WO2005054369A1

WO2005054369A1 - Polyarylene sulfide resin composition

Info

Publication number: WO2005054369A1
Application number: PCT/JP2004/017044
Authority: WO
Inventors: Yoshihito Fukazawa
Original assignee: Polyplastics Co., Ltd.
Priority date: 2003-12-03
Filing date: 2004-11-17
Publication date: 2005-06-16
Also published as: JP2005162886A

Abstract

Disclosed is a polyarylene sulfide resin composition which is greatly improved in impact resistance characteristics at low temperatures without deteriorating injection moldability. The polyarylene sulfide resin composition is obtained by blending (A) 100 parts by weight of a polyarylene sulfide resin, (B) 1-30 parts by weight of an olefin copolymer mainly containing an α-olefin and a glycidyl ester of an α,β-unsaturated acid, and (C) 10-50 parts by weight of an olefin copolymer between an ethylene and an α-olefin having 5 or more carbon atoms, which copolymer has a melt index measured according to ASTM D-1238 of not more than 5 g/10 min and a specific gravity of not more than 0.9.

Description

Specification

Polyarylene sulfide resin composition

Technical field

The present invention relates to a polyarylene sulfide resin composition having excellent low-temperature impact resistance and suitable for injection molding.

Background art

[0002] Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, Because of its flame retardancy, it is widely used in electrical and electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials, and the like. However, PAS resin has poor fundamental properties such as poor toughness and fragility, and insufficient mechanical properties such as impact resistance. As a conventional method to solve this problem, it is known to mix various elastomers! / In particular, an olefin copolymer containing α-olefin and a glycidyl ester of α, β unsaturated acid as main components has excellent compatibility with へ AS resin as shown in Patent Documents 13 to 13. Therefore, an improvement in impact resistance is observed. In recent years, however, the requirements for impact resistance of electrical and electronic equipment parts materials and automotive equipment parts materials have become stricter, and in particular, excellent impact resistance properties in low-temperature use environments have been increasing. The method described above has been insufficient in the effect of improving the impact resistance at low temperatures by the above-mentioned method.

[0003] On the other hand, for the purpose of further improving impact resistance, there has been proposed a method of blending an olefin copolymer of ethylene with an a-olefin having 5 or more carbon atoms (Patent Documents 417). These methods do not always provide sufficient impact resistance in a low-temperature use environment.

Patent Document 1: Japanese Patent Application Laid-Open No. 58-154757

Patent Document 2: JP-A-59-152953

Patent Document 3: JP-A-59-189166

Patent Document 4: Japanese Patent Publication No. 4 24388

Patent Document 5: JP-A-5-230370 Patent Document 6: JP-A-7-157660

Patent Document 7: JP-A-1149952

Disclosure of the invention

Problems to be solved by the invention

[0004] An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a PAS resin composition having improved impact resistance in a low-temperature use environment.

Means for solving the problem

[0005] The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the PAS resin was made of α-olefin and an olefin-based copolymer containing glycidyl esters of OC and β unsaturated acids as main components. The present inventors have found that the combined use of a specific ethylene one year-old olefin copolymer can significantly improve the impact resistance at low temperatures without impairing the injection moldability, and have completed the present invention.

[0006] That is, the present invention provides

(Α) 100 parts by weight of polyarylene sulfide resin,

(B) 1 to 30 parts by weight of an olefin polymer based on a olefin and a glycidyl ester of an (X, β unsaturated acid)

(C) 10-50 parts by weight of an olefin copolymer of ethylene and α-olefin having 5 or more carbon atoms having a melt index of 5 gZlO or less and a specific gravity of 0.9 or less according to ASTM D-1238.

And a polyarylene sulfide resin composition.

Detailed description of the invention

Hereinafter, the components of the present invention will be described in detail. The PAS resin as the component (ii) used in the present invention 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 ρ, ρ′-diphenylene sulfone group, and a ρ, ρ′-biphenylene group. Ρ, ρ′-diphenylene ether group, ρ, ρ′-diphenylenecarbol group, naphthalene group and the like can be used. In this case, the arylene sulfur also constitutes the above-mentioned arylene base. In addition to a polymer using the same repeating unit in the id group, that is, a homopolymer, a copolymer containing a different type of repeating unit may be preferable from the viewpoint of the processability of the composition and the! / ヽぅ point.

[0008] As the homopolymer, those having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group are particularly preferably used. As the copolymer, a combination of two or more different arylene sulfide groups among the above-mentioned arylene sulfide groups can be used. Among them, p-phenylene sulfide group and m-phenylene sulfide group are included. Combinations are particularly preferably used. Among them, those containing 70 mol% or more, preferably 80 mol% or more of p-phenylene sulfide group are suitable for the point force in terms of physical properties such as heat resistance, moldability, and mechanical properties.

[0009] Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound is particularly preferred. Although it can be used, in addition to PAS resin with a linear structure, when a condensation polymerization is carried out, a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents is used to partially form a branched structure. Alternatively, a polymer having a crosslinked structure can be used, or a low-molecular-weight linear polymer is heated at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking, thereby improving moldability. Can be used.

[0010] The PAS resin of the component (A) is mainly composed of the linear PAS (310 ° C * viscosity at a shear rate of 1200 sec- ¹ of 10 to 300 Pa's), and a part (1 Mixtures of 30% by weight, preferably 2 to 25% by weight) with a relatively high viscosity (300 to 3000 Pa's, preferably 500 to 2000 Pa's) branched or crosslinked PAS resin are also suitable.

[0011] Further, the PAS resin used in the present invention is preferably one which has been subjected to acid washing, hot water washing, and organic solvent washing (or a combination thereof) after polymerization to remove and remove by-product impurities and the like.ヽ.

Next, α-olefin as the component (B) and an olefin copolymer based on glycidyl ester of an a, j8-unsaturated acid used as the component (B) in the present invention are _a- olefin and _α , β-unsaturated. A copolymer with a glycidyl ester of a saturated acid, or a copolymer with a glycidyl ester of an α-olefin, an a, j8-unsaturated acid, or a compound copolymerizable therewith; One or two or more compounds can be used. In addition, A graft copolymer in which one or two or more polymers or copolymers are chemically bonded to the polymer in a branched or crosslinked structure can also be used.

Here, examples of the α-olefin include ethylene, propylene, and butylene, and ethylene is preferable. The glycidyl ester of _a , j8-unsaturated acid is preferably glycidyl methacrylate, which includes glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like.

[0014] A copolymer of one-year-old refine and a glycidyl ester of an ex, β unsaturated acid can be obtained by copolymerization by a well-known radical polymerization reaction. alpha-O-les fins and alpha, the ratio of the glycidyl ester of β-unsaturated acids, alpha-old Refuin 70- 99 by weight ^_0/0, a, ^j8- glycidyl ester 1 one 30% by weight preferred unsaturated acids It is.

[0015] The compounding amount of the component (B) is 1 to 30 parts by weight, preferably 3 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 impact resistance cannot be obtained. If the amount is too large, mechanical properties such as rigidity are impaired.

Next, in the present invention, as a component (C), an olefin copolymer of ethylene and a (X-year-old olefin) having 5 or more carbon atoms is blended as an essential component. Examples thereof include an ethylene-pentene copolymer, an ethylene-hexene copolymer, an ethylene heptene copolymer, an ethylene otaten copolymer, an ethylene nonene copolymer, an ethylene-decene copolymer, and the like. It is an olefin copolymer of ethylene such as a polymer and α-olefin having 6 to 12 carbon atoms.These copolymers are usually prepared by well-known radical polymerization.These copolymers have a narrow molecular weight distribution. For the purpose of obtaining a uniform copolymer, it is preferable to carry out polymerization using a metaceron catalyst as a polymerization catalyst.

One of the features of the present invention is that the component (C) has a melt index of 5 gZlO or less and a specific gravity of 0.9 or less, preferably 0.89 or less, as measured according to ASTM D-1238. Or 0.88 or less, that is, an orthoolefin copolymer of ethylene and α-olefin having 5 or more carbon atoms. When the melt index is larger than 5, and when the specific gravity is larger than 0.9, the effect of improving the low-temperature impact resistance aimed at by the present invention is hardly obtained. That is, when the melt index is greater than 5, the olefin copolymer is well dispersed in the PAS resin, and when the specific gravity is greater than 0.9, the olefin copolymer is soft. Because of their poor softness, none of them are effective in improving the impact resistance at low temperatures.

[0018] The component (C) is added in an amount of 10 to 50 parts by weight, preferably 20 to 40 parts by weight, per 100 parts by weight of the polyarylene sulfide resin (A). If the amount of the component (C) is too small, the effect of improving the impact resistance at low temperatures cannot be obtained. If the amount is too large, the mechanical properties such as rigidity are impaired, which is not preferable.

[0019] 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. For this purpose, 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, dinocone fiber, boron nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium, and copper. And inorganic fibrous materials such as fibrous materials of metals such as brass. Particularly typical fibrous fillers are glass fibers or carbon fibers. High melting point organic fiber materials such as polyamide, fluorine resin, and acrylic resin can also be used. On the other hand, powdered and granular fillers include silicates such as carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite, and oxides. Metal oxides such as iron, titanium oxide, zinc oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; calcium sulfates and metal sulfates such as barium sulfate; other silicon carbide, silicon nitride, boron nitride; Various metal powders are included. Further, examples of the plate-like filler include my strength, glass flakes, 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, a titanate compound, and the like. These compounds may be used in advance by applying a surface treatment or a convergence treatment, or may be added simultaneously with the preparation of the material. The amount of the inorganic filler used is 10-300 parts by weight per 100 parts by weight of the PAS resin (A) .If the amount is less than 10 parts by weight, the mechanical strength is slightly inferior. In addition, there is a problem with the mechanical strength of the molded product. [0020] In addition, the resin composition of the present invention may be blended with a silane conjugate 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 butyl silane, methacryloxy silane, epoxy silane, amino silane, and mercapto silane. Powers exemplified by silane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane and the like are not limited to these.

[0021] In addition, 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 dicarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate and diols or aromatic carboxylic acids such as aromatic polyesters, polyamides, polycarbonates, ABS, polyphenylene oxide, polyalkyl acrylates, polysulfones, polyethers Examples include sulfone, polyetherimide, polyetherketone, and fluorine resin. Also, these thermoplastic resins are used by mixing two or more kinds.

[0022] Further, as the molded article composition used in the present invention, known substances generally added to thermoplastic resin, that is, stabilizers such as antioxidants, flame retardants, coloring agents such as dyes and pigments, and lubricants An agent, a crystallization accelerator, a crystal nucleating agent, and the like can be appropriately added according to required performance.

[0023] 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 can be mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded into pellets for molding. The resin temperature during the melt-kneading is preferably 360 ° C. or lower in order to prevent thermal degradation of the olefin copolymer. It is also one of the preferable methods to melt-extrude the resin component and add and mix an inorganic component such as glass fiber during the extrusion. The material pellets obtained in this way can be molded using a generally known thermoplastic resin molding method such as injection molding, extrusion molding, vacuum molding, compression molding, etc. is there.

Example Next, the present invention will be concretely explained and explained with reference to practical examples and comparative examples, but the present invention is not described here. However, it is not limited to this. . In addition, each ((AA)), ((BB)), and ((CC)) used in the actual working example and the comparative example were concretely described. The physical substances are as follows. .

((AA)) Popolirifuee-renrensasarurufuidoido ((PPPPSS))

Wu Kureha emergence chemistry chemical engineering industrial industry ((Co. Ltd.)) made of steel ,, full Foo over Totoro Ron emissions KKPPSS ((331100 °° CC ,, Zuzuriri speed rate of 11220000ssee _CC - ¹¹ in Nio only only Ruru viscous Viscosity 114400PPaa--ss))

((BB)) aa-oleoleffinein and ((XX ,, ββ Unsaturated succinic acid, guglilicisidyl diester ester) as main components Luorefeffine-based copolymer copolymer

Β-2: Ethylene グラフト daricidyl methacrylate copolymer grafted with methyl methacrylate or butyl phthalate copolymer

(C) Olefin copolymer

C-1: Ethylene-hexene copolymer (melt index = 3gZlO content, specific gravity = 0.885)

C-2: Ethylene otene copolymer (melt index = 1.6 gZlO, specific gravity = 0.897)

C-3: ethylene-otene copolymer (melt index = lgZl〇, specific gravity = 0.857

)

C-4: ethylene-otene copolymer (melt index = 5 gZlO content, specific gravity = 0.870

)

C-1: Ethylene-hexene copolymer (melt index = 8gZlO content, specific gravity = 0.880)

C-2: Ethylene otene copolymer (melt index = 3.5 gZl0 min, specific gravity = 0.910)

Example 11-7, Comparative Example 11-9

The components (A), (B), and (C) shown in Table 1-2 were mixed with a Henschel mixer for 5 minutes, and the mixture was charged into a twin-screw extruder with a cylinder temperature of 320 ° C and a resin temperature of 350 ° C. The mixture was melted and kneaded to prepare a resin composition pellet. [0025] Next, Izod impact test pieces were molded using an injection molding machine at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C according to ASTM D-256 °, and the notch-side impact strength was measured. Further, after being left in an atmosphere of -30 ° C for 2 hours or more, the notch-side impact strength was measured. The results are shown in Table 1-2

[Table 1]

[Table 2]

Unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9

(A) PPS weight part 100 100 100 100 100 100 100 100 100

(B) -Self-refin -Gericilic ester copolymer type B-1 B-2 B-1 B-1 Parts by weight 15 15 15 15

(C) Ethylene---lefin copolymer Type G-1 C-2 C-3 C-4 C-1 C-2

30 30 30 30 30 30 Izod impact strength (23 ° C) J / m 30 270 300 50 50 50 50 760 F 00 Izod impact strength (_30 ° C) J / m 30 50 50 50 40 40 40 140 220

Claims

The scope of the claims

[1] 100 parts by weight of (A) polyarylene sulfide resin, and (B) 1 to 30 parts by weight of an olefin-based copolymer containing α-olefin and glycidyl ester of a, β-unsaturated acid as main components and (C) 10-50 parts by weight of an olefin copolymer of ethylene and α-olefin having 5 or more carbon atoms having a melt index of 5 gZlO or less and a specific gravity of 0.9 or less according to ASTM D-1238 A polyarylene sulfide resin composition comprising:

[2] In the component (—), the ratio of α-β-lefin to glycidyl ester of α, β-unsaturated acid is 70-99% by weight of α-β-lefin and a, j8-unsaturated acid. 2. The composition according to claim 1, wherein the amount of the glycidyl ester is 1 to 30% by weight.

[3] The composition according to claim 1, wherein the component (C) is an olefin copolymer of ethylene and α-olefin having 6 to 12 carbon atoms.

[4] The component (C) is selected from an ethylene pentene copolymer, an ethylene-hexene copolymer, an ethylene heptene copolymer, an ethylene otaten copolymer, an ethylene nonene copolymer, and an ethylene-decene copolymer. The composition according to 1.