JP2000265059A - Polyphenylene sulfide resin composition and molded article therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide(PPS) resin composition which has a balance in a higher level with respect to impact resistance, low temperature impact resistance, moldability and the like, as compared to those of conventional PPS resin materials, is well-balanced and excellent with respect to characteristics inherent to PPS resins such as mechanical properties other than impact resistance and hot-water resistance, and is excellent also with respect to the productivity and economy in commercial production. SOLUTION: The composition is prepared by compounding (A) 100 pts.wt. of PPS and (B) 1-100 pts.wt. of a modified polyolefin which is obtained by modifying an ethylene α-olefin copolymer, which comprises ethylene and a 3-20C α-olefin and has a weight average molecular weight (Mw)/number average molecular weight (Mn) ratio of 3.0 or less, as calculated by the gel permeation chromatography(GPC), with an olefin compound having at least one functional group selected from epoxy group, acid anhydride group, carboxy group and salts thereof, and carboxylates.

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, there has been proposed a method of blending various elastomers with a PPS resin. For example, Japanese Patent Application Laid-Open No. 58-154775 discloses a method in which an epoxy group-containing olefin resin is added to a PPS resin. JP-A-1-306467 discloses a method of compounding a polymer, and JP-A-1-306467 discloses a method of compounding an olefin copolymer containing an epoxy group and an elastomer containing no epoxy group or acid anhydride group with a PPS resin. Japanese Patent Application Laid-Open No. 62-172056 discloses a method in which an α-olefin copolymer modified with an unsaturated carboxylic acid or an anhydride thereof is mixed with a PPS resin.

[0004] However, in recent years, the demand for PPS resin materials has become increasingly severe, and even with these conventionally proposed PPS resin compositions, the material properties, especially the moldability, cannot be said to be sufficient, and higher impact resistance is required. In addition, there is a demand for a material which simultaneously satisfies low-temperature impact resistance and the like, has excellent productivity during molding, and is economically advantageous.

[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 is obtained by converting 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. The present inventors have found that the use of a modified polyolefin obtained by modification with an olefin compound in combination greatly improves moldability and processability over the prior art and solves the above-mentioned problems, and has 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
PC), an ethylene / α-olefin-based copolymer having a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 3.0 or less is an epoxy group, an acid anhydride A modified polyolefin obtained by modification with an olefin compound having at least one functional group selected from a group, a carboxyl group and a salt thereof, and a carboxylic acid ester. Polyphenylene sulfide resin composition,

[0008] 2. The modified polyolefin of the component (B) is an ethylene / α-olefin copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atoms,
Ethylene • α- having a density of 0.880 g / cm ³ or less
The polyphenylene sulfide resin composition, which is based on an olefin-based copolymer,

3. The α-olefin having 3 to 20 carbon atoms contained in the ethylene / α-olefin copolymer of the component (B).
3. The polyphenylene sulfide resin composition according to the above 1 or 2, wherein the olefin content is 7 to 25 mol%.

[0010] 4. The polyphenylene sulfide resin composition according to any one of the above 1 to 3, wherein the ethylene / α-olefin-based copolymer of the component (B) is a copolymer polymerized using a metallocene-based catalyst,

5. The polyphenylene sulfide resin composition according to any one of the above items 1 to 4, wherein the melt viscosity of the polyphenylene sulfide resin as the component (A) is 400 poise (310 ° C., shear rate 1000 / s) or more.

6. (1) The polyphenylene sulfide resin as the component (A), wherein the ash content of the polyphenylene sulfide resin is 0.2% by weight or less.
Polyphenylene sulfide resin composition according to any one of to 5;

7. Further, as a component (C), a filler is added in an amount of 1 to 4 parts by weight based on 100 parts by weight of polyphenylene sulfide resin.
The polyphenylene sulfide resin composition according to any one of the above 1 to 6, containing 00 parts by weight,

8. The filler (C) is a glass fiber and the content thereof is polyphenylene sulfide resin 1
The polyphenylene sulfide resin composition according to the above 7, which is 10 to 150 parts by weight relative to 00 parts by weight,

9. A molded article obtained by injection molding the polyphenylene sulfide fat composition according to any one of the above 1 to 8, and

10. A molded article obtained by extrusion molding the polyphenylene sulfide fat composition according to any one of the above 1 to 8.

[0017]

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,

[0018]

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From the viewpoint of heat resistance, such a repeating unit is
A polymer containing preferably at least 70 mol%, more preferably at least 90 mol% is preferred. Also, the PPS resin can constitute less than 30 mol% of the repeating unit with a repeating unit having the following structural formula.

[0020]

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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, especially 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 JP-B-45-3368, JP-B-52-12240, and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the gazette. In the present invention, the PPS resin obtained as described above is 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.

As a specific method for crosslinking / high molecular weight of the PPS resin by heating, the method may be carried out in an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method in which heating is performed in a heating vessel at a predetermined temperature under an atmosphere until a desired melt viscosity is obtained. The heat treatment temperature is usually
170-280 ° C is selected, preferably 200-27 ° C.
The temperature is 0 ° C., and the time is usually 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 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 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 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 modified polyolein (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, and has a specific molecular weight distribution and And / or an ethylene / α-olefin-based copolymer having a specific density is formed by an olefin compound having 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. It is obtained by denaturation. 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-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 copolymer used as a base in the present invention has a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) calculated by gel permeation chromatography (GPC). Mw
/ Mn) is 3.0 or less, or the density is 0.8
An ethylene / α-olefin-based copolymer having a weight of 80 g / cm ³ or less is necessary for obtaining excellent mechanical properties and moldability, and is particularly calculated by gel permeation chromatography (GPC). The ratio (Mw / M) between the average molecular weight (Mw) and the number average molecular weight (Mn)
n) is 3.0 or less and the density is 0.880 g / c
An ethylene / α-olefin-based copolymer having an m ³ or less is most preferably used.

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

In the present invention, the specific ethylene / α-olefin copolymer has 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. (B) a modified polyolefin obtained by modification with an olefin compound;
Used as a component.

Specific examples of such functional group-containing olefin compounds are represented by the following general formula, and glycidyl esters of α, β-unsaturated acids represented by glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate and the like.

[0039]

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(Where R represents a hydrogen atom or a lower alkyl group), methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, acrylic acid Α, β-unsaturated carboxylic acid alkyl esters such as isobutyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, and maleic acid Acid anhydrides such as anhydride, succinic anhydride and fumaric anhydride; carboxylic acids such as acrylic acid, methacrylic acid and vinyl acetate;
Salts such as a, Zn, K, Ca, and Mg can be mentioned. Among them, glycidyl methacrylate and maleic anhydride are preferably used in the present invention.

The method of modifying the ethylene / α-olefin-based copolymer using these olefin compounds is not particularly limited, and the reaction is carried out in a solution in the presence of a functional group-containing olefin compound and a radical generator. Well,
The reaction may be carried out in a molten state using an extruder or the like, but generally the latter is often used as a simpler method.

In the present invention, the amount of the modified polyolefin used as the component (B) is 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the polyphenylene sulfide resin as the component (A). If the amount of the modified polyolefin used is less than 1 part by weight, the resulting resin composition has an insufficient impact resistance, which is not preferable. On the contrary, if it exceeds 100 parts by weight, the heat resistance inherent in the polyphenylene sulfide resin is impaired. Absent.

In the present invention, from the viewpoint of obtaining better impact resistance and the like, an alkoxysilane compound is further added as an additional component to 100 parts by weight of the (A) PPS resin.
It is effective to add 0.05 to 5 parts by weight, preferably 0.1 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, 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 (C).

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, walasteinite, zeolite, sericite, mica, talc, kaolin, clay, pyrophyllite, bentonite, montmorillonite, asbestos, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, Metal compounds such as zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide Materials, glass beads, ceramic beads, non-fibrous fillers such as boron nitride, silicon carbide and silica. These may be hollow, and it is also possible to use two or more of these fillers in combination. is there. Also,
It is more advantageous to use these (C) fillers after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, or an organic ammonium salt. It is preferable in terms of obtaining high mechanical strength. Among them, fibrous fillers are preferable, and glass fibers and glass milled fibers are particularly preferable.

When the filler (C) is blended, the blending amount is from 1 to 400 with respect to 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.

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. 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.

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

The PPS resin composition obtained by the present invention can be applied to various moldings such as injection molding, extrusion molding, blow molding, transfer molding and film molding, and is particularly preferably used for injection molding and extrusion molding. Can be

The molded body obtained in this way 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, various valves such as exhaust gas valves, fuel-related, exhaust-system / intake-system pipes, and air intake nozzle snorkels , Intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, Over 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, wiper motor parts,
Distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, coils for fuel related electromagnetic valves, connectors for fuses, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, Lamp reflector,
Examples include automotive and vehicle-related parts such as a lamp housing, 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.

[0053]

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-HIP manufactured by Sumitomo Heavy Industries, Ltd.
Using RO · MIII, 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.

(4) Releasability: The shortest cooling time (second) for the test piece to automatically drop when the test piece is continuously injection-molded under the conditions of the injection pressure of the above-mentioned injection molding and the lower limit of molding pressure +5 kgf / cm2-G. Was measured as a measure of releasability. The smaller this measured value, the better the releasability.

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. 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
It was poured into 10 kg of NMP heated to 0 ° C., and after stirring for about 1 hour, 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 is washed 5 times with warm water and then 10 kg of NMP heated to 100 ° C.
After stirring for about 1 hour, the mixture was filtered and washed several times with hot water. This was heated to 90 ° C.
The solution was poured into 25 liters of an aqueous acetic acid solution of H4, 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 dried under reduced pressure at 80 ° C. for 24 hours. Thus, 2.44 kg of PPS-3 was obtained. This PP
The ash content of S was 0.05% by weight, and the melt viscosity was 2,300 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 polymerized using a metallocene catalyst =
2.8, α-olefin content = 6 mol%, density 0.8
94 g / cm ³ ethylene / 1-hexene copolymer 10
A mixture of 0 parts by weight, 1 part by weight of maleic anhydride and 0.1 part by weight of peroxide (2,5-dimethyl-2,5-t-butylhexane) is heated at 250 ° C. in a 30 mm diameter single screw extruder.
Modified polyolefin obtained by kneading under the conditions of B-2: Mw / Mn polymerized using a metallocene catalyst =
2.9, α-olefin content = 6 mol%, density 0.8
94 g / cm ³ of ethylene / 1-butene copolymer 100
Parts by weight of a mixture of 1 part by weight of maleic anhydride and 0.1 part by weight of peroxide (2,5-dimethyl-2,5-t-butylhexane) in a 30 mm diameter single screw extruder at 250 ° C. Modified polyolefin obtained by kneading. B-3: Mw / Mn polymerized using a metallocene catalyst
2.8, α-olefin content = 6 mol%, density 0.8
94 g / cm ³ of 100 parts by weight of ethylene / octene copolymer, 3 parts by weight of glycidyl methacrylate and 0.3 part by weight of
A mixture of parts by weight of peroxide (2,5-dimethyl-2,5-t-butylhexane) was mixed with a 30 mm diameter single screw extruder for 25 minutes.
Modified polyolefin obtained by kneading at 0 ° C. B-5: Mw / Mn polymerized using a metallocene catalyst =
2.5, α-olefin content = 20 mol%, density 0.
860 g / cm ³ ethylene / 1-butene copolymer 10
A mixture of 0 parts by weight, 1 part by weight of maleic anhydride and 0.1 part by weight of peroxide (2,5-dimethyl-2,5-t-butylhexane) is heated at 250 ° C. in a 30 mm diameter single screw extruder.
Modified polyolefin obtained by kneading under the conditions of B-6: Mw / Mn polymerized using a metallocene catalyst =
2.5, α-olefin content = 15 mol%, density 0.
870 g / cm ³ ethylene / octene copolymer 100
Parts by weight of a mixture of 1 part by weight of maleic anhydride and 0.1 part by weight of peroxide (2,5-dimethyl-2,5-t-butylhexane) in a 30 mm diameter single screw extruder at 250 ° C. Modified polyolefin obtained by kneading. MF
R is 2.16 kg according to ASTM D1238,
This is a value measured at 190 ° C.

(B ') Comparative polyolefin B'-4 (comparative example): a linear low-density polyethylene (Mw / Mn = 3.8) without metallocene catalyst (density 0.915 g / cm ³ ) And a modified polyolefin obtained by maleic anhydride modification according to the method described in B-1 above.

(C) Fibrous and / or non-fibrous filler C-1: glass fiber (CS0 manufactured by Asahi Fiberglass Co., Ltd.)
3MA497

Examples 1 to 9 and the components shown in Table 1 were 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, minimum molding pressure, and releasability were measured. Table 1 shows the measurement results.

[0066]

[Table 1]

Comparative Example 1 (B) No B'-4 metallocene catalyst was used in place of the specific ethylene / α-olefin copolymer.
Melt kneading, pelletizing, and measurement of each physical property were carried out in the same manner as in Example 1 except that a modified low-density polyethylene-based polyolefin having Mw / Mn = 3.8 was used. Table 1 shows the results. When a linear low-density polyethylene having a Mw / Mn of 3.8 without using a B'-4 metallocene-based catalyst was used, the results were clearly inferior in impact properties and the like.

Comparative Example 2 Melt kneading, pelletizing, and measurement of each physical property were carried out in the same manner as in Example 1 except that a commercially available modified ethylene / propylene copolymer ("Tuffmer" MP0610 manufactured by Mitsui Chemicals) was used as the component (B). The results are shown in Table 1. The resin composition obtained here was insufficient in releasability.

[0069]

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.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shima ▼ Saki ▲ Shuo 1st Toray Co., Ltd. Nagoya Office, 9-9 Oe-cho, Minato-ku, Nagoya, Aichi Prefecture (72) Inventor Kazuhiko Kobayashi, Oe-cho, Minato-ku, Nagoya-shi, Aichi No. 9 Toray, Nagoya Works (72) Inventor Akira Todo 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Chemicals, Inc. Basic Petrification Research Institute (72) Inventor Shinya Matsunaga Kuga, Yamaguchi Prefecture 6-1-2, Waki, Guniwakicho Mitsui Chemicals, Inc. Basic Petrochemical Research Laboratory F-term (reference) 4J002 BB202 CN011 DL006 FA046 FD016

Claims (10)

[Claims] (A) Polyphenylene sulfide 100
(B) an ethylene / α-olefin-based copolymer composed of ethylene and an α-olefin having 3 to 20 carbon atoms with respect to parts by weight, the weight average being calculated by gel permeation chromatography (GPC) Molecular weight (M
w) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer having a ratio (Mw / Mn) of 3.0 or less to an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid At least one selected from esters
A polyphenylene sulfide resin composition comprising 1 to 100 parts by weight of a modified polyolefin obtained by modification with an olefin compound having a kind of functional group. 2. The modified polyolefin of the component (B) is an ethylene / α-olefin copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atoms, and has a density of 0.880 g / cm ^3. The polyphenylene sulfide resin composition according to claim 1, which is based on the following ethylene / α-olefin-based copolymer. 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 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. 6. The polyphenylene sulfide resin as the component (A) has an ash content of 0.2% by weight or less.
6. The polyphenylene sulfide resin composition according to any one of claims 1 to 5. 7. As the component (C), a filler is used in an amount of 1 to 40 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 6, which contains 0 parts by weight. 8. The filler (C) is a glass fiber,
And the content thereof is polyphenylene sulfide resin 100
The polyphenylene sulfide resin composition according to claim 7, wherein the amount is 10 to 150 parts by weight with respect to parts by weight. 9. A molded article obtained by injection molding the polyphenylene sulfide fat composition according to claim 1. 10. A molded product obtained by extruding the polyphenylene sulfide fat composition according to claim 1.