JPH10279802A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyarylene sulfide resin compsn. which is excellent in impact strength, heat resistance, and moldability by compounding a polyarylene sulfide resin with an olefin copolymer produced mainly from an α-olefin and a glycidyl ester of an α,β-unsatd. acid, a phenolic antioxidant, and a thioether- based antioxidant. SOLUTION: 100 pts.wt. polyphenylene sulfide resin mixture mainly comprising a linear polyarylene sulfide resin having a viscosity (310 deg.C, a shear rate of 1,200 sec<-1> ) of 10-300 Pa.s and contg., as the minor component (1-30 wt.%), a branched or crosslinked polyphenylene sulfide resin having a relatively high viscosity (300-3,000 Pa.s) is compounded with 0.5-50 pts.wt. olefin copolymer produced mainly from an α-olefin and a glycidyl ester of an α,β-unsatd. acid, 0.05-5 pts.wt. phenolic antioxidant, and 0.05-5 pts.wt. thioether-based antioxidant.

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, JP-A-59-189166, JP-A-1-306467 and the like, PA
Due to the excellent compatibility with the S resin, an improvement in impact resistance is observed. However, since the processing temperature of the PAS resin is 300 ° C. or higher, the components of the olefin-based copolymer are thermally degraded, so that not only a sufficient impact resistance improvement effect cannot be obtained, but also gas is decomposed during molding to generate gas. Therefore, there is a problem that the moldability is significantly reduced. On the other hand, as a method for improving the heat resistance, a method of adding a hindered phenol-based stabilizer has been proposed as in JP-A-3-68656. However, even with this technique, a PAS resin composition having sufficient impact resistance, heat resistance, and moldability has not been obtained. In view of such a problem, the present invention provides a P which has a remarkably improved impact resistance and heat resistance, and is excellent in various molding workability and mechanical properties.
It is intended to provide an AS resin composition.

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by combining a specific olefin copolymer and two specific antioxidants with PAS resin, The inventors have found that the impact resistance and heat resistance are remarkably improved, and that they also have excellent physical properties such as other moldability, mechanical properties, and heat resistance, and have completed the present invention. That is, the present invention relates to (A) 100 to 100 parts by weight of a polyarylene sulfide resin, and (B) 0.5 to 50 parts by weight of an olefin-based copolymer mainly containing a glycidyl ester of an α-olefin and an α, β-unsaturated acid. , (C) phenolic antioxidant 0.05 to 5 parts by weight, (D) thioether antioxidant 0.05
The present invention relates to a polyarylene sulfide resin composition containing up to 5 parts by weight.

[0004]

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 olefin copolymer used in the present invention
(B) is an olefin-based copolymer containing α-olefin and a glycidyl ester of α, β-unsaturated acid as main components. As one component of the copolymerized portion, α-olefin, Ethylene, propylene, butylene and the like can be mentioned, and ethylene is preferable. Further, α, β which are other components of the olefin-based copolymer (B)
The glycidyl ester of an unsaturated acid is represented by the general formula (2)

[0006]

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(Wherein R ₁ represents a hydrogen atom or a lower alkyl group), such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc., preferably methacrylic acid. Glycidyl esters. α
A glycidyl ester of an olefin (eg, ethylene) and an α, β-unsaturated acid can be obtained by copolymerization by a generally well-known radical polymerization reaction. The olefin copolymer (B) is an α-olefin 100
The glycidyl ester of the unsaturated acid is 1 to 1 part by weight.
It is preferred to use 40 parts by weight for copolymerization. Further, the olefin copolymer (B) may be used to improve the impact resistance and heat resistance by using one or more of polymers or copolymers composed of repeating units represented by the following general formula (1). It is preferable that the graft copolymer is a chemically bonded branched or crosslinked structure.

[0008]

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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 ,

[0010]

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The polymer or copolymer segment to be graft-polymerized as a branched or crosslinked chain includes acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate. And butyl acrylate, butyl methacrylate, acrylonitrile, and styrene. Preferred are a methacrylic acid polymer, a copolymer of acrylonitrile and styrene, a copolymer of methyl methacrylate and butyl acrylate, and the like, and particularly preferred is a copolymer of methyl methacrylate and butyl acrylate. These polymers or copolymers are prepared by commonly known radical polymerization. Also, the branching or crosslinking reaction of these polymers or copolymers can be easily prepared by a radical reaction. For example, these polymers or copolymers generate free radicals with peroxides and the like, α
The desired olefin-based copolymer (B) can be prepared by melt-kneading a copolymer of an olefin and a glycidyl ester of an α, β-unsaturated acid. A branched or cross-linked chain
It is preferred that 10 to 100 parts by weight be branched or crosslinked with respect to 100 parts by weight of the glycidyl ester copolymer of an α-olefin and an α, β-unsaturated acid. Olefin copolymer
(B) is used in an amount of 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the polyarylene sulfide resin (A).

In the present invention, in order to obtain the desired impact resistance, heat resistance and moldability, a phenolic antioxidant (C)
It is essential to use a thioether-based antioxidant (D) together with a thioether-based antioxidant. Since the process temperature of the polyarylene sulfide resin is about 300 ° C. or higher, the olefin copolymer (B) compounded for improving toughness is significantly deteriorated by heat. For this reason, there are many mold deposits (mold deposits) during molding, and a complicated process of cleaning the mold is required. In order to suppress this thermal deterioration, it is sufficient to add phenol-based antioxidant (C), thioether-based antioxidant (D), or other phosphorus-based stabilizers, amine-based stabilizers, etc. each alone. The effects of improving moldability, impact resistance, and heat resistance were not obtained, and a process of cleaning the mold to remove the mold deposit was required. In contrast, by using a phenolic antioxidant (C) and a thioether antioxidant (D) in combination, the thermal deterioration of the olefin copolymer (B) is sufficiently suppressed, and excellent moldability and excellent moldability are obtained. The present inventors have found that a polyarylene sulfide resin composition having impact resistance and heat resistance can be obtained, and generation of mold deposit can be considerably suppressed, and the present invention has been completed. The present invention expresses the intended effect by a combination of two specific compounds, a phenolic antioxidant (C) and a thioether-based antioxidant (D). The object of the present invention cannot be achieved by using the agent (C) in combination with the phosphorus-based antioxidant (D).

The phenolic antioxidant used in the present invention
(C) is a compound having one or more alkylphenol groups in its molecular structure. Specific examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, stearyl- (3,5-di-methyl-4-hydroxybenzyl) thioglycolate, and stearyl-β- ( 4-
Hydroxy-3,5-di-tert-butylphenyl) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, distearyl (4-hydroxy-3-methyl-5-tert-butyl) ) Benzyl malonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1
-Methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy-3-tert-butylbutylphenyl) butyric acid] glycol ester,
4'-butylidenebis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-
5-tert-butylphenyl) butane, 1,3,5-tris (3,
5-di-tert-butyl-4-hydroxybenzyl) -2,4,
6-trimethylbenzene, tetrakis [methylene-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert-butyl) ) Phenoxy-1,3,5-triazine, 4,4′-thiobis (6-tert-butyl-m-cresol), triethyleneglycol-bis [3- (3-
Tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexyldiol-bis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis-octylthio-6- (4
-Hydroxy-3,5-di-tert-butylanilino) -1,3,
5-triazine, 2,2-thio-diethylenebis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5 Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, Tris- (3,5-di-third
Butyl-4-hydroxybenzyl) isocyanurate,
Isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; and 2,4-bis [(octylthio) methyl] -o-cresol. These can be used alone or in combination of two or more. The compounding amount of the phenolic antioxidant (C) is 0.05% with respect to 100 parts by weight of the polyarylene sulfide resin.
-5 parts by weight, preferably 0.1-3 parts by weight, is suitable.
If less than 0.05 part by weight, the heat resistance improving effect is insufficient,
If the amount is more than 5 parts by weight, the mold deposit of the mold at the time of molding becomes extremely large, which is not preferable.

Next, the thioether antioxidant (D) used in the present invention is a compound having at least one thioether bond in the molecular structure. Examples of thioether-based antioxidants include tetrakis [methylene-3-
(Dodecylthio) propionate] methane, dilauryl-3,3'-thiodipropionate, distearyl-3,3'-
And thiodipropionate. These may be used alone or in combination of two or more. The compounding amount of the thioether-based antioxidant (D) is 0.05 to 5 parts by weight, preferably 100 parts by weight of the polyarylene sulfide resin.
0.1 to 3 parts by weight is suitable. If the amount is less than 0.05 part by weight, the effect of improving heat resistance is insufficient. If the amount is more than 5 parts by weight, the mold deposit of the mold during molding 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.

The resin composition of the present invention may contain a silane compound 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.

The resin composition of the present invention may optionally contain a small amount of another thermoplastic resin in addition to the above components, depending on 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, a known substance generally added to a thermoplastic resin, that is, a flame retardant, a coloring agent such as a dye / pigment, a lubricant, a crystallization accelerator, a crystal nucleating agent, and the like are also required performance. Can be added as appropriate.

The resin composition of the present invention can be prepared by equipment and methods 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. .

[0019]

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) and (E) are as follows. (A) Polyphenylene sulfide (PPS) resin Fortron KPS manufactured by Kureha Chemical Industry Co., Ltd. (B) Olefin polymer B-1; Ethylene / glycidyl methacrylate copolymer B-2; Ethylene / glycidyl methacrylate copolymer and styrene / Acrylonitrile copolymer grafted copolymer B-3; Ethylene / glycidyl methacrylate copolymer grafted with methyl methacrylate / butyl acrylate copolymer B'-1; Ethylene / ethyl acrylate (C ) Phenolic antioxidant C-1; tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane C-2; triethylene glycol-bis [3- (3- Third
Butyl-5-methyl-4-hydroxyphenyl) propionate] (D) thioether antioxidant D-1; tetrakis [methylene-3- (dodecylthio) propionate] methane D-2; dilauryl-3,3'-thiodipro Pionate (E) Phosphorus antioxidant E-1; Tris (2,4-di-tert-butylphenyl) phosphite The evaluation methods evaluated in Examples and Comparative Examples are as follows. The notch side impact value was measured according to Izod impact strength ASTM D-256. Thermostability (TGA thermogravimetric change) Using a thermogravimetric analyzer (TGA), the weight change (%) at 300 ° C when the temperature was raised from 200 ° C to 300 ° C at 10 ° C / min was measured. The sample was prepared by mixing each pellet with 100
It was measured using mg. Moldability (Amount of Deposits on Mold) A specific molded product was 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 Adhesion amount is small B Adhesion amount is moderate between level A and level C Examples 1 to 9 and Comparative Examples 1 to 9 The components (A), (B), (C), (D) and (E) shown in Tables 1 and 2 were mixed with a Henschel mixer for 5 minutes. The mixture was melt-kneaded at a resin temperature of 350 ° C. in a twin-screw extruder having a cylinder temperature of 310 ° C. to form a resin composition pellet. Next, ASTM D at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C using an injection molding machine.
Izod impact test specimens were molded and measured according to -256. The results are shown in Tables 1 and 2.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

According to the present invention, a polyarylene sulfide resin composition having excellent impact resistance, heat resistance and moldability can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23:26)

Claims (4)

[Claims] (A) Polyarylene sulfide resin 100
(B) 0.5 to 50 parts by weight of an olefin copolymer containing a glycidyl ester of an α-olefin and an α, β-unsaturated acid as a main component, and (C) 0.05 to 5 parts by weight of a phenolic antioxidant. (D) 0.05 to 5 parts by weight of a thioether-based antioxidant. 2. The olefin copolymer (B) is composed of 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). The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide resin composition is a graft copolymer obtained by chemically bonding one or more of the obtained polymers or copolymers in a branched or crosslinked structure. 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 , -Indicates one or more groups selected from -CN) 3. An olefin copolymer comprising (B) an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid, wherein the olefin copolymer comprises acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate. 3. A graft copolymer obtained by polymerizing or copolymerizing one or more selected from butyl acrylate, butyl methacrylate, acrylonitrile and styrene, in a branched or cross-linked structure. The polyarylene sulfide resin composition according to the above. 4. The polyarylene sulfide resin composition according to claim 3, wherein (B) the olefin polymer is a graft copolymer obtained by chemically bonding a copolymer of methyl methacrylate and butyl acrylate as a branched chain. Stuff.