JPH0541664B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a polyphenylene sulfide resin composition that has the excellent properties of polyphenylene sulfide resin and also has excellent mechanical properties such as impact properties. <Conventional technology> Polyphenylene sulfide (hereinafter referred to as PPS) resin has excellent properties as an engineering plastic, such as excellent heat resistance, flame retardance, high rigidity, and electrical insulation, and is suitable for injection molding. It is used for various purposes, mainly. Furthermore, since PPS resin has a good affinity for inorganic additives, it can be filled with many types of additives and fibrous reinforcing agents to provide even better mechanical properties. Conventionally, PPS resin compositions containing polyamide resins have been disclosed in Japanese Patent Publication No. 59-1422 and Japanese Patent Application Laid-open No. 53-69255. <Problems to be Solved by the Invention> Since PPS resin has the above-mentioned excellent properties, it is used for various purposes, but its drawback is that its brittleness against impact cannot be sufficiently improved. In order to improve this drawback, it is common practice to add fibrous reinforcing agents, but this has not yet reached a satisfactory level for applications that require impact resistance. This is the actual situation. Additionally, for the purpose of improving the impact resistance of PPS resin, the above-mentioned publications propose a method of blending polyamide resin, but even if polyamide resin is blended with ordinary PPS resin, the compatibility of both resins is insufficient. As it is still insufficient, mechanical strength etc. are greatly reduced and impact strength is only slightly improved, so it is hard to say that the original purpose of the blend has been achieved. Therefore, in view of the above situation, the present inventors
As a result of intensive studies to obtain a PPS resin with improved impact resistance, the inventors discovered that this problem could be solved by blending a polyamide resin into a PPS resin that had undergone a specific treatment, leading to the present invention. <Means for solving the problems> That is, the present invention provides the following:
It is characterized by blending 99-1% by weight of polyamide resin with 1-99% by weight of PPS resin of 500ppm or less.
The present invention provides a PPS resin composition, and the deionization treatment includes acid treatment, hot water treatment, and organic solvent treatment. The 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 a relatively small molecular weight obtained by the production method typified by Japanese Patent Publication No. 1973-3368, and an essentially linear polymer obtained by the production method typified by JP-B 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, 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 by adding a PPS agent and heating it, and in the present invention, it is possible to use PPS obtained by any method, but PPS is essentially linear and has a relatively high degree of polymerization. More preferably, molecular weight polymers are used. Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula, etc. It is essential that the PPS used in the present invention has been subjected to acid treatment, hot water treatment, or washing with an organic solvent. The case of acid treatment is as follows. With this invention
The acid used for acid treatment of PPS is not particularly limited as long as it does not have the effect of decomposing PPS, such as 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. 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 a PH4 aqueous solution 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 cleaning is distilled water,
Preferably it is deionized water. When performing hot water treatment, the procedure is as follows. When treating the PPS used in the present invention with hot water, it is important that the temperature of the hot water be 100°C or higher, more preferably 120°C or higher, even more preferably 150°C or higher, particularly preferably 170°C or higher,
If the temperature is less than 100°C, the effect of the preferable chemical modification of PPS will be small, which is not preferable. The water used is preferably distilled water or deionized water in order to achieve the desired effect of chemical modification of PPS by hot water washing according to the present invention. Hydrothermal treatment operations typically involve adding a given amount of PPS to a given amount of water.
is heated and stirred in a pressure vessel. As for the ratio of PPS to water, a larger amount of water is preferable, but usually a bath ratio of 200 g or less of PPS to 1 part of water is selected. Furthermore, since decomposition of terminal groups is undesirable, the treatment atmosphere is preferably an inert atmosphere to avoid this. Furthermore, it is preferable to wash the PPS after this hot water treatment several times with hot water in order to physically remove any remaining components. When washing with an organic solvent, the procedure is as follows. The organic solvent used for cleaning PPS in the present invention is PPS
There is no particular restriction as long as it does not have the effect of decomposing, for example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1,3
- Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphorusamide, piperazinones, dimethyl sulfoxide, dimethyl sulfone,
Sulfoxide/sulfone solvents such as sulfolane,
Ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrahydrofuran. Halogenated solvents such as chloroethane, perchloroethane, chlorobenzene, methanol, ethanol, propanol,
Alcohol/phenolic solvents such as butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol,
Examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform, etc. is particularly preferred. Further, these organic solvents may be used alone or in combination of two or more. As a method for washing with an organic solvent, there is a method such as immersing PPS in an organic solvent, and it is also possible to stir or heat as appropriate if necessary. There are no particular restrictions on the cleaning temperature when cleaning PPS with an organic solvent, and any temperature from room temperature to about 300°C can be selected. The higher the cleaning temperature, the higher the cleaning efficiency, but usually from room temperature to 150℃
A sufficient effect can be obtained at a cleaning temperature of . It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Furthermore, there is no particular restriction on the cleaning time. Although it depends on the cleaning conditions, in the case of batch cleaning, sufficient effects can usually be obtained by cleaning for 5 minutes or more. It is also possible to wash continuously. Although it is sufficient to simply wash the PPS produced by polymerization with an organic solvent, in order to further exhibit the effects of the present invention, it is preferable to combine washing with water or hot water. In addition, when using a high-boiling water-soluble organic solvent such as N-methylpyrrolidone, washing with water or warm water after washing with the organic solvent
This is preferred because the residual organic solvent can be easily removed.
The water used for these washings is preferably distilled water or deionized water. In the present invention, it is essential to subject PPS to acid treatment, hot water treatment, or washing with an organic solvent, but it is also possible to combine two or more of these treatments, and there is no particular restriction on the order. In the present invention, the PPS to be subjected to acid treatment, hot water treatment, or cleaning with an organic solvent is preferably in the form of powder or granules from the viewpoint of efficiency of treatment and cleaning. PPS, which is usually produced by known methods, is obtained in the form of powder and granules, so it is preferable to use them for processing and cleaning without pelletizing them, and if necessary, they may be used after being classified or pulverized. It is possible. The sodium content of the deionized PPS used in the present invention must be 500 ppm or less, preferably 300 ppm or less. If PPS with a sodium content exceeding 500 ppm is used, it is undesirable because it has poor compatibility with polyamide resin. PPS obtained according to known methods is 1000 ~
Contains over 1500ppm sodium. As an effective means for reducing the sodium content of such PPS to 500 ppm or less, the above-mentioned treatments such as acid treatment, hot water treatment, or washing with an organic solvent can be used. The melt viscosity of PPS used in the present invention is not particularly limited as long as it can be kneaded with polyamide, but
Normally 100 to 10,000 poise (320℃, shear rate 10/sec)
are used. The polyamides used in the present invention include polyamides obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam, and amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Polyamides derived from ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,
4-/2,4,4-trimethylhexamethylenediamine, 1,3- and 1,4-bis(aminomethyl)cyclohexane, bis(4,4'-aminocyclohexyl)methane, meta- and para-xylylenediamine, etc. Aliphatic, cycloaliphatic, aromatic diamines and adipic acid, suberic acid, sebacic acid, dodecanedioic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid,
Polyamides derived from dimer acids and acid derivatives such as aliphatic, alicyclic, aromatic dicarboxylic acids such as acid chlorides, or acid derivatives such as acid halides, copolyamides and mixed polyamides thereof. Among these, polycaproamide (nylon 6), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene adipamide (nylon 66), and copolyamides containing these as main components are usually used. Useful. As a method for polymerizing polyamide, generally known melt polymerization, solid phase polymerization, solution polymerization, or a combination of these methods can be employed. The degree of polymerization of polyamide is not particularly limited, and the relative viscosity (1 g of polymer is dissolved in 100 ml of 98% concentrated sulfuric acid,
(measured at 25°C) within the range of 2.0 to 5.0 can be arbitrarily selected depending on the purpose. In the present invention, the blending ratio of PPS resin and polyamide resin is 1 to 99% by weight of polyamide resin to 99 to 1% by weight of PPS resin. In areas where the proportion of PPS resin is high, properties such as impact resistance can be imparted without impairing the inherent heat resistance and moisture resistance of PPS resin, and conversely, the proportion of polyamide resin is high. In this region, properties such as heat resistance and moisture resistance can be imparted to polyamide resin without impairing its inherent properties. in this way
A well-balanced resin composition can be obtained in both the blending range of PPS resin and polyamide resin. Although there are no particular limitations on the means for preparing the composition consisting of PPS and polyamide in the present invention, a typical method is to melt-knead PPS and polyamide in an extruder at a temperature higher than the melting point of PPS and polyamide, and then pelletize the mixture. It is. In addition, the resin composition composed of PPS and polyamide used in the present invention may contain antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, and flame retardants within the range that does not impair the effects of the present invention. Usual additives such as and small amounts of other polymers can be added,
Furthermore, for the purpose of controlling the degree of crosslinking of PPS, ordinary peroxidants and crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A-59-131650 or JP-A-58-204045 are used. , Japanese Patent Publication No. 1983-
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in Publication No. 204046 and the like. In the present invention, fibrous and/or granular reinforcing agents are not essential components, but PPS may be used as needed.
It can be blended in an amount not exceeding 400 parts by weight per 100 parts by weight of the total of 100 parts by weight of the polyamide resin and polyamide resin, and by blending in the range of 10 to 300 parts by weight, strength, rigidity, heat resistance, and dimensional stability are improved. It is possible to improve the following. 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, calcium 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. The present invention will be explained in more detail by giving Examples above. <Example> In this example, tensile strength, bending strength, Izod impact strength, heat distortion temperature, and water absorption were measured according to the following methods. Tensile strength: ASTM-D638 Bending strength: ASTM-D790 Flexural modulus: ASTM-D790 Izot impact strength: ASTM-D256 Heat distortion temperature: ASTM-D648 Water absorption: ASTM-D570 Reference example 1 (PPS) In the autoclave, 3.26 kg of sodium sulfide (25 moles, containing 40% water of crystallization), 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 residual 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 total sodium content in this PPS powder is
It was 1180ppm. The same operation was repeated and used in the examples described below. Example 1 Approximately 2 kg of the PPS powder obtained in Reference Example 1 was placed in a PH4 acetic acid aqueous solution heated to 90°C, and approximately
After stirring continuously for 30 minutes, rinse with deionized water at about 90℃ until the pH of the liquid becomes 7, and then boil at 120℃.
It was dried under reduced pressure for 24 hours to form a powder. The total sodium content in this PPS was 274 ppm. This powder and polyhexamethylene adipamide ((CM3001 manufactured by Toray Industries, Inc.) (hereinafter referred to as nylon 66))
After dry-blending the mixture with pellets in the proportions shown in Table 1, the mixture was melt-kneaded using a screw extruder set at 290-310°C and pelletized. Next, the pellets were supplied to a screw in-line injection molding machine set at 290 to 300°C, and test pieces for mechanical property evaluation were molded at a mold temperature of 150°C. The tensile strength (ASTM D-638) and bending strength (ASTM D-
790), flexural modulus (ASTM D-790), Izod impact strength (ASTM D-256), heat distortion temperature (ASTM D-648) and water absorption rate (ASTM D-
570) is as shown in Table 2, and it had extremely high impact strength, and the decrease in heat distortion temperature was smaller than that of the material that did not contain nylon 66. Comparative Examples 1 to 2 Using the PPS powder obtained in Reference Example 1 as it was (Comparative Example 1) and the one treated with acetic acid in the same manner as in Example 1, washed and dried (Comparative Example 2), polyamide resin was prepared. Pelletizing without adding
The tensile strength, flexural strength, flexural modulus, Izot impact strength, heat distortion temperature, and water absorption rate evaluated for the injection molded test pieces were as shown in Table 2. Example 2 Approximately 2 kg of the PPS powder obtained in Reference Example 1 and 10 kg of deionized water were placed in an autoclave, sealed at normal pressure, heated to 175°C, and heated for approximately 30 min while stirring.
After keeping warm for a minute, it was cooled. Remove the contents and add PPS to 70℃ deionized water for about 10 minutes.
The operations of dipping, stirring, and filtering were repeated five times. The total sodium content in this PPS was 288 ppm. Hereinafter, nylon 66 was prepared in exactly the same manner as in Example 1.
and melt mixing and pelletizing at the ratios listed in Table 1.
The characteristic values evaluated for the test pieces obtained by injection molding were as shown in Table 2. Example 3 About 2 kg of the powder obtained in Reference Example 1 was put into NMP20 heated to 100°C, stirred for about 30 minutes, filtered, and then washed with ion-exchanged water at about 90°C. The total sodium content in this PPS was 315 ppm. Hereinafter, nylon 66 was prepared in exactly the same manner as in Example 1.
and melt mixing and pelletizing at the ratios listed in Table 1.
The characteristic values evaluated for the test pieces obtained by injection molding were as shown in Table 2. Comparative Examples 3 and 4 The PPS obtained in Reference Example 1 was treated with hot water in the same manner as in Example 2, washed and dried (Comparative Example 3), and the PPS obtained in Reference Example 1 was treated with NMP in the same manner as in Example 3. , washed and dried (Comparative Example 4), pelletized without adding polyamide resin,
The characteristic values evaluated for the injection molded test pieces were as listed in Table 2. Examples 4 and 5 The same operations as in Example 1 were carried out, except that the blending ratio of nylon 66 was changed to 30% by weight as in Example 1 and was changed to the ratio shown in Table 1. The characteristic values evaluated for the obtained test pieces were as listed in Table 2. Comparative Examples 5 to 6 In Example 1, instead of using the PPS powder obtained in Reference Example 1 after treating it with acetic acid, PPS obtained in Reference Example 1 was used.
The same procedure as in Example 1 was carried out, except that the powder was used as it was and the proportion of nylon 66 was as shown in Table 1. The characteristic values evaluated for the obtained test pieces are listed in Table 2, and compared to those using deionized PPS,
The improvement in impact strength was minimal, and the mechanical strength was small. Comparative Examples 7 and 8 Nylon 66 alone (Comparative Example 7) and the PPS powder obtained in Reference Example 1 were used as they were and blended in the proportions listed in Table 1 (Comparative Example 8), and the same operations as in Example 1 were carried out. The characteristic values evaluated were as listed in Table 2. Compared with Examples 4 and 5 of the present invention, the heat distortion temperature, water absorption rate, etc. are inferior. Further, when Comparative Example 8 is compared with Example 4 of the present invention, it is clear that the physical properties are greatly improved by using the PPS treated with acetic acid of the present invention. Examples 6 to 8, Comparative Examples 9 to 11 The PPS powder obtained in Reference Example 1 was used as it was (Comparative Examples 9 to 11), and the PPS powder was treated with acetic acid in the same manner as in Example 1, washed, and dried ( Examples 6 to 8), and instead of using nylon 66 in Example 1, nylon 6 (CM1001 manufactured by Toray Industries, Inc.) (Example 6) and nylon 6I polymerized from isophthalic acid/hexamethylene diamine (Example 7) were used. ), 2, 4, 4-, 2, 2, 4
- Trimethylhexamethylenediamine/terephthalic acid polymer amorphous polyamide (Denamit)
Blending, melt-mixing, pelletizing, and injection molding were carried out in the same manner as in Example 1, except that Nobel's "Trogamide T" (Example 8) was used in the proportions listed in Table 1. The characteristic values evaluated for the obtained test pieces were as listed in Table 2. Examples 9 and 10 The PPS powder obtained in Reference Example 1 was treated with acetic acid in the same manner as in Example 1, and chopped strands of nylon 66 and glass fiber (Nippon Electric Glass Co., Ltd.)
manufactured by ESC03TN-102/P) in the proportions listed in Table 1, and melt-mixed, pelletized, and injection molded in exactly the same manner as in Example 1, and the characteristic values evaluated for the obtained test pieces were as follows. It was as stated in the second vote. Comparative Examples 12, 13 Except for using the PPS powder obtained in Reference Example 1 as is, the same operations as in Examples 9 and 10 were performed, and the characteristic values evaluated for the obtained test pieces are shown in Table 2. It was as described. Comparative Examples 14, 15 The PPS powder obtained in Reference Example 1 was used as it was (Comparative Example 14), and the one treated with acetic acid in the same manner as in Example 1, washed, and dried (Comparative Example 15) was used to prepare polyamide resin. Examples 9 and 10 without blending
The characteristic values evaluated for the test pieces obtained by carrying out exactly the same operation as described in Table 2 are as shown in Table 2. Example 11 In Example 3, 1,3-dimethylimidazolidinone (hereinafter abbreviated as DMI) was used instead of NMP for washing the PPS powder obtained in Reference Example 1 with an organic solvent. The same operation as in Example 3 was performed to obtain PPS powder. The total sodium content in this PPS was 330 ppm. Hereinafter, nylon 66 was prepared in exactly the same manner as in Example 9.
The test pieces were melt-mixed with glass fibers, pelletized, and injection molded, and the characteristic values evaluated for the obtained test pieces were as shown in Table 2. Example 12 In Example 1, the PPS powder obtained in Reference Example 1 was treated with an acid in the same manner as in Example 1, except that hydrochloric acid was used instead of acetic acid. A powder was obtained. The total sodium content in this PPS was 305 ppm. Hereinafter, nylon 6 was prepared in exactly the same manner as in Example 9.
and glass fiber in the proportions shown in Table 1, melt-mixed, pelletized and injection molded, and the characteristic values evaluated for the obtained test pieces were as shown in Table 2.

【table】

【table】

【table】

[Table] <Effects of the Invention> The polyphenylene sulfide resin composition obtained by the present invention has excellent mechanical properties including impact properties, as well as excellent heat resistance and moisture resistance.

Claims (1)

[Claims] 1. Sodium content subjected to deionization treatment
Polyphenylene sulfide resin 1 below 500ppm
A polyphenylene sulfide resin composition characterized in that 99 to 1% by weight of a polyamide resin is blended with 99% by weight of a polyamide resin. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the deionization treatment is acid treatment followed by washing with water. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the deionization treatment is a hydrothermal treatment with hot water of 100° C. or higher, followed by washing with water. 4. The polyphenylene sulfide resin composition according to claim 1, wherein the deionization treatment is washing with an organic solvent and then washing with water.