JP2012057139A - Polyphenylene sulfide resin composition and molded article formed thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a PPS resin composition and a molded article formed thereof which offer excellent low-temperature toughness, heat resistance, low gasification properties, and low moisture permeability.SOLUTION: The polyphenylene sulfide resin composition comprises a blend of (A) 100 pts.wt. of a polyphenylene sulfide resin, (B) 0.5-29.5 pts.wt. of the copolymer of ethylene and a 3C-12C α-olefin and with a tanδ value, measured at 190°C and 0.1 radian/sec, of 0.01 or more and less than 2.5, (C) 0.5-29.5 pts.wt. of a functional group-containing olefin-based copolymer having at least one kind of a functional group selected from among epoxy groups. acid anhydride groups, carboxy groups and their salts, and carboxylic acid esters, wherein the sum total of (B) and (C) is 1-30 pts.wt.

Description

  The present invention provides a PPS resin composition that exhibits excellent low-temperature toughness, heat resistance, low gas properties, and low moisture permeability, 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 resins generally tend to be 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, Patent Document 1 discloses a method of blending an ethylene / α-olefin copolymer having excellent toughness. It is shown. The addition of an ethylene / α-olefin copolymer to the PPS resin may result in an insufficient effect of improving toughness if the number of added parts is small, and conversely, if the number of added parts is large, molding processability may be impaired. That is, as a problem of molding processability, there are cases where the amount of deposits on the mold particularly during molding increases. Because PPS resin has a high temperature of 280 ° C or higher during molding, part of the ethylene / α-olefin copolymer is thermally decomposed in the process until the molded product is obtained, and the generated gas increases during molding. This is because the appearance of the molded product may be deteriorated due to clogging or dirt in the mold.

  A large number of such compositions have been used in the past, but in recent years, product shapes have become more complex and diversified, and there has been a demand for further gas reduction and improved appearance.

  In addition, PPS resin is used for automobile parts such as fuel pumps and water pumps, and water parts such as pump parts, pressure reducing valves and joints. In particular, these parts may be placed in a low-temperature environment such as a cold region, so the product may be damaged by external impacts such as a vehicle collision, tool or component dropping, or pressure from inside the product in a low-temperature environment. there's a possibility that. Therefore, not only high heat resistance and chemical resistance of PPS but also high toughness at low temperature is required. Even in such applications, many PPS resin compositions have been used in the past, but in recent years there has been a tendency for product shapes to become thinner, lighter, and more complex, requiring higher toughness at lower temperatures than ever before. It is getting to be.

  The improvement in toughness at low temperatures is also shown in Patent Document 2. Considering molding processability, it is preferable that the ethylene / α-olefin copolymer and the functional group-containing olefin copolymer have an effect of improving low-temperature toughness with a small addition amount. However, as described above, in recent years, there has been a tendency to demand further low-temperature toughness from materials due to an increase in demand for reduction in thickness and weight, and in the described ethylene / α-olefin copolymer, an additive that can satisfy moldability is added. In the amount range, there are cases where the low temperature impact resistance obtained is insufficient.

  In view of the above, there is a demand for a PPS resin having both low temperature toughness and moldability.

JP 2000-198923 A JP 2010-6858 A

  This invention makes it a subject to provide the PPS resin composition which shows the outstanding low-temperature toughness, heat resistance, low gas property, and low moisture permeability, and its molded article.

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

That is, the present invention provides the following.
1. (A) 100 parts by weight of the polyphenylene sulfide resin, (B) an ethylene and an α-olefin copolymer having 3 to 12 carbon atoms, and the tan delta measured at 190 ° C. and 0.1 radians / second is 0 0.5 to 29.5 parts by weight of a copolymer having a value of 0.01 or more and less than 2.5, at least one selected from (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester The functional group-containing olefin copolymer containing 0.5 to 29.5 parts by weight of the functional group is blended, and the total of (B) and (C) is 1 to 30 parts by weight. A polyphenylene sulfide resin composition.
2. 2. The polyphenylene sulfide resin composition according to 1 above, wherein the tan delta value measured at 190 ° C. and 0.1 radians / second of (B) is less than 2.2.
3. 3. The polyphenylene sulfide resin composition according to 1 or 2 above, wherein the melt flow rate measured at 190 ° C. and 2160 g of (B) is 0.01 or more and less than 0.5 g / 10 minutes.
4). (A) The polyphenylene sulfide resin composition according to any one of the above items 1 to 3, wherein 1 to 400 parts by weight of the inorganic filler (D) is blended with 100 parts by weight of the polyphenylene sulfide resin.
5. (D) The polyphenylene sulfide resin composition according to the above item 4, wherein the inorganic filler is at least one selected from glass fibers, glass beads, glass flakes, and calcium carbonate.
6). The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein 1 to 20 parts by weight of (E) a high-density polyethylene homopolymer is blended with 100 parts by weight of (A) polyphenylene sulfide resin.
7). A molded article comprising the polyphenylene sulfide resin composition according to any one of 1 to 6 above.

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

It is the schematic of the apparatus which performed the moisture permeability test in the Example.

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

  The (A) PPS resin 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 280 ° 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 if necessary, stirring or heating can be appropriately performed. 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, (B) which is an essential component of the present invention is ethylene and an α-olefin copolymer having 3 to 12 carbon atoms, and the tan delta measured at 190 ° C. and 0.1 radians / second is 0.00. It is a copolymer having a value of 01 or more and less than 2.5. Such a copolymer having a tan delta measured at 190 ° C. and 0.1 radians / second of not less than 0.01 and less than 2.5 can be obtained, for example, by incorporating a long chain branch in the polymer main chain. Can do. Having a long-chain branch means having 0.01 to 3 long-chain branches per 1000 carbon atoms with respect to the polymer main chain. Further, the long chain branch has the same copolymer distribution as the main chain, and has almost the same length as the length of the main chain of the polymer.

  Ethylene and an α-olefin copolymer having 3 to 12 carbon atoms that can be used in the present invention, wherein a tan delta measured at 190 ° C. and 0.1 radians / second is 0.01 or more and less than 2.5 Examples of long chain branching ethylene / α-olefin copolymers are described in US Pat. Nos. 5,272,236 and 5,278,272.

  Moreover, in order to obtain long chain branching, the ethylene / α-olefin copolymer having long chain branching that can be used in the present invention is also one of preferred embodiments. Examples of geometrically constrained catalysts and examples of such preparations are described in US Pat. Nos. 5,272,236, 5,278,272, 29,613,199.

  The (B) long chain branched ethylene / α-olefin copolymer that can be used in the present invention is preferably a copolymer that is randomly distributed in the molecule, and the copolymerization ratio in the polymer is the same. It is preferred to have an ethylene / α-olefin ratio.

  Further, (B) long chain branching in the ethylene / α-olefin copolymer having long chain branching that can be used in the present invention is determined using 13C nuclear magnetic resonance spectroscopy, and the Randall method. ("Rev. Macromol. Chem. Phys.", C29 (2 & 3), pp. 285-297).

  In the present invention, (B) a functional group selected from an epoxy group, an acid anhydride group, an amino group, a carboxyl group and a salt thereof, and a carboxylic acid ester is used as the ethylene and α-olefin copolymer having 3 to 12 carbon atoms. It is also possible to use what is contained. By using the (B) α-olefin copolymer containing such a functional group, at least one selected from (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester described later. The effect similar to the case where the functional group containing olefin type copolymer containing the functional group of these is used together can be acquired. However, it is actually an α-olefin copolymer having 3 to 12 carbon atoms with ethylene, and the tan delta measured at 190 ° C. and 0.1 radians / second is a value of 0.01 or more and less than 2.5. It is economical to obtain an α-olefin copolymer which is a certain copolymer and contains a functional group selected from an epoxy group, an acid anhydride group, an amino group, a carboxyl group and a salt thereof, and a carboxylic acid ester. Since it is disadvantageous, usually (B) an ethylene and an α-olefin copolymer having 3 to 12 carbon atoms are selected from an epoxy group, an acid anhydride group, an amino group, a carboxyl group and a salt thereof, and a carboxylic acid ester. That do not contain functional groups.

  The (B) ethylene / α-olefin copolymer used in the present invention is obtained by copolymerizing ethylene and at least one α-olefin having 3 to 12 carbon atoms.

  Specific examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. , 1-dodecene and combinations thereof. Among these α-olefins, a copolymer using an α-olefin having 4 to 8 carbon atoms is particularly preferable because improvement in mechanical strength and further improvement in the reforming effect can be seen.

  (B) an α-olefin copolymer having 3 to 12 carbon atoms and ethylene having a tan delta of 0.01 or more and less than 2.5 measured at 190 ° C. and 0.1 radians / second. The tan delta in a copolymer, which is also known as the loss tangent, defined as the decay peak (d a m p e n i n g p e a k), or the ratio of loss modulus to storage modulus . Damping is a very sensitive indicator of molecular motion that occurs in solid and molten materials. The decay peak is associated with an increased degree of freedom for a small segment of the chain at the glass transition. Tan delta also peaks when the material enters the viscous flow region where the entanglement effect is negligible and the frictional force is the only hindering flow. The tan delta value is a very good index for balancing the melt strength and the fluidity as it is, and by definition is the ratio of the viscous component to the elastic component. The material becomes more fluid as the tan delta rises or rises and becomes more elastic as the tan delta gets lower. Tan delta values as a function of temperature at a certain shear rate are via the viscous flow region, and such values can indicate the sensitivity of the polymer blend to temperature and shear rate during processing. Tan delta values are (Mechanical Properties of Polymers and Composites) by L. E. Nielson (Mechanical Properties of Polymers and Composites). esofPoly me rs nd po s es tes 1 vol., Mercer Decker (Mar cel Dek ker, Inc.). Publishing, pp. 1 3 9-1 5 0 (1 9 74).

  In general, ethylene having no long-chain branching and an α-olefin copolymer having 3 to 12 carbon atoms are in the region of low shear rate near 0.1 radians / second. -The olefin copolymer has a higher tan delta value. However, the (B) ethylene / α-olefin copolymer having a long chain branch that can be used in the present invention exhibits a low tan delta value in a wide shear rate region between 0.1 radians / second and 100 radians / second. . In other words, the storage elastic modulus, that is, the melt elasticity is kept high.

  The (B) ethylene and α-olefin copolymer having 3 to 12 carbon atoms used in the present invention has a tan delta of 0.01 or more and less than 2.5 measured at 190 ° C. and 0.1 radians / second. Yes, preferably the value of tan delta is 0.01 or more and less than 2.3, more preferably the value of tan delta is 0.01 or more and less than 2.2. In addition, when the value of tan delta measured at 190 ° C. and 0.1 radians / second of the (B) ethylene / α-olefin copolymer is less than 0.01, the fluidity is remarkably deteriorated. It is not preferable in terms of the aspect.

  The tan delta of the (B) ethylene / α-olefin copolymer used in the present invention is measured by the method described in JP-T 2010-514857. Specifically, it is a melt test performed on a disk cut from a 1/8 inch thick specimen, typically an injection molded ASTM D-790 tensile dogbone specimen. The sample is measured by placing it between two parallel plates of a dynamic mechanical spectrometer such as RMS-800 or ARES from Rheometrics. The tan delta test temperature is 190 ° C. Reference is made to the tan delta value at 190 deg.

  Some copolymers of ethylene and α-olefins that do not have long chain branches have short chain branches derived from the copolymer, and both within the same polymer chain and between different polymer chains. Some are evenly distributed. For example, as in the case of linear low density polyethylene polymers or linear high density polyethylene polymers made using a uniform branched distribution polymerization process as described by Elston in US Pat. No. 3,645,992, Lacks long chain branches. Commercially available examples of copolymers of ethylene and α-olefins without long chain branching include TAFMER ™ polymer supplied by Mitsui Chemical Company and EXACT ™ polymer supplied by ExxonMobil Chemical Company. Is mentioned.

  The (B) ethylene / α-olefin copolymer used in the present invention has a melt flow rate (hereinafter abbreviated as MFR) measured at 190 ° C. and a load of 2160 g according to ASTM-D1238 of 0.01 to 5 g / 10 min. The range of 0.01 to 1 g / 10 min is more preferable, and the range of 0.01 / 10 min to 0.5 g / 10 min is more preferable. From the viewpoint of impact properties of the resin composition, the MFR is preferably 0.01 g / 10 min or more, and from the viewpoint of fluidity of the resin composition, the MFR is preferably 5 g / 10 min or less.

  The blending amount of the (B) ethylene / α-olefin copolymer used in the present invention is selected in the range of 0.5 to 29.5 parts by weight, preferably 2 to 20 parts per 100 parts by weight of the PPS resin. Part by weight, more preferably 3 to 10 parts by weight. (B) If the blending amount of the ethylene / α-olefin copolymer is too small, the effect of improving toughness such as tensile elongation at break and impact strength is negligible, and if it is too large, the heat resistance and chemical resistance inherent to the PPS resin are inherent. Hot water resistance is significantly inhibited.

  Next, in the present invention, (C) a functional group-containing olefin copolymer containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester (B ) Blending with an ethylene / α-olefin copolymer is preferable for improving compatibility with the PPS resin. Here, the 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 is (B) ethylene. And an α-olefin copolymer having 3 to 12 carbon atoms, wherein the tan delta measured at 190 ° C. and 0.1 radians / second is a value of 0.01 or more and less than 2.5. Absent.

  (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 12 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 (C) functional group-containing olefin copolymer is random, alternating, block or graft of α-olefin (1), glycidyl ester of α, β-unsaturated acid (2) and monomer (3). For example, the monomer (3) is graft copolymerized with a random copolymer of α-olefin (1) and a glycidyl ester (2) of α, β-unsaturated acid. Such a copolymer may be a combination of two or more types of copolymerization.

  (C) The copolymerization ratio of the functional group-containing olefin copolymer is α-olefin (from the viewpoint of influence on the target effect, polymerization, gelation, heat resistance, fluidity, influence on strength, etc. 1) Glycidyl ester of / α, β-unsaturated acid (2) = 60 to 99% by weight / 40 to 1% by weight 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, Tylene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), 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-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, ethylene- Such as isobutyl methacrylate copolymer Refin- (meth) acrylic acid ester copolymer, methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, acrylic acid (Meth) acrylic acid ester-acrylonitrile copolymer, ethylene- (meth) acrylic acid copolymer and its Na, Zn, K, Ca, butyl-acrylonitrile copolymer, butyl methacrylate-acrylonitrile copolymer, etc. Metal salts such as Mg, ethylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-hexene-maleic anhydride copolymer Coalescence, ethylene-octene-male Acid anhydride copolymer, a propylene - maleic acid anhydride copolymer or maleic anhydride-modified SBS, SIS, SEBS, SEPS, ethylene - such as ethyl acrylate copolymer can be exemplified.

  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.

  In addition, the blending amount of the (C) functional group-containing olefin copolymer used in the present invention is selected in the range of 0.5 to 29.5 parts by weight, preferably 1 to 10 parts per 100 parts by weight of the PPS resin. Part by weight, more preferably 3 to 5 parts by weight. (C) When there are too few compounding quantities of a functional group containing olefin type copolymer, the effect which improves the compatibility of (A) PPS resin and (B) ethylene-alpha-olefin copolymer is not acquired, and there are too many. And PPS resin inherently have heat resistance, chemical resistance, hot water resistance, and fluidity significantly decreases due to thickening. Furthermore, (B) low temperature toughness is an effect of ethylene / α-olefin copolymer. The improvement effect is impaired.

  The total amount of (B) ethylene / α-olefin copolymer and (C) functional group-containing olefin copolymer is in the range of 1 to 30 parts by weight, preferably 2 with respect to 100 parts by weight of the polyphenylene sulfide resin. The range of ˜15 parts by weight, particularly 5 to 10 parts by weight is more preferably selected. If the blending amount is too large, molding processability is significantly lowered due to heat resistance, chemical resistance, hot water resistance, and gas generated during molding. On the other hand, if the blending amount is too small, the effect of improving toughness at temperature cannot be obtained.

  The blending ratio (weight ratio) of (B) the ethylene / α-olefin copolymer and (C) the functional group-containing olefin copolymer is preferably 28/2 to 10/20, particularly 25/5 to 15. / 15 is more preferably blended. By blending (B) an ethylene / α-olefin copolymer and (C) a functional group-containing olefin copolymer in a preferred range, an excellent toughness improving effect can be obtained, and fluidity during molding is also high. Therefore, it is excellent in moldability.

  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, you may mix | blend (D) inorganic filler further with the resin composition of this invention. (D) (D) Specific examples of the inorganic filler include fibrous or non-fibrous fillers such as plates, scales, granules, irregular shapes, and crushed products. Specifically, for example, glass Fiber, glass milled fiber, glass flat fiber, irregular 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, granule, irregular shape, crushed product), H glass (plate, scale, granule, irregular) Shape / crushed product), A glass (plate, scale-like, granular, irregular shape / crushed product), C glass (plate-like, scale-like, granular, irregular) Shape / crushed product), natural quartz glass (plate, scale, granule, irregular shape, crushed product), synthetic quartz glass (plate, scale, granule, irregular shape, crushed product), rock wool, hydrated alumina (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 and irregular glass, glass microballoons, clay, molybdenum disulfide, wollastonite, aluminum oxide (crushed), translucent alumina (fibrous, plate-like, scale-like, granular, irregular-shaped, Crushed products), titanium oxide (crushed), zinc oxide (fibrous, plate-like, scale-like, granular, irregular shape, crushed) Metal hydroxides such as metal oxides, aluminum hydroxide (fibrous, plate-like, scale-like, granular, irregular shape, crushed), aluminum nitride, translucent aluminum nitride (fibrous, plate-like, scale-like, Granular, 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, at least one selected from glass fibers, glass beads, glass flakes, and calcium carbonate is 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 (D) inorganic filler used in the present invention is preferably 1 to 400 parts by weight, more preferably 100 parts by weight of (A) PPS resin, from the balance of heat resistance, mechanical properties and the like. 5 to 200 parts by weight, more preferably 10 to 150 parts by weight. (D) By mix | blending an inorganic filler in this range, the composition in which heat resistance, mechanical characteristics, etc. were improved can be obtained.

From the viewpoint of cost reduction, the resin composition of the present invention may be blended with (E) a high-density polyethylene homopolymer within a range that does not significantly reduce moisture permeability. The blending amount of the (E) high-density polyethylene homopolymer used in the present invention is 1 to 20 parts by weight with respect to 100 parts by weight of the (A) PPS resin, preferably from the balance of heat resistance, moisture permeability, etc. 5 to 10 parts by weight. (E) By mix | blending the homopolymer of a high density polyethylene in this range, cost reduction can be achieved, maintaining moisture permeability.

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) ethylene / α-olefin copolymer, (C) functional group-containing olefin copolymer, (D) inorganic filler, (E) high It is prepared by premixing a homopolymer of density polyethylene and other additives, etc., or without supplying them to an extruder or the like and sufficiently melt-kneading them. 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. -Among olefin copolymers, (C) functional group-containing olefin copolymers, and (D) inorganic fillers, fillers other than glass fibers (excluding fibrous fillers) and other additives are charged from the extruder. And (D) It prepares by supplying fibrous fillers other than glass fiber and glass fiber to an extruder from a side feeder among inorganic fillers.

  Alternatively, (B) ethylene / α-olefin copolymer, (C) functional group-containing olefin copolymer, (B) ethylene / α-olefin copolymer, (C) functional group It is also one of preferable methods to supply all or part of the group-containing olefin copolymer from the side feeder to the extruder.

  In producing the PPS resin composition of the present invention, for example, 260 to 360 using a single-screw extruder, twin-screw, tri-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. In addition, the properties of the composition of the present invention are particularly effective for a molded body having a cylindrical portion.

  The molded body thus obtained 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. For example, electrical / electronic applications, automotive applications, water use applications, Useful for general miscellaneous goods, building materials, etc. Specifically, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, 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, computer related parts, etc. Electrical / electronic parts; VTR parts, TV , Iron, hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disc / compact disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Household, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, lighters, typewriters and other machine-related parts, microscopes, binoculars, Optical equipment such as cameras and watches, precision machinery-related parts; water faucet tops, mixing faucets, pump parts, pipe joints, valves, cheeses, fittings, sockets, water volume control valves, pressure reducing valves, relief valves, solenoid valves , Water temperature sensor, water volume sensor, water meter housing, etc. Parts: Valve alternator terminal, alternator connector, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, fuel-related / exhaust / intake system pipes, air intake nozzle 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, for air conditioner Thermostat base, heating hot air flow control valve, brush holder for radiator motor, water pump, war Turbine 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, coil for fuel related electromagnetic valve, 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 case, Vehicle speed sensor, Examples include automobile / vehicle-related parts such as cable liners and gasoline tanks, and other various uses. In particular, when there is a large amount of gas generated during molding, water-related parts will have poor appearance and will not be able to be formed as parts due to reduced water sealing properties. However, the PPS resin composition of the present invention does not generate gas during molding. Since there are few, it can be used conveniently. In addition to sealing performance to prevent electrolyte leakage, battery gaskets and packings need to suppress the deterioration of battery life due to moisture penetration from the outside, so the parts themselves must have low moisture permeability. is there. Since the PPS resin composition of the present invention has low moisture permeability, it can be suitably used for gaskets and packings.

  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 and PPS-2 obtained by the following method were measured according to JIS K7210.

[Reference Example 1] Polymerization of PPS (PPS-1)
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.94 kg (70.63 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 0.513 kg (6.25 mol), and ion-exchanged water 3.82 kg were charged to 245 ° C over about 3 hours while passing nitrogen at normal pressure. The mixture was gradually heated to distill out 8.09 kg of water and 0.28 kg of NMP, and then the reaction vessel was cooled to 200 ° C. The residual water content in the system per 1 mol 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., 10.34 kg (70.32 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, and reacted at 270 ° C. for 140 minutes. Thereafter, 2.67 kg (148.4 mol) of water was injected while cooling from 270 ° C. to 250 ° C. over 15 minutes. Next, the mixture was gradually cooled from 250 ° C. to 220 ° C. over 75 minutes, and then rapidly cooled to near room temperature, and the contents were taken out. The contents were diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and filtering through an 80 mesh wire net to collect the solid was repeated a total of 3 times. The obtained solid and 32 g of acetic acid were diluted with 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, filtered through an 80 mesh wire mesh, and further obtained solids were diluted with 70 liters of ion exchange water. The mixture was stirred at 70 ° C. for 30 minutes and then filtered through an 80 mesh wire net to collect a solid. The solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain dry PPS. The obtained PPS had an MFR of 600 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 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 residual water content in the system per 1 mol 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 had an MFR of 100 g / 10 min.

[Method of producing compounding material and PPS resin composition used in Examples and Comparative Examples]
The (A) PPS resin used in the examples and comparative examples is as follows.
PPS-1: PPS resin polymerized by the method described in Reference Example 1 PPS-2: PPS resin polymerized by the method described in Reference Example 2

(B) an α-olefin copolymer having 3 to 12 carbon atoms and ethylene used in the examples, wherein the tan delta measured at 190 ° C. and 0.1 radians / second is 0.01 or more and less than 2.5 The value of the copolymer is as follows.
B-1: ethylene / 1-butene copolymer (engaged HM7487 manufactured by Dow Chemical Co., Ltd., value of tan delta at 190 ° C. and 0.1 radians / second = 2.1, MFR = less than 0.5 g / 10 minutes)

The ethylene / α-olefin copolymers used in the comparative examples are as follows.
B-2: Ethylene / 1-octene copolymer (Dow Chemical Engage 8100, Tan delta value at 190 ° C. and 0.1 radians / second = 6.61, MFR = 1.0 g / 10 min)

The (C) functional group-containing olefin copolymer used in the examples and comparative examples is as follows.
C-1 Ethylene / glycidyl methacrylate copolymer (Bond First E manufactured by Sumitomo Chemical Co., Ltd.)

The (D) inorganic filler used in the present examples and comparative examples is as follows.
D-1 Chopped strand (manufactured by Nippon Electric Glass Co., Ltd. T-747H 3 mm length, average fiber diameter 10.5 μm)

The homopolymer of (E) high-density polyethylene used in this example is as follows.
E-1 High density polyethylene (Hi-Zex 1300J manufactured by Prime Polymer Co., Ltd.)

[Measuring method]
(1) Falling ball impact test Under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., a Sumitomo SE 100DU made by Sumitomo Heavy Industries, Ltd. was used to produce a square plate of 80 mm × 80 mm × 3 mm, and (vertical) 90 mm × ( Horizontal) Using a falling ball tester with 90 mm × (height) 50 mm cradle, place it on a cradle with a thickness of 3 mm and adjusted to 23 ° C., −20 ° C., and −35 ° C. 1000 g and 530 g of hard spheres were dropped at different heights, and cracks and the presence or absence of cracks were confirmed. The height at which the hard sphere was dropped and not cracked was determined. It can be said that the higher the height that does not break, the higher the falling ball impact. The lowest test height was 10 cm, and the one that broke at 10 cm was NG.

(2) Spiral flow length Using a spiral flow mold having a thickness of 1.0 mm, molding is performed under conditions of a cylinder temperature of 320 ° C., a mold temperature of 130 ° C., an injection speed of 230 mm / sec, an injection pressure of 98 MPa, an injection time of 5 sec, and a cooling time of 15 sec. Then, the flow length was measured (molding machine used: “SE-30D” manufactured by Sumitomo Heavy Industries). It can be said that the larger the value of the flow length, the better the melt fluidity.

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

(4) Tensile elongation At a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., a 1A type dumbbell piece (4.0 mm thickness) conforming to ISO 3167 is injection-molded, and ISO 527- under temperature conditions of 23 ° C. and −40 ° C. The measurement was performed at a pulling speed of 50 mm / min according to 1, -2.

(5) Moisture permeability test Under the conditions of a cylinder temperature of 320 ° C and a mold temperature of 130 ° C, a Sumitomo SE100DU made by Sumitomo Heavy Industries, Ltd. is used to produce a square plate of 80mm x 80mm x 1mm and cut into a 60mmφ circle. Process. After putting 15 cc of distilled water into an aluminum cup (permeation area: 12.6 cm ² ) shown in FIG. 1, it is sealed with the molded product of 60 mmφ, and heat-treated in an oven at 90 ° C. Heat treatment was performed until the permeation amount of the liquid became constant, and the transmission coefficient was determined according to Equation 1. A smaller value indicates lower moisture permeability.

Examples 1 and 2 and Comparative Examples 1 and 2
PPS obtained in Reference Examples 1 and 2 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 an intermediate addition port with a diameter of 44 mm. 100 parts by weight of resin (A) and (B) an ethylene / α-olefin copolymer having a long chain branch, and (C) a functional group-containing olefin copolymer are added from the raw material supply port in the weight ratio shown in Table 1. Then, a molten state was obtained, and (D) an inorganic filler was supplied from an intermediate addition port at a weight ratio 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. The results are shown in Table 1.

  Compared with Examples 1 and 2, Comparative Examples 1 and 2 had lower ball drop impact properties, particularly low ball drop impact properties at low temperatures.

Example 3 and Comparative Example 3
100 parts by weight of the PPS resin (A) obtained in Reference Example 1 using a 44 mm diameter twin screw extruder (TEX-44 manufactured by Nippon Steel) with a cylinder set temperature of 310 ° C. and a screw speed set to 200 rpm And (B) an ethylene / α-olefin copolymer having a long chain branch and (C) a functional group-containing olefin copolymer at a weight ratio shown in Table 2 to be melted by adding them from the raw material supply port. Pellets were obtained by melt-kneading at 40 kg / hour. The following properties were evaluated using this pellet. The results are shown in Table 2.

  Compared to Example 3, Comparative Example 3 had low elongation at low temperatures and low moisture permeability.

Example 4
The PPS resin obtained in Reference Example 1 (TEX-44, manufactured by Nippon Steel Works) was used, using a twin screw extruder (TEX-44, manufactured by Nippon Steel Works) with a cylinder setting temperature of 310 ° C. and a screw rotation speed of 200 rpm. Table 2 shows weights of A) 100 parts by weight and (B) a long chain branched ethylene / α-olefin copolymer, (C) a functional group-containing olefin copolymer and (D) a high-density polyethylene homopolymer. The mixture was added at a ratio from the raw material supply port to obtain a molten state, and melted and kneaded at a discharge rate of 40 kg / hour to obtain pellets. The following properties were evaluated using this pellet. The results are shown in Table 2.

  It can be seen that the low temperature toughness and the low moisture permeability are superior to those of Comparative Example 3.

  The resin composition of the present invention maintains the heat resistance, chemical resistance, hot water resistance, mechanical properties, and low temperature toughness inherently exhibited by the PPS resin. For example, it can be used in electrical / electronic applications, automotive applications, and water use applications. It is useful for general miscellaneous goods and building materials.

1 resin molded product 2 bolt 3 aluminum cup 4 water

Claims (7)

(A) 100 parts by weight of the polyphenylene sulfide resin, (B) an ethylene and an α-olefin copolymer having 3 to 12 carbon atoms, and the tan delta measured at 190 ° C. and 0.1 radians / second is 0 0.5 to 29.5 parts by weight of a copolymer having a value of 0.01 or more and less than 2.5, at least one selected from (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester The functional group-containing olefin copolymer containing 0.5 to 29.5 parts by weight of the functional group is blended, and the total of (B) and (C) is 1 to 30 parts by weight. A polyphenylene sulfide resin composition. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the tan delta value (B) measured at 190 ° C. and 0.1 radians / second is less than 2.2. 3. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the melt flow rate measured at 190 ° C. and 2160 g of (B) is 0.01 or more and less than 0.5 g / 10 minutes. 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. (D) The polyphenylene sulfide resin composition according to claim 4, wherein the inorganic filler is at least one selected from glass fibers, glass beads, glass flakes, and calcium carbonate. The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein 1 to 20 parts by weight of (E) a high-density polyethylene homopolymer is blended with 100 parts by weight of (A) polyphenylene sulfide resin. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 6.

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