KR940006475B1 - Polyarylene sulfide resin composition - Google Patents

Abstract

100 wt.pts. of polyarylene sulfide resin; 0.1-10 wt.pts. of bisphenol based diglycidyl ether epoxy resin of formula (I) or (II); and 10-400 wt.pts. of inorganic filler which is one or more selected from fiber form, powder form, granular form or plate form fillers. The polyarylene sulfide resin contains above 70 mol% of -(Ar-S)- as repeating unit where Ar is aryl, and has 10-20,000 poise of melting viscosity of 300 deg.C and 1,200/sec of shear rate. The obtd. resin compsn. has improved mechanical property and dimensional stability and in useful for electric, electronic and vehicle devices.

Description

Polyarylene sulfide resin composition

The present invention relates to a polyarylene sulfide resin composition.

More specifically, the present invention relates to a polyarylene sulfide resin composition having improved mechanical strength and dimensional stability. The demand for thermoplastic resins having excellent mechanical strength, heat resistance, chemical resistance and flame retardancy as materials for electric, electronic and automotive parts is increasing. Polyarylene sulfide resins represented by polyphenylene sulfide are thermoplastic resins having such characteristics. The demand is increasing because it can provide excellent physical properties at low cost. However, the polyarylene sulfide resin can obtain better physical properties when using a fibrous filler, a powder filler and a granular filler together than when using the resin alone.

Therefore, polyarylene silphide resins are used by adding a large amount of fibrous, powdery and granular fillers, in which case the state of adhesion and dispersion of the filler to the polyarylene sulfide resin has a mechanical property of the polyarylene sulfide composition. And dimension stability.

Accordingly, the present invention provides a combination of polyarylene sulfide resins that improves the adhesion and dispersion of fillers to polyarylene sulfide resins when a large amount of fibrous, powdery and granular fillers are added to the polyarylene sulfide resins. It relates to a coupling agent.

Previously, the following techniques have been proposed to solve this problem.

1. How to use KR 134S as coupling agent

(U.S. Patent No. 4,269,756)

2. Method of using trialkoxy silanes as coupling agent

(U.S. Patent No. 4,708,983)

3. How to Use Cresol Noblock Epoxy Resin as Coupling Agent

(Japanese Patent Publication: JP / 01 24825)

However, these methods have been found to have no significant effect on improving the mechanical properties and the dimensional stability.

In order to solve the above problems, the present inventors have found that the bisphenol-based diglycidyl ether epoxy resin as a coupling agent can solve the above problems, and have completed the present invention.

That is, the present invention relates to a polyarylene sulfide resin composition comprising 100 parts by weight of polyarylene sulfide resin, 0.1 to 10 parts by weight of bisphenol-based diglycidyl ether epoxy, and 10 to 400 parts by weight of inorganic filler.

의 반복단위가 70몰% 이상으로 이루어지는 중합체이다.Polyarylene sulfide resin used as a substrate resin in the present invention is a general formula wherein Ar is an aryl group

The repeating unit of is a polymer consisting of 70 mol% or more.

의 반복단위가 70몰% 이상으로 이루어진 폴리페닐렌 설파이드(이하 PPS수지로 약칭함)이고, 본 발명에서 사용된 PPS수지는 온도 310℃, 전단속도 1,200sec^-1에서 용융점도가 10∼20,000p이며, 특히 바람직한 것은 용융점도가 200∼5,000p인 PPS수지이다.A typical example of this resin is a structural formula wherein Ph is a phenyl group

Is a polyphenylene sulfide (hereinafter abbreviated as PPS resin) consisting of 70 mol% or more of the repeating unit, and the PPS resin used in the present invention has a melt viscosity of 10 to 20,000 p at a temperature of 310 ° C. and a shear rate of 1,200 sec ⁻¹ . Particularly preferred are PPS resins having a melt viscosity of 200 to 5,000 p.

가 70몰% 이상이고, 바람직하기는 80몰% 이상으로 이루어진 PPS수지이다.P-phenylene sulfide units in repeat units

Is 70 mol% or more, preferably PPS resin composed of 80 mol% or more.

, 디페닐케톤 설파이드,

,디페닐 설파이드

, 디페닐 에테르 설파이드

및 3작용기단위

등이있다.The linear PPS resin used in the present invention may use other comonomer units up to 30 mol%. M-phenylene sulfide

Diphenylketone sulfide,

Diphenyl sulfide

Diphenyl ether sulfide

And trifunctional units

Etc.

By the way, when using a trifunctional unit, it is more preferable that it is 0.1-0.8 mol% in order to prevent the fall of crystallinity.

, RE-305S

, RE-310S

, PGE-H

및 EBPS-300

이다.Coupling agent used in the present invention is a bisphenol-based diglycidyl ether epoxy resin of the general formula (I) is trade name RE-304

, RE-305S

, RE-310S

, PGE-H

And EBPS-300

to be.

(Wherein R ₁ and R ₂ are each hydrogen or a C _{1 to} C ₄ alkyl group, particularly preferably hydrogen or a methyl group, n is an integer of 0 to 10, and particularly preferably an integer of 2 to 5).

(In formula, n is an integer of 0-4, Most preferably, it is an integer of 2-3.).

The amount of the bisphenol-based diglycidyl ether epoxy resin coupling agent used is 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight. When used at 0.1 parts by weight or less, it does not function as a coupling agent, and at 10 parts by weight or more, there is a tendency to adversely affect mechanical properties.

The inorganic filler used in the present invention is preferable because it can obtain excellent molded articles having various properties such as mechanical strength, heat resistance and electrical properties. Inorganic fillers used include fibrous fillers, powdery fillers, granular fillers and plate-like fillers.

Fibrous fillers include glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, stainless fibers, aluminum fibers, titanium fibers and inorganic materials. Fiber can be mentioned. Typical examples of fibrous fillers are glass fibers and carbon.

As powdered or granular fillers, silicates such as carbon black, silica, quartz powder, glass beads, glass powder, kaolin, talc, clay, diatomaceous earth, and wollastonite are substituted with metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina, calcium carbonate and Metal carbides, such as magnesium carbonate, Metal sulfides, such as calcium sulfate and barium sulfate, etc. are mentioned.

Plate fillers include mica flakes, grease flakes and various metal foils. The amount of the inorganic filler is 10 to 400 parts by weight, the use of more than 400 parts by weight significantly decreases the processability and mechanical properties, and less than 10 parts by weight can not be expected various properties such as mechanical and electrical properties. In addition, known materials added to the thermoplastic or thermosetting resin, for example, antioxidants, ultraviolet absorbers, stabilizers, dyes, pigments and colorants, etc. may be appropriately added to the composition of the present invention according to the desired properties.

The polyarylene sulfide resin composition of this invention is manufactured using the apparatus and procedure conventionally used for the composition of synthetic resin. That is, the necessary ingredients are mixed and the mixture is kneaded using a single-screw or twin-screw extruder to form molding pellets, and sometimes some of the necessary ingredients are mixed with other ingredients in a master batch. And the method of shape | molding the mixture can also be used.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Example 1

: 토프렌사 제품) 100중량부에 EBPS-300 1중량부(메틸에틸케톤 용액상태)를 첨가하여 상온의 헨셀(Henshell) 혼합기에서 RPM 200으로 5분동안 미리 혼합하고 80℃ 오븐에서 5시간동안 메틸에틸케톤 용매를 건조시킨다. 그 다음 유리섬유(길이 1/8인치, 지름 10∼12μm) 65중량부와 함께 310∼320℃ 실린더 온도의 쌍-스크류 압출기를 사용하여 펠렛을 얻었다. 펠렛을 실린더 온도 320∼330℃, 금형온도 130℃인 사출성형기로 ASTM 시험편으로 성형하였으며, 물성치를 측정하여 표1에 나타내었다. 평가 항목 및 측정방법은 다음과 같다.PPS resin (Tohpren T-3

: 100 parts by weight of toprene) 1 part by weight of EBPS-300 (in methyl ethyl ketone solution) is added and premixed in a Henschel mixer at room temperature for 5 minutes at RPM 200 for 5 hours in an oven at 80 ° C. Methyl ethyl ketone solvent is dried. The pellet was then obtained using a twin-screw extruder at 310-320 ° C. cylinder temperature with 65 parts by weight of glass fibers (1/8 inch long, 10-12 μm in diameter). The pellet was molded into an ASTM test piece using an injection molding machine having a cylinder temperature of 320 to 330 ° C. and a mold temperature of 130 ° C., and the physical properties thereof were shown in Table 1 below. Evaluation items and measuring methods are as follows.

a) Tensile Strength: ASTM D-638

b) Izod impact strength: ASTM D-256

c) Linear expansion coefficient: TMA method (room temperature ~ 100 ℃)

Example 2

: 토프렌사 제품) 100중량부에 EBPS--300(메틸에틸케톤 용액상태) 1중량부, 규회석(입자크기 : 5∼10μm) 55중량부를 첨가하여 상온의 헨셀 혼합기에서 RPM 200으로 5분동안 미리 혼합하고 80℃ 오븐에서 5시간 동안 메틸에틸케톤 용매를 건조시킨다. 그후, 실시예 1과 같은 방법으로 성형하고 물성 측정하여 표1에 나타내었다.PPS resin (Tohpren T-3

: Toprene) 1 part by weight of EBPS-300 (in methyl ethyl ketone solution) and 55 parts by weight of wollastonite (particle size: 5-10 μm) are added to 100 parts by weight of RPM for 200 minutes in a Henschel mixer at room temperature. Premix and dry the methylethylketone solvent for 5 hours in an 80 ° C. oven. Thereafter, molding was carried out in the same manner as in Example 1, and physical properties were measured and shown in Table 1.

[Examples 3 to 8]

The composition and composition ratio of Table 1 were carried out in the same manner as in Example 1 or 2, the physical properties are shown in Table 1.

[Comparative Examples 1 to 4]

The composition and composition ratio of Table 1 were carried out in the same manner as in Example 1 or 2, the physical properties are shown in Table 1.

EBPS-300: Japanese Gunpowder Co. LTD products

RE-310S: Nippon Gunpowder Co., Ltd. LTD products

KR 134S: Achinamodo Co., Ltd. product

Claims (5)

A polyarylene sulfide resin composition comprising 100 parts by weight of a polyarylene sulfide resin, 0.1 to 10 parts by weight of a bisphenol-based diglycidyl ether epoxy resin, and 10 to 400 parts by weight of an inorganic filler. The polyarylene sulfide resin according to claim 1, wherein Ar is an aryl group.

Polyarylene sulfide resin composition, characterized in that the repeating unit is a polymer consisting of 70 mol% or more. The polyarylene sulfide resin composition according to claim 1 or 2, wherein the polyarylene sulfide resin has a melt viscosity of 10 to 20,000 p at a temperature of 310 ° C. and a shear rate of 1,200 sec ⁻¹ . The polyarylene sulfide resin composition according to claim 1, wherein the bisphenol-based diglycidyl ether epoxy resin has the following general formula.

(Wherein, R ₁ and R ₂ are each hydrogen or C ₁ ~C ₄ alkyl group, n is an integer of 0 to 10).

(Wherein n is an integer of 0 to 4). The polyarylene sulfide resin composition according to claim 1, wherein the inorganic filler is used alone or in combination of two or more as fibrous, powdery, granular, or plate fillers.