JPH07258465A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition suitable for sliding parts, etc., having excellent wear resistance, etc., by blending a thermoplastic resin with specific amounts of a reinforcing material and diamond powder. CONSTITUTION:This composition is obtained by blending 100 pts.wt. of a thermoplastic resin (preferably polyamide, thermoplastic polyester or PPS) with 0-150 pts.wt. of a reinforcing material (preferably carbon fibers, glass fibers, glass beads or mica) and 0.01-2 pts.wt. of diamond powder (preferably cluster diamond).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition having excellent abrasion resistance and suitable for sliding parts and the like. .

[0002]

2. Description of the Related Art Conventionally, as a method of imparting abrasion resistance to a resin, a method of compounding molybdenum disulfide and graphite has been proposed (Japanese Patent Laid-Open Nos. 51-66340 and 51-82345). No. However, in order to obtain high wear resistance, a large amount of molybdenum disulfide and graphite must be blended, and a decrease in mechanical strength, especially impact strength, cannot be avoided.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and provide a thermoplastic resin composition having excellent abrasion resistance.

[0004]

That is, the present invention is characterized in that 100 parts by weight of a thermoplastic resin is mixed with 0 to 150 parts by weight of a reinforcing material and 0.01 to 2 parts by weight of diamond powder. It is a thermoplastic resin composition.

The present invention will be described in detail below. The thermoplastic resin used in the present invention may be selected from various types without any particular limitation. Specifically, polypropylene, polyethylene, polyvinyl chloride, polystyrene, ABS, A
S, polymethylmethacrylate, polycarbonate,
Examples thereof include polyacetal, polyphenylene oxide, polyamide, thermoplastic polyester, PPS, polyimide, liquid crystal polymer, polyether ether ketone, and polyarylate. In particular, polyamide, thermoplastic polyester, and PPS are preferable for sliding parts.

The polyamide which can be used in the present invention is not particularly limited, and ethylenediamine, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1 , 3- and 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexyl) methane metaxylylenediamine, paraxylylenediamine and other aliphatic, alicyclic and aromatic diamines and adipic acid, speric acid By the polymerization of lactams such as polyamides, ε-caprolactam and ω-dodecaractam, which are derived from aliphatic, alicyclic and aromatic dicarboxylic acids such as sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and dimer acid. Obtained polyamide, 6-aminocap Polyamides derived from rosonic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like, and copolyamides and mixed polyamides thereof, and polycaproamide (nylon) in the sense of being industrially inexpensive and manufactured in large quantities. 6), polydodecamide (nylon 12), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), copolymers thereof, such as nylon 6/66 (hereinafter, “/”). The symbol means a copolymer), nylon 6/610, nylon 6/12, nylon 66/12, nylon 6/66/610/12, and mixtures thereof are useful.

The thermoplastic polyester used in the present invention is a polymer or copolymer obtained by a condensation reaction containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as main components. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid,
4,4′-diphenylcarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 1,2-bis (phenoxy)
Examples thereof include ethane-4,4'-dicarboxylic acid, dimer acid and their ester-forming derivatives.

The diol component has 2 to 1 carbon atoms.
0 aliphatic diols, namely ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-
Hexanediol, decamethylenediglycol, cyclohexanediol, etc., or molecular weight 400-600
0 long chain glycols, ie polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. and mixtures thereof.

The preferred thermoplastic polyesters used in the present invention are specifically polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene-
2,6-naphthalate, polyethylene 1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyester elastomer and the like can be mentioned.

The PPS used in the present invention has the general formula

[Chemical 1] Those containing 90 mol% or more of the structural unit represented by are preferable, and those having less than 90 mol% have poor physical properties. This polymer can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide. The method includes polymerization of p-chlorothiophenol, self-condensation of p-chlorothiophenol, etc., but sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. The method of causing is suitable. At this time, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to adjust the degree of polymerization. If less than 10 mol% as a copolymerization component, a meta bond

[Chemical 2] Ether bond

[Chemical 3] Sulfone bond

[Chemical 4] Biphenyl bond

[Chemical 5] Substituted phenyl sulfide bond

[Chemical 6] Trifunctional phenyl sulfide bond

[Chemical 7] It does not matter if the content of such a compound does not significantly affect the crystallinity of the polymer, but the content of the copolymerization component is preferably 5 mol% or less. In particular, when a phenyl, biphenyl, or naphthyl sulfide bond having a functionality of 3 or more is selected for the copolymerization, the content is preferably 3 mol% or less.

Examples of the reinforcing material used in the present invention include fiber reinforcing materials such as glass fiber, carbon fiber, metal fiber, whisker talc such as potassium titanate and gypsum fiber, clay, wollastonite, montmorillonite, mica, bentonite. ，
Examples include powdery reinforcing materials such as calcium carbonate and glass beads. In particular, carbon fiber, glass fiber, glass beads,
Mica is preferable and two or more kinds may be used in combination.

It is important that the amount of the reinforcing material used in the present invention is 0 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin. If the content of the reinforcing material exceeds 150 parts by weight, molding becomes impossible.

The diamond powder used in the present invention is generally used for abrasive grains, and synthetic diamond having an average grain size of 100 μm or less is used. Preferred diamond powders include cluster diamond in terms of shape and grain size. Such cluster diamonds are
A primary explosive is trimethylenetrinitroamine or tetramethylenetetranitramine, a secondary explosive is a mixed explosive of trinitrotoluene, and is synthesized by a shock compression method using trinitrotoluene as a carbon source. The shape is a particle size, and the average particle size is 50Å.

The amount of diamond powder used in the present invention is 0.01 to 2 with respect to 100 parts by weight of the thermoplastic resin.
It is essential that the amount is parts by weight. If it is less than 0.01 part by weight, abrasion resistance is poor, and if it exceeds 2 parts by weight, impact resistance is poor.

The composition of the present invention contains conventional additives such as antioxidants and heat stabilizers (for example, hindered phenols, hydroquinones, phosphites, thioethers and the like, as long as they do not impair the object of the present invention. Substitutes and combinations thereof), UV absorbers (eg various resorcinols, salicylates, benzotriazoles, benzophenones, etc.), lubricants and mold release agents (eg montanic acid, stearic acid and its salts, stearyl alcohol, stearyl amides, etc.) , Coloring agents containing dyes (eg nitrocin) and pigments (eg cadmium sulfide, phthalocyanine, carbon black etc.), flame retardants (eg decabromodiphenyl ether, brominated polycarbonate, brominated polystyrene, halogenated systems such as brominated epoxy oligomers) , Melamine or Cyanuric acid type, phosphorus type, etc., flame retardant aid (eg antimony trioxide, antimony pentoxide etc.), antistatic agent (eg sodium benzenesulfonate, polyalkyl glycol etc.), crystallization accelerator (eg polyethylene glycol etc.) ), One or more additives impregnated liquid (silicone oil, etc.) can be added.

The method for producing the composition of the present invention is not particularly limited, and various known methods can be used. For example, a method in which a mixture of a thermoplastic resin and diamond powder previously blended with a tumbler or the like is supplied from a hopper port of a kneading machine and a reinforcing material is supplied from a side feed port to form a pellet-shaped resin, and the resin is subjected to a molding step is exemplified. To be

[0017]

The thermoplastic resin composition of the present invention is excellent in abrasion resistance and is suitable for sliding parts and the like.

The present invention will be specifically described with reference to the following examples. The physical properties were evaluated according to the following methods. Impact resistance Izod impact strength (notched, 1/4 inch): AS
TMD256 amount of wear abrasion resistant resin: Suzuki type friction abrasion tester (manufactured by Toyo Baldwin Co., Ltd.) Measuring conditions: the sliding surface cross-sectional area 2 cm ² ring sliding surface pressure 1.5 kg / cm ² sliding speed 1 m / sec slide Amount of abrasion at 1000m Rejection material S-45C steel

Method for producing polyester elastomer 50.6 kg of dimethyl terephthalate, 33.2 kg of 1,4-butanediol, 11.7 kg of polytetramethylene glycol (molecular weight 1000) and 0.01 kg of tetra-n-butyl titanate as a transesterification catalyst. Was charged in a polymerization kettle, and methanol produced by heating to 210 ° C. was distilled out of the system to carry out a transesterification reaction. After the distillation of methanol was almost completed, tetra-n- was used as a polymerization catalyst.
Butyl titanate (0.06 kg) was added, and the temperature was raised to 250 ° C. and the degree of vacuum to 0.5 mmHg over 1 hour, and then polycondensation was performed to obtain a polyester elastomer having a relative viscosity of 2.5.

Examples 1 to 8 and Comparative Examples 1 to 4 Polyester elastomer obtained by the above method, polybutylene terephthalate (Kanebo PBT72 manufactured by Kanebo Co., Ltd.)
0), PPS (T-4 made by Topren) and 6 nylon (Kanebo Kanebo Nylon MC112L) each 10
Cluster diamond (manufactured by Tokyo Diamond Tool Mfg. Co., Ltd.) and a reinforcing material were blended in an amount of 0 part by weight in a composition shown in Table 1, kneaded with a twin-screw extruder having a diameter of 30 mm, and pellets were obtained.

The pellets thus obtained were dried under reduced pressure, injection-molded into test pieces, and subjected to physical property tests. The results are also shown in Table 1.

[0022]

[Table 1]

Comparative Examples 5 to 8 Polybutylene terephthalate 100 used in Example 2
To the parts by weight, the wear resistance imparting material shown in Table 2 is blended,
A resin composition was produced in the same manner as in Example 2. The evaluation results are also shown in Table 2.

[0024]

[Table 2]

Claims (4)

[Claims] 1. A reinforcing material of 0 to 150 parts by weight and a diamond powder of 0.01 to 2 relative to 100 parts by weight of a thermoplastic resin.
A thermoplastic resin composition, characterized by being mixed in parts by weight. 2. The thermoplastic resin is polyamide, thermoplastic polyester or PPS.
The thermoplastic resin composition described. 3. The thermoplastic resin composition according to claim 1, wherein the reinforcing material is one kind or two or more kinds selected from the group consisting of carbon fiber, glass fiber, glass beads and mica. 4. The thermoplastic resin composition according to claim 1, wherein the diamond powder is cluster diamond.