JPH0653848B2 - Polyphenylene sulfide composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide composition having improved impact resistance, and more specifically, it relates to a specific polyphenylene sulfide resin and an α-olefin-based copolymer. The present invention relates to a polyphenylene sulfide composition having improved impact resistance by containing a coalescence.

<Prior Art> Conventionally, polyphenylene having improved impact resistance Conventionally, as a polyphenylene sulfide resin composition having improved impact resistance, Japanese Unexamined Patent Publication (Kokai) No. 59-207921 discloses that polyphenylene sulfide resin is used as unsaturated carboxylic acid. A composition comprising an α-olefin graft-copolymerized with an acid or an anhydride thereof or a derivative thereof and an epoxy resin is disclosed.

<Problems to be Solved by the Invention> However, even with the compositions described in the above publications, the effect of improving impact resistance is insufficient. More specifically, since the molecular chain of an ordinary polyphenylene sulfide resin is poorly reactive as is conventionally known, a rubber component having high reactivity such as the copolymer described in the above publication, or the same reactive component. Even if an epoxy resin rich in water is blended, the effect of improving the impact resistance is not sufficient because the adhesion at the interface with the polyphenylene sulfide resin is insufficient.

Therefore, the present inventors have preferably modified the polyphenylene sulfide resin to impart reactivity, and have conducted intensive studies with a rubber as a subject. By adding a specific rubber component to the polyphenylene sulfide resin subjected to a specific treatment. The inventors have found that this problem can be solved and arrived at the present invention.

<Means for Solving Problems> That is, the present invention provides a polyphenylene sulfide resin treated with hot water at 100 ° C. or higher as an essential component.
Unsaturated carboxylic acid or its anhydride, or a derivative thereof graft-copolymerized with 0.05 to 10.0% by weight of α
-To provide a resin composition containing an olein-based copolymer.

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, and more preferably 90 mol% or more of the repeating unit represented by the above. 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 low molecular weight obtained by a production method represented by a relatively large molecular weight obtained by the production method represented by JP-B-45-3368 and a representative by JP-B-52-12240. There is an essentially linear polymer having a relatively high molecular weight obtained by the above-mentioned production method, and the polymer obtained by the method described in the above Japanese Patent Publication No. 45-3368 has a post-polymerization oxygen atmosphere. It is also possible to increase the degree of polymerization by heating or by adding a crosslinking agent such as peroxide and heating, and in the present invention, PPS obtained by any method can be used. However, because of the remarkable effect of the present invention and the excellent toughness of PPS itself, the production method represented by JP-B-52-12240 is used. Relatively high molecular weight polymer in the essentially linear resulting Ri may be used more preferably.

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.

In treating the PPS used in the present invention with hot water, the temperature of the hot water is 100 ° C. or higher, more preferably 120 ° C.
It is important to set the temperature to not less than 0 ° C, more preferably not less than 150 ° C, particularly preferably not less than 170 ° C, and if it is less than 100 ° C, the preferable chemical modification effect of PPS is small, which is not preferable.

The water to be used is preferably distilled water or deionized water in order to exhibit the effect of preferable chemical modification of PPS by the hot water washing of the present invention. The operation of hot water treatment is usually performed by charging a predetermined amount of water with a predetermined amount of PPS and heating and stirring in a pressure vessel. As for the ratio of PPS and water, it is preferable that the amount of water is large, but usually a bath ratio of 200 g or less of PPS to 1 part of water is selected.

In addition, since the decomposition of the terminal group is not preferable for the treatment atmosphere, an inert atmosphere is preferably used to avoid this. Further, it is preferable to wash the PPS after the hot water treatment operation with hot water several times in order to physically remove the remaining components.

The PPS to be subjected to the hot water treatment in the present invention is preferably a powder or granular material, and particularly preferably a fine powder or granular material in terms of treatment efficiency. Usually, PPS produced by a publicly known method is obtained in the form of powder or granules, so it is preferable to subject them to hot water treatment without pelletizing, etc. It is also possible to use them after classification or pulverization if necessary. Is.

It is also possible to directly subject the wet PPS after polymerization to hot water treatment.

The PPS used in the present invention contains an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, within a range that does not impair the effects of the present invention.
Ordinary additives such as UV inhibitors and colorants, and small amounts of other polymers can be added. Furthermore, for the purpose of controlling the degree of crosslinking of PPS, conventional peroxides and JP
Crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A-9-131650 or JP-A-58-2040.
It is also possible to add a crosslinking inhibitor such as dialkyltin dicarboxylate or aminotriazole described in JP-A-45-45, JP-A-58-204046 and the like.

The α-olefin-based copolymer used in the present invention is an α-olefin-based copolymer obtained by graft-copolymerizing an unsaturated carboxylic acid or an anhydride thereof, or a derivative thereof, and the α-olefin of the main component here. Examples of the system polymer include polymers such as ethylene, propylene, butene-1, isobutene, pentene-1, 4-methylpentene-1, and hexene-1, or copolymers thereof, and other copolymerizable other polymers. It may be a copolymer of monomers.

Examples of unsaturated carboxylic acids or their anhydrides that are graft-copolymerized to the α-olefin-based polymer of this trunk component include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, Methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, methyl hydrogen maleate, ethyl hydrogen maleate, methyl hydrogen fumarate, ethyl hydrogen fumarate, methyl itaconate, maleic anhydride, itaconic anhydride, methyl maleic anhydride, anhydrous Citraconic acid, endobicyclo- [2,
2,1] -5-heptene-2,3-dicarboxylic acid, endobicyclo- [2,2,1] -5-heptene-2,3-
It is a dicarboxylic acid anhydride, and these derivatives can be used, but maleic anhydride is more preferably used.

The copolymerization amount of these graft components is usually 0.05 to 1
0.0% by weight, particularly 0.1 to 5.0% by weight is preferred,
If less than 0.05% by weight, the desired effect cannot be obtained and 1
If it exceeds 0.0% by weight, gelation occurs during melt-kneading with PPS, or the resulting composition remarkably knits and weaves,
It is not preferable because problems such as deterioration of the appearance occur.

Here, the graft copolymerization means that a part or all of the α-olefin-based polymer of the trunk component is chemically bonded to the unsaturated carboxylic acid or its anhydride, or a derivative thereof, and these reactions are It can be carried out in a solution state, a suspension state, a slurry state or a molten state by a generally known method.

There is no particular limitation on the proportion of PPS and α-olefin copolymer blended, but if the α-olein copolymer is less than 3% by weight, the desired effect is difficult to obtain, and if it exceeds 30% by weight, PPS is exceeded. Not only may the strength, rigidity, and heat resistance of PPS7 be impaired, but gelation may occur during melt-kneading, impairing extrusion stability and moldability.
0-97% by weight, α-olefin copolymer 30
Is preferably 3 to 3% by weight, more preferably PPS 75 to 9
It is possible to preferably select a range of 25 to 5% by weight with respect to 5% by weight, and a range of 20 to 10% by weight of the α-olefin based copolymer with respect to 80 to 90% by weight of PPS.

In the present invention, the fibrous and / or granular reinforcing agent is not an essential component, but if necessary, blended within a range not exceeding 300 parts by weight with respect to 100 parts by weight of the total of PPS and the α-olefin copolymer. Is possible, usually 1
By blending in the range of 0 to 300 parts by weight, it is possible to improve strength, rigidity, heat resistance, dimensional stability and the like.

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, koukou fibers, 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 the α-olefin-based copolymer and the 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 α-olefin copolymer may be thermally deteriorated 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 same operation was repeated and used in the examples described below.

Reference Example 2 (Preparation of α-olein-based copolymer) 100 parts by weight of an ethylene / butene-1 copolymer consisting of 90 mol% of ethylene and 10 mol% of butene-1
After adding 0.1 parts by weight of di-t-butyl peroxide and 1.5 parts by weight of maleic anhydride dissolved in a small amount of acetone, the mixture was supplied to a screw extruder set at 200 ° C., kneaded, and pelletized. .

After crushing the pellets, unreacted maleic anhydride was extracted with acetone, and then the graft-polymerized maleic anhydride was determined by the absorption spectrum of cough on a press sheet to find 0.88% by weight of maleic anhydride. I found out.

Reference Example 3 (Preparation of α-Olein Copolymer) Reference example 2 was replaced with the use of the ethylene / butene-1 copolymer in Reference Example 2 except that 80 mol% of ethylene-propylene copolymer was used. Pellets were obtained in the same manner as in Example 2.

The amount of maleic anhydride graft-polymerized in the same manner as in Reference Example 2 was determined, and it was found to contain 0.92% by weight of maleic anhydride.

Reference Example 4 (Preparation of α-Olein Copolymer) Ethylene / butene-1 copolymer 100 used in Reference Example 2
After dissolving 1 part by weight in 500 parts by weight of toluene by heating with stirring at 90 ° C., 4 parts of maleic anhydride was added and dissolved. Next, the temperature of the solution was raised to 105 ° C., and a solution of 0.1 part by weight of di-t-butyl peroxide in 30 parts by weight of toluene was added dropwise over 30 months, and then the solution was kept at 105 ° C. for 5 hours. Polymerization was carried out. 500 parts by weight of toluene was added to the obtained graft copolymer solution to dilute it, and then an equal volume of 50 parts was added.
Graft-polymerized α-olefin-based copolymer was precipitated by dropping little by little into methanol at ℃, washed and dried. Regarding this α-olefin-based copolymer, Reference Example 2
The maleic anhydride content evaluated by exactly the same method as in Example 2 was 2.57% by weight.

Example 1 About 2 kg of the PPS powder obtained in Reference Example 1 and 10 deionized water
After charging and into an autoclave and sealing at normal pressure,
The temperature was raised to 180 ° C., the temperature was kept for about 30 minutes while stirring, and then the mixture was cooled. The contents are taken out and filtered, and further 70 ° C
The operation of immersing PPS in about 10 parts of deionized water, stirring, and filtering was repeated 5 times, and then dried under reduced pressure at 120 ° C. for 24 hours to obtain a powder.

This powder and the α-olefin-based copolymer obtained in Reference Example 2 were dry blended in a weight ratio of 80:20 to give 29
The mixture was melt-mixed by a screw extruder set to 0 to 310 ° C. and pelletized. Then pellets 290-300
It was supplied to a screw in-line type injection molding machine set at ℃, and a test piece for mechanical property evaluation was molded under the condition of a mold temperature of 150 ℃.

The Izod impact strength (ASTM D-256) and the tensile elongation (ASTM D-) measured on the obtained test piece were measured.
638) and heat distortion temperature (ASTM D-648) are as shown in Table 1, and the impact strength is extremely large,
The toughness was imparted, and the decrease in heat distortion temperature was small as compared with the case where the α-olefin copolymer was not blended.

Comparative Examples 1 and 2 The PPS powder obtained in Reference Example 1 was used as it is (Comparative Example 1).
And, a test piece which was subjected to hot water treatment in the same manner as in Example 1, washed and dried (Comparative Example 2), pelletized and injection-molded without blending the α-olefin copolymer. Table 1 shows the Izod impact strength, tensile elongation, and heat distortion temperature evaluated for.

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 hot water treatment. In the way
Table 1 shows the Izod impact strength, tensile elongation, and heat distortion temperature evaluated for the test pieces melt-mixed, pelletized, and injection-molded with the α-olefin-based copolymer.

Comparative Example 4 Instead of using the PPS powder obtained in Reference Example 1 in Example 1 with hot water treatment, the PPS powder obtained in Reference Example 1 was used as it was, and the PPS and α-olefin copolymer Total 1
Pelletization and injection molding were carried out in the same manner as in Example 1 except that 2 parts by weight of bisphenol A type epoxy resin (“Epicoat” 1007 manufactured by Yuka Shell Epoxy Co., Ltd.) was added to 100 parts by weight. I went.

The characteristic values evaluated for the obtained test pieces are as shown in Table 1.

Examples 2 to 4 and Comparative Example 5 In Example 1, in addition to using the temperature of 180 ° C. for the hot water treatment of the PPS powder obtained in Reference Example 1, the temperature shown in Table 1 was used. The same operation as in Example 1 was performed to obtain a test piece.

The characteristic values evaluated for the obtained test pieces are as shown in Table 1.

Examples 5 to 6 Instead of using the α-olefin-based copolymer obtained in Reference Example 2 in Example 1, it was obtained in Reference Example 3 (Example 5) and Reference Example 4 (Example 6), respectively. The same operation as in Example 1 was carried out except that the above α-olefin copolymer was used to obtain a test piece.

The characteristic values evaluated for the obtained test pieces are as shown in Table 1.

Example 7 In Example 1, the blending ratio of the α-olefin copolymer was 20.
The same operation as in Example 1 was performed except that the amount was 10% by weight instead of the amount 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 hot water in the same manner as in Example 1, the α-olefin-based copolymer obtained in Reference Example 2 and the glass fiber in the proportions shown in Table 1. Melt mixing, pelletizing and injection molding were carried out in the same manner as in Example 1, and the characteristic values evaluated for the obtained test pieces are as shown in Table 1.

Comparative Examples 6 to 7 PPS and glass fiber obtained in Reference Example 1 (Comparative Example 6),
The PPS obtained in Reference Example 1, the α-olefin-based copolymer obtained in Reference Example 2 and the glass fiber (Comparative Example 7) were respectively used in the same proportions as in Example 1 at the ratios shown in Table 1. The characteristic values evaluated for the test pieces obtained by melt-mixing, pelletizing and injection molding by the method described in Table 1 are as shown in Table 1.

From the results shown in Table 1, the resin composition using PPS which has been subjected to hot water treatment has particularly excellent impact resistance and toughness represented by tensile elongation at break as compared with those which are not subjected to hot water treatment. I knew it was.

Example 10 In Example 1, the epoxy resin 2 used in Comparative Example 4 was added to 100 parts by weight of the PPS and the α-olefin-based copolymer in total.
A test piece was obtained in the same manner as in Example 1 except that parts by weight were blended.

The Izod impact strength with cut / notch evaluated on the obtained test piece was 24 kg · cm / cm · notch, the heat deformation temperature (high load) was 103 ° C, and the heat deformation temperature (high load) was 100 ° C. there were.

Example 11 PPS powder treated with hot water in the same manner as in Example 1, the α-olefin copolymer obtained in Reference Example 2 and polyethylene were dry blended at a weight ratio of 80: 10-10. Then, melt mixing is performed in the same manner as in Example 1 below.
Pelletization and injection molding were performed to obtain test pieces. The Izod impact strength with cut / notch evaluated on the obtained test piece was 14 kg · cm / cm · notch, and the heat distortion temperature (high load) was 102 ° C.

<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 graft copolymerization of polyphenylene sulfide resin treated with hot water at 100 ° C. or higher with 0.05 to 10.0% by weight of unsaturated carboxylic acid or its anhydride or a derivative thereof as an essential component. A polyphenylene sulfide composition containing the above α-olein-based copolymer.