JPH10298430A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. excellent in tracking resistance by compounding a polyphenylene sulfide resin with kaolin and talc or magnesium hydroxide in a specified wt. ratio. SOLUTION: This compsn. contains 100 pts.wt. resin component comprising a polyphenylene sulfide resin having a melt viscosity (310 deg.C, a shear rate of 1,000 sec<-1> ) of 1,000 P or lower alone or together with 0.5-50 wt.% other resin, 15-300 pts.wt. kaolin, and 5-275 pts.wt. talc or magnesium hydroxide, the sum of kaolin and talc or magnesium hydroxide being 30-300 pts.wt., and further contains 10-300 pts.wt. other filler and 0.05-5 pts.wt. alkoxysilane compd. having at least one kind of functional group selected from among epoxy. amino, isocyanate, and hydroxyl groups, etc. Kaolin having an Al content (in terms of Al2 O3 ) of 35-42 wt.% and a wt. loss caused by heating from room temp. to 750 deg.C (in an air stream, at a temp. rise rate of 20 deg.C/min) of 3 wt.% or higher is used.

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 and an injection-molded article having excellent electrical properties such as tracking resistance and the like, and is used for electric parts such as electric parts, electronic parts or automobile electric parts. It is applied particularly usefully, and is applied to various wide fields.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter referred to as P
PS resin) has excellent properties such as excellent heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation, and wet heat resistance as engineering plastics. It is used for electronic parts, mechanical parts and automobile parts.

However, the PPS resin has a drawback that the tracking resistance is significantly inferior to other engineering plastics such as polyamide resin. Therefore, the PPS resin is exposed to a relatively high voltage despite having excellent properties as an electric component material such as high heat resistance, rigidity, electrical insulation, flame retardancy, and wet heat resistance. In fact, the application to such uses is limited.

[0004] Attempts to improve the tracking resistance of PPS resins have been made so far, for example, see JP-A-64-69.
No. 658 discloses that tracking resistance is improved by blending an aliphatic saturated ester comprising a long-chain alcohol or a short-chain polyalcohol with a long-chain carboxylic acid, an inorganic filler and a reinforcing material in a PPS resin. It is disclosed. However, the comparative tracking index (hereinafter abbreviated as CTI) shown in the examples is at most about 225 V, and it cannot be said that it has been sufficiently improved.

[0005]

Accordingly, the present invention relates to a PP
An object of the present invention is to obtain a PPS resin composition having excellent tracking resistance without significantly impairing various properties such as excellent heat resistance, electrical insulation, and low water absorption inherent in the S resin.
As a result of intensive studies to obtain such a PPS resin composition, the present inventors have found that the addition of kaolin, particularly unfired kaolin, to the PPS resin greatly improves tracking resistance, and reached the present invention.

On the other hand, a technique for blending kaolin with a PPS resin is disclosed in, for example, JP-A-63-245463. However, the amount of kaolin in this patent is up to 10 parts by weight with respect to 100 parts by weight of the PPS resin, and a large improvement in tracking resistance cannot be obtained with such an amount. The effect of the patent is to speed up the crystallization, and there is no description of the effect of improving the tracking resistance.

[0007]

The structure of the present invention is as follows.

(1) A polyphenylene sulfide resin composition containing (A) 15 to 300 parts by weight of kaolin per 100 parts by weight of polyphenylene sulfide resin.

(2) 100 parts by weight of a resin component comprising (A) 99.5 to 50% by weight of polyphenylene sulfide resin and (C) 0.5 to 50% by weight of a resin other than polyphenylene sulfide resin; 15 to 300
A polyphenylene sulfide resin composition containing parts by weight.

(3) (B) Kaolin is 750 from room temperature
° C when heated to a temperature of 20 ° C
Min), the polyphenylene sulfide resin composition according to the above (1) or (2), which is a kaolin having a weight loss rate of 3% by weight or more.

(4) (B) Kaolin is heated from room temperature to 750
° C when heated to a temperature of 20 ° C
Min), the polyphenylene sulfide resin composition according to any one of the above (1) to (3), wherein the weight loss rate is 8% by weight or more.

(5) (B) The polyphenylene sulfide resin composition according to any one of the above (1) to (4), wherein the kaolin has an aluminum content of 35 to 42% in terms of Al ₂ O ₃ . .

(6) Further, (D) talc and / or magnesium hydroxide is added in an amount of 5 to 2 with respect to 100 parts by weight of the resin component.
75 parts by weight, wherein the total amount of (B) kaolin and (C) talc and / or magnesium hydroxide is in the range of 30 to 300 parts by weight with respect to 100 parts by weight of the resin component. The polyphenylene sulfide resin composition according to any one of 1) to (5).

(7) The above (1) to (E), which further contain (E) a filler other than kaolin, talc and magnesium hydroxide in an amount of 10 to 300 parts by weight based on 100 parts by weight of the resin component.
The polyphenylene sulfide resin composition according to any one of (6).

(8) The (A) polyphenylene sulfide resin has a melt viscosity (310 ° C., a shear rate of 1000 /
The polyphenylene sulfide resin composition according to any one of the above (1) to (7), wherein the polyphenylene sulfide resin has a viscosity of 1000 poise or less.

(9) Further, (F) an epoxy group, an amino group,
An alkoxysilane compound having at least one functional group selected from an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group, wherein 0.05 to 5 parts by weight is added to 100 parts by weight of the resin component. (1)-
(8) The polyphenylene sulfide resin composition according to any of (8).

(10) The comparative tracking index is 280
The polyphenylene sulfide resin composition according to any one of the above (1) to (9), which has a V of not less than V.

(11) A molded article for electrical equipment parts obtained by injection molding the polyphenylene sulfide resin composition according to any one of the above (1) to (10).

[0019]

DETAILED DESCRIPTION OF THE INVENTION The polyphenylene sulfide resin used in the present invention refers to a repeating unit represented by the following structural formula.

Embedded image From the viewpoint of heat resistance, a polymer containing 70 mol% or more, particularly 90 mol% or more is preferable. Also PPS
Less than 30 mol% of the repeating unit of the resin can be composed of a repeating unit having the following structural formula.

[0020]

Embedded image

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
2,000 Pa · s (310 ° C., shear rate 1,000
0 / sec) is used, the range of 5 to 100 Pa · s is more preferable, and the range of 5 to 60 Pa · s is more preferable.

Such a PPS resin can be prepared by a generally known method, that is, a method of obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, JP-B-52-12240, and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the gazette. In the present invention, the PPS resin obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution, or the like. Of course, it is also possible to use after performing various treatments such as activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, and a functional group-containing disulfide compound.

As a specific method for crosslinking / high molecular weight of the PPS resin by heating, the method may be carried out in an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method in which heating is performed in a heating vessel at a predetermined temperature under an atmosphere until a desired melt viscosity is obtained. The heat treatment temperature is usually
170-280 ° C is selected, preferably 200-27 ° C.
The temperature is 0 ° C., and the time is usually 0.5 to 100 hours, preferably 2 to 50 hours. By controlling both of them, a target viscosity level can be obtained. The heating device may be an ordinary hot-air dryer or a heating device with a rotary or stirring blade. For efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. Is more preferred.

When the PPS resin is heat-treated in an inert gas atmosphere such as nitrogen or under reduced pressure, a specific method is as follows.
Heat treatment temperature 150 to 280 ° C, preferably 200 to 2
70 ° C., heating time is 0.5 to 100 hours, preferably 2 hours
A method of performing heat treatment for up to 50 hours can be exemplified. The heating device may be an ordinary hot-air dryer or a heating device with a rotary or stirring blade. For efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. Is more preferred.

The following method can be exemplified as a specific method for washing the PPS resin with an organic solvent. That is,
The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethylsulfoxide, dimethyl Sulfoxide and sulfone solvents such as sulfone, acetone, methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, ether solvents such as tetrahydrofuran, chloroform, methylene chloride,
Halogen-based solvents such as trichloroethylene, dichlorinated ethylene, dichloroethane, tetrachloroethane, and chlorobenzene; alcohol-phenol-based solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol And aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferred. These organic solvents are used alone or in combination of two or more.
As a method of washing with an organic solvent, PP in an organic solvent is used.
There are methods such as immersing the S resin, and if necessary, stirring or heating can be performed. P in organic solvent
There is no particular limitation on the washing temperature for washing the PS resin, and any temperature from room temperature to about 300 ° C. can be selected.
Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect can usually be obtained at a cleaning temperature of normal temperature to 150 ° C.

The organic solvent-washed PPS resin is preferably washed several times with water or hot water in order to remove the remaining organic solvent.

The following method can be exemplified as a specific method for treating the PPS resin with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a favorable effect of chemical modification of the PPS resin by washing with hot water. The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin into a predetermined amount of water, and heating and stirring the mixture at normal pressure or in a pressure vessel. The proportion of PPS resin to water is preferably as high as possible, but a bath ratio of 200 g or less of PPS resin to 1 liter of water is usually selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid. That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of an acid, or the like. If necessary, stirring or heating can be performed. The acid to be used is not particularly limited as long as it does not have an action of decomposing PPS, and may be an aliphatic saturated monocarboxylic acid such as formic acid, acetic acid, propionic acid or butyric acid, or a halo-substituted aliphatic saturated acid such as chloroacetic acid or dichloroacetic acid. Carboxylic acid, acrylic acid, aliphatic unsaturated monocarboxylic acid such as crotonic acid, benzoic acid, aromatic carboxylic acid such as salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, dicarboxylic acid such as fumaric acid, sulfuric acid, Examples include inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Among them, acetic acid and hydrochloric acid are more preferably used. The PPS resin subjected to the acid treatment is preferably washed several times with water or warm water in order to remove the remaining acid or salt. Further, the water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

Next, kaolin (B), which is an essential component in the present invention, will be described. Kaolin has the basic chemical formula A
A hydrous aluminum silicate represented by l ₂ Si ₂ O ₅ (OH) ₄ .nH ₂ O, the typical chemical composition of which is described below.

SiO ₂ : 42 to 55% Al ₂ O ₃ : 35 to 45% TiO ₂ : 0 to 3% Fe ₂ O ₃ : 0 to 2% CaO: 0 to 1% MgO: 0 to 0.3% K _{2 O: 0~0.5% Na 2 O} : in the 0 to 0.6% present invention is Al ₂ O ₃ in the kaolin particularly preferred in terms of obtaining better tracking resistance as 35-42%.

The particle size of kaolin used in the present invention is not particularly limited, but those having an average particle size of 0.1 to 6 μm are preferably used. There is no limit on the amount of oil absorption.
Those having a size of ６０60 lbs / 100 lbs are preferably used.

Although kaolin is often calcined at a high temperature, kaolin used in the present invention is particularly preferably uncalcined kaolin that has not been calcined. Such unfired kaolin has a greater weight loss rate during heating than fired kaolin. The kaolin used in the present invention is preferably a kaolin having a weight loss rate of 3% by weight or more when the temperature is raised from room temperature to 750 ° C. (in a stream of air, at a temperature rising rate of 20 ° C./min). Kaolins of at least 8% by weight are particularly preferred.

The amount of the kaolin is such that (B) is based on 100 parts by weight of a resin component consisting of (A) polyphenylene sulfide resin or (A) polyphenylene sulfide resin and (C) a resin other than polyphenylene sulfide resin.
Kaolin 15 to 300 parts by weight, preferably 25 to 300
A range of parts by weight is selected, with a range of 100 to 300 parts by weight being more preferred. (B) If the amount of kaolin is less than 15 parts by weight, the effect of improving tracking resistance is hardly obtained,
If the amount is more than 300 parts by weight, adverse effects such as an increase in melt viscosity and a decrease in mechanical strength become apparent, which is not preferable.

In the present invention, the use of (D) talc and / or magnesium hydroxide in combination with (B) kaolin is also effective in obtaining excellent tracking resistance, mechanical strength and the like.

Here, talc has a basic chemical formula of 3MgO.
A layered magnesium silicate represented by 4SiO ₂ · H ₂ O, the typical chemical composition is to be as follows.

SiO ₂ : 50 to 65% MgO: 25 to 30% Al ₂ O ₃ : 0 to 3% Fe ₂ O ₃ : 0 to 2% CaO: 0 to 4% The (D) talc is vinyltriethoxy. Silane, vinylsilane compounds such as vinyltrichlorosilane, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-
Epoxysilane compounds such as epoxycyclohexyl) ethyltrimethoxysilane, γ- (2-aminoethyl)
Aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-
It may be used after surface treatment with an aminosilane compound such as aminopropyltrimethoxysilane, a long-chain fatty acid or a long-chain aliphatic alcohol such as stearic acid, oleic acid, montanic acid, and stearyl alcohol.

On the other hand, as the magnesium hydroxide which is another component of (D) used as required in the present invention, an inorganic substance represented by the chemical formula Mg (OH) ₂ may be used.
Magnesium hydroxide containing at least 80% by weight of an inorganic substance represented by Mg (OH) ₂ , preferably from the viewpoint of tracking resistance, mechanical strength, and melt viscosity.
A CaO content of 5% by weight or less, a chlorine content of 1% by weight or less, more preferably 95% by weight or more of Mg (OH) ₂ ;
CaO content 1% by weight or less, chlorine content 0.5% by weight or less,
More preferably, high-purity magnesium hydroxide containing 98% by weight or more of Mg (OH) ₂ and having a CaO content of 0.1% by weight or less and a chlorine content of 0.1% by weight or less is suitable.

The shape of the magnesium hydroxide may be any of a particle, a flake and a fiber, but the particle and the flake are most preferred from the viewpoint of dispersibility. Further, the specific surface area is preferably 15 m ² / g or less, more preferably 10 m ² / g or less from the viewpoint of the dispersibility of magnesium hydroxide, the effect of improving tracking resistance, the mechanical strength, and the like. In the case of particles or flakes, the average particle size is 0.3 to 10 μm
m, preferably in the range of 0.3 to 2 μm is suitable for the balance between the effect of improving tracking resistance, mechanical strength and melt viscosity. When a fibrous material is used, the average fiber diameter is 0.1 to 2 μm and the aspect ratio is 20 to 60, preferably the average fiber diameter is 0.3 to 2 μm and the aspect ratio is 30 to 50.

The magnesium hydroxide (D) is converted into a vinylsilane compound such as vinyltriethoxysilane or vinyltrichlorosilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3 Epoxysilane compounds such as, 4-epoxycyclohexyl) ethyltrimethoxysilane;
Aminosilane compounds such as-(2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, stearic acid, oleic acid, montanic acid, stearyl alcohol It is preferable to use the surface treated with a long-chain fatty acid or a long-chain aliphatic alcohol such as, for example, a magnesium hydroxide (D) surface-treated with an epoxysilane compound or an aminosilane compound. It is suitable in terms of strength.

The blending amount of (D) talc and / or magnesium hydroxide is based on 100 parts by weight of a resin component composed of (A) polyphenylene sulfide resin or (A) polyphenylene sulfide resin and a resin other than (C) polyphenylene sulfide resin. The range of 5 to 275 parts by weight is selected, and the range of 10 to 100 parts by weight is more preferable. However, in view of the balance between tracking resistance, strength, and fluidity, the composition of the present invention is such that the total amount of (B) kaolin and (C) talc and / or magnesium hydroxide is 30 to 300 parts by weight per 100 parts by weight of the resin component. It is preferably in the range of parts by weight.

In the present invention, it is preferable to incorporate a filler other than (E) kaolin, talc and magnesium hydroxide from the viewpoint of improving strength. Any of fibrous and non-fibrous forms can be used as such a filler. Specific examples of such a filler include glass fiber, glass milled fiber, carbon fiber, potassium whisker, titanate whisker, zinc oxide whisker, and aluminum borate whisker. Aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber,
Fibrous fillers such as stone fiber, metal fiber, etc., wallastite, zeolite, sericite, mica, clay, pyrophyllite, bentonite, asbestos, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide Metal compounds such as titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; hydroxides such as calcium hydroxide and aluminum hydroxide; glass beads; and ceramics. Examples include non-fibrous fillers such as beads, boron nitride, silicon carbide, and silica. These may be hollow, and two or more of these fillers may be used in combination. In addition, it is preferable to use these fillers (E) after pre-treating them with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound. It is preferable in terms of obtaining strength. Among them, fibrous fillers are preferable, and glass fibers and glass milled fibers are particularly preferable.

The amount of the filler (E) is 100 parts by weight of (A) a PPS resin or 100 parts by weight of a resin component composed of a resin other than (A) a polyphenylene sulfide resin and (C) a resin other than the polyphenylene sulfide resin. On the other hand, the range of 10 to 300 parts by weight is selected, and the range of 30 to 100 parts by weight is particularly preferable from the viewpoint of balance between mechanical strength and melt fluidity.

In the present invention, (F) at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureide group is used in order to obtain a more excellent strength improving effect. It is effective to mix the alkoxysilane compound having the compound. Specific examples of such alkoxysilane compounds include epoxy group-containing compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Alkoxysilane compounds, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ
-Ureidopropyltrimethoxysilane, γ- (2-
Ureido group-containing alkoxysilane compounds such as ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyl Isocyanato group-containing alkoxysilane compounds such as diethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyl Amino group-containing alkoxysilane compounds such as dimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxyp Ropirtrimethoxysilane,
Hydroxy group-containing alkoxysilane compounds such as γ-hydroxypropyltriethoxysilane and the like, among which γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, β-
Epoxy group-containing alkoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxy Ureido group-containing alkoxysilane compounds such as silane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane,
amino-containing alkoxysilane compounds such as γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ- Isocyanato group-containing alkoxysilanes such as isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane Compounds are particularly preferred.

The (F) alkoxysilane compound is
It is used to obtain more excellent mechanical strength, and the amount added is (A) polyphenylene sulfide resin or (A)
A range of 0.05 to 5 parts by weight is selected with respect to 100 parts by weight of the resin component composed of the polyphenylene sulfide resin and the resin other than the polyphenylene sulfide resin (C),
A range of 0.1 to 3 parts by weight is more preferably selected.

In the present invention, a part of the (A) PPS resin is replaced with a resin other than the (C) PPS resin, and a resin other than the (C) PPS resin is used as a base resin.
The use of a resin component in combination with the S resin is also effective in obtaining a resin composition having an excellent balance between tracking resistance and melt viscosity. Specific examples of the resin other than (C) the PPS resin include fluorine resins such as polyester, polysulfone, and polyethylene tetrafluoride, polyetherimide, polyamideimide, polyamide, polyimide, polycarbonate, polyethersulfone, and polyetherketone. Polythioetherketone, polyetheretherketone, epoxy resin, phenolic resin, polyethylene, polystyrene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ABS
Resin, polyamide elastomer, polyester elastomer, polyalkylene oxide, or acid anhydride group,
Olefin-based copolymers containing a carboxyl group, a carboxylate, an epoxy group and the like, among which polyamide resins such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 46, polyethylene, polystyrene, Polypropylene, ethylene-
Polyolefins such as propylene copolymers, ethylene-butene-1 copolymers and olefin copolymers containing acid anhydride groups, carboxyl groups, carboxylate salts, epoxy groups, etc., polytetrafluoroethylene, polychlorotriol Fluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / Hexafluoropropylene / perfluoroalkylvinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer, chlorotrifluoroethylene / ethylene copolymer, chlorotrifluoroethylene On / vinylidene fluoride copolymer, vinylidene fluoride / hexafluoropropylene copolymer,
Fluorinated resins such as fluorinated ethylene / propylene copolymers are particularly preferably used.

The content of the resin other than the (C) PPS resin is 100% of the resin component (A) and the resin component (C).
(A) 99.5% by weight to 50% by weight of PPS resin, and (C) 0.5 to 5% of resin components other than PPS resin.
0% by weight, preferably (A) PPS resin 9
0.5-30% by weight for 9.5-70% by weight
Is selected.

In the PPS resin composition of the present invention, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds, talc, and organic phosphorus compounds as long as the effects of the present invention are not impaired. Nucleating agents such as polyetheretherketone, anti-coloring agents such as hypophosphite, antioxidants, heat stabilizers, lubricants, mold release agents, crystallization accelerators, UV inhibitors, coloring agents, flame retardants Ordinary additives such as a foaming agent can be added.

The method for preparing the PPS resin composition of the present invention is not particularly limited, but the mixture of the raw materials is supplied to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. 280-3
A typical example is a method of kneading at a temperature of 80 ° C. The order of mixing the raw materials is also not particularly limited, and is a method in which all the raw materials are blended and then melt-kneaded by the above-mentioned method. Any method may be used, such as a method of mixing some raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading by a single-screw or twin-screw extruder. Further, as for the small amount of the additive component, it is of course possible to knead the other component by the above-mentioned method and the like to form a pellet, and then add it before molding to provide for molding.

The PPS resin composition obtained according to the present invention has good tracking stability without significantly impairing the inherent thermal stability, melt fluidity, mechanical strength, electrical insulation and low water absorption of the PPS resin composition. Conventional PPS of improvement
It is a resin composition provided with new properties that were lacking in the resin. According to the present invention, in many cases, it is possible to obtain a PPS resin composition having a comparative tracking index of 280 V or more.
It is also possible to obtain an S resin composition.

The PPS resin composition thus obtained can be applied to various known molding methods such as injection molding, extrusion molding, compression molding, blow molding and injection compression molding, but is particularly suitable for injection molding. It is a resin composition. The molded article of the PPS resin composition of the present invention includes a generator, a motor, a transformer, a current transformer, a voltage regulator, a rectifier, an inverter, a relay, a power contact, a switch, a machine breaker, and a knife switch. , Other pole rods, electrical components such as electrical component cabinets, and is particularly suitable for sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches,
Coil bobbins, condensers, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones,
Headphone, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FD
Electronic components such as D chassis, motor brush holders, parabolic antennas, and computer-related components; VTR components, TV components, irons, hair dryers, rice cooker components, microwave oven components, audio components, audio laser disks, and compact disks Home and office electrical product parts such as audio equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc .; office computer related parts, telephone related parts, facsimile related parts, copier related parts Machine-related parts such as parts, cleaning jigs, motor parts, lighters, and typewriters: microscopes,
Optical equipment represented by binoculars, cameras, clocks, etc., precision machinery related parts; alternator terminal, alternator connector, IC regulator, potentiometer base for light drier, various valves such as exhaust gas valve, fuel related, exhaust system, intake System various pipes, air intake nozzle snorkel, intake manifold,
Fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor,
Crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch , Starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector, lamp housing, Automobiles such as brake pistons, solenoid bobbins, engine oil filters, and ignition device cases Vehicle-related parts, etc., can be applied to various applications.

[0051]

The present invention will be described in more detail with reference to the following examples.

The tracking resistance and bending strength shown in Examples and Comparative Examples were measured according to the following methods.

(1) Tracking resistance test: IEC112 method (solution A) using ASTM No. 1 test piece (injection molded product)
The comparative tracking index (CTI) was measured according to the following.

(2) Flexural strength: According to ASTM D790.

(3) Molding lower limit pressure: The minimum injection pressure required for completely filling the molded piece when the test piece for tracking resistance test and the test piece for bending strength measurement were injection-molded was read. The smaller this value is, the better the melt fluidity is.

(4) Measurement of weight loss rate of kaolin upon heating: using a TG / DTA200 system manufactured by Seiko Denshi Kogyo KK, at a heating rate of 20 ° C./min and an air flow rate of 50 ml / min.
The weight loss rate from room temperature to 750 ° C. was measured under the conditions of minutes.

Reference Example 1 (Polymerization of PPS resin) A-1 In an autoclave equipped with a stirrer, 6.005 kg (25 mol) of sodium sulfide / 9-hydrate, 0.61% of sodium acetate were added.
5 kg (7.5 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.734 kg (25.4 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added thereto.
After heating to ℃, the reaction was carried out at 272 ° C for 1 hour. Thereafter, the reaction solution was flashed while being stirred and heated to 250 ° C. with a cooling condenser to obtain a mixed powder of PPS and salts. This was slurried with 15 liters of ion-exchanged water at 70 ° C. and filtered with a centrifuge. The obtained cake, 15 liters of ion-exchanged water and 13 ml of glacial acetic acid were charged into an autoclave equipped with a stirrer, sealed under nitrogen gas, heated to 190 ° C, heated to 190 ° C, and then heated to 70 ° C.
Cooled down. The obtained slurry was filtered with a centrifugal separator, washed with 80 ° C. ion-exchanged water, and vacuum dried to obtain PPS (A-1) having a melt viscosity of 550 poise.

A-2 The above PPS (A-1) was heated at 220 ° C. in the air to obtain PPS (A-2) having a melt viscosity of 1030 poise.

Reference Example 2 (Other Compounds) (B) Kaolin B-1: Unfired kaolin, pH 3.5 to 5.0, average particle diameter 4.8 μm, weight loss rate 13.3% by weight,
Al ₂ O ₃ 38.8%.

B-2: calcined kaolin, pH 8.5 to 9.
5. Average particle size 1.4 μm, weight loss rate 1. 1 _{wt%, Al 2 O 3 44.6%} (C) a resin component other than PPS C-1: Nylon 6 having a relative viscosity 2.7 (in 98% sulfuric acid, the polymer concentration 1 wt%, measured at 2 5 ° C.) C-2: high-density polyethylene, melt flow index (D1238) 13 g / 10 minutes, density 0.9
65 (D) Talc, magnesium hydroxide D-1: Talc D-2: Magnesium hydroxide, "Kisuma" 5EU manufactured by Kyowa Chemical Industry Co., Ltd. (E) Filler E-1: E glass fiber having an average fiber diameter of 13 μm.

E-2: Calcium carbonate (F) alkoxysilane compound F-1: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

Examples 1 to 8 The components shown in Table 1 were dry-blended in the proportions shown in Table 1, then melt-kneaded by a screw type single screw extruder set at a temperature of 280 to 320 ° C., and then pelletized. Using the obtained pellets, a test piece for measuring tracking resistance and bending strength was molded, and the molding minimum pressure was measured. Table 1 shows CTI and bending strength measured for the obtained test pieces.

As can be seen from the comparison between Examples 1 and 2, a higher CTI value is obtained by using unfired kaolin than by using fired kaolin. When a PPS resin (A-2) having a high melt viscosity is used, the tracking resistance and the strength are almost at the same level, and rather, the melt fluidity is deteriorated.

Comparative Example 1 Melt kneading, pelletizing, and measurement of each physical property were carried out in the same manner as in Example 1 except that kaolin was not used. Table 1 shows the results
Shown in

Comparative Example 2 Melt kneading, pelletizing, and measurement of physical properties were carried out in the same manner as in Example 1 except that calcium carbonate was used instead of kaolin. Table 1 shows the results.

In each of Comparative Examples 1 and 2, the tracking resistance was insufficient, and the effect of mixing kaolin is clear.

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[Table 1]

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The present invention relates to a polyphenylene sulfide resin composition and an injection-molded article having excellent electrical properties such as tracking resistance, and is particularly useful for electric parts such as electric parts, electronic parts, and automobile electric parts. In addition to various fields.

Claims (11)

[Claims] 1. A polyphenylene sulfide resin (A)
A polyphenylene sulfide resin composition containing 15 to 300 parts by weight of (B) kaolin based on 0 parts by weight. 2. A polyphenylene sulfide resin (A)
Resin component 1 consisting of 9.5 to 50% by weight and 0.5 to 50% by weight of resin other than (C) polyphenylene sulfide resin
A polyphenylene sulfide resin composition containing (B) 15 to 300 parts by weight of kaolin based on 00 parts by weight. (B) When the temperature of kaolin is raised from room temperature to 750 ° C. (in a stream of air, at a temperature rising rate of 20 ° C./min),
3. The polyphenylene sulfide resin composition according to claim 1, wherein the weight loss rate is 3% by weight or more of kaolin. (B) when the temperature of kaolin is raised from room temperature to 750 ° C. (in a stream of air, at a heating rate of 20 ° C./min);
A kaolin having a weight loss rate of 8% by weight or more.
4. The polyphenylene sulfide resin composition according to any one of 3. 5. The polyphenylene sulfide resin composition according to claim 1, wherein (B) kaolin has an aluminum content of 35 to 42% in terms of Al ₂ O ₃ . 6. A composition comprising (D) talc and / or magnesium hydroxide in an amount of 5 to 275 parts by weight based on 100 parts by weight of a resin component, wherein (B) kaolin and (C) talc and / or The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein the total amount of magnesium hydroxide is in the range of 30 to 300 parts by weight based on 100 parts by weight of the resin component. 7. The polyphenylene sulfide according to claim 1, further comprising (E) 10 to 300 parts by weight of a filler other than kaolin, talc and magnesium hydroxide based on 100 parts by weight of the resin component. Resin composition. 8. The polyphenylene sulfide resin (A),
The polyphenylene sulfide resin composition according to any one of claims 1 to 7, which is a polyphenylene sulfide resin having a melt viscosity (310 ° C, shear rate 1000 / sec) of 1,000 poise or less. 9. An alkoxysilane compound having at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureide group, is added to 100 parts by weight of the resin component. On the other hand, 0.
The polyphenylene sulfide resin composition according to any one of claims 1 to 8, which is added in an amount of from 0.5 to 5 parts by weight. 10. The polyphenylene sulfide resin composition according to claim 1, which has a comparative tracking index of 280 V or more. 11. A molded article for electrical equipment parts obtained by injection molding the polyphenylene sulfide resin composition according to any one of claims 1 to 10.