JP2021134267A - Resin composition for polyarylene sulfide complex - Google Patents

Abstract

To provide a polyarylene sulfide resin composition that holds excellent properties of a polyarylene sulfide resin, while having reduced gas generation, and having excellent metal bonding strength, impact resistance, weld strength and low-temperature moldability.SOLUTION: A resin composition for polyarylene sulfide complex contains, based on (A) polyarylene sulfide resin (A component) 100 pts.wt., (B) silicone elastomer (B component) 1-50 pts.wt, (C) a mercapto group-bearing silane coupling agent (C component) 0.001-2 pts.wt. and (D) a functional group-bearing mercaptan or disulfide compound (D component) 0.001-10 pts.wt.SELECTED DRAWING: None

Description

The present invention is a resin composition composed of a polyarylene sulfide resin, a silicone elastomer, a silane coupling agent having a mercapto group, and mercaptans or a disulfide compound having a functional group, and retains the excellent properties of the polyarylene sulfide resin. However, the present invention relates to a resin composition for a polyarylene sulfide composite, which produces a small amount of gas and is excellent in bonding strength with a metal, impact resistance, weld strength and moldability at a low temperature.

Polyarylene sulfide resin is an engineering plastic having excellent chemical resistance, heat resistance, mechanical properties, and the like. For this reason, polyarylene sulfide resins are widely used as electrical and electronic parts, vehicle-related parts, aircraft parts, and housing equipment parts. In recent years, electronic devices such as digital cameras and tablets, and vehicle-related parts such as automobiles have been made smaller and lighter due to energy saving. It is being considered. In particular, the metal-resin composite technology is attracting particular attention because it has features such as weight reduction of parts by integral molding of metal and resin, cost reduction by simplifying the bonding process of parts, and improvement of durability by adhesive-free. ing. In the composite of metal and resin, not only mechanical strength, heat resistance and chemical resistance of resin, but also impact resistance (toughness) of resin and high bonding strength between metal and resin are required. However, although the polyarylene sulfide resin itself has heat resistance and chemical resistance as compared with other resins, the impact strength and the bonding strength with the metal are not sufficient in the composite of the metal and the resin.

As a means for solving this problem, Patent Documents 1 to 3 propose a composition containing a polyarylene sulfide resin, a silicone elastomer, a milled fiber, a fatty acid ester and a silane coupling agent as essential components, but a polyphenylene sulfide resin. Although it mentions the improvement of adhesiveness with other insulating resins and the insulation life, it does not describe the adhesiveness with metals. Patent Documents 4 to 6 propose resin compositions composed of polyphenylene sulfide resins, inorganic fillers, polyethylene-based copolymers, silane coupling agents or reactive functionalized siloxane polymers, and modified siloxane compounds, respectively. Although the improvement of impact resistance and the improvement of adhesion to the epoxy resin are mentioned, the bonding strength between the metal and the resin and the silane coupling agent having a mercapto group are not described. Patent Document 7 discloses a resin composition composed of a polyphenylene sulfide resin having a carboxyl group terminal, an inorganic filler, and a modified olefin copolymer, but mentions improvement in impact resistance and improvement in adhesiveness to an epoxy resin. However, there is no description regarding the bonding strength between metal and resin. Patent Document 8 discloses a resin composition composed of a polyphenylene sulfide resin having a carboxyl group terminal, an inorganic filler, and a modified olefin copolymer, but for improving impact resistance and adhesiveness between a metal and a resin. Although mentioned, the bonding strength between the resin and the metal was not satisfactory due to the generated gas derived from the olefin copolymer. Patent Document 9 discloses a resin composition comprising a polyphenylene sulfide resin having a functional group, an inorganic filler, a modified olefin copolymer, and a silane coupling agent. Although mentioning the improvement of adhesiveness, the bonding strength between the resin and the metal was not satisfactory due to the generated gas derived from the olefin-based copolymer. Patent Document 10 discloses a resin composition composed of a polyphenylene sulfide resin, a mercaptan having a functional group or a disulfide compound, and an inorganic filler, but does not describe the improvement of adhesiveness between a metal and a resin. No. Patent Document 11 discloses a resin composition composed of a polyphenylene sulfide resin having a functional group, a silicone elastomer, a silane coupling agent having a mercapto group, and an inorganic filler, but for improving the adhesiveness between a metal and a resin. Although mentioned, there was room for improvement in moldability due to the need for molding at high temperatures.

JP-A-2018-53003 WO2017 / 057559 WO2016 / 093309 Japanese Unexamined Patent Publication No. 2008-144002 Special Table 2015-513000 Japanese Patent Application Laid-Open No. 2015-523416 Japanese Unexamined Patent Publication No. 2008-69274 WO2015 / 146718 JP-A-2009-143990 JP-A-2017-171936 JP-A-2019-89925

An object of the present invention is a polyarylene sulfide resin which retains the excellent properties of a polyarylene sulfide resin, generates less gas, and has excellent bonding strength with a metal, impact resistance, weld strength, and moldability at a low temperature. To provide a composition.

As a result of diligent studies, the present inventor has found that a polyarylene sulfide resin is a resin composition composed of a polyarylene sulfide resin, a silicone elastomer, a silane coupling agent having a mercapto group, and mercaptans or disulfide compounds containing a functional group. The present invention has been made by finding that the amount of gas generated is small, the bonding strength with a metal, the impact resistance, the weld strength, and the moldability at a low temperature are excellent while maintaining the excellent properties of the resin.

Specifically, the above-mentioned problem is a silane cup having (B) 1 to 50 parts by weight of a silicone elastomer (component B) and (C) a mercapto group with respect to 100 parts by weight of (A) polyarylene sulfide resin (component A). Resin composition for polyarylene sulfide composite containing 0.001 to 2 parts by weight of ring agent (C component) and 0.001 to 10 parts by weight of mercaptans or disulfide compound (D component) containing (D) functional group. Achieved by.

Hereinafter, the details of the present invention will be described.

(Component A: Polyarylene sulfide resin)
As the polyarylene sulfide resin used as the component A of the present invention, any polyarylene sulfide resin may be used as long as it belongs to the category called polyarylene sulfide resin.

The polyarylene sulfide resin has, as its constituent units, for example, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, diphenylene sulfide unit. , Phenylene sulfide unit containing substituent, phenylene sulfide unit containing branched structure, etc. Among them, those containing 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide unit. Preferably, poly (p-phenylene sulfide) is more preferable.

The total chlorine content of the polyarylene sulfide resin used as the component A of the present invention is preferably 500 ppm or less, more preferably 450 ppm or less, still more preferably 300 ppm or less, and particularly preferably 50 ppm or less. When the total chlorine content exceeds 500 ppm, the amount of generated gas may increase and the bonding strength between the metal and the resin may decrease.

The total sodium content of the polyarylene sulfide resin used as the component A of the present invention is preferably 39 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, and particularly preferably 8 ppm or less. If it exceeds 39 ppm, the amount of generated gas may increase and the bonding strength between the metal and the resin may decrease.

The dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyarylene sulfide resin used as the component A of the present invention is preferably 2.7 or more, more preferably 2 It is 8.8 or more, more preferably 2.9 or more. If the degree of dispersion is less than 2.7, burrs may be generated during molding. The upper limit of the degree of dispersion (Mw / Mn) is not particularly specified, but is preferably 10 or less. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). 1-Chloronaphthalene was used as a solvent, and the column temperature was 210 ° C.

The method for producing the polyarylene sulfide resin is not particularly limited, and polymerization is carried out by a known method. Particularly suitable polymerization methods are US Registered Patents Nos. 4,746,758 and 4,786. , 713, Japanese Patent Application Laid-Open No. 2013-522385, Japanese Patent Application Laid-Open No. 2012-233210, Japanese Patent No. 5167276, and the like. These production methods are methods in which a diiodoaryl compound and solid sulfur are directly heated and polymerized without a polar solvent.

The production method includes an iodide step and a polymerization step. In the iodination step, the aryl compound is reacted with iodine to obtain a diiodoaryl compound. In the subsequent polymerization step, a polyarylene sulfide resin is produced by polymerizing a diiodoaryl compound with solid sulfur using a polymerization terminator. Iodine is generated in the form of gas in this step, and it is recovered and used again in the iodination step. Iodine is essentially a catalyst.

As a typical solid sulfur used in the above-mentioned production method, a cycloocta-sulfur form (S8 _{) in which eight} atoms are linked at room temperature can be mentioned. However, the sulfur compound used in the polymerization reaction is not limited, and any form can be used as long as it is solid or liquid at room temperature.

Typical diiodoaryl compounds used in the above-mentioned production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, and alkyl. Derivatives of iodoaryl compounds to which groups or sulfone groups are bonded or oxygen or nitrogen is introduced are also used. Iodoaryl compounds are classified into different isomers depending on the bond position of their iodine atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p, p'-diiodine. Iodine is a compound such as biphenyl that is symmetrically located at both ends of the molecule of the aryl compound. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

Typical polymerization terminators used in the above-mentioned production method include monoiodoaryl compounds, benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferred examples of the monoiodoaryl compound include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferred examples of the benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole. Preferred examples of the benzothiazole sulfenamides are N-cyclohexylbenzothiazole2-sulfenamide, N, N-dicyclohexyl-2-benzothiazolesulfenamide, 2-morpholinothiobenzothiazole, benzothiazolesulfenamide. , Dibenzothiazole disulfide, N-dicyclohexylbenzothiazole 2-sulfenamide, at least one selected from the group. Preferred examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferred examples of the dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferred examples of the aromatic sulfide compound include at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl and benzophenone. Further, in any of the polymerization inhibitors, one or more functional groups may be substituted on the conjugated aromatic ring skeleton. Examples of the functional group include a hydroxy group, a carboxyl group, a mercapto group, an amino group, a cyano group, a sulfo group, a nitro group and the like. in the FT-IR spectrum, a carboxyl group showing the peak of 1600～1800Cm ^-1 or 3300～3500Cm ^-1, and amino groups. The content of the polymerization inhibitor is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

A polymerization reaction catalyst may be used in the above-mentioned production method, and a nitrobenzene-based catalyst can be mentioned as a typical polymerization reaction catalyst. Preferred examples of nitrobenzene-based catalysts are 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, and 2,6-diiodo-4-. At least one selected from the group consisting of nitroamines can be mentioned. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

By using this polymerization method, it is not necessary to substantially reduce the chlorine content and the sodium content, and a polyphenylene sulfide resin having excellent cost performance can be obtained.

(B component: silicone elastomer)
As the silicone elastomer used as the B component of the present invention, any silicone elastomer may be used as long as it belongs to the category called silicone elastomer particles. The shape of the silicone elastomer is not particularly limited, and examples thereof include a spherical shape, a flat shape, and an indefinite shape. Among them, a spherical shape is preferable from the viewpoint of impact strength. The silicone elastomer constituting the B component of the present invention has a main skeleton represented by the formulas RSiO _1/2 , RSiO _2/2 , RSiO _3/2 and RSiO _4/2 .

R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl. Alkyl groups such as groups, undecyl groups, dodecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups and nonadesyl groups; alkenyl groups such as vinyl groups; aryl groups such as phenyl groups, trill groups and naphthyl groups; Aralkyl groups such as benzyl group and phenethyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are halogen atoms, unsubstituted or substituted. Indicates at least one hydrocarbon group selected from the group consisting of a monovalent hydrocarbon group substituted with an amino group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a glycidoxy group, a mercapto group, a carboxyl group or the like.

Further, the silicone elastomer preferably contains a bifunctional siloxane unit in which R is a methyl group, that is, a dimethylsiloxane unit. Further, a silicone elastomer containing a reactive functional group such as a silicon atom-bonded alkoxy group, a silicon atom-bonded epoxy group-containing organic group, a silicon atom-bonded acryloxy group-containing organic group, and a silicon atom-bonded methacrylate group-containing organic group can also be used. Examples of such silicone elastomers include EP-5500, EP-5518, EP-2600, EP-2601, EP-2720 manufactured by Toray Dow Corning Co., Ltd., MX-153, MX manufactured by Kaneka Co., Ltd. It is commercially available as -257, MX-960, MX-170, MX-136, MX-965, MX-217, MX-416, and MX-551 and is easily available. Further, such a silicone elastomer may be used alone or in combination of two or more. Of these, a silicone elastomer having a reactive functional group is preferable from the viewpoint of bonding strength with a metal and impact strength. Examples of the functional group include a hydroxy group, a carboxyl group, a mercapto group, an amino group, an epoxy group, a cyano group, a sulfo group, a nitro group and the like, and among them, a carboxyl group, a thiol group and an epoxy group are preferable, and thiol is used. A group and an epoxy group are more preferable, and an epoxy group is particularly preferable. When an elastomer other than the silicone elastomer is used, the impact resistance is improved, but the bond strength with the metal and the weld strength are lowered due to the large amount of generated gas.

The average primary particle size of the silicone elastomer is not particularly limited, but is preferably 0.1 to 5.0 μm, more preferably 1.0 to 4.0 μm, and even more preferably 1.5 to 3.5 μm from the viewpoint of impact strength. .. Further, the silicone elastomer may carry silicone oil or the like, and can be used as a dispersion dispersed in water or silicone oil.

The content of the B component is 1 to 50 parts by weight, preferably 2 to 45 parts by weight, and more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the A component. If the content of the B component is less than 1 part by weight, the bonding strength with the metal and the impact strength are not sufficiently improved, and the moldability at a low temperature is also inferior. If it exceeds 50 parts by weight, the amount of generated gas is large, so that the bonding strength with the metal and the weld strength are lowered.

(C component: silane coupling agent having a mercapto group)
As the silane coupling agent having a mercapto group used as the C component of the present invention, any silane coupling agent belonging to the category called alkoxylan may be used. For example, mercaptofunctional alkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane can be mentioned. Such a silane coupling agent having a mercapto group may be used alone or in combination of two or more. Of these, 3-mercaptopropyltrimethoxysilane is preferable from the viewpoint of impact resistance and bonding strength with a metal. Examples of such silane coupling agents are commercially available as KBM-803 and KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd. and are easily available. When a silane coupling agent having no mercapto group is used, the amount of gas generated increases and the bonding strength between the metal and the resin decreases.

The content of the C component is 0.001 to 2 parts by weight, preferably 0.005 to 1.5 parts by weight, and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the A component. If the content of the C component is less than 0.001 part by weight, the bonding strength with the metal is not sufficiently improved, and if it exceeds 2 parts by weight, surging or ignition occurs during kneading extrusion, and productivity or workability is lowered. There is a problem that it cannot be extruded.

(Component D: mercaptans or disulfide compounds containing functional groups)
The functional group-containing mercaptans or disulfide compounds used in the present invention are preferably compounds represented by the following general formula (1) or the following general formula (2).

(In the formula (1), R ¹ is a cycloalkyl group containing up to 20 carbon atoms and containing at least one group selected from the group consisting of a carboxyl group, an amino group, a hydroxy group and an epoxy group at the terminal. It is an aryl group or a heterocyclic hydrocarbon group.)

(In formula (2), R ² and R ³ may be the same or different, and independently contain up to 20 carbon atoms, and are composed of a group consisting of a carboxyl group, an amino group, a hydroxy group and an epoxy group at the end. A cycloalkyl group, an aryl group or a heterocyclic hydrocarbon group containing at least one selected group.)

Examples of functional group-containing disulfide compounds include 2,2'-benzimidazole, dithioglycolic acid, α, α'-dithiodilactic acid, β, β'-dithiodilactic acid, 2,2'-dithiodianiline. , 3,3'-dithiodianiline, 4,4'-dithiodianiline, 3,3'-dithiodipyridine, 2,2'-dithiobis (benzothiazole), 2,2'-dithiobis (benzimidazole), Examples thereof include 2,2'-dithiobis (benzoxazole) and 2- (4'-morpholinodithio) benzothiazole.

Examples of mercaptans containing functional groups include 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, thioglycolic acid, thiolactic acid, 2-mercaptoaniline, 3-mercaptoaniline, 4 -Mercaptoaniline, 2-mercaptopyridine, 4-mercaptopyridine, 2-mercaptobenzothiazole can be mentioned.

When mercaptans or disulfide compounds that do not contain functional groups are used, the adhesiveness to the metal deteriorates.

The content of the D component is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the A component. If the content of the D component is less than 0.001 part by weight, the adhesiveness to the metal is inferior, and the fluidity of the resin is inferior. Therefore, it is necessary to raise the mold temperature. And it causes a problem of increasing the maintenance frequency of the mold. If it exceeds 10 parts by weight, the resin is plasticized, the impact strength and the bonding strength are lowered, and burrs are deteriorated, resulting in poor moldability.

(Component E: Filler)
The filler used in the present invention is preferably at least one filler selected from the group consisting of a fibrous filler (E-1 component) and a non-fibrous filler (E-2 component). Examples of the E-2 component include plate-like, powder-like, and granular forms. The E-1 component includes organic fibers such as glass fiber, glass milled fiber, wallastnite, carbon fiber, and total aromatic polyamide fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, and asbestos. Examples thereof include fibers, stone fiber, metal fiber and the like, and glass fiber, glass milled fiber, wallastnite, carbon fiber and total aromatic polyamide fiber are preferably used. E-2 components include silicates such as cericite, kaolin, mica, clay, bentonite, asbestos, talc and alumina silicate, swellable layered silicates such as montmorillonite and synthetic mica, alumina, silicon oxide, magnesium oxide, etc. Metal compounds such as zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass flakes, glass beads, ceramic beads, boron nitride, Examples thereof include silicon carbide, calcium phosphate and silica, and glass flakes, mica, talc, calcium carbonate and glass beads are preferably used. These may be hollow, and it is also possible to use two or more kinds of these fillers in combination.

Further, these fillers are pretreated with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound and an epoxy compound, and a swellable layered silicate with an organic onium ion. Use is preferred in the sense of obtaining better mechanical strength.

Examples of the filler for imparting conductivity to the resin composition of the present invention include a conductive filler. The conductive filler is not particularly limited as long as it is a conductive filler usually used for making a resin conductive, and specific examples thereof include metal powder, metal flakes, metal ribbons, metal fibers, metal oxides, and conductive substances. Examples include coated inorganic fillers, carbon powders, graphite, carbon fibers, carbon flakes, scaly carbon and the like. Specific examples of metal powders, metal flakes, and metal types of metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of the metal type of the metal fiber include iron, copper, stainless steel, aluminum, brass and the like. The metal powder, metal flakes, metal ribbon, and metal fiber may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based, or silane-based.

Specific examples of the metal oxide include SnO2 (antimony doping), In2O3 (antimony doping), ZnO (aluminum doping), and the like, and these are surface treatment agents such as titanate-based, aluminum-based, and silane-based coupling agents. It may be treated.

Specific examples of the conductive substance in the inorganic filler coated with the conductive substance include aluminum, nickel, silver, carbon, SnO2 (antimony doping), In2O3 (antimony doping) and the like. The inorganic fillers to be coated include mica, glass beads, glass fibers, carbon fibers, potassium titanate whiskers, barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide whiskers, titanic acid whiskers, and carbonized steel. An example is a silicon whisker. Examples of the coating method include a vacuum vapor deposition method, a sputtering method, an electroless plating method, and a baking method. Further, these may be surface-treated with a surface treatment agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

Carbon powder is classified into acetylene black, gas black, oil black, naphthaline black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc. according to its raw material and manufacturing method. The raw material and production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used.

The content of the E component is preferably 10 to 250 parts by weight, more preferably 15 to 200 parts by weight, and further preferably 20 to 180 parts by weight with respect to 100 parts by weight of the A component. If the content of the E component is less than 10 parts by weight, the bonding strength with the bonded metal may be inferior, and if it exceeds 250 parts by weight, the productivity or formability may decrease, and there may be a problem that extrusion cannot be performed. ..

By the way, as the E component in the present invention, a carbon fiber having a tensile elastic modulus of 250 GPa or more measured by JIS R7608 is preferable from the viewpoint of the effect of the present invention. Specific examples of carbon fibers include carbon fibers, carbon milled fibers, carbon nanotubes, and the like. The carbon nanotubes preferably have a fiber diameter of 0.003 to 0.1 μm. Further, they may be single-layer, two-layer, or multi-layer, and multi-layer (so-called MWCNT) is preferable. The carbon milled fiber preferably has an average fiber length of 0.05 to 0.2 mm. Among these, carbon fiber is preferable in terms of excellent mechanical strength. As the carbon fiber, any of cellulosic type, polyacrylonitrile type, pitch type and the like can be used. Further, it is obtained by spinning or molding a raw material composition consisting of a polymer and a solvent by a methylene-type bond of aromatic sulfonic acids or salts thereof, and then spinning without undergoing an infusibilization step represented by a method such as carbonization. Can also be used. Among these, a polyacrylonitrile-based high elastic modulus type is particularly preferable. However, if the tensile elastic modulus of the carbon fiber exceeds 600 GPa, the carbon fiber becomes very expensive and the versatility is lowered from the viewpoint of raw material supply. Therefore, the preferable range of the tensile elastic modulus of the carbon fiber used is 250 to 600 GPa. , More preferably 260-500 GPa. The tensile strength of the carbon fiber measured by JIS R7608 is preferably 3,000 MPa or more. However, if the tensile strength of the carbon fiber exceeds 7,000 MPa, the carbon fiber becomes very expensive as well as the tensile elastic modulus, and the versatility is lowered from the viewpoint of raw material supply. Therefore, the preferable range of the tensile strength of the carbon fiber to be used is It is 3,000 to 7,000 MPa, more preferably 5,000 to 6,500 MPa. The average fiber diameter of the carbon fiber is not particularly limited, but is preferably 3 to 15 μm, and more preferably 4 to 13 μm. A carbon fiber having an average fiber diameter in such a range can exhibit good mechanical strength and fatigue characteristics without impairing the appearance of the molded product. The fiber length of the carbon fiber is preferably 60 to 500 μm, more preferably 80 to 400 μm, and particularly preferably 100 to 300 μm as the number average fiber length in the resin composition. The number average fiber length is a value calculated by an image analyzer from the residue of carbon fibers collected by high-temperature ashing of the molded product, dissolution with a solvent, decomposition with chemicals, etc. by observation with an optical microscope. be. Further, when calculating such a value, a value having a length shorter than or equal to the fiber length is a value obtained by a method that does not count.

The above carbon fiber may be coated with a metal layer on the surface of the carbon fiber. Examples of the metal include silver, copper, nickel, and aluminum, and nickel is preferable from the viewpoint of corrosion resistance of the metal layer. As the metal coating method, various methods described above for surface coating with different materials in the glass filler can be adopted. Above all, the plating method is preferably used. Further, also in the case of such a metal-coated carbon fiber, the carbon fiber mentioned above can be used as the original carbon fiber. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably, it is 0.2 to 0.35 μm. The metal-uncoated carbon fiber and the metal-coated carbon fiber are preferably those which have been focused with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, urethane-based resin and carbon fiber treated with epoxy-based resin are suitable in the present invention because of their excellent mechanical strength. The amount of the uncoated carbon fiber and the amount of the metal-coated carbon fiber is not particularly limited, but it is preferable that the amount of the sizing agent is small in terms of improving the weld strength. The preferred amount of sizing agent is 0 to 4%, more preferably 0.1 to 3%.

When carbon fiber is used as the E component, the content is preferably 15 to 180 parts by weight, more preferably 18 to 150 parts by weight, and further preferably 20 to 140 parts by weight with respect to 100 parts by weight of the A component. When the total aromatic polyamide fiber is used as the E component, the content is preferably 15 to 180 parts by weight, more preferably 18 to 150 parts by weight, and further preferably 20 to 140 parts by weight with respect to 100 parts by weight of the A component. It is a department.

(Other ingredients)
The resin composition in the present invention may contain other thermoplastic resins as long as the effects of the present invention are not impaired. Examples of other thermoplastic resins include general-purpose plastics typified by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, liquid crystal polyester resin, polyamide resin, and cyclic resin. Engineering plastics typified by polyolefin resins, polyarylate resins (acrystalline polyarylate, liquid crystal polyarylate), etc., polytetrafluoroethylene, polyether ether ketone, polyetherimide, polysulfone, polyether sulfone, etc. The so-called super engineering plastics can be mentioned.

The resin composition in the present invention is an antioxidant, a heat-resistant stabilizer (hindered phenol-based, hydroquinone-based, phosphite-based and substitutes thereof, etc.) and a weather-resistant agent (resorcinol-based, etc.) as long as the effects of the present invention are not impaired. Salicylate type, benzotriazole type, benzophenone type, hindered amine type, etc.), antistatic agent and lubricant (montanoic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax, etc.) , Pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (niglosin, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plastic agents (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.) ), Antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium salt-type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine-based amphoteric antistatic agents, etc. ), Flame retardant (red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin Alternatively, a combination of these bromine-based flame retardants and antimony trioxide, etc.) and other polymers can be added.

(Manufacturing of resin composition)
The resin composition of the present invention can be produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, or an extruder. It is preferable to melt-knead by a twin-screw extruder, and if necessary, it is preferable to supply an arbitrary component to other melt-mixed components from the second supply port using a side feeder or the like. As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign substances and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign substances from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like. The screws used in the twin-screw extruder are made by inserting screw pieces of various shapes between the forward flight pieces for transportation, combining them in a complicated manner, and integrating them into one screw. A screw piece such as a forward kneading piece, a reverse kneading piece, a reverse flight piece, a forward flight piece having a notch, and a reverse flight piece are arranged and combined in an appropriate order and position in consideration of the characteristics of the raw material to be processed. Can be mentioned. Examples of the melt kneader include a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more shafts, in addition to the twin-screw extruder.

The resin extruded as described above is either directly cut and pelletized, or the strands are cut with a pelletizer after forming the strands and pelletized. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. The shape of the obtained pellet can take a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, still more preferably 2.5 to 4 mm.

(About molded products)
A molded product made of the resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, it is obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulating metal. Examples thereof include mold molding, rapid heating and cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultra-high-speed injection molding. Further, either a cold runner method or a hot runner method can be selected for molding. Further, in extrusion molding, various deformed extrusion molded products, sheets, films and the like can be obtained. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be made into a molded product by rotary molding, blow molding or the like.

(Composite parts made by integrally molding metal)
The metal forming the composite part formed by integrally molding the resin composition of the present invention and the metal is not particularly limited, and a known metal can be appropriately selected depending on the intended use. For example, iron, various stainless steels, aluminum or alloys thereof, copper, magnesium and alloys containing them can be mentioned. Among these, aluminum (aluminum simple substance) and an aluminum alloy are preferable, and an aluminum alloy is more preferable, from the viewpoint of light weight and high strength. The metal molded body is processed into, for example, a flat plate shape, a curved plate shape, a rod shape, a tubular shape, a lump shape, etc. by plastic working such as cutting, pressing, punching, cutting, polishing, electric discharge machining, etc. NS. The surface of the metal molded body preferably has a large surface area in order to improve the adhesion to the resin, and specifically, the surface is preferably roughened. As a method for roughening the surface of the metal member, a chemical etching method using a known etching agent is preferably used.

(Creation of composite parts made by integrally molding metal)
The composite part formed by integrally molding the resin composition of the present invention and a metal is not particularly limited, and is injection molding, extrusion molding, heat press molding, compression molding, transfer molding, laser welding molding, reaction injection molding ( Resin molding methods such as RIM molding), rim molding (LIM molding), and spray molding can be mentioned. Further, when producing a composite composed of an aluminum resin composition film in which a resin composition film is coated on an aluminum surface, a coating method in which the resin composition is dissolved or dispersed in a solvent and applied, and various other coating methods are mentioned. be able to. Other coating methods include baking coating, electrodeposition coating, electrostatic coating, powder coating, ultraviolet curing coating and the like. Above all, injection molding and transfer molding are preferable from the viewpoint of the degree of freedom in the shape of the resin composition portion and productivity. As the molding conditions of the molding methods listed above, known conditions can be adopted depending on the resin composition.

The resin composition of the present invention is a resin composition composed of a polyarylene sulfide resin, a silicone elastomer, a silane coupling agent having a mercapto group, and mercaplans or disulfide compounds containing a functional group, wherein the polyarylene sulfide resin is Since it is a resin composition that retains its excellent properties, generates less gas, and has excellent bonding strength with metals, impact resistance, weld strength, and moldability at low temperatures, it can be used for personal computers, tablets, and so on. Mobile phone housing, display, OA equipment, mobile phone, mobile information terminal, facsimile, compact disk, portable MD, portable radio cassette, PDA (mobile information terminal such as electronic notebook), video camera, digital still camera, optical equipment , Audio, air conditioners, lighting equipment, entertainment products, toy products, and other electrical and electronic equipment housings and internal parts such as trays and chassis, and their cases, mechanical parts, panels and other building materials, motor parts, etc. Alternator terminal, alternator connector, IC regulator, balance meter base for light deer, suspension parts, various valves such as exhaust gas valve, fuel related, exhaust system or intake system various pipes, air intake nozzle snorkel, intake manifold, various arms, various frames , Various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine cooling water joints, carburetor main body, carburetor spacers, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, cranks Shaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch , Starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, battery tray, AT bracket, head lamp support, pedal housing, handle, door beam, protector, chassis, Frame, armrest, horn terminal, fuel Motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, radiator support, spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device case, undercover, scuff plate, pillar trim, propeller shaft, Wheels, fenders, facers, bumpers, bumper beams, bonnets, aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules for automobiles, motorcycle-related parts, parts and skins, landing gear pods, wings, etc. Widely useful in aircraft-related parts such as let, spoiler, edge, rudder, elevator, failing, ribs, parts and skins, windmill blades, etc., especially housings for computers, notebooks, ultrabooks, tablets and mobile phones. , It is widely useful in electronic device housings such as inverter housings for hybrid vehicles and electric vehicles, and its industrial effect is exceptional.

The embodiment of the present invention, which the present inventor considers to be the best at present, is a collection of preferable ranges of the above-mentioned requirements. For example, a representative example thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

[Evaluation of resin composition]
(1) Metal Bonding Strength The metal bonding strength was measured using a test piece having a width of 10 mm, a length of 170 mm, and a thickness of 4 mmt. As a test piece, the pellet was dried at 130 ° C. for 6 hours in a hot air circulation type dryer, and then used in an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) to have a resin temperature of 300 ° C. and a mold temperature of 150. An aluminum piece (A5052P) (width 10 mm, length 50 mm, thickness 2 mm) that has been humidity-controlled for 24 hours under the conditions of 23 ° C. and 50% RH at ° C. is preheated at 150 ° C. and then injected in a mold. An insert molding test piece obtained by molding was used. The aluminum piece is previously immersed in a mixture of 16.8% by weight aqueous solution of sodium hydroxide, 12.5% by weight aqueous solution of zinc nitrate, and 1.0% by weight of sodium thiosulfate under a liquid temperature of 35 ° C. and shaken. By doing so, only 4 μm of the surface layer was etched, washed with water, immersed in a 15 wt% aqueous nitric acid solution (25 ° C.), shaken for 60 seconds, washed with water, and dried. It was used. Using the obtained insert molding test piece using Autograph AG-X plus 50kN manufactured by Shimadzu Corporation, the tensile fracture strength was determined under the conditions of a tensile speed of 5 mm / min, a distance between marked lines of 50 mm, and a distance between grips of 115 mm. It was measured. The larger this value is, the better the bonding strength between the resin composition and the metal is.

(2) Charpy impact strength The impact strength (without notch) was measured in accordance with ISO179 (measurement condition 23 ° C.). The test piece was obtained by drying the obtained pellets at 130 ° C. for 6 hours in a hot air circulation type dryer, and then using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300 ° C. and a mold temperature. It was molded under the condition of 150 ° C. The larger this value is, the more excellent the impact strength of the resin composition is. It should be noted that NB (Non-Break) is unbroken, which means that the impact strength is very excellent.

(3) Amount of gas generated With a differential thermal balance (TG-DTA8121 manufactured by Rigaku Co., Ltd.), the weight loss rate when the pellets were held at 320 ° C. for 30 minutes in a nitrogen atmosphere was measured. The smaller this value is, the smaller the amount of gas generated.

(4) Weld strength A test piece having a weld was prepared under the same conditions as in "(2) Charpy impact strength". At that time, resin was filled from the side gates provided on both sides of the test piece to prepare a weld in the center of the test piece. The tensile breaking strength was measured by a method conforming to ISO527. The larger this value is, the more excellent the tensile breaking strength in the weld portion of the resin composition is.

(5) Moldability at Low Temperature The bonding strength was measured by the same method as in "(1) Metal bonding strength" except that the mold temperature was set to 130 ° C. Those in which the bonding strength at 130 ° C. maintained 80% or more of the bonding strength at 150 ° C. were rated as “◯” because the resin composition was excellent in moldability at low temperature.

[Examples 1 to 15, Comparative Examples 1 to 10]
A bent twin-screw extruder using a polyarylene sulfide resin, a silicone elastomer, a silane coupling agent having a mercapto group, a mercaptan containing a functional group or a disulfide compound, and a filler at the respective blending amounts shown in Tables 1 and 2. It was melt-kneaded using the pellets. As the vent type twin-screw extruder, the Japan Steel Works, Ltd .: TEX-30XSST (complete meshing, rotating in the same direction) was used. The extrusion conditions were a discharge rate of 12 kg / h, a screw rotation speed of 150 rpm, a degree of vacuum of the vent of 3 kPa, and an extrusion temperature of 320 ° C. from the first supply port to the die portion. The filler other than the particulate filler (calcium carbonate) is supplied from the second supply port using the side feeder of the extruder, and is a polyarylene sulfide resin, a silicone elastomer, and a silane coupling agent having a mercapto group. , Functional group-containing mercaptans or disulfide compounds and particulate filler (calcium carbonate) were supplied to the extruder from the first supply port. The first supply port referred to here is the supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port. The obtained pellets are dried at 130 ° C. for 6 hours in a hot air circulation type dryer, and then by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300 ° C. and a mold temperature of 130 ° C. Under the conditions, a test piece for evaluation was molded. The total chlorine content of the polyphenylene sulfide resin _{was quantified by an ion chromatograph method (IC method) by burning the pellets in an Ar / O 2} air stream at 900 ° C. to absorb the generated gas into an absorption liquid. The total sodium content of the polyphenylene sulfide resin is determined by adding sulfuric acid to the pellet, ashing it, melting it with potassium hydrogensulfate, dissolving it in dilute nitrate, and deciding it with pure water, and then ICP emission spectrometry (ICP-AES method). ) Was used for quantitative analysis. The measuring device used was ICP-AES VISTA-MPX manufactured by Varian.

Each component of the symbolic notation shown in Table 1 and Table 2 is as follows.

<Component A>
A-1: Polyphenylene sulfide resin obtained in Production Method 1 [Production Method 1]
To 300.00 g of paradiiodobenzene and 27.00 g of sulfur, 0.60 g of diphenyl disulfide (content of 0.65% by weight based on the weight of finally polymerized PPS) was added as a polymerization inhibitor to 180 ° C. After heating to completely melt and mix them, the temperature was raised to 220 ° C. and the pressure was lowered to 200 Torr. The obtained mixture was polymerized for 8 hours while gradually changing the temperature and pressure so that the final temperature and pressure were 320 ° C. and 1 Torr, respectively, to produce a polyphenylene sulfide resin. The total chlorine content was 20 ppm or less (below the detection limit), and the total sodium content was 7 ppm. The dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) was 3.4.
A-2: Polyphenylene sulfide resin obtained in Production Method 2 [Production Method 2]
A reaction product containing 5130 g of paradiiodobenzene and 450 g of sulfur and 4 g of mercaptobenzothiazole as a reaction initiator is heated to 180 ° C. to completely melt and mix, then the temperature is raised to 220 ° C. and the pressure is 350 Torr. The pressure was lowered. The polymerization reaction of the obtained mixture proceeded while gradually changing the temperature and pressure so that the final temperature and pressure were 300 ° C. and 1 Torr or less, respectively. When the polymerization reaction proceeded by 80% (the degree of progress of the polymerization reaction was confirmed by the method of relative ratio by viscosity ((current viscosity / target viscosity) × 100%)), 25 g of mercaptobenzothiazole was added as a polymerization terminator. And reacted. After 1 hour, 51 g of 4-iodobenzoic acid was added and the reaction was carried out in a nitrogen atmosphere for 10 minutes. Was produced at the end of the main chain. In the FT-IR spectrum of the obtained polyarylene sulfide, the presence of a carboxyl group peak of ^{1600 to 1800 cm -1 was confirmed.} Further, when the height intensity of the aromatic ring expansion / contraction peak appearing at 1400 to 1600 cm ^-1 was 100%, the relative height intensity of the peak at ^{1600 to 1800 cm -1 was 3.4%.} The total chlorine content was 20 ppm or less (below the detection limit), and the total sodium content was 7 ppm.

<B component>
B-1: Epoxy-modified silicone elastomer (EP-2601 manufactured by Toray Dow Corning Co., Ltd.)
B-2: Methyl acrylate-ethylene glycidyl methacrylate copolymer (BF-7M manufactured by Sumitomo Chemical Co., Ltd.)

<C component>
C-1: 3-Mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.)
C-2: 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)

<D component>
D-1: 2,2'-dithionibenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-2: 4-Mercaptobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: 4,4'-dithiodianiline (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-4: 4-Mercaptoaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-5: Diphenyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.)

<E component>
E-1: Circular cross-section chopped glass fiber (T-732H manufactured by Nippon Electric Glass Co., Ltd.)
E-2: Calcium carbonate (KSS-1000 manufactured by Calfine Co., Ltd.)
E-3: Carbon fiber (IM C702 6mm manufactured by Toho Tenax Co., Ltd.)
E-4: Total aromatic polyamide fiber (Para-based total aromatic polyamide fiber T322EH 3-12 manufactured by Teijin Limited)

Claims (6)

(A) Polyarylene sulfide resin (component A) 100 parts by weight, (B) silicone elastomer (component B) 1 to 50 parts by weight, (C) silane coupling agent having a mercapto group (component C) 0.001 A resin composition for a polyarylene sulfide composite containing 0.001 to 10 parts by weight of a mercaptan or a disulfide compound (component D) containing ~ 2 parts by weight and (D) a functional group. The resin composition according to claim 1, wherein the component D is a mercaptan represented by the following general formula (1) or a disulfide compound represented by the following general formula (2).

(In the formula (1), R ¹ is a cycloalkyl group containing up to 20 carbon atoms and containing at least one group selected from the group consisting of a carboxyl group, an amino group, a hydroxy group and an epoxy group at the terminal. It is an aryl group or a heterocyclic hydrocarbon group.)

(In formula (2), R ² and R ³ may be the same or different, and independently contain up to 20 carbon atoms, and are composed of a group consisting of a carboxyl group, an amino group, a hydroxy group and an epoxy group at the end. A cycloalkyl group, an aryl group or a heterocyclic hydrocarbon group containing at least one selected group.) The resin composition according to claim 1 or 2, wherein 10 to 250 parts by weight of the filler (E component) is contained with respect to 100 parts by weight of the A component. The resin composition according to claim 3, wherein the component E is at least one filler selected from the group consisting of glass fibers, carbon fibers and organic fibers. The resin composition according to any one of claims 1 to 4, which is used for joining with a metal material. A molded product comprising the resin composition according to any one of claims 1 to 5.