JP2593728B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition having excellent heat resistance, mechanical properties and moldability. More specifically, the heat resistance of the maleimide copolymer and the moldability of the polyarylene sulfide are improved, comprising a maleimide copolymer, polyarylene sulfide, and an epoxy resin. The present invention relates to a finished thermoplastic resin composition.

[Conventional technology]

Polyarylene sulfide represented by polyphenylene sulfide resin has attracted attention in recent years as an engineering plastic with excellent heat resistance, chemical resistance, and flame retardancy, but the resin alone is weak and has poor moldability and practical use. Sexability is severely restricted. For this reason, various properties are imparted by a compounding technique such as addition of a reinforcing material such as glass fiber or the like, and the material is put to practical use.

The polyphenylene sulfide resin composition obtained in this manner makes use of the respective characteristics,
They are used as automotive equipment parts, chemical equipment parts, and the like, but in each field, precision and miniaturization have been progressing with the advancement of technical level. From such a background, in each field, appearance of a material excellent in all of heat resistance, molding workability, and mechanical strength is expected.

In response to these requirements, attempts have been made to mix or react various polymer substances with polyphenylene sulfide resin. For example, as a method for improving the impact resistance of a polyphenylene sulfide resin, a composition with a glycidyl group-containing olefin copolymer (Japanese Patent Application Laid-Open No.
As a method for improving the processability of polyphenylene sulfide resin, a composition containing a novolak type epoxy resin (Japanese Patent Application Laid-Open No. 59-51945) is known. Further, for the purpose of lowering the melt viscosity of the polyphenylene sulfide resin, a composition in which a copolymer of a vinyl aromatic monomer and a maleimide monomer is mixed (Japanese Patent Application Laid-Open No. 61-1986)
No. 9452) is known.

[Problems to be solved by the invention]

However, there is no example in the above-mentioned known examples in which the properties of a composition of a copolymer of a vinyl aromatic monomer and a maleimide monomer and a polyarylene sulfide resin are improved by adding an epoxy resin.

An object of the present invention is to improve the moldability of polyarylene sulfide resin.

[Means for solving the problem]

In general, the present invention relates to a thermoplastic resin composition, and comprises (a) an aromatic vinyl monomer residue 30
~ 70 mol%, maleimide monomer residue 30-50 mol%, unsaturated dicarboxylic anhydride monomer residue 1-20 mol% and acrylic monomer residue 0-50 mol% Resin composition comprising 1 to 99% by weight of a copolymer (b) 99 to 1% by weight of a polyarylene sulfide and (c) 0.1 to 50% by weight of an epoxy resin other than a thermoplastic elastomer
It is characterized in that a filler is mixed with 0 to 80% by weight with respect to% by weight.

It has been found that the composition of the present invention has high heat resistance and excellent moldability.

The method for producing the maleimide-based copolymer used in the present invention is not particularly limited. For example, a radical copolymer of an aromatic vinyl monomer, a maleimide-based monomer, an unsaturated dicarboxylic anhydride monomer, and an acrylic monomer may be used. It can be produced by polymerization.

Specific examples of the aromatic vinyl monomer include styrene and α-
There are methylstyrene, vinyltoluene, t-butylstyrene and the like, and specific examples of the maleimide monomer include maleimide, N-methylmaleimide, N-ethylmaleimide,
N-propylmaleimide, N-hexylmaleimide, N
-Cyclohexylmaleimide, N-phenylmaleimide, N-tolylmaleimide and the like. Specific examples of unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, Ethyl maleic acid, phenylmaleic anhydride and the like, 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, glycidyl (meth) acrylate and the like, and these can be used alone or in combination. However, here methyl (meth)
Acrylate means methyl acrylate or methyl methacrylate. The method for radical copolymerization of these monomers is not particularly limited, and any known radical copolymerization method can be applied.

As another method for producing a maleimide-based copolymer used in the present invention, a copolymer of an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride monomer and an acrylic monomer with ammonia or a primary amine is used. A method of imidizing an acid anhydride residue by reacting can be exemplified. Examples of primary amines used for imidization include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, bromophenylamine, dibromophenylamine and the like. .

The method of the imidation reaction is arbitrary, and the reaction can be carried out in a solution state, a bulk molten state, or a suspension state using an autoclave. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder.

The solvent used for the solution reaction is arbitrary, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, tetrahydrofuran,
Examples thereof include ethers such as 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone. The imidization reaction temperature is preferably in the range of 50 to 350 ° C, particularly preferably in the range of 100 to 300 ° C.

Imidation does not necessarily require the presence of a catalyst, but if used, tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-diethylaniline are preferred.

Polyarylene sulfide resin used in the present invention,
A polymer containing at least 70 mol% of a repeating unit represented by the structural formula (-Ar-S-) (where Ar is p- or m-phenylene, biphenylene, naphthalene, or the like). Is a polyphenyl sulfide having at least 70 mol% of a structural unit represented by If the amount is less than 70 mol%, it is difficult to obtain a composition having excellent characteristics. As a method of synthesizing this resin,
For example, a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent, and
Self-condensation of chlorothiophenol, etc.
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, it is preferable to add an alkali metal salt of carboxylic acid or sulfonic acid or to add alkali hydroxide to adjust the degree of polymerization. Further, as a preferable example of the copolymer component, if it is less than 30 mol%, a meta bond Ortho coupling Ether bond Sulfone bond Biphenyl bond Substituted phenyl sulfide bond R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a metal base such as a carboxylic acid group) and a trifunctional bond It does not matter if it is in a range that does not greatly affect the crystallinity of the resin even if it contains etc., but preferably the copolymer component is 10
It is preferably at most mol%.

As a specific method for producing such a polyarylene sulfide resin, for example, (1) the reaction of a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 2513188, JP-B-44-27671 and JP-B-45-3368) Refer to each publication),
(2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat. No. 3,274,165,
(See British Patent No. 1160660), (3) Condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (JP-B-46-27255, Belgian Patent No. 29439) and the like. .

Next, the epoxy resin used in the present invention is an epoxy resin other than the thermoplastic elastomer. Examples of suitably used epoxy resins include glycidyl ether epoxy resins such as bisphenol A diglycidyl ether type, novolac glycidyl ether type, glycidyl ester epoxy resins such as glycidyl ester hexahydrophthalate and glycidyl dimer, Triglycidyl isocyanurate, glycidyl methane type epoxy resin such as tetraglycidyl diaminodiphenylmethane, epoxidized polybutadiene, linear aliphatic epoxy resin such as epoxidized soybean oil, 3,4-epoxy-6-methylcyclohexylmethyl carboxylate and the like There are aliphatic epoxy resins and the like.

Furthermore, in the present invention, organic, inorganic and metal fillers such as glass fiber, potassium titanate fiber, aramid fiber, etc.
Silica fiber, alumina fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel fiber, aluminum fiber, titanium fiber, copper fiber, brass fiber, magnesium fiber, polyamide fiber, polyester fiber, polyethylene Fiber, polyacrylic fiber, fibrous reinforcing material such as fluorine fiber, or wollastenite, sericite, kaolin, mica, clay,
Silicates such as bentonite, asbestos, talc, alumina silicate, etc., metal oxides such as alumina, silicon chloride, magnesium oxide, zirconia, titanium oxide, carbonates such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate Granular fillers such as sulfate, glass beads, boron nitride, silicon carbide, and silica can be used. Two or more of these fillers can be used in combination, and if necessary, can be used after being pretreated with a silane-based or titanium-based coupling agent.

In the present invention, 1 to 99% by weight of a maleimide copolymer, 99 to 1% by weight of a polyarylene sulfide, and 0.1% of an epoxy resin are used.
A composition is prepared by mixing 80 to 0% by weight of a filler with 20 to 100% by weight of a resin composition consisting of 1 to 50% by weight. If it exceeds 50% by weight, properties of polyarylene sulfide such as rigidity are lost. As a resin composition having improved moldability, preferably 1 to 50% by weight of a maleimide copolymer
And a resin composition comprising 99 to 50% by weight of a polyarylene sulfide and 0.1 to 50% by weight of an epoxy resin, and a fat composition comprising a filler of 80 to 0% by weight with respect to a resin composition of 20 to 100% by weight.
More preferably, the filler is 80 to 0% by weight based on 20 to 100% by weight of a resin composition comprising 5 to 45% by weight of a maleimide copolymer, 95 to 45% by weight of a polyarylene sulfide and 0.5 to 30% by weight of an epoxy resin. And a resin composition comprising:

The preparation of the composition according to the invention is possible by various known methods. For example, there is a method in which raw materials are uniformly mixed in advance with a mixer such as a tumbler or a Henschel mixer, then supplied to a single-screw or twin-screw extruder, melt-kneaded, and then prepared as pellets.

The substrate of the present invention can be processed into films, sheets, fibers, and the like, which can be extruded, hollow and foamed, as well as injection molded and compressed. In particular, it can be suitably used for injection molding.

〔Example〕

EXAMPLES Examples and comparative examples will be described below in order to explain the present invention in more detail, but the present invention is not limited to these examples.

<Method for producing maleimide copolymer> Styrene 60 was placed in an autoclave equipped with a stirrer.
And 50 parts of methyl isobutyl ketone, and the inside of the system was purged with nitrogen gas, and then the internal temperature was raised to 85 ° C. Separately, a solution was prepared by dissolving 40 parts of maleic anhydride and 0.15 part of benzoyl peroxide in 250 parts of methyl isobutyl ketone, and this was continuously added to the system over 8 hours. After the addition is complete,
The reaction was continued at 85 ° C. for 3 hours. A part of the reaction solution was sampled, and the polymerization rate was determined by gas chromatography. As a result, both styrene and maleic anhydride were 99% or more.

Then, aniline 30 parts, triethylamine 0.3
And stirring was continued at 140 ° C. for 7 hours.

After cooling, the content was supplied to a co-rotating twin-screw extruder equipped with a vacuum vent and having a dewatering function, dewatered, devolatilized and pelletized, and this polymer was used as a maleimide-based copolymer.

Polyphenylene sulfide is manufactured by Topren Co., Ltd.
The trade name "T-4" was used.

Epoxy resin is amine type epoxy resin manufactured by Toto Kasei Co., Ltd., trade name "YH434" and Dow Chemical Japan Co., Ltd.
Novolak epoxy resin, trade name "DER-662UH"
It was used.

The glass fiber used was Nippon Electric Glass Co., Ltd., trade name “Chopped Strand ECS03T-717P”.

Example 1, Comparative Example 1 Maleimide-based copolymer, polyphenylene sulfide,
Epoxy resin and glass fiber were blended in the proportions shown in Table 1. Then, using a twin screw extruder, the cylinder temperature was 300 ° C.
After extruding and kneading, the strand was air-cooled and cut to obtain pellets. After drying the pellets at 130 ° C for 2 hours,
A test piece was prepared using an injection molding machine (cylinder temperature 280 ° C., mold temperature 170 ° C.), and the bending strength, impact strength, heat deformation temperature and sink rate were measured. Measurements of bending strength, impact strength, and heat distortion temperature are JIS K-7203, JIS K-7110, and JI, respectively.
It was measured according to SK-7207. The sink mark was measured according to the following definition based on the maximum thickness L and the minimum thickness I at the center of the test piece.

Sinking rate (%) = (L-1) * 100 / L The results are shown in Table 1.

Example 1, polyphenylene sulfide from Comparative Example 1,
It can be seen that the addition of an epoxy resin to the maleic acid copolymer improves strength, heat resistance, and moldability (sinking).

〔The invention's effect〕

In the present invention, a polyarylene sulfide resin composition having extremely excellent moldability can be obtained by blending an epoxy resin other than a maleimide copolymer and a thermoplastic elastomer.

Claims (1)

(57) [Claims] (1) (a) 30 to 70 mol% of an aromatic vinyl monomer residue, 30 to 50 mol% of a maleimide monomer residue, 1 to 20 mol of an unsaturated dicarboxylic anhydride monomer residue % And a maleimide copolymer comprising 0 to 50 mol% of acrylic monomer residues, and (b) polyarylene sulfide 99 to 1
A thermoplastic resin composition obtained by mixing 0 to 80% by weight of a filler with 20 to 100% by weight of a resin composition comprising 0.1 to 50% by weight of an epoxy resin other than a thermoplastic elastomer (c).