JP2001329171A - Polymer molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer molding material and molded article containing a polyphenylene sulfide resin and a polyamide resin in high compatibility and having excellent impact resistance and elongation property. SOLUTION: The objective polymer molding material is produced by adding 1-30 wt.% rubbery polymer modified with an unsaturated carboxylic acid, its anhydride or their derivatives and 0.5-5 wt.% epoxy resin to a mixture of a polyphenylene sulfide resin and a polyamide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer molding material containing a polyphenylene sulfide resin and a polyamide resin as main components, and a molded article formed from the polymer molding material.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin has excellent heat resistance and chemical resistance, but is a brittle material having small elongation. On the other hand, polyamide resin has high strength and elasticity, and has excellent solvent resistance, but has a drawback that it is easily affected by humidity. Japanese Patent Publication No. Sho 59-1422 discloses blending these polyphenylene sulfide resins and polyamide resins in order to compensate for their disadvantages while maintaining their respective advantages. Blend polymers of these resins are also commercially available.

[0003]

However, in the above-mentioned blended polymer, there is a problem that the mechanical strength, particularly the impact strength, is low because the compatibility between the polyphenylene sulfide resin and the polyamide resin is insufficient.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and to provide a polymer molding material having excellent compatibility between a polyphenylene sulfide resin and a polyamide resin, excellent in impact resistance and elongation characteristics, and the polymer. It is to provide a molded article using a molding material.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a polymer molding material comprising a mixture of a polyphenylene sulfide resin and a polyamide resin, and a rubbery polymer modified with an unsaturated carboxylic acid, an anhydride thereof, or a derivative thereof. Coupling 1
It is characterized in that 30% by weight and 0.5 to 5% by weight of an epoxy resin are blended.

In the present invention, the rubbery polymer includes
A maleic acid-modified rubbery polymer modified with maleic acid or maleic anhydride is preferably used. As the epoxy resin, a bisphenol-glycidyl ether-based glycidyl epoxy resin is preferably used.

A molded article of the present invention is characterized by being molded from the above-mentioned polymer molding material of the present invention.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene sulfide resin used in the present invention contains a general polyphenylene sulfide resin. For example, the structural unit shown in the following (Chemical Formula 1) contains 70 mol% or more, more preferably 90 mol% or more. % Or more.

[0009]

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The content of the polyphenylene sulfide resin in the polymer molding material of the present invention is preferably 50 to 95% by weight, more preferably 65 to 80% by weight.
% By weight.

Examples of the polyamide resin used in the present invention include conventionally known polyamides such as nylon 6, nylon 66, nylon 46, and nylon 12, and nylon 6 is preferably used. The content of the polyamide resin in the polymer molding material of the present invention is preferably 2 to 30% by weight, and more preferably 5 to 15% by weight.

The rubbery polymer used in the present invention can be used without particular limitation as long as it is a rubbery polymer modified with an unsaturated carboxylic acid, an anhydride thereof, or a derivative thereof.

Examples of the rubbery polymer component to be modified include polybutadiene, SBR, EPR, EVA, polyacrylate, polyisoprene, hydrogenated polyisoprene, acrylic elastomer, polyester / polyether coelastomer, polyamide elastomer, ethylene·
Butene 1 copolymer, styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer,
Ethylene / propylene / ethylidene norbonene copolymer, thermoplastic polyester elastomer, hydrogenated SEBS
Elastomers, ethylene-α olefin copolymers, propylene-α olefin copolymers, MBS-based elastomers, and the like, particularly EPR, hydrogenated SEBS
Elastomers, ethylene-α-olefin copolymers, and propylene-α-olefin copolymers are preferably used.

The unsaturated carboxylic acids or anhydrides or derivatives thereof for modifying the rubbery polymer include maleic acid, fumaric acid, itaconic acid, methylmaleic acid, 3,6-endomethylene-delta-4-tetrahydro. Phthalic acid, acrylic acid, methacrylic acid, crotonic acid,
Citraconic acid, maleic anhydride, itaconic anhydride, methylmaleic anhydride, 3,6-endomethylene-delta-
4-tetrahydrophthalic anhydride, 2-methyl-3,6
-Endomethylene-delta-4-tetrahydrophthalic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, alkyl cyanoacrylate having 1 to 20 carbon atoms, etc. Derivatives are exemplified, and particularly preferably, maleic acid and maleic anhydride are used. As a method for modifying the rubbery polymer with an unsaturated carboxylic acid or the like, for example, a method of graft-copolymerizing an unsaturated carboxylic acid or the like to the rubbery polymer may be mentioned.

[0015] The content of the rubbery aggregate in the polymer molding material of the present invention is 1 to 30% by weight, preferably 5 to 20% by weight. If it is less than 1% by weight,
If the effect of improving the impact resistance is not sufficiently recognized, and if the content exceeds 30% by weight, the excellent properties of the blend of the polyphenylene sulfide resin and the polyamide resin will not be sufficiently exhibited.

The epoxy resin used in the present invention contains one or two or more epoxy groups in a molecule, and may be a liquid or solid epoxy resin.
For example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane,
4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5
Glycidyl ethers of bisphenols such as tetrakis (4-hydroxyphenyl) hexane, halogenated bisphenols instead of bisphenols, glycidyl ethers such as diglycidyl ether of butanediol, and glycidyl esters such as glycidyl phthalate;
Glycidyl epoxy resins such as glycidylamines such as N-glycidylaniline, linear systems such as epoxidized polyolefins and epoxidized soybean oils, and cyclic non-glycidyl epoxy resins such as vinylcyclohexene dioxide and dicyclopentadiene dioxide. Is exemplified. Particularly preferably, a bisphenol-glycidyl ether-based glycidyl epoxy resin is used.

A novolak type epoxy resin may be used as the epoxy resin. The novolak type epoxy resin contains two or more epoxy groups in a molecule and is usually obtained by reacting a novolak type phenol resin with epichlorohydrin.

The content of the epoxy resin in the polymer molding material of the present invention is 0.5 to 5% by weight, preferably 1 to 5% by weight.
３3% by weight. If it is less than 0.5% by weight, the compatibility between the polyphenylene sulfide resin and the polyamide resin becomes insufficient, and the mechanical strength decreases. If the content exceeds 5% by weight, excellent properties as a blend of a polyphenylene sulfide resin and a polyamide resin are difficult to be exhibited, and the mechanical strength is reduced.

The polymer molding material of the present invention includes glass fiber, potassium titanate fiber, metal fiber, ceramic fiber, calcium carbonate, calcium silicate, magnesium silicate, calcium sulfate as long as the effects of the present invention are not impaired. , Barium sulfate, iron oxide, graphite, carbon black,
Including reinforcing fillers such as mica, asbestos, ceramic, metal flakes, glass beads or glass powder,
It may contain conventional auxiliary components such as nucleating agents, pigments, dyes, plasticizers, release agents, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers, foaming agents, flame retardants, coupling agents and the like. .

The polymer molding material of the present invention comprises a polyphenylene sulfide resin, a polyamide resin, a rubbery polymer,
It can be obtained by melt-blending an epoxy resin. The melting temperature in this case may be any temperature at which these components are melted, and is generally 270 ° C or higher, preferably 280 ° C to 300 ° C. At the time of this melt blending, the above-mentioned reinforcing filler and auxiliary components can be added as necessary. The polymer molding material of the present invention can be usually handled in the form of pellets.

The polymer molding material of the present invention has both the properties of both polyphenylene sulfide resin and polyamide resin, and has excellent impact resistance and elongation characteristics by containing a rubbery polymer and an epoxy resin. It shows.

The molded article of the present invention is molded from the above-mentioned polymer molding material of the present invention. By melting and molding the above-mentioned polymer molding material of the present invention, the molded article of various shapes can be formed. Goods. As a molding method, a conventionally known heat molding method can be used, and examples thereof include extrusion molding, injection molding, blow molding, and calendar molding. Examples of the molded product include various shapes such as a film shape and a container shape.

[0023]

The present invention will be described below in more detail with reference to examples and comparative examples. The present invention is not limited by these examples.

After mixing the components in the mixing ratio shown in Table 1, the mixture was supplied to a twin-screw extruder (KTX 46, Kobe Steel Ltd.) to obtain a pellet composition. The obtained pellet-shaped composition was injection molded to prepare a test piece. Table 1
The materials used in each of the examples and comparative examples shown below are as follows. In addition, the compounding ratio shown in Table 1 is shown by weight%.

Polyphenylene sulfide resin; product name "Ryton 2120-60" manufactured by Toray Industries, Ltd. Polyamide resin; product name "Amilan CM1017" manufactured by Toray Co., Ltd. MAH-EPR; maleic anhydride-modified EPR, Mitsui Chemicals, Inc. Company name, “Tuffmer MP0610” Bisphenol A type epoxy resin; product name, “Epototo; YD-014” manufactured by Toto Kasei Co., Ltd. The mechanical strength was measured according to the following criteria. Tensile strength, tensile elongation: JIS K 7113 Flexural strength: JIS K 7171 Notched Izod impact value: JIS K 7110

[0026]

[Table 1]

As is clear from the results shown in Table 1, Examples 1 to 3 according to the present invention show superior Izod impact value and tensile elongation as compared with Comparative Examples 1 to 3. Example 2
Each molded article sample of Comparative Example 3 was observed with a transmission electron microscope (TEM). A section was cut out in a direction perpendicular to the flow direction at the time of molding of each molded article sample, and the polyamide phase was dyed using a 10% by weight aqueous solution of phosphotungstic acid and observed with a TEM. 1 and 2 show a molded product of Example 2, and FIGS.
Indicates a molded product of Comparative Example 3. 1 and 3 show a magnification of 50,000, FIG. 2 shows a magnification of 25,000, and FIG. 4 shows a magnification of 30,000.

FIG. 5 is a diagram schematically showing FIG. 1, and FIG. 6 is a diagram schematically showing FIG. 1 and 5
As shown in the figure, in the molded article of Example 2, a polyamide (PA6) layer exists around MAH-EPR which is a rubbery polymer, and a rubbery polymer is contained in a polyphenylene sulfide (PPS) resin matrix. And that the polyamide resin is uniformly dispersed. On the other hand, as shown in FIG. 3 and FIG. 6, in the molded article of Comparative Example 3, the polyamide (PA6) resin
It can be seen that it is scattered on the surface of (H-EPR) particles and in the polyphenylene sulfide (PPS) resin and has a different aspect from the molded article of Example 2 according to the present invention.

As described above, according to the present invention, the presence of the polyamide on the surface of the rubbery polymer particles
It is thought that the impact resistance was improved, and the elongation properties were further improved.

[0030]

According to the present invention, a polymer molding material having good compatibility between polyphenylene sulfide resin and polyamide resin, excellent in impact resistance and elongation characteristics, and a molded article using the same can be obtained.

[Brief description of the drawings]

FIG. 1 is a transmission electron micrograph showing a cross section of a molded article of an example according to the present invention.

FIG. 2 is a transmission electron micrograph showing a cross section of a molded article of an example according to the present invention.

FIG. 3 is a transmission electron micrograph showing a cross section of a molded article of a comparative example.

FIG. 4 is a transmission electron micrograph showing a cross section of a molded article of a comparative example.

FIG. 5 is a diagram schematically showing a photograph of FIG. 1;

FIG. 6 is a diagram schematically showing the photograph of FIG. 3;

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Claims (3)

[Claims] 1. A polymer molding material obtained by mixing a polyphenylene sulfide resin and a polyamide resin, wherein 1 to 30% by weight of a rubbery polymer modified with an unsaturated carboxylic acid or an anhydride thereof or a derivative thereof, A polymer molding material containing 0.5 to 5% by weight of a resin. 2. The rubbery polymer is a maleic acid-modified rubbery polymer, and the epoxy resin is a bisphenol-
The polymer molding material according to claim 1, wherein the material is a glycidyl ether-based glycidyl epoxy resin. 3. A molded article formed from the polymer molding material according to claim 1 or 2.