JPH0959514A - Unreinforced polyphenylene sulfide resin composition and method for producing the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To obtain a non-reinforced polyphenylene sulfide resin composition having a small friction coefficient and excellent extrusion stability without impairing heat resistance and chemical resistance. SOLUTION: An α-containing 70 to 99% by weight of a polyphenylene sulfide resin having a Na content of 2000 ppm or less and (B) a maleic anhydride group at a ratio of 10% by weight or less.
One or more kinds of functional group-containing organic compounds such as (C) silane coupling agent and epoxy resin are contained in an amount of 0.1 to 10 with respect to 100 parts by weight of the resin composition (1) consisting of 1 to 30% by weight of the olefin copolymer. 100 parts by weight of the resin composition (2) containing the above components (A), (B) and (C), and (D) at 25 ° C. for 100 seconds.
^-1 A non-reinforced polyphenylene sulfide resin composition having a polyorganosiloxane having a viscosity of 1000 poise or more in the range of 0.1 to 10 parts by weight. [Effect] A non-reinforced resin composition suitable for use as a heat resistant sliding member having a small coefficient of friction and excellent extrusion stability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-reinforced polyphenylene sulfide resin composition suitable as a heat resistant sliding member having a small coefficient of friction without impairing the heat resistance and chemical resistance of the polyphenylene sulfide resin and having excellent extrusion stability. It is about.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP)
Resin (abbreviated as S) itself has excellent heat resistance and chemical resistance. Among them, molding materials reinforced with reinforcing materials such as glass fiber are used as metal substitutes in the fields of automobile parts and electronics-related parts. It has been used for a long time and has been growing in demand in recent years.

However, it does not substantially contain various reinforcing materials known as fillers for reinforcing PPS resin,
So-called non-reinforced PPS resin has poor extrusion stability and moldability, and the resulting molded product lacks toughness due to insufficient mechanical properties such as impact resistance and tensile elongation, and is not reinforced in the injection molding field. The use of as a molding material was limited, and those using a reinforcing material were the mainstream. In addition, since it is inferior in toughness and tensile elongation for extrusion molding of tubes, pipes, etc., it is used only in an extremely small amount.

Conventionally, as a method of improving the impact resistance of PPS resin, a method of blending or alloying a thermoplastic elastomer or an uncrosslinked rubber-like elastic material with PPS resin has been carried out. As a specific example, a method of adding a hydrogenated SBR copolymer (Japanese Patent Laid-Open No. 167040/1984).
No.), a method of adding a hydrogenated SBR copolymer of dicarboxylic acid anhydride (JP-A-56-115355), a method of adding an ionomer (JP-A-2-49062), an unsaturated carboxylic acid or an acid anhydride thereof is grafted. Copolymerized α
A method of adding an olefin copolymer (JP-A-59-2
07921), addition of a copolymer of α-olefin and glycidyl ester of α, β-unsaturated acid (JP-A-58-15).
4757), addition of a copolymer obtained by graft-polymerizing a vinyl monomer to a copolymer of an α-olefin and a glycidyl ester of an α, β-unsaturated acid (JP-A-1-198664).
No.), an α-olefin and an α, β-unsaturated carboxylic acid alkyl ester, and a copolymer of maleic anhydride (JP-A-62-151460).

[0005]

Although each of the above-mentioned methods has an effect of improving impact resistance, the thermal stability of the impact resistance improver is inferior, and the impact resistance improver decomposes when molded at the processing temperature of the PPS resin. However, there are drawbacks such as not being able to sufficiently improve the impact resistance, and in extrusion molding of pipes, tubes and the like, it may cause the generation of eyes and eyes, and it is difficult to obtain a molded product having excellent surface smoothness. Furthermore, α-olefin and α,
Addition of copolymer of glycidyl ester of β-unsaturated acid (JP-A-58-154757), graft polymerization of vinyl monomer onto copolymer of α-olefin and glycidyl ester of α, β-unsaturated acid. When an impact modifier prepared by copolymerizing a glycidyl ester, such as the addition of a copolymer described in JP-A-1-198664, is used, the glycidyl group in the olefin copolymer causes an undesirable side reaction during molding. This causes problems such as thickening or especially gelation. In addition, α-olefin and α,
The non-reinforced PPS resin to which the copolymer of glycidyl ester of β-unsaturated acid is added is inferior in slidability and is difficult to be applied to sliding members such as bearings and gears. In order to improve this, an example of adding silicone oil is disclosed in JP-A-3-686.
No. 55, but it did not improve the above-mentioned increase in viscosity during formation and generation of gel matter. Further, as an example of using a reinforcing material such as glass fiber, Japanese Patent Laid-Open No. 2-91155 can be mentioned, but since a fibrous inorganic filler is used, it was insufficient to improve the slidability.

Among the above-mentioned impact modifiers, a method of adding an α-olefin copolymer obtained by graft-copolymerizing an unsaturated carboxylic acid or an acid anhydride thereof (JP-A-59-2079).
21) is an improving material which has an excellent effect of improving impact resistance and does not cause thickening and gelation as seen by the addition of a glycidyl ester-containing olefin copolymer at the time of molding, especially at the time of extrusion molding, and has relatively few defects. there were. However, the obtained molded product has poor wear resistance and has a problem in being applied to sliding members such as bearings and gears.

Therefore, the present invention has excellent impact resistance and tensile properties, improved extrusion properties, and excellent sliding properties with substantially no filler for strengthening. It is intended to obtain a reinforced PPS resin composition.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that PPS resin and a specific α
-The above problem is solved by further adding a small amount of a polyorganosiloxane-based resin to a resin composition of an olefin copolymer and a specific reactive organic compound,
It has been found that a PPS resin composition having good impact resistance, tensile properties, extrusion properties and sliding properties can be obtained, and the present invention has been completed.

That is, the present invention essentially requires (A) 70 to 99% by weight of polyphenylene sulfide resin, (B) at least one selected from α, β-unsaturated carboxylic acids or acid anhydrides thereof, or alkyl esters thereof. Α-Olefin-based copolymer 1 to be contained as a copolymerization component
(C) A silane coupling agent (C1), an organic compound (C2) containing two or more organic functional groups in the molecule other than (C1) per 100 parts by weight of a resin composition (1) consisting of 30% by weight. At least one or more functional group-containing organic compounds selected from the range of 0.1 to 10 parts by weight, further (A),
Non-reinforced polyphenylene sulfide, characterized in that (D) the polyorganosiloxane resin is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition (2) comprising (B) and (C). Involved in resin compositions. Further, the present invention provides the above-mentioned (A), (B), (C),
In addition to the component (D), a polyamide resin (E) is further added in an amount of 0.
The present invention relates to a non-reinforced polyphenylene sulfide resin composition containing 1 to 10 parts by weight. Furthermore, the present invention relates to (D) a polyorganosiloxane resin and (E)
The present invention relates to a method for producing a non-reinforced polyphenylene sulfide resin composition, which comprises melt-kneading with a polyamide resin in advance, blending the resulting mixture with other components, and then melt-kneading the mixture.

A preferred PPS resin (a) for use in the present invention is a PPS resin containing 70 mol% or more of the repeating unit [-φ-S-] (where -φ- is a p-phenylene group). is there. 70 mol% of this repeating unit
When it is above, the crystallinity, which is a characteristic of the crystalline polymer, is high, sufficient strength is obtained, and the toughness and chemical resistance are excellent.

PPS resins are generally known to have a substantially linear molecular structure having no branched or crosslinked structure and one having a branched or crosslinked structure depending on the production method.
In the present invention, both types are effective. As an example of a method for producing a PPS resin, Japanese Patent Publication No. 45-3
A high degree of polymerization is obtained by heating a polymer having a relatively small molecular weight obtained by the production method typified by Japanese Patent No. 368, after polymerization in an oxidizing atmosphere or by adding a crosslinking agent such as peroxide and heating. PPS resin having a so-called cross-linking structure, used in Japanese Patent Publication No. 52-12240
There is an essentially linear polymer having a relatively high molecular weight, which is obtained by the production method typified by the publication. However, the present invention does not particularly define the method for producing these PPS resins.

Such PPS resin may contain less than 50 mol%, preferably less than 30 mol%, of other copolymerized structural units shown below.

[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

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[0021]

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And the like. Of these, the trifunctional unit is 1
It is also preferable that the content is mol% or less from the viewpoint of not lowering the crystallinity. Further, as the PPS resin used in the present invention, it is preferable to use a PPS resin having a sodium content of 2000 ppm or less in order to exhibit good impact resistance and tensile properties. PP with a sodium content of 2000 ppm or less
As a method of obtaining S, a known method is used. For example, a method of performing washing treatment such as hot water washing, organic solvent washing, and acid washing as described in JP-A-2-200415 after polymerization of the PPS resin is preferably used.
The present invention does not define this, and it is important to use a PPS resin having a sodium content of 2000 ppm or less in order to achieve the effects of the present invention.

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as a molded product can be obtained,
When the injection molding method is used, when the melt viscosity is represented by a melt flow rate, the melt flow rate at 316 ° C. and 5000 g load is preferably 50 g / 10 min or more,
When molding by extrusion molding method, 200g / 10min
The following is preferred.

The α-olefin (co) polymer (B) to be blended with the PPS resin (A) means at least one selected from α, β-unsaturated carboxylic acids or their acid anhydrides or their alkyl esters. It is an α-olefin copolymer containing at least one species as an essential copolymer component. Specifically, a copolymer of α-olefin and α, β-unsaturated carboxylic acid alkyl ester, for example, α-olefin 5 to 95% by weight and α, β-unsaturated carboxylic acid alkyl ester 5 to 95% by weight. A copolymer consisting of;
In addition to an olefin and an α, β-unsaturated carboxylic acid alkyl ester, an acid containing an unsaturated carboxylic acid or its acid anhydride in an amount of 10 wt% or less, preferably 1 to 8 wt% as an essential copolymerization component (an acid anhydride) ) Group-modified α-olefin / α, β-unsaturated carboxylic acid alkyl ester copolymer; an acid containing α-olefin as a main component and an unsaturated carboxylic acid or an acid anhydride thereof as a modifier component ( Acid anhydride) group-containing olefin-based copolymer, for example, α-
An olefin-based copolymer such as an acid (anhydride) modified copolymer obtained by copolymerizing an olefin (co) polymer with an unsaturated carboxylic acid or its acid anhydride in an amount of 10% by weight or less, preferably 1 to 8% by weight. Polymers may be mentioned. In addition, in such a copolymer, a small amount of a monomer other than the above-mentioned essential monomer components may be added within a range not departing from the gist of the present invention. The copolymer described here includes all of random copolymers, block copolymers, and graft copolymers.

As the α-olefin which is a monomer component of such an olefin (co) polymer (B),
One or more kinds selected from ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, decene-1, octene-1 and the like are used. Ethylene and propylene are preferably used.

Further, the α, β-unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid or methacrylic acid. Methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t acrylate
-Butyl, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate
There are butyl, t-butyl methacrylate, isobutyl methacrylate, and the like. Of these, methyl acrylate, ethyl acrylate, and n-butyl acrylate are particularly preferably used. Further, these α, β-unsaturated carboxylic acid alkyl esters may be used alone or in combination of two or more.

The α, β-unsaturated carboxylic acid or its acid anhydride used as the modifier component is acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid. ,
Mesaconic acid, citraconic acid, glutaconic acid, monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methylmaleic anhydride, maleic anhydride, methylmaleic anhydride, citraconic anhydride, etc. Or used in two or more kinds. Although these derivatives can be used, maleic anhydride is more preferably used.

The compounding ratio of the PPS resin (A) and the α-olefin copolymer (B) is (A) / (B) = 7.
0 to 99% by weight / 1 to 30% by weight, preferably (A) / (B) = 80 to 97% by weight / 3 to 20% by weight,
More preferably (A) / (B) = 85-95% by weight / 5
１５15% by weight. When the amount of the α-olefin copolymer is large, the heat resistance of the PPS resin is impaired, and when the amount is small, the effect of improving the impact resistance is not seen.

In the composition of the present invention, in addition to the components of the PAS resin (A) and the α-olefin copolymer (B), the silane coupling agent (C1) (C1) is used for the purpose of further improving the physical properties. ), At least 1 selected from the organic compounds (C2) containing two or more organic functional groups in the molecule other than the above (C1)
One or more functional group-containing organic compound (C) is added.

The functional group-containing organic compound (C) used in the present invention is specifically a vinyl group, a hydroxyl group, a carboxyl group, an acid anhydride group of dicarboxylic acid, a glycidyl group, an amino group, an isocyanate group, a mercapto group, It is an organic compound containing two or more functional groups of at least one kind selected from an oxazoline group and an isocyanurate group. The above-mentioned organic compound (C) may be a thermoplastic resin or a thermosetting resin containing two or more of at least one of these organic functional groups. When using it, it is properly selected and used from these.

Specific examples of the functional group-containing organic compound (C) include a silane coupling agent (C1) and an organic compound (C2) containing two or more organic functional groups in the molecule other than (C1).

Silane coupling agent used in the present invention
(C1) is at least one organic functional group and at least one alkoxysilane group represented by the following formula in one molecule.

[0033]

Embedded image −Si (OR) _n

(Wherein R represents an alkyl group having 1 to 8 carbon atoms and n represents 1 to 3) is an organosilicon monomer or polymer.

Specific examples of the silane coupling agent (C1) include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Examples include mercaptopropylmethyldimethoxysilane and the like, and further include these polymers. Of these, γ-glycidoxypropyltrimethoxysilane is preferably used.

Examples of the organic compound (C2) containing two or more organic functional groups in the molecule other than the silane coupling agent (C1) include ethanedithiol, propanedithiol,
Mercapto compounds such as 1,2-benzenedithiol, 1,3-benzenedithiol and 1,4-benzenedithiol; ethylene glycol diglycidyl ether, catechol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether, resorcinol Multivalent glycidyl ethers such as diglycidyl ether, benzenetriol triglycidyl ether, benzenetetraol tetraglycidyl ether;
1,3-phenylene bis- (2-oxazoline), 1,
Bis- (2-oxazoline) compounds such as 4-phenylene bis (2-oxazoline) and ethylene bis- (2-oxazoline); 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, hexamethylene diisocyanate, 4 Diisocyanate compounds such as 4-diphenylmethane diisocyanate; trimellitic anhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-tetracarboxybenzophenone dianhydride, 4.4′-methylenebis (benzene-1,2-dicarboxylic acid) Polycarboxylic acid anhydrides such as dianhydride; 1,2-phenylenediamine,
Examples thereof include diamine compounds such as 1,3-phenylenediamine, 1,4-phenylenediamine, diaminodiphenyl ether, hexamethylenediamine, and ethylenediamine. Examples of the thermoplastic resin having an organic functional group include a glycidyl group-containing polyolefin resin, an oxazoline group-containing polystyrene resin, a polyamide resin, a polyester resin, and a polycaprolactone resin. Further, as the thermosetting resin, at least 2 in one molecule.
Epoxy resin, vinyl ester resin, unsaturated polyester resin having two or more glycidyl groups, triazine resin having two or more isocyanurate groups in one molecule, and two or more maleimide groups in one molecule Examples thereof include bismaleimide-based resins, phenol-based resins, and carbodiimide-based compounds having two or more carbodiimide groups in the molecule. Among these, preferable organic compounds (C) include glycidyl group-containing polyolefin resins, oxazoline group-containing polystyrene resins, polyamide resins, epoxy resins, carbodiimide compounds and the like.

The ratio of the functional group-containing organic compound (C) used is (A) polyphenylene sulfide resin and (B) α-.
Resin composition (1) 100 comprising an olefin-based copolymer
0.1 to 10 parts by weight, preferably 0.3 to parts by weight
~ 5 parts by weight are used. If it exceeds 10 parts by weight, gas generation or thickening during molding occurs and the disadvantage in molding is considered, and if it is less than 0.1 part by weight, the effect of the present invention is difficult to be recognized.

The polyorganosiloxane resin (D) used in the present invention is a polyorganosiloxane resin represented by polydimethylsiloxane and a part of the side chain and / or terminal methyl groups of polydimethylsiloxane. Is a modified polyorganosiloxane resin having at least one reactive substituent such as an epoxy group, a carboxyl group, an amino group, a hydroxyl group, and a mercapto group, and is generally called a silicone oil. It is an organosiloxane resin.

The viscosity of the polyorganosiloxane resin is not particularly limited, but it is usually effective at 1 poise or higher at 25 ° C., preferably 100 poise or higher, especially in the form of a gum that does not show fluidity at room temperature of 25 ° C., and a capillary rheometer. It is preferable that the viscosity at 25 ° C. and the shear rate of 100 sec ^-1 is 1000 poise or more.

The polyorganosiloxane resin (D) is added in an amount of 100 parts by weight of a composition comprising a PPS resin (A), an α-olefin copolymer (B), and a functional group-containing organic compound (C). On the other hand, it is in the range of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight. 0.1
If it is less than 10 parts by weight, the effect of improving the sliding property is small, and if it exceeds 10 parts by weight, the physical properties such as tensile properties and impact resistance are not preferable.

Next, the polyamide resin used as the component (E) in the present invention is a polymer compound having an acid amide (-CONH-) as a repeating unit, which is obtained by ring-opening polymerization of lactam depending on the polymerization mode, diamine. And polybasic acid of dibasic acid and polycarboxylic acid of aminocarboxylic acid. These have the common name of nylon, such as nylon 6, nylon 12, nylon 9,
Examples thereof include nylon 11, nylon 66, nylon 610, nylon 46, and aromatic polyamides using an aromatic compound as a monomer. Of these, nylon 6, nylon 66, and aromatic polyamide are preferable. Polyamide-imide resin is also used as the polyamide resin.

The compounding amount of the polyamide resin (E) is as follows: PPS resin (A), α-olefin (co) polymer (B), functional group-containing organic compound (C) and polyorganosiloxane resin (E). 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the composition consisting of 0.1 to 10 parts by weight, the sliding property improving effect is small, and 10 to 10 parts by weight or more the PPS resin. The heat resistance of is impaired.

The polyorganosiloxane-based resin (D) and the polyamide-based resin (E) described above in preparing the composition of the present invention containing the above-mentioned components (A) to (E) are the melting points of the polyamide-based resin in advance. ~ It is preferable to use after melt-kneading at a melting point + 100 ° C or less. A known method is used as a method for melt-kneading the polyorganosiloxane resin (D) and the polyamide resin (E). Specifically, the polyamide resin and the polyorganosiloxane resin are mixed by a Henschel mixer, a Banbury mixer, etc., and the melting point of the polyamide resin to the melting point + 100 ° C.
In the following, kneading with a single-screw extruder or a twin-screw extruder, extruded in a strand shape, and a method of cutting into pellets, etc. are used, but the present invention is not limited to this, and a polyamide resin A characteristic is that a mixture of polyorganosiloxane-based resins is prepared in advance and used.

In order to maintain the thermal stability of the molten resin during extrusion processing or injection molding of the composition, the resin composition of the present invention comprises
Alternatively, it is preferable to add a stabilizer (F) for the purpose of maintaining the heat aging property of the molded product. As the preferred heat stabilizer in the present invention, at least one compound selected from hindered phenol compounds (F1), thiodipropionate compound (F2) and phosphite compound (F3) is used. Is preferred. Especially hindant phenolic compounds (F1) and thiodipropionate compounds
It is preferable to use (F2) or the hindered phenol compound (F1) and the phosphite compound (F3) in combination. Furthermore, all three of the above compounds may be used in combination.

The hindered phenol compound used in the present invention is a compound having at least one hindered phenol structure represented by the following formula in one molecule.

[0046]

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Or the following formula

[0048]

[Chemical 12]

(In the formula, R2 and R3 are hydrocarbon groups having 1 to 6 carbon atoms, and these may be the same or different groups.)

Specifically, 2,6-t-dibutyl-p-cresol, 2,6-t-dibutyl-4-ethylphenol, stearyl-β- (3,5-dibutyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-ethyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β
-(3-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-
Tetraoxaspiro [5,5] undecane, 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-
4′-hydroxyphenyl) propionate] methane,
1,3,5-tris (3 ′, 5′-di-t-butyl-
4'-hydroxybenzyl) -S-triazine-2,
4,6- (1H, 3H, 5H) trione, 1,1,3
-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-octadecyl-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t)
-Butylphenol), 2-t-butyl-6- (3-t
-Butyl-2-hydroxy-5-methylbenzyl) -4
-Methylphenyl acrylate, 4,4'-butylidene bis (3-methyl-6-t-butylphenol) and the like, but not limited thereto. In the present invention 1,
1,3, -tris (2-methyl-4-hydroxy-5-
t-Butylphenyl) butane and tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane are preferably used.

Thiodipropionate compound (F2)
Is a compound having at least one sulfur compound represented by the following formula in the molecule.

[0052]

Embedded image (—S—CH ₂ CH ₂ COO—)

Specifically, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, ditridecyl, 3,3'-thiodiprone. Peonate,
Tetrakis [methylene-3- (dodecylthio) propionate] methane, bis [2-methyl-4-{3-n-alkyl (C ₁₂ or C ₁₄₎ thio propionyloxy} -
Examples thereof include, but are not limited to, 5-t-butylphenyl] sulfide. In the present invention, tetrakis [methylene-3- (dodecylthio) propionate] methane is preferably used.

The phosphite compound (F3) used in the present invention is a compound having at least one trivalent phosphate ester structure represented by the following formula in the molecule.

[0055]

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Specific examples include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl isodecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenylditridecyl).
Phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di) -T-butylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,
6-di-t-butylphenyl) octyl phosphite,
Tetrakis (2,4-di-t-butylphenyl) 4,
Examples thereof include, but are not limited to, 4'-biphenylene-di-phosphonite. In the present invention, 2,2-
Methylenebis (4,6-di-t-butylphenyl) octylphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene-di-phosphonite, tris (2,4-di-t) -Butylphenyl) phosphite is preferably used.

These hindantophenol compounds (F
1), at least one stabilizer (F) selected from thiodipropionate compound (F2) and phosphite compound (F3) is added in an amount of 100 parts by weight of the composition of the present invention. On the other hand, the amount is 0.05 to 5 parts by weight, and if it is less than 0.05 parts by weight, the effect of the present invention is not obtained, and if it exceeds 5 parts by weight, the generation of gas increases, which is not preferable for molding.

Further, a fluorine-based resin typified by polytetrafluoroethylene may be added to the composition of the present invention, if necessary.

Further, other thermoplastic resins may be added to the composition of the present invention within the range not departing from the gist of the present invention. Other thermoplastic resins include polyethylene, polypropylene, polystyrene, imide-modified polystyrene, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyamides other than the above, polycarbonate, ABS resin, imide modified. ABS resin, AES
Resin, polysulfone, polyphenylene ether, copolymer of polyphenylene ether and polystyrene, and / or
Alternatively, a mixture, a polyethersulfone, a polysulfide ketone, a polysulfide sulfone, a polyether ether ketone, a polyamide imide, a thermoplastic resin such as a fluororesin typified by polytetrafluoroethylene, a polyester-based, a polyamide-based, a polyurethane-based,
Polyolefin-based, polystyrene-based thermoplastic elastomers, and these thermoplastic elastomers by glycidyl group, a carboxylic acid and its acid anhydride, an amino group, an isocyanate group, an organic compound containing an organic functional group such as an mercapto group, an oxazoline group Examples include modified denatured products.

In the present invention, an inorganic flame retardant such as magnesium hydroxide, aluminum hydroxide or antimony trioxide, a halogen-based compound, or a halogen-based compound, is used without departing from the scope of the present invention.
Phosphorus-based organic flame retardants, UV inhibitors, lubricants, crystal nucleating agents, dispersants, silane coupling agents other than the present invention, titanium coupling agents, foaming agents, cross-linking agents, colorants, plasticizers,
Additives such as polyorganosiloxane resins other than the present invention can be added.

As a method for producing a molded article from the PPS resin composition of the present invention, a general production method is used. The most common method is to uniformly mix the compound in a suitable mixer such as a tumbler, a Henschel mixer, a tumbler, etc., and feed the mixture into a single-screw or twin-screw extruder, at a temperature higher than the melting point of the PPS resin, and in the extruder. The product extruded in a strand form, which is retained for 15 seconds or more and less than 300 seconds and melted and kneaded, can be cooled and cut into a product (eg, pellets) for a molding material, but is not particularly limited thereto. .

The composition of the present invention is superior in impact resistance and sliding property as compared with the conventional PPS resin composition, and does not impair mechanical properties and heat resistance. Therefore, the conventional P
Like PS resin, it can be used for various functional parts. For example, injection molded products can be used for automobile parts, electric machines,
Electronic parts, encapsulating materials, and extrusion products commonly used for profile extrusion, tubes, hoses, pipes,
It is useful as a material for extrusion of fibers, films, wire coatings, etc., blow molding, and material for rotational molding, but the present invention does not define molding conditions and molding methods for these molded products.

[0063]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below. The preferred non-reinforced polyphenylene sulfide resin composition in the present invention comprises (A) 70 to 99% by weight of a polyphenylene sulfide resin having a sodium content of 2000 ppm or less and (B) an α, β-unsaturated carboxylic acid or an acid anhydride thereof. With respect to 100 parts by weight of the resin composition (1) consisting of 1 to 30% by weight of the α-olefin copolymer contained at a ratio of not more than 10% by weight, (C) a silane coupling agent, a vinyl group other than the above, Hydroxyl group,
One or more of organic compounds containing at least one functional group selected from a carboxyl group, an acid anhydride group of dicarboxylic acid, a glycidyl group, an amino group, an isocyanate group, a mercapto group, an oxazoline group and an isocyanurate group are 0. 1 to 10 parts by weight, further (A),
Resin composition (2) 10 comprising components (B) and (C)
0 parts by weight of (D) 0.1% of polyorganosiloxane having a viscosity of 1000 poise or more at 25 ° C. for 100 sec ^-1
A resin composition 1 which is a non-reinforced polyphenylene sulfide resin composition which is contained in an amount of from 10 to 10 parts by weight, and which further comprises the above essential components (A) to (D).
(E) polyamide resin 0.1 to 100 parts by weight
An unreinforced polyphenylene sulfide resin composition containing 10 parts by weight. In addition, before adding the (E) polyamide resin as an essential constituent, (D)
A method in which the polyorganosiloxane-based resin and the (E) polyamide resin are melt-kneaded, the resulting mixture is blended with other constituent components, and then these are melt-kneaded is preferable.
The resin composition thus obtained can be suitably used as a heat resistant sliding member having a small friction coefficient and excellent extrusion stability without impairing the heat resistance and chemical resistance of the polyphenylene sulfide resin.

[0064]

The present invention will be further described with reference to examples.

(1) Melt index of PPS resin
(MI) Measurement After drying about 6 g of the sample at 120 ° C. for 3 hours, the melt indexer () was set to a predetermined temperature (315.6 ° C.) using an orifice having a diameter of 2.096 mm and a length of 8.001 mm. Toyo Seiki Co., Ltd. T01 type), after removing air bubbles, applying a predetermined load (5000 g) and preheating for 5 minutes, and then measuring.

(2) HDT (Heat Strain Temperature) Measuring Method The measurement is performed according to ASTM D648. Test piece: length 125 mm x width 12.5 mm x thickness 3.0 mm (injection molded product) Measuring instrument: HDT tester S3FH type manufactured by Toyo Seiki Seisakusho Co., Ltd. Load: 4.6 kgf / cm ²

(3) Tensile test, Izod impact test Measurement is ASTM D-638 (tensile test), ASTM
D-256 (Izod impact test).

Tensile test Specimen: ASTM No. 4 dumbbell Thickness 1.6 mm (injection molded product) Tensile speed: 10 mm / min Mark spacing: 25 mm Measuring machine: Shimadzu AUTOGRAPH AG5000C

Izod impact test Specimen: Length 63.5 mm x Width 12.5 mm x Thickness 3.0 mm (Injection molded product) Notch is a cutting notch Hammer load: Notched 30 kg-cm: No notch 60 kg-cm Measuring instrument: UNIVERSAL IMPACT manufactured by Toyo Seiki TESTER

(4) Dynamic friction coefficient measuring machine: Orientic Co., Ltd. EFM-III-F (Suzuki type abrasion tester) Test piece: Length 50 mm x width 50 mm x thickness 2.0 mm (injection molded product) Counterpart material: S45C ( Carbon steel) Rotation speed: 10 m / min Measured under the condition of PV value of 750 (kg / cm ² ) (m / min). Dynamic friction coefficient is measured 30 minutes after the start of rotation.

Examples 1 to 4 and Comparative Examples 1 to 4 Crosslinked PPS resin having MI of 25 g / 10 min and sodium content of 910 ppm was used as PPS resin (A), and maleic anhydride was used as α-olefin copolymer (B). Acid 1.8
A functional group-containing organic compound (C), a polyorganosiloxane-based resin (D), and a hindered phenol-based compound ((F1), thiodipropionic acid) as a stabilizer (F) containing an ethylene-propylene copolymer in an amount of 1% by weight. Ester compound (F
2) was blended with the composition shown in Table-1, and the barrel temperature was 290
The mixture was kneaded with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) set to ° C, and the extruded strand was cooled and solidified, and then pelletized. The resulting pellets are 4 at 120 ° C
After drying for an hour, an injection molding machine (IS-50AM: made by Toshiba Machine) has a cylinder temperature of 290 ° C. and a mold surface temperature of 15
Molding was performed at 0 ° C., HDT test pieces, tensile test test pieces, Izod impact test test pieces, and wear test test pieces were molded, and the respective physical properties were measured according to the methods described above.

As a comparative example, the same tests were conducted with the formulations shown in Table-1. The results are shown in Table 1. The resin composition of the present invention has small impact resistance, tensile elongation, heat resistance and coefficient of dynamic friction, and is a well-balanced material as a sliding material.

[0073]

[Table 1]

Examples 5 to 7 and Comparative Examples 5 to 8 A linear PPS resin having an MI of 100 g / 10 min and a sodium content of 1100 ppm was used as the PPS resin (A), and maleic anhydride was used as the α-olefin copolymer (B). A copolymer of acid 1.8% by weight, ethyl acrylate 27% by weight, ethylene 71.2% by weight, a functional group-containing organic compound (C), a polyorganosiloxane resin (D) and a polyamide resin (E). Blended with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) having a barrel temperature of 280 ° C. (polyorganosiloxane-based resin 50).
% By weight), a stabilizer (F), a hindered phenol compound (F1), a thiodipropionate compound (F)
2), the phosphoric acid ester compound (F3) was blended with the composition shown in Table-2, kneaded with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) having a barrel temperature of 290 ° C, and extruded strands. Was solidified by cooling and then pelletized. After drying the obtained pellets at 120 ° C. for 4 hours, the pellets were molded with an injection molding machine (IS-50AM: manufactured by Toshiba Machine) at a cylinder temperature of 290 ° C. and a mold surface temperature of 150 ° C., and HDT.
Test pieces, tensile test pieces, Izod impact test pieces, and wear test pieces were molded, and their physical properties were measured according to the methods described above.

As a comparative example, the same test was conducted with the formulations shown in Table-2. Table 2 shows the results. The resin composition of the present invention has small impact resistance, tensile elongation, heat resistance and coefficient of dynamic friction, and is a well-balanced material as a sliding material.

[0076]

[Table 2]

Examples 8 to 10 and Comparative Examples 9 to 10 Using the materials used in Examples 1, 4 and 6, Comparative Example 1 and Comparative Example 2, a 30φ mm uniaxial extruder (I.
K. G, PMS30-25), outer diameter 8φ mm, inner diameter 6
φmm tube die attached, cylinder temperature 29
0 ℃, die temperature 280 ℃, screw rotation speed 30 rpm
Extrude the above materials with and cool with water, 16m / min
Speed take-off machine (roll take-up machine MOD
EL-150-TIR R.M. Co., Ltd.) to obtain a tube having an outer diameter of 3 ± 0.2 mm and a wall thickness of 0.3 ± 0.05 mm. This tube was cut into a length of 100 mm, and a tensile test was carried out at a tensile speed of 10 mm / min and a marked line interval of 50 mm to measure tensile properties. In addition, the screw torque during extrusion and the state of occurrence in the eyes and eyes were examined. The results are shown in Table-3.

[0078]

[Table 3]

The composition of the present invention has a low screw torque and does not cause eyes and eyes. It also has good tensile properties,
It has excellent extrusion processability and good physical properties as a tube.

[0080]

INDUSTRIAL APPLICABILITY According to the present invention, a non-reinforced polyphenylene sulfide resin composition suitable as a heat resistant sliding member having a small friction coefficient without impairing the heat resistance and chemical resistance of the polyphenylene sulfide resin and having excellent extrusion stability. The thing is obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 33:04 83:04)

Claims (9)

[Claims] 1. A polyphenylene sulfide resin (A) 7
An α-olefin copolymer 1 containing 0 to 99% by weight of (B) an α, β-unsaturated carboxylic acid or an acid anhydride thereof, or at least one selected from alkyl esters thereof as an essential copolymerization component 1. To 30 parts by weight of the resin composition (1) 100 parts by weight, (C) a silane coupling agent (C1), an organic compound (C2) containing two or more organic functional groups in the molecule other than (C1). 0.1 to 10 parts by weight of at least one or more functional group-containing organic compound selected from the group consisting of (A), (B) and (C).
(D) to 100 parts by weight of the resin composition (2)
A non-reinforced polyphenylene sulfide resin composition, wherein the polyorganosiloxane resin is in the range of 0.1 to 10 parts by weight. 2. A polyphenylene sulfide resin (A)
The resin composition according to claim 1, wherein is a heat-crosslinking type, a branching type, a linear type, or a mixture of two or more thereof. 3. The α-olefin-based copolymer (B) contains an α, β-unsaturated carboxylic acid or its acid anhydride as an essential copolymerization component thereof in a proportion of 10% by weight or less. Item 1. The resin composition according to Item 1. 4. The functional group-containing organic compound (C), wherein the functional group is a vinyl group, a hydroxyl group, a carboxyl group, an acid anhydride group of dicarboxylic acid, a glycidyl group, an amino group, an isocyanate group, a mercapto group, an oxazoline group, or an isocyanate group. The resin composition according to claim 1, which is at least one functional group selected from nurate groups. 5. A polyorganosiloxane resin (D)
The resin composition according to claim 1, which has a viscosity of 1000 poise or more at 25 ° C for 100 sec ^-1 . 6. A non-reinforced polyphenylene sulfide resin, characterized in that (E) polyamide resin is contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition according to claim 1. Composition. 7. The resin composition 1 according to claim 1 or 6.
(F) hindant phenolic compound (F1), thiodipropionic acid ester compound (F2),
A non-reinforced polyphenylene sulfide resin composition comprising 0.05 to 5 parts by weight of at least one stabilizer selected from the phosphite compound (F3). 8. A polyphenylene sulfide resin (A)
Is a polyphenylene sulfide resin having a sodium content of 2000 ppm or less, The resin composition according to claim 1 or 2. 9. The (D) polyorganosiloxane-based resin and the (E) polyamide resin are melt-kneaded in advance, the resulting mixture is blended with other constituent components, and then this is melt-kneaded. A method for producing the non-reinforced polyphenylene sulfide resin composition according to claim 6.