JPS59152953A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by adding an olefin copolymer composed of an alpha-olefin and a glycidyl ester of an alpha,beta-unsaturated carboxylic acid and glass fibers, thus showing high impact strength, toughness and heat resistance. CONSTITUTION:The objective composition is obtained by combining (A) 20- 90wt% of polyarylene sulfide with (B) 5-70wt% of fiber glass and (C) 5-50wt% of an olefin copolymer composed of an alpha-olefin and a glycidyl ester of an alpha,beta- unsaturated acid. As the component C, is preferably a copolymer from ethylene and glycidyl methacrylate. The glass fiber is 0.1-10mm. long and treated with an aminosilane beforehand.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyarylene sulfide resin compositions with improved impact properties.

Polyarylene sulfide resins such as polyphenylene sulfide are used as engineering plastics with excellent heat resistance, flame retardancy, and chemical resistance.
In recent years, it has been attracting attention and demand is increasing, especially for applications such as electrical parts and automobile parts.

However, the resin has poor ductility, is brittle, and r 1
) It has serious drawbacks such as: By blending fibrous reinforcing materials such as glass fiber and arm fiber with the resin,
It is known that the properties required for engineering plastics, such as strength, rigidity, toughness, heat resistance, and dimensional stability, are greatly improved. However, even with the combination of the fibrous reinforcing material, it is still more fragile than other engineering plastics such as polyacetal, modified ppOs polysulfone, and polyethersulfone.
Despite its excellent properties, its application to many applications is limited.

In view of the above-mentioned situation, the inventors of the present invention have conducted extensive research and found that by blending polyarylene sulfide with an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid, the inventors have solved the above-mentioned drawbacks. The present invention was achieved based on the discovery that the method can be improved.

The present invention provides tetrapolyarylene sulfide 50-99.
5wt% and skewer) α-olefin and α.

(2) A polyarylene sulfide resin composition characterized by comprising 5 wt % of olefin copolymers 50 to Q consisting of glycidyl esters of β-unsaturated acids.

The polyarylene sulfide used in the present invention is a polymer represented by the general formula -(-Ar-8-4. Here, -Ar- is a divalent aromatic compound containing at least one 6-membered carbon ring, such as group residue, and each aromatic ring further has F.

Substituents such as et, Br, CjLla may also be introduced.

In particular, polyphenylene sulfide, represented by the typical polyarylene sulfide, is commonly sold by Phillips Petroleum Company of the United States under the trademark I Rydon Vehicle. The manufacturing method is U.S. Patent No. 3 and 8.
Specification No. 54,129 and the corresponding Japanese Patent Publication No. 1973
It can be produced by reacting balata (Na28-M2(J)) in N-methylpyrrolidone solvent under pressure conditions of 160 to 250°C. Publication No. 52-12240, Special Publication No. 53-25588 and Special Publication No. 58
As disclosed in Japanese Patent No. 25589, PP8 with a higher degree of polymerization can be produced by using a melting medium such as lithium acetate or lithium chloride in combination.

α-olefin used in the present invention and glycidyl ester of α, β-unsaturated acid.
Butene-1 and the like are preferred, and ethylene is more preferred. Glycidyl esters of α,β-unsaturated acids are compounds represented by the general formula (in the formula, the hyphen is a hydrogen atom or lower alkyl), and specifically, glycidyl acrylate, glycidyl methacrylate, etc. These include glycidyl and glycidyl ethacrylate, with glycidyl methacrylate being more preferred. The copolymerization m of α,β-unsaturated glycidyl ester is suitably in the range of 1 to 50 moJ%. Furthermore, if the amount is 40 mol% or less, other unsaturated monomers that can be copolymerized with the above monomers, such as vinyl ethers; vinyl ester acids such as vinyl acetate and vinyl propionate; methyl, ethyl, furobil, etc. One or more esters of acrylic acid and methacrylic acid such as ζacrylonitrile, styrene, and carbon oxide may be copolymerized.

The mixture of these olefin copolymers into PP8 is
"C" based on the total amount of PPS and the olefin copolymer
(A) PPs 5 0 to 99.5 wt%, 50 to Q, 5 wt% of the olefin copolymer is suitable, and PP8 is 99. 5 wt%, and the olefin copolymer has a Q. If it is less than 5 wt%, the effect of improving the target fragility is insufficient, and the PPS is less than 5 wt%.
Q less than wt%, the olefin copolymer is 50 wt%
If it exceeds this, the rigidity and heat resistance, which are the characteristics of PP8, will drop significantly, which is not preferable.

The means of blending the composition of the present invention is not particularly limited. PP8
It is possible to feed each of the olefin copolymers separately to a melt mixer, or to mix these raw materials in advance using a mortar, mixer, ball mill, ribbon blender, etc. It can also be fed to a melt mixer.

The composition of the present invention may contain antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, colorants such as dyes and pigments, flame retardants, One or more conventional additives such as flame retardant aids, antistatic agents, crystallization promoters, etc. can be added.

Also small amounts of other thermoplastics (e.g. polyethylene,
polypropylene, polyamide, polycarbonate, polysulfone, polyethersulfone, modified polyphenylene oxide, etc.).

One or more types of thermosetting resins (eg, phenolic resins, epoxy resins, etc.) can be added.

In addition, reinforcing agents such as glass fiber, carbon fiber, boron fiber, silicon carbide fine, asbestos fiber, metal fiber, etc.
It is also possible to incorporate fillers such as clay, mica, silica, graphite, glass beads, alumina, and calcium carbonate. In particular, filling glass fibers or carbon fibers has a remarkable effect of improving rigidity and heat resistance, and in order to provide a more useful composition, 10 to 5 Q wt% of the total composition is added. It is preferable to fill the range. The fibers are chopped strands made of hundreds to thousands of single fibers with a diameter of 5 to 15 μm and a length of 8 to 8 μm, or chopped strands or rovings, which are long fibers, and are incorporated into the final composition. Average fiber length is 0.15-0.5
It is preferable to uniformly disperse it so that it falls within the desired range.

The present invention will be described below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto.

Examples 1 to B Polyphenylene sulfide (Phillips Petroleum AS, Rydon SS PP8 P4) and ethylene-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bondfurth PE) were mixed in the composition shown in Table 1. , -Screw extruder (Tanabe Plastic V8-80-28
), the strands were melt-kneaded at a temperature of 280°C, then water-cooled and cut to obtain pellets.

The obtained pellets were injection molded (Sumitomo-Nestal 4'I
/28 injection molding machine, cylinder temperature 310°C, mold temperature 180°C), Izotsu impact test piece, bending test piece,
A test piece for measuring heat distortion temperature was obtained.

ASTM D-256, D-790, D-64 respectively
Measured according to 8. Excellent values were obtained in both cases.

Comparative Examples 1-2 PP8 and ethylene-glycidyl methacrylate copolymer used in Examples 1-8 were mixed in the proportions shown in Table 1,
The same processing as in Examples 1 to 8 was performed and the physical properties were measured.

It is significantly inferior to the example.

Table 1 Examples 4 to 5 Polyphenylene sulfide (manufactured by Phillips Petroleum Co., Ltd., Rydon // PP8 P6), ethylene-glycidyl methacrylate-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bond 7 Ayuto ■ 2B), and Glass fiber (Asahi Fiberglass Co., Ltd. 080B-MA4g7
, chopped strands with a length of 8 fins) were mixed with the composition shown in Table 2, and the mixture was mixed using a twin-screw extruder (PCM-80 manufactured by Ikegai Iron Works).
After melt-kneading at a temperature of 290°C, the strands were water-cooled and cut to obtain pellets.

The obtained pellets were injection molded (Sumitomo-Nescool 47/
28 injection molding machine, cylinder temperature 820°C, mold temperature 180°C), Izotsu impact test piece, bending test piece,
A test piece for measuring heat distortion temperature was obtained. ASTM D
-256, D-790, and D-648.

Good values were obtained in both cases.

Comparative Example 8 The PPS and glass fiber used in Examples 4 to 5 were mixed in the proportions shown in Table 2, and processed in the same manner as in Examples 4 to 5.
Physical properties were measured.

It is significantly inferior to the example.

Table 2 (Note) Example “ppji 跣 [X 100=90
(wt%) T mouth ■ “X 100 = 10 (wt%)
Example 5 Knee 11-×lO100-80(%) PPS
10B, F ''

Procedural amendment (voluntary) June 6, 1982 Patent Application No. 26818 2, Name of the invention Polyarylene Sulfide Resin Composition 8, Relationship with the person making the amendment Patent applicant address Higashi-ku, Osaka City Kitahama 5-15 name
(209) Sumitomo Chemical Co., Ltd. Representative Sat
Person: Takeshi 4, Agent name: Patent attorney (8597) Mitsuhiro Moroishi (Haka 1) 5,
Subject of amendment 几゛"(06+220-3"°"Full text 6, Subject of amendment as shown in the attached sheet) Amended specification 1, Title of invention: Polyarylene sulfide resin set, acid product 2, Scope of claims 1 liter Olefin copolymer consisting of α-olefin and glycidyl ester of a, β-unsaturated acid 5 to 5 Q w
A polyarylene sulfide resin composition comprising: t%.

3. Detailed Description of the Invention The present invention relates to a polyarylene sulfide resin composition with improved impact properties.

Polyarylene sulfide resins such as polyphenylene sulfide are used as engineering plastics with excellent heat resistance, flame retardancy, and chemical resistance.
In recent years, it has attracted attention for applications such as electrical parts and automobile parts, and demand is increasing.

However, this resin has serious drawbacks such as low ductility and brittleness (1). By blending fibrous reinforcing materials such as glass fiber and carbon fiber with the resin,
It is known that the properties required for engineering plastics, such as strength, rigidity, toughness, heat resistance, and dimensional stability, are greatly improved. However, even with the combination of the fibrous reinforcing material, it is still more fragile than other engineering plastics such as polyacetal, modified ppO, polysulfone, and polyethersulfone.
Despite its excellent properties, its application to many applications is limited.

In view of the above-mentioned situation, the present inventors have conducted extensive research and found that by blending polyarylene sulfide with an olefin-based copolymer consisting of a glass fiber monoolefin and a glycidyl ester of an α,β-unsaturated acid, the inventors have solved the above-mentioned drawbacks. It has been discovered that a composition having high impact strength, rigidity, and heat resistance can be obtained by improving this, and the present invention has been achieved.

The present invention comprises (Al polyarylene sulfide (2) 20 to 9 Qwt%, tBl glass fiber 5 to 7 Qwt%, and (C1 α-olefin and α,β-unsaturated acid glycidyl ester olefin copolymer 5 to 5 Qwt%).
t% of the polyarylene sulfide resin composition.

The polyarylene sulfide used in the present invention is a polymer represented by the general formula fAr-8→n. Here-
Ar- is, for example, -〇-1-〇-so・-〇-0-〇-〇-〇-9Cf(
, 3, and further includes F in each aromatic ring.

Substituents such as cl, Br, OHa, etc. may also be introduced.

Particularly typical polyarylene sulfide (PPS)
) is a polyphenylene sulfide represented by the general formula ←○-8+n, and is generally commercially available from Phillips Petroleum Company in the United States under the trademark 'Rydon.' Its manufacturing method is described in US Pat. 854,
Specification No. 129 and the corresponding Japanese Patent Publication No. 45-88
No. 68 discloses that baladichlorobenzene (c4-Q-cz) and sodium sulfide (Na2S.■
20) can be produced by reacting.

Also, Special Publication No. 52-12240, Special Publication No. 58-2
As disclosed in Japanese Patent Publication No. 5588 and Japanese Patent Publication No. 5B-25589, when a catalyst such as lithium acetate or lithium chloride is used in combination, PP8 with a higher degree of polymerization can be produced.

The glass fiber used in the present invention is 8i0z.

B2O3, AI! zOa, OaO, NazO, K2O
Depending on the purpose, alkali-free glass (E glass), alkali-containing glass (C glass, A glass), etc. are used.
E glass, which is generally used for reinforcing resins, is preferable because it has a high reinforcing effect.

The fiber length is preferably 0.1 to 10 threads, but chopped strands or long fiber rovings having a length of about 8 threads or 6 threads, which are usually used for resin filling, are used. The glass fibers can be used without any treatment, but in order to make them compatible with polyarylene sulfide, they may be treated with a silane coupling agent such as aminosilane or epoxysilane, a chromium-based coupling agent, and a chromium-based coupling agent for the purpose of binding the fibers. A plastic-based sizing agent that has been treated with other materials depending on the purpose is used.

The α-olefins used in the present invention are ethylene, propylene, butene, etc.
1, etc., and ethylene is more preferable. Also α, β−
Glycidyl esters of unsaturated acids are compounds represented by the general formula (5) (wherein R is a hydrogen atom or a lower alkyl group), and specifically include glycidyl acrylate, glycidyl methacrylate, and ethacrylate. The copolymerization amount of α, β-unsaturated glycidyl ester, which is glycidyl acid, more preferably glycidyl methacrylate, is 1
A range of 50 mol % is suitable. Furthermore, 40 mol%
Other unsaturated monomers which are copolymerizable with the above monomers, i.e. vinyl ethers; beer ester acids such as vinyl acetate and vinyl propionate; acrylic acids and methacrylic acids such as methyl, ethyl and propyl; esters; acrylonitrile, styrene, -
One or more types of carbon oxide etc. may be copolymerized.

The amount of these glass fibers and olefin copolymer to be blended into PP8 is based on the total amount of PPS, glass fiber, and the olefin copolymer (AI PP 820 to 90w).
t%, fBl glass fiber 5 to 70 wt%, (C1 olefin copolymer 5 to 50 wt%, total amount of fBl and (6) (C) in the total resin composition, l; 10 to
8 Qwt% is appropriate, PPB exceeds 90 wt%, and the total amount of glass fiber and the olefin copolymer is 19
If it is less than 50 wt%, the effect of improving the desired brittleness and rigidity will be insufficient, and if the PPS is less than 20 wt% and the olefin copolymer is more than 50 wt%, the PPS will not be effective. The characteristic rigidity and heat resistance are significantly reduced,
Undesirable.

Even if PP8 is 20 to 9 Q wt%, if the amount of glass #J2 fibers exceeds 70 wt%, the bulk density of PPS and glass fibers will be significantly different, resulting in insufficient mixing and compounding. The process becomes difficult and a uniform composition cannot be obtained. If the amount of glass fiber is less than 5 wt%, the effect of improving stiffness is insufficient, and conversely, if the amount of the olefin copolymer is less than 5 wt%, the effect of improving brittleness is insufficient.

The means of blending the composition of the present invention is not particularly limited. PP8
, glass fiber, and the olefin copolymer can be fed separately to a melt mixer, and these raw materials can be premixed in advance using a mortar, Henschel mixer, ball mill, ribbon blender, etc. It can also be fed to a melt mixer.

The composition of the present invention may contain antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, colorants such as dyes and pigments, flame retardants, One or more conventional additives such as flame retardant aids, antistatic agents, crystallization promoters, etc. can be added.

It is also possible to incorporate reinforcing agents such as carbon fiber, boron fiber, silicon carbide fiber, asbestos fiber, and metal fiber, and fillers such as clay, mica, silica, graphite, glass peas, alumina, and calcium carbonate.

The present invention will be described below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto.

Examples 1 to 8 Polyphenylene sulfide (I Rydon-PP8MR-08, manufactured by Phillips Petroleum), glass fiber (0808-MA497, chopped strand, length 8, manufactured by Asahi Fiberglass), and ethylene-glycidyl methacrylate A copolymer (manufactured by Sumima Kagaku Kogyo Co., Ltd., Bond First (E) E) was mixed with the composition shown in Table 1, and a -screw extruder (manufactured by Tanabe Plastics VS-80-28) was used.
After melt-kneading at a temperature of 290° C., the strands were water-cooled and cut to obtain pellets.

Injection molding of the obtained pellets (Dweller-Nestal 47/
28 injection molding machine, cylinder temperature 820℃, mold temperature 1
80°C) to obtain an Izot impact test piece, a bending test piece, and a heat distortion temperature measurement test piece.

respectively gA8TM D-256, 1)-790, D-
Measured according to 648. Excellent values were obtained in both cases.

(9)”,.

Comparative Examples 1 to 5 The PPS used in Examples 1 to 8, glass fiber, and ethylene-glycidyl methacrylate copolymer were mixed in the proportions shown in Table 1, and the same processing as in Examples 1 to 8 was performed to determine the physical properties. It was measured.

It is significantly inferior to the example.

Table 1 (10) Examples 4 to 5 Polyphenylene sulfide (Rydon PP8 P-6 manufactured by Phillips Petroleum) and ethylene-
Glycidyl methacrylate-vinyl acetate copolymer (manufactured by Sumima Kagaku Kogyo, Bond First Co., Ltd. 2B) and glass fiber (Asahi Fiberglass Company!!!I!080 B)
-MA497, chopped strands with a length of 8M) were mixed with the composition shown in Table 2, and a twin-screw extruder (Ikegai Iron Works E
CM-80) at a temperature of 290°C, the strands were water-cooled and cut to obtain pellets.

Injection molding of the obtained pellets (Dweller-Nestal 47/
28 injection molding machine, cylinder temperature 820℃, mold temperature 1
80°C) to obtain an Izot impact test piece, a bending test piece, and a heat distortion temperature measurement test piece. Each ASTM D-2
56, D-790, 1)-648. High values were obtained in both cases.

Comparative Example 6 PP8 used in Examples 4 to 5 and glass fiber were mixed in the proportions shown in Table 2, and processed in the same manner as in Examples 4 to 5.
Physical properties were measured.

It is significantly inferior to the example.

Table 2

Claims (1)

[Claims] (A) Polyarylene sulfide 50-99.5
Olefin copolymer consisting of glycidyl ester of α-olefin and α, β-unsaturated acid 50 to Q, 5 wt%
A polyarylene sulfide resin composition comprising wt%.