JP2008163222A - Polyphenylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition which has the heat resistance of class B level defined by ISO 6722 and excellent abrasion resistance by compounding a PPS resin, a polyamide resin, an olefin/glycidyl methacrylate copolymer, and an unmodified olefin copolymer by a specific method. <P>SOLUTION: The polyphenylene sulfide resin composition comprises (A) 100 pts.wt. polyphenylene sulfide resin, (B) 12-100 pts.wt. polyamide resin, (C) 1.5-3.5 pts.wt. olefin/glycidyl methacrylate copolymer, and (D) 3.5-10 pts.wt. unmodified olefin copolymer, and the components (A), (C), and (D) are previously mixed, and thereafter the component (B) is mixed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition excellent in wear resistance and heat resistance suitable for wire coating applications.

  Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has suitable properties as engineering plastics, such as excellent heat resistance, thermal stability, chemical resistance, electrical insulation, and moist heat resistance. It is used for various electric / electronic parts, machine parts and automobile parts.

  A large amount of polyvinyl chloride (hereinafter abbreviated as PVC) is used as a coating resin for automotive wires, but the environmental impact of incineration and disposal has been pointed out, and heat resistance that can withstand automotive applications without using PVC. There is a need for an electric wire covering material. While PPS resin has high heat resistance, its wear resistance and toughness are low, and it is difficult to use it as it is for electric wire coating, and its improvement is strongly desired.

For example, Patent Document 1 proposes a resin composition in which a copolymerized polyamide resin is blended with a PPS resin, and Patent Document 2 proposes a resin composition in which an amorphous polyamide resin is blended with a PPS resin. There was a problem that the coating was torn in the low-temperature winding test after the dry heat treatment defined in ISO6722. Patent Document 3 proposes a resin composition in which a polyamide and a carboxyl group-containing olefin copolymer are blended with a PPS resin by a specific method, but it has low wear resistance, and further after dry heat treatment as defined in ISO 6722. There was a problem that the coating was torn in the low temperature winding test.
JP 2006-137852 A (Claim 1) JP-A-61-53356 (Claim 1) JP-A-5-39419 (Claim 1)

  The present invention is an electric wire coating excellent in wear resistance, heat resistance, and colorability by blending a specific amount and a specific method of a PPS resin and a polyamide resin, an olefin / glycidyl methacrylate copolymer, and an unmodified olefin copolymer. An object of the present invention is to provide a resin composition.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have blended PPS resin, polyamide resin, olefin / glycidyl methacrylate copolymer, unmodified olefin copolymer in a specific amount and a specific method, It has been found that the object can be achieved, and the present invention has been achieved.

That is, the present invention
(1) (A) 12 to 100 parts by weight of polyamide resin, (C) 1.5 to 3.5 parts by weight of olefin / glycidyl methacrylate copolymer with respect to 100 parts by weight of (A) polyphenylene sulfide resin, ( D) A polyphenylene sulfide resin composition obtained by blending 3.5 to 10 parts by weight of an unmodified olefin copolymer. After mixing the components (A), (C) and (D) in advance, the component (B) A polyphenylene sulfide resin composition obtained by mixing,
(2) The polyphenylene sulfide resin composition according to (1), wherein the (B) polyamide resin is a copolymer of (b-1) caproamide units and (b-2) hexamethylene adipamide units. ,
(3) (B) Polyamide resin is (b-1), (b-2) as a total of 100% by weight, (b-1) 70 to 90% by weight of caproamide units and (b-2) hexamethylene adipamide A polyphenylene sulfide resin composition according to (2), which is a copolymer (polyamide 6/66) comprising 10 to 30% by weight of units,
(4) A method for producing a polyphenylene sulfide resin composition according to any one of (1) to (3), wherein (A) a polyphenylene sulfide resin, (C) an olefin / glycidyl methacrylate copolymer, (D) (B) A method for producing a polyphenylene sulfide resin composition comprising mixing a modified olefin copolymer and then mixing a polyamide resin (B),
(5) The polyphenylene sulfide resin composition according to any one of (1) to (3), wherein 0 to 10 parts by weight of the colorant (E) is blended with 100 parts by weight of the (A) polyphenylene sulfide resin.
(6) A molded article comprising the polyphenylene sulfide resin composition according to (1), (2), (3) or (5), and (7) a molded article according to (6), wherein the molded article is a wire coating,
It is.

  The resin composition of the present invention is excellent in wire coating processability, has high wear resistance and heat resistance, and can provide a resin composition suitable for wire coating.

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

  The (A) polyphenylene sulfide resin used in the present invention is a polymer having a repeating unit represented by the following structural formula (Formula 1):

From the viewpoint of heat resistance, the polymer preferably contains 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula. In addition, about 30 mol% or less of the repeating unit of PPS may be composed of a repeating unit having the following structure (Chemical Formula 2).

  The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible. However, the melt flow rate measured at 316 ° C. under a load of 5000 g is 10 to 20,000 g / 10 min. It is preferable that it is 20 to 10,000 g / 10min.

  PPS satisfying such properties is a method for obtaining a polymer having a relatively low molecular weight obtained by a production method represented by Japanese Patent Publication No. 45-3368, or Japanese Patent Publication No. 52-12240 and Japanese Patent Publication No. 61-7332. It can be produced by a known method such as a method for obtaining a polymer having a relatively large molecular weight described in the publication.

  The PPS resin obtained as described above may be used as it is, or it may be used for crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, organic solvent, hot water. It is also possible to use after washing with an acid aqueous solution or the like.

  In the case of washing with an organic solvent, the organic solvent to be used is not particularly limited as long as it does not have an action of decomposing PPS. For example, N-methylpyrrolidone, dimethylformaldehyde, dimethylacetamide, 1,3-dimethylimidazolidinone , Nitrogen-containing polar solvents such as hexamethylphosphorus amide and piperazinones, sulfoxide and sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone, dimethyl ether and dipropyl ether -Ether solvents such as tellurium, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchloroethylene, monochloroethane, dichloroethane, tetrachloro Halogen solvents such as ethane, perchloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanole, ethylene glycol, propylene glycol, phenol, cresol And alcohol / phenol solvents such as polyethylene glycol and polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene and xylene.

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

  Although there is no restriction | limiting in particular as another component with which it mix | blends with the said PPS resin, In the range which does not impair the effect of this invention, normal additives, such as a silane compound, a mold release agent, and a crystal nucleating agent, and a small amount of modified olefins System resins or other polymers can be added.

  The (B) polyamide resin 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, and tetramethylenediamine. , Hexamethylenediamine, 1,5-pentanediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5 5-trimethylsick Fats such as sun, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine , Cycloaliphatic, 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 Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. Polyamide homopolymers or copolymers derived from the raw materials of Each can be used alone or in the form of mixtures.

  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 (polyamide 6), polyhexamethylene adipamide. (Polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecane Amide (polyamide 11), polydodecanamide (polyamide 12), polycaproamide / polyhexamethylene adipamide copolymer (polyamide 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (polyamide 6 / 6T), polyhexamethy Adipamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (polyamide 6T / 12) , Polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyxylylene adipamide (polyamide XD6), polyhexamethylene terephthalamide / poly-2- Mention may be made of methylpentamethylene terephthalamide copolymers (polyamide 6T / M5T) and copolymers having polynomethylene terephthalamide phthalamide units. Can, furthermore also practically preferable to use a mixture in accordance with the required characteristics such as these polyamide resins moldability, compatibility. A balance between surface hardness and flexibility is important for wear resistance, and particularly preferred polyamide resins are copolyamides composed of caproamide units and hexamethylene adipamide units, and polyamide 6/66.

  This polyamide 6/66 copolymerized polyamide has a copolymer weight ratio of (b-1), (b-2) total 100 parts by weight, and (b-1) 70 to 90% by weight of caproamide units (b-2). It is preferable that it consists of 10 to 30% by weight of hexamethylene adipamide units from the balance of flexibility and wear resistance of the covered electric wire. More preferably, the range is (b-1) 75 to 90% by weight of caproamide units and (b-2) 10 to 25% by weight of hexamethylene adipamide units.

  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 2.0 to 7.0. More preferably, it is 2.2-6.0, Most preferably, it is the range of 2.5-5.5.

  The (B) polyamide resin in the present invention needs to be 12 to 100% by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. If it is 12 parts by weight or less, the wear resistance is impaired, and if it is 100 parts by weight or more, the heat resistance and flame propagation are impaired. Preferably it is 14 to 90 weight%, More preferably, it is the range of 15 to 85 weight part.

  The (C) olefin / glycidyl methacrylate copolymer of the present invention is a copolymer obtained by introducing a glycidyl methacrylate monomer component into an olefin polymer, and is particularly excellent in reactivity with a PPS resin.

  Preferable specific examples of the olefin polymer portion include an ethylene polymer, a propylene polymer, an ethylene / propylene copolymer, an ethylene / butene-1 copolymer, an ethylene / methyl acrylate copolymer, and an ethylene / ethyl acrylate. Examples thereof include a copolymer, an ethylene / butyl acrylate copolymer, an ethylene / methyl methacrylate copolymer, an ethylene / ethyl methacrylate copolymer, and an ethylene / butyl methacrylate copolymer. An ethylene polymer is preferable from the viewpoint of compatibility.

  The method for introducing the functional group-containing component into these olefin polymer portions is not particularly limited, and methods such as copolymerization or graft introduction into the olefin polymer using a radical initiator can be used. The amount of the functional group-containing component introduced is suitably in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on the whole modified olefin polymer. As a typical example that is commercially available, Bond First E manufactured by Sumitomo Chemical Co., Ltd. may be mentioned.

  The (C) olefin / glycidyl methacrylate copolymer in the present invention needs to be 1.5 to 3.5 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. If it is 1.5 parts by weight or less, the toughness is impaired, and if it is 3.5 parts by weight or more, the wear resistance is impaired. Preferably it is 1.6-3 weight part, More preferably, it is the range of 1.8-2.8 weight part.

  The (D) unmodified olefin polymer of the present invention is obtained by polymerizing an α-olefin such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, isobutylene alone or in combination of two or more. Polymers, α-olefins and α, β-unsaturated acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and alkyl esters thereof; And monomers containing ionomers such as metal carboxylate complexes.

Of these, ethylene / α-olefin copolymers are particularly preferred from the viewpoint of improving toughness. A specific example of the ethylene / α-olefin copolymer is a copolymer containing ethylene and at least one α-olefin having 3 to 20 carbon atoms as constituent components. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,
4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and These combinations are mentioned. Among these α-olefins, a copolymer using an α-olefin having 6 to 12 carbon atoms is more preferable because an improvement in toughness and a further improvement in the reforming effect can be seen. As a typical example that is commercially available, Tafmer TX610 manufactured by Mitsui Chemicals, Inc. may be mentioned.

  The (D) unmodified olefin polymer in the present invention needs to be 3.5 to 10 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. If it is 3.5 parts by weight or less, the toughness is impaired, and if it is 10 parts by weight or more, the wear resistance is impaired. Preferably it is 3.8-8 weight part, More preferably, it is the range of 4-7 weight part.

  The polyphenylene sulfide resin composition of the present invention is a mixture of (A) a polyphenylene sulfide resin, (C) an olefin / glycidyl methacrylate copolymer, (D) an unmodified olefin polymer, and then (B) a polyamide resin. It is necessary. This is because mixing (A) polyphenylene sulfide resin, (B) polyamide resin, (C) olefin / glycidyl methacrylate copolymer, and (D) unmodified olefin polymer at the same time impairs toughness and wear resistance. This is because, from the viewpoint of compatibility, when these are mixed at once, the (C) olefin / glycidyl methacrylate copolymer reacts not only with the PPS resin but also with the polyamide resin at the time of melt mixing. It is considered that wear resistance and heat resistance defined by ISO 6722 are reduced. When (A) polyphenylene sulfide resin and (C) olefin / glycidyl methacrylate copolymer are sufficiently reacted in advance and (B) polyamide resin is mixed, a larger number of olefin polymer components are dispersed in PPS resin than polyamide resin. It is considered that the above problem can be suppressed. In addition, (D) the unmodified olefin polymer is considered to be incorporated into the (C) olefin / glycidyl methacrylate copolymer, and is considered to have improved toughness.

  To the polyphenylene sulfide resin composition of the present invention, by further adding (E) a colorant, the composition is suitable for wire coating applications that can be identified by color in the assembly process, such as automobiles and home appliances. This is preferable. (E) There is no restriction | limiting in particular as a coloring agent, Arbitrary things, such as a pigment, an organic pigment, dye, can be used. A pigment is more preferable from the viewpoint of heat resistance. Typical examples of the pigment include blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, black pigments, and a single pigment or a plurality of pigments can be used. Representative examples of organic pigments include azo, phthalocyanine, quinacridone, benzimidazolone, isoindoline non, dioxazine, indanthrene, and perylene types. Can be used. Representative examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. I can do it. Also, pigments, organic pigments, and dyes can be used at the same time.

  The (E) colorant of the present invention is preferably 0 to 10 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. From the viewpoint of the colorability and wear resistance of the resin composition and the flexibility during the winding test, 0.1 to 10 parts by weight is preferable, and 0.1 to 6 parts by weight is more preferable.

  The polyphenylene sulfide resin composition of the present invention further includes other polymers, copper-based heat stabilizers, hindered phenol-based, phosphorus-based, sulfur-based antioxidants and the like as long as the object of the present invention is not impaired. One or more usual additives such as ultraviolet absorbers, lubricants, mold release agents, antistatic agents, and flame retardants can be added.

  Examples of the mixing of the polyphenylene sulfide resin composition of the present invention include a method of melt kneading at a temperature of 280 to 350 ° C. using a kneader such as a monoaxial or biaxial extruder or a kneader. There are no particular restrictions.

  Since the resin composition of the present invention can achieve both extremely high wear resistance that could not be achieved in the past and heat resistance defined by ISO 6722, it is particularly suitable for wire coating applications.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited by these. Measurement methods used in Examples and Comparative Examples are shown below.

(1) Evaluation of Abrasion Resistance The covered electric wire prepared according to Reference Example 3 was evaluated according to ISO 6722 9.3. The diameter of the needle used was 0.45 mm.

(2) Evaluation of heat resistance The covered electric wire prepared according to Reference Example 3 was subjected to a dry heat treatment at 125 ° C. for 240 hours in accordance with ISO 6722 10.1 and heat resistance class class B, and a winding test was performed in a −25 ° C. atmosphere. .

(3) Winding test The covered electric wire prepared according to Reference Example 3 was subjected to a winding test at room temperature with reference to ISO 6722, item 8, and used as an index of flexibility. Judgment criteria are as follows.
(Double-circle): A coating crack does not generate | occur | produce even once in 5 times.
○: Coating crack occurs once out of 5 times.
(Triangle | delta): Cover tearing generate | occur | produced 2 to 3 times in 5 times.
X: Cover tear occurs 4 to 5 times out of 5 times.

(4) Evaluation of flame propagation property The covered electric wire prepared according to Reference Example 3 was evaluated according to ISO 6722, item 12.

(5) Evaluation of coating processing stability About the covered electric wire 10m produced according to the reference example 3, the presence or absence of the foreign material was confirmed visually. If the coating processing stability deteriorates, the cylinder stays and foreign matter is generated. Judgment criteria are as follows.
A: No noticeable foreign matter is seen.
○: One or more conspicuous foreign matters are seen.
Δ: 3 to 910 conspicuous foreign matters are seen.
X: Ten or more conspicuous foreign matters are seen.

Reference Example 1 Production of PPS resin An autoclave equipped with a stirrer was charged with 6.005 kg (25 mol) of sodium sulfide nonahydrate, 0.205 kg (2.5 mol) of sodium acetate and 5 kg of NMP, and gradually heated to 205 ° C. through nitrogen. Then, 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C., 3.719 kg (25.3 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated to 270 ° C. Reacted for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water, then heated to 100 ° C., poured into 10 kg of NMP, stirred for about 1 hour, filtered, and washed several times with hot water. This was poured into 25 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and stirred for about 1 hour, filtered, washed with ion-exchanged water at about 90 ° C. until the pH of filtration became 7, It dried under reduced pressure at 80 degreeC for 24 hours, and obtained the polyphenylene sulfide resin of MFR600 (g / 10min). The MFR was measured according to ISO 1133 under the conditions of 316 ° C. and a load of 5000 g.

Reference Example 2 The copolymerized polyamide resin used in the production examples of the copolymerized polyamide 6/66 resin and the comparative example was polymerized by the following method. Hexamethylenediamine and adipic acid equimolar salt and ε-caprolactam were added in the weight ratios shown in the table, respectively, and the same amount of pure water as the total amount added was added, and the inside of the polymerization vessel was replaced with N ₂ , followed by stirring. Then, heating was started, and the final achieved temperature was set to 270 ° C. while the internal pressure of the can was adjusted to 20 kg / cm ² at maximum. The polymer discharged into the water bath was pelletized with a strand cutter. The pellet was dried at 80 ° C. for 50 hours or more to obtain a copolymerized polyamide 6/66 resin having a viscosity number of 230 (ml / g). The viscosity number was measured in accordance with ISO 307 using 96% by weight sulfuric acid.

Reference Example 3 Production of polyamide 6 resin The polyamide 6 resin used in the examples and comparative examples was polymerized by the following method. 1500 g of ε-caprolactam (manufactured by Toray Industries, Inc.) and 375 g of ion-exchanged water were weighed, charged into a polymerization can, and reacted at a final reached temperature of 260 ° C. while stirring under normal pressure and nitrogen flow. The polymer discharged into the water bath was pelletized with a strand cutter. The obtained pellets were treated in hot water at 95 ° C. for 20 hours to extract and remove unreacted monomers and low polymer. The pellet after extraction was dried at 80 ° C. for 50 hours or more to obtain a polyamide 6 resin having a viscosity number of 240 (ml / g). The viscosity number was measured in accordance with ISO 307 using 96% by weight sulfuric acid.

Reference Example 4 Method for Creating Covered Electric Wire The coated electric wires used in Examples and Comparative Examples were prepared by the following method. Polyphenylene sulfide resin composition shown in the examples in an outer diameter of 0.48 mm, a tin-plated wire of 7 wires, using a 30 mmφ wire coating device manufactured by Seisakusho, at a cylinder temperature of 310 ° C., a screw rotation speed of 30 prm, and a take-up speed of 80 m / min. The product was covered by extrusion to obtain a covered electric wire having an outer diameter of 0.88 mm.

Example 1
100 parts by weight of (A) PPS resin produced by the polymerization method shown in Reference Example 1, 2.1 parts by weight of (C) olefin / glycidyl methacrylate copolymer (Bond First E manufactured by Sumitomo Chemical Co., Ltd.) , (D) 5.0 parts by weight of unmodified olefin copolymer (Mitsui Chemicals Co., Ltd. Toughmer TX610) using a twin-screw extruder (Toshiba Machine Co., Ltd .: TEM58), cylinder set temperature 310 ° C., screw rotation Under the condition of several 250 rpm, all were top-feeded (incorporated feed) and melt-kneaded, and then a strand-like gut was formed, cooled in a cooling bath, and granulated with a cutter to obtain pellets. 71.4 parts by weight of (B) polyamide resin produced by copolymerization weight ratio of 80% by weight of caproamide unit and 20% by weight of hexamethylene adipamide by the polymerization method shown in Reference Example 2 and the obtained pellets Using a twin-screw extruder, all are top-feeded (incorporated feed) and melt-kneaded under the conditions of a cylinder set temperature of 310 ° C and a screw rotation speed of 250 rpm, and then a strand-shaped gut is formed and cooled in a cooling bath. Thereafter, it was granulated with a cutter to obtain pellets. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

Examples 2 and 3
(B) Pellets and molded products were obtained in the same manner as in Example 1 except that the polyamide resin was in parts by weight shown in the table, and various characteristics were examined. The results are shown in the table.

Examples 4, 5, 6, 7
(B) Pellets and molded products were obtained in the same manner as in Example 2 except that the copolymerization weight ratio of the polyamide resin was the ratio shown in the table, and various characteristics were examined. The results are shown in the table.

Example 8
(B) Except that the polyamide resin is a polyamide 6 resin produced by the polymerization method shown in Reference Example 3, pellets and molded products were obtained in the same manner as in Example 2 and various characteristics were examined. The results are shown in the table.

Examples 9, 10, 11, 12, 13, 14
Pellets and molded articles were obtained in the same manner as in Example 2 except that the parts (E) of the colorant shown in the table were added by weight, and various characteristics were examined. The results are shown in the table.

Comparative Example 1
100 parts by weight of (A) PPS resin produced by the polymerization method shown in Reference Example 1 and 80% by weight of caproamide units and 20% by weight of hexamethylene adipamide units by the polymerization method shown in Reference Example 2 Pellets were obtained in the same manner as in Example 1 by using 42.9 parts by weight of the (B) polyamide resin produced in a ratio using a twin screw extruder. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

Comparative Example 2
Pellets were obtained in the same manner as in Example 1 using 100 parts by weight of the (A) PPS resin produced by the polymerization method shown in Reference Example 1 using a twin screw extruder. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

Comparative Examples 3, 4, 5, 6
(A) PPS resin, (B) Polyamide resin, (C) Olefin / glycidyl methacrylate copolymer, (D) Unmodified olefin copolymer is in the same manner as in Example 1 except that it is in parts by weight. Various properties were examined by obtaining pellets and molded products. The results are shown in the table.

Comparative Example 7
(A) 100 parts by weight of PPS resin, (C) 2.5 parts by weight of olefin / glycidyl methacrylate copolymer using a twin screw extruder under the conditions of a cylinder set temperature of 310 ° C. and a screw rotation speed of 250 rpm. After top feed (base feed) and melt kneading, a strand-like gut was formed, cooled with a cooling bath, and granulated with a cutter to obtain pellets. 35.7 parts by weight of (B) polyamide resin produced by copolymerization weight ratio of 80% by weight of caproamide units and 20% by weight of hexamethylene adipamide by the polymerization method shown in Reference Example 2 with the obtained pellets Using a twin-screw extruder, top feed and melt kneading all at a cylinder setting temperature of 310 ° C and a screw rotation speed of 250 rpm, then forming a strand-shaped gut, cooling with a cooling bath, and then making with a cutter. Granulated pellets were obtained. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

Comparative Example 8
(A) 100 parts by weight of PPS resin, (D) 5.0 parts by weight of unmodified olefin copolymer, maleic acid modified olefin copolymer (Tafmer HP7010 manufactured by Mitsui Chemicals, Inc.) 2.1 parts by weight are biaxial Using an extruder, under the conditions of a cylinder set temperature of 310 ° C. and a screw rotation speed of 250 rpm, all top feed (base feed) is melted and kneaded, then a strand gut is formed, cooled in a cooling bath, and then cutter To obtain pellets. 35.7 parts by weight of (B) polyamide resin produced by copolymerization weight ratio of 80% by weight of caproamide units and 20% by weight of hexamethylene adipamide by the polymerization method shown in Reference Example 2 with the obtained pellets Using a twin-screw extruder, top feed and melt kneading all at a cylinder setting temperature of 310 ° C and a screw rotation speed of 250 rpm, then forming a strand-shaped gut, cooling with a cooling bath, and then making with a cutter. Granulated pellets were obtained. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

Comparative Example 9
(A) 100 parts by weight of PPS resin and 2.5 parts by weight of maleic acid-modified olefin copolymer are all top-feeded using a twin screw extruder under conditions of a cylinder set temperature of 310 ° C. and a screw rotation speed of 250 rpm. Feed) and melt-kneading, and then forming a strand-like gut, cooling with a cooling bath, and granulating with a cutter to obtain pellets. 35.7 parts by weight of (B) polyamide resin produced by copolymerization weight ratio of 80% by weight of caproamide units and 20% by weight of hexamethylene adipamide by the polymerization method shown in Reference Example 2 with the obtained pellets Using a twin-screw extruder, top feed and melt kneading all at a cylinder setting temperature of 310 ° C and a screw rotation speed of 250 rpm, then forming a strand-shaped gut, cooling with a cooling bath, and then making with a cutter. Granulated pellets were obtained. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

Comparative Example 10
(A) PPS resin, (B) polyamide resin, (C) olefin / glycidyl methacrylate copolymer, (D) unmodified olefin copolymer in cylinders using a twin-screw extruder in the weight parts shown in the table Under the conditions of a temperature of 310 ° C. and a screw rotation speed of 250 rpm, all top feed (base feed) is melted and kneaded, then a strand gut is formed, cooled in a cooling bath, granulated with a cutter, and pellets are obtained. It was. A coated electric wire was prepared from the obtained pellet by the method shown in Reference Example 4, and various characteristics were examined by the measurement method described above. The results are shown in the table.

  Resin compositions obtained by blending PPS resin, polyamide resin, olefin / glycidyl methacrylate copolymer, and unmodified olefin copolymer in specific ratios and specific methods from Examples 1-14 and Comparative Examples 1-10 It was confirmed that a resin composition having excellent wear resistance and heat resistance can be obtained. Moreover, it was confirmed that by using a polyamide resin as a copolymerized polyamide 6/66 resin, a resin composition that is further excellent in flexibility and particularly excellent as a wire coating resin can be obtained. Furthermore, it was confirmed that a resin composition particularly excellent as a wire coating resin can be obtained by blending a colorant.

Claims (7)

(A) 12-100 parts by weight of polyamide resin, (C) 1.5-3.5 parts by weight of olefin / glycidyl methacrylate copolymer, (D) not yet added to 100 parts by weight of polyphenylene sulfide resin It is a polyphenylene sulfide resin composition comprising 3.5 to 10 parts by weight of a modified olefin copolymer, and after previously mixing the components (A), (C) and (D), the component (B) is mixed. Obtained polyphenylene sulfide resin composition. The polyphenylene sulfide resin composition according to claim 1, wherein the (B) polyamide resin is a copolymer of (b-1) caproamide units and (b-2) hexamethylene adipamide units. (B) Polyamide resin is (b-1), (b-2) as a total of 100% by weight, (b-1) 70 to 90% by weight of caproamide units and (b-2) hexamethylene adipamide units 10 to 10%. The polyphenylene sulfide resin composition according to claim 2, which is a copolymer (polyamide 6/66) comprising 30% by weight.   It is a manufacturing method of the polyphenylene sulfide resin composition in any one of Claim 1 to 3, Comprising: (A) Polyphenylene sulfide resin, (C) Olefin / glycidyl methacrylate copolymer, (D) Unmodified olefin copolymer (B) A method for producing a polyphenylene sulfide resin composition, which comprises mixing a polyamide resin. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein 0 to 10 parts by weight of (E) a colorant is blended with 100 parts by weight of (A) polyphenylene sulfide resin. A molded article comprising the polyphenylene sulfide resin composition according to claim 1, 2, 3 or 5. The molded article according to claim 6, wherein the molded article is a wire coating.