JP6325295B2 - Insert molding resin composition, metal resin composite molded body using the same, and method for producing the same - Google Patents

Description

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

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

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

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

JP 2010-167475 A

  In the metal-resin composite molded body, in addition to the resin member being excellent in impact resistance, it is practically necessary that the insert metal member and the resin member be sufficiently integrated. Therefore, the metal-resin composite molded body is required to have high bonding strength between the insert metal member and the resin member. In addition, there is an increasing need to apply a metal resin composite molded body to, for example, a high-frequency component, and it is desired that both the dielectric constant and dielectric loss tangent of the resin member in the metal resin composite molded body are low. Furthermore, there is an increasing need to apply a metal resin composite molded body to, for example, a housing for electrical and electronic equipment. Especially when a metal resin composite molded body is used as a white member exposed to the outside, a metal resin composite molded body is used. It is desired that the whiteness of the resin member in the molded body is high.

  An object of the present invention is to provide a metal-resin composite molded body having a strong bonding strength between an insert metal member and a resin member, and excellent in impact resistance and low dielectric properties (low dielectric constant and low dielectric loss tangent). Another object of the present invention is to provide a resin composition for insert molding having high whiteness, a metal resin composite molded body using the same, and a method for producing the same.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by a resin composition in which an epoxy group-containing olefin copolymer and a polystyrene resin are used in combination, and the content of each component is adjusted to a predetermined range. It came to be completed. More specifically, the present invention provides the following.

(1) A resin composition for insert molding on an insert metal member subjected to physical treatment and / or chemical treatment,
The resin composition comprises (A) 100 parts by mass of a polyarylene sulfide resin, (B) 3 to 55 parts by mass of an epoxy group-containing olefin copolymer, and (C) 5 to 60 parts by mass of a polystyrene resin. Including
The resin composition in which the ratio ((B) / (C)) of the content of the (B) epoxy group-containing olefin copolymer to the content of the (C) polystyrene resin is 0.3 to 5.0. object.

  (2) The (B) epoxy group-containing olefin copolymer is an olefin copolymer containing a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid ( The resin composition as described in 1).

  (3) The resin composition according to (1) or (2), wherein the (B) epoxy group-containing olefin copolymer is an olefin copolymer further containing a structural unit derived from a (meth) acrylic acid ester. .

  (4) The epoxy group content in the (B) epoxy group-containing olefin copolymer is 0.05 to 0.20% by mass in the total composition, according to any one of (1) to (3). Resin composition.

  (5) Furthermore, (A) 5 to 80 parts by mass of an inorganic filler, (E) 0.01 to 10 parts by mass of an epoxy group-containing compound, and (F) an epoxy with respect to 100 parts by mass of (A) polyarylene sulfide resin The resin composition according to any one of (1) to (4), which contains at least one kind of group-free olefin-based compound of 0.01 to 25 parts by mass.

  (6) The resin composition according to (5), wherein the (E) epoxy group-containing compound is an epoxy resin.

  (7) The resin composition according to (5) or (6), wherein the (E) epoxy group-containing compound is a bisphenol type epoxy resin.

  (8) The resin composition according to any one of (5) to (7), wherein an epoxy group content in the (E) epoxy group-containing compound is 0.2% by mass or less in the entire composition.

  (9) The resin composition according to any one of (1) to (8), further comprising (G) at least one white pigment selected from the group consisting of titanium oxide, zinc sulfide, magnesium oxide, and barium sulfate. .

  (10) An insert metal member, and a resin member made of the resin composition according to any one of (1) to (9) and insert-molded on the insert metal member, A metal resin composite molded body in which at least a part of a surface in contact with the resin member is subjected to physical treatment and / or chemical treatment.

  (11) The resin according to any one of (1) to (9), wherein an insert metal member whose surface is at least partially subjected to physical treatment and / or chemical treatment is disposed in an injection mold. A method for producing a metal-resin composite molded body, comprising an integration step of injecting the composition into a mold for injection molding in a molten state and integrating the insert metal member with a resin member.

  According to the present invention, a metal-resin composite molded body having a strong bonding strength between an insert metal member and a resin member is provided, and excellent in impact resistance and low dielectric properties (low dielectric constant and low dielectric loss tangent). In addition, a resin composition for insert molding having high whiteness, a metal resin composite molded body using the same, and a method for producing the same can be provided.

FIG. 1 is a diagram schematically showing a metal resin composite molded body used in Examples and Comparative Examples, (a) is an exploded perspective view, (b) is a perspective view, and (c) is a metal. It is a figure which shows only a part. FIG. 2 is a diagram schematically illustrating a method for measuring the bonding strength between the resin portion and the metal portion, performed in the example.

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

<Resin composition>
The resin composition according to the present invention is for insert molding on an insert metal member that has been subjected to physical treatment and / or chemical treatment, and (A) 100 parts by mass of polyarylene sulfide resin; B) 3 to 55 parts by mass of an epoxy group-containing olefin copolymer and (C) 5 to 60 parts by mass of a polystyrene resin. Hereinafter, each component contained in the resin composition will be described.

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

  (A) Since polyarylene sulfide resin provides better adhesion between the insert metal member and the resin member, the melt viscosity at a shear rate of 1216 / sec, measured at 310 ° C., is 8 to 300 Pa · s. Is preferable, and 10 to 200 Pa · s is particularly preferable.

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

  Examples of the (B) epoxy group-containing olefin copolymer include an olefin copolymer including a structural unit derived from an α-olefin and a structural unit derived from a glycidyl ester of an α, β-unsaturated acid. Among them, an olefin copolymer containing a structural unit derived from (meth) acrylic acid ester is more preferable because a particularly excellent metal resin composite molded body can be obtained. Hereinafter, (meth) acrylic acid ester is also referred to as (meth) acrylate. For example, glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate. In this specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid, and “(meth) acrylate” means both acrylate and methacrylate.

  The α-olefin is not particularly limited, and examples thereof include ethylene, propylene, butylene, and ethylene is particularly preferable. The α-olefin can be used alone or in combination of two or more. (B) Since the epoxy group-containing olefin copolymer contains a structural unit derived from α-olefin, flexibility is easily imparted to the resin member. The softening of the resin member due to the provision of flexibility contributes to an improvement in bonding strength between the insert metal member and the resin member, and also contributes to an improvement in impact resistance.

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

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

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

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

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

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

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

  (B) Content of an 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 15-40 mass parts. When the content is less than 3 parts by mass, the bonding strength between the insert metal member and the resin member is lowered, the impact resistance of the resin composition is lowered, or the dielectric constant is easily increased. In addition, the linear expansion difference between these members has influenced the adhesiveness of an insert metal member and a resin member. (B) It is considered that the epoxy group-containing olefin copolymer realizes stress relaxation, thereby reducing strain and improving the joint strength. Toughness is effective for stress relaxation, and toughness can be evaluated by tensile elongation. When the content of the (B) epoxy group-containing olefin copolymer that functions as an elastomer is small, it is considered that the tensile elongation is small and a sufficient stress relaxation effect cannot be obtained. Stress relaxation also contributes to improved impact resistance. On the other hand, when the content exceeds 55 parts by mass, the dielectric loss tangent of the resin composition tends to increase, and the fluidity during insert molding tends to decrease.

  Moreover, it is preferable that the epoxy group content in (B) epoxy group containing olefin type copolymer is 0.05-0.20 mass% in the whole composition, and 0.08-0.18 mass%. It is more preferable that When the epoxy group content is 0.05 to 0.20% by mass in the total composition, the bonding strength between the insert metal member and the resin member is easily maintained, and the mold release at the time of insert molding This is preferable in that the property is not easily deteriorated and the amount of generated gas tends to be suppressed, and the frequency of mold maintenance tends to be low.

  The content of (B) epoxy group-containing olefin copolymer is the content (unit) of (B) epoxy group-containing olefin copolymer relative to the content (unit: parts by mass) of (C) polystyrene resin described later. : Parts by mass) is adjusted so that the ratio ((B) / (C)) is 0.3 to 5.0. By adjusting (B) / (C) to such a range, both the impact resistance and low dielectric properties (low dielectric constant and low dielectric loss tangent) of the molded product obtained from the resin composition containing these components are improved. can do. When (B) / (C) is less than 0.3, the molded article obtained from the resin composition is inferior in impact resistance. When (B) / (C) is more than 5.0, the low dielectric property of the molded product obtained from the resin composition is inferior.

[(C) Polystyrene resin]
(C) The polystyrene resin is not particularly limited. (C) A polystyrene-type resin can be used individually by 1 type or in combination of 2 or more types.

  (C) Examples of polystyrene resins include polystyrene; poly (alkyl styrene); poly (halogenated styrene); poly (alkoxy styrene); poly (vinyl benzoate); styrene, alkyl styrene, halogenated styrene, alkoxy. Examples include at least two kinds of copolymers selected from the group consisting of styrene and vinyl benzoate.

  The poly (alkylstyrene) may be a homopolymer or a copolymer. Examples of the alkyl styrene include methyl styrene, ethyl styrene, isopropyl styrene, and t-butyl styrene. Thus, as poly (alkylstyrene), for example, poly (methylstyrene); poly (ethylstyrene); poly (isopropylstyrene); poly (t-butylstyrene); methylstyrene, ethylstyrene, isopropylstyrene, and t- Examples include at least two types of copolymers selected from the group consisting of butylstyrene.

  The poly (halogenated styrene) may be a homopolymer or a copolymer. Examples of the halogenated styrene include chlorostyrene, bromostyrene, and fluorostyrene. Therefore, as the poly (halogenated styrene), for example, at least two selected from the group consisting of poly (chlorostyrene); poly (bromostyrene); poly (fluorostyrene); chlorostyrene, bromostyrene, and fluorostyrene Copolymers of each other can be mentioned.

  The poly (alkoxystyrene) may be a homopolymer or a copolymer. Examples of alkoxy styrene include methoxy styrene and ethoxy styrene. Accordingly, examples of poly (alkoxystyrene) include poly (methoxystyrene), poly (ethoxystyrene), and methoxystyrene-ethoxystyrene copolymer.

  Of these, polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (pt-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly ( p-fluorostyrene), a copolymer of styrene and p-methylstyrene is preferred, and polystyrene is particularly preferred.

  (C) The structure of the polystyrene resin is not particularly limited, and may be any of an atactic structure, an isotactic structure, and a syndiotactic structure. The polystyrene resin having an atactic structure refers to a resin having a three-dimensional structure in which a phenyl group or a substituted phenyl group as a side chain is randomly located with respect to a main chain formed from a carbon-carbon bond. The polystyrene-based resin having an isotactic structure refers to a resin having a three-dimensional structure in which all phenyl groups and substituted phenyl groups as side chains are located in the same direction with respect to the main chain formed from carbon-carbon bonds. A polystyrene-based resin having a syndiotactic structure (hereinafter also referred to as “SPS resin”) is alternately opposed to a phenyl group or a substituted phenyl group which is a side chain with respect to a main chain formed from a carbon-carbon bond. It has a three-dimensional structure located in the direction. For example, the SPS resin has a melting point of 180 to 310 ° C., and has excellent heat resistance as compared with a polystyrene resin having an atactic structure. Therefore, from the viewpoint of heat resistance of the obtained resin member, a polystyrene resin having a syndiotactic structure is preferable.

  (C) The polystyrene resin can be produced by a conventionally known method. In particular, the SPS resin is a styrenic monomer (for example, an SPS resin) in the presence of an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and trialkylaluminum as a catalyst. It can be produced by polymerizing a monomer corresponding to the constituent unit contained (see, for example, JP-A-62-187708).

  (C) Content of polystyrene-type resin is 5-60 mass parts normally with respect to 100 mass parts of (A) polyarylene sulfide resin, Preferably it is 5-40 mass parts. When the content is less than 5 parts by mass, the dielectric constant of the resin composition tends to increase. When the said content exceeds 60 mass parts, the impact resistance of a resin composition will fall easily.

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

  The content of the (D) inorganic filler is preferably 5 to 80 parts by mass and more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the (A) polyarylene sulfide resin. When the content is 5 to 80 parts by mass, the resin composition according to the present invention (D) while maintaining good bonding strength between the insert metal member and the resin member and fluidity at the time of insert molding (D ) It is preferable in that it is easy to obtain an effect by adding an inorganic filler. Moreover, the obtained resin composition tends to have excellent low dielectric properties (low dielectric constant and low dielectric loss tangent).

[(E) Epoxy group-containing compound]
The resin composition according to the present invention may include (E) an epoxy group-containing compound. When (E) an epoxy group-containing compound is added to the resin composition according to the present invention, the bonding strength between the insert metal member and the resin member is more likely to be improved in the resulting metal resin composite molded article. The (E) epoxy group-containing compound is not particularly limited as long as it is an epoxy group-containing compound other than the (B) epoxy group-containing olefin copolymer. (E) An epoxy group containing compound can be used individually by 1 type or in combination of 2 or more types.

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

  (E) The content of the epoxy group-containing compound is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 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 more likely to be improved.

  Further, the epoxy group content in the (E) epoxy group-containing compound is preferably 0.2% by mass or less (for example, more than 0% by mass and 0.2% by mass or less) in the total composition. More preferably, it is 1 mass% or less (for example, more than 0 mass% and 0.1 mass% or less). When the epoxy group content is 0.2% by mass or less in the total composition, the peel resistance between the insert metal member and the resin member is unlikely to decrease. In particular, interfacial peeling is unlikely to occur even at the flow end of the resin composition in a molten state during insert molding. Moreover, since the mold release property at the time of insert molding is difficult to deteriorate, it is preferable in that a desired molded product can be easily obtained and productivity is hardly lowered.

[(F) Epoxy group-free olefin compound]
The resin composition according to the present invention may include (F) an epoxy group-free olefin compound. Addition of (F) an epoxy group-free olefin compound to the resin composition according to the present invention is preferable in that the impact resistance of the resin composition is easily improved and the dielectric constant is easily lowered. (F) The epoxy group-free olefin compound is not particularly limited as long as it is an epoxy group-free olefin polymer. (F) Epoxy group-free olefinic compounds can be used singly or in combination of two or more.

  (F) Epoxy group-free olefinic compounds are substituted with functional groups containing atoms other than carbon atoms and hydrogen atoms, such as halogen atoms such as chlorine and bromine atoms, hydroxyl groups, amino groups, carboxyl groups and alkoxycarbonyl groups. However, from the viewpoint of low dielectric properties (low dielectric constant and low dielectric loss tangent), it is preferably composed of only carbon atoms and hydrogen atoms.

  Examples of the non-epoxy group-containing olefin polymer include α-olefins such as ethylene, propylene, 1-butene and 1-octene; alkenes other than α-olefins such as 2-butene and 2-pentene; butadiene and isoprene. , 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and other dienes; triene, tetraene and other polyenes other than dienes, such as homopolymers and copolymers. . Examples of the homopolymer include polyethylene and polybutene. Examples of the copolymer include an ethylene-octene copolymer and an ethylene-ethyl acrylate copolymer, and an ethylene-octene copolymer is particularly preferable.

  The content of the (F) epoxy group-free olefinic compound is preferably 0.01 to 25 parts by mass with respect to 100 parts by mass of the (A) polyarylene sulfide resin. When the content is 0.01 to 25 parts by mass, the bonding strength between the insert metal member and the resin member and the fluidity at the time of insert molding are easily maintained well.

[(G) White pigment]
The resin composition according to the present invention may include (G) at least one white pigment selected from the group consisting of titanium oxide, zinc sulfide, magnesium oxide, and barium sulfate. The resin composition according to the present invention has high whiteness even when it does not contain the (G) component (hue L value is 80 or more), but by containing the (G) component, the hue b value becomes small, Yellowness is suppressed and whiteness is further improved. From the viewpoint of low dielectric properties (low dielectric constant and low dielectric loss tangent), titanium oxide and zinc sulfide are preferable, and zinc sulfide is particularly preferable.

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

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

<Metal resin composite molding>
The metal resin composite molded body according to the present invention includes an insert metal member and a resin member made of the resin composition according to the present invention and insert-molded on the insert metal member. At least a part of the surface of the insert metal member in contact with the resin member is subjected to physical treatment and / or chemical treatment. The metal resin composite molded body according to the present invention is a resin composition in which (B) an epoxy group-containing olefin copolymer and (C) a polystyrene resin are used in combination, and the content of each component is adjusted to a predetermined range. Because it is used, the bonding strength between the insert metal member and the resin member is strong, and the impact resistance and low dielectric properties (low dielectric constant and low dielectric loss tangent) of the resin member are excellent. Is expensive.

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

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

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

  In this invention, the insert metal member shape | molded in the desired shape according to a use etc. is used. For example, an insert metal member having a desired shape can be obtained by pouring molten metal or the like into a mold having a desired shape. Further, in order to form the insert metal member into a desired shape, cutting by a machine tool or the like may be used.

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

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

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

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

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

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

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

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

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

<Preparation of resin composition>
After dry blending the following raw material components, the mixture was put into a twin screw extruder having a cylinder temperature of 320 ° C. and melt-kneaded to obtain a pelletized thermoplastic resin composition. The compounding amount (parts by mass) of each component is as shown in Tables 1 to 3.
Polyphenylene sulfide resin A-1: Fortron KPS W214A (product name), melt viscosity: 130 Pa · s (shear rate: 1216 / second, temperature: 310 ° C.), manufactured by Kureha Co., Ltd. A-2: Fortron KPS W205AH (Product name), melt viscosity: 55 Pa · s (shear rate: 1216 / sec, temperature: 310 ° C.), manufactured by Kureha Co., Ltd., epoxy group-containing olefin copolymer B-1: ethylene-glycidyl methacrylate-acrylic acid Methyl copolymer, bond first 7L (product name), epoxy group content: 3% by mass, manufactured by Sumitomo Chemical Co., Ltd. B-2: ethylene-glycidyl methacrylate copolymer, bond first E (product name), epoxy group Content: 12% by mass, polystyrene resin made by Sumitomo Chemical Co., Ltd. C-1: Syndiotactic polystyrene tree Fat, XAREC 130ZC (product name), manufactured by Idemitsu Kosan Co., Ltd., inorganic filler D-1: Glass fiber (chopped strand), CS GL-HF (product name), manufactured by Owens Corning Manufacturing Co., Ltd. D-2: Glass fiber (chopped strand), T-747 (product name), manufactured by Nippon Electric Glass Co., Ltd. Epoxy group-containing compound E-1: Bisphenol A type epoxy resin (solid), jER (formerly “Epicoat”) , Both are registered trademarks) 1004K (product name), epoxy group content: 4.6 mass%, epoxy equivalent 925, molecular weight: 1650, manufactured by Mitsubishi Chemical Corporation, epoxy group-free olefin compound F-1: ethylene -Octene copolymer, Engage 8003 (product name), manufactured by Dow Chemical Japan Co., Ltd. F-2: Ethylene-octene copolymer, Enga ge 8440 (product name), manufactured by Dow Chemical Japan Co., Ltd., white pigment G-1: titanium oxide, TITON SR-1 (product name), Sakai Chemical Industry Co., Ltd. G-2: zinc sulfide The measuring method of a viscosity is as follows.

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

<Evaluation of impact resistance>
For the resin compositions prepared in any of Examples 1 to 10 and Comparative Examples 1 to 8, Charpy impact test pieces were produced by injection molding at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., and changed to ISO 179 / 1eA. Evaluation was performed under the condition of 23 ° C. in accordance with the established evaluation criteria. The results are shown in Tables 1 to 3.

<Evaluation of dielectric properties>
About the resin composition prepared in any of Examples 1 to 10 and Comparative Examples 1 to 8, a test of 1.8 mm × 1.8 mm × 80 mm at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. by injection molding. A piece was molded and left in an air-conditioned room room temperature (23 ° C. ± 2 ° C., 50% RH ± 5% RH) atmosphere for 2 hours or longer, and then a network analyzer 8757D manufactured by Agilent Technologies, a synthesized sweeper 83650L, and ( Using a 2 GHz cavity resonator manufactured by Kanto Applied Electronics Co., Ltd., the relative permittivity (εr) and dielectric loss tangent (tan δ) at 2 GHz were measured by the cavity resonance perturbation method. The results are shown in Tables 1 to 3.

<Physical treatment or chemical treatment of insert metal member>
As the insert metal member, a plate-like material made of copper (C-1100P, thickness 2 mm) or aluminum (A5052, thickness 2 mm) and subjected to physical treatment or chemical treatment as follows was used. These plate-like insert metal members have a joining surface at a portion indicated by hatching in FIG. In Tables 1 to 3, “Physics”, “Chemical 1”, and “Chemical 2” refer to the following physical treatment, chemical treatment 1, and chemical treatment 2, respectively.

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

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

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

<Production of metal resin composite molded body>
An insert metal member subjected to physical treatment or chemical treatment is placed in a mold, and the insert metal member is made of a resin composition prepared in any one of Examples 1 to 10 and Comparative Examples 1 to 8. The integration process to integrate was performed. The molding conditions are as follows. The shape of the metal resin composite molded body is as shown in FIG.
[Molding condition]
Molding machine: Sodick TR-40VR (vertical injection molding machine)
Cylinder temperature: 320 ° C
Mold temperature: 150 ° C
Injection speed: 70mm / s
Holding pressure: 80 MPa x 5 seconds

<Evaluation of metal resin composite molded body>
About the metal resin composite molded object produced by said method, the fracture | rupture form after peeling a resin member from an insert metal member, and peeling resistance were evaluated. The results are shown in Tables 1 to 3. The specific evaluation method is as follows.

[Destruction mode and peel resistance]
As shown in FIG. 2, the metal-resin composite molded body having the shape shown in FIG. 1 is placed on a pedestal (jig), and the resin member is pushed away from the insert metal member in the direction of the arrow at a speed of 1 mm / min. I moved the jig. The area that was the joint was visually observed, and whether the fracture occurred only at the interface between the insert metal member and the resin member (interface peeling, indicated by x), or at least in the resin member (cohesive failure, ◎ Display).
In addition, by visually observing the insert metal member side of the region that was the joint portion, find the ratio of the area occupied by the resin member adhering to the insert metal member and the area of the entire region that was the joint portion, Evaluation was made according to the following criteria.
A: 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.
Δ: 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 peel resistance is extremely poor.

<Evaluation of hue>
About the resin composition prepared in any of Examples 11 to 13, a dumbbell test piece having a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. and a thickness of 4 mmt was produced by injection molding, and Nippon Denshoku Industries Co., Ltd. Using a color difference meter, color measurement is performed by the 0 ° -d method defined in JIS Z 8722, and based on the result, hue L (lightness) and hue b (yellow) are determined by the Hunter color difference formula defined in JIS Z 8730. Degree) and hue a (redness). The results are shown in Table 4.

  As shown in Table 1 to Table 5, 3 to 55 parts by mass of (B) an epoxy group-containing olefin copolymer and 5 to 60 parts by mass of (C) polystyrene resin are used in combination, and (C) polystyrene The ratio of the content of the (B) epoxy group-containing olefin copolymer to the content of the resin ((B) / (C)) is adjusted to 0.3 to 5.0, and the content of each component is predetermined. In Examples 1-14 adjusted to the range, the joint strength between the insert metal member and the resin member in the metal-resin composite molded body was strong, and the resin member was excellent in impact resistance and low dielectric properties.

  In contrast, in Comparative Examples 1 to 3, in which the content of (C) polystyrene-based resin is less than 5 parts by mass, the low dielectric properties were inferior compared to Examples 1 to 14 (the relative dielectric constant was high). .

  In Comparative Examples 4 and 5, in which the content of the (C) polystyrene-based resin is less than 5 parts by mass and the content of the (F) epoxy group-free olefinic compound is more than 25 parts by mass, Examples 1 to Compared to 14, the peel resistance was inferior.

  (C) In Comparative Example 6 in which the content of the polystyrene-based resin was more than 60 parts by mass, the impact resistance was inferior compared to Examples 1-14.

  (B) In Comparative Example 7 in which the content of the epoxy group-containing olefin copolymer is less than 3 parts by mass, the impact resistance and low dielectric properties are inferior to those of Examples 1 to 14 (relative dielectric constant is Furthermore, the bonding strength between the insert metal member and the resin member in the metal-resin composite molded body was inferior.

  (B) In Comparative Example 8 in which the content of the epoxy group-containing olefin copolymer is more than 55 parts by mass, the low dielectric properties were inferior compared to Examples 1 to 14 (dielectric loss tangent was high).

  Comparative Example 9 in which (B) / (C) was less than 0.3 was inferior in impact resistance as compared with Examples 1-14.

  Comparative Example 10 in which (B) / (C) was more than 5.0 was inferior in low dielectric properties (high dielectric loss tangent) compared to Examples 1-14.

  As shown in Table 6, the resin composition of Example 15 had high whiteness even when it did not contain the white pigment of component (G) (hue L value was 80 or more).

  On the other hand, the resin compositions of Examples 16 and 17 containing the white pigment of component (G) have a smaller hue b value and a lower yellowness than the resin composition of Example 15, and are further white. The degree was improving.

Claims (13)

A resin composition for insert molding on an insert metal member subjected to physical treatment and / or chemical treatment,
The resin composition comprises (A) a polyarylene sulfide resin 100 parts by weight, (B) an epoxy group-containing olefin copolymer 3 to 55 parts by weight, (C) a polystyrene resin 5 to 60 parts by weight, ( D) 5 to 80 parts by mass of an inorganic filler ,
The resin composition in which the ratio ((B) / (C)) of the content of the (B) epoxy group-containing olefin copolymer to the content of the (C) polystyrene resin is 0.3 to 5.0. object. The resin composition according to claim 1, wherein the (C) polystyrene resin is a syndiotactic polystyrene resin. The resin composition according to claim 1 or 2, wherein the (D) inorganic filler is a glass fiber. (B) the epoxy group-containing olefin copolymer, a structural unit derived from α- olefin alpha, claim 1 is an olefin-based copolymer containing a constitutional unit derived from the glycidyl ester of β- unsaturated acids 4. The resin composition according to any one of 3 . The resin composition according to any one of claims 1 to 4, wherein the (B) epoxy group-containing olefin copolymer is an olefin copolymer further comprising a structural unit derived from a (meth) acrylic acid ester. The resin composition according to any one of claims 1 to 5 , wherein an epoxy group content in the (B) epoxy group-containing olefin copolymer is 0.05 to 0.20 mass% in the entire composition. Further, at least 100 parts by mass of (A) polyarylene sulfide resin, at least 0.01 to 10 parts by mass of (E) an epoxy group-containing compound, and 0.01 to 25 parts by mass of (F) an epoxy group-free olefin compound. The resin composition according to any one of claims 1 to 6 , comprising one kind. The resin composition according to claim 7 , wherein the (E) epoxy group-containing compound is an epoxy resin. The resin composition according to claim 7 or 8 , wherein the (E) epoxy group-containing compound is a bisphenol-type epoxy resin. The resin composition according to any one of claims 7 to 9 , wherein an epoxy group content in the (E) epoxy group-containing compound is 0.2% by mass or less in the entire composition. The resin composition according to any one of claims 1 to 10 , further comprising (G) at least one white pigment selected from the group consisting of titanium oxide, zinc sulfide, magnesium oxide, and barium sulfate. An insert metal member and a resin member made of the resin composition according to any one of claims 1 to 11 and insert-molded on the insert metal member, wherein the insert metal member is in contact with the resin member. A metal resin composite molded body in which at least a part of the surface is subjected to physical treatment and / or chemical treatment. An insert metal member having at least a part of the surface subjected to physical treatment and / or chemical treatment is disposed in an injection mold, and the resin composition according to any one of claims 1 to 11 is in a molten state. The method for producing a metal-resin composite molded body comprising an integration step in which the insert metal member is integrated with the resin member by being injected into the injection mold.

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