JP5494526B2 - Polyphenylene sulfide resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a polyphenylene sulfide resin composition that is excellent in toughness at low temperatures and generates less gas during use during heating or molding, and a molded product thereof.

  Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has a good balance of rigidity, heat resistance, hot water resistance, chemical resistance, and molding processability, so it is widely used in electrical / electronic parts, watering parts and automobile parts. It has been.

  However, PPS resin has a problem that it is inferior in toughness indicated by tensile elongation at break and impact strength compared to other engineering plastics.

  In order to solve such problems, a method of blending various elastomers with a PPS resin has been proposed so far. For example, JP 2000-198923 blends an ethylene / α-olefin copolymer having excellent toughness. However, since the process temperature of the PPS resin is 300 ° C. or higher, the ethylene / α-olefin copolymer which is inferior in heat resistance in the process until obtaining a molded product is thermally decomposed, There is a problem in that the gas generated during molding increases, the appearance of the molded product deteriorates due to clogging and dirt of the mold, and further, corrosion of the mold easily occurs. Japanese Patent Application Laid-Open No. 11-49952 proposes a PPS resin composition using an olefin copolymer of ethylene and an α-olefin having 5 or more carbon atoms as an elastomer in order to reduce mold contamination due to the generated gas. Yes. However, a general ethylene / α-olefin copolymer is a random copolymer, and when the ethylene component is increased to improve heat resistance, the glass transition point is also increased, and the toughness of the resulting PPS resin composition at low temperatures is increased. It is insufficient, and is unsuitable for automobile applications and water use applications that require cold resistance, cold heat resistance, and freeze resistance.

  From the above, a PPS resin having both low temperature toughness and low gas properties has been demanded.

JP 2000-198923 A JP 11-49952 A (paragraph [0016])

  An object of the present invention is to provide a PPS resin composition exhibiting excellent low-temperature toughness, heat resistance, and low gas properties, and a molded product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

That is, the present invention
(1) A polyphenylene sulfide resin composition obtained by blending 1 to 100 parts by weight of (B) an ethylene / α-olefin block copolymer with respect to 100 parts by weight of (A) polyphenylene sulfide resin, ) An ethylene / α-olefin block copolymer is obtained by combining a catalyst for highly selective polymerization of ethylene, a catalyst for highly selective polymerization of α-olefin, and a reversible chain transfer agent, having a melting point of 100 ° C. or more and Ri block copolymer der having a glass transition point of -50 ° C. or less, wherein (B) constituting the ethylene · alpha-olefin block copolymer alpha-olefin, isobutylene, 1-butene, 1- At least selected from pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene Polyphenylene sulfide resin composition characterized 1 Tanedea Rukoto,
(Here, the melting point of the (B) ethylene / α-olefin block copolymer was measured using a differential scanning calorimeter and the temperature of the polymer from room temperature to 20 ° C./min by differential calorimetry. After observing the endothermic peak temperature observed at the time, the temperature was raised to a temperature of 180 ° C., held at that temperature for 3 minutes, then cooled to −30 ° C. under a temperature drop condition of 20 ° C./min, and then 10 ° C. This is the endothermic peak temperature observed when measured under the temperature rise condition / min. Similarly, the glass transition point is observed when measured under the temperature rise condition at 20 ° C./min with a differential scanning heat flow meter. After observing the endothermic peak temperature, the temperature was raised to 130 ° C., held at that temperature for 3 minutes, then cooled to −100 ° C. at 10 ° C./min, and from the obtained DSC curve, in accordance with JIS K7191 (This is the calculated value.)
( 2 ) The polyphenylene sulfide resin composition according to ( 1 ), wherein the α-olefin constituting the ethylene / α-olefin block copolymer (B) is 1-butene and / or 1-octene,
( 3 ) (A) The functional group containing at least one functional group selected from (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester with respect to 100 parts by weight of the polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to (1) or (2), wherein 1 to 100 parts by weight of an olefin copolymer is blended,
( 4 ) (A) The polyphenylene sulfide resin composition according to any one of (1) to ( 3 ), wherein 100 parts by weight of the polyphenylene sulfide resin is blended with 1 to 400 parts by weight of an inorganic filler (D).
(5) (D) an inorganic filler of glass fibers, glass beads, glass flakes, at least one selected from calcium carbonate (4) Symbol mounting of the polyphenylene sulfide resin composition (6) (1) - (5 ) A molded article comprising the polyphenylene sulfide resin composition according to any one of
( 7 ) The molded product according to ( 6 ), wherein the molded product is a water-borne part.

  Since the PPS resin composition of the present invention is excellent in low temperature toughness and low gas property, electrical / electronic related equipment, precision machinery related equipment, watering parts, office equipment, automobile / vehicle related parts, building materials, packaging materials, furniture It is useful for daily goods, especially for automobiles and water applications.

It is the schematic of the metal mold | die molded article for gas evaluation shape | molded in the Example.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The (A) PPS tree of the present invention is a polymer having a repeating unit represented by the following structural formula,

  A polymer containing 70 mol% or more, particularly 90 mol% or more of the repeating unit represented by the above structural formula is preferable from the viewpoint of heat resistance. Moreover, PPS resin can be comprised with the repeating unit etc. which have the following structure in less than 30 mol% of the repeating unit.

  Further, when a PPS having a high melt viscosity is desired, it is also possible to apply a branched PPS obtained by copolymerizing dihalobenzene as a main monomer and less than 3 mol% of trihalobenzene.

(Polymerization of PPS resin)
Such PPS resins are generally known in the art, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight. In the present invention, the PPS resin obtained as described above is crosslinked / polymerized by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, aqueous acid solution, etc. Of course, it can be used after various treatments such as activation with a functional group-containing compound such as an acid anhydride, amine, isocyanate, or a functional group-containing disulfide compound.

  As a specific method for crosslinking / high molecular weight by heating PPS resin, it can be performed in an oxidizing gas atmosphere such as air or oxygen, or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method in which heating is performed in a heating container at a predetermined temperature until a desired melt viscosity is obtained. The heat treatment temperature is usually selected from 170 ° C. to 80 ° C., preferably from 200 to 270 ° C., and the time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. By controlling both temperature and time, the target viscosity level can be obtained. As the heat treatment apparatus, it is more preferable to use an ordinary hot air drier or a heating apparatus with a rotary type or a stirring blade.

  As a specific method for heat-treating the PPS resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200 to 200 ° C. under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at 270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade, but a heating apparatus with a rotary or stirring blade is used for efficient and more uniform treatment. Is more preferable.

  In the present invention, it is preferable to use a PPS resin in which the ash content in PPS is reduced to 0.2% by weight or less by deionization treatment or the like in terms of obtaining better toughness and moldability. Specific examples of such deionization treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment, and these treatments may be used in combination of two or more methods. Here, the amount of ash was measured according to the following method. About 5 g of dry PPS bulk powder is weighed in a crucible and baked until it becomes a black lump on an electric stove. Next, the firing is continued in the electric furnace set at 550 ° C. until the carbide is completely fired. Then, after cooling in a desiccator, the weight is measured, and the ash content is calculated from comparison with the initial weight.

  The following method can be illustrated as a specific method when the PPS resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have the action of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethyl Sulfoxide and sulfone solvents such as sulfoxide and dimethyl sulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone, ether solvents such as dimethyl ether, dipropyl ether and tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, Halogen solvents such as dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene group Call, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The PPS resin that has been subjected to organic solvent washing is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method when the PPS resin is treated with hot water. That is, in order to express a preferable chemical modification effect of the PPS resin by hot water washing, the water used is preferably distilled water or deionized water. The operation of the hot water treatment is usually performed by putting a predetermined amount of PPS resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably larger, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating PPS resin. That is, there is a method of immersing the PPS resin in an acid or an acid aqueous solution, and stirring or heating can be appropriately performed as necessary. The acid used is not particularly limited as long as it does not have an action of decomposing PPS, and is saturated with aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic saturated compounds such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as carboxylic acid, acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, sulfuric acid, Examples include inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of the PPS resin by acid treatment.

  Next, the (B) ethylene / α-olefin block copolymer, which is an essential component of the invention, is obtained by copolymerizing ethylene and at least one α-olefin having 3 to 20 carbon atoms. However, it is a feature that the mode of copolymerization is block copolymerization.

The (B) ethylene / α-olefin block copolymer used in the present invention is characterized by a plurality of blocks of two or more polymerized monomer units having different chemical or physical properties, so-called segments, The following formula:
(AB) n
In the formula, n is an integer of at least 1 and preferably greater than 1, A represents a hard segment in which only ethylene is copolymerized, and B represents a soft segment in which only α-olefin is copolymerized. Due to the molecular skeleton in which the hard segment and the soft segment coexist, it has a lamellar structure like other crystalline resins.

  A method for producing (B) an ethylene / α-olefin block copolymer used in the present invention is disclosed in JP-T-2008-545016, and a catalyst for highly selectively polymerizing ethylene, an α-olefin is highly polymerized. By combining a selectively polymerizing catalyst and a reversible chain transfer agent, a block copolymer different from random copolymerization, which is a conventional copolymerization mode of an ethylene / α-olefin copolymer, can be obtained. The conventional ethylene / α-olefin copolymer is obtained only by a metallocene catalyst composed of a cyclopentadienyl derivative of a group IV metal such as titanium or zirconium and a cocatalyst. The mode of copolymerization obtained is random copolymerization. Moreover, before the manufacturing method by a metallocene catalyst was established, the manufacturing method by a Ziegler catalyst was used, but the copolymerization mode obtained is also random copolymerization.

  Examples of the (B) ethylene / α-olefin block copolymer (B) α-olefin having 3 to 20 carbon atoms used in the present invention include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, Examples include 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like, and 1-butene and 1-octene are particularly preferable.

  The melting point and glass transition point of the (B) ethylene / α-olefin block copolymer used in the present invention have a melting point of 100 ° C. or higher and a glass transition point of −50 ° C. or lower, preferably 110 ° C. The glass transition point is −55 ° C. or lower, more preferably the melting point is 115 ° C. or higher and the glass transition point is −60 ° C. or lower. Mold fouling can be reduced when the melting point is 100 ° C. or higher, and low-temperature toughness of the PPS resin can be improved when the glass transition point is −50 ° C. or lower.

  The melting point of the ethylene / α-olefin block copolymer (B) is determined by using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation), and the temperature of the polymer is increased from room temperature to 20 ° C./min by differential calorimetry. After observing the endothermic peak temperature observed when measured under the conditions, the temperature was raised to a temperature of 180 ° C., held at that temperature for 3 minutes, and then cooled to −30 ° C. under a temperature drop condition of 20 ° C./min. Thereafter, the endothermic peak temperature observed when measured under a temperature rising condition of 10 ° C./min was determined and taken as the melting point.

  Further, the glass transition point of the (B) ethylene / α-olefin block copolymer is an endothermic peak observed when measured under the temperature rising condition of 20 ° C./min by the differential scanning heat flow meter. After observing the temperature, the temperature was raised to 130 ° C., kept at the same temperature for 3 minutes, then cooled to −100 ° C. at 10 ° C./min, and obtained from the obtained DSC curve according to JIS K7191.

The density of the (B) ethylene / α-olefin block copolymer used in the present invention is 1.00 g / cm ³ or less, preferably 0.95 g / cm ³ or less, more preferably 0.90 g. / Cm ³ or less. When the density is 1.00 g / cm ³ or less, the toughness of the resulting PPS resin composition can be improved.

  The blending amount of the (B) ethylene / α-olefin block copolymer used in the present invention is selected in the range of 1 to 100 parts by weight, preferably 2 to 70 parts by weight, with respect to 100 parts by weight of the PPS resin. More preferably, it is 3 to 50 parts by weight. (B) If the blending amount of the ethylene / α-olefin block copolymer is too small, the effect of improving toughness such as tensile elongation at break and impact strength is negligible. If it is too large, the heat resistance and chemical resistance inherent to the PPS resin are inherent. Properties and hot water resistance are significantly impaired.

  Next, (C) the functional group-containing olefin copolymer containing at least one functional group selected from epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester used in the present invention is ( B) Blending with the ethylene / α-olefin block copolymer is important for improving the compatibility with the PPS resin.

  (C) As an aspect of the functional group-containing olefin copolymer, an olefin copolymer in which a monomer having an epoxy group is copolymerized is mentioned, and in particular, α-olefin and α, β-unsaturated glycidyl ester. An epoxy group-containing olefin copolymer obtained by copolymerizing (C) is preferable.

  Examples of the α-olefin of the (C) functional group-containing olefin copolymer include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1-octene, and the like. Is preferably used. Moreover, these can also use 2 or more types simultaneously.

  The (C) glycidyl ester of α, β-unsaturated acid of the functional group-containing olefin copolymer is a general formula.

(Wherein R represents a hydrogen atom or a lower alkyl group), specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, among which glycidyl methacrylate is preferably used.

  The copolymerization mode of the α-olefin of the (C) functional group-containing olefin copolymer used in the present invention and the glycidyl ester of α, β-unsaturated acid may be random, alternating, block, or graft copolymerization.

  In addition to the α-olefin (1) and α, β-unsaturated glycidyl ester (2), the (C) functional group-containing olefin copolymer used in the present invention is a monomer represented by the following general formula. An epoxy group-containing olefin copolymer having the monomer (3) as an essential component is also preferably used.

(Wherein R ¹ represents hydrogen or a lower alkyl group, X represents a group selected from —COOR ² group, —CN group or aromatic group. R ² represents an alkyl group having 1 to 10 carbon atoms)

  The details of the α-olefin and α, β-unsaturated glycidyl ester used in such an olefin copolymer are the same as described above.

  On the other hand, specific examples of the monomer (3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, and methacrylic acid. Α, β-unsaturated carboxylic acid alkyl esters such as methyl, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, acrylonitrile, styrene, α- Examples thereof include methylstyrene, styrene having an aromatic ring substituted with an alkyl group, and acrylonitrile-styrene copolymer, and two or more of these may be used simultaneously.

  Such an olefin copolymer is a random, alternating, block or graft copolymerization mode of α-olefin (1), glycidyl ester (2) of α, β-unsaturated acid and monomer (3). For example, for a random copolymer of α-olefin (1) and glycidyl ester (2) of α, β-unsaturated acid, two or more types in which monomer (3) is graft copolymerized may be used. It may be a copolymer in which copolymerization modes are combined.

  The copolymerization ratio of the olefin copolymer is α-olefin (1) / α, β from the viewpoint of influence on the target effect, polymerization, gelation, heat resistance, fluidity, influence on strength, and the like. -Glycidyl ester of unsaturated acid (2) = 60-99 wt% / 40-1 wt% is preferably selected. The copolymerization ratio of the monomer (3) was 95% to 40% by weight of the monomer (3) with respect to the total amount of α-olefin (1) and glycidyl ester (2) of α, β-unsaturated acid. ) In the range of 5 to 60% by weight (where the sum of (1), (2) and (3) is 100% by weight) is preferably selected.

  Another preferred embodiment of the epoxy-containing olefin polymer in the present invention is an epoxidized diene block copolymer.

  Such an epoxidized diene block copolymer is a block copolymer obtained by epoxidizing a double bond derived from a conjugated diene compound of a block copolymer or a partially hydrogenated block copolymer. Is a block copolymer composed of a polymer block A mainly composed of at least one aromatic vinyl compound and B mainly composed of at least one conjugated diene compound. For example, AB, A- It is an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as B-A, (A-B) 4-Si, or A-B-A-B-A. The partially hydrogenated block copolymer is obtained by hydrogenating the block copolymer. The block copolymer and the partially hydrogenated block copolymer will be described in detail below.

  This block copolymer contains 5% by weight or more and less than 95% by weight of an aromatic vinyl compound, preferably 10 to 60% by weight, more preferably 10 to 50% by weight, and a polymer block mainly composed of an aromatic vinyl compound. A has a structure of a homopolymer block of an aromatic vinyl compound or a copolymer block of an aromatic vinyl compound and a conjugated diene compound containing 50% by weight, preferably 70% by weight or more of an aromatic vinyl compound. Further, the polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound, or a conjugated diene compound containing 50% by weight, preferably 70% by weight or more of a conjugated diene compound, and an aromatic vinyl compound. It has the structure of a copolymer block. In addition, the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds are the distribution of the conjugated diene compound or aromatic vinyl compound in the molecular chain in each polymer block. May be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially in the form of a block, or any combination thereof, and a polymer block mainly composed of the aromatic vinyl compound When there are two or more polymer blocks each mainly composed of the conjugated diene compound, each polymer block may have the same structure or a different structure.

  As the aromatic vinyl compound constituting the block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, 1,1-diphenylethylene and the like are selected. Among them, styrene is preferable. Further, as the conjugated diene compound, for example, one or two or more kinds can be selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. Among them, butadiene, isoprene, and these A combination is preferred. The polymer block mainly composed of the conjugated diene compound can be arbitrarily selected in the microstructure of the block. For example, in the polybutadiene block, the 1,2-vinyl bond structure is preferably in the range of 5 to 65%, Especially preferably, it is 10 to 50% of range.

  The number average molecular weight of the block copolymer having the above structure of the epoxidized diene block copolymer is usually 5,000 to 1,000,000, preferably 10,000 to 800,000, more preferably 30. The molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)] is 10 or less. Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

  As a manufacturing method of these block copolymers, any manufacturing method may be used as long as it has the above structure.

  The partially hydrogenated block copolymer is obtained by hydrogenating the above aromatic vinyl compound-conjugated diene compound block copolymer. As a method for producing this hydrogenated block copolymer, Is not particularly limited as long as the properties of the PPS resin composition of the present invention are not impaired.

  Next, the epoxidized diene block copolymer that can be used as one of the (C) functional group-containing olefin copolymer of the present invention is a block copolymer having the above-described structure, or a partially hydrogenated block copolymer. An epoxidizing agent is reacted to epoxidize an aliphatic double bond based on a conjugated diene compound. The manufacturing method of the epoxidized diene block copolymer used for this invention will not be limited unless the characteristic of the PPS resin composition of this invention is impaired.

  Examples of the olefin copolymer containing a carboxyl group and a salt thereof, a carboxylic acid ester group, and an acid anhydride group used as one of (C) a functional group-containing olefin copolymer in the present invention include ethylene -Copolymers of ethylene and α-olefin such as butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, polybutene, 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, Polyolefin copolymers such as a tylene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-ethylene-propylene-styrene block copolymer (SEPS), and the ethylene / α-olefin copolymer described in (B) above. Polymers include maleic anhydride, succinic anhydride, fumaric anhydride and other acid anhydrides, acrylic acid, methacrylic acid, vinyl acetate and other carboxylic acids, acrylic acid, methacrylic acid, vinyl acetate and other carboxylic acids and Its salts such as Na, Zn, K, Ca, Mg, carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate Olefin copolymer copolymerized with Specifically, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic n-propyl copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer , Ethylene-t-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-methacrylic n-propyl copolymer, ethylene-isopropyl methacrylate copolymer, ethylene -Olefin- (meth) acrylate copolymer such as n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, methyl acrylate-acrylonitrile copolymer Copolymer, methyl methacrylate-acrylonitrile copolymer (Meth) acrylic acid ester-acrylonitrile copolymer such as propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, butyl methacrylate-acrylonitrile copolymer Coal, ethylene- (meth) acrylic acid copolymer and its metal salts such as Na, Zn, K, Ca, Mg, ethylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, Ethylene-propylene-maleic anhydride copolymer, ethylene-hexene-maleic anhydride copolymer, ethylene-octene-maleic anhydride copolymer, propylene-maleic anhydride copolymer or maleic anhydride modified SBS, SIS, SEBS, SEPS, ethylene Examples thereof include an ethyl acrylate copolymer.

  The copolymerization mode of the (C) functional group-containing olefin copolymer is not particularly limited, and any copolymer mode such as a random copolymer, a graft copolymer, or a block copolymer may be used.

  In addition, as the functional group-containing olefin copolymer containing at least one functional group selected from the above (C) epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester, two or more ( C) A functional group-containing olefin copolymer may be used in combination.

  Moreover, the range of 1-100 weight part is selected with respect to 100 weight part of PPS resin, and, as for the compounding quantity of (C) functional group containing olefin type copolymer used for this invention, Preferably it is 2-70 weight part, Preferably it is 3-50 weight part. If the amount of the (C) functional group-containing olefin copolymer is too small, the effect of improving the compatibility of the (A) PPS resin and (B) the ethylene / α-olefin block copolymer cannot be obtained. If the amount is too large, the heat resistance, chemical resistance, hot water resistance inherent in the PPS resin, and the fluidity will be significantly reduced due to thickening. Furthermore, this is the effect of (B) an ethylene / α-olefin block copolymer. The effect of improving toughness at low temperatures is impaired.

  In the present invention, from the viewpoint of obtaining superior toughness and the like, as an additional component, an alkoxysilane compound is added in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 100 parts by weight of (A) polyphenylene sulfide resin. It is useful to add ~ 2 parts by weight.

  Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) ) Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2- Amino group-containing alkoxysilane compounds such as aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-hydroxypropyltrimethoxysilane, γ- Examples include hydroxyl group-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane, and dimer or higher oligomerized compounds may be used. Among these, an epoxy group-containing alkoxysilane compound is desirable.

  Next, specific examples of the (D) inorganic filler used in the present invention include non-fibrous fillers such as fibrous or plate-like, scaly, granular, indeterminate, and crushed products. For example, glass fiber, glass milled fiber, glass flat fiber, modified cross-section glass fiber, glass cut fiber, stainless steel fiber, metal fiber such as aluminum fiber and brass fiber, organic fiber such as aromatic polyamide fiber and Kevlar fibril, gypsum fiber , Ceramic fiber, Asbestos fiber, Zirconia fiber, Alumina fiber, Silica fiber, Titanium oxide fiber, Silicon carbide fiber, E glass (plate, scale, granular, irregular shape, crushed product), H glass (plate, scale)・ Granular, irregular shape, crushed product), A glass (plate, scale, granular, irregular shape, crushed product), C glass (plate, scale) , Granular, irregular shape, crushed product), natural quartz glass (plate, scale, granular, irregular shape, crushed product), synthetic quartz glass (plate, scale, granular, irregular shape, crushed product), lock Wool, Alumina Hydrate (Whisker / Plate), Potassium titanate whisker, Barium titanate whisker, Aluminum borate whisker, Silicon nitride whisker, Talc, Kaolin, Silica (crushed / spherical), Quartz, Calcium carbonate, Zinc carbonate , Mica, glass beads, glass flakes, crushed / indeterminate glass, glass microballoons, clay, molybdenum disulfide, wollastonite, aluminum oxide (crushed), translucent alumina (fibrous / plate / scale / Granular, irregular shape, crushed product), titanium oxide (crushed), zinc oxide (fibrous, plate, scale-like, granular, irregular shape, Metal oxides such as crushed products), metal hydroxides such as aluminum hydroxide (fibrous, plate-like, scale-like, granular, irregular shape, crushed), aluminum nitride, translucent aluminum nitride (fibrous, plate Shape, scale shape, granular shape, irregular shape, crushed product), calcium polyphosphate, graphite, metal powder, metal flake, metal ribbon, metal oxide and the like. Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Also, carbon fillers such as carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes, PAN-based and pitch-based carbon fibers can be mentioned, and two or more kinds of these fillers can be used in combination. Among these, glass fibers, glass beads, glass flakes, calcium carbonate, talc, and carbon fibers are more preferable.

  The glass fiber and other fillers used in the present invention are treated with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agent. Can also be used.

  The blending amount of the inorganic filler (D) used in the present invention is 1 to 400 parts by weight, preferably 5 parts per 100 parts by weight of the (A) PPS resin, from the balance of heat resistance, mechanical properties and the like. It is -200 weight part, More preferably, it is 10-150 weight part. (D) When there are too few compounding quantities of an inorganic filler, the improvement effects, such as heat resistance and mechanical characteristics by mix | blending it, are not remarkable, and when too large, there exists a tendency for toughness and fluidity | liquidity to fall.

  In the PPS resin composition of the present invention, other components such as a heat stabilizer (such as a hindered phenol, hydroquinone, phosphite, and substituted products thereof) and a weathering agent (in the range not impairing the effects of the present invention). Resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), release agents and lubricants (montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, stearamide, various bisamides, bisureas and polyethylene) Waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (eg, nigrosine), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type) Anionic antistatic agent, 4 Ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (eg red phosphorus, phosphate ester, melamine cyanurate, (Hydroxides such as magnesium hydroxide and aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or combinations of these brominated flame retardants with antimony trioxide) Other polymers (for example, amorphous resins such as polyamideimide, polyarylate, polyethersulfone, polyetherimide, polysulfone, polyphenylene ether, elastomer, etc.) can be added.

Blending of Components The method for producing the PPS resin composition of the present invention is usually produced by a known method. For example, (A) PPS resin, (B) an ethylene / α-olefin block copolymer, (C) a functional group-containing olefin copolymer, (D) an inorganic filler, and other optional components It is prepared by premixing an agent or the like and supplying it to an extruder or the like and sufficiently melting and kneading it. In addition, among the inorganic fillers (D), when adding a fibrous filler with a filler other than glass fiber or glass fiber, (A) PPS resin, (B) ethylene / α is preferred in order to suppress breakage. -Of the olefin-based block copolymer, (C) functional group-containing olefin-based copolymer, (D) inorganic filler, fillers other than glass fibers (excluding fibrous fillers) and other additives are used at the origin of the extruder. (D) Among inorganic fillers, glass fibers and fibrous fillers other than glass fibers are prepared by feeding them to an extruder using a side feeder.

  When producing the PPS resin composition of the present invention, for example, 180 to 380 using a single screw extruder, twin screw, three screw extruder and kneader type kneader equipped with a “unimelt” (R) type screw. It can be melt-kneaded at a temperature of 0 ° C. to obtain a composition.

Molding / Use of PPS Resin Composition The PPS resin composition of the present invention is generally known as a thermoplastic resin molding method such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, transfer molding, vacuum molding, etc. Of these, injection molding and extrusion molding are preferred.

  Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.

Reference Example Polymerization of PPS Resin The MFR values of PPS-1 to 4 obtained by the following method were measured according to JIS K7210.

[Reference Example 1] Polymerization of PPS (PPS-1)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 2583.00 g (31.50 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours under nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS-1 was linear and the MFR value was 300 g / 10 min.

[Reference Example 2] Polymerization of PPS (PPS-2)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 1722.00 g (21.00 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours while flowing nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS-2 was linear and the MFR value was 600 g / 10 min.

[Reference Example 3] Polymerization of PPS (PPS-3)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 861.00 g (10.5 mol), and ion-exchanged water 10500 g, and gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS-3 was linear and the MFR value was 1000 g / min.

[Reference Example 4] Polymerization of PPS (PPS-4)
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 -Charged 11.45 kg (115.50 mol) of pyrrolidone (NMP) and 10.5 kg of ion-exchanged water, gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure, 14.78 kg of water and NMP0 After distilling 28 kg, the reaction vessel was cooled to 200 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Thereafter, the mixture was cooled to 200 ° C., 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C. for 100 minutes, the bottom valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP. .

  The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.

  The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and acetic acid was added so that the pH was 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.
This was heat-treated at 200 ° C. in an oxygen stream until the MFR value reached 300 g / 10 minutes, to obtain PPS-4.

[Method of producing compounding material and PPS resin composition used in Examples and Comparative Examples]
PPS obtained in Reference Examples 1 to 4 using a twin screw extruder (TEX-44 manufactured by Nippon Steel Works) having a cylinder addition temperature of 310 ° C. and a screw rotation speed of 200 rpm and having a 44 mm diameter intermediate addition port. Resin (A) 100 parts by weight and (B) an ethylene / α-olefin block copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atoms, (C) a functional group-containing olefin copolymer and others The additive was added from the raw material supply port to a molten state, and (D) the inorganic filler was supplied from the intermediate addition port at the rate shown in Table 1, and melt-kneaded at a discharge rate of 40 kg / hour to obtain pellets. The following properties were evaluated using this pellet. In addition, the measurement and test of the physical property in an Example were performed with the following method. The results are shown in Table 1.

(B) an ethylene / α-olefin block copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atoms, (C) a functional group-containing olefin copolymer, (D) an inorganic filler, and As other additives, the following were used.
B1 ethylene-1-octene block copolymer (Dow Chemical Co. Infuse 9107, a density 866kg / ^{m 3,} melting point 121 ° C., a glass transition point -62 ° C.)
B2 ethylene / 1-octene block copolymer (Infuse 9100 manufactured by Dow Chemical Company, density 877 kg / m ³ , melting point 120 ° C., glass transition point −62 ° C.)
B3 ethylene / 1-octene block copolymer (Infuse 9807 manufactured by Dow Chemical Company, density 866 kg / m ³ , melting point 118 ° C., glass transition point −62 ° C.)
b1 (Comparative Example) Ethylene / 1-butene random copolymer (Tafmer TX650 manufactured by Mitsui Chemicals, Inc., density 864 kg / m ³ , no melting point, glass transition point −64 ° C.)
b2 (Comparative example) Ethylene / 1-hexene random copolymer (Mitsui Chemicals, Inc. Exelen FX CX2001, density 898 kg / m ³ , melting point 94 ° C., glass transition point unknown)
b3 (Comparative Example) Ethylene / 1-octene random copolymer (Dow Chemical Engage 8100, density 870 kg / m ³ , no melting point, glass transition point −55 ° C.)
C1 ethylene glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd. Bond First E, density 940 kg / m ³ , melting point 103 ° C., glass transition point −26 ° C.)
D1 chopped strand (manufactured by Nippon Electric Glass Co., Ltd. T-747 3 mm long, average fiber diameter 13 μm)
Other additives E1 Fatty acid ester wax (Lycowax E manufactured by Clariant Japan).

[Measuring method]
(1) Tensile properties: conformed to ISO 527-1 and 2.
(2) Impact characteristics: Conforms to ISO 179-1.
(3) Low gasity: Using the PPS resin composition of the present invention, the maximum size of the molded product is 55 mm, the width is 20 mm, the thickness is 2 mm, the gate size is the width of 2 mm, the thickness is 1 mm (side gate), and the gas vent portion is the maximum length. A gas evaluation mold having a length of 20 mm, a width of 10 mm, and a depth of 5 μm, using SE-30D manufactured by Sumitomo Heavy Industries, Ltd., with a cylinder temperature of 305 ° C., a mold temperature of 130 ° C., and an injection speed of 100 mm / s. The injection pressure is set within 50 to 80 MPa so that the filling time for each resin composition is 0.4 seconds, and further continuous molding is performed with a holding pressure of 25 MPa, a holding pressure speed of 30 mm / s, and a holding time of 3 seconds, When no dirt was found in the gas vent part and the cavity part upon completion of 200 shots, it was judged as “excellent” (double circle), and when dirt was seen, it was judged “inferior” (cross). Also, the dirt attached to the gas vent part and cavity part after completion of the above molding is collected with a microsampling knife while checking with an optical microscope, and collected in a Rudy Swiss tin boat for elemental analysis that has been weighed in advance. Then, the mass was measured with a micro balance XP2U manufactured by METTLER TOLEDO.

  The molded body comprising the polyphenylene sulfide resin composition of the present invention maintains the heat resistance, chemical resistance, hot water resistance and mechanical properties inherently exhibited by the PPS resin and is excellent in low temperature toughness. Useful for automobiles, watering applications, general sundries applications, building materials, etc. Specifically, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups , Oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, porcelain head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna , Such as computer-related parts Electronic 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, typewriters Home, office electrical product parts such as parts and word processor parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters, typewriters, etc. Machine-related parts, microscopes, binoculars, cameras, optical instruments represented by watches, precision machine-related parts; water faucet tops, mixing faucets, pump parts, pipe joints, valves, cheese, fittings, sockets, water volume control valves , Pressure reducing valve, relief valve, solenoid valve, hot water temperature sensor, water volume sensor Water-related parts such as water meter housings; valve alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, fuel-related / exhaust / intake system pipes, air intake nozzles Snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, hot water 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 hot air flow control valve, brush for radiator motor Holder, Water pump, Water pump impeller, Water inlet, Water outlet, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay, Transmission wire harness, Window washer nozzle, Air conditioner panel switch board, Fuel related electromagnetic valve Coil, fuse connector, horn terminal, electrical component insulation plate, ECU case, condenser case, power module component, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device Cases, vehicle speed sensors, cable liners, gasoline tanks, and other automobile / vehicle related parts, etc. Seed application may be exemplified. In particular, when there are a lot of gas generated at the time of molding, water-related parts not only have a poor appearance, but also deteriorate the sealing performance of water and cannot be formed as parts. However, when the PPS resin composition of the present invention is used, molding is performed. Since the amount of generated gas is small, it can be suitably used.

  G Gate

Claims (7)

(A) A polyphenylene sulfide resin composition obtained by blending 1 to 100 parts by weight of (B) ethylene / α-olefin block copolymer with respect to 100 parts by weight of polyphenylene sulfide resin, The α-olefin block copolymer is obtained by combining a catalyst for highly selectively polymerizing ethylene, a catalyst for highly selectively polymerizing α-olefin, and a reversible chain transfer agent, and has a melting point of 100 ° C. or higher. a glass transition point of -50 ° C. Ri block copolymer der below, the (B) constituting the ethylene · alpha-olefin block copolymer alpha-olefin, isobutylene, 1-butene, 1-pentene, 1 -Hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, at least one selected from 1-decene Oh polyphenylene sulfide resin composition characterized Rukoto.
(Here, the melting point of the (B) ethylene / α-olefin block copolymer was measured using a differential scanning calorimeter and the temperature of the polymer from room temperature to 20 ° C./min by differential calorimetry. After observing the endothermic peak temperature observed at the time, the temperature was raised to a temperature of 180 ° C., held at that temperature for 3 minutes, then cooled to −30 ° C. under a temperature drop condition of 20 ° C./min, and then 10 ° C. This is the endothermic peak temperature observed when measured under the temperature rise condition / min. Similarly, the glass transition point is observed when measured under the temperature rise condition at 20 ° C./min with a differential scanning heat flow meter. After observing the endothermic peak temperature, the temperature was raised to 130 ° C., held at that temperature for 3 minutes, then cooled to −100 ° C. at 10 ° C./min, and from the obtained DSC curve, in accordance with JIS K7191 (This is the calculated value.) The (B) alpha-olefin constituting the ethylene · alpha-olefin block copolymer, 1-butene and / or polyphenylene sulfide resin composition according to claim 1, wherein 1-octene. (A) A functional group-containing olefin copolymer containing at least one functional group selected from (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester with respect to 100 parts by weight of the polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to claim 1 or 2, comprising 1 to 100 parts by weight of a polymer. The polyphenylene sulfide resin composition according to any one of claims 1 to 3 , wherein (D) 1 to 400 parts by weight of an inorganic filler is blended with 100 parts by weight of (A) polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to claim 4 , wherein the inorganic filler (D) is at least one selected from glass fibers, glass beads, glass flakes, and calcium carbonate. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 5 . The molded article according to claim 6 , wherein the molded article is a water-borne part.

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