JPH06279676A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific polyphenylene sulfide resin and a specific olefin copolymer, having excellent heat-resistance and impact resistance and useful for electric part items, electronic part items, etc. CONSTITUTION:The objective composition contains (A) preferably 50-99wt.% of a polyphenylene sulfide resin washed with acetone and (B) preferably 50-1wt.% of an olefin copolymer having glycidyl group and containing 60-99.5wt.% of an alpha-olefin and 0.5-40wt.% of an alpha,beta-unsaturated acid glycidyl ester as essential components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition having improved impact properties. More specifically, the impact properties of polyphenylene sulfide resin can be improved by incorporating an olefin copolymer into a specific polyphenylene sulfide resin. The present invention relates to an improved polyphenylene sulfide resin composition.

[0002]

2. Description of the Related Art Conventionally, as a polyphenylene sulfide resin composition having improved impact properties, Japanese Patent Application Laid-Open No. 58-15 has been proposed.
Japanese Patent No. 4757 discloses a composition obtained by blending an olefin-based copolymer composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid.

[0003]

However, even in the composition described in the above publication, the usual polyphenylene sulfide resin is blended as it is with the rubber component containing an epoxy group such as the olefin copolymer described in the above publication, The current situation is that a sufficient effect of improving impact properties has not been obtained. Therefore, an object of the present invention is to obtain a polyphenylene sulfide resin composition having a remarkable impact improving effect of a rubber component.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and by blending a specific polyphenylene sulfide resin with a specific rubber component,
The inventors have found that the above problems can be solved and reached the present invention.

That is, according to the present invention, a polyphenylene sulfide resin washed with acetone is used as an α-olefin 60-9.
A polyphenylene sulfide resin composition containing an olefinic copolymer having a glycidyl group containing 9.5% by weight and 0.5 to 40% by weight of a glycidyl ester of an α, β-unsaturated acid as an essential component. Is provided.

The polyphenylene sulfide (hereinafter referred to as PPS) used in the present invention is a polymer containing a repeating unit represented by the following structural formula in an amount of 70 mol% or more, more preferably 90 mol% or more. If the repeating unit content is less than 70 mol%, the heat resistance tends to be impaired, which is not practical.

[0007]

[Chemical 1]

PPS is generally disclosed in Japanese Examined Patent Publication No. 45-3368.
A polymer having a relatively small molecular weight obtained by the production method represented by JP-B No. 52-12240, and an essentially linear polymer having a relatively high molecular weight obtained by the production method represented by JP-B-52-12240. In the polymer obtained by the method described in JP-B-45-3368, after polymerization,
It is also possible to increase the degree of polymerization by heating in an oxygen atmosphere or by adding a crosslinking agent such as a peroxide and heating. In the present invention, PPS obtained by any method can be used, but the effect of the present invention is remarkable, and PP
Because of the excellent toughness of S itself, the above Japanese Patent Publication No. 52-
The essentially linear and relatively high molecular weight polymer obtained by the production method represented by 12240 can be more preferably used.

Further, PPS is 30 mol% of the repeating unit.
It is possible to configure less than the repeating unit having the following structural formula.

[0010]

[Chemical 2]

The melt viscosity of PPS used in the present invention is
There is no particular limitation as long as a molded product can be obtained.
From the standpoint of toughness of PS itself, 100 poise or more is preferable, and from the viewpoint of moldability, those of 10,000 poise or less are more preferably used.

The most important point of the present invention is that PPS is washed with acetone before use. Although the detailed reason is not clear, impact properties are remarkably improved by washing PPS with acetone and blending the olefin-based copolymer.

As a method of washing with acetone, there is a method of immersing PPS in acetone or the like, and it is also possible to appropriately stir or heat if necessary.

The time of washing with acetone is not particularly limited as long as it is after the polymerization of PPS, and it is possible to subject the post-treatment / drying of PPS to the acetone washing after the polymerization, and to use the polymerization solvent after the polymerization. It is also possible to wash the infiltrated PPS with water after washing with water or acetone with the water after washing with water as it is. Furthermore, the reaction mixture after completion of PPS polymerization is put into washing acetone or washed into the reaction mixture. It is also possible to wash by adding acetone.

The washing temperature for washing the PPS with acetone is not particularly limited, and any temperature in the range of normal temperature to the boiling point of acetone can be selected. The higher the cleaning temperature is, the higher the cleaning efficiency tends to be. However, cleaning at room temperature is usually sufficient.

It is also possible to wash under pressure at a temperature above the boiling point of acetone in a pressure vessel. Also, the washing time is not particularly limited. Although it depends on the washing conditions, in the case of batch type washing, by washing for 5 minutes or more,
A sufficient effect can be obtained. It is also possible to wash in a continuous manner.

It is sufficient to wash the PPS produced by the polymerization with acetone, but it is preferable to combine it with water washing or warm water washing in order to further exert the effects of the present invention.

In the PPS used in the present invention, the usual additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, UV inhibitors, and colorants, etc. may be added as long as the effects of the present invention are not impaired. It is possible to add small amounts of other polymers,
For the purpose of controlling the degree of crosslinking of PPS, a common peroxide and a crosslinking accelerator such as a metal thiophosphinic acid salt described in JP-A-59-131650 or JP-A-5-135650.
It is also possible to add a crosslinking inhibitor such as dialkyltin dicarboxylate and aminotriazole described in JP-A-8-204045 and JP-A-58-204046. The olefin copolymer used in the present invention is a copolymer composed of α-olefin and a glycidyl ester of α, β-unsaturated acid, and the α-olefin here is ethylene, propylene, butene-1 or the like. Among them, ethylene is preferably used.

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

[Chemical 3] (R represents a hydrogen atom or a lower alkyl group.)

Specific examples of the compound include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like. Of these, glycidyl methacrylate is preferably used. The copolymerization amount of the glycidyl ester of α, β-unsaturated acid in the olefin copolymer is preferably 0.5 to 40% by weight, particularly preferably 3 to 30% by weight, and if less than 0.5% by weight, the desired effect is obtained. If it exceeds 40% by weight, gelation occurs during melt-kneading with PPS, and extrusion stability, moldability and mechanical properties deteriorate, which is not preferable.

Further, the olefin-based copolymer contains 40% by weight or less, and other copolymerizable unsaturated monomers such as vinyl ether, vinyl acetate and propionic acid within a range not impairing the object of the present invention. Vinyl, methyl acrylate, methyl methacrylate, acrylonitrile, styrene and the like may be copolymerized.

The proportion of PPS and the olefin copolymer to be blended is not particularly limited, but in order to sufficiently exert the intended effect, the olefin copolymer is 1% by weight or more, and the heat resistance In view of suppression of gelation at the time of melt-kneading, extrusion stability, and moldability, it is preferably blended in a range of 50% by weight or less. In particular, it is preferable that the olefin copolymer is blended in the range of 50 to 1 wt% with respect to 50 to 99 wt% of PPS. Further, for applications requiring rigidity and strength, it is more preferable to blend the olefin copolymer in the range of 30 to 1% by weight with respect to 70 to 99% by weight of PPS.

In the present invention, the fibrous and / or granular reinforcing agent is not an essential component, but PPS may be added if necessary.
It is possible to mix in a range not exceeding 400 parts by weight with respect to a total of 100 parts by weight of the composition of and an olefinic copolymer, and 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, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, and carbon fibers.

Further, as a granular reinforcing agent, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, alumina, silicon chloride, magnesium oxide, zirconium oxide, titanium oxide, etc. Metal oxides, calcium carbonate, magnesium carbonate, dolomite and other carbonates, calcium sulfate, barium sulfate and other sulfates, glass beads,
Examples thereof include boron nitride, silicon carbide and silica, which may be hollow. These reinforcing agents can be used in combination of two or more kinds, and if necessary, they can be used after being pretreated with a coupling agent such as a silane type and a titanium type.

The means for preparing the composition of the present invention is not particularly limited, but PPS, an olefinic copolymer and, if necessary, a reinforcing agent are melt-kneaded in an extruder at a temperature not lower than the melting point of PPS and then pelletized. The method of doing is typical.

The melt-kneading temperature is preferably 280 ° C. or higher in order to sufficiently melt PPS, and 340 ° C. or lower in order to prevent thermal deterioration and gelation of the olefin copolymer.

Further, it is possible to add other polymers to the PPS resin composition of the present invention within a range not impairing the effects of the present invention, and it is included in the scope of the present invention.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples.

The percentages, parts and ratios used in the examples represent% by weight, parts by weight and ratios by weight, respectively, unless otherwise specified.

The Izod impact strength and heat distortion temperature in this example were measured by the following measuring methods.

Izod impact strength ASTM-D-25
6 Heat Deformation Temperature ASTM-D-648 (High load 18.6 kg / cm ² ) Reference Example 1 (Polymerization of PPS) 3.26 kg of sodium sulfide (25 mol, containing 40% of water of crystallization) and 4 g of sodium hydroxide in an autoclave. , 1.36 kg (about 10 mol) of sodium acetate trihydrate and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP)
7.9 kg was charged, the temperature was gradually raised to 205 ° C. with stirring, and about 1.5 l of distilled water containing 1.36 kg of water was removed. 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 2.5
About 2 kg of powdered PPS at 00 poise (320 ° C., shear rate 1,000 sec ⁻¹ ) was obtained.

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

Example 1 About 2 kg of the powder obtained in Reference Example 1 was mixed with 20 l of acetone at room temperature.
The mixture was poured into the flask, stirred for about 30 minutes, filtered, washed with ion-exchanged water at about 90 ° C., and vacuum dried at 120 ° C. for 24 hours to obtain a powdery product.

The powder thus obtained and an ethylene / glycidyl methacrylate (88/12 ratio) copolymer were dry blended at a ratio of 80:20, and then screw type extrusion was carried out under the temperature condition of 290 to 310 ° C. Melt / Pelletize by machine. Next, a test piece for mechanical property evaluation was molded with a screw line molding machine using the obtained pellets (temperature condition setting: 290 to 300 ° C, mold temperature setting: 140 to 150 ° C). The Izod impact strength and heat distortion temperature measured on the obtained test piece are as shown in Table 1, and the polyphenylene sulfide resin composition of the present invention has an extremely high impact strength and does not contain an olefin copolymer. The decrease in heat distortion temperature was smaller than that of

Comparative Examples 1 and 2 The PPS powder obtained in Reference Example 1 was used as it is (Comparative Example 1).
Also, using an acetone-washed / water-washed / dried product (Comparative Example 2) in the same manner as in Example 1, extruding / pelletizing and injection-molding a test piece without blending an olefinic copolymer with an Izod impact. When the strength and heat distortion temperature were evaluated, the results shown in Table 1 were obtained.

As described above, as compared with Example 1 of the present invention, the one without the olefinic copolymer blended has a significantly lower Izod impact strength.

Comparative Example 3 Instead of using the PPS powder obtained in Reference Example 1 in Example 1 after washing with acetone, the PP obtained in Reference Example 1 was used.
Exactly the same as in Example 1 except that S powder was used as it was,
Melt-mix pelletizing by blending olefin-based copolymer,
Injection molding was performed to obtain a test piece. When the Izod impact strength and the heat distortion temperature of these test pieces were measured in the same manner as in Example 1, the results shown in Table 1 were obtained.

Compared with Example 1 of the present invention which uses PPS thus washed with acetone, PPS washed with water only
The Izod impact strength of this comparative example in which is used is extremely inferior, and the improvement of the impact strength due to the incorporation of the olefin copolymer is very slight.

Example 2 Polymerization was carried out in the same manner as in Reference Example 1 to obtain a reaction mixture. The reaction mixture was put into 20 l of acetone, stirred for about 30 minutes and then filtered to isolate the produced PPS. The isolated PPS was then washed 5 times with warm water at 70 ° C and washed at 120 ° C for 2 times.
After vacuum drying for 4 hours, about 2 kg of powdered PPS was obtained.

The powder thus obtained and the olefinic copolymer were dry blended at a ratio of 90:10, and melt mixing pelletizing and injection molding were carried out in the same manner as in Example 1 to obtain a test piece. When the Izod impact strength and the heat distortion temperature of these test pieces were measured in the same manner as in Example 1, the results shown in Table 1 were obtained.

Comparative Example 4 A test piece was obtained by the same procedure as in Example 1 except that 20 l of methanol was used in place of 20 l of acetone, the polymerization operation, the post-treatment operation, the melt mixing pelletization and the injection molding. The results of measuring the Izod impact strength and the heat distortion temperature of these test pieces are shown in Table 1.

Examples 3, 4 PPS washed with acetone in the same manner as in Example 1
The powder, olefinic copolymer and glass fiber are shown in Table 1.
Melt mixing pelletization and injection molding were performed in the same manner as in Example 1 at the ratios described to obtain test pieces. Table 1 shows the results of evaluating the physical properties of the obtained test pieces. All of them show excellent impact strength, and the decrease in heat distortion temperature due to the incorporation of the olefin copolymer is slight.

[0044]

[Table 1]

[0045]

INDUSTRIAL APPLICABILITY The polyphenylene sulfide resin composition of the present invention greatly improves the impact resistance characteristics without substantially impairing the heat resistance originally possessed by PPS.

The PPS composition of the present invention can be widely used in the fields of electric / electronic products, automobile parts, office equipment parts, aerospace equipment parts, etc. by utilizing its excellent properties.

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Claims (1)

[Claims] 1. A polyphenylene sulfide resin which has been washed with acetone is added to a polyphenylene sulfide resin in an amount of 60 to 99.5% by weight of α-olefin and 0.5 to 4 of a glycidyl ester of an α, β-unsaturated acid.
A polyphenylene sulfide resin composition, which contains an olefin-based copolymer having a glycidyl group whose essential component is 0% by weight.