JPH0565386A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition which is excellent in moldability and heat resistance and particularly can prevent the occurrence of flash from metal molds by using a resin mixture comprising a polyarylene sulfide resin, a polyamide resin, and a maleimide copolymer. CONSTITUTION:The objective thermoplastic resin composition consists of 20-100wt.% resin mixture comprising 98-1wt.% polyarylene sulfide resin, 1-98wt.% polyamide resin, and 1-98wt.% maleimide copolymer consisting of 30-70mol% aromatic vinyl groups, 30-50mol% maleimide groups, 1-20mol% unsaturated dicarboxylic acid anhydride groups, and 0-50mol% acrylic acid groups; and 0-80wt.% filler. This composition can be injection molded, extruded, hollow molded, and foam molded, and can be processed into film, sheet, fiber, etc. Particularly, it can be suitably used for injection molding.

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 having excellent compatibility, good appearance of molded articles, and excellent heat resistance, mechanical properties and moldability.

[0002]

2. Description of the Related Art Polyarylene sulfide resins represented by polyphenylene sulfide resins have excellent heat resistance,
In recent years, it has attracted attention as an engineering plastic having chemical resistance and flame retardancy. However, the polyarylene sulfide resin alone is fragile and has poor molding processability, which significantly limits its practicality. Therefore, the resin is provided with various characteristics by a composite technology such as addition of a reinforcing material such as glass fiber, and is put into practical use.
The drawbacks such as the tendency to generate burrs have not been solved yet.

However, the polyarylene sulfide resin composition thus obtained is used as electric / electronic equipment parts, automobile equipment parts, chemical equipment parts, etc. by making the best use of the respective characteristics, and the technology is used in each field. Precision and miniaturization are progressing with the advancement of the level. From such a background, in each field, the emergence of a material excellent in heat resistance, moldability and mechanical strength is awaited.

However, these diversified and highly functionalized requirements cannot be adequately answered by using the polyarylene sulfide resin alone as a raw material, and therefore polymer alloys are frequently used to meet the demand. ing. Then, for example, a composition in which a polyamide resin is blended with a polyarylene sulfide resin has been studied (Japanese Patent Laid-Open Nos. 59-155462 and 63-69).
832 publication).

[0005]

However, in the composition of the polyarylene sulfide resin and the polyamide resin of the above-mentioned known examples, for example, burrs are generated from the mold due to the decrease of the melt viscosity of the resin at the time of injection molding, and the molded article is formed. However, there was a drawback in that the elastic modulus of was decreased. The purpose of the present invention is to
This drawback has been solved, and by combining the resin composition with a maleimide copolymer, it is excellent in moldability and heat resistance without deteriorating the properties of conventional resin compositions, especially from a mold. The present invention has been completed to find out that the occurrence of burrs is suppressed.

[0006]

The present invention will be described in brief. The present invention relates to a thermoplastic resin composition, which comprises a)
Polyarylene sulfide resin 98-1% by weight, b) polyamide resin 1-98% by weight and c) aromatic vinyl group 30-70% by mole, maleimide group 30-50% by mole, unsaturated dicarboxylic anhydride group 1-20. Maleimide Copolymer 1 Consisting of Mol% and Acrylic Acid Group 0-50 Mol%
.About.98 wt.% Resin mixture 20-100 wt.% And filler 0-80 wt.%.

The polyarylene sulfide resin used in the present invention has a structural formula (-Ar-S-) (where Ar is p- or m-).
(Phenylene, biphenylene, naphthalene, etc.) is a polymer containing 70 mol% or more of repeating units represented by the structural formula [Chemical Formula 1].
It is a polyphenylene sulfide having a mol% or more. Further, if the amount is less than 70 mol%, it is difficult to obtain a composition having excellent properties.

[0008]

[Chemical 1]

The resin can be synthesized by, for example, polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent. And a method of polymerizing in the presence of p-chlorothiophenol, and self-condensation of p-chlorothiophenol. As another synthetic method, there is a method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane.

At this time, in order to control the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide. Further, as preferable examples of the copolymerization component, if it is less than 30 mol%, the meta bond shown in [Chemical Formula 2],
The ortho bond shown in, the ether bond shown in [Chemical formula 4], the sulfone bond shown in [Chemical formula 5], the biphenyl bond shown in [Chemical formula 6] and the substituted phenyl sulfide bond shown in [Chemical formula 7] (wherein R is an alkyl group, A metal base such as a nitro group, a phenyl group, an alkoxy group, or a carboxylic acid group) and a trifunctional bond represented by [Chemical formula 8] may be contained as long as they do not significantly affect the crystallinity of the resin. However, the copolymerization component is preferably 10 mol% or less.

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

As a concrete method for producing such a polyarylene sulfide resin, for example, (1) a reaction between a halogen-substituted aromatic compound and an alkali sulfide (US Pat. No. 251).
No. 3188, Japanese Patent Publication No. 44-27671, No. 45
No. 3368), (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat. No. 3,274,165, British Patent 11).
60660), (3) condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 27255/46, Belgian Patent No. 29437).

Next, the polyamide resin used in the present invention is
There is no particular limitation, and it may be a polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, a polyamide obtained from an aminocarboxylic acid or a cyclic lactam, and the like. ,
Nylon 6.6, Nylon 6.9, Nylon 6/10,
Aliphatic polyamides such as nylon 6/12, nylon 4.6, nylon 11 and nylon 12, poly (hexamethylene terephthalamide), poly (hexamethylene isophthalamide) and poly (m-xylylene adipamide) Polyamides containing aromatic rings are available, and these can be used alone or in combination.

As the method for polymerizing the polyamide resin, generally known melt polymerization, solid phase polymerization and a combination thereof can be adopted.

The method for producing the maleimide copolymer used in the present invention is not particularly limited, and examples thereof include an aromatic vinyl monomer, a maleimide monomer, an unsaturated dicarboxylic acid anhydride monomer, and if necessary. It can be produced by radical copolymerization of an acrylic monomer.

Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene and t-.
Butyl styrene and the like.

Specific examples of maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-tolylmaleimide. Is.

Specific examples of the unsaturated dicarboxylic acid anhydride monomer include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, ethylmaleic anhydride and phenylmaleic anhydride.

Specific examples of acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
Butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate and glycidyl (meth) acrylate Is.

These can be used alone or in combination. However, methyl (meth) acrylate here means methyl acrylate or methyl methacrylate. The radical copolymerization method of these monomers is not particularly limited, and a known method of radical copolymerization can be arbitrarily applied.

As another method for producing the maleimide copolymer used in the present invention, a copolymerization of an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride monomer and optionally an acrylic monomer is carried out. A method of reacting the combined product with ammonia or a primary amine to imidize the acid anhydride residue can be exemplified.

Examples of primary amines used for imidization include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, bromophenylamine and dibromophenylamine. Etc.

The method of imidization reaction is arbitrary, and the reaction can be carried out in a solution state, a massive molten state or a suspended state. It is also possible to carry out the reaction in a molten state by using a melt-kneading device such as a screw extruder.

Further, the filler used in the present invention is not particularly limited as long as it is an organic, inorganic or metal powder of each shape, and is a granular, flake, bead or fibrous filler.

For example, in the fibrous form, glass fiber, potassium titanate fiber, silica fiber, alumina fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, asbestos fiber, gypsum fiber, stainless fiber. , Aluminum fibers, titanium fibers, copper fibers, brass fibers, inorganic fibers such as magnesium fibers,
Examples include organic fibrous reinforcing materials such as aramid fibers, polyamide fibers, polyester fibers, polyethylene fibers, polyacrylic fibers, and fluorine fibers.

In powder form, beads or granules, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, talc, asbestos and alumina silicate, alumina, silicon chloride, magnesium oxide, zirconia oxide and titanium oxide. Metal oxides such as calcium carbonate, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfate glass beads such as calcium sulfate and barium sulfate, and granular fillers such as boron nitride, silicon carbide and silica can also be used.

These fillers can be used in combination of two or more, and if necessary, they can be used after pretreatment with a coupling agent such as a silane type or titanium type.

The composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are uniformly mixed in advance with a mixer such as a tumbler or a Henschel mixer, then fed to a uniaxial or biaxial extruder or the like, melt-kneaded, and then prepared as pellets.

The composition of the present invention can be injection-molded, compression-molded, extrusion-molded, blow-molded and foam-molded and can be processed into films, sheets and fibers. Particularly, it can be suitably used for injection molding.

The resin composition of the present invention can be usefully used in applications such as electric / electronic equipment parts, automobile equipment parts and chemical equipment parts.

[0037]

EXAMPLES Examples and comparative examples will be given below to explain the present invention in more detail, but the present invention is not limited to these examples. In each example, parts are based on weight. Polyarylene Sulfide Resin
Product name "T-4" manufactured by Topren Co., Ltd. (hereinafter PPS
Used). As the polyamide resin, a product name “CM-1017” (hereinafter referred to as nylon 6) manufactured by Toray Industries, Inc. was used. Maleimide copolymer is styrene 60
Part, a copolymer of 40 parts of maleic anhydride was modified with 30 parts of aniline. As a result of analysis, the composition was found to be 59.5 mol% of styrene groups, 35.5 mol% of maleic acid imide groups, and 5.0 mol% of maleic anhydride groups. The glass fiber is manufactured by Nippon Electric Glass Co., Ltd., trade name "Chopped Strand ECS".
O3T-717P "was used.

Example 1 and Comparative Example 1 PPS, nylon 6, maleimide copolymer and glass fiber were blended in the proportions shown in Table 1. Then, the mixture was extruded and kneaded at a cylinder temperature of 300 ° C. using a twin-screw extruder, and then the strand was air-cooled and cut to obtain pellets. After drying the pellets at 110 ° C. for 3 hours, the pellets were molded by an injection molding machine (cylinder temperature 300 ° C., mold temperature 130 ° C.) to prepare test pieces, and bending strength, bending elastic modulus, MFR,
The heat distortion temperature and the burr length were measured. The results are summarized in Table 1. PP from Example 1 and Comparative Example 1
By adding a maleimide-based copolymer to S and nylon 6, there is little decrease in bending strength, and the bending elastic modulus,
It can be seen that the heat resistance and the molding processability (the occurrence of burrs is small) are improved. In addition, the heat resistance is poor and the MFR is 1 (g / g) only by adding the maleimide copolymer to PPS.
It becomes less than 10 minutes and is not practical.

[0039]

[Table 1]

Example 2 and Comparative Example 2 PPS, nylon 6 and maleimide copolymers are shown in Table 2.
The same operation as in Example 1 was carried out except that the mixture was added in the proportion shown in. The results are shown in Table 2.

[0041]

[Table 2]

The physical properties were measured by the following methods. 1. Bending strength: JIS K-7203 2. Flexural modulus: JIS K-7203 3. MFR: ASTM D-1238 4. Heat distortion temperature: JIS K-7207 5. Burr length: The length of the burr protruding to the clearance of 20 μm of the air vent portion on the surface of the dumbbell mold part mounted on the injection molding machine was measured.

[0043]

EFFECTS OF THE INVENTION In the present invention, by blending a polyamide resin and a maleimide-based copolymer, it is excellent in molding processability and heat resistance and, in particular, is an extremely excellent polyarylene capable of suppressing the occurrence of burrs during injection molding. The sulfide resin composition is characterized by being obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 81/02 LRG 7167-4J

Claims (1)

[Claims] 1. A) polyarylene sulfide resin 98
˜1% by weight, b) 1 to 98% by weight of polyamide resin and c) 30 to 70 mol% of aromatic vinyl group, 3 of maleimide group.
0 to 50 mol%, unsaturated dicarboxylic acid anhydride group 1 to 20
Resin mixture 20 to 1 containing 1 to 98% by weight of a maleimide-based copolymer composed of 0 to 50% by mole of acrylic acid group
A thermoplastic resin composition comprising 00% by weight and a filler of 0 to 80% by weight.