JPS62169854A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent impact resistance, consisting of a polyphenylene sulfide resin which has been treated with an acid and then washed and a specified alpha-olefin copolymer. CONSTITUTION:A particulate polyphenylene resin having a melt viscosity of 100-10,000P, composed of at least 20mol% of a repeating unit of the formula, is treated by immersing it in an aq. soln. contg. an acid such as acetic acid, hydrochloric acid, etc. and having a pH of about 4 at 80-90 deg.C for about 30min. The resin is then washed with distilled water or deionized water. 0.05-10.0wt% unsaturated carboxylic acid (anhydride) or derivative (e.g., maleic anhydride) is graft-polymerized onto an alpha-olefin (e.g., ethylene) to obtain an alpha-olefin copolymer. 100pts.wt. mixture composed of 70-97wt% said polyphenylene sulfide resin and 30-3wt% said alpha-olefin copolymer is blended with 10-300pts.wt. fibrous and/or particulate reinforcing agent (e.g., glass fiber) and the mixture is melt-kneaded at 280-340 deg.C.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has a high resistance to g! The present invention relates to a polyphenylene sulfide resin composition with improved Js properties, and more specifically, a polyphenylene sulfide resin composition with improved impact resistance by incorporating an α-olefin copolymer into a specific polyphenylene sulfide resin. It is related to.

<Prior Art> Conventionally, as a polyphenylene sulfide resin composition with improved impact resistance, Japanese Patent Laid-Open No. 59-207921 discloses a polyphenylene sulfide resin containing an unsaturated carboxylic acid, its anhydride, or a derivative thereof. A composition comprising a graft copolymerized α-olefin and an epoxy resin is disclosed.

<Problems to be Solved by the Invention> However, even in the composition described in the above-mentioned publication, the effect of improving impact resistance is insufficient. More specifically, as is conventionally known, the molecular chains of ordinary polyphenylene sulfide resins have poor reactivity, so rubber components with high reactivity such as the copolymer described in the above publication or similarly reactive Even if a polyphenylene sulfide-rich epoxy resin is blended, the adhesion at the interface with polyphenylene sulfide is insufficient, so the current situation is that a sufficient effect of improving impact resistance cannot be obtained.

Therefore, the inventors of the present invention have conducted intensive studies with the aim of obtaining a resin composition that has a remarkable effect of improving the impact properties of the rubber component by modifying polyphenylene sulfide resin in a preferable manner, imparting reactivity, and carrying out specific treatments. The inventors have discovered that this problem can be solved by blending a specific rubber component into polyphenylene sulfide resin, and have arrived at the present invention.

Means for Solving the Problems> That is, the present invention adds 0.05% of an unsaturated carboxylic acid, an anhydride thereof, or a derivative thereof as an essential component to a polyphenylene sulfide resin that has been acid-treated and then washed. The present invention provides a resin composition containing ~10.0% by weight of a graft copolymerized α-oleic copolymer.

Polyphenylene sulfide (hereinafter referred to as PP) used in the present invention
S) means 70 mol% or more, more preferably 90 mol% of repeating units represented by the structural formula -+-@-30.
It is a polymer containing the above, and the above repeating unit is 70 mol%
If it is less than that, heat resistance will be impaired, which is not preferable.

PPS is generally a polymer with a relatively small molecular weight 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. There are relatively high molecular weight polymers, etc., and in the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, by heating in an oxygen atmosphere, it is necessary to remove peroxides, etc. It is also possible to increase the degree of polymerization by adding a crosslinking agent and heating it, and in the present invention, it is possible to use PPS obtained by any method, but the effect of the present invention is remarkable. The essentially linear and relatively high molecular weight polymer obtained by the production method typified by the above-mentioned Japanese Patent Publication No. 52-12240 is more preferable because PPS itself has excellent toughness. can be used.

Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula, etc.

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 in terms of toughness of PPS itself, it is 100 poise or more, but in terms of moldability, it is io, ooo poise. The following are more preferably used.

The acid used in the acid treatment of PPS in the present invention is not particularly limited as long as it does not have the effect of decomposing PPS, and includes acetic acid,
Examples include hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propylic acid, etc. Among them, acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate PPS, such as nitric acid, are not preferred.

In the present invention, it is necessary to treat PPS'&-acid, and salts, alkalis, etc. are not preferred because they do not achieve the desired chemical modification of PPS.

The acid treatment may be carried out by immersing PPS in an acid or an aqueous solution of the acid, and stirring or heating may be carried out as necessary. For example, when using acetic acid, p
A sufficient effect can be obtained by immersing the PPS powder in an aqueous solution of H4 heated to 80 to 90°C and stirring for 30 minutes. PPS that has been subjected to acid treatment needs to be washed several times with water or hot water in order 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 preferable chemical modification effect of PPS by acid treatment. Further, in order to improve the efficiency of cleaning, it is also possible to wash with hot water of 100'C or more in a pressure vessel.

The PPS to be subjected to acid treatment in the present invention is preferably in the form of powder or granules from the viewpoint of efficiency of acid treatment and cleaning. PPS, which is usually produced by a known method, is obtained in the form of powder or granules, so it is preferable to use them without pelletizing them and then acid-treating and washing them.If necessary, they can be used after being classified or pulverized. is also possible.

Further, it is also possible to directly subject PPS in a wet state after polymerization to acid treatment.

In addition, the PPS used in the present invention may contain ordinary additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, and small amounts of various other additives, to the extent that the effects of the present invention are not impaired. A polymer can be added, and in addition, for the purpose of controlling the degree of crosslinking of PPS, a general peroxidant and a crosslinking wt accelerator such as a thiophosphinic acid metal salt described in JP-A-59-131650 can be added. agent or JP-A-58-20
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP-A-4045, JP-A-58-204046, and the like.

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

Examples of unsaturated carboxylic acids or their anhydrides that are graft copolymerized with the α-olefin polymer as the main component include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
itaconic acid, crotonic acid, methylmaleic acid, methylfumaric 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, methylmaleic anhydride, citraconic anhydride, endobicyclo-[2,2,1
]-5-hebutene-2,3-dicarboxylic acid, endobicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic anhydride, and derivatives thereof may also be used,
Among them, maleic anhydride is more preferably used.

The copolymerization amount of these graft components is 0.05 to 10.0
% by weight, especially 0.1 to 5.0% by weight, preferably 0.0
If it is less than 5% by weight, the desired effect cannot be obtained;
If it exceeds % by weight, it is not preferable because problems such as gelation occurring during melt-kneading with PPS or significant discoloration of the resulting composition and impaired appearance occur.

Graft copolymerization here means that part or all of the α-olefin polymer as the backbone component is chemically bonded to an unsaturated carboxylic acid, its anhydride, or a derivative thereof, and these reactions is in solution state, suspension state,
It can be carried out in a slurry state or in a molten state by a commonly known method.

There is no particular restriction on the ratio of PPS and α-olefin copolymer to be blended, but if the α-olefin copolymer is less than 3% by weight, it is difficult to obtain the desired effect;
If the P
PP87 is preferably 30 to 3% by weight of the α-olefin copolymer based on P570 to 97% by weight.
5 to 95% by weight, α-olefin copolymer 25
~5% by weight, especially for 580-90% by weight of PP, α-
The range of 20 to 10% by weight of the olefin copolymer can be preferably selected.

In the present invention, the tJA fibrous and/or granular reinforcing agent is not an essential component, but may be added in an amount of 300 parts per 100 parts of PPS and α-olefin copolymer in total.
It can be blended in an amount not exceeding 1 part by weight, and by blending in a range of 10 to 300 fflff 1 part, it is possible to improve strength, rigidity, heat resistance, dimensional stability, etc.

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

Particulate reinforcing agents 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, and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide, Saroyan, and silica.
These may be hollow. Two or more of these reinforcing agents can be used in combination, and if necessary, the reinforcing agent can be pretreated with a coupling agent such as a silane type or a titanium type before use.

The means for preparing the composition of the present invention is not particularly limited, but PPS
A typical method is to melt and mix PPS, an α-olefin copolymer, and a reinforcing agent in an extruder at a temperature higher than the melting point of PPS, and then pelletize the mixture.

In addition, the melting crosstalk temperature is preferably 280 to 340°C, and 280 to 340°C.
If the temperature is lower than 80°C, the melting of PPS may become insufficient, and if the temperature exceeds 340°C, the α-olefin copolymer may undergo thermal deterioration and gelation, so care must be taken.

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

<Example> Reference Example 1 (Polymerization of PPS) In an autoclave, 3.26 kg of sodium sulfide (25 mol, containing 40% crystal water), 4 g of thorium hydroxide, and 1.36 kg of sodium acetate trihydrate (approximately 10 mol) were placed in an autoclave. ) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP)>7.9Kg, and gradually heated to 205°C while stirring.
Distilled water containing 1°36Ng of water is heated to about 1.5. I
! was removed. The remaining mixture contains 3.751 g (25.5 mol) of 1,4-dichlorobenzene and N M P 2
Kg was 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 about 2 Kg of powdered PPS with a melt viscosity of about 2500 poise (320'C, shear rate 1000 s-1). Obtained.

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

Reference Example 2 (Preparation of α-oleic copolymer) To 100 parts by weight of an ethylene-butene-1 copolymer consisting of 90 mol% ethylene and 10 mol% butene-1, a mixture of monobutyl peroxide 0.1
After adding 11.51° C. parts of chlorine and anhydrous maleic, the mixture was fed to a screw extruder set at 200° C.
The mixture was kneaded and pelletized.

After pulverizing the pellets, unreacted maleic anhydride was extracted with acetone, and the amount of polymerized maleic anhydride was determined using the infrared absorption spectrum of the press sheet (Graph 1). It was found that it contains.

Reference example 3 (Preparation of α-oleic copolymer) Reference example 2
Instead of using ethylene-butene-1 copolymer in
1 q of pellets were prepared in exactly the same manner as in Reference Example 2 except that mol% of ethylene-propylene copolymer was used.

When maleic anhydride graft-polymerized in exactly the same manner as in Reference Example 2 was quantitatively determined, it contained 0.92 double toothed portions of maleic anhydride.

Reference example 4 (Preparation of α-oleic copolymer) Reference example 2
After dissolving 100 parts by weight of the ethylene-butene-1 copolymer used in 500 parts by weight of toluene by heating and 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 30 parts by weight of toluene was added with di-t.
A solution in which 0.1 part by weight of -butyl peroxide was dissolved was added dropwise over 30 minutes, and then held at 105°C for 5 hours to perform polymerization. The obtained graft copolymer solution was diluted by adding 500 parts by weight of toluene, and then added dropwise little by little to an equal amount of methanol at 50°C to obtain the graft-polymerized α-
The olefin copolymer was precipitated, washed, and dried. The maleic anhydride content of this α-olefin copolymer was evaluated in the same manner as in Reference Example 2 and was 2.57.
It was a heavy percentage.

Example 1 Approximately 2 Kl of PPS powder obtained in Reference Example 1 was heated at 90°C.
The mixture was poured into an acetic acid aqueous solution 20β heated to 20°C, kept stirring for about 30 minutes, filtered, washed with deionized water at about 80°C until the pH of the filtrate became 7, and heated at 120°C. It was dried under reduced pressure for 24 hours to form a powder.

This powder and the α-olefin copolymer obtained in Reference Example 2 were triblended at a weight ratio of 80:20.
The mixture was melt-mixed and pelletized using a screw extruder set at 0 to 310°C. Next, add pellets to 290-300
The sample was supplied to a screw in-line injection molding machine set at 150'C, and a test piece for mechanical property evaluation was molded at a mold temperature of 150'C.

The Izod impact strength (
ASTM D-256>, tensile elongation (ASTM D
-638> and heat distortion temperature (ASTM D-648
) is as shown in Table 1, and has extremely high impact strength and toughness, and the decrease in heat distortion temperature was smaller than that of those not containing an α-olefin copolymer.

Comparative Examples 1-2 The PPS powder obtained in Reference Example 1 was used as it was (Comparative Example 1)
And, a test in which pelletizing and injection molding were performed using chichinoku comparative example 2) treated with vinegar in the same manner as in Example 1, washed and dried, without blending the α-olefin copolymer. The Izot impact strength, tensile elongation, and heat distortion temperature evaluated for the pieces were as shown in Table 1.

Comparative Example 3 The PPS powder obtained in Example 1 and Reference Example 1 was mixed with vinegar M91.
In the same manner as in Example 1, except that the PPS powder obtained in Reference Example 1 was used as it was instead of the PPS powder obtained in Reference Example 1, it was melt-mixed, pelletized, and injected with an α-olefin copolymer. The Izot impact strength, tensile elongation, and heat distortion temperature evaluated for the molded test pieces were as shown in Table 1.

Comparative Example 4 Instead of treating the PPS powder obtained in Reference Example 1 with acetic acid and using it in Example 1, the PPS powder obtained in Reference Example 1 was used as it was, and the total amount of PPS and α-olefin copolymer was 1
Pelletizing and injection molding were carried out in exactly 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 00 parts by weight. I did it. .

The characteristic values evaluated for the obtained test piece were as shown in Table 1.

Example 2 The procedure was exactly the same as in Example 1, except that hydrochloric acid at pH 4 was used instead of acetic acid when acid-treating the PPS powder prepared in Example 1 and Reference Example 1. A test piece was obtained.

The characteristic values evaluated for the obtained test piece were as shown in Table 1.

Examples 3 to 4 Instead of using the α-olefin copolymer obtained in Reference Example 2 in Example 1, the α-olefin copolymers obtained in Reference Example 3 (Example 3) and Reference Example 4 (Example 4) were used, respectively. A test piece was obtained by carrying out exactly the same operation as in Example 1, except that the α-olefin copolymer was used.

The characteristic values evaluated for the obtained test piece were as shown in Table 1.

Example 5 In Example 1, the blending ratio of the α-olefin copolymer was changed to 20
The same operation as in Example 1 was carried out except that instead of using weight %, 10 weight % was used.

The characteristic values evaluated for the obtained test piece were as shown in Table 1.

Examples 6-7 PPS powder treated with acid in the same manner as in Example 1,
The α-olefin copolymer obtained by 1σ in Reference Example 2 and glass fiber were melt-mixed, pelletized, and injection molded in exactly the same manner as in Example 1 in the proportions listed in Table 1, and the resulting test The characteristic values evaluated for the pieces were as listed in Table 1.

Comparative Examples 5-6 PPS and glass fiber obtained in Reference Example 1 (Comparative Example 5),
The PPS obtained in Reference Example 1, the α-olefin copolymer obtained in Reference Example 2, and glass fiber (Comparative Example 6) were mixed in the same proportions as in Example 1, respectively, as shown in Table 1. The characteristic values evaluated for the test pieces obtained by melt-mixing, pelletizing, and injection molding using the method described in Table 1 are as shown in Table 1.

From the results in Table 1, the resin compositions using acid-treated PPS have extremely superior impact resistance compared to those without acid treatment, and in Examples 1 to 5, the impact resistance It was also found that the toughness represented by the tensile elongation at break was particularly excellent.

Example 8 In Example 1, the epoxy resin 2 used in Comparative Example 4 was added to a total of 100 parts by weight of PPS and α-olefin copolymer.
A test piece was obtained in exactly the same manner as in Example 1 except that the parts by weight were blended.

The cut and notched Izot impact strength evaluated for the obtained test piece was 23.3cm/cm.notch, the heat distortion temperature (high load) was 103°C, and the heat distortion temperature (high load) was It was heated at 100℃.

Example 9 PPS powder treated with acid in the same manner as in Example 1,
The α-olefin copolymer obtained in Reference Example 2 and polyethylene were triblended at a weight ratio of 80:10:10, and then melt-mixed, pelletized, and injection molded in exactly the same manner as in Example 1. A test piece was obtained. The cut and notched Izot impact strength evaluated for the obtained test piece was 13 kg·cm / cm·notch, and the heat distortion temperature (high load) was 104°C.

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

Claims (1)

[Claims] The polyphenylene sulfide resin that has been acid-treated and washed has an unsaturated carboxylic acid, its anhydride, or a derivative thereof as an essential component of 0.05 to 10.0
A resin composition containing a graft copolymerized α-oleic copolymer in an amount of % by weight.