JPH04255757A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition consisting essentially of a polyphenylene sulfide resin, a polyamide resin and a copper compound without losing excellent characteristics such as heat and chemical resistance and mechanical strength essentially possessed thereby even in using regenerated materials. CONSTITUTION:A polyphenylene sulfide resin composition is obtained by blending 100 pts.wt. resin composition composed of (A) 99-50wt.% polyphenylene sulfide resin containing >=70mol%, preferably >=90mol% recurring units expressed by the formula and (B) 1-50wt.% polyamide resin (e.g. nylon 66 or nylon 6T) having 2-5 relative viscosity (at 25 deg.C) with (C) 0.005-5 pts.wt., preferably 0.01-1 pt.wt. copper compound (preferably cuprous iodide or cuprous acetate) and, as necessary, an alkali halide (preferably potassium iodide or sodium iodide) in combination and further, as necessary, (D) 0-300 pts.wt., normally 10-250 pts.wt. fibrous and/or or nonfibrous inorganic filler and melt kneading the resultant blend.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a polyphenylene sulfide resin that has excellent heat resistance, chemical resistance, mechanical properties such as strength and impact resistance, and also has excellent properties when recycled materials are used. .

0002

[Prior art] Polyphenylene sulfide (hereinafter referred to as PP)
Resin (abbreviated as S) has favorable properties as an engineering plastic, such as excellent heat resistance, rigidity, and chemical resistance, as well as good flame retardancy and insulation properties, so it is mainly used for injection molded products. It is used in a wide variety of applications, including automobile parts, electrical/electronic parts, and general equipment parts. However, P.P.
S resin is more brittle than nylon resin, polybutylene terephthalate resin, etc., and has problems such as low tensile elongation, low bending strain, and low impact strength, and is also expensive, so its applications are limited. The reality is that you can't get it. In order to compensate for these drawbacks of PPS resin, techniques for blending PPS resin and nylon resin have been studied. JP-A-61-126172, etc.), and a method of combining PPS resin, nylon resin, and epoxy resin (JP-A-59-155462).

0003

[Problems to be Solved by the Invention] However, although the above-mentioned conventional techniques are all effective in improving heat resistance and mechanical strength, it is difficult to collect sprues, runners, etc. generated during resin molding and use them as recycled materials. When this happens, there is a problem in that the mechanical properties are significantly reduced. In the molding process of resins, the availability of recycled materials is directly linked to the product yield and therefore greatly influences the economic efficiency, and a significant deterioration in the properties of the recycled materials will limit the practical use of the resins.

[0004] Therefore, the present inventors set out to obtain a resin composition that does not lose its strength, heat resistance, and chemical resistance when using a regenerating agent in the range of resin compositions whose main components are PPS resin and nylon resin. do.

[0005]

[Means for Solving the Problems] That is, the present invention provides (A
) Polyphenylene sulfide resin 99-50% by weight, (
B) 1 to 50% by weight of polyamide resin, and (C) 0.005 to 5 parts by weight of the copper compound to 100 parts by weight of the resin composition.
The object of the present invention is to provide a polyphenylene sulfide resin composition containing 0 to 300 parts by weight of a fibrous and/or non-fibrous inorganic filler.

In the present invention, it is important to add a small amount of a copper compound in addition to the two components of PPS resin and polyamide resin, thereby solving the above problems at once and creating a PPS resin composition with extremely excellent properties. It is something that can be obtained.

[0007] The PPS resin used in the present invention has the following structural formula:

[0008]

[Chemical formula 1]

A polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by
If the content of the repeating unit is less than 70 mol%, heat resistance will be impaired, which is not preferable.

[0010] PPS resin is generally manufactured by Japanese Patent Publication No. 45-3368.
Polymers with relatively low molecular weight obtained by the production method typified by Japanese Patent Publication No. 12240/1982, and essentially linear polymers with relatively high molecular weight obtained by the production method typified by Japanese Patent Publication No. 12240/1983. There is, and the above-mentioned Special Publication No. 45-3368
In the polymer obtained by the method described in the publication, it is also possible to increase the degree of polymerization and use it by heating in an oxygen atmosphere after polymerization, or by adding a crosslinking agent such as peroxide and heating. It is.

[0011] In the present invention, it is possible to use PPS resin obtained by any method, but it is more preferable to use a PPS resin that is essentially linear and has a relatively high molecular weight. Furthermore, in the present invention, the PPS resin obtained through the above polymerization step may be subjected to known acid treatment, hot water treatment, or organic solvent treatment for the purpose of improving the mechanical properties of the final product composition.

[0012] PPS resin also has 3 repeating units.
Less than 0 mol% can be composed of repeating units having the following structural formula.

[0013]

[Case 2]

Next, the polyamide used for blending in the PPS resin in the present invention includes polyamide obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam, 6-aminocaproic acid, and 11-aminocaproic acid. Polyamides derived from amino acids such as undecanoic acid and 12-aminododecanoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4
-/2,4,4-trimethylhexamethylenediamine,
Aliphatic, cycloaliphatic, aromatic diamines such as 1,3- and 1,4-bis(aminomethyl)cyclohexane, bis(4,4-aminocyclohexyl)methane, meta- and para-xylylene diamine and adipic acid, suberin acids, sebacic acid, dodecanedioic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid,
Polyamides derived from aliphatic, alicyclic, aromatic dicarboxylic acids such as dimer acids or acid derivatives such as acid halides, copolyamides and mixed polyamides of these, and among these, polycaproamide ( nylon 6), polyundecaneamide (nylon 11)
), polydodecanamide (nylon 12), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene terephthalamide (nylon 6T), and copolyamides containing these as main components is useful. As a polymerization method for these polyamides, commonly known melt polymerization, solid phase polymerization, solution polymerization, and a combination of these methods can be employed.

There is no particular limit to the degree of polymerization of polyamide, and relative viscosity (1 g of polymer is mixed with 100 ml of 98% concentrated sulfuric acid)
Depending on the purpose, polyamides having a melting point of 2.0 to 5.0 (measured at 25° C.) can be arbitrarily selected.

Examples of copper compounds used in the present invention include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide,
Cuprous iodide, cupric iodide, cupric sulfate, cupric nitrate, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, dibenzoate Examples include complex compounds of copper and the above-mentioned inorganic copper halides with xylene diamine, 2-mercaptobenzimidazole, benzimidazole, and the like. Among these, cuprous iodide and cuprous acetate are preferred. The appropriate amount of the copper compound to be used is 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total amount of PPS resin and nylon resin. If the amount of copper added is less than 0.005 parts by weight, the effect of improving the strength of the recycled material will be small, while if the copper compound is used in excess of 5 parts by weight, copper metal will be liberated during molding and the product value will decrease due to coloring. So I don't like it. In the present invention, it is also possible to add an alkali halide in combination with the copper compound. Examples of the alkali halide compounds include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide, and sodium iodide. Among these, potassium iodide and sodium iodide are preferred.

[0017] In the present invention, fibrous and/or non-fibrous inorganic fillers are not essential components, but if necessary, a total of 100% of the PPS resin and polyamide resin of the present invention may be added.
It can be blended in an amount not exceeding 300 parts by weight, and it is usually blended in a range of 10 to 250 parts by weight to improve strength, rigidity, heat resistance, dimensional stability, etc. It is possible.

Examples of such fibrous inorganic fillers include glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers,
Examples include inorganic fibers such as asbestos fibers, gypsum fibers, and metal fibers, and carbon fibers.

Examples of non-fibrous inorganic fillers include wollastenite, sericite, kaolin, mica, clay,
Silicates such as bentonite, asbestos, talc, alumina silicate, metal compounds such as alumina, silicon chloride, magnesium oxide, zirconium oxide, titanium oxide, carbonates such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, etc. sulfates, glass beads, boron nitride, silicon carbide, and silica, which may be hollow. Two or more types of these reinforcing materials can be used in combination.

[0020] The method for preparing the resin composition of the present invention is not particularly limited. An example of this is a method of melt-kneading using a twin-screw extruder at a temperature of 270°C to 380°C. Among these methods, melt-kneading is carried out using a single-screw or twin-screw extruder with sufficient kneading power. This method is representative and efficient.

The resin composition of the present invention may contain conventional additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, flame retardants, etc., to the extent that the effects of the present invention are not impaired. and small amounts of other polymers can be added, and further,
For the purpose of controlling the crosslinking strength of PPS, ordinary peroxidants and crosslinking accelerators such as thiophosphinate metal salts described in JP-A-59-131650 or JP-A-58-204045 are used. , Japanese Patent Publication No. 58-204046
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in the above publications.

The resin composition of the present invention contains γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. for the purpose of improving mechanical strength and moldability such as burrs, to the extent that the effects of the present invention are not impaired. Glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane,
γ-ureidopropyltrimethoxysilane and γ-(
2-ureidomethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ
-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanato Organic silane compounds such as propyltrichlorosilane can be added.

[0023]

[Examples] The present invention will be explained in more detail with reference to Examples below. Various properties such as tensile properties, bending properties, impact properties, and heat distortion temperatures in Examples and Comparative Examples are as follows: Tensile properties: ASTM-D638 Bending properties: ASTM-D790 Impact properties: ASTM-D256 Heat distortion temperatures: ASTM-D648 (18.6kg/cm
2).

Reference Example 1 In an autoclave, 3.36 kg of sodium sulfide (25 moles, containing 40% water of crystallization), 4 g of sodium hydroxide, 1.36 kg of sodium acetate trihydrate (approximately 10 moles) and N 7.9 kg of -methyl-2-pyrrolidone (hereinafter abbreviated as NMP) was charged, and the temperature was gradually raised to 205° C. while stirring, and about 1.5 liters of distilled water containing 1.36 kg of water was removed. 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added to the residual mixture, and the mixture was 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 give a melt viscosity of about 1500 poise (320°C, shear rate 10 s).
About 2 kg of powdered PPS (A-1) of 1) was obtained.

[0025] The same operation was repeated and used in the examples described below.

Reference Example 2 The PPS powder obtained in Reference Example 1 was stirred at 80°C for 30 minutes in an acetic acid aqueous solution adjusted to pH 4, washed three times with ion-exchanged water at 70°C, and vacuumed at 80°C for 24 hours. Dry and P
A PS bulk powder (A-2) was obtained and supplied to the following examples.

Reference Example 3 The PPS powder obtained in Reference Example 1 and ion-exchanged water were placed in an autoclave, and the temperature was raised to 150°C while stirring.
After being maintained at this temperature for 30 minutes, it was cooled, further washed once with ion-exchanged water at 70°C, and vacuum dried at 80°C for 24 hours to obtain PPS powder (A-3), which was used in the following examples. did.

Example 1 70 parts by weight of PPS (A-1) obtained in Reference Example 1, 30 parts by weight of nylon 66 with a relative viscosity of 2.7, 0.01 part by weight of cuprous iodide, and 13 μm in diameter. After dry-blending 65 parts by weight of glass fibers using a Henschel mixer, the cylinder temperature was 31°C using a 40mmφ single-screw extruder.
Kneading was carried out under the conditions of 0° C. and screw rotation speed of 80 rpm to form pellets. The pellets were vacuum dried at 100° C. for 16 hours and then injection molded at a cylinder temperature of 310° C. and a mold temperature of 150° C. to obtain molded pieces with good appearance. Furthermore, the obtained molded piece was crushed into pellets using a crusher, dried with hot air at 150° C. for 4 hours, and then injection molded under the same conditions as above. The above recycling process was repeated three times to obtain molded pieces with good appearance. The properties of the molded product obtained here are as shown in Table 1, and it was found that the molded product has high mechanical strength and high retention rate of heat distortion temperature when recycled materials are used, and has high practical value.

Comparative Example 1 PPS, nylon 66 and glass fiber were melt-kneaded in the same manner as in Example 1 except that cuprous iodide was not used.
Injection molding was performed, and the properties of the molded product obtained are shown in Table 1. This product was extremely unsatisfactory in terms of mechanical strength and reduction in heat distortion temperature when recycled material was used.

[0030]

[Table 1]

Examples 2 to 3 Melt-kneading and injection molding were carried out in the same manner as in Example 1, with different types and amounts of PPS, polyamide, copper compound, and inorganic reinforcing material. Molded products with good appearance were obtained in all cases. I got it. These properties are summarized in Table 2, and it has been found that all of the recycled products have high mechanical strength and retention of heat distortion temperature, and are of high practical value.

[0032]

[Table 2]

[0033]

INDUSTRIAL APPLICABILITY The object of the present invention was to obtain a PPS resin composition that does not lose its inherent excellent properties such as heat resistance, chemical resistance, and mechanical strength even when recycled materials are used. The above object was achieved by combining PPS, nylon, and a copper compound, and a PPS resin composition with high practical value could be obtained.

Claims (1)

[Claims] Claim 1: (A) Polyphenylene sulfide resin 99
~50% by weight, (B) polyamide resin 1~50% by weight,
A polyphenylene sulfide resin prepared by blending 0.005 to 5 parts by weight of a copper compound (C) and 0 to 300 parts by weight of a fibrous and/or non-fibrous inorganic filler with respect to 100 parts by weight of a resin composition consisting of Composition.