JPH0374273B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition, particularly a thermoplastic resin composition used as a resin molded article requiring abrasion resistance. More specifically, thermoplastics are used to obtain molded products that require good friction and abrasion resistance by blending 0.01 to 50 parts by weight of polyamide elastomer with 100 parts by weight of polyphenylene ether resin. This invention relates to a resin composition. Polyphenylene ether resins have poor abrasion resistance and have not been applied to parts that are subject to friction abrasion. In addition, if there are parts that require partial friction and abrasion resistance due to the design, insert molding of small parts made of resin with good abrasion and abrasion resistance such as nylon resin or acetal resin is possible. Partial reinforcement is achieved by inlaying or inlaying. or,
In cases where flat surface friction and abrasion resistance is required, the application can be satisfied by laminating sheets or films made of fluororesin or nylon resin. However, although such combined use of resins can be applied to simple shapes, it is difficult to assemble resin molded products with complex shapes, and the inserts become complicated. It's hard to get caught. In this way, the combined use of resins has many problems because there are limits to its use depending on the shape, and it also requires a lot of man-hours. The object of the present invention is to avoid the above-mentioned disadvantages,
It is an object of the present invention to provide a resin composition that can be used to make a molded article with good frictional abrasion characteristics using a polyphenylene ether resin, and that can also be used to obtain a complex molded article. As a result of intensive studies to obtain such a resin composition, the present inventor has developed a thermoplastic resin composition in which 0.01 to 40 parts by weight of a polyamide elastomer is mixed with 100 parts by weight of a polyphenylene ether resin. This goal was achieved. Polyamide elastomer itself differs from polyamide in that it has a low critical PV value and does not have particularly good friction properties. Also, unlike silicone oil, carbon, etc., it does not itself have lubricity. A molded product obtained by mixing such a polymer compound with the above-mentioned polyphenylene ether resin has significantly improved frictional properties, even though it is based on a polyphenylene ether resin. They discovered this. The polyphenylene ether used in the present invention is a polyphenylene ether obtained by polycondensing one or more monocyclic phenols represented by the general formula (), and it can be a homopolymer or a copolymer. Polyphenylene ether may be vinyl aromatic. (Here, R ₁ is a lower alkyl group having 1 to 3 carbon atoms,
R ₂ and R ₃ are hydrogen atoms or lower alkyl groups having 1 to 3 carbon atoms, and a lower alkyl substituent must always be present at the ortho position of at least one of the hydroxyl groups. ) Graft copolymers obtained by graft polymerization of aromatic compounds are also included. Furthermore, the definition of polyphenylene ether resin in the present invention also includes a composition obtained by mixing the polyphenylene ether and other resin components. Examples of the monocyclic phenol represented by the general formula () include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2- Methyl-6-propylphenol,
2-ethyl-6-propylphenol, m-cresol, 2,3-dimethylphenol, 2,3-
Diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-
Methyl-3-propylphenol, 2-ethyl-
3-methylphenol, 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol,
2,3,6-trimethylphenol, 2,3,6
-triethylphenol, 2,3,6-tripropylphenol, 2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-3-prohylphenol, and the like. Examples of polyphenylene ether obtained by polycondensation of one or more of these phenols include poly(2,6
-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6) −
Ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, 2,6- Dimethylphenol/2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol/
2,3,6-triethylphenol copolymer,
Examples include 2,6-diethylphenol/2,3,6-trimethylphenol copolymer and 2,6-dipropylphenol/2,3,6-trimethylphenol copolymer. As the other thermoplastic resin component to be mixed with polyphenylene ether, vinyl aromatic resin is suitable. A resin having at least 25% by weight or more of a monomer structural unit represented by the following general formula () in its polymer, (Here, R ₄ is a hydrogen atom or a lower alkyl group, Z
represents a halogen atom or a lower alkyl group, and p is 0 or a positive integer of 1 to 3.) For example, polystyrene, rubber-reinforced polystyrene, poly(styrene/acrylonitrile) copolymer, rubber-reinforced (styrene/acrylonitrile) copolymer. Some of these styrene or acrylonitrile may be polymers that can be copolymerized with styrene, such as α-methylstyrene, acrylic esters, methacrylic esters, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides. Examples include monomers substituted with saturated monomers, and these
A mixture of two or more species may also be used. Other thermoplastic resins include copolymers of diene compounds such as polybutadiene and polyisoprene and vinyl aromatic compounds, nitrile rubber, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, thiol rubber, and polysulfide. The present invention can also be applied to elastomers such as rubber, acrylic rubber, polyurethane, and polyester elastomer. The polyamide elastomer referred to in the present invention is
A polyamide copolymer containing 95 to 10, preferably 90 to 20, more preferably 80 to 30% by weight of hard segments consisting of aminocarboxylic acids or lactams having 6 or more carbon atoms or nylon mn salts with m+n≧12. be. Aminocarboxylic acid or lactam with 6 or more carbon atoms or nylon mn with m+n≧12
Examples of the salt (a) include amino acids such as ω-aminocaproic acid, ω-aminoenanthate, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundeganic acid, and 12-aminododecanoic acid. Carboxylic acids or lactams such as caprolactam and laurolactam, nylon 6, 6, 6, 10,
6.12, 11.6, 11.10, 11.12, 12.6, 12.
Examples include nylon salts such as 10, 12, and 12. The soft segment, which is the second component of the polyamide copolymer of the present invention, is a material other than nylon that is compatible with the polyphenyl ether resin to a certain extent and can be copolymerized with the polyamide component. Specifically, there are poly(alkylene oxide) glycol, polyenter polyol, polycaprolactone polyol, polycarbonate polyol, and the like. Further, the OH groups of these polyols may be aminated or carboxylated. Poly(alkylene oxide) glycols include polyethylene glycol, poly(1,2 and 1,3 propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random of ethylene oxide and propylene oxide. Examples include copolymers, block or random copolymers of ethylene oxide and tetrahydrofuran, and the like. The average molecular weight of this product is 500-3000. In the present invention, both ends of the poly(alkylene oxide) glycol may be aminated or carboxylated. The bond between the first component and the second component may be an ester bond or an amide bond depending on the terminal group of the second component. A third component such as a carboxylic acid or diamine can be used depending on the bond. As a specific synthesis method, for example,
No. 45419, Japanese Patent Application Laid-open No. 133424/1983, etc. Possible dicarboxylic acids include those having 4 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,
4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4dicarboxylic acid. Mention may be made of alicyclic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid. As the diamine, aromatic, alicyclic, and aliphatic diamines are used. Specifically, hexamethylene diamine is considered as the aliphatic diamine. 0.01 to 40 parts by weight of polyamide elastomer per 100 parts by weight of polyphenylene ether resin,
The amount is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight. If the amount of the polyamide elastomer blended is less than 0.01 part per 100 parts by weight of the polyphenylene ether resin, the effect of improving frictional friction properties will be small. Further, if the amount is 40 parts by weight or more based on 100 parts by weight of the polyphenylene ether resin, it is not preferable because the mechanical strength will decrease. The resin composition of the present invention is effective as a material for molded products having sliding parts as described above, and molded products having sliding parts specifically include shaft bearings, cams, pistons, and VTR cassettes. Examples include hub pulleys, ratchet gears, small power transmission gears, push pulls, switches, control levers for car heaters and air conditioners, enclosures for equipment with rotating bearings, and cassette cables for recording. It goes without saying that the resin composition of the present invention may further contain lubricants, dispersants, stabilizers, dyes and pigments, flame retardants, antistatic agents, fillers or reinforcing agents such as glass fiber, etc., as necessary. be. Examples and comparative examples will be described below. Examples and Comparative Examples In this experiment, EPL's resin containing 5 parts by weight or more of polyphenylene ether, grade 731J, trade name "Noryl", was used as the polyphenylene ether resin, while the polyamide elastomer was The product name "Diamid PAE E47L" manufactured by Daicel Chemical Industries, Ltd. was used. E47L was synthesized from 50% by weight of lauryllactam, 41% by weight of α.ω-dihydroxy(polytetrahydrofuran) with an average molecular weight of 1000, and 9% by weight of dodecanedicarboxylic acid. Table 1 shows the positions of the individual components used as raw materials. The above raw materials are shown in Table 2. Weigh according to the mixing ratio, mix each, and add the mixture.
A resin composition was obtained by kneading and extrusion using a 40 mmφ extruder (L/D=26) and pelletizing. The resin composition pellets thus obtained were injection molded using an injection molding machine TS-100 manufactured by Nissei Plastics. The friction wear test piece has an inner diameter of 20mmφ and an outer diameter of 26mm.
A cylindrical test piece with a diameter of φ and a height of 15 mm for a Suzuki type friction friction tester was molded. Molding conditions are cylinder temperature
The test piece was molded at 260° C., mold temperature 50° C., injection pressure 65 Kg/cm ² G, and cycle time 60 seconds. The same injection molding machine was used for measuring mechanical properties, cylinder temperature 260℃, mold temperature 50℃, injection pressure 65Kg/
cm ² G, cycles were performed for 60 seconds. Frictional wear tests and mechanical strength tests were conducted using the thus formed test pieces. In the friction abrasion test, a steel test piece with the same shape as this test piece was installed in the lower rotating part of the Suzuki type friction abrasion tester, a compound molded test piece was installed in the upper stationary part, and a surface pressure of 1 kg/
The measurement was carried out without lubrication under sliding conditions of cm ² and average circumferential speed of 10 m/min. The amount of heat exchanger (unit: mm ³ /Kg·Km) was calculated using the following formula. Heat capacity (mm ³ /Kg・Km) = Grind weight (mg) / Density (mg/mm ³ ) x Load (Kg) x Mileage distance Km) As a polyphenylene ether resin in the same manner as in the example EPL's resin, product name "Noryl",
Grade 731J was used, and friction abrasion tests were conducted on a mixture of polyester elastomer (Pelprene P-150B) and "Noryl Grade 731J" itself. The conditions for molding the test piece and the conditions for measurement were the same as in the examples. Mechanical properties are measured using ASTM D638, ASTM
Based on the method of D790 and ASTM D256. Table 3 shows the results measured under the conditions described above.

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Claims (1)

[Claims] 1 A nylon mn salt consisting of an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a dicarboxylic acid having m carbon atoms and a diamine having n carbon atoms, with m+n≧12, based on 100 parts by weight of polyphenylene ether resin. Hard segment consisting of things 95~
Polyamide elastomer consisting of a copolymer of 10% by weight of poly(alkylene oxide) glycol, polyether glycol, polycaprolactone polyol, polycarbonate polyol, or a soft segment with aminated or carboxylated hydroxyl groups at both ends of these. 0.01~40
A thermoplastic resin composition characterized in that it contains parts by weight.