JP2008075049A - Polyphenylene sulfide resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition which is excellent in flowability and low warpage property, especially excellent in both low anisotropy of linear expansion coefficient and heat cycle resistance, while keeping the excellence in rigidity, heat resistance, dimensional stability, chemical resistance, low water absorptivity, flame resistance, etc. inherent in a conventional polyphenylene sulfide resin, and to provide a metal inserted molded product and a molded product having good sealing and adhesion properties, comprised of the same. <P>SOLUTION: The polyphenylene sulfide resin composition comprises (A) a 100 pts.wt. polyphenylene sulfide resin, (B) a 1-25 pts.wt. olefin copolymer prepared by copolymerization of ethylene and glycidyl methacrylate or glycidyl acrylate, (C) a 30-150 pts.wt. glass fiber, and (D) a 10-100 pts.wt. mica having a 10-100 μm weight average particle diameter. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a reinforced polyphenylene sulfide resin capable of obtaining a molded product having excellent linear expansion coefficient, low anisotropy and heat cycle resistance, and more specifically, rigidity, heat resistance, dimensional stability, chemical resistance. The present invention relates to a polyphenylene sulfide resin composition excellent in low water absorption, low balance in warpage and fluidity, and a metal insert molded product and a molded product having sealing and adhesion.

  Since polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has suitable properties as engineering plastics such as excellent heat resistance, rigidity, dimensional stability, and flame retardancy, various types are mainly used for injection molding. Widely used in electrical / electronic parts, machine parts and automobile parts.

  However, PPS resin is inferior in toughness compared to other engineering plastics. In addition, in applications where metal is used as an insert, there is a problem that it is brittle with respect to a thermal cycle by repeated low and high temperatures, or thermal shock, and is inferior in thermal properties.

  Under such circumstances, several olefin resins have been studied so far for the purpose of improving the impact properties of PPS resins.

For example, Patent Document 1 discloses a PPS resin composition reinforced with PPS resin with an elastomer, glass fibers, and glass flakes, but there is a large amount of wear with metal terminals and the like due to glass fibers and glass flakes of reinforcing materials, The fluidity was insufficient. Patent Document 2 discloses a PPS resin composition composed of a PPS resin, glass fiber, and mica, but has low low temperature toughness and insufficient heat cycle resistance. In Patent Document 3, a PPS resin composition comprising an ethylene copolymer containing ethylene, an α, β-unsaturated carboxylic acid alkyl ester and maleic anhydride, a glass fiber and mica is added to a PPS resin which is not thermally oxidized and crosslinked. It is disclosed. However, according to the study by the present inventors, heat cycle resistance was low only by blending an ethylene-based copolymer containing ethylene, an α, β-unsaturated carboxylic acid alkyl ester and maleic anhydride. Patent Document 4 discloses a PPS resin composition comprising glass fibers in a copolymerized polyolefin obtained by copolymerizing PPS resin with ethylene and glycidyl methacrylate or glycidyl acrylate, but the reinforcing material is anisotropic only with glass fibers. The properties were large and the warpage was poor.
JP 2002-129014 A (page 1-5) JP-A-6-65503 (page 1-3) JP-A-6-287449 (page 1-4) Japanese Patent Laying-Open No. 2005-248170 (page 1-8)

  The present invention maintains the excellent rigidity, heat resistance, dimensional stability, chemical resistance, low water absorption and flame retardancy of the conventional PPS resin described above, and is excellent in fluidity and low warpage, and particularly excellent in wire. An object of the present invention is to provide a PPS resin composition having both low anisotropy of expansion coefficient and heat cycle resistance, a metal insert molded product made of the composition, and a molded product having sealing and adhesion.

  As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that PPS is obtained by blending specific polyolefin and copolymer polyolefin obtained by copolymerizing glycidyl methacrylate or glycidyl acrylate, glass fiber, and mica having a specific size. The present inventors have found that the above problems can be solved by using a resin composition, and have arrived at the present invention.

That is, the present invention
(1) (A) 100 parts by weight of a polyphenylene sulfide resin, (B) 1 to 25 parts by weight of a copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate, and (C) 30 to 150 parts by weight of glass fibers. (D) A polyphenylene sulfide resin composition comprising 10 to 100 parts by weight of mica having a weight average particle diameter of 10 to 100 μm,
(2) (D) The polyphenylene sulfide resin composition according to (1), wherein the mica is either white mica or gold mica,
(3) The polyphenylene sulfide resin composition according to (1) or (2), wherein (E) 2 to 50 parts by weight of unmodified olefin resin is blended with 100 parts by weight of (A) polyphenylene sulfide resin,
(4) (E) Unmodified olefin resin is polyethylene, ethylene / α-olefin copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-diene copolymer, ethylene- The polyphenylene sulfide resin composition according to any one of (1) to (3), which is an olefin resin selected from an ethyl acrylate copolymer and an ethylene-butyl acrylate copolymer,
(5) A molded article comprising the polyphenylene sulfide resin composition according to any one of (1) to (4),
(6) The molded product according to (5), which is a molded product in which a metal is inserted, and (7) the molded product according to (5) or (6) obtained by bonding and / or sealing with a silicone resin or an epoxy resin. It is.

  The present invention maintains the excellent rigidity, heat resistance, dimensional stability, chemical resistance, low water absorption and flame retardancy of the conventional PPS resin described above, and is excellent in fluidity and low warpage, and particularly excellent in wire. An object of the present invention is to provide a PPS resin composition having both low anisotropy of expansion coefficient and heat cycle resistance, a metal insert molded product made of the composition, and a molded product having sealing and adhesion.

  The present invention will be described more specifically. In the present invention, “weight” means “mass”.

  The PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula (I),

From the viewpoint of heat resistance, the polymer preferably contains 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula. In addition, about 30 mol% or less of the repeating units of PPS may be composed of repeating units having the following structure.

  The PPS resin is obtained by a method for obtaining a polymer having a relatively small molecular weight obtained by a production method represented by Japanese Patent Publication No. 45-3368, or Japanese Patent Publication Nos. 52-12240 and 61-7332. It can be produced by a known method such as a method for obtaining a polymer having a relatively large molecular weight as described.

The PPS resin obtained as described above may be used as it is, or it may be used for crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, organic solvent, hot water. It is also possible to use after washing with an acid aqueous solution or the like.
The production method for obtaining the PPS resin having the above properties is not particularly limited as long as the above properties can be obtained, but the polymer is a substantially linear polymer with few impurities, and the desired properties are obtained. A method of washing with an organic solvent, hot water, an acid aqueous solution, or the like until is obtained. In particular, it is more preferable that the PPS resin is reinforced at 371 ° C. for 1 hour with a weight loss of 0.5% by weight or less.

  In the case of washing with an organic solvent, the organic solvent to be used is not particularly limited as long as it does not have an action of decomposing PPS. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformaldehyde, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxides and sulfones such as dimethylsulfoxide, dimethylsulfone, and sulfolane Solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, perchlorethylene, monochloroethane, dichloroethane , Halogen solvents such as tetrachloroethane, perchlorethane, chlorobenzene, methanol, ethanol, propanol, Nord, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, alcohol phenol based solvents such as polypropylene glycol, and benzene, toluene, and aromatic hydrocarbon solvents such as xylene.

  There is no restriction | limiting in particular also about washing | cleaning temperature, Usually, about normal temperature-about 300 degreeC are selected. In the case of washing with an acid aqueous solution, the acid to be used is not particularly limited as long as it does not have an action of decomposing PPS, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. Moreover, it can also be used after performing various treatments such as activation with a functional group-containing compound such as an acid anhydride group, an epoxy group, or an isocyanate group. When used in the present invention, those washed with an aqueous acid solution are preferred.

  As the PPS resin used in the present invention, two or more kinds of PPS resins having different molecular weight distributions can be mixed and used. When two or more types having a molecular weight distribution are used in combination, a combination of one having a high molecular weight and one having a low molecular weight is used, so that the speed dependency at the time of molding becomes smaller than that of one type having the same average molecular weight. Suppressed and preferred.

  The MFR used as the base polymer of the PPS resin used in the present invention (although blended when two or more PPS resins are used in combination) is not particularly limited as long as it can be melt-kneaded. It is preferably 10000 g / 10 min or less as a measured value using a melt indexer under the condition of staying for 5 minutes and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm), and 5000 g / 10 min or less. More preferably, it is 3000 g / 10 minutes or less. Although there is no restriction | limiting in particular as a minimum, From the point of melt viscosity, it is good that it is 10 g / 10min or more, and it is more preferable that it is 50 g / 10min or more.

  When two or more types of molecular weight distributions are used in combination as the PPS resin, at least one type preferably has an MFR of 10 to 1000 g / 10 min, more preferably 50 to 800 g / 10 min. At least one kind of is preferably 500 to 10000 g / 10 minutes, and more preferably 800 to 8000 g / 10 minutes. When two or more molecular weight distributions are used in combination, the difference between at least two MFRs of the high molecular weight PPS resin and the low molecular weight PPS resin is preferably 50 to 8000 g / 10 minutes, It is more preferably 6000 g / 10 minutes, and further preferably 100 to 3000 g / 10 minutes.

There is no particular limitation on the composition of the copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate used as the component (B) used in the present invention, but the total of ethylene and glycidyl methacrylate or glycidyl acrylate When it is 100% by weight, ethylene is preferably 99 to 50% by weight and glycidyl methacrylate or glycidyl acrylate is preferably 1 to 50% by weight, and ethylene is 99 to 60% by weight and glycidyl methacrylate or glycidyl acrylate is 1 to 40% by weight. % Is more preferable. If the copolymerization amount is too small, the heat cycle resistance of the PPS resin composition tends to be impaired, whereas if the copolymerization amount is too large, the PPS resin composition tends to exhibit a gelation tendency.
There is no limitation on the type of copolymerization of the copolymerized polyolefin comprising (B) ethylene and glycidyl methacrylate or glycidyl acrylate as main constituents, and any known method may be used, including high-pressure radical copolymerization and graft copolymerization. Manufactured by polymerization or the like.

  The copolymer polyolefin of the above (B) does not impair the characteristics of the resin composition of the present invention, preferably within a range of 30% by weight or less with respect to the copolymer polyolefin, and other olefinic monomers such as methyl acrylate, acrylic Ethyl acetate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n methacrylate -Α, β-unsaturated carboxylic acid alkyl esters such as butyl, t-butyl methacrylate, isobutyl methacrylate, acrylonitrile, styrene, α-methylstyrene, styrene having an aromatic ring substituted with an alkyl group, acrylonitrile-styrene copolymer Combined unit or the like Random in the form of compounds, blocks, may be introduced graft-copolymerization.

The degree of polymerization of the copolymerized polyolefin (B) is not particularly limited, and the MFR at 190 ° C./2160 g measured by the method defined in JIS K6760 is 0.00. The thing of the range of 1-100 g / 10min can be used. The MFR is more preferably 0.1 to 30 g / 10 minutes, and further preferably 0.1 to 20 g / 10 minutes.
The blending amount of the (B) copolymer polyolefin is 1 to 25 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the (A) PPS resin. If the blending amount of the copolymerized polyolefin is too small, the heat cycle resistance of the PPS resin composition is lowered, which is not preferable. Conversely, if the blending amount is too large, the amount of gas generated in the PPS resin composition increases and the gold during molding is increased. This is not preferable because mold contamination becomes remarkable.

  (C) glass fiber used in the present invention is not particularly limited in composition, but as glass composition, E glass (non-alkali glass composition), A glass (alkali resistant glass composition), C glass (acid resistant alkaline lime) Glass composition), D glass (composition realizing low dielectric constant), S glass (composition realizing high strength and high elastic modulus), T glass (composition realizing high strength and high elastic modulus) and H glass ( Among them, it is preferable to use E glass or H glass.

  Moreover, although there is no restriction | limiting in particular in an average fiber diameter, it is preferable that the average fiber diameter of glass fiber is 4 micrometers-20 micrometers, More preferably, an average fiber diameter is 5 micrometers-16 micrometers. There is no restriction | limiting in particular in a lower limit, and if it is 4 micrometers or more normally, a sufficient effect can be acquired. When the average fiber diameter exceeds 20 μm, the strength tends to decrease. In general, the average fiber diameter is observed with an electronic scanning microscope (SEM) at a magnification of 800 times, 100 or more glass fibers are measured, and the number average fiber diameter is calculated and used.

  The blending amount of the (C) glass fiber is 30 to 150 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the (A) PPS resin. An excessive amount of glass fiber is not preferable because the fluidity is lowered. If the amount is too small, the thermal rigidity is lowered, which is not preferable.

  The glass fiber of the above (C) can be subjected to a surface treatment within a range that does not impair the effects of the present invention, and examples of the treatment agent include a surface treatment agent and a sizing agent. Examples thereof include compounds, isocyanate compounds, organosilane compounds, organic titanate compounds, and organic borane treatment.

  The kind of (D) mica used in the present invention is not limited, but it is preferable to use white mica (mascobite), gold mica (phlogopite), black mica (biotite), and suzolite. Of these, gold mica and white mica are particularly preferable. Moreover, it is preferable that a weight average particle diameter is 10 micrometers-100 micrometers, More preferably, a weight average particle diameter is 20 micrometers-80 micrometers. When the weight average particle size exceeds 100 μm, the strength and the appearance of the molded product tend to decrease. The aspect ratio (weight average particle diameter / weight average thickness) is preferably 20 to 90. If it is less than 20, the anisotropy cannot be reduced, and the warpage increases. On the other hand, if it is larger than 90, the moldability is lowered.

  The weight average particle diameter referred to in the present invention was measured according to a weight average diameter (laser method) determined based on a diameter distribution measured according to a conventional method using a laser diffraction particle size distribution analyzer, or according to a dry sieving method. It is a value obtained by a weight average particle diameter obtained based on a diameter distribution. Generally, a fine powder having a weight average particle size of 30 μm or less is a laser method, and a coarse powder having a weight average particle size of more than that is a dry sieving method.

  The aspect ratio referred to in the present invention is a value obtained by calculating the weight average thickness according to the water surface particle film method and calculating the ratio with the weight average particle diameter.

  The blending amount of the (D) mica is 15 to 100 parts by weight with respect to 100 parts by weight of the (A) PPS resin, and preferably 20 to 90 parts by weight. An excessively large amount of mica is not preferable because strength and fluidity are lowered. If the amount is too small, anisotropy and thermal rigidity are lowered, which is not preferable.

  The (D) mica can be surface-treated within a range not impairing the effects of the present invention, and examples of the treatment agent include a surface treatment agent and a sizing agent. Specifically, an epoxy compound, Examples thereof include isocyanate compounds, organosilane compounds, organic titanate compounds, and organic borane treatment. Furthermore, it is preferable to add mica in a granular form because it improves the workability.

  In the present invention, it is desirable to use (B) a copolymerized polyolefin and (E) an unmodified olefin resin in combination for obtaining excellent flow characteristics and toughness.

Specific examples of the (E) unmodified olefin resin used in the present invention include ethylene / α-olefin copolymers, and specific examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- Octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl In the case where an ethylene / α-olefin copolymer is used in the present invention, the density is 880 kg / kg. 1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. An ethylene / α-olefin copolymer in the range of m ³ or less, preferably in the range of 830 to 880 kg / m ³ , more preferably in the range of 850 to 875 kg / m ³ , is particularly preferable for obtaining excellent toughness. The above density can be measured according to ASTM D1505 underwater replacement method.

  Moreover, as a preferable copolymerization amount of the ethylene / α-olefin copolymer, the α-olefin content is preferably 4 to 25 mol%, more preferably 7 to 25 mol%, and still more preferably 12 to 22 mol%. A range is mentioned. By using an ethylene / α-olefin copolymer having an α-olefin content in the above range, a resin composition having superior toughness can be obtained.

  As the ethylene / α-olefin copolymer, a polymer polymerized using a metallocene catalyst can be used. The metallocene catalyst is composed of a cyclopentadienyl derivative of a group IV metal such as titanium or zirconium and a cocatalyst. Metallocene catalysts are highly active, and the molecular weight distribution of the resulting polymer is narrow compared to conventional catalysts typified by Ziegler catalysts, and the distribution of α-olefin, which is a comonomer component of the copolymer, is uniform. It has the feature that it is excellent in flexibility and impact resistance.

  Further, (E) as specific examples of unmodified olefin resin, polyethylene, polypropylene, polybutene, polystyrene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer (SBS) , Styrene-isoprene-styrene block copolymer (SIS), polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene- Polyolefin (co) polymers such as ethylene / propylene-styrene block copolymer (SEPS) can also be suitably used.

  (E) When a polyethylene resin is used as the unmodified olefin resin, the MFR is preferably 0.05 to 70 g / 10 minutes as measured at 190 ° C. and a load of 2160 g, and 0.05 to 50 g / 10. Minutes are preferred.

  When (E) the unmodified elastomer is used, the preferred blending amount is in the range of 2 to 50 parts by weight, particularly in the range of 5 to 40 parts by weight, with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. Is more preferable. If the amount is too small, the toughness decreases, which is not preferable. If the amount is too large, the rigidity and fluidity decrease, which is not preferable.

  Moreover, there is no restriction | limiting in particular as a ratio which uses (B) copolymerization polyolefin in this invention, and (E) unmodified olefin resin together, (B) / (E) = 5/95 weight ratio-95/5 The weight ratio is preferable, and the range of (B) / (E) = 10/90 weight ratio to 60/40 weight ratio is more preferable. Within this range, the balance between fluidity and toughness during molding is particularly excellent.

  You may mix | blend another thermoplastic resin with the resin composition of this invention in the range which does not impair the effect in this invention. Specific examples include ABS resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, polyamide resin, aromatic polyamide resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyether. Imide resin, polyarylate resin, liquid crystal polymer, polyether sulfone resin, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, polyimide resin, polyamideimide resin, tetrafluoropolyethylene resin, thermoplastic polyurethane resin, Polyamide elastomer, polyester elastomer, polyester resin, polyphenylene ether resin, SAN resin, AS resin, acrylic resin, various elastomers The chromatography and the like, can be blended in a range not impairing the effects of the present invention. Furthermore, these can also be used in combination of 2 or more types.

  Furthermore, you may mix | blend inorganic fillers, such as another fibrous form, plate shape, powder form, and a granule, with the resin composition of this invention in the range which does not impair the effect of this invention. Specific examples include fibrous fillers such as carbon fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, metal fiber, calcium carbonate fiber, wollastonite, selenium. Sites, kaolin, clay, bentonite, asbestos, talc, alumina silicate, etc., swellable layered silicates such as montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, etc. Metal compounds, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, ceramic beads, silica, wet method white carbon, granular wollastonite, zeolite, calcium hydroxide, magnesium hydroxide, water acid Hydroxides such as aluminum, glass beads, boron nitride, silicon carbide, graphite, pyrophyllite, include non-fibrous fillers such as calcium phosphate. These may be hollow, and two or more of these fillers may be used in combination. In addition, the inorganic filler can be surface-treated within a range that does not impair the effects of the present invention, and examples of the treatment agent include a surface treatment agent and a sizing agent. Specifically, an epoxy compound, Examples thereof include isocyanate compounds, organosilane compounds, organic titanate compounds, and organic borane treatment.

  Furthermore, a silane coupling agent can be used in the resin composition of the present invention as long as the effects of the present invention are not impaired, and the material is not particularly limited, but may be blended. Silane coupling agents are a type of coupling agent that is generally used as a surface treatment agent for various fillers, as a primer in adhesives and coatings, among which epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, ureidos. An alkoxysilane having at least one functional group selected from a group, a vinyl group, and a methacryloxy group is preferably used. Specific examples include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-mercapto. Mercapto group-containing alkoxysilanes such as propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, etc. Ureido group-containing alkoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiet Isocyanato group-containing alkoxysilane such as silane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, Hydroxy group-containing alkoxysilanes such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, and other amino group-containing alkoxysilanes, γ-hydroxypropyltrimethoxysilane, and γ-hydroxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, and other vinyl group-containing alkoxysilanes, and γ-methacryloxypropyltrimethoxysilane, etc., methacryloxy group-containing alkoxysilanes And the like. Of these, epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred.

  Furthermore, in the resin composition of the present invention, a conductive filler can be used as long as the effects of the present invention are not impaired, and the material is not particularly limited. There is no particular limitation as long as it is a conductive filler used for conductive resin, and specific examples thereof include metal powder, metal flake, metal ribbon, metal fiber, metal oxide, an inorganic filler coated with a conductive substance, Examples thereof include carbon powder, graphite, carbon fiber, carbon flake, and scaly carbon.

Specific examples of the metal species of the metal fiber include iron, copper, stainless steel, aluminum, and brass. Such metal powders, metal flakes, metal ribbons, and metal fibers may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), etc., and these include the surface of titanate, aluminum, and silane coupling agents. Surface treatment may be performed with a treating agent. Further, two or more of these conductive fillers may be used in combination.

  Furthermore, carbon black can be used in the resin composition of the present invention as long as the effects of the present invention are not impaired, and C (carbon) is the main component and its raw material and production method are not particularly limited. Specific examples include acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, and disk black. Acetylene black and furnace black are particularly preferably used. Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. Carbon black is compounded (added by blending with raw materials during extrusion kneading), masterbatch added (added by blending carbon black master before molding such as injection molding), dry color ( You may use by any addition method of the method of adding by coating carbon black on the surface of a resin composition pellet. Further, two or more of these carbon blacks may be used in combination.

  Furthermore, in the resin composition of the present invention, a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic phosphorus compound, an inorganic fine particle, and an organic phosphorus compound, as long as the effects of the present invention are not impaired. Crystal nucleating agents such as metal oxides and polyether ether ketones, polyolefins such as polyethylene and polypropylene, montanic acid waxes, montanic acid and metal salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide, various bisamides, bis Metal soaps such as urea, polyethylene wax, lithium stearate, aluminum stearate, ethylenediamine / stearic acid / sebacic acid polycondensates, mold release agents such as silicone compounds, anti-coloring agents such as hypophosphite, phosphorus Antioxidant, sulfur Antioxidants such as antioxidants, weathering agents and ultraviolet ray inhibitors (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), heat stabilizers (hindered phenol, hydroquinone, phosphite) These substitutes), foaming agents, pigments (cadmium sulfide, phthalocyanine, carbon black, metallic pigments, etc.), dyes (such as nigrosine), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cations) Antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (eg red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide) Such as hydroxide, ammonium polyphosphate Arm, brominated polystyrene, can be added brominated polyphenylene ether, brominated polycarbonate, conventional additives such as combinations) with brominated epoxy resin or these brominated flame retardants and antimony trioxide.

  The method for preparing the resin composition used in the present invention is not particularly limited, but it can be obtained by melt-kneading the components (A) to (E) and other raw materials added as necessary. Specific examples include a method of supplying a mixture of raw materials to a commonly known melt mixer such as a single or twin screw extruder, Banbury mixer, kneader, mixing roll, and kneading at a temperature of 280 to 400 ° C. be able to. Also, the mixing order of the raw materials is not particularly limited, and all the raw materials are melt-kneaded by the above method, some raw materials are melt-kneaded by the above method, and the remaining raw materials are melt-kneaded, or one Any method may be used, such as a method in which the remaining raw materials are mixed using a side feeder during melt kneading of the raw materials of the part using a single-screw or twin-screw extruder. Preferably, the PPS resin, copolymer polyolefin and unmodified polyolefin resin are melt-kneaded, glass fiber and mica are added, and melt-kneaded for production. Among them, using a twin screw extruder, PPS resin, copolymer polyolefin and unmodified polyolefin resin are supplied, melt kneaded, glass fiber and mica are supplied and kneaded using a side feeder, and then exposed to a vacuum state. A preferred method is to remove the generated gas. By obtaining the PPS resin composition by such an extrusion process, it is possible to obtain good strength with less generated gas. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

  The MFR of the PPS resin composition obtained in the present invention is not particularly limited as long as it can be molded, but it is 315.5 ° C. for 5 minutes, preload 1000 g, measurement load 2160 g (orifice diameter 2.095 mm, length The measured value using a melt indexer under the condition of 8.00 mm) is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less from the viewpoint of strength. The lower limit is preferably 0.5 g / 10 min or more from the viewpoint of fluidity, and more preferably 1 g / 10 min or more. The MFR of the PPS resin composition depends mainly on the amount of the MPS of the PPS resin to be used, the components (B) to (E), etc., and by using the PPS having a low MFR or the components (B) to (E) Since the MFR tends to decrease as the amount increases, a PPS resin composition having the above range can be obtained by appropriately adjusting these.

  The PPS resin composition obtained by the present invention can be molded by various known molding methods such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, and in particular, molding by injection molding. Is preferred.

  Since the resin composition of the present invention is excellent in heat cycle resistance, it is suitable for molded articles in which metals such as protection and support members and motors for electric / electronic component integrated modules are inserted, especially in low and high temperature repeated environments. It can be preferably used for a molded product that undergoes changes. Although there is no restriction | limiting in particular in a temperature change, Preferably the characteristic which was excellent in the heat cycle property of a resin composition can be exhibited to the thing with a temperature change of 20 degreeC or more.

  Furthermore, the resin composition of the present invention seals and bonds a plurality of individual semiconductors or modules to a box-shaped protective / support member for an electric / electronic component integrated module with a thermosetting resin such as epoxy resin or silicone resin. In this case, since the anisotropy of the linear expansion coefficient is small, excellent practical performance is exhibited such as good adhesion to the sealing material and good adhesion.

  The resin composition of the present invention is excellent in rigidity, heat resistance, dimensional stability, chemical resistance, low water absorption, fluidity, and low warpage, and particularly excellent in low anisotropy of linear expansion coefficient and heat cycle resistance. Therefore, several individual semiconductors or modules are encapsulated with thermosetting resins such as epoxy resin and silicone resin in protective / support members for parts that require heat cycle resistance and box-type electrical / electronic component integrated modules. In addition to being particularly useful for the purpose of fastening and joining, it is suitable for structural parts such as housings and electrical parts cases. Sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, Small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons , Hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, wardrobe Homes, office electrical product parts, office computer related parts, telephone equipment related parts, facsimile related parts, copier related parts, such as sesser parts, water heaters, hot water in baths, water supply equipment parts such as temperature sensors, etc. Machine-related parts represented by cleaning jigs, motor parts, lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, precision machine-related parts; Alternator terminals, alternator connectors, IC regulators, Potentiometer base for light deer, relay block, inhibitor switch, various valves such as exhaust gas valve, fuel-related / exhaust system / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, key Bretter main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating temperature Wind flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter relay, transmission Wire harness, window washer nozzle, air conditioner panel switch base Automobiles such as plates, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc.・ Applicable to vehicle-related parts and other various uses.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by a following example.

  The tensile strength, Charpy impact strength, linear expansion coefficient, heat cycle resistance, and fluidity described in the examples and comparative examples were measured according to the following methods.

[Measurement of tensile strength]
A 1A type tensile test piece (4.0 mm thickness) according to ISO 3167 was injection molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and measured according to ISO 527-1 and -2 at a temperature condition of 23 ° C. It is a thing. If it is 130 MPa or more, it can be said that the product strength level has no practical problem, but the higher this value, the better the rigidity and the better.

[Measurement of Charpy impact strength]
A 1A type dumbbell piece (4.0 mm thickness) according to ISO 3167 was injection molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and a V-notch test piece (4.0 mm width) cut into a center part of 80 mm. , With notch) and measured according to ISO 179 under a temperature condition of 23 ° C. If it is 6 kJ / m ² or more, it can be said that the product strength level has no practical problem, but the higher this value, the better the toughness and the better.

[Measurement of linear expansion coefficient]
A square plate (80 mm × 80 mm × 3.0 mm thickness, film gate) is injection-molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and a test piece (10 mm) in the direction of resin flow from the center and in a direction perpendicular thereto. X4 mm x 3 mm). The linear expansion coefficient of −40 ° C. to 150 ° C. in the longitudinal direction of the test piece is measured according to ASTM D696 using a thermomechanical analyzer (TMA). The smaller the value of the linear expansion coefficient and the closer the ratio of the flow direction (MD) and the perpendicular direction (TD) is to 1.0, the smaller the anisotropy of the expansion change, and the better the low warpage and heat cycle resistance.

[Evaluation of heat cycle resistance]
A metal insert test piece shown in FIG. 1 in which a metal block was insert-molded under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. was used. This was treated at 130 ° C. × 1 hr and then treated at −40 ° C. × 1 hr as one cycle, and was subjected to a thermal cycle treatment, and the presence / absence of cracks was visually confirmed every 5 cycles. The number of cold cycle treatments in which cracks were observed was defined as heat cycle resistance. If cracks do not occur for 40 cycles or more, it can be said that the product level has no problem in practical use.

  Fig.1 (a) is a top view of a metal insert test piece, and FIG.1 (b) is the side view.

  An insert metal of 48.8 × 48.8 × 28.6 mm is coated with a resin by injection molding (insert molding). The obtained test piece is a rectangular parallelepiped of 50 × 50 × 30 mm, and the mold thickness is 0.6 ± 0.2 mm.

[Liquidity]
Using a spiral flow mold having a thickness of 1 mm, the cylinder temperature was 320 ° C., the mold temperature was 140 ° C., the injection speed was 230 mm / sec, the injection pressure was 98 MPa, the injection time was 5 sec, and the cooling time was 15 sec, and the flow length was measured. . (Used molding machine: “SE-30D” manufactured by Sumitomo Heavy Industries) The flow length is 100 mm or more, and it can be said that there is no practical problem. However, the larger the value, the better the fluidity and the better.

[Reference example]
(Production of PPS-1)
An autoclave equipped with a stirrer was charged with 2.98 kg (25 mol) of a 47% sodium hydrosulfide aqueous solution, 2.17 kg (26 mol) of 48% sodium hydroxide and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). The temperature was raised to 205 ° C., and 2.8 liters of extracted water containing 2.7 kg of water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2.5 kg of NMP were added and heated at 270 ° C. for 1 hour. The reaction product was washed twice with warm water and dried under reduced pressure at 120 ° C. for 24 hours to obtain MFR6000 (g / 10 min) of PPS-1. The MFR was measured using a melt indexer under conditions of 315.5 ° C., 5 minutes residence, and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm). Further, the loss on heating of the PPS resin was 0.5% by weight. In addition, 1 g of PPS resin was put into an aluminum cup, preliminarily dried for 1 hour in an atmosphere of 150 ° C., and then the weight was measured. The weight loss was measured in air at 371 ° C. for 1 hour, and the weight was measured again. The weight loss due to the treatment at 371 ° C. was gradually expressed as a percentage by the weight before the treatment, and was regarded as the heat loss.

(Production of PPS-2)
An autoclave equipped with a stirrer was charged with 2.98 kg (25 mol) of a 47% aqueous sodium hydrosulfide solution, 2.17 kg (26 mol) of 48% sodium hydroxide, 656 g (8 mol) of sodium acetate and 5 kg of NMP, and the temperature was gradually raised to 205 ° C. Then, 2.8 liters of extracted water containing 2.7 kg of water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2.5 kg of NMP were added and heated at 270 ° C. for 1 hour. The reaction product was washed twice with warm water, dried under reduced pressure at 120 ° C. for 24 hours, and then heat-treated at 230 ° C. for 16 hours to obtain MFR120 (g / 10 min) of PPS-2.

  The MFR was measured using a melt indexer under conditions of 315.5 ° C., 5 minutes residence, and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm). The heat loss of the PPS resin was 0.4% by weight. In addition, 1 g of PPS resin was put into an aluminum cup, preliminarily dried for 1 hour in an atmosphere of 150 ° C., and then the weight was measured. The weight loss was measured in air at 371 ° C. for 1 hour, and the weight was measured again. The weight loss due to the treatment at 371 ° C. was gradually expressed as a percentage by the weight before the treatment, and was regarded as the heat loss.

(Production of PPS-3)
An autoclave equipped with a stirrer was charged with 4.67 kg (25 mol) of an aqueous sodium hydrosulfide solution, 2.00 kg (25 mol) of 50% sodium hydroxide, and 8 kg of NMP. The temperature was gradually raised to 205 ° C. while stirring, and 3.8 kg of water was added. 4.1 liters of extracted water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added and heated at 230 ° C. for 1 hour and further at 260 ° C. for 30 minutes. The reaction product was washed twice with warm water, dried under reduced pressure at 120 ° C. for 24 hours, and further subjected to heat treatment at 230 ° C. for 16 hours to obtain MFR700 (g / 10 min) of PPS-3. The MFR was measured using a melt indexer under conditions of 315.5 ° C., 5 minutes residence, and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm). Further, the loss on heating of the PPS resin was 0.5% by weight. In addition, 1 g of PPS resin was put into an aluminum cup, preliminarily dried for 1 hour in an atmosphere of 150 ° C., and then the weight was measured. The weight loss was measured in air at 371 ° C. for 1 hour, and the weight was measured again. The weight loss due to the treatment at 371 ° C. was gradually expressed as a percentage by the weight before the treatment, and was regarded as the heat loss.

[Compounding materials used in Examples and Comparative Examples]
(Copolymerized polyolefin)
B-1: ethylene / glycidyl methacrylate copolymer (E / GMA = 88/12% by weight), MFR = 3 g / 10 minutes B-2: ethylene / methyl acrylate / glycidyl methacrylate copolymer (E / MA / GMA = 64/30/6 wt%), MFR = 8 g / 10 min MFR was measured by the method defined in JIS K6760 (190 ° C., 2160 g load).

(Glass fiber)
C: Glass fiber: “T-747” average fiber diameter 13 μm (manufactured by Nippon Electric Glass)
In the above, the average fiber diameter of the glass fiber is an average fiber diameter measured by an ordinary method using an electron scanning microscope.

(Mica)
D-1: Gold mica, weight average particle size 55 μm, weight average aspect ratio 55 “S-200HG” (manufactured by Repco)
D-2: White mica, weight average particle size 55 μm, weight average aspect ratio 33 “M-200” (manufactured by Repco)
D-3: Gold mica, weight average particle size 185 μm, weight average aspect ratio 80 ”S-60H (manufactured by Repco)
D-4: Suzolite mica, weight average particle size 40 μm, weight average aspect ratio 30 "325S" (manufactured by Kuraray)
In the above, the weight average particle size of mica was calculated from the particle size distribution curve by measuring the particle size according to the dry sieving method. The weight average aspect ratio was calculated from the weight average thickness determined according to the water surface particle film method and the weight average particle size.

(Glass flakes)
D′-5: Glass flake: Alkali-free glass, thickness 5 μm, weight average particle size 600 μm, “REFG-112” (manufactured by Nippon Sheet Glass)
The weight average particle size was determined by measuring the particle size according to the dry sieving method and calculating from the particle size distribution curve, and the thickness was determined by measuring the thickness using a scanning electron microscope (SEM). .

(Unmodified olefin resin)
E-1: Ethylene / 1-butene copolymer, density 860 kg / cm ³ , MFR 0.5 g / 10 min, “Toughmer TX610” (Mitsui Chemicals)
E-2: Metallocene olefin plastomer copolymer, density 880 kg / cm ³ , MFR ³⁰ g / 10 min, “Excellen FX CX5501” (manufactured by Sumitomo Chemical)
E-3: Metallocene polyethylene density 905 kg / cm ³ , MFR 4.0 g / 10 min, “Evolue SP0540” (Mitsui Chemicals)
E-4: Ethylene / 1-butene copolymer, density 885 kg / cm ³ , MFR 3.6 g / 10 min, “Toughmer A4085” (manufactured by Mitsui Chemicals)
The MFR was measured according to ASTM D1238 (190 ° C., 2160 g load).

Examples 1-9
After dry blending the PPS (A), copolymerized polyolefin (B), glass fiber (C), mica (D), and unmodified olefin resin (E) prepared as described above at a ratio shown in Table 1, 320 (A), (B), and (E) blended using a screw type twin screw extruder (“TEX-44” manufactured by Nippon Steel Works) set to the extrusion condition at ℃, and after melt-kneading, After supplying the fillers (C) and (D) from the side feeder, the gas generated by exposure to a vacuum state was removed and pelletized. The obtained pellets are dried and then injection molded using an injection molding machine (“NEX1000” manufactured by Nissei Plastics and “SE-30D” manufactured by Sumitomo Heavy Industries) at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. A predetermined test piece for characteristic evaluation was obtained. About the obtained test piece and pellet, tensile strength, Charpy impact strength, linear expansion coefficient, heat cycle resistance, and fluidity were measured by the method described above. The results are shown in Table 1.

  The obtained resin composition and molded article had low anisotropy of rigidity, toughness, and linear expansion coefficient, and had excellent heat cycle resistance and high practicality.

Comparative Example 1
Glass fiber and mica were dry blended in the proportions shown in Table 1 in the same manner as in Example, using only PPS resin, not containing copolymer polyolefin, and then melt-kneaded, pelletized, molded, and evaluated. . The results are shown in Table 1.

  When the copolymerized polyolefin was not blended, the heat cycle resistance was low and not practical.

Comparative Example 2
Using glass flakes instead of mica as the reinforcing material, and dry blending in the proportions shown in Table 1 in the same manner as in the examples, melt kneading, pelletizing, molding, and evaluation were performed. The results are shown in Table 1.

  When glass flakes were used, fluidity was poor and not practical.

Comparative Example 3
Without blending mica into the reinforcing material, only glass fibers were used and dry blended in the proportions shown in Table 1 in the same manner as in Examples, and then melt-kneading, pelletizing, molding, and evaluation were performed. The results are shown in Table 1.

  When mica was not blended, the anisotropy of the linear expansion coefficient was large, the fluidity and heat cycle resistance were low, and it was not at a practical level.

Comparative Example 4
Without blending glass fibers into the reinforcing material, only mica was used and dry blended in the proportions shown in Table 1 in the same manner as in Examples, followed by melt-kneading, pelletizing, molding, and evaluation. The results are shown in Table 1.

  When glass fiber was not blended, the anisotropy of the linear expansion coefficient was small, but the strength and heat cycle resistance were low and not at a practical level.

Comparative Example 5
Using the PPS resin and the unmodified olefin resin as the base, after dry blending in the proportions shown in Table 1 in the same manner as in the Examples, melt-kneading, pelletizing, molding, and evaluation were performed. The results are shown in Table 1.

  When mixing without using a copolymerized olefin, the heat cycle resistance was low and it was not at a practical level.

Comparative Example 6
Using mica having a weight average particle diameter of 185 μm, dry blending was carried out in the proportions shown in Table 1 in the same manner as in Examples, and then melt-kneading, pelletizing, molding, and evaluation were performed. The results are shown in Table 1.

  When mica having a weight average particle diameter of 185 μm was blended, the heat cycle resistance was low and it was not at a practical level.

Fig.1 (a) is a top view of a metal insert test piece, and FIG.1 (b) is the side view.

Explanation of symbols

1. Insert metal2. Gate 3. Metal insert test piece

Claims (7)

(A) 100 parts by weight of polyphenylene sulfide resin, (B) 1 to 25 parts by weight of copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or ethylene and glycidyl acrylate, (C) 30 to 150 parts by weight of glass fiber (D) A polyphenylene sulfide resin composition comprising 10 to 100 parts by weight of mica having a weight average particle diameter of 10 to 100 μm. (D) The polyphenylene sulfide resin composition according to claim 1, wherein the mica is either white mica or gold mica. The polyphenylene sulfide resin composition according to claim 1 or 2, wherein 2 to 50 parts by weight of (E) unmodified olefin resin is blended with 100 parts by weight of (A) polyphenylene sulfide resin. (E) Unmodified olefin resin is polyethylene, ethylene / α-olefin copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-diene copolymer, ethylene-ethyl acrylate. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, which is at least one olefin resin selected from a copolymer and an ethylene-butyl acrylate copolymer. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 4. The molded product according to claim 5, which is a molded product in which a metal is inserted. The molded article according to claim 5 or 6, which is a molded article obtained by bonding and / or sealing with a silicone resin or an epoxy resin.

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