JPH0368655A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To prepare a polyphenylene sulfide resin compsn. excellent in the impact resistance, extrusion moldability, and sliding properties by compounding a small amt. of a silicone oil into a compsn. comprising a polyhpenylene sulfide resin and a specific olefin copolymer. CONSTITUTION:100 pts.wt. compsn. comprising 50-95wt.% polyphenylene sulfide resin and 5-50wt.% olefin copolymer, obtd. by copolymerizing essential components consisting of 60-99wt.% alpha-olefin, pref. ethylene, and 1-40wt.% glycidyl alpha,beta-unsatd. carboxylate, pref. glycidyl methacrylate, is compounded with 0.05-10 pts.wt. silicone oil, thus producing a polyphenylene sulfide resin compsn. excellent in the heat resistance, impact strength, extrusion stability, and sliding properties in a good balance.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyphenylene sulfide resin composition that is excellent in heat resistance, impact resistance, extrusion stability, and slidability in a well-balanced manner.

<Prior art> Polyphenylene sulfide resin (hereinafter abbreviated as PP5t!I resin) is known as an engineering plastic with excellent heat resistance, chemical resistance, flame retardance, and dimensional stability. Widely used in fields such as parts, automobile parts, and films. Also, PPS
In recent years, efforts have been made to improve the low WI impact resistance, which is a drawback of resins.
JP-A-62-153343 discloses a composition comprising an olefin copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid as an epoxy group-containing olefin polymer. Publication, JP-A-62
-153344 publication and JP-A-62-153345
The publication discloses a composition in which an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid is blended with a specifically treated PPSta fat.

<Problems to be Solved by the Invention> However, in the above-mentioned conventional blended composition of PPS resin and an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid, it is difficult to melt and knead both. When doing so, there are problems such as thickening due to undesirable side reactions of glycidyl groups in the olefin copolymer, or generation of gel especially during abnormal retention during kneading. Furthermore, although the resin composition produced by kneading has high impact resistance, it suffers from severe wear when applied to sliding parts such as bearings and gears.

Therefore, the present invention has developed PPS that has good impact resistance, improved extrusion properties, and also has excellent sliding properties.
The objective is to obtain a resin composition.

Means for Solving the Problem> As a result of intensive studies to achieve the above object, the present inventors developed a resin consisting of a copolymer of PPS resin, α-olefin, and α,β-unsaturated acid glycidyl ester. For the composition,
By adding a small amount of silicone oil,
The inventors have discovered that the above problems can be solved at once, and a PP5vIJ resin composition having good #WI impact resistance, extrusion processability, and sliding properties can be obtained, and the present invention has been achieved.

That is, the present invention provides (8) 50 to 95% by weight of PPSI fat.
and CB) α-olefin 60-99% by weight and α, β
~ Olefin copolymerization containing 1 to 40% by weight of glycidyl ester of unsaturated carboxylic acid as an essential component # 0.05 to 10 parts by weight of silicone oil is blended to 100 parts by weight of a composition consisting of 5 to 50% by weight. The present invention provides a polyphenylene sulfide resin composition characterized by:

The PPS resin used in the present invention is a polymer containing structural formula % or more, more preferably 90 mol % or more, and if the repeating unit is less than 70 mol %, heat resistance will be impaired, so it is not preferable.

PPS resins are generally made of a relatively low molecular weight polymer obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by Japanese Patent Publication No. 52-12240. In the case of the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, crosslinking by heating in an oxygen atmosphere after polymerization or by crosslinking with peroxide etc. It is also possible to increase the degree of polymerization and use it by adding an agent and heating it, and in the present invention, it is possible to use PPS resin obtained by any method, but the effect of the present invention is remarkable. Koto and ppsv! Because the toughness of the fat itself is excellent,
Essentially linear and relatively high molecular weight polymers obtained by the production method typified by Japanese Patent No. 2240 are more preferably used.

In addition, less than 30 mol% of the repeating units in the PP5vIJ resin can be composed of repeating units having the following structural formula.

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it is possible to obtain a molded product, but the PPS resin itself should have a toughness of 100 poise or more, and a moldability of 10. Those of OOO poise or less are more preferably used.

The PPS resin used in the present invention is preferably one that is produced through the above polymerization step and then subjected to acid treatment, hot water treatment, or washing with an organic solvent.

In the case of acid treatment, the PPS in the present invention is as follows.
The acid used for the acid treatment of the resin is not particularly limited as long as it does not have the effect of decomposing the PPS resin, and examples include acetic acid, hydrochloric acid,
Examples include sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propylic acid, among which acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate the PPS resin, such as nitric acid, are not preferred.

The acid treatment method is to add 5 liters of PP to an acid or an aqueous solution of an acid! There are methods such as immersing PPS resin powder in the resin, and it is also possible to stir or heat as necessary.1 For example, when using acetic acid, PPS resin powder is immersed in an aqueous solution with a pH of 4 heated to 80 to 90'C. A sufficient effect can be obtained by stirring for 30 minutes. The acid-treated PPS resin needs to be washed several times with water or warm water to physically remove residual acids or salts.

The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the effect of chemical modification of the PPS resin by acid treatment.

When performing hot water treatment, the procedure is as follows.

When treating the ppsVIj fat used in the present invention with hot water, it is important that the temperature of the hot water be 100°C or higher, more preferably 120°C or higher, even more preferably 150°C or higher, particularly preferably 170°C or higher. and 1
If the temperature is 00° C., the desired chemical modification effect of the PPS resin will be small, which is not preferable.

In order to achieve the desired effect of chemical modification of PPS resin by hot water washing of the present invention, the water used is preferably distilled water or deionized water.The hot water treatment operation is as follows:
Usually, this is done by adding a predetermined amount of PPS resin to a predetermined amount of water, heating and stirring it in a pressure vessel.The ratio of PPS resin to water is preferably as much water as possible; (For which, a bath ratio of 200 g or less of pps resin is selected.

In addition, since decomposition of the terminal group is undesirable, the treatment atmosphere is preferably an inert atmosphere to avoid this. Furthermore, PP5t1 after this hot water treatment operation
! It is preferable to wash the lubricant several times with warm water to physically remove any remaining components.

When washing with an organic solvent, the procedure is as follows.

The organic solvent used for washing ppsvfJ fat in the present invention is P
There is no particular restriction as long as it does not have the effect of decomposing the PS resin, such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphorusamide,
Nitrogen-containing polar solvents such as piperazinones, sulfoxide/sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane, ketone solvents such as acetone, methyl ethyl getone, diethyl ketone, and acetophenone, dimethyl ether, dipropyl ether, dioxane, Ether solvents such as tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchloroethane,
Halogenated solvents such as chlorobenzene, methanol, ethanol, propanol, butanol, pentanol,
Examples include alcohol/phenol solvents such as ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, it is particularly preferred to use N-methylpyrrolidone, acetone, dimethylformamide and chloroform.
Further, these organic solvents may be used alone or in combination of two or more.

As a method of cleaning with an organic solvent, PP is added in an organic solvent.
5v! There are methods such as immersing J fat, and it is also possible to stir or heat as necessary.

There is no particular restriction on the washing temperature when washing the PPS resin with an organic solvent, and any temperature from room temperature to about 300°C can be selected. Although there is a tendency that the higher the cleaning temperature, the higher the cleaning efficiency, a sufficient effect can usually be obtained at a cleaning temperature of room temperature to 150°C.

It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Further, there is no particular restriction on the cleaning time, and although it depends on the cleaning conditions, in the case of batch cleaning, a sufficient effect can usually be obtained by cleaning for 5 minutes or more.

It is also possible to wash continuously.

Although it is sufficient to simply wash the ppsvIJ resin produced by polymerization with an organic solvent, in order to further exhibit the effects of the present invention, it is preferable to combine washing with water or hot water. When a high-boiling water-soluble organic solvent is used, it is preferable to wash with water or hot water after washing the organic solvent, as the residual organic solvent can be easily removed.The water used for these washings is distilled water or deionized water. Preferably it is water.

In addition, the PP5vfJ resin used in the present invention may contain antioxidants, heat stabilizers, lubricants, etc. within the range that does not impair the effects of the present invention.
Usual additives such as crystal nucleating agents, UV inhibitors, coloring agents, and small amounts of other polymers can be added;
For the purpose of controlling the degree of crosslinking of the P5vIJ fat, common peroxidants and crosslinking promoters such as thiophosphinic acid metal salts described in JP-A-59-131650, or JP-A-58-204045, Japanese Patent Publication No. 58-2040
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in Publication No. 6 and the like.

Next, the olefin copolymer used in the present invention is a copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid. 1, among others, ethylene is preferably used. In addition, glycidyl esters of α,β-unsaturated acids are compounds represented by the general formula (R represents a hydrogen atom or a lower alkyl group), and specifically include glycidyl acrylate, glycidyl methacrylate, and ethacrylic acid. Among them, glycidyl methacrylate is preferably used. α in olefin copolymers
, the amount of copolymerization of glycidyl ester of β-unsaturated acid is 0.
5~401! % by weight, especially 3 to 30% by weight, preferably 0
．． If it is less than 5% by weight, no impact property improvement effect can be obtained;
If the weight percentage is exceeded, PP5t! This is not preferred because gelation occurs during melt-kneading with I fat, resulting in deterioration of extrusion stability, moldability, and mechanical properties.

In addition, the olefin copolymer may contain other copolymerizable unsaturated monomers, such as vinyl ether, vinyl acetate, vinyl propionate, acrylic acid, in an amount of 40% by weight or less and within a range that does not impair the purpose of the present invention. Methyl, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized.

Regarding the blending ratio of PPS resin and olefin copolymer, if the olefin copolymer is less than 5% by weight, it is difficult to obtain the effect of improving impact properties, and if it exceeds 50% by weight, PP
Not only is there a risk that the strength, rigidity, and heat resistance of the S resin may be impaired, but also gelation occurs during melt mixing, which tends to impair extrusion stability and moldability.
I fat 50-95% by weight, olefin polymer 50%
~5% by weight is preferred, more preferably PP5vIj
60 to 95% by weight of fat, 40% of olefin copolymer
~5% by weight, especially ppsv! A range of 30 to 1 (1% by weight) of the olefin polymer can be selected for 70 to 90% by weight of 1 fat.

In addition, in the present invention, ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/(meth)acrylic acid and derivatives thereof copolymers, hydrogenated products of styrene/butadiene/styrene block copolymers, etc. An elastomer component can also be used in combination with the above olefin copolymer.

The silicone oil used in the present invention includes polyorganosiloxanes such as polydimethylsiloxane, and epoxy groups, carboxyl groups, amino groups, hydroxyl groups, and mercapto groups in a part of the m chain and/or terminal methyl group of polydimethylsiloxane. This is a modified polyorganosiloxane into which a reactive substituent has been introduced.

The viscosity of the silicone oil is not particularly limited, and those with a viscosity at 25°C of 10 to 10 to 10,000 OOCS can be used, but from the viewpoint of improving handling properties and molding characteristics, it is preferably in the range of 100 to 50.0OOC8. Particularly preferred are those.

The amount of silicone oil is based on 100 parts by weight of the pps* fat composition containing the olefin copolymer.
A range of 0.05 to 10 parts by weight, preferably 0.1 to 7 parts by weight is suitable. If the amount is 0.05 parts by weight without grooves, the desired effect of improving sliding properties and extrusion stability cannot be obtained, and if it is more than 10 parts by weight, the impact strength of the composition will decrease, which is not preferable.

In the present invention, 1Iji fibrous and/or granular reinforcing agents are not essential components, but PP5f! I
It can be blended in an amount not exceeding 300 parts by weight based on the total of 100 parts by weight of fat and olefin copolymer, and strength, rigidity, and heat resistance are usually improved by blending in a range of 10 to 300 parts by weight. , it is possible to improve dimensional stability, etc.

Such male reinforcing materials include glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, and asbestos 4311.
Examples include fibers, gypsum fibers, metal fibers, *fibers, and carbon fibers.

Granular reinforcing materials include wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, and metals such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. Examples include oxides, carbonates such as calcium carbonate, magnesium carbonate, dolomite, sulfates such as calcium sulfate, barium sulfate, glass beads, boron nitride, silicon carbide and silica, which may be hollow.

These reinforcing materials can be used in combination of two or more,
If necessary, it can be used after being pretreated with a silane-based or titanium-based coupling agent.

There are no particular limitations on the means for preparing the composition of the present invention, but PP5
T! A typical method is to melt-knead I fat, olefin polymer, silicone oil, and reinforcing material if necessary in an extruder at a temperature equal to or higher than the melting point of the PPS resin, and then pelletize.

In addition, the melt-kneading temperature is set to sufficiently melt the composition.
Generally, the temperature is preferably 280°C or higher, and 340°C or lower, ie, 280 to 340°C, from the viewpoint of preventing thermal deterioration and gelation of the olefin copolymer.

The present invention will be explained in more detail with reference to Examples below.

<Example> Reference Example 1 (Polymerization of PPS resin) In an autoclave, 3.26 kg of sodium sulfide (25 mol, containing 40% of water of crystallization), 4 g of sodium hydroxide, 1.36 kg of sodium hexate trihydrate and +r ( About 10 mol) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 7.9 kir were added, and while stirring, gradually added 2
Distilled water heated to 0.05°C and containing 1.36 kg of water
1 was removed, the remaining mixture contained 3.75 kir (25,5 mol) of 1,4-dichlorobenzene and NMP
The reaction product was washed 5 times with hot water at 70°C and dried under reduced pressure at 80°C for 24 hours to give a melt viscosity of about 2.500 poise (320°C, shear rate 1 ,000 seconds-') powdered PPS resin approximately 2k
I got g.

The same operation was repeated and used in the examples described below.

Example 1 Approximately 2 k[9 PP5vfJ fat powder obtained in Reference Example 1]
It was poured into an acetic acid aqueous solution 201 with a pH of 4 heated to 0°C, and after continued stirring for about 30 minutes, it was filtered and the pH of the furnace solution was adjusted to 7.
Rinse with deionized water at approximately 90°C until
The mixture was dried under reduced pressure for 24 hours to form a powder.

After tri-blending this PPS resin powder, ethylene-glycidyl methacrylate (88/12 weight ratio) copolymer (hereinafter abbreviated as olefin copolymer) and silicone oil with the composition shown in Table 1, 320℃
The mixture was supplied to a single screw extruder with a diameter of 40r=mφ and melt-kneaded to obtain PP5il fat composition pellets. In addition, during melt-kneading, the presence or absence of gel-like material generation due to abnormal retention was determined by visually observing the appearance of the extrusion gut surface.

This pellet was supplied to an injection molding machine set at a cylinder temperature of 300 to 320°C and a mold temperature of 150°C to form a test piece. The Izot impact strength and sliding properties of the above resin composition were measured according to the following methods, and the results are shown in Table 1.

A. Izot impact strength: ASTM D256B, sliding properties (dynamic friction coefficient and wear coefficient) Suzuki thrust abrasion tester Load: 15 glare f/cd Speed: 30 m/min Compatible material: SCM 21 As is clear from Table 1. It can be seen that the PPS resin composition of the present invention has high Izod impact strength, and is a material with excellent sliding properties with extremely low dynamic friction coefficient and wear coefficient.

Comparative Example 1 The same procedure as Example 1 was carried out except that the olefin copolymer was not blended, and the results are shown in Table 1.

Although the coefficient of dynamic friction and the coefficient of wear were reduced, the material had low Izot impact strength.

Comparative Example 2 The same procedure as in Example 1 was carried out except that silicone oil was not blended, and the results are shown in Table 1. A large number of foreign substances were found in the extrusion gut of this composition, and although the molded product had high Izot impact strength, it was a material with a large coefficient of dynamic friction and coefficient of wear.

Comparative Example 3 Example 1 except that 12 parts by weight of silicone oil was added.
The results are shown in Table 1. Izotsu impact strength decreased significantly.

<Effects of the Invention> The ppst! of the present invention! I fat composition has heat resistance, impact resistance,
Due to its balanced and excellent extrusion stability and sliding properties,
It has great practical value as a sliding material for insulation sleeves, gears, tubes, etc.

Patent application Daitoshi Co., Ltd.

Claims (2)

[Claims] (1) (A) Polyphenylene sulfide resin 50-95
% by weight and (6) 60-99% by weight of α-olefin and 1-4 glycidyl esters of α, β-unsaturated carboxylic acids.
Olefin copolymer containing 0% by weight as an essential component 5 to 5
A polyphenylene sulfide resin composition comprising 0.05 to 10 parts by weight of silicone oil per 100 parts by weight of the composition comprising 0% by weight. (2) The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin has been subjected to acid treatment, hot water treatment, or cleaning treatment with an organic solvent.