JP2001031867A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide(PPS) resin composition having excellent toughness, moldability, low gas emission and high weld strength as well as excellent heat-resistance and mechanical properties. SOLUTION: The objective PPS resin composition contains (A) 100 pts.wt. of a PPS resin and (B) 1.5-35 pts.wt. of an epoxy-containing olefin copolymer produced by the copolymerization of an α-olefin, an α,β-unsaturated carboxylic acid alkyl ester and an epoxy-containing vinyl monomer as essential copolymerization units. The copolymerization ratio of the α-olefin is 52-95 wt.% and that of the α,β-unsaturated carboxylic acid alkyl ester is 5-48 wt.%. The amount of the epoxy-containing vinyl monomer is 0.5-15 wt.% based on 85-99.5 wt.% of the sum of the α-olefin and the α,β-unsaturated carboxylic acid alkyl ester.

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 having excellent heat resistance and mechanical properties, as well as excellent toughness, moldability, low gas properties, weld strength, and the like, and an injection molded article thereof.

[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, PPS resin is made of nylon or PBT.
At present, its toughness is lower than that of other engineering plastics and its application is limited, and improvement thereof is strongly desired.

As one of the methods for improving the toughness of a PPS resin, a method of melt-blending various soft resins and the like has been studied. For example, JP-A-59-16704
No. 0 discloses a method of adding a hydrogenated SBR copolymer, and JP-A-56-115355 discloses a method of adding a dicarboxylic anhydride hydrogenated SBR copolymer. However, these SBR-based copolymers are PP
The miscibility with the S resin is low, and a sufficient toughness improving effect cannot be obtained.

Further, Japanese Patent Application Laid-Open No. 58-154775 discloses that
A method of adding an olefin-based copolymer comprising a glycidyl ester of an α-olefin and an α, β-unsaturated acid is disclosed, but in this method, moldability such as mold release properties may be reduced. . Japanese Patent Application Laid-Open No. 62-151460 discloses a method of adding an olefin-based copolymer comprising ethylene, an alkyl ester of α, β-unsaturated acid and maleic anhydride, but this method has a sufficient toughness. It is necessary to add a large amount of a copolymer in order to express the above, which causes a problem that the amount of generated gas is increased.

JP-A-6-179791, JP-A-6-2
No. 99071 discloses an α-olefin (10 to 50% by weight) and an α, β-unsaturated carboxylic acid alkyl ester (5
0 to 90% by weight) and a total amount of 70 to 99.5% by weight of a copolymer comprising a glycidyl ester of an α, β-unsaturated acid (0.5 to 60% by weight). Although disclosed, the copolymer in which the α, β-unsaturated carboxylic acid alkyl ester is excessively applied to the α-olefin as described above increases the amount of generated gas, decreases the contamination of the mold and the strength of the weld portion. And so on.

[0007]

The present invention relates to a polyphenylene sulfide resin composition which is excellent in heat resistance, mechanical properties, toughness, moldability, low gas properties, weld strength and the like, and an injection molded article thereof. .

[0008]

The inventors of the present invention have studied to solve the above problems, and as a result, blended an olefin-based copolymer having a specific copolymerization ratio with a PPS resin, The present inventors have found that a PPS resin composition that solves the above problems can be obtained by adding an additive, and have reached the present invention.

That is, the present invention comprises the following items. 1. An epoxy group-containing olefin copolymer obtained by copolymerizing (a) 100 parts by weight of a polyphenylene sulfide resin and (b) an α-olefin, an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer. The copolymerization ratio of the α-olefin 52 ~
95% by weight and 5-48% by weight of an α, β-unsaturated carboxylic acid alkyl ester, and an α-olefin and α,
β-unsaturated carboxylic acid alkyl ester in total 85 to 9
A polyphenylene sulfide resin composition containing 1.5 to 35 parts by weight of an epoxy group-containing olefin copolymer which is 0.5 to 15 parts by weight of an epoxy group-containing vinyl monomer with respect to 9.5% by weight. And
(C) The epoxy-free olefin-based copolymer obtained by copolymerizing an α-olefin and an α, β-unsaturated carboxylic acid alkyl ester is not contained, or the content is 5 parts by weight or less. A polyphenylene sulfide resin composition characterized by the following: 2. (A) The melt viscosity of the polyphenylene sulfide resin (300 ° C., shear rate 1,000 / sec) is 10 to 200.
The polyphenylene sulfide resin composition described above, which has 0 poise. 3. Further, 0.1 to 5 parts by weight of an alkoxysilane compound selected from (d) an epoxy group, an amino group, a ureide group and an isocyanate group is added to (a) 100 parts by weight of the polyphenylene sulfide resin. Polyphenylene sulfide resin composition. 4. Further, (e) 0.1 to 5 parts by weight of a polyfunctional epoxy compound having two or more epoxy groups in one molecule per 100 parts by weight of the polyphenylene sulfide resin (a). The polyphenylene sulfide resin composition according to the above. 5. Further, (f) an ester compound obtained by reacting an aliphatic carboxylic acid having 12 to 40 carbon atoms with a polyhydric alcohol,
(A) The polyphenylene sulfide resin composition according to any one of the above, which is added in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. 6. The phenylene sulfide resin composition according to any one of claims 1 to 4, further comprising 10 to 250 parts by weight of (g) a filler based on 100 parts by weight of (a) the polyphenylene sulfide resin. 7. The polyphenylene sulfide resin composition according to any of the above, wherein the melt flow rate (315.5 ° C, 5000 g load) is 20 to 200 g / 10 minutes. 8. An injection-molded article obtained by injection-molding the polyphenylene sulfide resin composition according to any one of the above, wherein the number of gates is two or more.

[0010]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The (a) polyphenylene sulfide resin used in the present invention is a compound represented by the following structural formula:

[0012]

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It is a polymer containing at least 70 mol%, more preferably at least 90 mol%. If the amount of the repeating unit is too small, the heat resistance tends to be impaired. Also, the PPS resin can constitute less than 30 mol% of the repeating unit with a repeating unit having the following structural formula.

[0014]

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The melt viscosity of the (a) PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
Usually, 10 to 50,000 poise (300 ° C., shear rate 1,000 / sec) is used, and 10 to 5,000 poise is used.
The range of pois is more preferable, and the range of 10 to 2,000 poise is still more preferable. Further, all of the PPS resin used, or at least 30% by weight or more of PPS resin
It is preferable to use a low-viscosity PPS resin of 0 to 500 poise in order to obtain excellent fluidity and molding characteristics. When such a low-viscosity PPS resin is applied, (d) an alkoxysilane compound selected from an epoxy group, an amino group, a ureide group, an isocyanate group, and / or (e) having two or more epoxy groups in one molecule, The combined use of a polyfunctional epoxy compound having a molecular weight of 2000 or less is particularly effective for obtaining high weld strength and excellent molding characteristics.

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 as 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 obtained as described above
Crosslinking / polymerization of resin by heating in air, heat treatment under inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, acid anhydride, amine, isocyanate, functional group containing Of course, it is also possible to use after performing various treatments such as activation with a functional group-containing compound such as a disulfide compound.

As a specific method for crosslinking / high molecular weight of the PPS resin by heating, a specific method may be used 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 atmosphere of an inert gas 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.

As a specific method for washing the PPS resin with an organic solvent, the following method can be exemplified. 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 solvents such as trichloroethylene, dichlorinated ethylene, dichloroethane, tetrachloroethane, and chlorobenzene; alcohol and phenol 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. Further, the PPS resin subjected to the organic solvent washing is preferably washed several times with water or warm 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, and 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 is an aliphatic saturated monocarboxylic acid such as formic acid, acetic acid, propionic acid, and butyric acid, and a halo-substituted aliphatic saturated acid such as chloroacetic acid and dichloroacetic acid. Carboxylic acids, acrylic acid, aliphatic unsaturated monocarboxylic acids such as crotonic acid, benzoic acid, aromatic carboxylic acids such as salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, dicarboxylic acids 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 hot 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.

Among the PPS produced by using some of the above-mentioned post-treatments, in particular, all or at least 30% by weight or more of PPS having an ash content of 0.4% by weight or less, more preferably 0.2% by weight or less. It is preferable to use it in order to obtain excellent toughness, mechanical strength, and molding characteristics. The total ash content was obtained by placing 5 g of resin dried at 150 ° C. for 1 hour in a crucible, measuring the residue weight after burning at 540 ° C. for 6 hours, and calculating the ratio of the residue weight to the resin (5 g) after drying. It is.

Next, an epoxy group-containing olefin copolymer obtained by copolymerizing (b) an α-olefin, an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer, which is another essential component in the present invention, is used. The polymer is, specifically, an α-olefin of 52 to 95% by weight and α,
β-unsaturated carboxylic acid alkyl ester 5-48% by weight
And 0.5 to 15% by weight of an epoxy group-containing vinyl monomer with respect to a total of 85 to 99.5% by weight of α-olefin and α, β-unsaturated carboxylic acid alkyl ester.
Is an epoxy group-containing olefin copolymer obtained by copolymerization at a copolymerization ratio of More preferably, the copolymerization ratio is α
60 to 85% by weight of an olefin and 15 to 40% by weight of an α, β-unsaturated carboxylic acid alkyl ester, and
It is an epoxy group-containing olefin-based copolymer in which an epoxy group-containing vinyl monomer is 0.5 to 15% by weight based on a total of 85 to 99.5% by weight of α-olefin and α, β-unsaturated carboxylic acid alkyl ester.

If the copolymerization amount of the α, β-unsaturated carboxylic acid alkyl ester is too small, the effect of improving moldability such as releasability is reduced, while the copolymerization of the α, β-unsaturated carboxylic acid alkyl ester is reduced. If the amount is too large, the amount of gas generated at the time of molding increases, which results in contamination of the mold and deterioration of the surface properties of the molded piece.

If the copolymerization amount of the epoxy group-containing vinyl monomer is too small, the miscibility with the PPS resin decreases,
On the other hand, if the copolymerization amount of the epoxy group-containing vinyl monomer is too large, the amount of generated gas at the time of molding increases, and stains on the mold and the surface properties of the molded piece are deteriorated. .

The form of copolymerization of the (b) epoxy group-containing olefin copolymer may be any of random, block, and graft, and may be a composite form of these. Is more preferable.

Here, specific examples of the α-olefin which is a monomer component of the epoxy group-containing olefin copolymer (b) include ethylene, propylene, butene-1,4-
Examples thereof include methylpentene-1, hexene-1, decene-1, and octene-1, and among them, ethylene is preferably used. Also, two or more of these can be used simultaneously.

(B) The α, β-unsaturated carboxylic acid alkyl ester which is a monomer component of the epoxy group-containing olefin copolymer includes unsaturated carboxylic acids having 3 to 8 carbon atoms, such as acrylic acid, An alkyl ester such as acrylic acid, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-acrylate
Butyl, isobutyl acrylate, hexyl acrylate,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, and the like,
Of these, methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, n-acrylate
-Butyl and n-butyl methacrylate are preferably used. Also, two or more of these can be used simultaneously. (B) Examples of the epoxy group-containing vinyl monomer, which is a monomer component of the epoxy group-containing olefin copolymer, include glycidyl esters and glycidyl ethers of α, β-unsaturated acids, and are particularly represented by the following general formula. Glycidyl esters of α, β-unsaturated acids

[0030]

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(Wherein R represents a hydrogen atom or a lower alkyl group). Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like. Among them, glycidyl methacrylate is preferably used.

The amount of the (b) epoxy group-containing olefin copolymer in the composition is 1.5 to 35 parts by weight, preferably 5 to 35 parts by weight, per 100 parts by weight of the (a) polyphenylene sulfide resin. A range of 20 parts by weight is selected. If the amount is too small, the effect of improving toughness is reduced. If the amount is too large, problems such as impairment of heat resistance and an increase in the amount of gas generated during molding are not preferred.

Next, the (c) olefin-based copolymer having no epoxy group obtained by copolymerizing an α-olefin and an alkyl α, β-unsaturated carboxylate is referred to as the α-olefin and the α-olefin. Olefin-based copolymers obtained by copolymerizing alkyl esters of α, β-unsaturated carboxylic acids, or olefin-based copolymers obtained by further copolymerizing functional group-containing monomers other than epoxy group-containing vinyl monomers, such as maleic anhydride. Can be illustrated.

In the present invention, the addition of the (c) olefinic copolymer containing no epoxy group, which is obtained by copolymerizing an α-olefin and an α, β-unsaturated carboxylic acid alkyl ester, results in a reduction in the amount of gas generated. This is basically not preferable because it causes problems such as an increase in the amount of the olefin copolymer component, poor dispersion of the olefin copolymer component, and deterioration of the moldability (for example, an increase in the amount of generated burrs). However, PPS resin 100
If it is a small amount of less than 5 parts by weight with respect to parts by weight, it may be added in a range that does not exert a significant adverse effect.

In the present invention, 0.1 to 5 parts by weight of (d) an alkoxysilane compound selected from an epoxy group, an amino group, a ureide group, and an isocyanate group is added to (a) 100 parts by weight of a polyphenylene sulfide resin. Preferably 0.9 to 2.0 parts by weight, more preferably 1.2.
Addition of up to 2.0 parts by weight is preferable from the viewpoint of obtaining high toughness, excellent weld strength, and excellent molding characteristics (for example, reduction in the amount of burrs).

Specific examples of such compounds include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. -Containing alkoxysilane compound, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, etc. ureido group-containing alkoxysilane compound, γ-isocyanatopropyltri Ethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopro Le ethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as .gamma.-isocyanatopropyl trichlorosilane, .gamma. (2
Amino-containing alkoxysilane compounds such as -aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane.
Among them, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) amino Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane and the like are particularly preferred.

In the present invention, (e) a polyfunctional epoxy compound having two or more epoxy groups in one molecule is represented by (a)
For 100 parts by weight of polyphenylene sulfide resin,
Adding 0.1 to 5 parts by weight, more preferably 0.9 to 2.0 parts by weight, and still more preferably 1.2 to 2.0 parts by weight, results in high toughness, excellent weld strength, and excellent molding processing. This is preferable from the viewpoint of obtaining characteristics (for example, a reduction in the amount of burr generated).

Examples of the polyfunctional epoxy compound (e) having two or more epoxy groups in one molecule include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD, 4,4'-dihydroxybiphenyl, resorcinol, Saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, their halogen-substituted and alkyl-substituted products, two hydroxyl groups such as butanediol, ethylene glycol, erythrit, novolak, glycerin, and polyoxyalkylene in the molecule. Glycidyl ethers synthesized from the compounds contained above and epichlorohydrin, glycidyl esters such as glycidyl phthalate, aniline, diaminodiphenylmethane, meta-xylenediamine, Glycidylamine resins synthesized from primary or secondary amines such as 1,3-bisaminimethylcyclohexane and epichlorohydrin, etc., glycidyl epoxy resins, epoxidized soybean oil, vinylcyclohexene dioxide, dicyclopentadiene dioxide Examples thereof include non-glycidyl epoxy resins and the like. Among them, polyfunctional phenol type epoxy resins shown below are preferable, and orthocresol novolac glycidyl ether is particularly preferable.

[0039]

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(E) As the polyfunctional epoxy compound having two or more epoxy groups in one molecule, the above-mentioned (b) α-
Epoxy group-containing olefin copolymers such as an epoxy group-containing olefin copolymer obtained by copolymerizing an olefin with an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer are excluded.

Further, in the present invention, (f) an aliphatic carboxylic acid having 12 to 40 carbon atoms is used in order to suppress an increase in the amount of generated gas while imparting particularly excellent molding characteristics such as releasability. Ester compound consisting of a dihydric alcohol,
(A) 0.05 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, per 100 parts by weight of polyphenylene sulfide resin
It is preferable to mix by weight.

Examples of such compounds include long-chain aliphatic carboxylic acids such as stearic acid, oleic acid, behenic acid and montanic acid and ethylene glycol, pentaerythritol, polypentaerythritol, glycerin, trimethylolpropane and polytrimethylolpropane. Examples include an ester compound obtained by reacting a polyhydric alcohol, specifically, ethylene glycol distearate, pentaerythritol tetrastearate, polypentaerythritol polystearate, glycerin tristearate,
Trimethylolpropane tristearate, polytrimethylolpropane polystearate, ethylene glycol dimontanate, pentaerythritol tetramontanate, polypentaerythritol polymontanate,
Glycerin trimontanate, trimethylolpropane trimontanate, polytrimethylolpropane polymontanate and the like can be exemplified.

In the present invention, (g) a filler is further
(A) 10 to 250 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of polyphenylene sulfide resin
It is preferable to add 20 parts by weight, more preferably 20 to 60 parts by weight, from the viewpoint of obtaining more excellent mechanical strength and dimensional stability.

The shape of the filler may be either fibrous or non-fibrous, and may be used in combination. Specific examples thereof include glass fiber, carbon fiber, potassium whisker titanate, zinc oxide whisker, aluminum borate whisker, aramid fiber,
Fibrous filler such as alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, metal fiber,
Silicates such as wollastonite, zeolite, sericite, mica, talc, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate,
Metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, 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, magnesium hydroxide and aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, graphite, carbon black,
Examples include non-fibrous fillers such as dolomite and silica, which may be hollow, and two or more of these fillers may be used in combination. In addition, when these fillers are pre-treated 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, more excellent mechanical strength can be obtained. Preferred in meaning. Among them, a fibrous filler is preferable.

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, kaolin, and organic compounds are used as long as the effects of the present invention are not impaired. Antioxidants for crystal nucleating agents such as phosphorus compounds, release agents such as polyolefin compounds, silicone compounds, long-chain aliphatic ester compounds and long-chain aliphatic amide compounds, hindered phenol compounds and hindered amine compounds Conventional additives such as lubricants, heat stabilizers, lubricants such as calcium stearate, aluminum stearate, and lithium stearate, ultraviolet inhibitors, coloring agents, flame retardants, and foaming agents can be added.

In the PPS resin composition of the present invention, as long as the effects of the present invention are not impaired, polyphenylene oxide, polysulfone, polyethylene tetrafluoride, polyetherimide, polyamideimide, polyimide, polycarbonate, polyether -Tersulfone, polyether ketone, polythioether ketone, polyether ether ketone, epoxy resin, phenol resin, nylon 6, nylon 66, nylon 610, nylon 1
Other resins such as 1, nylon 12, aromatic nylon, polybutylene terephthalate, polyethylene terephthalate, polycyclylhexyl dimethylene terephthalate, ABS resin, polyamide elastomer, polyester elastomer, and polyalkylene oxide may be included.

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. 280-4
A method of kneading at a temperature of 50 ° C. can be given as a typical example. 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 of the present invention has a melt flow rate (315.5 ° C., 5000 g load, residence time of 5 minutes, from the viewpoint of reducing the amount of gas generated during injection molding).
It is preferable that the resin composition has an orifice diameter of 0.0825 inches and an orifice length of 0.315 inches) in the range of 20 to 200 g / 10 minutes. If the melt viscosity is too high, the amount of gas generation increases due to decomposition of the olefin copolymer during molding and the like, causing mold fouling and a decrease in weld strength.

The resin composition of the present invention is a PPS resin composition having excellent toughness and particularly excellent weld strength, and is used for injection molded articles having two or more gates in which welds are easily generated. Especially useful for: Also, taking advantage of this feature, it is suitable for metal insert molded articles.

Other uses include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors,
Variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor Electrical and electronic parts such as brush holders, motor insulators, parabolic antennas, and computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser disk compacts Home and office electrical product parts such as audio equipment parts such as discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts; office computer related parts, telephone Related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, machine-related parts represented by lighters, typewriters, etc .: optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machinery Related parts: water faucet top, mixing faucet, pump parts, pipe joint, water flow control valve, relief valve,
Plumbing parts such as hot water temperature sensor, water volume sensor, water meter housing; valve alternator terminal,
Alternator connector, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, 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, air conditioner thermostat base, 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 plate, Flop motor rotor, lamp socket, lamp reflector, lamp housing,
Examples include automobile / vehicle-related parts such as a brake piston, a solenoid bobbin, an engine oil filter, an ignition device case, a vehicle speed sensor, a cable liner, and other various uses.

[0051]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the following examples, evaluations of Izod impact strength, bending strength, weld strength, and rate of weight loss during heating were performed by the following methods.

[Izod Impact Strength with Notch] AST
It was evaluated according to MD256.

[Weld strength] Injection molding machine (resin set temperature 310 ° C., molding pressure = (minimum molding pressure + 3 kgf / c)
with m ² gauge)), AST having a gate on both ends
The resin composition was injected from both ends of the M1 dumbbell piece to obtain a test piece having a weld at the center. Using this test piece, a tensile test was performed at a chuck distance of 114 mm and a strain rate of 5 mm / min, and the breaking strength was taken as the weld strength.

[Weight loss rate during heating] The resin composition pellets were baked at 350 ° C. for 3 hours or more and cooled to room temperature in a desiccator (upper diameter 73 mm, lower diameter 47 mm, depth 54 mm). About 20 g was weighed. Then, at 130 ° C, remove 3
Preliminary drying was performed for a time, and once cooled to room temperature in a desiccator, a reference weight was measured. Next, this treatment was performed at 320 ° C. for 2 hours (air atmosphere), cooled to room temperature in a desiccator, weighed, and based on the weight after pre-drying at 130 ° C., the weight loss rate due to the treatment at 320 ° C. for 2 hours (%) Was calculated.

[Bending strength] The bending strength was evaluated according to ASTM D790.

(A) PPS resin a1: Linear PPS resin, melt viscosity 500 poise (31
0 ° C., shear rate 1000 / sec), ash content 0.08% by weight (washing with acidic aqueous solution, washing with warm water) a2: Linear PPS resin, melt viscosity 200 poise (31)
0 ° C., shear rate 1000 / sec), ash content 0.21% by weight (washing with acidic aqueous solution, washing with hot water) (b) Epoxy-containing olefin copolymer b1: ethylene / methyl acrylate / glycidyl methacrylate ( (Copolymerization ratio = 64/30/6 (wt%)) copolymer. b2: ethylene / n-butyl acrylate / glycidyl methacrylate (copolymerization ratio = 79/15/6 (% by weight))
Copolymer. b3: Ethylene / methyl acrylate / glycidyl methacrylate (copolymerization ratio = 38.7 / 59 / 2.3 (% by weight)) copolymer (outside the specified range of the present invention).

(C) Olefin copolymer containing no epoxy group c1: ethylene / ethyl acrylate (copolymerization ratio = 85 /
15 (% by weight)) copolymer.

(D) Alkoxysilane compound d1: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane d2: γ- (2-ureidoethyl) aminopropyltrimethoxysilane

(E) Polyfunctional epoxy compound having two or more epoxy groups in one molecule e1: ortho-cresol novolac glycidyl ether compound SUMI-EPOXY ESCN195HH (manufactured by Sumitomo Chemical Co., Ltd.).

(F) Ester compound obtained by reacting an aliphatic carboxylic acid with a polyhydric alcohol f1: Pentaerythritol tetrastearate.

(G) Filler g1: Glass fiber, E glass, fiber type 10 μm, fiber length 3 mm, loss on ignition 0.44% by weight. g2: calcium carbonate.

Examples 1 to 5 (a) PPS resin, (b) epoxy group-containing olefin copolymer, and other additives were dry blended in the proportions shown in Table 1 and preliminarily mixed in a tumbler for 2 minutes. Thereafter, the mixture was melt-kneaded with a twin-screw extruder set at a cylinder temperature of 300 to 340 ° C, pelletized by a strand cutter, and dried at 120 ° C overnight. Using these pellets, IZOD impact strength, bending strength, and test pieces for evaluating weld strength were injection molded, and the weight loss rate upon heating and the melt flow rate were evaluated. Table 1 shows the results.

Comparative Example 1 As an olefin copolymer, b3 (ethylene / methyl acrylate / glycidyl methacrylate (copolymerization ratio = 3)
8.7 / 59 / 2.3 (wt%)), melt kneading and evaluation were performed in the same manner as in Example 1 except that the copolymer (outside the specified range of the present invention) was used. Table 1 shows the results. In this case, the weight loss rate during heating was high and the weld strength was low.

COMPARATIVE EXAMPLE 2 (c) Example 1 except that an olefinic copolymer containing no epoxy group and obtained by copolymerizing an α-olefin and an alkyl α, β-unsaturated carboxylate was further added. Melt kneading and evaluation were performed in the same manner as described above. Table 1 shows the results
Shown in In this case, the weight loss rate during heating was high and the weld strength was low. Moreover, compared with Examples 1 and 3, the amount of burrs generated on the weld test piece was large, and the results were inferior in terms of moldability.

Example 6 Melt kneading and evaluation were performed in the same manner as in Example 1 except that (f) the ester compound was not added. Table 1 shows the results
Shown in Although an excellent composition was obtained in terms of mechanical properties, weld strength, and weight loss rate upon heating, the molded piece sometimes stuck to the mold during injection molding, resulting in a slightly inferior releasability.

[0067]

[Table 1]

[0068]

As described above, the present invention is a polyphenylene sulfide resin composition having excellent heat resistance, mechanical properties, and excellent toughness, moldability, low gas properties, and the like.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 23, 1999 (1999.7.2)
3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction contents]

[0067]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 7/02 C08K 7/02 9/06 9/06 C08L 23/02 C08L 23/02 63/00 63 / 00 CF term (reference) 4F071 AA14X AA33X AA39X AA42 AA62 AA67 AA76 AB02 AB03 AB18 AB20 AB24 AB26 AB27 AB28 AB29 AB30 AC10 AD01 AD02 AE02 AF14 AF45 AH07 AH12 AH16 AH17 BA01 BB05 BC02 BC03 BC05X13 BBBBXBBB BBX BBX BB BBX BBX BBX BBX BBY BB19X BB19Y CD00U CD01U CD02U CD05U CD06U CD10U CD11U CD13U CD16U CN011 CP05Z CP09Z DA017 DE077 DE097 DE107 DE137 DE147 DE187 DE237 DG057 DJ007 DJ017 DJ027 DJ047 DJ057 DK007 DL007 EH046 FA047 FA067 GM00 GN00

Claims (8)

[Claims] 1. A polyphenylene sulfide resin (a)
0 parts by weight and (b) an epoxy group-containing olefin-based copolymer obtained by copolymerizing an α-olefin, an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer, the copolymerization ratio of Is from 52 to 95% by weight of an α-olefin and from 5 to 48% by weight of an α, β-unsaturated carboxylic acid alkyl ester, and a total of from 85 to 99.95% of α-olefin and α, β-unsaturated carboxylic acid alkyl ester. A polyphenylene sulfide resin composition comprising 1.5 to 35 parts by weight of an epoxy group-containing olefin copolymer which is 0.5 to 15% by weight of an epoxy group-containing vinyl monomer with respect to 5% by weight. And (c) an olefin-based copolymer having no epoxy group, which is obtained by copolymerizing an α-olefin and an α, β-unsaturated carboxylic acid alkyl ester. A polyphenylene sulfide resin composition having no or no more than 5 parts by weight. 2. The melt viscosity of the (a) polyphenylene sulfide resin (300 ° C., shear rate 1,000 / sec) is 10 to 10.
The polyphenylene sulfide resin composition according to claim 1, wherein the composition is 2,000 poise. 3. An alkoxysilane compound selected from (d) an epoxy group, an amino group, a ureide group and an isocyanate group, and (a) a polyphenylene sulfide resin
The polyphenylene sulfide resin composition according to any one of claims 1 to 2, wherein the polyphenylene sulfide resin composition is blended in an amount of 0.1 to 5 parts by weight based on parts by weight. 4. A method according to claim 1, wherein (e) a polyfunctional epoxy compound having two or more epoxy groups in one molecule is compounded in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin (a). The polyphenylene sulfide resin composition according to any one of claims 1 to 3. 5. An ester compound obtained by reacting (f) an aliphatic carboxylic acid having 12 to 40 carbon atoms with a polyhydric alcohol is added in an amount of 0.05 to 5 parts by weight per 100 parts by weight of (a) polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein the composition is blended in parts. 6. The filler (g) is added in an amount of 10 to 250 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin (a).
The polyphenylene sulfide resin composition according to any one of claims 1 to 5, which is blended in parts by weight. 7. A melt flow rate (315.5 ° C., 50
The polyphenylene sulfide resin composition according to any one of claims 1 to 6, wherein the (00g load) is 20 to 200 g / 10 minutes. 8. A molded article obtained by injection molding the polyphenylene sulfide resin composition according to claim 1, wherein the molded article has two or more gates.