin member adhering on the insert metal member to the area of the entire region which was the bonding region. Respectively. The results are shown in Tables 1 to 3.

?: The above ratio is 50% or more, and the peel resistance is very good.

?: The above ratio is 20% or more and less than 50%, and the peel resistance is good.

?: The above ratio is more than 0% and less than 20%, and the peel resistance is poor.

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

<Other Evaluation>

[Evaluation of flame retardancy]

A test piece (thickness: 0.8 mm) prepared by injection molding the resin composition prepared above at a cylinder temperature of 320 캜 and a mold temperature of 150 캜 was subjected to UL-94 standard vertical burning test in accordance with the UL of the United States, The flame retardancy was evaluated. The results are shown in Tables 1 to 3.

?: The grade of flame retardancy reaches V-0, and the flame retardancy is good.

X: The grade of flame retardancy does not reach V-0, and the flame retardancy is poor.

As shown in Table 1, when the resin composition in which the content of the silicone oil (C) is a specific range is used, the bonding strength between the insert metal member and the resin member is strong and the resin member has excellent flame retardancy even at a thin thickness .

As shown in Table 2, when a resin composition in which the melt viscosity of the polyarylene sulfide resin (A) is within a specific range and the content of the silicone rubber (C) is within a specific range is used, the insert metal member and the resin member And the resin member was excellent in flame retardancy even at a thin thickness.

As shown in Table 3, in the case of using a resin composition in which the content of the epoxy group-containing olefin-based copolymer (B) is within a specific range and the content of the silicone rubber as the silicon compound (C) is within a specific range, the insert metal member and the resin member And the resin member was excellent in flame retardancy even at a thin thickness. When the epoxy group-containing olefin copolymer (B) and the epoxy group-containing compound (E) are used in combination and the epoxy group content in each of these components is adjusted to a predetermined range, the bonding strength between the insert metal member and the resin member is strong, It was confirmed that the peelability was excellent.

As is clear from the comparison between Example 2 and Example 3, in the case of using silicone oil as the (C) silicon compound, the relative bonding strength was lowered greatly, but the comparison between Example 8 and Example 14, And the contrast of Example 11 or the comparison between Example 12 and Example 13, the silicone rubber was used as the silicon compound (C), and the decrease in the relative bonding strength was small. As described above, it was confirmed that when the silicone rubber was used as the (C) silicon compound, it was possible to further suppress the decrease in the bonding strength between the insert metal member and the resin member.

Claims (12)

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 chemical treatment A metal-resin composite formed article,
Wherein the resin composition comprises (A) 100 parts by mass of a polyarylene sulfide resin, (B) 3 to 15 parts by mass of an epoxy group-containing olefin copolymer, and (C) 0.3 to 5 parts by mass of a silicon compound Composite molding. The method according to claim 1,
(A) the melt viscosity of the polyarylene sulfide resin measured at a temperature of 310 DEG C and a shear rate of 1216 / second (C) is at least 90 Pa · s. The method according to claim 1,
Wherein the silicone compound (C) is a silicone rubber and the content of the epoxy group-containing olefin copolymer (B) is 3 to 9 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A). The method according to claim 1,
And (C) the silicon compound is a silicone oil. 5. The method according to any one of claims 1 to 4,
Wherein the epoxy group-containing olefin-based copolymer (B) is an olefin-based copolymer comprising a constituent unit derived from an? -Olefin and a constituent unit derived from a glycidyl ester of an?,? - unsaturated acid. 5. The method according to any one of claims 1 to 4,
(A) 1 to 250 parts by mass of (D) an inorganic filler, and (E) 0.01 to 10 parts by mass of an epoxy group-containing compound based on 100 parts by mass of the polyarylene sulfide resin. Placing an insert metal member subjected to physical treatment and / or chemical treatment at least a part of its surface in a mold for injection molding and injecting the resin composition into the mold for injection molding in a molten state, A method for producing a metal-resin composite molded article,
Wherein the resin composition comprises (A) 100 parts by mass of a polyarylene sulfide resin, (B) 3 to 15 parts by mass of an epoxy group-containing olefin copolymer, and (C) 0.3 to 5 parts by mass of a silicon compound A method for manufacturing a complex formed article. 8. The method of claim 7,
(C) the silicone compound is a silicone rubber, and the melt viscosity of the polyarylene sulfide resin (A) measured at a temperature of 310 ° C and a shear rate of 1216 / second is 90 Pa · s or more. 8. The method of claim 7,
Wherein the silicone compound (C) is a silicone rubber and the content of the epoxy group-containing olefin copolymer (B) is 3 to 9 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A). 8. The method of claim 7,
(C) the silicon compound is a silicone oil. 11. The method according to any one of claims 7 to 10,
Wherein the epoxy group-containing olefin-based copolymer (B) is an olefin-based copolymer comprising a constituent unit derived from an -olefin and a constituent unit derived from a glycidyl ester of an?,? - unsaturated acid. 11. The method according to any one of claims 7 to 10,
(A) 1 to 250 parts by mass of an inorganic filler (D) and 0.01 to 10 parts by mass of an epoxy group-containing compound (E) relative to 100 parts by mass of a polyarylene sulfide resin .

Images