JPH0653846B2 - Polyphenylene sulfide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition having improved impact properties, and more specifically, it relates to a specific polyphenylene sulfide resin containing an olefin copolymer. The present invention relates to a polyphenylene sulfide resin composition having improved impact properties by including it.

<Prior Art> Conventionally, as a polyphenylene sulfide resin composition having improved impact properties, Japanese Patent Application Laid-Open No. 58-154757 discloses an olein-based copolymer composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid. A composition containing a polymer is disclosed.

<Problems to be Solved by the Invention> However, even the compositions described in the above publications have insufficient effect of improving impact properties. More specifically, since the molecular chain of an ordinary polyphenylene sulfide resin is poor in reactivity as conventionally known, a rubber component having a high reactivity including an epoxy group such as the olefin copolymer described in the above publication. However, the present situation is that even if the above is blended, the effect of improving the impact properties is not sufficiently obtained because the adhesion at the interface with the polyphenylene sulfide is insufficient. Therefore, the present inventors have conducted diligent studies for the purpose of obtaining a polyphenylene sulfide resin composition having a remarkable impact improving effect of a rubber component, and by blending a specific rubber with a specific polyphenylene sulfide resin, this purpose is achieved. The inventors have found that they can be achieved and have reached the present invention.

<Means for Solving Problems> That is, according to the present invention, a polyphenylene sulfide resin having a sodium content of 900 ppm or less is added to an α-olefin 60 to 99.5% by weight and a glycidyl ester of an α, β-unsaturated acid. The present invention provides a polyphenylene sulfide resin composition, characterized by containing an olein-based copolymer containing 5 to 40% by weight as an essential component.

The polyphenylene sulfide used in the present invention (hereinafter PP
Is referred to as S) is a structural formula Is a polymer containing 70 mol% or more, more preferably 90 mol% or more, of the repeating unit represented by, and if the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable.

PPS is generally a polymer having a relatively small molecular weight obtained by the production method represented by JP-B-45-3368 and an essentially linear polymer obtained by the production method represented by JP-B-52-12240. In the polymer obtained by the method described in JP-B-45-3368, the polymer obtained by the method described in JP-B-45-3368 is heated by heating in an oxygen atmosphere after the polymerization or cross-linked with a peroxide or the like. It is also possible to use it after increasing the degree of polymerization by adding an agent and heating, and it is possible to use PPS obtained by any method in the present invention, but the effect of the present invention is remarkable , And because of the excellent toughness of PPS itself, the essentially linear and relatively high molecular weight heavy metal obtained by the production method typified by Japanese Patent Publication No. 52-12240. Body may be more preferably used.

Further, PPS can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

The melt viscosity of PPS used in the present invention is not particularly limited as long as it is possible to obtain a molded product, but PPS itself has a toughness of 100 poise or more, but a moldability of 10,000 poise. The following are more preferably used.

The PPS used in the present invention has a sodium content of 900
must be below ppm, more preferably 70
The amount used is 0 ppm or less, more preferably 500 ppm or less, and particularly preferably 300 ppm or less. The use of PPS having a sodium content of more than 900 ppm is not preferable because the remarkable effect of improving the impact properties due to the olefin copolymer cannot be obtained.

The PPS obtained according to the known method is 1000 to 150.
It contains 0 ppm or more of sodium.

Treatment such as acid treatment or hot water treatment can be used as an effective means for reducing the sodium content of PPS to 900 ppm or less. These methods include, for example, immersing PPS in an acid such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, or propyl acid or an aqueous solution thereof, and optionally heating and stirring, heating in a pressure vessel. Examples thereof include a method of treating water and a method of combining these. When these treatments are performed, it is preferable to wash with warm water several times in order to remove the remaining acid, salt and the like. By these treatments, it is necessary to be surely lowered to 900 ppm or less.

In addition, the PPS used in the present invention contains usual additives such as an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an anti-UV agent, and a coloring agent, as well as a small amount of other components, within a range not impairing the effects of the present invention. A seed polymer can be added, and further, for the purpose of controlling the degree of crosslinking of PPS, an ordinary peroxide and crosslinking acceleration of a metal salt of thiophosphinic acid described in JP-A-59-131650 are promoted. Agent or JP-A-58-20
It is also possible to blend a crosslinking inhibitor such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 4045 and JP-A No. 58-204046.

The olefin-based copolymer used in the present invention is a copolymer composed of α-olefin and α, β glycidyl ester of an unsaturated acid, and the α-olefin here is ethylene, propylene, butene-1 or the like. However, ethylene is preferably used. Further, the glycidyl ester of an α, β-unsaturated acid has the general formula (R represents a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylic acid. Among them, glycidyl methacrylate is preferably used. . Α, β in olefin copolymers
-Copolymerization amount of glycidyl ester of unsaturated acid is 0.5-
40% by weight, particularly 3 to 30% by weight is preferable, and if less than 0.5% by weight, the desired effect cannot be obtained, and if more than 40% by weight, gelation occurs during melt kneading with PPS, and extrusion stability, Moldability and mechanical properties are reduced, which is not preferable.

Further, in the olefinic copolymer, 40% by weight or less, and other copolymerizable unsaturated monomers such as vinyl ether, vinyl acetate, vinyl propionate, and acrylic, as long as the object of the present invention is not impaired. Methyl acid, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized.

The ratio of the PPS and the olefin-based copolymer to be blended is not particularly limited and can be appropriately selected depending on the intended use and performance. However, when the material is designed in consideration of rigidity, heat resistance, moldability, etc., the compounding ratio is PP
Olefin-based copolymer 30 based on S70 to 97% by weight
˜3 wt% is more preferred.

In the present invention, the fibrous and / or granular reinforcing agent is not an essential component, but PPS may be blended, if necessary, in a range not exceeding 300 parts by weight with respect to 100 parts by weight of the total amount of the olefin copolymer. Is possible, usually 10
Strength, rigidity, and
It is possible to improve heat resistance and dimensional stability.

Examples of such fibrous reinforcing agents include inorganic fibers such as glass fibers, shirasu glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers, and carbon fibers.

Further, as a granular strengthening agent, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc and alumina silicate, metal oxides such as alumina, silicon chloride, magnesium oxide, zirconium oxide and titanium oxide. Substances, calcium carbonate, magnesium carbonate, dolomite and other carbonates, calcium sulfate, barium sulfate and other sulfates, glass beads, boron nitride, silicon carbide, saloyan, silica and the like, which may be hollow. . Two or more of these reinforcing agents can be used in combination, and if necessary, they can be used after pretreatment with a coupling agent such as a silane-based or titanium-based coupling agent.

The preparation method of the composition of the present invention is not particularly limited, but PPS
A typical method is to melt-knead an olefin-based copolymer and a reinforcing agent at a temperature equal to or higher than the melting point of PPS in an extruder and then pelletize.

The melt-kneading temperature is preferably 280 to 340 ° C, and 2
If the temperature is lower than 80 ° C., melting of PPS may be insufficient, and if the temperature exceeds 340 ° C., the olefin-based copolymer may be deteriorated due to heat and gelled.

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

<Example> Reference Example 1 (Polymerization of PPS) 3.26 kg of sodium sulfide (25 mol, containing 40% of water of crystallization), 4 g of sodium hydroxide, 1.36 kg (about 10 mol) of sodium acetate trihydrate in an autoclave. And N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP)
7.9 kg was charged and the temperature was gradually raised to 205 ° C. with stirring to remove about 1.5 of distilled water containing 1.36 kg of water. 3.75 kg of 1,4-dichlorobenzene in the residual mixture
(25.5 mol) and 2 kg of NMP were added and heated at 265 ° C. for 4 hours. 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 obtain a melt viscosity of about 250.
About 2 kg of powdered PPS having 0 poise (320 ° C., shear rate 1000 sec ⁻¹ ) was obtained.

The total sodium content in this PPS powder is 1,130 pp
It was m.

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

Example 1 About 2 kg of the PPS powder obtained in Reference Example 1 was put into an acetic acid aqueous solution 20 having a pH of 4 and heated at 90 ° C., and the mixture was stirred for about 30 minutes and then filtered, and the pH of the filtrate became 7. Until about 9
It was washed with deionized water at 0 ° C. and dried under reduced pressure at 120 ° C. for 24 hours to give a powder.

The total sodium content in this PPS was 273 ppm.

This powder and ethylene-glycidyl methacrylate (88
/ 12 weight ratio) A copolymer (hereinafter abbreviated as an olefin-based copolymer) is dry blended at a weight ratio of 80:20,
The mixture was melt-mixed by a screw extruder set at 290 to 310 ° C. and pelletized. Then pellets 290-3
It was supplied to a screw in-line type injection molding machine set at 00 ° C, and a test piece for mechanical property evaluation was molded under the condition of a mold temperature of 140 to 150 ° C.

Izod impact strength (ASTM D-256), heat distortion temperature (ASTM D) measured on the obtained test piece
-648) is as described in Table 1, the impact strength was extremely large, and the decrease in heat distortion temperature was small as compared with the case where no olefin copolymer was blended.

Comparative Examples 1 and 2 The PPS powder obtained in Reference Example 1 was used as it is (Comparative Example 1).
Then, the test piece which was subjected to acetic acid treatment in the same manner as in Example 1, washed and dried (Comparative Example 2) was used, and the pelletized and injection-molded test pieces were evaluated without blending the olefin copolymer. The Izod impact strength and heat distortion temperature were as shown in Table 1.

Comparative Example 3 The same as Example 1 except that the PPS powder obtained in Reference Example 1 was used as it is instead of using the PPS powder obtained in Reference Example 1 after acetic acid treatment. By the way
The Izod impact strength and the heat distortion temperature evaluated for the test pieces melt-mixed, pelletized, and injection-molded with the olefin-based copolymer were as shown in Table 1.

Examples 2-5, Comparative Example 4 2 kg of the PPS powder obtained in Reference Example 1 and deionized water 10
After charging and into an autoclave and sealing at normal pressure, the temperature was raised to the temperature shown in Table 1 for each example,
The mixture was kept warm (treated with hot water) for about 30 minutes with stirring and then cooled. The contents were taken out, filtered, further immersed in about 10 ° C. deionized water of about 10, stirred and filtered 5 times, and dried under reduced pressure at 120 ° C. for 24 hours to obtain a powder. The total sodium content in each PPS powder was as shown in Table 1.

Hereinafter, melt-mixing, pelletizing and injection molding with an olefinic copolymer were carried out in the same manner as in Example 1, and the obtained test pieces were evaluated for their characteristic values as shown in Table 1. It was

Example 6 In Example 1, ethylene-glycidyl methacrylate (88 /
12 weight ratio) Instead of using the copolymer, the copolymerization ratio is 94
A test piece was obtained in the same manner as in Example 1 except that a / 6 (weight ratio) copolymer was used. The characteristic values evaluated for the obtained test pieces are as shown in Table 1.

Example 7 The same operation as in Example 1 was performed except that the blending ratio of the olefin-based copolymer in Example 1 was set to 10% by weight instead of 20% by weight. The characteristic values evaluated for the obtained test pieces are as shown in Table 1.

Examples 8 to 9 PPS powder treated with an acid in the same manner as in Example 1,
The olefin copolymer and the glass fiber were melt-mixed, pelletized and injection-molded in the ratios shown in Table 1 in the same manner as in Example 1, and the characteristic values evaluated for the obtained test piece were the first. It was as described in the table.

Comparative Examples 5 to 6 PPS and glass fiber obtained in Reference Example 1 (Comparative Example 5),
The PPS, the olefinic copolymer, and the glass fiber (Comparative Example 6) obtained in Reference Example 1 were melt-mixed, pelletized, and injected in the same manner as in Example 1 at the ratios shown in Table 1. The characteristic values evaluated for the molded and obtained test pieces are as shown in Table 1.

Example 10 PPS powder that has been acid-treated in the same manner as in Example 1,
An olefin copolymer and polyethylene were dry blended in a weight ratio of 80:10:10, and melt mixing, pelletizing and injection molding were carried out in the same manner as in Example 1 to obtain a test piece. The Izod impact strength with cut / notch evaluated for the obtained test piece was 37 kg · cm / cm · notch, and the heat distortion temperature (high load) was 103 ° C.

Example 11 Instead of using polyethylene in Example 10, a polyethylene-polypropylene copolymer grafted with maleic anhydride (“N-Tufmer” MP manufactured by Mitsui Petrochemical Co., Ltd.)
-0610 ") was used, and a test piece was obtained by the same method as in Example 10. The Izod impact strength with cut / notch evaluated on the obtained test piece was 41.
kg ・ cm / cm ・ notch, heat deformation temperature (high load) is 1
It was 04 ° C.

Example 12 The same PPS and olefinic copolymer as in Example 1 were used except that the blending ratio of the olefinic copolymer in Example 1 was set to 50% by weight instead of 20% by weight. The same operation was performed to obtain a test piece. The Izod impact strength with cut notch evaluated for the obtained test piece was 77 kg · cm / cm · notch, and the notched Izod impact strength was 120 kg · cm / cm ² or more.

<Effects of the Invention> According to the present invention, a polyphenylene sulfide resin composition having extremely excellent impact resistance can be obtained.

Claims (1)

[Claims] 1. A polyphenylene sulfide resin having a sodium content of 900 ppm or less, and an α-olefin 60
A polyphenylene sulfide resin composition comprising an olefin-based copolymer containing 9 to 99.5% by weight and 0.5 to 40% by weight of a glycidyl ester of an α, β-unsaturated acid as an essential component.