JPH1149952A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which is greatly improved in impact resistance as well as molding character sticks such as moldability, esp. mold reliability, deposits on the mold surface and the like, and excellent in various physical properties like other mechanical properties by blending a polyarylene sulfide resin, an olefinic graft copolymer and an ethylene-α-olefin copolymer in a specific ratio. SOLUTION: With 100 pts.wt. of a polyarylene sulfide resin are blended 0.5-50 pts.wt. of a graft copolymer prepd. by chemically bonding, through a branching or a crosslinking structure, a (co) polymer composed of a repeating unit described by formula I (wherein R is H or lower alkyl; and X is-COOCH3 ,- COOC2 H5 ,-COOC4 H9 ,-COOCH2 CH(C2 H5 )C4 H9 , formula II or-CN) to an olefinic copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsatd. acid, and 0.5-30 pts.wt. of a copolymer of ethylene and an α-olefin with 5C or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition. More specifically, the present invention relates to a polyarylene sulfide resin composition having excellent impact resistance, heat resistance, and moldability.

[0002]

2. Description of the Related Art Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin has high heat resistance, mechanical properties, and chemical resistance. Electrical properties, dimensional stability and flame retardancy,
Widely used for electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials, etc. However, PAS resins have a fundamental drawback that they have poor toughness and are brittle, and their mechanical properties such as impact resistance are insufficient. As a conventional method for solving this problem, it is known to mix various elastomers. In particular, olefin copolymers containing glycidyl esters of α-olefins and α, β-unsaturated acids as main components are disclosed in JP-A-58-154757.
As shown in JP-A-59-152953 and JP-A-59-189166, the impact resistance is improved due to the excellent compatibility with the PAS resin. However, a composition in which a PAS resin is blended with an olefin-based copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated acid as a main component has a release resistance when the molded article is taken out of the mold at the time of molding. There is a problem that continuous molding cannot be performed because the force is remarkably increased and mold release failure occurs. As a method of improving the release failure, a method of adding a release agent is generally known, but this method has insufficient effect of improving the release property.
On the other hand, JP-A-1-306467 discloses a composition in which an olefin copolymer is added as a third component in order to improve moldability, but the olefin copolymer described in JP-A-1-306467 is disclosed. In the coalescence, there are many mold deposits during molding,
The complicated work of cleaning the mold was required. In view of the above problems, the present invention dramatically improves the impact resistance, and the moldability, particularly the mold release property, the molding processing problem such as the adhesion of a mold, and the other physical properties such as mechanical properties. Is intended to provide an excellent PAS resin composition.

[0003]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, the combined use of a specific olefin-based copolymer with PAS resin has dramatically improved the impact resistance and heat resistance. The present invention has been found to have improved properties and to have excellent physical properties such as moldability, mechanical properties, and heat resistance, and have completed the present invention. That is, the present invention relates to (A) 100 parts by weight of a polyarylene sulfide resin, (B)
An olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid contains one or more of a polymer or a copolymer composed of a repeating unit represented by the following general formula (1). 0.5 to 50 parts by weight of graft copolymer chemically bonded in a branched or crosslinked structure

[0004]

Embedded image

(Where R is hydrogen or a lower alkyl group, X
Is -COOCH ₃ , -COOC ₂ H ₅ , -COOC ₄ H ₉ , -COOCH ₂ CH (C ₂ H ₅ ) C ₄ H
₉ ,

[0006]

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(C) represents one or more groups selected from the group consisting of -CN) (C) Polyarylene prepared by mixing 0.5 to 30 parts by weight of an olefin copolymer of ethylene and an α-olefin having 5 or more carbon atoms The present invention relates to a sulfide resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The constituents of the present invention will be described in detail below. PAS as the component (A) used in the present invention
The resin is mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit. Examples of the arylene group include a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, a p, p′-diphenylene sulfone group, a p, p′-biphenylene group, and p, p′-.
A diphenylene ether group, a p, p'-diphenylenecarbonyl group, a naphthalene group and the like can be used. In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, in addition to a polymer using the same repeating unit, that is, a homopolymer, from the viewpoint of processability of the composition,
Copolymers containing heterogeneous repeat units may be preferred. As the homopolymer, one having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group is particularly preferably used. or,
As the copolymer, two or more different combinations among the above-mentioned arylene sulfide groups composed of an arylene group can be used. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. Among them, the p-phenylene sulfide group accounts for 70 mol% or more, preferably 80 mol%.
Those containing the above are suitable in terms of physical properties such as heat resistance, moldability, and mechanical properties. Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly containing a bifunctional halogen aromatic compound can be particularly preferably used. In addition to the PAS resin having a structure, a polymer having a partially branched or cross-linked structure formed by using a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents when polycondensing is used. Alternatively, a polymer obtained by heating a low molecular weight linear structure polymer at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking and improving the moldability can be used.
Further, the PAS resin of the component (A) is a linear PAS (310
(Viscosity at 10 ° C / shear speed 1200sec- ¹ )
And a part thereof (1 to 30% by weight, preferably 2 to 30% by weight).
25% by weight), and a mixed system with a branched or crosslinked PAS resin having a relatively high viscosity (300 to 3000 Pa · s, preferably 500 to 2000 Pa · s) is also suitable. The PAS resin used in the present invention is:
After the polymerization, it is preferable to carry out acid washing, hot water washing, and organic solvent washing (or a combination thereof) to remove and purify by-product impurities and the like.

Next, the graft (B) used in the present invention is α-
One or two or more kinds of a polymer or a copolymer composed of a repeating unit represented by the following general formula (1) are branched into an olefin-based copolymer composed of an olefin and a glycidyl ester of an α, β-unsaturated acid. It is a graft copolymer chemically bonded in a crosslinked structure.

[0010]

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(Where R is hydrogen or a lower alkyl group, X
Is -COOCH ₃ , -COOC ₂ H ₅ , -COOC ₄ H ₉ , -COOCH ₂ CH (C ₂ H ₅ ) C ₄ H
₉ ,

[0012]

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Wherein one or more groups selected from —CN are represented by the following formula: wherein α is one of monomers of an olefin-based copolymer composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid. -Examples of the olefin include ethylene, propylene, and butylene, and ethylene is preferable. The glycidyl ester of α, β-unsaturated acid, which is another monomer, is represented by the general formula (2)

[0014]

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Wherein R ₁ represents a hydrogen atom or a lower alkyl group, such as glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate; and glycidyl methacrylate Is preferred. An olefin copolymer comprising an α-olefin (eg, ethylene) and a glycidyl ester of an α, β-unsaturated acid can be obtained by copolymerization by a generally well-known radical polymerization reaction. The ratio of the α-olefin to the glycidyl ester of the α, β-unsaturated acid is from 70 to 70%.
99% by weight, glycidyl ester of α, β-unsaturated acid 1
30% by weight is preferred. The component (B) of the present invention may be added to the above-mentioned olefin-based copolymer to further improve the impact resistance and heat resistance of a polymer or a copolymer comprising a repeating unit represented by the above general formula (1). Is a graft copolymer in which one or two or more of the above are chemically bonded in a branched or crosslinked structure. As a polymer or copolymer segment to be graft-polymerized as a branched or crosslinked chain, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyphenyl acrylate, polybutyl methacrylate, poly (2-ethylhexyl acrylate), Polystyrene, polyacrylonitrile, polyacrylonitrile-styrene copolymer,
A copolymer of poly (methyl methacrylate) and poly (butyl acrylate), a copolymer of poly (butyl acrylate) and polystyrene, and the like can be given. Preferably, X in the general formula (1) is one or two or more groups selected from —COOCH ₃ and —COOC ₄ H ₉ , and particularly a copolymer of methyl methacrylate and butyl acrylate Is preferred. Also, the branching or crosslinking reaction of these polymers or copolymers can be easily prepared by a radical reaction. For example, in the presence of a glycidyl group-containing olefin-based copolymer, a vinyl monomer of a polymer or a copolymer constituting at least one kind of a branched or crosslinked structure and a specific radical (co) polymerized organic peroxide (peroxide A vinyl compound having a group) to form a peroxide group-containing copolymer, which is kneaded by heating and chemically bonding the two polymers by the reaction of the peroxide group in the vinyl copolymer. A graft copolymer is prepared.
The branched or crosslinked chain is an olefin-based copolymer composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid.
It is preferable that 10 to 100 parts by weight is branched or crosslinked with respect to 00 parts by weight. The amount of the graft copolymer (B) to be used is 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyarylene sulfide resin (A). If the amount of the component (B) is too small, the effect of improving the impact resistance cannot be obtained. If the amount is too large, the heat deformation temperature is lowered and mechanical properties such as rigidity are unfavorably deteriorated.

In the present invention, the graft copolymer (B), ethylene and carbon number are improved in order to improve the desired moldability such as improvement of impact resistance, heat resistance, mold releasability and reduction of adhesion to a mold. Olefin copolymer with 5 or more α-olefins
(C) must be used together. When such an olefin copolymer of the component (C) ethylene and an α-olefin having 5 or more carbon atoms is not blended, the mold release resistance at the time of molding is remarkably increased, resulting in poor mold release. In addition, when an α-olefin having 4 or less carbon atoms is used as a component of the olefin copolymer of the component (C), the olefin copolymer undergoes significant thermal degradation,
A lot of substances adhere to the mold during molding, and complicated mold cleaning work is required. On the other hand, ethylene and α having 5 or more carbon atoms
-Polyarylene sulfide resin composition with good impact resistance and heat resistance, good mold releasability and low adhesion to molds during molding by using olefin copolymer (C) together with olefin. Things can be provided. Specific examples of the olefin copolymer (C) of ethylene and an α-olefin having 5 or more carbon atoms used in the present invention include ethylene-
Penten copolymer, ethylene-hexene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, ethylene-nonene copolymer, ethylene-decene copolymer, and the like, preferably ethylene-octene copolymer It is an olefin copolymer of ethylene such as a polymer and an α-olefin having 6 to 12 carbon atoms. These copolymers are usually prepared by well-known radical polymerization. These copolymers are preferably polymerized using a metaceron catalyst as a polymerization catalyst in order to obtain a uniform copolymer having a narrow molecular weight distribution. The compounding amount of the olefin copolymer (C) of ethylene and an α-olefin having 5 or more carbon atoms is suitably 0.5 to 30 parts by weight, preferably 1 to 100 parts by weight of the polyarylene sulfide resin (A). ~ 20 parts by weight. When the amount is less than 0.5 part by weight, the releasability improving effect is insufficient, and when the amount is more than 30 parts by weight, the amount of deposits on the mold during molding (mold deposit) is undesirably increased.

The resin composition of the present invention may contain an inorganic filler for improving performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warpage), and electrical properties. A fibrous, powdery or plate-like filler is used depending on the purpose. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum,
Inorganic fibrous materials such as fibrous materials of metals such as titanium, copper, and brass are exemplified. Particularly typical fibrous fillers are glass fibers or carbon fibers. In addition, a high melting point organic fiber material such as polyamide, fluororesin, and acrylic resin can also be used. On the other hand, as the particulate filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin,
Silicates such as talc, clay, diatomaceous earth, wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, calcium sulfate, sulfuric acid Sulfates of metals such as barium, other silicon carbide, silicon nitride, boron nitride, and various metal powders. Examples of the plate-like filler include mica, glass flake, and various metal foils. These inorganic fillers can be used alone or in combination of two or more. When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary.
This example is a functional compound such as an epoxy compound, an isocyanate compound, a silane compound and a titanate compound. These compounds may be used after being subjected to a surface treatment or a convergence treatment in advance, or may be added simultaneously with the preparation of the material. The amount of the inorganic filler used is P of component (A)
10 to 300 parts by weight per 100 parts by weight of AS resin. If the amount is less than 10 parts by weight, the mechanical strength is slightly inferior. If the amount is too large, the molding operation becomes difficult, and the mechanical strength of the molded article is also a problem. coming out.

Further, a silane compound can be added to the resin composition of the present invention for the purpose of improving burrs and the like as long as the effects of the present invention are not impaired. Examples of the silane compound include various types such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, and mercapto silane, for example, vinyl trichlorosilane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane , Γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like, but are not limited thereto.

In the resin composition of the present invention, it is possible to use a small amount of other thermoplastic resin in addition to the above-mentioned components in accordance with the purpose. The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate and aromatic dicarboxylic acid and diol or oxycarboxylic acid, polyamide, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polysulfone, polyether sulfone, polyetherimide , Polyether ketone, fluorine resin and the like. These thermoplastic resins can be used as a mixture of two or more kinds. Furthermore,
As the molded article composition used in the present invention, known substances generally added to a thermoplastic resin, that is, stabilizers such as antioxidants, flame retardants, coloring agents such as dyes and pigments, lubricants and crystallization accelerators , A nucleating agent and the like can be appropriately added according to required performance.

[0020] The resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. Generally, necessary components are mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form molding pellets. The resin temperature during the melt-kneading is preferably 360 ° C. or lower in order to prevent thermal deterioration of the olefin copolymer. It is also a preferable method to melt-extrude a resin component and add and mix an inorganic component such as glass fiber during the extrusion. The material pellets obtained in this manner can be molded using a generally known thermoplastic resin molding method such as injection molding, extrusion molding, vacuum molding, compression molding, etc., but the most preferred is injection molding. .

[0021]

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, each (A), (B), (C),
Specific substances of (D) are as follows. (A) Polyphenylene sulfide (PPS) resin Fortron KPS manufactured by Kureha Chemical Industry Co., Ltd. (B) Graft copolymer B-1; An ethylene / glycidyl methacrylate copolymer was grafted with a methyl methacrylate / butyl acrylate copolymer. Copolymer B-2: Copolymer of ethylene / glycidyl methacrylate copolymer with methyl methacrylate B-3; Copolymer of ethylene / glycidyl methacrylate copolymer with styrene / acrylonitrile copolymer B '-1; ethylene / glycidyl methacrylate copolymer (C) olefin copolymer C-1; ethylene-octene copolymer C-2; ethylene-heptene copolymer C'-1; ethylene-propylene copolymer C '-2; Ethylene-ethyl acrylate copolymer (D) glass fiber Examples and Comparative Examples Evaluation method of evaluation is as follows. The notch side impact value was measured according to Izod impact strength ASTM D-256. Moldability (Amount of Deposits on Mold) Molded products were continuously molded for 8 hours using an injection molding machine under the following conditions, and the amount of deposits on the mold was visually determined. Injection molding machine: Sumitomo SG25 Cylinder temperature: 310 ° C Injection time: 1 second Cooling time: 15 seconds Mold temperature: 80 ° C Visual judgment level A The amount of adhesion is 0% or more and less than 5% of the projected area of the mold cavity. 5% or more and less than 20% of the projected area of the mold cavity. C Adhesion amount is 20% or more of the projected area of the mold cavity. Moldability (Release resistance of molded pieces). Then, the force when the molded piece was extruded from the mold was measured, and the measured value was defined as the release resistance value. Release resistance measuring machine: MOBAC cavity pressure sensor Injection molding machine: Nikko J75SSII-A Cylinder temperature: 310 ° C Injection time: 12 seconds Cooling time: 45 seconds Mold temperature: 140 ° C Examples 1 to 7 and Comparative Examples 1 to 1 8 The components (A), (B), (C) and (D) shown in Tables 1-2 were mixed with a Henschel mixer for 5 minutes, and the mixture was heated at a cylinder temperature of 310.
The mixture was melt-kneaded at 350 ° C. in a twin-screw extruder at a temperature of 350 ° C. to form pellets of the resin composition. Next, ASTM D-256 using an injection molding machine at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C.
An Izod impact test piece was molded according to the method described in the above and measured. The results are shown in Tables 1 and 2.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

According to the present invention, the problems of impact resistance and moldability, especially moldability, moldability such as adhesion to a mold, etc. are drastically improved, and various other properties such as mechanical properties are improved. P with excellent physical properties
An AS resin composition can be provided.

Claims (3)

[Claims] (A) Polyarylene sulfide resin 100
(B) a polymer or copolymer composed of a repeating unit represented by the following general formula (1) and (B) an olefin-based copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid; 0.5 to 50 parts by weight of a graft copolymer in which one or two or more kinds of coalesced are chemically bonded in a branched or cross-linked structure. (Where R is hydrogen or a lower alkyl group, X is -COOCH ₃ ,
-COOC ₂ H ₅ , -COOC ₄ H ₉ , -COOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ , (C) a polyarylene sulfide resin composition comprising 0.5 to 30 parts by weight of an olefin copolymer of ethylene and an α-olefin having 5 or more carbon atoms. Stuff. 2. The graft copolymer (B) comprises an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid comprising a repeating unit represented by the following general formula (1). 2. The polyarylene sulfide resin composition according to claim 1, wherein one or more of the above polymers or copolymers are graft copolymers in which they are chemically bonded in a branched or crosslinked structure. Embedded image (Where R is hydrogen or a lower alkyl group, X is -COOCH ₃ ,
-Indicates one or more groups selected from -COOC ₄ H ₉ ) 3. The polyarylene sulfide resin composition according to claim 1, wherein the olefin copolymer (C) is an olefin copolymer of ethylene and an α-olefin having 6 to 12 carbon atoms.