JP2000198923A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide(PPS) resin compsn. which realizes more excellent balance in a higher level with respect to shock resistance, low temp. shock resistance, molding property, etc., than conventional PPS resin material and also is excellent and well-balanced in characteristics inherent in PPS resin such as mechanical properties other than shock resistance, hot-water resistance, etc., and further is excellent in industrial productivity and economy. SOLUTION: This compsn. comprises 1-100 pts.wt. ethylene/α-olefin copolymer (B) comprising ethylene and a 3-20C α-olefin and having a ratio (Mw/Mn) of weight average mol.wt. (Mw) and number average mol.wt. (Mn) determined by GPC of not greater than 3.0 and 1-100 pts.wt. olefinic polymer or a copolymer contg a functional group (C) having at least one functional group selected from epoxy group, an acid anhydrate group, carboxyl group and its salt, a carboxylic acid ester to 100 pts.wt. PPS (A).

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 excellent in impact resistance, moldability and the like, and a 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, the PPS resin has a problem that it is inferior in impact resistance to other engineering plastics such as polyamide resin.

[0003] In order to solve such a problem, a method of blending various elastomers with a PPS resin has been proposed so far. For example, Japanese Patent Application Laid-Open No.
A method of blending an epoxy group-containing olefin copolymer with a PS resin is disclosed in JP-A-1-306467.
A method is disclosed in which an epoxy group-containing olefin copolymer and an elastomer containing no epoxy group and no acid anhydride group are blended with a resin.

However, in recent years, demands for PPS resin materials have become more and more severe, and these conventionally proposed thermoplastic resin compositions cannot be said to be sufficient in material properties, and higher impact resistance, lower temperature impact resistance, A material that simultaneously satisfies molding workability and the like and is economically advantageous is required.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to realize a higher balance of impact resistance, low-temperature impact resistance, molding workability, etc., which are better than the above-mentioned conventional PPS resin materials.
It is another object of the present invention to obtain a PPS resin composition which is excellent in mechanical properties other than impact resistance, inherent properties of PPS resin such as hot water resistance, and is also excellent in industrial productivity and economic efficiency.

[0006]

The present inventors have studied to solve the above-mentioned problems, and as a result, have found that (A) PPS resin and (B) ethylene and carbon atom having a specific structure, molecular weight distribution and density. An ethylene / α-olefin-based copolymer comprising α-olefins of formulas 3 to 20, and (C) at least one functional group selected from epoxy groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid esters It has been found that the above-mentioned problems can be solved by selectively combining and using a functional group-containing olefin-based polymer or copolymer containing the present invention, and reached the present invention.

That is, the present invention provides: (B) An ethylene / α-olefin-based copolymer comprising (B) ethylene and an α-olefin having 3 to 20 carbon atoms per 100 parts by weight of polyphenylene sulfide, and is a gel permeation chromatography (G
1-100 parts by weight of an ethylene / α-olefin copolymer having a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by PC) of 3.0 or less, and (C) 1 to 100 parts by weight of a functional group-containing olefin polymer or copolymer containing at least one functional group selected from epoxy groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid esters. 1. a polyphenylene sulfide resin composition, characterized in that: (A) An ethylene / α-olefin-based copolymer comprising (B-2) ethylene and an α-olefin having 3 to 20 carbon atoms, based on 100 parts by weight of polyphenylene sulfide, and having a density of 0.880 g / cm ³ ethylene · alpha-olefin copolymer to 100 parts by weight or less,
And (C) 1 to 100 parts by weight of a functional group-containing olefin polymer or copolymer containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. 2. a polyphenylene sulfide resin composition characterized by being blended; The polyphenylene sulfide resin composition, wherein the content of the α-olefin having 3 to 20 carbon atoms contained in the ethylene / α-olefin-based copolymer of the component (B) is 7 to 25 mol%, 4. 4. The above polyphenylene sulfide resin composition, wherein the ethylene / α-olefin-based copolymer as the component (B) is a copolymer obtained by polymerization using a metallocene-based catalyst. (C) an epoxy group-containing olefin copolymer obtained by copolymerizing the functional group-containing olefin polymer or copolymer of the component (C) with a glycidyl ester of an α-olefin and an α, β-unsaturated acid. 5. The above polyphenylene sulfide resin composition, The epoxy group-containing olefin copolymer (C) essentially comprises an α-olefin (1), a glycidyl ester of an α, β-unsaturated acid (2) and a monomer (3) represented by the following general formula. The polyphenylene sulfide resin composition is an olefin copolymer obtained by copolymerizing a monomer as a component,

Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Represents one or more groups selected from a —COOR ² group, a —CN group and an aromatic group. R ² has 1 to 10 carbon atoms.
Represents an alkyl group). 7. The above polyphenylene sulfide resin composition, wherein the functional group-containing olefin polymer or copolymer of the component (C) is an epoxidized diene block copolymer. The epoxidized diene block copolymer of the component (C) is a block comprising at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound. 8. The above polyphenylene sulfide resin composition, which is an epoxidized diene copolymer obtained by epoxidizing a double bond derived from a conjugated diene compound of a copolymer; The melt viscosity of the polyphenylene sulfide resin of the component (A) is 400 poise (310 ° C., shear rate 1).
9. The above polyphenylene sulfide resin composition, which is not less than 000 / s). 10. The above polyphenylene sulfide resin composition, wherein the polyphenylene sulfide resin as the component (A) has an ash content of 0.2% by weight or less. Further, as the component (D), a polyamide resin and / or
11. The above-mentioned polyphenylene sulfide resin composition containing a thermoplastic polyester resin in an amount of 1 to 99 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. 12. The above polyphenylene sulfide resin composition further containing (F) a filler in an amount of 1 to 400 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. 13. a polyphenylene sulfide resin composition wherein the filler (E) is a conductive filler and the content thereof is 0.5 to 50 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin; 14. A molded product obtained by injection molding the polyphenylene sulfide fat composition described above, and It is a molded article obtained by extrusion-molding the polyphenylene sulfide fat composition described above.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) polyphenylene sulfide resin (PPS resin) used in the present invention is a polymer having a repeating unit represented by the following structural formula,

Embedded image In view of heat resistance, such a repeating unit is preferably 7
A polymer containing 0 mol% or more, more preferably 90 mol% or more is preferable. Also, the PPS resin can constitute less than 30 mol% of the repeating unit with a repeating unit having the following structural formula.

[0009]

Embedded image

In particular, when a PPS having a high melt viscosity is desired, it is also possible to use a branched PPS having dihalobenzene as a main monomer and copolymerizing less than 3 mol% of trihalobenzene.

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible. However, in order to obtain better impact resistance, particularly low-temperature impact resistance, the melt viscosity is 400 poise (310 ° C., The shear rate is preferably at least 1000 / s), particularly preferably at least 700 poise. In particular, when it is used for extrusion molding, it is more preferably at least 1,000 poise.

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 Japanese Patent Publication No. 45-3368, Japanese Patent Publication No. 52-12240, or Japanese Patent Application Laid-Open No. 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 crosslinked / high molecular weight 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.

[0013] As a specific method for crosslinking / polymerizing 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 selected from 0.5 to 100 hours, preferably from 2 to 50 hours. It is possible to obtain the target viscosity level by controlling both the heating temperature and the time. it can. The heating device may be an ordinary hot air dryer or a rotary or heating device with a stirring blade, but for efficient and more uniform processing, 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 rotary or heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary or stirring blade is used. Is more preferred.

In the present invention, it is preferable to use a PPS resin in which the ash content in the PPS is reduced to 0.2% by weight or less by deionization or the like in order to obtain more excellent toughness and moldability. Specific examples of such a deionization treatment include an acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment, and these treatments may be used in combination of two or more kinds of methods. The ash content was measured according to the following method. PPS in dry state
About 5 g of the bulk powder is weighed in a crucible and fired on an electric stove until a black mass is formed. Next, this is fired in an electric furnace set at 550 ° C. until the carbide is completely fired. Then, after cooling in a desiccator, the weight is measured, and the ash content is calculated from the comparison with the initial weight.

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 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.

Next, the specific ethylene / α-olefin copolymer (B), which is an essential component of the present invention, is obtained by copolymerizing ethylene and at least one α-olefin having 3 to 20 carbon atoms. Specific molecular weight distribution and / or
Alternatively, it is a copolymer having a specific density. As the α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-
Heptene, 1-octene, 1-nonene, 1-decene, 1
-Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1
-Heptadecene, 1-octadecene, 1-nonadecene,
1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4
-Dimethyl-1-hexene, 4,4-dimethyl-1-
Pentene, 4-ethyl-1-hexene, 3-ethyl-1
-Hexene, 9-methyl-1-decene, 11-methyl-
Examples include 1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. Among these α-olefins, a copolymer using an α-olefin having 6 to 12 carbon atoms is more preferable because improvement in mechanical strength and further improvement in a reforming effect can be seen.

The ethylene / α-olefin-based copolymer used in the present invention has a weight average molecular weight (M) calculated by gel permeation chromatography (GPC).
w) and the number average molecular weight (Mn) ratio (Mw / Mn) is 3.0 or less, or the density is 0.880 g / c.
It is necessary that the copolymer be an ethylene / α-olefin copolymer having an m ³ or less in order to obtain excellent mechanical properties and moldability, and in particular, a weight average molecular weight calculated by gel permeation chromatography (GPC) (Mw)
And the ratio (Mw / Mn) between the number average molecular weight (Mn) and 3.0 is 3.0.
Or less and an ethylene / α-olefin copolymer having a density of 0.880 g / cm ³ or less is most preferably used.

The weight average molecular weight (M) of the ethylene / α-olefin copolymer used in the present invention calculated by gel permeation chromatography (GPC)
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is preferably 3.0 or less, more preferably 2.
9 or less, particularly preferably 2.8 or less. The copolymer whose molecular weight distribution is limited to an extremely narrow range of 3.0 or less has a small amount of low molecular weight components and is excellent in mechanical properties and moldability, so that the use of the copolymer results in excellent properties of the composition of the present invention. It becomes possible.

The ethylene / α-olefin-based copolymer used in the present invention preferably has a density of 0.880 g / cm ³ or less, and 0.830 to 0.880 g / cm ^3.
The range of cm ³ is more preferable, especially 0.850 to 0.8
A range of 75 g / cm ³ is preferred. Such ethylene-α
-By using an olefin-based copolymer, excellent moldability such as excellent releasability from a mold during injection molding,
In addition, it is possible to obtain a composition having excellent mechanical properties, particularly excellent toughness.

The ethylene / α-olefin copolymer preferably has an α-olefin content of 4 to 25 mol%,
More preferably 7 to 25 mol%, even more preferably 12 to 25 mol%.
22 mol%. By using an ethylene / α-olefin copolymer having an α-olefin content in the above range, a PPS resin composition capable of providing a molded article having excellent flexibility and impact resistance can be obtained.

Such an ethylene / α-olefin copolymer can be produced by polymerization using a metallocene catalyst. The metallocene-based catalyst is composed of a cyclopentadienyl derivative of a Group IV metal such as titanium or zirconium and a co-catalyst. Metallocene-based catalysts are highly active, and compared to conventional catalysts represented by Ziegler-based catalysts,
The resulting polymer has a narrow molecular weight distribution and a uniform distribution of the α-olefin, which is a comonomer component of the copolymer, so that it has excellent flexibility and impact resistance.

The ethylene / α-olefin-based copolymer used in the present invention has a total ash content of 0.01 to 0.2% by weight, preferably 0.01 to 0.1% by weight. Used.

The blending amount of the specific ethylene / α-olefin copolymer (B) is selected from the range of 1 to 100 parts by weight, based on 100 parts by weight of the PPS resin. A range of 3 to 50 parts by weight is more preferred.
(B) If the blending amount of the specific ethylene / α-olefin-based copolymer is too small, the intended improvement effect such as impact characteristics is negligible, while if too large, the high heat resistance inherent in the PPS resin is obtained. Tend to be significantly impaired.

Next, in the present invention, (C) an epoxy group,
(B) a functional group-containing olefin polymer or copolymer containing at least one functional group selected from an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester;
It is indispensable to mix it with a specific ethylene / α-olefin copolymer in order to obtain the excellent improvement effect of the present invention.

(C) Epoxy group-containing olefin (co) polymer, which is one of the functional group-containing olefin (co) polymers, includes olefin copolymers having glycidyl ester, glycidyl ether, etc. in the side chain. Examples thereof include those obtained by epoxy oxidation of a double bond portion of an olefin-based copolymer having a double bond or a double bond.

The epoxy group-containing olefin (co)
As a more specific embodiment of the polymer, an olefin-based copolymer in which a monomer having an epoxy group is copolymerized, and particularly, by copolymerizing an α-olefin and a glycidyl ester of an α, β-unsaturated acid. (C) The epoxy group-containing olefin copolymer obtained is preferably used.

Specific examples of such α-olefin include:
Examples thereof include ethylene, propylene, butene-1, 4-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.

On the other hand, glycidyl esters of α, β-unsaturated acids are represented by the general formula

Embedded image (Where R represents a hydrogen atom or a lower alkyl group), specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, among which glycidyl methacrylate is preferably used.

The olefin-based copolymer obtained by copolymerizing the α-olefin and the glycidyl ester of an α, β-unsaturated acid can be prepared by randomizing the α-olefin and the glycidyl ester of an α, β-unsaturated acid. Alternating, block,
Any copolymerization mode of the graft copolymer may be used.

The amount of the glycidyl ester of the α, β-unsaturated acid in the olefin-based copolymer obtained by copolymerizing the glycidyl ester of the α-olefin and the α, β-unsaturated acid may have a desired effect. From the viewpoint of the effect on the polymer, gelation, heat resistance, flowability, and strength
0.5 to 40% by weight, especially 3 to 30% by weight is preferred.

In the present invention, in addition to the α-olefin (1) and the glycidyl ester of α, β-unsaturated acid (2), the epoxy group-containing olefin copolymer further comprises a monomer represented by the following general formula: Epoxy group-containing olefin copolymers containing 3) as an essential component are also suitably used.

[0035]

Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Is a group selected from a —COOR ² group, a —CN group and an aromatic group. R ² represents an alkyl group having 1 to 10 carbon atoms)

The details of the α-olefin (1) and the glycidyl ester of an α, β-unsaturated acid (2) used in the olefin copolymer are the same as those of the olefin copolymer (B).

On the other hand, specific examples of the monomer (3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, Α, β-unsaturated carboxylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate, acrylonitrile, styrene, Examples thereof include α-methylstyrene, styrene in which an aromatic ring is substituted with an alkyl group, and acrylonitrile-styrene copolymer, and two or more of these can be used simultaneously.

Such an olefin-based copolymer includes any of random, alternating, block and graft copolymers of α-olefin (1), glycidyl ester of α, β-unsaturated acid (2) and monomer (3). The form may be, for example, α-
Combination of two or more copolymerization modes, such as graft copolymerization of monomer (3) with random copolymer of olefin (1) and glycidyl ester of α, β-unsaturated acid (2) It may be a copolymer.

The copolymerization ratio of the olefin-based copolymer is determined from the viewpoint of the effect on the desired effect, the polymerizability, gelation, heat resistance, fluidity, strength, etc. Glycidyl esters of α, β-unsaturated acids (2)
= 60-99% by weight / 40-1% by weight is preferably selected. The copolymerization ratio of the monomer (3) is based on the total amount of the α-olefin (1) and the glycidyl ester of the α, β-unsaturated acid (2) being 95 to 40% by weight, and A range of 5 to 60% by weight (provided that the sum of (1), (2) and (3) is 100% by weight) is preferably selected.

Further, as another preferred embodiment of the epoxy group-containing olefin (co) polymer in the present invention,
Epoxidized diene-based block copolymers are exemplified.

The epoxidized diene-based block copolymer is obtained by epoxidizing a double bond derived from a conjugated diene compound of a block copolymer or a partially hydrogenated block copolymer. The copolymer is
A block copolymer composed of at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound, for example, AB, A -B-A, B-A-B-
It is an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as A, (AB-) 4-Si, ABABA, or the like. The partially hydrogenated block copolymer is obtained by hydrogenating the block copolymer. Hereinafter, the block copolymer and the partially hydrogenated block copolymer will be described in more detail.

This block copolymer contains the aromatic vinyl compound in an amount of 5% by weight or more and less than 95% by weight, preferably 10% by weight or less.
60% by weight, more preferably 10 to 50% by weight,
Polymer block A mainly composed of an aromatic vinyl compound,
It has a structure of a homopolymer block of an aromatic vinyl compound or a copolymer block of an aromatic vinyl compound containing more than 50% by weight, preferably 70% by weight or more of an aromatic vinyl compound and a conjugated diene compound. And a conjugated diene compound and / or an aromatic vinyl compound in which the polymer block B mainly composed of a conjugated diene compound is a homopolymer block of the conjugated diene compound or contains a conjugated diene compound in an amount of more than 50% by weight, preferably 70% by weight or more. Having the structure of a copolymer block. Further, the polymer block A mainly composed of an aromatic vinyl compound and the polymer block B mainly composed of a conjugated diene compound are formed by the distribution of the conjugated diene compound or the aromatic vinyl compound in the molecular chain in each polymer block. May be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped or in any combination thereof, and a polymer block mainly composed of the aromatic vinyl compound. When there are two or more polymer blocks mainly composed of the conjugated diene compound, each of the polymer blocks may have the same structure or different structures.

Examples of the aromatic vinyl compound constituting the block copolymer include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, 1,1
One or more of diphenylethylene and the like can be selected, and among them, styrene is preferable. As the conjugated diene compound, for example, butadiene, isoprene,
One or more kinds are selected from 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable. The polymer block mainly composed of a conjugated diene compound can arbitrarily select a microstructure in the block. For example, in a polybutadiene block, the 1,2-vinyl bond structure is preferably in a range of 5 to 65%, and in particular, Preferably it is in the range of 10 to 50%.

The number average molecular weight of the block copolymer having the above structure is usually from 5,000 to 1,000,000.
0, preferably 10,000 to 800,000, more preferably 30,000 to 500,000, and a molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn). )] Is 10 or less.
Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

The method for producing these block copolymers may be any method as long as it has the above-mentioned structure. For example,
According to the method described in JP-B-40-23798, an aromatic vinyl compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst.

The partially hydrogenated block copolymer is obtained by hydrogenating the above aromatic vinyl compound-conjugated diene compound block copolymer. Examples of the production method include JP-B-42-8704 and JP-B-43-8704.
Although the method described in US Pat. No. 6,636,659 can be employed, it was synthesized using a titanium-based hydrogenation catalyst exhibiting particularly excellent weather resistance and heat deterioration resistance of the obtained hydrogenated block copolymer. Most preferred is a hydrogenated block copolymer,
For example, JP-A-59-133203, JP-A-60-133
According to the method described in JP-79005-A, a block copolymer having the above structure is hydrogenated in an inert solvent in the presence of a titanium-based hydrogenation catalyst to synthesize a hydrogenated block copolymer. Can be. At this time, the aliphatic double bond based on the conjugated diene compound of the aromatic vinyl compound-conjugated diene compound block copolymer is obtained by hydrogenating 0 to 99%, preferably hydrogenating 0 to 70%. . These block copolymers and partially hydrogenated block copolymers are on the market and can be easily obtained.

Next, the epoxidized diene-based block copolymer which can be used as one of the components (C) of the present invention is obtained by adding an epoxidizing agent to a block copolymer having the above-mentioned structure or a partially hydrogenated block copolymer. Is reacted to epoxidize the aliphatic double bond based on the conjugated diene compound. The epoxidized diene block copolymer used in the present invention is obtained by reacting the above block copolymer or partially hydrogenated block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. Obtainable. As the peracids, a mixture of formic acid, peracetic acid, and perbenzoic acid with hydrogen peroxide, or an organic acid with hydrogen peroxide,
Alternatively, a catalytic effect can be obtained by using molybdenum hexacarbonyl in combination with tertiary butyl hydroperoxide. Also, the optimal amount of epoxidizing agent can be determined by such variables as the particular epoxidizing agent used, the desired degree of epoxidation, the particular block copolymer used, and the like. The obtained epoxidized diene block copolymer can be isolated by an appropriate method, for example, a method of precipitating with a poor solvent, a method of throwing the polymer into hot water with stirring and distilling off the solvent, or a method of directly removing the solvent. It can be performed by a desolvation method or the like.

The degree of epoxidation of the epoxidized diene-based block copolymer is not particularly limited, but the oxirane oxygen concentration is preferably 0.1% by weight to 7% by weight, more preferably 1.0% by weight or more. It is preferably at most 5% by weight. If the oxirane oxygen concentration is within the above range, P
PS resin composition has good impact strengthening and appearance characteristics,
This is preferable in that delamination is suppressed and stable heat resistance is obtained.

In the present invention, (C) an olefin (co) polymer containing a carboxyl group and a salt thereof, a carboxylic acid ester group and an acid anhydride group which can be used as a functional group-containing olefin (co) polymer component. Examples are ethylene-butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer and other ethylene-α-olefin copolymers, polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, polybutene , Ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polybutadiene, butadiene-acrylonitrile copolymer Coalescence, polyisoprene, butene-a Puren copolymer, styrene - ethylene - butylene - styrene block copolymer (SEB
S), a polystyrene (co) polymer such as a styrene-ethylene-propylene-styrene block copolymer (SEPS) and an ethylene-α-olefin copolymer described in (B) above, and maleic anhydride and succinic acid. Anhydrides, acid anhydrides such as fumaric anhydride, acrylic acid, methacrylic acid, carboxylic acids such as vinyl acetate and their Na, Zn,
K, Ca, salts such as Mg, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
Propyl acrylate, propyl methacrylate, butyl acrylate, olefin copolymers in which carboxylic acid esters such as butyl methacrylate are copolymerized, and more specifically, ethylene-methyl acrylate copolymer, ethylene -Ethyl acrylate copolymer, ethylene-
N-propyl acrylate copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-t-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene -Methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer,
Olefins such as ethylene-t-butyl methacrylate copolymer and ethylene-isobutyl methacrylate copolymer
(Meth) acrylate copolymer, methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, acrylic acid (Meth) acrylates such as butyl-acrylonitrile copolymer, butyl methacrylate-acrylonitrile copolymer,
Acrylonitrile copolymer, ethylene- (meth) acrylic acid copolymer and its metal salts such as Na, Zn, K, Ca, Mg, ethylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer Polymer, ethylene-propylene-maleic anhydride copolymer, ethylene-
Hexene-maleic anhydride copolymer, ethylene-octene-maleic anhydride copolymer, propylene-maleic anhydride copolymer or maleic anhydride-modified SB
Examples thereof include S, SIS, SEBS, SEPS, and ethylene-ethyl acrylate copolymer.

The copolymerization mode of the olefin (co) polymer is not particularly limited, and may be any copolymer mode such as a random copolymer, a graft copolymer, and a block copolymer.

The compounding amount of the olefin copolymer (C) containing at least one functional group selected from the group consisting of an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group has an excellent resistance. From the viewpoints of impact properties, moldability, low gas properties, and the like, the range of 1 to 100 parts by weight, preferably 3 to 50 parts by weight, and particularly 3 to 50 parts by weight, per 100 parts by weight of (A) PPS resin is selected. A range of 20 parts by weight is more preferably selected.

If the amount of the (C) olefin copolymer containing at least one functional group selected from epoxy groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid ester groups is too small, The intended improvement effect is insufficient, while if too large, the moldability tends to be impaired.

The above (C) epoxy group, acid anhydride group,
As the olefin copolymer containing at least one functional group selected from a carboxyl group, a salt thereof, and a carboxylate group, two or more (C) functional group-containing olefin copolymers may be used in combination. .

In the present invention, from the viewpoint of obtaining superior impact resistance and the like, an alkoxysilane compound is further added as an additional component to the polyphenylene sulfide resin (A).
0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per part by weight.
It is effective to add 1 to 2 parts by weight.

As such an alkoxysilane compound,
At least one selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group
Preferred are alkoxysilanes having various kinds of functional groups. Specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrisilane. Epoxy group-containing alkoxysilane compounds such as methoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane Silane, ureido group-containing alkoxysilane compounds such as γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanate Isocyanato group-containing alkoxysilane compounds such as natopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane , Γ- (2
Amino-containing alkoxysilane compounds such as -aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ- Hydroxy group-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane, etc., among which γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing alkoxysilane compounds such as trimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, etc. Amino group-containing alkoxysilane compounds such as ureido group-containing alkoxysilane compounds, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane Γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ
-Isocyanatopropylmethyldimethoxysilane, γ-
Isocyanato group-containing alkoxysilane compounds such as isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane are particularly preferred.

In the present invention, as the component (D),
Incorporation of a polyamide resin and / or a thermoplastic polyester resin is effective in further improving the moldability together with excellent impact resistance. Further, when laminating the resin composition of the present invention with another resin composition such as a polyamide resin composition or a polyester resin composition, for example, when laminating by co-extrusion molding or the like, the adhesiveness at the interface between both resins is improved. The above is also valid. The polyamide resin and the thermoplastic polyester resin may be used alone or in combination.

The polyamide resin used as the component (D) is a polyamide containing amino acids, lactams or diamines and dicarboxylic acids as main raw materials. Representative examples of the raw materials include 6-aminocaproic acid, 11
Aminoaminodecanoic acid, 12-aminododecanoic acid, amino acids such as paraaminomethylbenzoic acid, lactams such as ε-caprolactam, ω-laurolactam, tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, Undecamethylenediamine, dodecamethylenediamine, 2,2
4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl ) Cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-
Aminocyclohexyl) methane, bis (3-methyl-4)
-Aminocyclohexyl) methane, 2,2-bis (4-
Aliphatic, alicyclic and aromatic diamines such as aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid,
Such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid Examples thereof include aliphatic, alicyclic, and aromatic dicarboxylic acids. In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, particularly useful polyamide resins are polyamide resins having a melting point of 150 ° C. or higher and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecaneamide (nylon 1)
1), polydodecaneamide (nylon 12), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexa Methylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 /
6T / 6I), polyxylylene adipamide (nylon X
D6), polyhexamethylene terephthalamide / poly-
Examples include 2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T) and mixtures thereof.

Particularly preferred polyamide resins include nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 6/66 copolymer, nylon 6T / 66 copolymer and nylon 6T.
And copolymers having hexamethyl terephthalamide units such as Nylon / 6I copolymer and Nylon 6T / 6 copolymer. Further, these polyamide resins can be used in accordance with required properties such as impact resistance, molding processability, and compatibility. It is also practically preferable to use it as a mixture.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 7.0, and more preferably 2.0 to 7 .0
Is preferable, but from the viewpoint of obtaining more excellent impact resistance, the range of 3.0 to 7.0 is particularly preferable.

On the other hand, preferred thermoplastic polyester resins used as component (D) include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and the like.
Examples include polyethylene naphthalate, polycyclohexylene dimethylene terephthalate / polyethylene terephthalate copolymer, and the like.

The degree of polymerization of these thermoplastic polyester resins, particularly preferably used polybutylene terephthalate (hereinafter abbreviated as PBT resin), is not particularly limited.
The relative viscosity of a 0.5% orthochlorophenol solution measured at 25 ° C. is in the range of 0.5 to 2.5, especially 0.8 to 2.
Those in the range of 0 are preferred. Also, the degree of polymerization of polyethylene terephthalate is not particularly limited, and 0.5%
The intrinsic viscosity of the orthochlorophenol solution measured at 25 ° C. is preferably in the range of 0.54 to 1.5, particularly preferably in the range of 0.6 to 1.2.

When the polyamide resin and the thermoplastic polyester resin are compounded as the component (D), the preferable compounding amount is 100 parts by weight of the polyphenylene sulfide resin.
1 to 99 parts by weight, more preferably 5 to 70 parts by weight, based on parts by weight
The range of parts by weight can be exemplified.

In the present invention, when high rigidity and dimensional stability are required at the same time as high impact characteristics,
Further, it is preferable to blend a filler as the component (E).

The shape of the filler may be fibrous or non-fibrous, and may be used in combination. Specific examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber,
Fibrous fillers such as metal fibers, wallastenite, zeolite, sericite, mica, talc, kaolin, clay, pyrophyllite, bentonite, asbestos, silicates such as alumina silicate, alumina, silicon oxide,
Metal compounds such as 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, calcium hydroxide, magnesium hydroxide, aluminum hydroxide and the like Non-fibrous fillers such as hydroxides, glass beads, ceramic beads, boron nitride, silicon carbide and silica may be mentioned, these may be hollow, and two or more of these fillers may be used in combination. Is also possible. 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 preferred, especially glass fibers,
Glass milled fibers are preferred.

The amount of the filler (E) is 1 to 400 parts by weight based on 100 parts by weight of the (A) PPS resin.
A range of parts by weight can be exemplified, and a range of 20 to 250 parts by weight is more preferable.

The composition of the present invention is obtained by blending a conductive filler (conductive filler) among the components (E) to obtain a conductive PPS resin composition having excellent impact resistance. But it is useful. As such a conductive filler, the conductive filler is not particularly limited as long as it is a conductive filler that is usually used for conducting a resin, and specific examples thereof include metal powder, metal flake, metal ribbon, metal fiber, and metal. Examples include an oxide, an inorganic filler coated with a conductive substance, carbon powder, graphite, carbon fiber, carbon flake, and flaky carbon.

Specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal species of the metal fiber include iron,
Examples thereof include copper, stainless steel, aluminum, and brass.

The metal powder, metal flake, metal ribbon, and metal fiber may be subjected to a surface treatment with a titanate-based, aluminum-based, or silane-based surface treatment agent.

Specific examples of the metal oxide include SnO ₂ (antimony doped), In ₂ O ₃ (antimony doped),
Examples thereof include ZnO (aluminum dope), and these may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony-doped),
Examples include n ₂ O ₃ (antimony doping). As the inorganic filler to be coated, mica, glass beads, glass fiber, carbon fiber, potassium whisker,
Examples include barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide whiskers, titanic acid whiskers, and silicon carbide whiskers. Examples of the coating method include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. These may be subjected to a surface treatment with a surface treating agent such as titanate, aluminum, or silane.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black and the like according to the raw material and production method. The raw material and the production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used. Various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in these properties, but from the viewpoint of a balance between toughness and conductivity,
The average particle size is preferably 500 nm or less, particularly preferably 5 to 100 nm, more preferably 10 to 70 nm. Surface area (BET method)
10 m ² / g or more, even 300 meters ² / g or more, particularly 500 to 1500 ² / g are preferred. The DBP oil absorption is 50 ml / 100 g or more, especially 100 ml / 100 g.
g, more preferably 370 ml / 100 g or more. The ash content is preferably 0.5% or less, particularly preferably 0.3% or less.

The carbon powder may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane. It is also possible to use those granulated for improving the workability of the melt-kneading.

From the viewpoint of obtaining excellent surface smoothness, the conductive filler used in the present invention is more powdery, granular, plate-like, scale-like or resinous than fibrous filler having a high aspect ratio. It is preferable that the medium has any fibrous form having a length / diameter ratio of 200 or less.

The conductive filler may be used in combination of two or more kinds. Among such conductive fillers, carbon powder is particularly preferably used in terms of strength and cost.

When such a conductive filler is compounded, the compounding amount is 0.5 parts with respect to 100 parts by weight of the PPS resin.
A range of from 50 to 50 parts by weight is selected, and a range of from 1 to 20 parts by weight can be exemplified from the viewpoint of exhibiting particularly excellent impact resistance.

The PPS resin composition of the present invention contains a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic phosphorus compound, talc, kaolin, or an organic compound as long as the effects of the present invention are not impaired. Crystal nucleating agents such as phosphorus compounds, polyolefin compounds, silicone compounds, long-chain aliphatic ester compounds, release agents such as long-chain aliphatic amide compounds, antioxidants, heat stabilizers, calcium stearate, stearic acid Lubricants such as aluminum and lithium stearate,
Usual additives such as UV inhibitors, colorants, flame retardants, and foaming agents can be added.

Further, the PPS resin composition of the present invention may contain polyphenylene oxide, as long as the effects of the present invention are not impaired.
Polysulfone, polyethylene tetrafluoride, polyetherimide, polyamideimide, polyimide, polycarbonate
Polyether sulfone, polyether ketone, polythioether ketone, polyether ether ketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, polyamide elastomer, polyester elastomer, polyalkylene oxide, etc. It may contain a resin.

The method for preparing the PPS resin composition of the present invention is not particularly limited, and 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 by the present invention can be used for various moldings such as injection molding, extrusion molding (molding of a tubular body such as a tube or a pipe or molding of a round bar), blow molding, transfer molding, film molding and the like. Although applicable, it is particularly preferably used for injection molding and extrusion molding.

The molded body thus obtained has heat resistance,
In addition to the inherent properties of PPS, such as hot water resistance and solvent resistance, it is also excellent in impact resistance, moldability, etc. For applications such as sensors, LED lamps, connectors, sockets, resistors, relay cases , Switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, Electric and electronic parts such as FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment Laser de Home and office electrical product parts such as audio equipment parts such as discs and compact discs, 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, cleaning jigs, motor parts, lighters,
Machine-related parts such as typewriters: optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machine-related parts; water faucets, mixing faucets, pump parts, pipe joints, water flow control valves, relief Plumbing parts such as valves, hot water temperature sensors, water volume sensors, and water meter housings; valve alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, various valves such as exhaust gas valves, fuel related exhaust systems, etc. Intake system 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 padware sensor Chromatography, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensors, air conditioner thermostat base, heating warm air flow control valve, brush holder for radiator motor,
Water pump impeller, turbine vane, parts related to wiper motor, dust distributor, starter switch, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve,
Automotive / vehicle related such as fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, vehicle speed sensor, cable liner, etc. Parts and other various uses can be exemplified.

[0083]

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. Further, in the following examples, the material strength,
The liquidity was evaluated by the following method.

[Measurement Method] (1) Tensile Properties: According to ASTM D638 method.

(2) IZOD impact strength with mold notch: According to ASTM D256 method. (3) Minimum molding pressure: Test pieces (bending test pieces, impact test pieces, and tensile test pieces) for evaluating mechanical strength characteristics were injection-molded using the PPS resin composition of the present invention. As an injection molding machine, SG-HIPRO MII manufactured by Sumitomo Heavy Industries, Ltd.
Using I, molding was performed at a mold set temperature of 140 ° C and a cylinder set temperature of 300 to 320 ° C. The minimum injection pressure required to completely fill the test piece with the resin was defined as the molding lower limit pressure. The lower the lower molding pressure limit, the better the fluidity.

Reference Example (Polymerization of PPS resin) (1) In an autoclave equipped with a stirrer, 6.005 kg (25 mol) of sodium sulfide nonahydrate, 0.6 mol of sodium acetate were added.
56 kg (8 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, after cooling the reaction vessel to 180 ° C., 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added thereto, and the mixture was sealed under nitrogen and sealed.
After heating to 270 ° C, the reaction was carried out at 270 ° C for 2.5 hours. After cooling, the reaction product was washed five times with warm water, and dried under reduced pressure at 80 ° C. for 24 hours to obtain about 2.45 kg of PPS (PPS-1).
I got The ash content of this PPS was 0.5% by weight.

(2) The reaction was carried out at 270 ° C. for 2.5 hours, and after cooling, polymerization was carried out in the same manner as in the above (1) until the reaction product was washed five times with warm water. Then 10
The mixture was heated to 0 ° C. and charged in 10 kg of NMP. After stirring for about 1 hour, the mixture was filtered and further washed with hot water several times. This is heated to 90 ° C. and an aqueous solution of acetic acid at pH 4 25
After stirring for about 1 hour, the mixture was filtered, washed with ion-exchanged water at about 90 ° C. until the pH of the filtrate reached 7, then dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-2.
2.45 kg were obtained. The PPS had an ash content of 0.07% by weight and a melt viscosity of 900 poise (310 ° C., 1000 /
s).

(3) In an autoclave equipped with a stirrer, 6.005 kg (25 mol) of sodium sulfide nonahydrate, 0.656 kg (8 mol) of sodium acetate and N-methyl-2 were added.
-5 kg of pyrrolidone (hereinafter abbreviated as NMP) was charged, the temperature was gradually raised to 205 ° C while passing nitrogen, and 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C,
3.727 kg (25.35 kg) of 1,4-dichlorobenzene
Mol) and NMP (3.7 kg), sealed under nitrogen, heated to 225 ° C and reacted for 5 hours, and then heated to 270 ° C and reacted for 3 hours. After cooling, the reaction product was washed five times with warm water, then heated to 100 ° C., poured into 10 kg of NMP, stirred for about 1 hour, filtered, and washed several times with hot water. This is heated to 90 ° C
The solution was poured into 25 liters of an aqueous acetic acid solution of Example No. 4 and stirred continuously for about 1 hour, and then filtered.
After washing with ion-exchanged water at 0 ° C., it was dried under reduced pressure at 80 ° C. for 24 hours to obtain 2.44 kg of PPS-3. This PPS
Had an ash content of 0.05% by weight and a melt viscosity of 2300 poise (310 ° C., 1000 / s).

(4) In an autoclave equipped with a stirrer, 6.005 kg (25 mol) of sodium sulfide nonahydrate, 0.11 kg (1.35 mol) of sodium acetate and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were placed. 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 3.756 kg of 1,4-dichlorobenzene (2
(5.55 mol) and 3.7 kg of NMP, sealed under nitrogen, heated to 270 ° C.
Reacted for hours. After cooling, the reaction product was washed five times with warm water, then heated to 100 ° C., poured into 10 kg of NMP, stirred for about 1 hour, filtered, and washed several times with hot water. This was poured into 25 liters of an aqueous acetic acid solution of pH 4 heated to 90 ° C., and the mixture was stirred for about 1 hour, filtered, washed with ion-exchanged water at about 90 ° C. until the pH of the filtrate reached 7, and then washed. Dry under reduced pressure at 80 ° C for 24 hours
2.43 kg of PS-4 was obtained. The PPS has an ash content of 0.04% by weight and a melt viscosity of 300 poise (310 ° C.,
1000 / s).

[Blending Materials Used in Examples and Comparative Examples] (B) Specific ethylene / α-olefin-based copolymer B-1: Mw / Mn = 2.8, α-olefin content =
6 mol% ethylene / 1-hexene copolymer, density 0.
Polymerization using 894 g / cm ³ , metallocene catalyst.

B-2: Polymerization using an ethylene / 1-hexene copolymer having Mw / Mn = 2.6, α-olefin content = 8 mol%, density 0.888 g / cm ³ , and a metallocene catalyst.

B-3: Polymerization using an ethylene / 1-butene copolymer having Mw / Mn = 2.9, α-olefin content = 6 mol%, density 0.894 g / cm ³ , and a metallocene catalyst.

B-4: Polymerization using an ethylene / 1-octene copolymer having Mw / Mn = 2.8, α-olefin content = 6 mol%, density 0.894 g / cm ³ , and a metallocene catalyst.

B-6: ethylene / 1-butene copolymer having Mw / Mn = 2.5, α-olefin content = 20 mol%, density 0.860 g / cm ³ , melt flow rate =
Polymerization using a metallocene catalyst at 0.5 g / 10 min.

B-7: ethylene-octene copolymer having Mw / Mn = 2.5, α-olefin content = 15 mol%, density 0.870 g / cm ³ , melt flow rate =
Polymerization using a metallocene catalyst for 4 g / 10 minutes.

B-8: Ethylene / octene copolymer having Mw / Mn = 2.5, α-olefin content = 20 mol%, density 0.863 g / cm ³ , melt flow rate =
Polymerization using a metallocene catalyst for 4 g / 10 minutes.

B-9: ethylene / 1-butene copolymer having Mw / Mn = 2.5, α-olefin content = 20 mol%, density 0.860 g / cm ³ , melt flow rate =
Polymerization using a metallocene catalyst at 35 g / 10 min.

The MFR is a value measured at a load of 2.16 kg and 190 ° C. in accordance with ASTM D1238.

(B ') Comparative polyolefin B'-5 (comparative example): a linear low-density polyethylene (Mw / Mn = 3.8) without metallocene catalyst (density 0.915 g / cm ³ )

(C) Functional Group-Containing Olefin (Co) polymer C-1: An olefin copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated acid as a main component ethylene / glycidyl methacrylate -C = 88/12 (wt%) copolymer C-2: ethylene / glycidyl methacrylate (E / G
MA) having a main skeleton of 85/15 (% by weight) and graft copolymerization of acrylonitrile / styrene (AS) = 30/70 (% by weight), wherein (E / GMA) /
(AS) = 70/30 (% by weight) copolymer C-3: partially hydrogenated styrene-butadiene block copolymer (styrene / butadiene weight ratio = 3/7, hydrogenation ratio 80)
%) Was epoxidized with peracetic acid. The oxirane oxygen concentration was 3.04% by weight.

C-4: C-2: maleic anhydride (0.5
wt%) Graft-modified ethylene-butene copolymer

(D) Polyamide resin or thermoplastic polyester resin D-1: nylon 6 relative viscosity 2.35 D-2: nylon 6 relative viscosity 4.30 D-3: polybutylene terephthalate (Toray PB)
T-1100S)) D-4: Nylon 12 ("Amilan" manufactured by Toray Industries, Inc.)
CM5051F)

(E) Fibrous and / or non-fibrous filler E-1: Glass fiber (CS0 manufactured by Asahi Fiberglass Co., Ltd.)
3MA497 E-2 (conductive filler): carbon black (EC6 manufactured by Ketjen Black International Co., Ltd.)
00JD, DBP oil absorption 495ml / 100g, BET
Method surface area 1270m ² / g, average particle size 30nm, ash content 0.2%

Examples 1 to 9 Each component shown in Table 1 was dry-blended in the proportions shown in Table 1, and then melted by a screw type single screw extruder (screw: Dalmage) set at a temperature of 280 to 320 ° C. After kneading, it was pelletized. Using the obtained pellets, mechanical properties and molding minimum pressure were measured. Table 1 shows the measurement results.

[0105]

[Table 1]

Examples 10 to 12 (A) PPS resin shown in Table 2 and (B) a specific ethylene
The C-1 component of the α-olefin-based copolymer and the (C) functional group-containing olefin-based (co) polymer was dry-blended at a ratio shown in Table 2. Thereafter, the mixture was melt-kneaded with a screw-type single screw extruder (screw: Dalmage) set to a temperature condition of 280 to 320 ° C, and then pelletized. Next, the pellet, the C-4 component and the polyamide resin (D) were dry-blended at the ratios shown in Table 2 to obtain 280-320.
The mixture was melt-kneaded by a screw type single screw extruder (screw: Dalmage) set to a temperature condition of ° C., and then pelletized. Using the obtained pellets, mechanical properties and molding minimum pressure were measured. Table 2 shows the measurement results.

Example 13 After the components shown in Table 2 were dry-blended in the proportions shown in Table 2, the mixture was melt-kneaded by a screw type single screw extruder (screw: dalmage) set at a temperature of 280 to 320 ° C., and then pelletized. . Using the obtained pellets, mechanical properties and molding minimum pressure were measured. Table 2 shows the measurement results.

Example 14 The components shown in Table 2 were dry-blended at the ratios shown in Table 2, and then melt-kneaded by a screw type single screw extruder (screw: full flight) set at a temperature of 280 to 320 ° C., followed by pelletizing. did. Using the obtained pellets, mechanical properties and molding minimum pressure were measured. Table 2 shows the measurement results.

Examples 15 to 16 (A) PPS resin shown in Table 2 and (B) a specific ethylene
The α-olefin copolymer and the (C) functional group-containing olefin (co) polymer component were dry-blended at the ratios shown in Table 2. Thereafter, the mixture was melt-kneaded with a screw-type twin-screw extruder set at a temperature of 280 to 320 ° C., and then pelletized. Next, the pellets and the E-2 conductive filler component were dry-blended at the ratios shown in Table 2, and 280-320.
The mixture was melt-kneaded by a screw-type twin-screw extruder set to a temperature condition of ° C. and pelletized. Using the obtained pellets, mechanical properties and molding minimum pressure were measured. Table 2 shows the measurement results.

Comparative Examples 1 and 3 (B) No B'-5 metallocene catalyst was used in place of the specific ethylene / α-olefin copolymer.
Melt kneading, pelletizing, and measurement of each physical property were performed in the same manner as in Examples 1 and 10, except that a linear low-density polyethylene having Mw / Mn = 3.8 was used. Table 2 shows the results.

When a linear low-density polyethylene having a Mw / Mn of 3.8 without using the B′-5 metallocene catalyst was used, the impact characteristics and the like were clearly deteriorated.

Comparative Example 2 (B) Instead of using a specific ethylene / α-olefin copolymer, (C) a functional group-containing olefin (co)
Melt kneading, pelletizing, and measurement of each physical property were carried out in the same manner as in Example 1 except that the amount of the polymer was increased. Table 2 shows the results.

According to this method, the fluidity was greatly deteriorated, and the low-temperature impact characteristics were low.

[0114]

[Table 2]

Examples 17 to 20 The components shown in Table 3 were dry-blended in the proportions shown in Table 3, and then melt-kneaded by a screw type single screw extruder (screw: Dalmage) set at a temperature of 280 to 320 ° C. Later pelletized. Using the obtained pellets, mechanical properties and molding minimum pressure were measured. Table 3 shows the measurement results.

[0116]

[Table 3]

[Extrusion tube molding (1)] Nylon 6 ("Amilan" CM1056, manufactured by Toray Industries, Inc.) was used for the outer layer.
The pellet obtained in Example 15 was used for the inner layer with the intermediate layer adhesive layer (composition of Example 11) interposed therebetween. Outer diameter: 8 mm, inner diameter: 6 mm, outer layer thickness: 0.7 mm, intermediate layer thickness 0.1
mm, a three-layer tube having an inner layer thickness of 0.2 mm was formed. As a molding apparatus, three 30 mm single screw extruders set at a resin temperature of 210 to 300 ° C., and an adapter (temperature: 270 to 300) discharged from the three extruders.
C.) and a sizing die for cooling and controlling the size of the tube and a take-off machine were used, and the tube was formed at a take-off speed of 50 cm / min. As a result, the inner surface is excellent in smoothness and interlayer adhesion, and the electric resistance value of the inner surface of the tube is 5 × 10 ³ Ω /.
A 5 cm conductive tube was obtained.

[Extrusion Tube Molding (2)] Nylon 11 (Toray Co., Ltd. “Rilsan” BESNO F15X)
N), using the pellet obtained in Example 16 for the inner layer with the intermediate layer adhesive layer (composition of Example 12) interposed therebetween, outer diameter: 8 mm, inner diameter: 6 mm, outer layer thickness: 0.7 mm, middle A three-layer tube having a layer thickness of 0.1 mm and an inner layer thickness of 0.2 mm was formed. As a molding device, the resin temperature 210 to 210
Three single-screw extruders of 30 mm each set at 300 ° C., and a resin discharged from the three extruders were supplied to an adapter (temperature: 2).
(70-300 ° C.), a die formed of a tube, a sizing die for cooling and controlling the size of the tube, and a take-off machine.
Tube molding was performed at 00 cm / min. As a result, a conductive tube having excellent inner surface smoothness and interlayer adhesion and having an electric resistance value of 4 × 10 ³ Ω / 5 cm on the inner surface of the tube was obtained.

[0119]

As described above, according to the PPS resin composition of the present invention, a polyphenylene sulfide resin composition excellent in impact resistance, molding workability, and the like, and a molded article thereof can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Todo 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside the Basic Petrochemical Research Laboratory, Mitsui Chemicals, Inc. 6-1-2 Ki, F-term in Basic Petrochemical Research Laboratory, Mitsui Chemicals, Inc. F-term (reference) FA045 FA046 FA066 FD015 FD016

Claims (15)

[Claims] (A) Polyphenylene sulfide 100
(B-1) Ethylene and 3 to 2 carbon atoms to parts by weight
An ethylene / α-olefin-based copolymer comprising α-olefin of 0 and a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) calculated by gel permeation chromatography (GPC) ( Mw / Mn)
Is from 1 to 100 parts by weight of an ethylene / α-olefin copolymer having a value of 3.0 or less, and (C) at least one kind selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. A polyphenylene sulfide resin composition comprising 1 to 100 parts by weight of a functional group-containing olefin polymer or copolymer containing a functional group. 2. (A) Polyphenylene sulfide 100
(B-2) ethylene and 3 to 2 carbon atoms to parts by weight
Ethylene-α-olefin copolymers having a density of 0.880 g / cm ³ or less.
0 parts by weight and (C) a functional group-containing olefin polymer or copolymer 1 containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. A polyphenylene sulfide resin composition comprising 100 parts by weight. 3. The content of the α-olefin having 3 to 20 carbon atoms contained in the ethylene / α-olefin-based copolymer of the component (B) is 7 to 25 mol%. 3. The polyphenylene sulfide resin composition according to 1 or 2. 4. The polyphenylene according to claim 1, wherein the ethylene / α-olefin-based copolymer as the component (B) is a copolymer polymerized using a metallocene-based catalyst. Sulfide resin composition. 5. The functional group-containing olefin polymer or copolymer of the component (C) is an α-olefin and α,
The polyphenylene sulfide resin composition according to any one of claims 1 to 4, which is an epoxy group-containing olefin-based copolymer (C) obtained by copolymerizing a glycidyl ester of β-unsaturated acid. 6. An epoxy group-containing olefin copolymer (C) comprising an α-olefin (1), a glycidyl ester of an α, β-unsaturated acid (2) and a monomer represented by the following general formula: The polyphenylene sulfide resin composition according to any one of claims 1 to 5, which is an olefin-based copolymer obtained by copolymerizing a monomer having (3) as an essential component. Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Represents one or more groups selected from a —COOR ² group, a —CN group and an aromatic group. R ² has 1 to 1 carbon atoms.
Represents an alkyl group of 0) 7. The polyphenylene sulfide resin composition according to claim 1, wherein the functional group-containing olefin polymer or copolymer as the component (C) is an epoxidized diene block copolymer. 8. The epoxidized diene-based block copolymer as the component (C) is a polymer mainly composed of at least one polymer block mainly composed of an aromatic vinyl compound and at least one conjugated diene compound. The polyphenylene sulfide resin composition according to claim 7, which is an epoxidized diene copolymer obtained by epoxidizing a double bond derived from a conjugated diene compound of a block copolymer composed of blocks. 9. The polyphenylene sulfide resin composition according to claim 1, wherein the melt viscosity of the polyphenylene sulfide resin as the component (A) is 400 poise (310 ° C., shear rate 1000 / s) or more. 10. The polyphenylene sulfide resin composition according to claim 1, wherein the ash content of the polyphenylene sulfide resin as the component (A) is 0.2% by weight or less. 11. The polyphenylene sulfide according to claim 1, further comprising 1 to 99 parts by weight of a polyamide resin and / or a thermoplastic polyester resin as the component (D) based on 100 parts by weight of the polyphenylene sulfide resin. Resin composition. 12. As the component (E), a filler is used in an amount of 1 to 4 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin.
The polyphenylene sulfide resin composition according to any one of claims 1 to 11, which contained 00 parts by weight. 13. The polyphenylene sulfide resin according to claim 12, wherein the filler (E) is a conductive filler, and the content thereof is 0.5 to 50 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. Composition. 14. A molded product obtained by injection molding the polyphenylene sulfide fat composition according to claim 1. 15. A molded product obtained by extrusion molding the polyphenylene sulfide fat composition according to claim 1.