JP2006104222A - Polyphenylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition that retains an excellent heat resistance, rigidity, dimensional stability, flame retardant, etc., of a polyphenylene sulfide resin, is excellent in strength and slidability and is particularly excellent in welding property and airtightness, a vessel-shaped molded product made thereof, and an injection-molded product having a joint part. <P>SOLUTION: The polyphenylene sulfide resin composition comprises (A) >50 wt.% but ≤94 wt.% polyphenylene sulfide resin, (B) 5-35 wt.% polyamide resin, (C) 0-25 wt.% at least one polyolefin resin chosen from the group consisting of a polyethylene resin and a polypropylene resin and (D) 1-19 wt.% polyolefin copolymer prepared by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate, provided that the total content of components (A)-(D) is 100 wt.%. Here, (E) 10-200 pts.wt. inorganic filler is compounded with 100 pts.wt. composition comprising components (A)-(D). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a reinforced polyphenylene sulfide resin from which a molded article having excellent bonding properties and airtightness can be obtained. More specifically, the present invention has excellent weldability and airtightness, and rigidity, heat resistance, slidability, and dimensions. The present invention relates to a polyphenylene sulfide resin composition having an excellent balance of properties such as stability, chemical resistance, low water absorption, and excellent fluidity, a container-shaped molded product comprising the same, and an injection-molded product having a joint portion.

  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, when used for molded products that require weldability, an elastomer or the like is blended in order to improve the solidification characteristics. However, the PPS resin has a problem that the elastomer has a high melting point and is easily gelled during processing. In addition, when a high melting point polymer having excellent thermal stability is blended, the weldability is lowered, so that it is difficult to achieve both weldability and fluidity.

Therefore, several studies have been made so far for the purpose of improving the weldability of the PPS resin. For example, Patent Document 1 discloses a vibration welding resin composition composed of a PPS resin and a polyamide resin, but the compatibility between the PPS resin and the polyamide resin is poor and the welding strength is still insufficient. In addition, the amount of polyamide blended was large, and the rigidity reduction during water absorption was large. Patent Document 2 discloses a composition containing an olefin copolymer composed of an unsaturated acid glycidyl ester. However, according to the study by the present inventors, fluidity was lowered and bonding strength was low only by blending an olefin copolymer composed of unsaturated acid glycidyl ester. Patent Document 3 discloses a composition having a phase structure composed of a polyolefin resin and a PPS resin, the PPS resin as a matrix resin, and the polyolefin resin as a dispersion layer. However, in the specifically disclosed composition, The bonding strength was low.
JP-A-10-237304 (page 1-4) JP-A-5-239363 (page 1-5) JP 2001-302917 A (page 1-12)

  The present invention maintains the excellent heat resistance, rigidity, dimensional stability, flame retardancy, etc. of the conventional polyphenylene sulfide resin described above, and has rigidity, heat resistance, slidability, dimensional stability, chemical resistance, and low water absorption. It is an object of the present invention to provide a PPS resin composition that is excellent in properties and fluidity and has both particularly excellent weldability and airtightness, a container-shaped molded product comprising the same, and an injection-molded product having a joint portion.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have formulated a PPS resin composition in which a PPS resin is blended with a polyamide resin, a polyolefin resin, and a copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate. As a result, the inventors have found that the above problems can be solved, and have come up with the present invention.

That is, the gist of the present invention is the following (1) to (8).
(1) One or more polyolefin resins selected from (A) polyphenylene sulfide resin more than 50% by weight, 94% by weight or less, (B) 5 to 35% by weight polyamide resin, (C) polyethylene resin, polypropylene resin 0 -25 wt%, (D) 1 to 19 wt% of a copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate, and a total of 100 wt% of the components (A) to (D), A polyphenylene sulfide resin composition comprising (E) 10 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of the composition of (A) to (D).
(2) The polyphenylene sulfide resin composition according to (1), wherein the weight ratio ((B) + (C)) / (D)) of (B) + (C) to (D) is 1 to 6.8.
(3) The polyphenylene sulfide resin composition according to (1) or (2), wherein (E) the inorganic filler is glass fiber.
(4) The polyphenylene sulfide resin according to any one of (1) to (3), wherein the (B) polyamide resin is at least one selected from polyamide 6, polyamide 66, and a copolymer polyamide containing them as a main component. Composition.
(5) The polyphenylene sulfide resin composition according to any one of (1) to (4), wherein the (C) polyolefin resin is a polyethylene resin having a density of 900 to 950 kg / m ³ .
(6) A container-shaped molded article that receives an internal pressure of 30 kPa or more using the polyphenylene sulfide resin composition according to any one of (1) to (5).
(7) An injection-molded article having a bonding site using the polyphenylene sulfide resin composition according to any one of (1) to (5).
(8) The polyphenylene sulfide resin composition according to any one of (1) to (5) is any one or more of vibration welding, ultrasonic welding, hot plate welding, two-stage injection molding bonding, and two-color molding bonding. An injection molded product that is welded by a joining method.

  The present invention maintains the excellent heat resistance, rigidity, dimensional stability, flame retardancy, etc. of the conventional polyphenylene sulfide resin described above, and has rigidity, heat resistance, slidability, dimensional stability, chemical resistance, and low water absorption. It is an object of the present invention to provide a PPS resin composition that is excellent in properties and fluidity and has both particularly excellent weldability and airtightness, a container-shaped molded product comprising the same, and an injection-molded product having a joint portion.

  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.

  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. Moreover, about 30 mol% or less of the repeating unit of the PPS resin may be composed of a repeating unit 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 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 the PPS resin. Examples of the organic solvent include nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformaldehyde, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, dimethyl sulfoxide, dimethyl sulfone, and sulfolane. Sulfoxide / sulfone 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 dichloride , Halogen solvents such as chloroethylene, monochloroethane, dichloroethane, tetrachloroethane, perchloroethane, chlorobenzene, methanol, ethanol Alcohol / phenol solvents such as propanol, butanol, pentaanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, etc. And aromatic hydrocarbon solvents such as benzene, toluene and 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 aqueous acid solution, the acid used is not particularly limited as long as it does not have an action of decomposing the PPS resin, 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 melt flow rate (MFR) used as a 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 melt kneading is possible, The measured value using a melt indexer under conditions of 315.5 ° C., 5-minute residence, and load 5000 g (orifice diameter 2.095 mm, length 8.00 mm) is preferably 10000 g / 10 min or less. It is more preferably 10 minutes or less, and more preferably 4500 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 1000 to 6000 g / 10 minutes.

  In the present invention, the amount of the (A) PPS resin used is more than 50 wt% and not more than 94 wt%, more than 50 wt% and 90 wt%, with respect to the total 100 wt% of the components (A) to (D). Or less, more preferably more than 50% by weight and 80% by weight or less. (A) If the amount of the PPS resin is too small, the heat resistance and fluidity of the PPS resin composition are undesirably lowered. Conversely, if the amount is too large, the impact strength of the PPS resin composition is undesirably decreased.

  The polyamide resin used as the component (B) used in the present invention is not particularly limited, but a particularly useful polyamide resin is a polyamide resin having a melting point of 200 ° C. or more and excellent in heat resistance and strength. As polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide) 612), polyhexamethylene terephthalamide / polycaproamide copolymer (polyamide 6T / 6), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene Isophthalua Copolymer (polyamide 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer ( Polyamide 6T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene) terephthalamide copolymer (polyamide 6T / M5T), polyxylylene adipamide (polyamide XD6) and mixtures or copolymers thereof. Can be mentioned. Particularly preferred examples include polyamide 6, polyamide 66, polyamide 610, polyamide 6/66 copolymer, polyamide 6T / 66 copolymer, polyamide 6T / 6I copolymer, polyamide 6T / 6 copolymer, etc. Of these, polyamide 6, polyamide 66 and copolymers thereof are preferred. Furthermore, it is also practically preferable to use these polyamide resins as a mixture depending on necessary properties such as moldability, heat resistance, and vibration weldability.

  The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a concentrated sulfuric acid solution of JIS K6810 98% is in the range of 1.5 to 5.0, particularly 2.0 to 4.0. The thing of the range of is preferable.

  In this invention, the usage-amount of (B) polyamide resin is 5-35 weight% with respect to a total of 100 weight% of (A)-(D) component, and it is preferable that it is 10-35 weight%. (B) If the polyamide resin is less than 5% by weight, the joining property of the PPS resin composition is lowered, which is not preferable. Conversely, if the blending amount is more than 35% by weight, the thermal rigidity of the PPS resin composition is lowered. Therefore, it is not preferable.

  The (C) polyolefin resin used in the present invention is not an essential component. The polyolefin resin may be used in combination as long as it is one or more selected from polyethylene resins and polypropylene resins. Of these, polyethylene resin is particularly preferable.

The (C) polyolefin resin has a density of 900 to 990 kg / m ³ . Of these preferred density 900~950kg / ^{m 3,} more preferably 900~930kg / ^{m 3.} In particular, the effect of the present invention is remarkable when a polyethylene resin having the above density range is used.

  The density of the polyolefin can be measured according to ASTM D1505.

  The MFR of the above (C) is not particularly limited as long as it can be melt-kneaded, but it is preferably 70 g / 10 min or less as a measured value using a melt indexer under conditions according to ASTM D1238. / 10 minutes or less is more preferable, and 12 g / 10 minutes or less is more preferable. If it exceeds 70 g / 10 min, the bonding strength may be lowered, which is not preferable. Although there is no restriction | limiting in particular as a minimum, It is preferable that it is 0.05 g / 10min or more from a fluid point. When a polyethylene resin is used, the MFR is preferably 0.05 to 70 g / 10 minutes and more preferably 0.05 to 12 g / 10 minutes as measured at 190 ° C. and a load of 2160 g. When a polypropylene resin is used, the MFR is preferably 0.05 to 70 g / 10 minutes, more preferably 0.05 to 12 g / 10 minutes, measured at 230 ° C. and a load of 2160 g.

  The method for producing the (C) polyolefin resin used in the present invention is not particularly limited, and any method such as radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, or coordination polymerization using a metallocene catalyst may be used. Can be used.

  In the present invention, part or all of the (C) polyolefin resin can be modified with at least one compound selected from unsaturated carboxylic acids or derivatives thereof. When a modified polyolefin resin is used, the compatibility is improved.

  Examples of unsaturated carboxylic acids or derivatives thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, Glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, methacrylic acid 2 -Ethylhexyl, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2, 3-dicarboxylic acid Endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate (but copolymerized with ethylene) Glycidyl methacrylate (except when copolymerized with ethylene), glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Of these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferred, and maleic acid and maleic anhydride are particularly preferred.

  As a method for introducing these unsaturated carboxylic acid or its derivative component into the polyolefin resin, the unsaturated carboxylic acid or its derivative compound is introduced into the unmodified polyolefin resin by grafting using a radical initiator. The method is preferably used. The amount of unsaturated carboxylic acid or its derivative component introduced is preferably within the range of 0.001 to 20 mol%, more preferably 0.01 to 10 mol%, based on the total olefin monomer in the modified polyolefin. It is.

  The blending amount of the polyolefin resin (C) is 0 to 25% by weight, preferably 0 to 20% by weight, based on 100% by weight of the total of (A) to (D). If the amount is too small, the balance between the bonding strength and the fluidity is poor, which is not preferable. If the amount is too large, the strength and rigidity decrease, which is not preferable.

  There is no particular limitation on the composition of the copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate used as component (D) 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 amount of copolymerization is too small, the impact resistance of the PPS resin composition tends to be impaired. On the other hand, if the amount of copolymerization is too large, the PPS resin composition tends to exhibit a gelation tendency.

  There is no limitation on the type of copolymerization of the above-mentioned copolymer polyolefin containing ethylene and glycidyl methacrylate or glycidyl acrylate as main constituents, and any known method can be used, such as high-pressure radical copolymerization and graft copolymerization. Manufactured by polymerization or the like.

  The copolymerized polyolefin of the above (D) is within a range that does not impair the properties of the resin composition of the present invention, preferably within a range of 30% by weight or less with respect to the copolymerized polyolefin, and other olefinic monomers such as methyl acrylate, methacrylic Methyl acid, acrylonitrile, styrene or the like may be introduced by random, block or graft copolymerization in the form of a single substance or a mixture.

  The degree of polymerization of the copolymerized polyolefin (D) is not particularly limited, and those having an MFR in the range of 0.1 to 100 g / 10 min at 190 ° C./2160 g measured by the method defined in JISK6760 should be used. Can do. The MFR is more preferably 0.1 to 30 g / 10 minutes, and further preferably 0.1 to 20 g / 10 minutes.

  (D) The ratio of the copolymerized polyolefin (A) to (D) to the total of 100% by weight is 1 to 19% by weight, preferably 4 to 15% by weight. If the amount of the copolymerized polyolefin is too small, it is not preferable because the bondability of the PPS resin composition is lowered. Conversely, if the amount is too large, the fluidity of the PPS resin composition is lowered, which is not preferable.

  In the present invention, the weight ratio ((B) + (C)) / (D) of the sum [(B) + (C)] and (D) of (B) and (C) is 1 to 6.8. Is preferable, and it is more preferable that it is 1.1-6.1.

  As the (E) inorganic filler used in the present invention, fillers such as fibers, plates, powders, and granules can be used. Specifically, for example, fiber fillers such as glass fiber, 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, Silicate silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, swellable layered silicates such as montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, oxidation Metal compounds such as titanium and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, ceramic beads, silica, wet white carbon, granular wollastonite, zeolite, water Calcium oxide, water Magnesium, hydroxides such as aluminum hydroxide, glass beads, boron nitride, silicon carbide, graphite, pyrophyllite, include non-fibrous fillers such as calcium phosphate. Glass fiber or wollastonite as a fibrous filler is preferable. These may be hollow, and two or more of these fillers can be used in combination.

  The particle diameter and average fiber diameter of (E) are not particularly limited, but the average fiber diameter of the fibrous filler is preferably 20 μm or less, and more preferably the average fiber diameter is 16 μm or less. There is no particular limitation on the lower limit, and it is preferable that the lower limit is as small as possible. When the average fiber diameter exceeds 20 μm, the strength tends to decrease. In general, the average fiber diameter is a weight average fiber diameter determined based on a diameter distribution measured according to a conventional method using a laser diffraction particle size distribution analyzer. However, the average fiber diameter of glass fiber, whisker, etc., which is not suitable for laser diffraction particle size distribution measurement, with a fiber length to fiber diameter ratio of 25 or more, is the average fiber diameter measured by an ordinary method using an electronic scanning microscope. . Moreover, there is no restriction | limiting in particular about purity.

  The blending amount of the (E) inorganic filler is 10 to 200 parts by weight, preferably 20 to 180 parts by weight, based on 100 parts by weight of the compositions (A) to (D). -150 parts by weight are particularly preferred. Too much is not preferable because the fluidity is lowered. If the amount is too small, the thermal rigidity is lowered, which is not preferable.

  The inorganic filler of the above (E) can be subjected to a surface treatment 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. Compounds, isocyanate compounds, organic silane compounds, organic titanate compounds, and organic borane treatment.

  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, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyetherimide resin, polyarylate resin, liquid crystal Polymer, Polyethersulfone resin, Polyetherketone resin, Polythioetherketone resin, Polyetheretherketone resin, Polyimide resin, Polyamideimide resin, Polytetrafluoroethylene resin, Thermoplastic polyurethane resin, Polyamide elastomer, Polyester elastomer, Polyester resin , Polyphenylene ether resin, SAN resin, acrylic resin, SBS, SEBS, various elastomers, etc. It can be blended in the have range. Furthermore, these can also be used in combination of 2 or more types.

  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.

  The silane coupling agent is preferably 0.01 to 5 parts by weight, and more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight as a total of the components (A) to (D).

  Furthermore, in the present invention, when it is desired to impart conductivity, it is possible to use a conductive filler as part or all of the inorganic filler, and the material is not particularly limited. The filler is not particularly limited as long as it is a conductive filler that is usually used for conducting a resin. Specific examples thereof include metal powder, metal flake, metal ribbon, metal fiber, metal oxide, and a conductive substance. Inorganic fillers, carbon powder, graphite, carbon fibers, carbon flakes, scale-like carbon, and the like.

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 subjected to surface treatment 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.

  Furthermore, it is possible to mix | blend carbon black as said electroconductive filler in this invention. As carbon black, C (carbon) is the main component, and its raw materials and manufacturing methods are used for acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc. being classified. The carbon powder that can be used in the present invention is not particularly limited in its raw material and production method, but 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.

  Two or more of the conductive fillers may be used in combination. Among such conductive fillers, carbon black is particularly preferably used in terms of strength and economy.

  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, it 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. Specifically, the mixture of raw materials is supplied to a generally known melt mixer such as a single or twin screw extruder, Banbury mixer, kneader, or mixin gall, and kneaded at a temperature of 280 to 450 ° C. The method of doing can be given as an example. 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, polyamide resin, polyolefin resin, and copolymerized polyolefin are melt-kneaded, then an inorganic filler is added, and melt-kneaded for production. Among them, PPS resin, polyamide resin, polyolefin resin and copolymer polyolefin are supplied using a twin screw extruder, melt kneaded, inorganic filler is supplied using a side feeder, kneaded, and then exposed to vacuum. A preferred method is to remove the gas to be removed. By obtaining the PPS resin composition by such an extrusion process, it is possible to obtain good impact strength with less generated gas. As for a small amount of additive component, other components can be kneaded and pelletized by the above-described method or the like, 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, the load is 5000 g (orifice diameter 2.095 mm, length 8.00 mm). The measured value using a melt indexer under the conditions is preferably 150 g / 10 min or less, more preferably 100 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 resin composition of the present invention can employ injection molding methods such as injection molding, injection compression molding, two-color molding, and two-stage injection molding, in particular, as a molding method for obtaining a melt-molded product. Further, the molding temperature is usually selected from a temperature range 5 to 50 ° C. higher than the melting point of the thermoplastic resin other than the polyolefin resin, and is generally a single layer, but by a method such as a two-color injection molding method. A multilayer structure may also be used.

  The resin composition of the present invention is suitable for a container mold product and can be preferably used for a container mold product that is particularly subjected to internal pressure. The internal pressure is not particularly limited, but the resin composition having excellent rigidity and durability can be exhibited preferably at a pressure of 30 kPa or more.

  Furthermore, the resin composition of the present invention is excellent in bondability and is suitable for a molded body having a bonding site. The bonding method is not particularly limited as long as the resin is melted and fused. Specifically, there are vibration welding, ultrasonic welding, hot plate welding, two-stage injection molding bonding, two-color molding bonding, and the like. Of these, vibration welding, hot plate welding, and two-stage injection molding joining are preferable.

  The resin composition of the present invention is excellent in impact strength, fluidity, low gasity, slidability, and particularly in parts that require toughness due to excellent impact strength and fluidity, particularly container parts such as tanks and cases. Suitable for structural parts such as housings and electrical parts cases. For example, exterior parts of automobiles such as doors and wheel caps, engine covers for two- and four-wheel automobiles, intake manifolds, cylinder head covers and integrated parts thereof, housings such as pumps, structural parts, fuel tanks, canisters, washer fluid tanks, oil reservoirs In addition to being suitable for molded articles such as various tanks such as tanks and oils, underhood parts such as pumps, and other containers, there are uses for automotive interior and exterior parts such as relay blocks, inhibitor switches and combination switch levers. Suitable for other structural materials. OA equipment parts such as notebook PC housings, printer housings, home appliance housings, covers, tanks, cut-off valves attached to bottles, valves and fittings such as ORVR valves, attached pump gauges, cases, etc. Parts, fuel filler underpipe, ORVR hose, reserve hose, vent hose and other fuel tube connection parts (connectors, etc.), oil tube connection parts, brake hose connection parts, nozzle for window washer fluid, cooling water, refrigerant Cooling hose connection parts, air conditioner refrigerant tube connection parts, floor heating pipe connection parts, fire extinguishers and fire extinguishing equipment hoses, medical cooling equipment tube connection parts and valves, pipes and pumps Case, valve, flange, auto parts, Combustion engine applications, including machine parts, such as an electric tool housing compounds, electrical and electronic components, medical care, food, home and office supplies, toilet seat around parts, building materials-related parts, and parts for furniture Naga is.

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

  Specific gravity, tensile strength, impact strength, weld strength, and two-stage injection-molded joint strength described in the examples and comparative examples were measured according to the following methods.

[specific gravity]
Specific gravity was measured according to an underwater displacement method using an ASTM D638 TYPE I dumbbell test piece.

[Measurement of tensile strength]
A tensile test piece (1/8 inch (3.2 mm) thickness) according to ASTM D638 was injection molded at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and in accordance with ASTM D638 under a temperature condition of 23 ° C. It is measured. If it is 100 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 impact strength]
An impact test piece (1/8 inch (3.2 mm) wide, with notch) conforming to ASTM D256 was injection molded at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and ASTM D256 under a temperature condition of 23 ° C. It was measured according to. If it is 80 J / m 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 vibration welding strength]
FIG. 1 shows a half-divided shape of a test specimen for measuring bending fatigue. A test piece 1 having a surface shape shown in FIG. 1 and a thickness of 10 mm was molded by an injection molding method. The test piece 1 is fixed to the vibration welding machine up and down as shown in FIG. 2 and melted and joined by rubbing part A (end part) by overlapping vibration. Using a Branson 2850 type vibration welding apparatus, welding was performed under the following conditions. Frequency: 240 Hz, pressure: 2.3 MPa, amplitude: 1.5 mm, welding allowance: 1.5 mm. The shape of the molded product obtained by welding is shown in FIG.

  The center part B of this welding test piece was cut with a width of 8 mm, the bending strength was measured using this, and the value was taken as the adhesive strength. If the bending strength is 20 MPa or more, it can be said that the product strength level has no practical problem. However, the higher this value, the better the weldability and the better.

[Measurement of joint strength of two-stage injection molding]
Molding machine: J-220EII-2M resin temperature, 325 ° C., manufactured by Nippon Steel, Ltd. Note that the primary injection and secondary injection are performed at the same resin temperature Mold temperature: 130 (movable) / 130 (fixed) ° C., primary injection speed: 100 %, Secondary injection speed: 100%, primary injection pressure: 35%, secondary injection pressure: 25%, primary cooling time: 20 seconds, secondary cooling time: 25 seconds.

  Two divided pieces 2 shown in FIGS. 4A to 4D and FIGS. 5A to 5C were obtained by the primary injection. Using the slide structure of the mold, the two divided pieces are made to face each other in the mold, and then the secondary injection is performed under the above conditions. The internal volume is 500 cc, the general part thickness is 3 mm, and the flange thickness is 5 mm. A hollow molded article 3 shown in a) to FIG. 6C was obtained. The molded product 3 was loaded with a water pressure of 1.13 g / second by an electric water pump (manufactured by Iwaki Co., Ltd.), and the pressure at the time of rupture at which the joint was ruptured was defined as the joint strength. The higher this value, the better the airtightness and the better.

[Evaluation of molded product peeling]
Using a tensile test piece, it was visually determined whether peeling occurred on the surface of the molded product from the gate portion to the flow end. Judgment results were as follows: ◯: no peeling, x: peeling. Those in which peeling does not occur are preferable because the composition is uniform and excellent in various properties.

[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 heat-treated at 230 ° C. for 16 hours to obtain MFR550 (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]
(Polyamide resin)
B-1: Toray nylon resin “Amilan” CM1021, polyamide 6 resin, relative viscosity 3.40
B-2: Toray nylon resin “Amilan” CM3001N, polyamide 66 resin, relative viscosity 2.95
The relative viscosity was measured by a 98% sulfuric acid solution viscosity method according to JIS K6810.
(Polyolefin resin)
C-1: Polyethylene Density 903kg ^/ cm 3, MFR4.0g ^/ 10 min C-2: Polyethylene Density 968kg ^/ cm 3, MFR4.5g ^/ 10 min C-3: Polypropylene Density 910kg ^/ cm 3, MFR0.5g ^/ 10 Minute MFR was measured according to ASTM D1238 (polyethylene: 190 ° C., polypropylene: 230 ° C.) (2160 g load).
(Copolymerized polyolefin)
D-1: Ethylene / glycidyl methacrylate copolymer (E / GMA = 88/12% by weight), MFR = 3 g / 10 minutes D-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 JISK6760 (190 ° C., 2160 g load).
(Inorganic filler)
E-1: Glass fiber: “T-747” average fiber diameter 13 μm (manufactured by Nippon Electric Glass)
E-2: Wollastonite: “FPW # 400” average fiber diameter 9.5 μm (manufactured by Kinsei Matec)

In the above, the average fiber diameter of the glass fiber is an average fiber diameter measured by an ordinary method using an electronic scanning microscope. The average fiber diameter of wollastonite is a weight average fiber diameter determined on the basis of a fiber diameter distribution measured according to a conventional method using a laser diffraction particle size distribution analyzer.
(Coupling agent)
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) was used.

Examples 1-11
PPS (A), polyamide resin (B), polyolefin resin (C), and copolymerized polyolefin (D) prepared as described above were dry blended in the proportions shown in Table 1, and then the extrusion conditions were set to 350 ° C. (A) to (D) blended using a screw-type twin screw extruder (“TEX-44” manufactured by Nippon Steel Works) are supplied and supplied, and after melt-kneading, the inorganic filler (E) is fed from the side feeder. After feeding, the gas generated by exposure to vacuum was removed and pelletized. After drying the obtained pellets, injection is performed under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C. using an injection molding machine (“IS-100” manufactured by Toshiba Machine or J-220EII-2M manufactured by Nippon Steel Works). By molding, a predetermined test piece for characteristic evaluation was obtained. About the obtained test piece and pellet, specific gravity, tensile strength, impact strength, welding strength, two-stage injection molding bonding strength, and molded product peeling were measured by the methods described above. The results are shown in Table 1.

  The resin composition and the molded body obtained here had bonding strength and rigidity and were highly practical without peeling.

Comparative Example 1
After blending in the proportions shown in Table 1 in the same manner as in Examples, using only a PPS resin without blending a polyamide resin, a polyolefin resin and a copolymerized polyolefin resin, melt kneading, pelletizing, molding, evaluation Went. The results are shown in Table 1.

  When the polyamide resin and the polyolefin were not blended, the bonding strength was low and not practical.

Comparative Example 2
Using a polyamide resin + polyolefin resin / copolymerized polyolefin having a ratio of 10 and a PPS resin as a base, and dry blending in the proportions shown in Table 1 in the same manner as in the Examples, melt-kneading, pelletizing, molding, evaluation Went. The results are shown in Table 1.

  When the ratio of polyamide resin + polyolefin resin and copolymer polyolefin was used as a base, peeling occurred when the welding strength was low, which was not at a practical level.

Comparative Example 3
In the same manner as in the Examples, a non-polyamide resin compound was dry-blended in the same manner as in the Examples, and then melt-kneaded, pelletized, molded, and evaluated. The results are shown in Table 1.

  When a base not blended with a polyamide resin was used, the tensile strength and bonding strength were low and not practical.

Comparative Example 4
A non-copolymerized polyolefin was dry blended at the ratio shown in Table 1 in the same manner as in the Examples using the base resin and the filler, and then melt-kneaded, pelletized, molded, and evaluated. The results are shown in Table 1.

  When the copolymer polyolefin was not used, impact strength and bonding strength were low, and the molded product was peeled off, which was not at a practical level.

Comparative Example 5
Using a mixture of PPS resin and other base resin at a ratio of 0.5 and PPS resin as a base, and dry blending at the ratios shown in Table 1 in the same manner as in the examples, melt kneading, pelletizing, molding And evaluated. The results are shown in Table 1.

  When the PPS resin and other base resin were mixed at a ratio of 0.5, the bonding strength was low, and the molded product was peeled off, which was not at a practical level.

Comparative Example 6
Using a mixture of a copolymerized polyolefin, a polyamide resin and a polyolefin resin in a ratio of 7.0 and a PPS resin as a base, and dry-blending at the ratio 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 blended at a ratio of 7.0 between copolymerized polyolefin, polyamide resin and polyolefin resin, the bonding strength was low and not practical.

It is a top view which shows the shape before welding of the test piece for welding strength measurement used in the Example. It is a top view which shows the welding shape of the test piece for the welding strength measurement used in the Example. It is the test piece which measured bending strength from what was welded in the Example. It is a primary injection-molded product (divided piece) of the test piece for two-stage injection-molded joint strength measurement used in the examples, (a) is a plan view showing the shape, (b) is a side view thereof, and (c). Is a front view thereof, and (d) is a bottom view thereof. It is a primary injection-molded product (divided piece) of the test piece for two-stage injection-molded joint strength measurement used in the examples, (a) is a plan view showing the shape, (b) is a side view thereof, and (c). Is a front view thereof. It is a hollow molded product obtained by superimposing the primary injection molded product of the two-stage injection molding bond strength measurement test piece used in the examples and performing the secondary injection molding and joining the test piece, (a) The top view which shows the shape, (b) is the side view, (c) is the front view.

Explanation of symbols

1 Test piece 2 Divided piece 3 Hollow molded product

Claims (8)

(A) Polyphenylene sulfide resin more than 50% by weight, 94% by weight or less, (B) Polyamide resin 5 to 35% by weight, (C) One or more polyolefin resins selected from polyethylene resin and polypropylene resin 0 to 25% by weight %, (D) 1-19% by weight of a copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate, and a total of 100% by weight of the components (A) to (D), A polyphenylene sulfide resin composition comprising (E) 10 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of the composition of (A) to (D). The polyphenylene sulfide resin composition according to claim 1, wherein the weight ratio ((B) + (C)) / (D)) of (B) + (C) to (D) is 1 to 6.8. (E) The polyphenylene sulfide resin composition according to claim 1 or 2, wherein the inorganic filler is glass fiber. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the (B) polyamide resin is at least one selected from polyamide 6, polyamide 66, and a copolymer polyamide containing them as a main component. (C) Polyolefin sulfide resin composition in any one of Claims 1-4 whose polyolefin resin is a polyethylene resin with a density of 900-950 kg / m < ³ >. A container mold product using the polyphenylene sulfide resin composition according to any one of claims 1 to 5 and receiving an internal pressure of 30 kPa or more. An injection-molded article having a bonding site using the polyphenylene sulfide resin composition according to any one of claims 1 to 5. The polyphenylene sulfide resin composition according to any one of claims 1 to 5 is welded by any one or more joining methods of vibration welding, ultrasonic welding, hot plate welding, two-stage injection molding joining, and two-color molding joining. An injection molded product.

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