JP4894168B2 - Polyamide resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a polyamide resin composition in which a polyolefin resin is dispersed on the nanometer order in a resin composition comprising a polyamide resin and a polyolefin resin, and a method for producing the same. More specifically, the present invention relates to a polyamide resin composition and a method for producing the same, in which the chemical resistance is greatly improved while maintaining the excellent thermal properties inherent in the polyamide resin.

  Polyamide resins have excellent mechanical properties, toughness, thermal properties, and other properties that are suitable as engineering plastics. Therefore, various types of electrical / electronic parts, mechanical parts, automobile parts, etc. are mainly used for injection molding. Widely used in applications. However, the polyamide resin has problems such as moisture absorption that causes dimensional change and rigidity reduction, hydrolysis when exposed to high temperature steam for a long time, resistance to chemicals such as antifreezing agent (calcium chloride) and low resistance to antifreeze. Have.

  In order to compensate for the drawbacks of such polyamide resins, many resin compositions in which a polyolefin resin is combined with a polyamide resin have been proposed. For example, Patent Document 1 discloses that an average dispersed phase diameter is 0.5 to 5 μm in a composition comprising a polyolefin resin modified with a polyamide resin and an unsaturated carboxylic acid or its anhydride, or a polyolefin resin mixture comprising a polyolefin and the modified polyolefin. However, there is a demand for further chemical resistance. Patent Document 2 and Patent Document 3 disclose a resin composition in which a polyolefin resin is further finely dispersed by improving kneading conditions, compatibility and the like in polyamide and polyolefin resin. It is difficult to achieve such dispersion of 100 nm or less.

Patent Document 4 discloses a polyamide resin composition having a two-phase continuous structure having a structural period of 0.01 to 1 μm or a dispersed structure having a distance between particles of 0.01 to 1 μm with respect to an alloy of a polyamide resin and another resin. It has been shown that a polyamide resin composition having excellent toughness, mechanical properties, and water resistance can be obtained by finely controlling the structure. However, this is a technique for constructing a fine structure by phase separation from a compatible state by spinodal decomposition, and is difficult to apply to the combination of the polyamide resin and the polyolefin resin used in the present invention.
Japanese Patent Laid-Open No. 6-234897 (Claims) JP 9-31325 A (Claims) JP-A-11-140237 (Claims) JP 2003-113304 A (Claims)

  The present invention is a polyamide in which the chemical resistance is greatly improved by maintaining the excellent thermal properties inherent in the polyamide resin by dispersing the polyolefin resin in a specific dispersion state (nanometer order) in the polyamide resin. It is an object to provide a resin composition.

That is, the present invention is,
(1 ) A resin composition comprising 50 to 99% by weight of polyamide resin (a), 0.5 to 40% by weight of polyolefin resin (b), and 0.5 to 30% by weight of polyphenylene sulfide resin (c). In the resin phase separation structure observed with an electron microscope in the resin composition, the polyamide resin (a) forms a continuous phase, the polyolefin resin (b) and the polyphenylene sulfide resin (c) form a dispersed phase, and the polyolefin resin A polyamide resin composition characterized by having a resin phase separation structure in which (b) and the polyphenylene sulfide resin (c) are each dispersed with a dispersed particle diameter of 1 to 100 nm,
( 2 ) Among the resins constituting the polyamide resin composition, when the melting point of the resin having the highest melting point is Tp (° C.), the resin composition is melted and retained for 30 minutes at a temperature of Tp + 20 ° C. and cooled in a water bath. In the resin phase separation structure observed with an electron microscope in the product, the dispersion particle size change rate defined by the following formula (1) is 20% or less, (1 ) polyamide resin composition,

( 3 ) The polyamide resin composition according to (1) or (2) , wherein the thickness of the interfacial phase of the polyolefin resin (b) and the polyphenylene sulfide resin (c) forming the dispersed phase is 30 to 70 nm,
( 4 ) The polyamide resin composition according to any one of (1) to ( 3 ), wherein the polyolefin resin (b) is at least one selected from polyethylene, polypropylene, and an ethylene / α-olefin copolymer. ,
( 5 ) A part or all of the polyolefin resin (b) is a polyolefin resin modified with at least one compound selected from unsaturated carboxylic acids or derivatives thereof. (1) to ( 4 ) Any polyamide resin composition,
( 6 ) The polyamide resin composition according to any one of (1) to ( 5 ), comprising 5 to 100 parts by weight of a filler (d) with respect to 100 parts by weight of the polyamide resin composition,
( 7 ) The molten resin mixture constituting the polyamide resin composition is produced by applying kneading energy of 0.3 kWh / kg or more while controlling the resin temperature at 250 ° C. to 320 ° C. (1)-the manufacturing method of the polyamide resin composition in any one of ( 6 ),
(8) A method for producing a polyamide resin composition in which a resin constituting the polyamide resin composition is melt-kneaded using a twin-screw extruder having a plasticizing part and a kneading part, and the cylinder temperature of the plasticizing part is set Among the polyamide resin (a), the polyolefin resin (b) and the polyphenylene sulfide resin (c), the melting point of the resin having the highest melting point is in the range of the melting point + 20 ° C., and the cylinder temperature of the kneading part is in the range of 100-250 ° C. (7) a method for producing a polyamide resin,
(9) Polyamide resin (a) 50 to 99% by weight, polyolefin resin (b) 1 to 50% by weight, in the resin phase separation structure observed with an electron microscope in the resin composition, polyamide resin (a ) Is a continuous phase, the polyolefin resin (b) forms a dispersed phase, and the polyolefin resin (b) is a method for producing a polyamide resin composition having a resin phase separation structure dispersed with a dispersed particle diameter of 1 to 100 nm, A polyamide resin composition produced by applying a kneading energy of 0.3 kWh / kg or more to a molten mixture of resins constituting the polyamide resin composition while controlling a resin temperature at 250 ° C. to 320 ° C. Manufacturing method,
(10) A method for producing a polyamide resin composition in which a resin constituting the polyamide resin composition is melt-kneaded using a twin-screw extruder having a plasticizing part and a kneading part, and the cylinder temperature of the plasticizing part is set Of the polyamide resin (a) and the polyolefin resin (b), the melting point of the resin having the highest melting point is in the range of the melting point + 20 ° C., and the cylinder temperature of the kneading part is in the range of 100 to 250 ° C. (9) A method for producing a polyamide resin of
Is to provide.

  According to the present invention, it is possible to obtain a polyamide resin composition in which the chemical resistance is greatly improved while maintaining the excellent thermal properties inherent in the polyamide resin. The polyamide resin composition obtained here is used for machine parts, electrical / electronic parts, medical, food, household / office supplies, building materials related parts, furniture parts, etc. that require heat resistance and chemical resistance. Especially suitable for.

  Hereinafter, the present invention will be described in detail. In the present invention, “weight” means “mass”.

  The polyamide resin (a) used in the present invention is a polyamide mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, pentamethylenediamine , Hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, Metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Bis (4-aminosi Chlohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acids, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, nylon derived from these raw materials Homopolymers or copolymers, each alone or in the form of a mixture It can be used.

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide. (Nylon 66), polypentamethylene adipamide (nylon 56), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon) 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide Copolymer (Nai 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / Polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6) Polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polynonamethylene terephthalamide (nylon 9T) and Mixtures of al and the like.

  Among these, preferable polyamide resins include nylon 6, nylon 66, nylon 12, nylon 610, nylon 6/66 copolymer, nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 12, nylon 6T / 6 copolymer, and the like. The copolymer which has the hexamethyl terephthalamide unit of this can be mentioned, Especially preferably, nylon 66 can be mentioned. Furthermore, it is also practically preferable to use these polyamide resins as a mixture depending on necessary properties such as impact resistance and molding processability.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Particularly preferred is a polyamide resin in the range of 2.0 to 6.0.

  Moreover, a copper compound is preferably used in the polyamide resin of the present invention in order to improve long-term heat resistance. Specific examples of copper compounds include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, nitric acid. Cupric, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and inorganic copper halides and xylylenediamine, 2-mercaptobenzimidazole And complex compounds such as benzimidazole. Of these, monovalent copper compounds, particularly monovalent copper halide compounds are preferred, and cuprous acetate, cuprous iodide, and the like can be exemplified as particularly suitable copper compounds. The addition amount of the copper compound is usually preferably 0.01 to 2 parts by weight and more preferably 0.015 to 1 part by weight with respect to 100 parts by weight of the polyamide resin. If the amount added is too large, liberation of metallic copper occurs during melt molding, and the value of the product is reduced by coloring. In the present invention, an alkali halide can be added in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide. Sodium chloride is particularly preferred.

  The polyolefin resin (b) used in the present invention is a thermoplastic resin obtained by polymerizing or copolymerizing olefins such as ethylene, propylene, butene, isoprene and pentene. Specific examples include homopolymers and copolymers such as polyethylene, polypropylene, polystyrene, poly 1-butene, poly 1-pentene, polymethyl pentene, ethylene / α-olefin copolymers, conjugated dienes and vinyl aromatic carbonization. A block copolymer with hydrogen and a hydride of the block copolymer are used. The ethylene / α-olefin copolymer here is a copolymer of ethylene and at least one of α-olefins having 3 to 20 carbon atoms, and the above-mentioned α-olefin having 3 to 20 carbon atoms. Are specifically propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1- Tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-he Sen, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. Among these α-olefins, a copolymer using an α-olefin having 3 to 12 carbon atoms is preferable from the viewpoint of improving mechanical strength. This ethylene / α-olefin copolymer preferably has an α-olefin content of 1 to 30 mol%, more preferably 2 to 25 mol%, and still more preferably 3 to 20 mol%.

  Further, non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1'-propenyl) -2-norbornene, etc. At least one kind may be copolymerized.

Among these polyolefin resins, low, medium and high density polyethylene, polypropylene, copolymer polypropylene based on polypropylene, ethylene / α-olefin copolymer and mixtures thereof are preferable. More preferred are polypropylene, copolymerized polypropylene based on polypropylene, and mixtures thereof.
As the polypropylene used in the present invention, any of isotactic, atactic, syndiotactic and the like can be used, and a small amount within a range that does not impair the properties as a propylene homopolymer (for example, less than 0.5 wt%). Polypropylene containing other monomer components can also be used.

  The copolymerized polypropylene used in the present invention is a random or block copolymer of propylene and an α-olefin, and the α-olefin is an α-olefin having 2 to 8 carbon atoms (excluding 3 carbon atoms). preferable. Among them, a propylene / ethylene block copolymer is particularly preferable, and a propylene / ethylene block copolymer having an ethylene content of 0.5 to 15% by weight is preferably used because of excellent balance between flexural modulus and impact strength.

  The melt flow rate (hereinafter abbreviated as MFR: ASTM D 1238) of the polyolefin resin (b) of the present invention is preferably 0.01 to 70 g / 10 min, more preferably 0.03 to 60 g / 10 min. is there. When the MFR is less than 0.01 g / 10 minutes, the fluidity is poor, and when it exceeds 70 g / 10 minutes, the impact strength may be lowered depending on the shape of the molded product, which is not preferable. These MFRs may be prepared by thermally decomposing a polymerized polymer together with an organic peroxide.

  There is no restriction | limiting in particular about the manufacturing method of polyolefin resin (b) used for this invention, It uses by any methods, such as radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, and coordination polymerization using a metallocene catalyst. be able to.

  In the present invention, it is preferable that a part or all of the polyolefin resin (b) is modified with at least one compound selected from unsaturated carboxylic acids or derivatives thereof. When a modified polyolefin resin is used, the compatibility is improved, and the controllability of the phase separation structure of the resulting resin composition is improved, which is one of preferred embodiments.

  Examples of unsaturated carboxylic acids or derivatives thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, Glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, methacrylic acid 2 -Ethylhexyl, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2, 3-dicarboxylic acid Endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, methacryl Glycidyl acid, glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Of these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferred, and maleic acid and maleic anhydride are particularly preferred. Among these, maleic anhydride is particularly preferably used because the interfacial phase of the polyolefin resin dispersed in the polyamide resin composition can be increased.

  The method for introducing these unsaturated carboxylic acid or its derivative component into the polyolefin resin is not particularly limited, and the olefin compound as the main component and the unsaturated carboxylic acid or its derivative compound may be copolymerized in advance, or may not be added to the unmodified polyolefin resin. A method such as introducing a saturated carboxylic acid or a derivative compound thereof by grafting using a radical initiator can be used. The amount of unsaturated carboxylic acid or its derivative component introduced is preferably within the range of 0.001 to 40 mol%, more preferably 0.01 to 35 mol%, based on the entire olefin monomer in the modified polyolefin. It is.

  The blending ratio of the polyamide resin (a) and the polyolefin resin (b) of the present invention is such that the polyamide resin (a) and the polyolefin resin (b) are 100% by weight in total, and the polyamide resin (a) is 50 to 99% by weight. (B) 1 to 50% by weight, preferably 65 to 95% by weight of polyamide resin and 5 to 35% by weight of polyolefin resin. When the polyolefin resin (b) is 5 to 35% by weight, the composition is preferable because the balance between mechanical properties and chemical resistance is particularly excellent. If the polyolefin resin (b) is less than 1% by weight, it is difficult to obtain the effect of improving the chemical resistance of the present invention, and if it exceeds 50% by weight, the mechanical properties inherent to the polyamide resin (a) are remarkably lowered.

  The polyamide resin composition of the present invention has a resin phase in which the polyamide resin (a) forms a continuous phase, the polyolefin resin (b) forms a dispersed phase, and the polyolefin resin (b) disperses with a dispersed particle size in the range of 1 to 100 nm. It has a separation structure. The dispersed particle size referred to here is a thickness of 500 μm from the molding surface of ASTM No. 1 dumbbell prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 300 ° C., mold temperature 80 ° C.). By cutting an 80 nm thin piece in the direction of the cross-sectional area of the dumbbell piece and processing the electron micrograph observed with a transmission electron microscope (magnification: 1000 times) using image analysis software “Scion Image” (manufactured by Scion Corporation) The calculated average particle diameter. A particularly preferable range of the dispersed particle diameter is 1 to 90 nm. When the dispersed particle diameter of the polyolefin resin (b) is outside the range of 1 to 100 nm, it is not possible to obtain a polyamide resin composition having excellent mechanical properties and improved chemical resistance, which is the subject of the present invention. .

  By adding a polyphenyl sulfide resin (hereinafter also referred to as PPS resin) (c) to the polyamide resin composition, a polyamide resin composition having further excellent mechanical properties and improved chemical resistance can be obtained. . As the PPS resin (c) used in the present invention, a polymer having a repeating unit represented by the following structural formula can be used.

  From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the structural formula is preferable. Moreover, about 30 mol% or less of the repeating units of the PPS resin may be composed of repeating units having any of the following structures. Of these, a p-phenylene sulfide / m-phenylene sulfide copolymer (m-phenylene sulfide unit of 20% or less) can be preferably used because it has both moldability and barrier properties.

  Such a PPS resin can be produced in a high yield by recovering and post-treating a PPS resin obtained by reacting a polyhalogen aromatic compound and a sulfidizing agent in a polar organic solvent. Specifically, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or a relatively molecular weight described in JP-B-52-12240 and JP-A-61-7332 is disclosed. It can also be produced by a method for obtaining a large polymer. Crosslinking / high molecular weight of the PPS resin obtained as described above by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, etc., acid anhydride It can also be used after being subjected to various treatments such as activation with functional group-containing compounds such as amines, isocyanates, and functional group-containing disulfide compounds.

  As a specific method for crosslinking / high molecular weight of PPS resin by heating, under an oxidizing gas atmosphere such as air or oxygen or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Examples of the method include heating in a heating container at a predetermined temperature until a desired melt viscosity is obtained. The heat treatment temperature is usually 170 to 280 ° C, preferably 200 to 270 ° C. The heat treatment time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. By controlling both of these, the target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. It is preferable to use an apparatus.

  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 drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. More preferably, an apparatus is used.

  The PPS resin (c) used in the present invention is preferably a PPS resin that has been subjected to a cleaning treatment. Specific examples of the cleaning treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment. These treatments may be used in combination of two or more methods.

  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 an action of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethyl sulfoxide Sulfoxides such as dimethylsulfone, sulfone solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane , Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol Lumpur, phenol, cresol, alcohols such as polyethylene glycol, phenolic solvents, 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 washed with an organic solvent 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 washed with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to express the preferable chemical modification effect of the PPS resin by hot water washing. The operation of the hot water treatment is usually performed by charging 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.

  Further, when washing with hot water, it is preferable to use an aqueous solution containing a Group II metal element of the periodic table. The aqueous solution containing a Group II metal element of the periodic table is obtained by adding a water-soluble salt containing a Group II metal element of the periodic table to the water. The concentration of the water-soluble salt having a Group II metal element in the periodic table with respect to water is preferably in the range of about 0.001 to 5% by weight.

Among the Group II metal elements of the periodic table used here, preferred metal elements include Ca, Mg, Ba and Zn, and the counter anions include acetate ions, halide ions, hydroxide ions. And carbonate ions. More specific and preferred compounds include Ca acetate, Mg acetate, Zn acetate, CaCl ₂ , CaBr ₂ , ZnCl ₂ , CaCO ₃ , Ca (OH) ₂ and CaO, and particularly preferably Ca acetate. is there.

  The temperature of the aqueous solution containing a Group II metal element in the periodic table is preferably 130 ° C. or higher, more preferably 150 ° C. or higher. Although there is no restriction | limiting in particular about the upper limit of washing | cleaning temperature, When using a normal autoclave, about 250 degreeC is a limit.

  The bath ratio of the aqueous solution containing the Group II metal element in the periodic table is preferably selected in the range of 2 to 100, more preferably 4 to 50, and 5 to 15 with respect to the dry polymer 1 by weight. More preferably, it is in the range.

  The following method can be illustrated as a specific method when the PPS resin is washed with an acid aqueous solution. That is, there is a method of immersing a PPS resin in an acid or an aqueous solution of an acid, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have an action of decomposing PPS resin, and is saturated with aliphatic monocarboxylic acid such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as saturated 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 Inorganic acid compounds such as phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. It is preferable to wash the acid-treated PPS resin several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by acid treatment is not impaired.

  The ash content of the PPS resin (c) used in the present invention is preferably in a relatively large range of 0.1 to 2% by weight from the viewpoint of imparting characteristics such as fluidity during processing and molding cycle, and is preferably 0.2 to The range of 1% by weight is more preferable, and the range of 0.3 to 0.8% by weight is further preferable.

Here, the amount of ash refers to the amount of inorganic components in the PPS resin determined by the following method.
(1) Weigh 5-6 g of PPS resin in a platinum dish fired and cooled at 583 ° C.
(2) The PPS resin is pre-baked at 450 to 500 ° C. together with the platinum dish.
(3) Put a PPS resin sample pre-fired with a platinum plate in a muffle furnace set at 583 ° C., and fire it for about 6 hours until it completely incinerates.
(4) Weigh after cooling in a desiccator.
The ash content is calculated by the formula (5): Ash content (wt%) = (ash content (g) / sample weight (g)) × 100.

  The melt viscosity of the PPS resin (c) used in the present invention is such that MFR = 50 to 5000 g / 10 min (315.5 ° C., 5 kg) from the viewpoint of imparting chemical resistance improvements and fluidity during processing. The range of (load) is preferably selected, more preferably in the range of 70 to 3000 g / 10 minutes, and still more preferably in the range of 100 to 1000 g / 10 minutes.

  Chloroform extraction amount (calculated from the residual amount at the time of 5 hours treatment with Soxhlet extraction), which is an index of the amount of the organic low polymerization component (oligomer) of the PPS resin (c) used in the present invention, A relatively high range of 1 to 5% by weight is preferable from the viewpoint of imparting characteristics such as improvement in chemical properties and fluidity during processing, more preferably 1.5 to 4% by weight, and 2 to 4% by weight. More preferably, it is in the range.

  The polyamide resin (a), polyolefin resin (b), and PPS resin (c) of the present invention are mixed in a polyamide resin (a), polyolefin resin (b), and PPS resin (c) in a total amount of 100% by weight. Resin (a) 50-99 wt%, polyolefin resin (b) 0.5-40 wt%, and PPS resin (c) 0.5-30 wt%, preferably polyamide resin 65-95 wt%, 1 to 20% by weight of polyolefin resin and 1 to 20% by weight of PPS resin. If the polyamide resin (a) is less than 50% by weight, the mechanical properties inherently deteriorated remarkably, and if it exceeds 50% by weight, it is difficult to obtain the effect of improving the chemical resistance of the present invention. It is not preferable because the effect of improving the chemical resistance is difficult to obtain.

  In the polyamide resin composition of the present invention, the polyamide resin (a) forms a continuous phase, the polyolefin resin (b) and the PPS resin (c) form a dispersed phase, and the polyolefin resin (b) and the PPS resin (c) are both 1 It is preferable to have a resin phase separation structure dispersed with a dispersed particle size in the range of ˜100 nm. As used herein, the dispersed particle size refers to injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 300 ° C.) as in the case of the two components of the polyamide resin (a) and the polyolefin resin (b). Electrons observed by a transmission electron microscope (magnification: 1000 times) from a molding surface of ASTM No. 1 dumbbell prepared at a mold temperature of 80 ° C., by cutting a thin piece having a thickness of 80 nm from the inside to 500 μm in the cross-sectional area direction of the dumbbell piece. It is an average particle diameter calculated by processing a micrograph using image analysis software “Scion Image” (manufactured by Scion Corporation). At this time, even in the case of the three components of the polyamide resin (a), the polyolefin resin (b), and the PPS resin (c), the staining method at the time of observation with a transmission electron microscope and the image processing by the image analysis software “Scion Image” should be used. Thus, the dispersed particle diameters of the polyolefin resin (b) and the PPS resin (c) can be calculated individually. A particularly preferable range of the dispersed particle diameter is 1 to 90 nm. When the dispersed particle diameter of the polyolefin resin (b) and the PPS resin (c) is outside the range of 1 to 100 nm, the polyamide resin composition having excellent mechanical properties and improved chemical resistance, which is the subject of the present invention I can't get anything.

  The dispersion structure in the polyamide resin composition of the present invention is stable, and it is preferable that the dispersed particle size of the dispersed phase does not change greatly even when melted and retained. That is, the polyamide resin composition of the present invention is charged into a melt indexer, and among the resins constituting the polyamide resin composition of the present invention, the melting point of the resin having the highest melting point (Tp (° C.)) + 20 ° C. at 30 ° C. It is preferable that the rate of change in the dispersed particle size defined by the following formula (1) is 20% or less when the molten composition is discharged for a minute and then the molten composition is discharged and the sample cooled in a water bath is observed.

Thus, since the polyamide resin composition of the present invention does not have a large change in the dispersed particle size even after the melt residence, the molded product obtained without melting and staying in the molded product obtained after being melted and retained for a long time In comparison, the mechanical properties are not significantly reduced. When the rate of change in the dispersed particle size after melting and staying is larger than 20%, it is not preferable because it becomes impossible to obtain a thermoplastic resin composition having excellent mechanical properties, which is the subject of the present invention, depending on the melting and staying conditions.
In the polyamide resin composition of the present invention, when the polyamide resin forms a continuous phase and the other resins form a dispersed phase, and the dispersed phase is dispersed with a dispersed particle diameter in the range of 1 to 100 nm, at the boundary between both resins. When the thickness of the interface phase in which both components coexist is 30 to 70 nm, the chemical resistance is remarkably improved, and more preferably 35 to 60 nm. The thickness of the interfacial phase of the polyolefin resin dispersed in the polyamide resin composition of the present invention is such that a thin piece having a thickness of 80 nm is cut from the center of the injection-molded piece in the direction of the cross-sectional area of the dumbbell piece, and the polyolefin resin is dyed (such as ruthenium tetroxide). Using the difference in dyeability, the thickness was directly measured and the average value of the values obtained by directly measuring the thickness was obtained from a photograph taken with a transmission electron microscope. The thickness of the interfacial phase of the PPS resin dispersed in the polyamide resin composition of the present invention was determined by cutting a thin piece having a thickness of 80 nm from the center of the injection-molded piece in the direction of the cross-sectional area of the dumbbell piece, and using an electric field emission electron microscope. 1 is subjected to EDX ray analysis (energy dispersive X-ray spectroscopic analysis) on a line crossing the particle as shown in FIG. 1, and the oxygen atom concentration of the polyamide resin and the sulfur atom concentration of the PPS resin continuously change. It calculated | required as an average value of the value obtained by measuring the length of an area | region part. When the thickness of the interface phase is less than 30 nm, the chemical resistance is deteriorated, which is not preferable. On the other hand, if the thickness of the interfacial phase exceeds 70 nm, the fluidity decreases and the workability deteriorates, which is not preferable. Further, in order to control the thickness of the interfacial phase as described above, it is important to appropriately select the amount of the modifier for the polyolefin resin.

As the filler (d) used in the present invention, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber , Fibrous fillers such as asbestos fiber, masonry fiber, metal fiber, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, montmorillonite Swellable layered silicates such as synthetic mica, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, Sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide and other hydroxides, glass flakes, glass powder, carbon black and Non-fibrous fillers such as silica and graphite are used, these may be hollow, and two or more of these fillers can be used in combination. Preferred are swellable layered silicates such as glass fiber, carbon fiber, montmorillonite, and synthetic mica, and particularly preferred is glass fiber. These fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, a urethane compound, and an epoxy compound. Glass fibers pretreated with a urethane compound, an epoxy compound, or an organosilane compound are preferably used.
As content of the filler (d) contained in the polyamide resin composition of this invention, 1-150 weight part is preferable with respect to 100 weight part of polyamide resin compositions, More preferably, it is 5-100 weight part. Yes, particularly preferably 10 to 50 parts by weight. When the content of the filler (d) is less than 5 parts by weight, it is not preferable because the effect of improving the physical properties is small, and when it exceeds 100 parts by weight, the melt viscosity is remarkably increased and the fluidity is lowered.

  A compatibilizing agent can be added to the polyamide resin composition of the present invention for the purpose of improving the compatibility. Specific examples of the compatibilizer include organic silane compounds such as alkoxysilanes having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. A functional epoxy compound etc. are mentioned, These can also be used simultaneously 2 or more types. Here, the polyfunctional epoxy compound contains two or more epoxy groups in the molecule, and a liquid or solid one can be used. For example, a copolymer of an α-olefin such as ethylene, propylene, 1-butene and an α, β-unsaturated glycidyl ester such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, bisphenol A, resorcinol, hydroquinone, Pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2, Bisphenol-glycidyl ether type epoxy compounds such as 5,5-tetrakis (4-hydroxyphenyl) hexane, glycidyl ester type epoxy compounds such as glycidyl phthalate, N-glycidyl aniline, etc. Glycidyl amine-based epoxy compounds, novolak type novolak epoxy resins phenol resin is reacted with epichlorohydrin is exemplified. Preferably, a bisphenol-glycidyl ether epoxy compound, an organosilane compound having an epoxy group, or an organosilane compound having an isocyanate group is used. In particular, the use of an organosilane compound having an isocyanate group is particularly preferable because the interfacial phase thickness can be increased. The blending ratio of the compatibilizer is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyamide resin composition of the present invention. When the addition amount is 0.01 parts by weight or less, a sufficient compatibility improving effect cannot be obtained, and when it exceeds 10 parts by weight, the melt viscosity of the polyamide resin composition is remarkably increased and the fluidity is lowered.

  Furthermore, in this invention, in order to maintain heat stability, 1 or more types of antioxidant chosen from the phenol type and the phosphorus type compound can be contained. The blending amount of the antioxidant is preferably 0.01 parts by weight or more, particularly 0.02 parts by weight or more with respect to 100 parts by weight of the polyamide resin composition of the present invention from the viewpoint of heat resistance improvement effect, From the viewpoint of the gas component generated sometimes, it is preferably 5 parts by weight or less, particularly 1 part by weight or less. In addition, the combined use of phenolic and phosphorus antioxidants is particularly preferable because of their large heat resistance, thermal stability and fluidity retention effect.

  As the phenolic antioxidant, a hindered phenolic compound is preferably used. Specific examples include triethylene glycol-bis [3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4 Hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-). Hydroxyphenyl) propionate] methane and the like are preferably used.

  Next, phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl). ) Pentaerythritol di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphite Examples include phonate diethyl ester. Among them, those having a high melting point of the antioxidant are preferably used in order to reduce volatilization and decomposition of the antioxidant in the polyamide resin compound.

  Furthermore, resins other than polyamide resin, polyolefin resin, and PPS resin can be added to the polyamide resin composition of the present invention as long as the effects of the present invention are not impaired. However, if it exceeds 30 parts by weight relative to 100 parts by weight of the entire polyamide resin composition of the present invention, the original characteristics of the polyamide resin are impaired, and in particular, addition of 20 parts by weight or less is preferably used.

  Specific examples of the resin include polyester resin, ABS resin, polyalkylene oxide resin, modified polyphenylene ether resin, polysulfone resin, polyketone resin, polyetherimide resin, polyarylate resin, polyether sulfone resin, polyether ketone resin, Examples thereof include a polythioether ketone resin, a polyether ether ketone resin, a polyimide resin, a polyamideimide resin, and a tetrafluoropolyethylene resin. Moreover, the following compounds can be added for the purpose of modification. Coupling agents such as organic titanate compounds and organic borane compounds, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds and organophosphorus compounds, talc, kaolin, organophosphorus compounds, polyether ethers Crystal nucleating agents such as ketones, montanic acid waxes, metal soaps such as lithium stearate and aluminum stearate, release agents such as ethylenediamine, stearic acid and sebacic acid heavy compound, silicone compounds, hypophosphites Ordinary additives such as a lubricant, an ultraviolet light inhibitor, a colorant, a flame retardant, and a foaming agent can be blended. Any of the above compounds is not preferable because the original properties of the polyamide resin are impaired when the amount exceeds 20 parts by weight relative to 100 parts by weight of the entire polyamide resin composition of the present invention. Addition is good.

  The kneading machine used for the production of the polyamide resin composition of the present invention is supplied to a generally known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll to process the melting point of the polyamide resin or higher. The method of kneading at a temperature can be given as a representative example, but in order to control the morphology of the present invention and the particle size of the dispersed phase as described above, the kneading energy during extrusion (extruder work amount per discharge amount) It is necessary to increase (kW / (kg / h))). As a result, the dispersed phase can be finely dispersed. The kneading energy is preferably 0.3 or more, particularly preferably 0.5 or more. However, if the kneading energy is usually increased, the resin temperature rises due to heat generated by shearing, causing thermal decomposition of the polyamide resin, making it difficult to form the desired phase separation structure. Therefore, the resin temperature during extrusion is preferably 250 to 320 ° C, more preferably 280 to 310 ° C. By controlling the kneading energy and the resin temperature in this way, it is possible to form a target resin phase separation structure. Specifically, in melt kneading using a twin-screw extruder, a method in which the cylinder temperature is low and the screw rotation speed is high can obtain high shear, 0.3 kW / (kg / h) or more The kneading energy can be achieved, so that it is preferably used. However, when a conventional kneading disk is used for the screw element of the kneading part, the amount of heat generated by shearing is large, and it is difficult to achieve a resin temperature of 250 to 320 ° C. during extrusion. On the other hand, it is preferable to use a low exothermic kneading element for the screw element of the kneading part because heat generation due to shearing can be suppressed and a resin temperature of 250 ° C. to 320 ° C. during extrusion can be achieved. A method of introducing supercritical carbon dioxide or supercritical nitrogen into the kneading part is also preferable because heat generation due to shearing can be suppressed. When the cylinder temperature of the twin screw extruder is divided into a plasticizing part for plasticizing the resin charged in the twin screw extruder and a kneading part for melting and kneading the plasticized molten resin, the plasticizing part is made of a polyamide resin ( Of the a), polyolefin resin (b) and polyphenylene sulfide resin (c), it is preferable that the temperature of the resin having the highest melting point is the melting point to the melting point + 20 ° C., and the cylinder temperature of the kneading part is in the range of 100 to 250 ° C. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and melt-kneaded by the above method, and the remaining raw materials are further blended Any method may be used such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading with a single or twin screw extruder. In addition, as for the small amount additive component, other components may be kneaded and pelletized by the above-described method or the like, and then added before molding and used for molding.

  The polyamide resin composition of the present invention is particularly useful for injection molding applications because of its excellent balance of mechanical properties, heat resistance and chemical resistance. Taking advantage of these features, it is particularly suitable for use in machine parts, electrical / electronic parts, medical, food, household / office supplies, building material-related parts, furniture parts, etc. that require heat and chemical resistance. Yes.

  The present invention will be described more specifically with reference to the following examples. The material properties were evaluated according to the following method.

  [Resin temperature] The melted resin discharged from the extruder die during melt kneading in the twin-screw extruder was measured with a thermometer.

  [Dispersed particle size] The dispersed particle size of the dispersed phase was measured as follows. SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. was used to cut a 80 nm-thick slice from 500 nm inside from the molding surface of ASTM No. 1 dumbbell molded at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C., and a magnification of 1000 with a transmission electron microscope You can obtain a straight line by performing a Debye plot from the profile obtained by performing a Fourier transform on the photograph obtained by observing at a magnification using the image processing software `` Scion Image '' and circularly averaging the obtained inverse space image it can. By looking at this straight line as the Ornstein-Zernik type equation (2) for the concentration fluctuation of the concentrated polymer solution, the correlation length ξ of the density fluctuation is obtained from the slope and y-intercept of this plot. The specific surface area was calculated from the volume fraction φ according to the formula (3), and further calculated as the average particle diameter using the formula (4).

  [Dispersed particle size after melt residence, rate of change of dispersed particle size] The dispersion particle size of the dispersed phase after melt residence was measured by using a polyamide resin composition that had been vacuum dried at 80 ° C. for 12 hours, as a melt indexer manufactured by Toyo Seiki. Example 1-6, Examples 14-17, Comparative Examples 2-3, Comparative Example 5, Comparative Example 7, and Comparative Example 9 are 285 ° C., Examples 8-13, Examples 18-20, and Comparative Examples 4. Comparative Example 8 was measured at 300 ° C., and Example 7 was melted and retained at 245 ° C. for 30 minutes, then the molten resin was discharged and measured in the same manner as the dispersed particle size after cooling in a water bath. The rate of change in the dispersed particle size was calculated according to the following formula (1) using the dispersed particle size and the dispersed particle size after melt residence.

  [Lower molding pressure] When molding ATSM1 dumbbell by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C, mold temperature 130 ° C), the ATSM1 dumbbell should be molded without causing poor filling. The minimum filling pressure at which molding is possible was defined as the molding lower limit pressure. The lower the molding lower limit pressure, the better the fluidity.

  [Tensile test] Using an ASTM No. 1 dumbbell prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 300 ° C, mold temperature 80 ° C), a tensile test was performed at 23 ° C according to ASTM-D638, The elongation at break was measured.

  [High temperature tensile strength] Except that the temperature atmosphere was 80 ° C., the measurement was performed in the same manner as in the tensile test, and the strength was measured.

  [Calcium chloride resistance] Examples 1 to 13 and Comparative Examples 1 to 5 were evaluated in accordance with Evaluation Method 1, and Examples 14 to 20 and Comparative Examples 6 to 9 were evaluated in accordance with Evaluation Method 2.

(Evaluation method 1)
The ASTM No. 1 dumbbell piece prepared by the above method was immersed in hot water at 95 ° C. for saturated water absorption, and then a 50 wt% calcium chloride aqueous solution was applied to the dumbbell piece and dried in hot air at 80 ° C. for 3 hours. Thereafter, a tensile test was performed in accordance with ASTM-D638, the elongation at break was measured, and the retention rate from the untreated tensile elongation at break was evaluated.
A: Retention rate (tensile elongation at break after treatment / tensile elongation at break when untreated) = 80 to 100%
○: Retention rate = 60-80%
Δ: Retention rate = 30-60%
X: Retention rate = 0 to 30%.

(Evaluation method 2)
After the ASTM No. 1 dumbbell piece prepared by the above method was immersed in 95 ° C. hot water for 22 hours to absorb water, 0.5 cc of a 50 wt% calcium chloride aqueous solution was dropped on the dumbbell piece and placed in a 100 ° C. hot air oven for 2 hours. put. The treatment (humidity control → calcium chloride aqueous solution dropping → standing in the oven) was set as one cycle and repeated for a maximum of 10 cycles.
(Double-circle): A crack does not generate | occur | produce even if it repeats 10 cycles.
Δ: Cracks occurred in 5 to 9 cycles.
X: Cracking occurred in 5 cycles or less.

  [Interfacial phase thickness] The interfacial phase thickness of the resin in the dispersed phase was measured as follows. A thin 80-nm-thick piece is cut in the cross-sectional area direction of the dumbbell piece from the center of ASTM No. 1 dumbbell piece prepared by the above method, and the interfacial phase thickness of the polyolefin resin is a transmission type obtained by staining with ruthenium tetroxide. Observation was performed using an electron microscope (TEM), and the thickness of the interface portion in the obtained micrograph was measured. As for the PPS resin, with respect to any 10 dispersed particles by a field emission electron microscope, as shown in FIG. 1, the atomic concentration on a line crossing the particles is subjected to EDX ray analysis (energy dispersive X-ray spectroscopic analysis), The length of the region where the sulfur atom concentration of the PPS resin continuously changed was measured to obtain an average value.

  [Solubility] ASTM No. 1 dumbbell pieces were immersed in PEA (phenol / ethanol = 85/15% mixed solvent) at room temperature for 2 hours, and the weight reduction rate of the dumbbell pieces after drying was measured.

[Examples 1 to 13], [Comparative Examples 1 to 5]
After dry blending each component shown below at each ratio shown in Table 1, with a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set the cylinder temperature and screw rotation speed to the conditions shown in Table 1, Examples 1 to 13 and Comparative Example 5 use a screw in which a low exothermic kneading element is introduced into a screw kneading part, and Comparative Examples 2 to 4 use a screw in which a conventional kneading disk is introduced into a screw kneading part. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. Thereafter, a test piece was prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 300 ° C., mold temperature 80 ° C.) using pellets that were vacuum-dried at 80 ° C. for 12 hours. The results of evaluating the mechanical properties and chemical resistance of each sample are shown in Table 1. In Comparative Example 2, melt kneading was performed under conventional cylinder temperature conditions, but the target resin phase separation structure could not be achieved, and the high temperature tensile strength and calcium chloride resistance were poor. In Comparative Examples 3 and 4, the kneading part was melted and kneaded with high screw rotation at a low cylinder temperature. However, since a conventional kneading disk screw was used in the screw kneading part, heat generation was large and the resin temperature was high. Since it rose, the target resin phase separation structure could not be achieved, the elongation at break was low, and the calcium chloride resistance was poor. In Comparative Example 5, since the polyamide resin and the polyolefin resin became a co-continuous phase, the high-temperature tensile strength was greatly inferior. In this example, compared with Comparative Examples 1-5, it was excellent in balance with mechanical properties, particularly high temperature physical properties and chemical resistance.

[Examples 14 to 20], [Comparative Examples 6 to 9]
After the pellets prepared by the above-described method were vacuum-dried at 80 ° C. for 12 hours, the fillers were blended in the proportions shown in Table 2, and the cylinder temperature was 300 ° C. with a VS40-32 type single screw extruder manufactured by Tanabe Plastic Machine. The melt was kneaded at a screw speed of 80 rpm and pelletized with a strand cutter. Then, the obtained pellet was vacuum-dried at 80 ° C. for 12 hours, and a test piece was prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 300 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties and chemical resistance of each sample are shown in Table 2. In Comparative Examples 7 and 8, the desired resin phase separation structure could not be achieved, and the calcium chloride resistance was poor. In Comparative Example 9, since the polyamide resin and the polyolefin resin became a co-continuous phase, the high-temperature tensile strength was greatly inferior. Examples 14 to 20 were superior to Comparative Examples 6 to 9 in balance with mechanical properties, particularly high-temperature physical properties and chemical resistance.

[Examples 21 to 25], [Comparative Examples 10 to 12]
After dry blending each component shown below at each ratio shown in Table 3, with a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set the cylinder temperature and screw rotation speed to the conditions shown in Table 3, Examples 21 to 25 use a screw with a low exothermic kneading element introduced into the screw kneading part, and Comparative Examples 11 to 12 perform melt kneading using a screw with a conventional kneading disk introduced into the screw kneading part. The discharged gut was immediately cooled in a water bath and pelletized with a strand cutter. Thereafter, a test piece was prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 300 ° C., mold temperature 80 ° C.) using pellets that were vacuum-dried at 80 ° C. for 12 hours. The results of evaluating the mechanical properties and chemical resistance of each sample are shown in Table 3. In this example, compared with the comparative example, the mechanical properties, particularly high temperature physical properties, chemical resistance, and solubility were excellent.

The polyamide resin (a) used in the examples and comparative examples is as follows.
(A-1): Nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of 2.90 at 98% sulfuric acid 1 g / dl.
(A-2): Nylon 66 resin having a melting point of 265 ° C. and 98% sulfuric acid of 1 g / dl and a relative viscosity of 3.30.
(A-3): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 2.80 at 98% sulfuric acid 1 g / dl.

Similarly, polyolefin (b) is as follows.
(B-1): Melting point 160 ° C., MFR = 0.5 g / 10 min (230 ° C., 2.16 kg load), density 0.910 g / cm ³ of polypropylene resin 100 parts by weight, maleic anhydride 1 part by weight and radical A resin obtained by dry blending 0.1 part by weight of a generator (Perhexa 25B: manufactured by NOF Corporation) and melt-kneading at a cylinder temperature of 230 ° C.
(B-2): Melting point 160 ° C., MFR = 0.5 g / 10 minutes (230 ° C., 2.16 kg load), density 0.910 g / cm ³ of polypropylene resin 100 parts by weight and maleic anhydride 0.5 parts by weight And a radical generator (Perhexa 25B: manufactured by NOF Corporation) by dry blending, and melt-kneading at a cylinder temperature of 230 ° C.
(B-3): Melting point 110 ° C., MFR = 4.0 g / 10 min (190 ° C., 2.16 kg load), 100 parts by weight of a linear low density polyethylene resin having a density of 0.905 g / cm ³ and maleic anhydride A resin obtained by dry blending 1 part by weight and 0.1 part by weight of a radical generator (Perhexa 25B: manufactured by NOF Corporation) and melt-kneading at a cylinder temperature of 230 ° C.
(B-4): Melting point 160 ° C., MFR = 0.5 g / 10 min (230 ° C., 2.16 kg load), density 0.910 g / cm ³ of polypropylene resin 100 parts by weight, maleic anhydride 1 part by weight and radical A resin obtained by dry blending 0.2 parts by weight of a generator (Perhexa 25B: manufactured by NOF Corporation) and melt-kneading at a cylinder temperature of 230 ° C.

Similarly, the PPS resin (c) is as follows.
(C-1): PPS resin having a melting point of 280 ° C. and MFR = 200 g / 10 minutes (315.5 ° C., 5 kg load).
(C-2): PPS resin having a melting point of 280 ° C. and MFR = 100 g / 10 min (315.5 ° C., 5 kg load).

Similarly, the filler (d) is as follows.
(D-1): Glass fiber (T-747GH manufactured by Nippon Electric Glass Co., Ltd.)
Similarly, the compatibilizer is as follows.
(Compatibilizer): 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Silicone)

It is a model figure which shows an example of a field emission type electron microscope-EDX-ray analysis when measuring the interface phase thickness of PPS resin disperse | distributed to the polyamide resin continuous phase.

Claims (10)

A resin composition comprising 50 to 99% by weight of a polyamide resin (a), 0.5 to 40% by weight of a polyolefin resin (b), and 0.5 to 30% by weight of a polyphenylene sulfide resin (c), In the resin phase separation structure observed with an electron microscope in the resin composition, the polyamide resin (a) forms a continuous phase, the polyolefin resin (b) and the polyphenylene sulfide resin (c) form a dispersed phase, and the polyolefin resin (b) And a polyamide resin composition having a resin phase separation structure in which the polyphenylene sulfide resin (c) is dispersed in a dispersed particle diameter of 1 to 100 nm. Among the resins constituting the polyamide resin composition, when the melting point of the resin having the highest melting point is Tp (° C.), the resin is melted and retained for 30 minutes at a temperature of Tp + 20 ° C. and cooled in a water bath. 2. The polyamide resin composition according to claim 1, wherein the dispersion phase change rate defined by the following formula (1) is 20% or less in a resin phase separation structure observed with an electron microscope.

The polyamide resin composition according to claim 1 or 2, wherein the thickness of the interfacial phase of the polyolefin resin (b) and the polyphenylene sulfide resin (c) forming the dispersed phase is 30 to 70 nm. The polyamide resin composition according to any one of claims 1 to 3, wherein the polyolefin resin (b) is at least one selected from polyethylene, polypropylene, and an ethylene / α-olefin copolymer. 5. The polyolefin resin according to claim 1, wherein a part or all of the polyolefin resin (b) is a polyolefin resin modified with at least one compound selected from unsaturated carboxylic acids or derivatives thereof. Polyamide resin composition. The polyamide resin composition according to any one of claims 1 to 5, comprising 5 to 100 parts by weight of a filler (d) with respect to 100 parts by weight of the polyamide resin composition. 2. The molten resin mixture constituting the polyamide resin composition is produced by applying a kneading energy of 0.3 kWh / kg or more while controlling a resin temperature at 250 ° C. to 320 ° C. 2. The manufacturing method of the polyamide resin composition in any one of -6. A method for producing a polyamide resin composition in which a resin constituting the polyamide resin composition is melt-kneaded using a twin screw extruder having a plasticizing part and a kneading part, and the cylinder temperature of the plasticizing part is set to a polyamide resin ( a), a polyolefin resin (b) and a polyphenylene sulfide resin (c) having a melting point of the highest melting point to a melting point of + 20 ° C., and a cylinder temperature of the kneading part is set to a range of 100 to 250 ° C. The method for producing a polyamide resin according to claim 7. Polyamide resin (a) is composed of 50 to 99% by weight and polyolefin resin (b) is composed of 1 to 50% by weight. In the resin phase separation structure observed in an electron microscope in the resin composition, the polyamide resin (a) is continuous. And a method for producing a polyamide resin composition having a resin phase separation structure in which a polyolefin resin (b) forms a dispersed phase and the polyolefin resin (b) is dispersed with a dispersed particle diameter of 1 to 100 nm, Manufacture of a polyamide resin composition characterized in that it is produced by applying a kneading energy of 0.3 kWh / kg or more to a molten mixture of resins constituting the composition while controlling the resin temperature at 250 ° C to 320 ° C. Method. A method for producing a polyamide resin composition in which a resin constituting the polyamide resin composition is melt-kneaded using a twin screw extruder having a plasticizing part and a kneading part, and the cylinder temperature of the plasticizing part is set to a polyamide resin ( The temperature of the resin having the highest melting point among a) and the polyolefin resin (b) is in the range of melting point to melting point + 20 ° C, and the cylinder temperature of the kneading part is in the range of 100 to 250 ° C. A method for producing a polyamide resin.