JPH0354989B2 - - Google Patents

Description

[Detailed description of the invention]

<Field of Industrial Application> The present invention relates to a polyphenylene sulfide resin composition with improved impact properties, and more specifically, a polyphenylene sulfide resin composition containing an olefin copolymer in a specific polyphenylene sulfide resin. The present invention relates to a polyphenylene sulfide resin composition that has improved impact properties by increasing the impact properties. <Prior art> Conventionally, as a polyphenylene sulfide resin composition with improved impact properties, Japanese Patent Application Laid-Open No. 58-154757
JP-A-2006-100001 discloses a composition comprising an olefin copolymer comprising an α-olefin and a glycidyl ester of an α,β-unsaturated acid. <Problems to be Solved by the Invention> However, even in the composition described in the above-mentioned publication, the effect of improving impact properties is insufficient. More specifically, as is conventionally known, the molecular chains of ordinary polyphenylene sulfide resins are poor in reactivity, so polyphenylene sulfide resins containing highly reactive epoxy groups, such as the olefin-based copolymers described in the above-mentioned publication, Even if a rubber component is blended, the adhesion at the interface with polyphenylene sulfide is insufficient, so the current situation is that a sufficient effect of improving impact properties cannot be obtained. Therefore, the present inventors conducted extensive studies with the aim of obtaining a polyphenylene sulfide resin composition that has a remarkable effect of improving the impact properties of the rubber component, and added a specific rubber component to a specific polyphenylene sulfide resin. It has been discovered that this objective can be achieved by blending, and the present invention has been achieved. <Means for solving the problem> That is, the present invention adds 60 to 99.5% by weight of α-olefin and α,β-unsaturated acid to polyphenylene sulfide resin that has been acid-treated and then washed. The present invention provides a polyphenylene sulfide resin composition containing an oleic copolymer containing 0.5 to 40% by weight of glycidyl ester as an essential component. The polyphenylene sulfide (hereinafter referred to as PPS) used in the present invention has the structural formula

It is a polymer containing 70 mol % or more, more preferably 90 mol % or more of the repeating unit represented by the formula. If the repeating unit is less than 70 mol %, heat resistance will be impaired, so it is not preferable. PPS is generally a polymer with relatively low 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 polymers with relatively high molecular weight, etc., and in the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, it is possible to cure the polymer 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 obtained by any method, but the effects of the present invention are remarkable. , and because PPS itself has excellent toughness, essentially linear and relatively high molecular weight polymers obtained by the production method typified by the above-mentioned Japanese Patent Publication No. 52-12240 are more preferably used. obtain. Furthermore, less than 30 mol% of the repeating units in PPS can be composed of repeating units having the following structural formula, etc.

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[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 article, but
In terms of toughness of PPS itself, it is over 100 poise.
In terms of moldability, those having a diameter of 10,000 poise or less 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 examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propylic acid, etc. Even acetic acid, hydrochloric acid may be used more preferably, but PPS such as nitric acid
Anything that decomposes or deteriorates is undesirable. In the present invention, it is necessary to treat PPS with an acid, and salts, alkalis, etc. are not preferred because they do not achieve the desired chemical modification of PPS. The acid treatment includes methods such as immersing PPS in an acid or an aqueous solution of an acid, and it is also possible to stir or heat as appropriate, if necessary. For example, when using acetic acid, a sufficient effect can be obtained by immersing PPS powder in an aqueous solution of PH4 heated to 80 to 90°C and stirring for 30 minutes. acid treated
PPS needs to be washed several times with water or hot water to physically remove residual acids or salts. The water used for washing may be distilled water,
Preferably it is deionized water. Additionally, in order to improve cleaning efficiency, it is also possible to wash with hot water of 100°C or higher 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 in terms of efficiency of acid treatment and cleaning. PPS, which is usually produced by known methods, is obtained in the form of powder or granules, so it is preferable to use them without pelletizing and then acid treatment and washing.If necessary, they can be used after being classified or pulverized. is also possible. Furthermore, 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 they do not impair the effects of the present invention. Polymers can be added and further, for the purpose of controlling the degree of crosslinking of PPS,
Common peroxidants and crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A-59-131650, or JP-A-58-204045, JP-A-Sho.
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP 58-204046 and the like. The olefin copolymer used in the present invention is α-
It is a copolymer consisting of olefin and glycidyl ester of α,β-unsaturated acid, and α-olefin here refers to ethylene, propylene, butene-1
etc., but ethylene is preferably used. In addition, glycidyl ester of α,β-unsaturated acid has the general formula (R represents a hydrogen atom or a lower alkyl group) Specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, among which glycidyl methacrylate is preferably used. . The amount of copolymerized glycidyl ester of α,β-unsaturated acid in the olefin copolymer is 0.5 to 40% by weight,
Particularly preferred is 3 to 30% by weight; if it is less than 0.5% by weight, the desired effect cannot be obtained, and if it exceeds 40% by weight, gelation occurs during melt-kneading with PPS, resulting in poor extrusion stability, moldability, and mechanical properties. This is not preferable because it reduces the In addition, the olefinic copolymer may contain other copolymerizable unsaturated monomers, such as vinyl ether, vinyl acetate, vinyl propionate, etc., in an amount of 40% by weight or less and within a range that does not impair the purpose of the present invention.
Methyl acrylate, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized. There is no particular limitation on the proportion of PPS and olefin copolymer to be blended. In the present invention, fibrous and/or granular reinforcing agents are not essential components, but PPS may be used as needed.
It is possible to blend in an amount not exceeding 300 parts by weight with respect to a total of 100 parts by weight of the olefin copolymer and the olefin copolymer.Usually, by blending in the range of 10 to 300 parts by weight, strength, rigidity, heat resistance, It is possible to improve dimensional stability and the like. Such fibrous reinforcing agents include glass fiber, shirasu glass fiber, alumina fiber, silicon carbide fiber,
Ceramic fiber, asbestos fiber, gypsum fiber,
Examples include inorganic fibers such as metal fibers and carbon fibers. In addition, as particulate reinforcing agents, wollastenite,
Silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, metal oxides such as alumina, silicon chloride, magnesium oxide, zirconium oxide, titanium oxide, cowsium carbonate, magnesium carbonate, dolomite, etc. carbonate, calcium sulfate,
Examples include sulfates such as barium sulfate, glass beads, boron nitride, silicon carbide, Saroyan, silica, etc., and these may be hollow. Two or more of these reinforcing agents can be used in combination, and if necessary, they can be pretreated with coupling agents such as silane and titanium before use. There are no particular limitations on the means for preparing the composition of the present invention, but PPS, an olefinic copolymer, and a reinforcing agent are used.
A typical method is to melt and knead PPS in an extruder at a temperature higher than the melting point of PPS and then pelletize it. In addition, the melt-kneading temperature is preferably 280 to 340°C,
If the temperature is lower than 280°C, the melting of PPS may become insufficient, and if the temperature exceeds 340°C, the olefin copolymer may undergo thermal deterioration and gelation, so care must be taken. The present invention will be explained in more detail with reference to Examples below. <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 sodium hydroxide,
1.36 kg (approximately 10 mol) of sodium acetate trihydrate and 7.9 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, and the mixture was gradually heated to 205 kg while stirring.
The temperature was raised to ℃, and about 1.5 kg of distilled water containing 1.36 kg of water was removed. Add 3.75 Kg (25.5 mol) of 1,4-dichlorobenzene and 2 Kg of NMP to the remaining mixture.
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 approximately 2500 poise (320°C, shear rate 1000 s ^-1 ).
Approximately 2 kg of powdered PPS was obtained. The same operation was repeated and used in the examples described below. Example 1 Approximately 2 kg of PPS powder obtained in Reference Example 1 was poured into a PH4 acetic acid aqueous solution heated to 90°C, and the mixture was heated to approximately 30°C.
After stirring for a minute, filter, wash with deionized water at about 90°C until the pH of the filtrate is 7, and heat at 120°C.
It was dried under reduced pressure for 24 hours to form a powder. This powder was dry blended with ethylene-glycidyl methacrylate (88/12 weight ratio) copolymer (hereinafter referred to as olefin copolymer) at a weight ratio of 80:20, and then The mixture was melt-mixed using an extruder and pelletized. Next, the pellets are fed to a screw in-line injection molding machine set at 290-300℃, and the mold temperature is 140-150℃.
A test piece for mechanical property evaluation was molded under the following conditions. The Izot impact strength (ASTM D-256) and heat distortion temperature (ASTM D-648) measured for the obtained test piece are as shown in Table 1, and the impact strength is extremely high and the olefin copolymer The decrease in heat deformation temperature was smaller than in the case where no coalescence was added. Comparative Examples 1 to 2 Olefin-based The Izod impact strength and heat distortion temperature evaluated for test pieces pelletized and injection molded without blending the copolymer were as shown in Table 1. Comparative Example 3 In Example 1, instead of using the PPS powder obtained in Reference Example 1 after treating it with acetic acid, the PPS powder obtained in Reference Example 1 was used.
The Izod impact strength and heat distortion temperature of the test pieces evaluated by melt-mixing with the olefin copolymer, pelletizing, and injection molding were performed in exactly the same manner as in Example 1 except that the powder was used as it was. It was as described in the table. Example 2 The procedure was exactly the same as in Example 1, except that hydrochloric acid with a pH of 4 was used instead of acetic acid when the PPS powder obtained in Reference Example 1 was acid-treated. A test piece was obtained. The characteristic values evaluated for the obtained test piece were the first
It was as described in the table. Example 3 Except that instead of using the ethylene-glycidyl methacrylate (88/12 weight ratio) copolymer in Example 1, a copolymer with a copolymerization ratio of 94/6 (weight ratio) was used. A test piece was obtained by performing exactly the same operation as in Example 1. The characteristic values evaluated for the obtained test piece were as listed in Table 1. Example 4 The blending ratio of the olefin copolymer in Example 1 was
The same operation as in Example 1 was carried out except that the concentration was changed to 10% by weight instead of 20% by weight. The characteristic values evaluated for the obtained test piece were as listed in Table 1. Examples 5 to 6 PPS powder treated with acid in the same manner as in Example 1, olefin copolymer, and glass fiber were melted in exactly the same manner as in Example 1 in the proportions listed in Table 1. The characteristic values evaluated for the test pieces obtained by mixing, pelletizing, and injection molding were as shown in Table 1. Comparative Examples 4 to 5 PPS obtained in Reference Example 1 and glass fiber (Comparative Example 4), PPS obtained in Reference Example 1, olefin copolymer, and glass fiber (Comparative Example 5),
The test pieces were melt-mixed, pelletized, and injection molded in exactly the same manner as in Example 1 at the ratios listed in Table 1, and the characteristic values evaluated for the obtained test pieces were as listed in Table 1.

[Table] Example 7 PPS powder treated with acid in the same manner as in Example 1, olefin copolymer, and polyethylene were combined.
Dry blend at a weight ratio of 80:10:10, and the following:
A test piece was obtained by performing melt mixing, pelletizing, and injection molding in exactly the same manner as in Example 1. The cut/notch Izo impact strength evaluated for the obtained test piece was 38 Kg·cm/cm·notch, and the heat distortion temperature (high load) was 103°C. Example 8 Instead of using polyethylene in Example 7, a polyethylene-polypropylene copolymer grafted with maleic anhydride (manufactured by Mitsui Petrochemical Industries, Ltd. "N-") was used.
In addition to using Tafmar “MP-0610”),
A test piece was obtained in exactly the same manner as in Example 7. The cut/notch Izo impact strength evaluated for the obtained test piece was 42 kg·cm/cm·notch, and the heat distortion temperature (high load) was 104°C. Example 9 PPS powder treated with an acid in the same manner as in Example 1 and an olefin copolymer were dry blended at a ratio of 60:40, and then melt-mixed in the same manner as in Example 1. A test piece was obtained by pelletizing and injection molding. The cut/notch impact strength evaluated for the obtained test piece was 76 kg・cm/
cm・Notch, Izotsu impact strength without notch
It was 120Kg·cm/cm ² or more, and the heat distortion temperature was 98°C. Example 10 PPS powder/olefin copolymer/glass fiber treated with acid in the same manner as in Example 1 = 65/
A test piece was obtained by melt mixing pelletizing and injection molding in the same manner as in Example 5 at a ratio of 35/70. The cut/notch Izo impact strength evaluated for the obtained test piece was 20 kg·cm/cm·notch, and the heat distortion temperature was 251°C. Example 11 Acid treatment was carried out in the same manner as in Example 2. PPS
The powder and ethylene-glycidyl methacrylate (94/6 weight ratio) copolymer were dry blended at a ratio of 55:45, and then melt-mixed pelletizing and injection molding were performed in exactly the same manner as in Example 1 to obtain test pieces. I got it. The cut/notch impact strength evaluated for the obtained test piece was 77Kg・cm/
cm・Notch, Izotsu impact strength without notch
It was 120Kg·cm/cm ² or more, and the heat distortion temperature was 97°C. <Effects of the Invention> According to the present invention, a polyphenylene sulfide resin composition having extremely excellent impact resistance can now be obtained.

Claims (1)

[Claims] 1. α-olefin 60 to 99.5 is added to polyphenylene sulfide resin that has been acid-treated and washed.
1. A resin composition comprising an olefinic copolymer containing 0.5 to 40% by weight of a glycidyl ester of an α,β-unsaturated acid as an essential component.