JPH06179791A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition composed of a polyarylene sulfide resin and a specific olefinic copolymer and useful for various functional parts having excellent impact resistance and toughness. CONSTITUTION:The resin composition is composed of (A) a polyarylene sulfide resin and (B) a glycidyl-containing olefinic copolymer produced by copolymerizing 0.5-15wt.% of preferably an alpha, beta-unsaturated carboxylic acid glycidyl ester to 85-99.5wt.% of an olefinic copolymer composed of 10-50wt.% of an alpha-olefin and 50-90wt.% of an alpha, beta-unsaturated carboxylic acid alkyl ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent impact resistance and toughness such as tensile elongation.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP
Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by S) has excellent heat resistance and chemical resistance in itself, and a molding material reinforced with a reinforcing material such as glass fiber is , Is being used as a metal substitute in the fields of automobile parts and electronics-related parts,
In recent years, demand has greatly increased.

However, the unreinforced PAS resin which is not reinforced with a reinforcing material such as glass fiber is inferior in extrusion stability and moldability, and the obtained molded product is not only black and has a poor appearance but also has a high impact resistance. It lacks toughness due to insufficient mechanical properties such as mechanical properties and tensile elongation. Therefore, in the field of injection molding, the use as a non-reinforcing molding material is limited, and a material using a reinforcing material has been the mainstream.

[0004]

As a method for improving the toughness of a PAS resin typified by a PPS resin, a method of adding a hydrogenated SBR copolymer (JP-A-59-167040) and a dicarboxylic acid anhydride hydrogenated SBR copolymer are known. There is a method of adding (JP-A-56-115355), but these SBR
The system copolymer has poor compatibility with the PPS resin, has a poor appearance, and is not sufficiently improved in impact resistance. Further, the addition of an ionomer (Japanese Patent Laid-Open No. 2-49062) has a poor heat resistance of the ionomer and is apt to cause a burn during molding. Furthermore, α
-Addition of an olefin copolymer consisting of 70 to 99% by weight of olefin and 1 to 30% by weight of glycidyl ester of α, β-unsaturated acid (JP-A-58-154757), α-
Addition of a copolymer obtained by graft-polymerizing a vinyl monomer to a copolymer of an olefin and a glycidyl ester of an α, β-unsaturated acid (JP-A-1-198664), ethylene 50
.About.90% by weight, .alpha.,. Beta.-unsaturated carboxylic acid alkyl ester 5 to 49% by weight, and maleic anhydride 0.5 to 10% by weight added ethylene copolymer (JP-A-62-1)
51460) and the like. These copolymers have good compatibility with PAS resins, but when these copolymers are substantially added, the appearance is deteriorated, and the impact resistance and tensile elongation tend to be low. Further α-
When a large amount of a copolymer of an olefin and a glycidyl ester of an α, β-unsaturated acid was added to a PAS resin, the PAS resin became a gel and the amount used was limited.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have improved the mechanical properties such as impact resistance and tensile elongation of PAS resin without using a reinforcing material such as glass fiber. It is intended to provide goods.

[0006]

Means for Solving the Problems In considering the improvement of impact resistance and toughness such as tensile elongation of PAS resin, the present inventors have studied the improvement of PAS resin by blending a specific olefin copolymer. The inventors have found that the various properties for the above purpose are improved in balance while maintaining excellent heat resistance, and the toughness is improved, leading to the present invention.

That is, according to the present invention, the polyarylene sulfide resin (A) and 10 to 50% by weight of α-olefin and α,
The present invention relates to a resin composition comprising an olefin-based copolymer (B) containing 50 to 90% by weight of a β-unsaturated carboxylic acid alkyl ester.

In the present invention, the PAS resin (A) used as the substrate is represented by the general formula [-Ar-S-] (wherein -Ar- is a divalent aromatic group containing at least one carbon 6-membered ring). A polymer containing 70 mol% or more of the repeating unit represented by the formula (1), a typical substance thereof is [-φ-S-] (however,
-Φ- is a repeating unit represented by a phenylene group) 70
It is a PPS resin containing more than mol%.

PAS resins are generally known to have a substantially linear molecular structure having no branched or crosslinked structure and one having a branched or crosslinked structure depending on the production method.
In the present invention, both types are effective.

The preferred PAS resin for use in the present invention is the repeating unit [-φ-S-] (provided that-
φ- is phenylene group) PPS containing 70 mol% or more
It is a resin. When this repeating unit is 70 mol% or more, sufficient strength, which is a characteristic of a crystalline polymer, can be obtained, and toughness and chemical resistance are excellent.

Other copolymerizable structural units that may be contained in the PPS resin include, for example,

[0012]

[Chemical 1]

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

And the like. Of these, the trifunctional unit is 1
It is also preferable that the content is mol% or less from the viewpoint of not lowering the crystallinity.

On the other hand, the olefin copolymer used as the component (B) in the present invention means α-olefin and α, β.
A random or / and block copolymer composed of unsaturated carboxylic acid alkyl esters.

Here, the α-olefin is selected from ethylene, propylene, butene-1,4-methylpentene-1, hexene-1, decene-1, octene-1 and the like.
More than one species may be used, preferably ethylene.

Further, the α, β-unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms,
For example, it is an alkyl ester such as acrylic acid or methacrylic acid, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, and acrylic. Acid isobutyl, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate,
There are isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, and the like. Of these, methyl acrylate,
Ethyl acrylate and n-butyl acrylate are preferably used. Further, these α, β-unsaturated carboxylic acid alkyl esters may be used alone or in combination of two or more.

The composition of the olefin copolymer (B) is 10 to 50% by weight of α-olefin and 50 to 90% by weight of α, β-unsaturated carboxylic acid alkyl ester,
Preferably, 20 to 45% by weight of α-olefin, α, β
-Unsaturated carboxylic acid alkyl ester 55-80% by weight
Is. When the α, β-unsaturated carboxylic acid alkyl ester is in the above range, the compatibility with the PPS resin is excellent and the PPS
It does not impair the heat resistance of the resin.

The olefin copolymer (B) may be further copolymerized with a glycidyl ester of an α, β-unsaturated acid, an unsaturated carboxylic acid or an acid anhydride thereof as a third component.

The glycidyl ester of α, β-unsaturated acid used has the following general formula:

[0025]

[Chemical 7]

(Wherein R 1 represents a hydrogen atom or a lower alkyl group), and for example, glycidyl acrylate, glycidyl methacrylate, and particularly glycidyl methacrylate are preferably used.

The method for producing these olefinic copolymers (B) is not particularly limited, but they are usually obtained by a well-known radical polymerization reaction.

The amount of glycidyl ester of α, β-unsaturated acid used is 10 to 50% by weight of α-olefin and α, β-.
The amount is 0.5 to 15% by weight, and preferably 1 to 10% by weight, based on 85 to 99.5% by weight of the olefin copolymer composed of 50 to 90% by weight of unsaturated carboxylic acid alkyl ester. When the amount of the glycidyl ester of α, β-unsaturated acid exceeds 15% by weight, the resin composition tends to be gelled.

Examples of the unsaturated carboxylic acid or its acid anhydride include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid and glutacon. Acid, monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methylmaleic anhydride, maleic anhydride, methylmaleic anhydride, citraconic anhydride, etc., and these are used alone or in combination of two or more. It Although these derivatives can be used, maleic anhydride is more preferably used.

The amount of the unsaturated carboxylic acid or its acid anhydride used is 10 to 50% by weight of α-olefin and α,
Olefin-based copolymer consisting of 50-90% by weight of β-unsaturated carboxylic acid alkyl ester 90-99.5% by weight
To 0.5 to 10% by weight, preferably 1 to 7
% By weight. When the amount of unsaturated carboxylic acid or its acid anhydride exceeds 10% by weight, the resin composition tends to be gelled.

The blending ratio of the PAS resin (A) and the olefinic copolymer (B) in the composition of the present invention can be appropriately selected according to the purpose.

In the present invention, an isocyanate compound, an isocyanurate compound, a bisoxazoline compound, an epoxy resin, an epoxy group-containing polymer for the purpose of further listing the compatibility between the PAS resin (A) and the olefin copolymer (B). A polymer such as an oxazoline group-containing polymer may be blended.

The composition of the present invention may optionally contain
The following reinforcing materials and / or fillers are usually used as resin 1
It can be blended in a ratio of 200 parts by weight or less with respect to 00 parts by weight. Examples of these reinforcing materials and / or fillers include powdery, flat, scale-like, needle-like, spherical or hollow and fibrous forms. Specifically, calcium sulfate, calcium silicate, clay, talc, alumina, silica sand, glass powder, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride,
Granular filler such as carbon black, mica, glass plate, sericite, metal foil such as aluminum flake, flat or scale-like filler such as graphite, shirasu balloon, metal balloon, hollow filler such as glass balloon, Examples thereof include organic fibrous fillers such as glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, asbestos, wosnite, fibrous fillers and aromatic polyamide fibers.

Other thermoplastic resin (C) may be added to the composition of the present invention. Other thermoplastic resins (C) include polyethylene, polypropylene, polystyrene, imide-modified polystyrene, polybutylene terephthalate, polyethylene terephthalate,
Polyethylene naphthalate, polybutylene naphthalate
, Polyamide, polycarbonate, ABS resin, imide-modified ABS resin, AES resin, polysulfone, polyphenylene ether, copolymer and / or mixture of polyphenylene ether and polystyrene, polyether sulfone, polysulfide ketone, polysulfide sulfone , Thermoplastic resins such as polyether ether ketone and polyamide imide, and thermoplastic elastomers such as polyester, polyamide, polyurethane, polyolefin and polystyrene. Preferred are polypropylene, polybutylene terephthalate, polyamide, polyphenylene ether, and a copolymer and / or mixture of polyphenylene ether and polystyrene.

In the present invention, inorganic flame retardants such as magnesium hydroxide, aluminum hydroxide and antimony trioxide, halogen-based and phosphorus-based organic flame retardants, and antioxidants are used within the scope of the present invention. Additives such as a UV inhibitor, a lubricant, a dispersant, a coupling agent, a foaming agent, a cross-linking agent, and a coloring agent can be added.

As a method for producing the composition of the present invention, a general method is used. The most general method is to uniformly mix the compound with a suitable mixer such as a tumbler, a Henschel mixer, a tumbler, etc., and supply the mixture to an extruder for melt-kneading.
The extruded product in the form of a strand is cooled and cut into a product for a molding material. More simply, a method of melting and kneading the compound of the present invention directly in a molding machine and omitting the extrusion step may be used, but the method is not particularly limited thereto.

[0037]

The present invention will be further described with reference to examples.

Measurement of Melt Index (MI) After drying about 6 g of a sample at 120 ° C. for 3 hours, a predetermined temperature (315.6 ° C.) was set using an orifice having a diameter of 2.096 mm and a length of 8.001 mm. It is put into a melt indexer (T01 type manufactured by Toyo Seiki Co., Ltd.) to remove air bubbles, apply a predetermined load (5000 g), preheat for 5 minutes, and then measure.

[0039] Tensile conduct a tensile test under the following conditions and the resulting tensile test dumbbell by testing injection molding.

Measuring instrument Shimadzu Autograph IS
-2000 Pulling speed 10 mm / min Distance between marked lines 25 mm Distance between grips 50 mm

Izod impact test A test piece for measuring Izod impact value obtained by injection molding is subjected to a tensile test under the following conditions.

Test piece dimensions Length 63.5 mm x width 1
2.7mm × thickness 3.17mm Cutting notch measuring device Universal impact tester Universal type Toyo Seiki hammer load 30Kg-cm

Examples 1 to 5 and Comparative Examples 1 to 3 PPS resin (A) having a MI of 35 g / 10 min
PS resin, ethyl acrylate shown in the table below as the olefin-based copolymer (B), and the olefin-based copolymer (B) having an ethylene weight% ratio were blended using a tumbler. Then, the mixture was kneaded with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) having a barrel temperature of 290 ° C., and the extruded strand was cooled and solidified, and then pelletized. After drying the obtained pellets at 120 ° C. for 4 hours, the cylinder temperature was 2 using an injection molding machine (IS-50AM: manufactured by Toshiba Machine).
Molding was performed at 90 ° C. and a mold temperature of 120 ° C. to obtain a dumbbell for tensile test (ASTM IV, thickness 1.6 mm) and a test piece for Izod test. A tensile test and an Izod test were performed using this test piece. The results are shown in the table below.

[0044]

[Table 1]

[0045]

[Table 2]

As is clear from the results, the composition of the present invention has excellent tensile elongation and impact resistance.

Examples 6 to 9 and Comparative Examples 4 to 6 PPS resin having MI of 35 g / 10 min as PPS resin, glycidyl group-containing olefin copolymer (B) as glycidyl methacrylic acid 2.3% by weight, acrylic acid An olefin copolymer composed of 59% by weight of methyl and 38.7% by weight of ethylene was blended by using a tumbler in the composition shown in the table below. Then, barrel temperature 290 ℃
With a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) set to, kneading was carried out with the composition shown in Table-2, and the extruded strand was cooled and solidified, and then pelletized. The obtained pellets were dried at 120 ° C. for 4 hours, and then the injection molding machine (IS-
50AM: manufactured by Toshiba Machine Co., Ltd., cylinder-temperature 290 ° C,
Molding was performed at a mold temperature of 120 ° C. to obtain a dumbbell for a tensile test (ASTM IV, thickness 1.6 mm) and a test piece for an Izod test. A tensile test and an Izod test were performed using this test piece.

As a comparative example, glycidyl methacrylic acid
The results of using an olefin-based copolymer composed of 2.3% by weight, 30% by weight of methyl acrylate, and 67.7% by weight of ethylene are also shown in the table below.

[0049]

[Table 3]

[0050]

[Table 4]

As is clear from the results, the composition of the present invention is excellent in tensile elongation and impact resistance.

Examples 10 to 13 and Comparative Examples 7 to 9 PPS resin (A) with P having MI of 35 g / 10 min
An olefin copolymer composed of PS resin and 2.3% by weight of maleic anhydride, 59% by weight of methyl acrylate, and 38.7% by weight of ethylene as a olefin copolymer was added as a tumbler in a composition shown in the table below. Blended with. Then, the mixture was kneaded with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) having a barrel temperature of 290 ° C., and the extruded strand was cooled and solidified, and then pelletized. After drying the obtained pellets at 120 ° C. for 4 hours, the pellets were molded with an injection molding machine (IS-50AM: manufactured by Toshiba Machine) at a cylinder temperature of 290 ° C. and a mold temperature of 120 ° C., and a tensile test dumbbell (ASTM IV thickness 1.6 mm) and Izod test specimens were obtained. A tensile test and an Izod test were performed using this test piece.

As a comparative example, maleic anhydride 2.0% by weight, ethylene 70% by weight, ethyl acrylate 28
An example using an olefin-based copolymer composed of wt% is also shown in the table below.

[0054]

[Table 5]

[0055]

[Table 6]

As is clear from the results, the composition of the present invention has excellent tensile elongation and impact resistance.

[0057]

The composition of the present invention is superior in impact resistance and tensile elongation as compared with conventional compositions. Also, unreinforced PP
It can be used as an S resin composition and can be expected as a material suitable for use as various functional parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 81/02 LRG 7308-4J 101/00 LSY 7242-4J

Claims (5)

[Claims] 1. An olefin copolymer (B) comprising a polyarylene sulfide resin (A), 10 to 50% by weight of an α-olefin and 50 to 90% by weight of an α, β-unsaturated carboxylic acid alkyl ester. A resin composition comprising: 2. An olefin-based copolymer (B) comprising 10 to 50% by weight of an α-olefin and 50 to 90% by weight of an α, β-unsaturated carboxylic acid alkyl ester. The resin composition according to claim 1, which is an olefin copolymer containing a glycidyl group, which is obtained by copolymerizing 0.5 to 15% by weight of a glycidyl ester of an α, β-unsaturated acid with respect to 5% by weight. 3. The olefin-based copolymer (B) is an olefin-based copolymer 90 to 99., which comprises 10 to 50% by weight of an α-olefin and 50 to 90% by weight of an α, β-unsaturated carboxylic acid alkyl ester. The resin composition according to claim 1, which is an acid group-containing olefin copolymer obtained by copolymerizing 0.5 to 10% by weight of an unsaturated carboxylic acid or an acid anhydride thereof with respect to 5% by weight. 4. The resin composition according to claim 1, which further comprises a reinforcing material and / or a filler. 5. The resin composition according to claim 1, further comprising another thermoplastic resin (C).