JP2002003716A - Polyphenylene sulfide resin composition and injection molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a polyphenylene sulfide resin composition having a weld strength, especially an extremely high weld strength formed at the side of a cylindrical part and an injection molding. SOLUTION: This polyphenylene sulfide resin composition is characterized in that the polyphenylene sulfide resin composition is obtained by compounding (a) 100 pts.wt. of a polyphenylene sulfide resin with (b) 4.5-15 pts.wt. of an olefin-based (co)polymer and (c) 20-90 pts.wt. of an inorganic filler and at least one kind of an epoxy group-containing olefin-based copolymer is contained as the (b) the olefin-based (co)polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition having an extremely high weld strength, particularly a weld strength formed on a side surface of a cylindrical portion, and an injection molded article thereof.

[0002]

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

In recent years, PPS resins have been applied to hollow cylindrical members through which hot and cold water, gasoline, oil, and the like flow, making use of their high chemical resistance and wet heat resistance. When a cylindrical member is injection-molded, a weld portion is often formed on the side surface portion thereof. Therefore, in order to develop such a use, improvement of the strength of the weld portion is an important technical problem.

[0004] With respect to the technique for improving the weld strength of PPS, for example, Japanese Unexamined Patent Publication No. Hei.
A technique of adding a silane compound to an S resin is disclosed. However, the measurement of the weld strength is a measurement using a test piece having a weld portion at the center, and at present, there has been almost no study focused on the weld strength of a cylindrical member, which is currently an issue. According to the study results of the present inventors, the strength of the weld portion having a simple shape such as a test piece and the weld strength of the cylindrical side surface do not necessarily match, and the weld strength of the cylindrical side surface is excellent. Further investigation was needed to obtain the composition.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a polyphenylene sulfide resin composition having an extremely high weld strength, particularly a weld strength formed on the side surface of a cylindrical portion, and an injection molded article thereof.

[0006]

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, mixed a PPS resin with a specific olefin (co) polymer and an inorganic filler in a specific compounding range. As a result, it was found that a specifically high cylindrical portion weld strength was developed. Furthermore, they have found that the combined use of a fibrous filler and a non-fibrous filler as the inorganic filler is particularly effective for improving the weld strength of the cylindrical portion, and have reached the present invention.

That is, the present invention comprises the following items. 1. (B) 5 to 15 parts by weight of an olefin (co) polymer and (c) 20 to 90 parts by weight of an inorganic filler with respect to 100 parts by weight of a polyphenylene sulfide resin. So,
(B) As the olefin (co) polymer, (b) 'α-
A polyphenylene sulfide resin composition comprising, as an essential component, an epoxy group-containing olefin copolymer obtained by copolymerizing an olefin, an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer. 2. (B) ′ The copolymerization ratio of the epoxy group-containing olefin-based copolymer is such that the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester have a copolymerization ratio of 52
(B) ′ in the epoxy group olefin copolymer, the α-olefin and the α, β-unsaturated carboxylic acid 85-99.
5% by weight of the epoxy group-containing vinyl monomer 0.5
2. An epoxy resin containing an epoxy group-containing olefin copolymer in an amount of from 15 to 15% by weight as an essential component.
The polyphenylene sulfide resin composition according to the above. 3. (C) The polyphenylene sulfide resin composition according to any one of (1) to (2) above, wherein at least one of a fibrous filler and a non-fibrous filler is contained as the inorganic filler. 4. (C) As an inorganic filler, at least one type of each of a fibrous filler and a non-fibrous filler is contained, and the weight ratio of the fibrous filler / non-fibrous filler is 1/3 to 3 /
4. The polyphenylene sulfide resin composition according to the above item 3, wherein the composition is 1. 5. The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein a glassy non-fibrous inorganic filler is used as the non-fibrous filler. 6. (A) The polyphenylene sulfide resin composition according to any one of the above items 1 to 5, wherein a substantially linear polyphenylene sulfide resin is used as the polyphenylene sulfide resin. 7. (A) As a polyphenylene sulfide resin, the melt viscosity (310 ° C., shear rate 1,000 / sec) is 100 to
7. The polyphenylene sulfide resin composition according to any one of the above items 1 to 6, wherein a polyphenylene sulfide resin having a pressure of 400 Pa · s is used. 8. Further, 0.1 to 5 parts by weight of an alkoxysilane compound selected from (d) an epoxy group, an amino group, a ureide group and an isocyanate group is added to (a) 100 parts by weight of the polyphenylene sulfide resin. Item 8. The polyphenylene sulfide resin composition according to any one of Items 1 to 7. 9. Further, (e) 0.1 to 5 parts by weight of a polyfunctional epoxy compound having two or more epoxy groups in one molecule per 100 parts by weight of the polyphenylene sulfide resin (a). Item 8. The polyphenylene sulfide resin composition according to any one of items 8. 10. (B) 5 to 15 parts of (b) olefin (co) polymer per 100 parts by weight of polyphenylene sulfide resin.
Parts by weight, (c) a polyphenylene sulfide resin composition comprising 20 to 90 parts by weight of an inorganic filler,
(B) at least one olefin (co) polymer;
A polyphenylene sulfide resin composition for an injection-molded article having a cylindrical portion, comprising a kind of epoxy group-containing olefin copolymer. 11. The above 1 to 9 which are for an injection molded article having a cylindrical portion
The polyphenylene sulfide resin composition according to any one of the above items. 12. 12. A molded article having a cylindrical portion obtained by injection molding the polyphenylene sulfide resin composition according to the above item 10 or 11.

[0008]

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

The polyphenylene sulfide resin (a) used in the present invention includes a repeating unit represented by the following structural formula.

[0010]

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

[0012]

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The melt viscosity of the (a) PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
Usually, a material having a pressure of 10 to 1,000 Pa · s (310 ° C., a shear rate of 1,000 / sec) is used.
-The range of s is more preferably used. In the present invention, from the viewpoint of obtaining particularly excellent cylindrical part weld strength, 1
It is preferable to use a PPS resin of 100 to 400 Pa · s. In addition, from the viewpoint of the balance with the fluidity, 10 Pa
・ PSP resin of 100 s or more and less than 100 Pa · s and 100 Pa
It is also preferable to use a PPS of not less than s and not more than 400 Pss.

Such a PPS resin can be prepared by a generally known method, that is, a method of obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368, JP-B-52-12240, and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the gazette.

In the present invention, the PPS obtained as described above
Crosslinking / polymerization of resin by heating in air, heat treatment under inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, acid anhydride, amine, isocyanate, functional group containing Of course, it is also possible to use after performing various treatments such as activation with a functional group-containing compound such as a disulfide compound. However, it is particularly preferable to use a linear PPS resin into which a crosslinked structure is not introduced by heating in the air, in order to obtain more excellent cylindrical weld strength.

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

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

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.

As a specific method for treating the PPS resin with hot water, the following method can be exemplified. 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 a saturated aliphatic monocarboxylic acid such as formic acid, acetic acid, propionic acid, and butyric 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 olefin (co) polymer (b) in the present invention will be described. (B) in the present invention
The olefin (co) polymer needs to contain at least one type of epoxy group-containing olefin copolymer.

The epoxy group-containing olefin copolymer includes an olefin copolymer having a glycidyl ester or glycidyl ether in a side chain or a double bond portion of an olefin copolymer having a double bond. Epoxy-oxidized products may be used.

Such epoxy group-containing olefins (co)
More specific embodiments of the polymer include an olefin copolymer in which a monomer having an epoxy group is copolymerized, and in particular, at least one α-olefin and at least one α, β-unsaturated acid. Epoxy group-containing olefin copolymers obtained by copolymerizing glycidyl esters of the above are 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

[0026]

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(Where R represents a hydrogen atom or a lower alkyl group), specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, etc., with glycidyl methacrylate being preferred. Used.

The olefin copolymer obtained by copolymerizing the α-olefin and the glycidyl ester of an α, β-unsaturated acid can be obtained 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 an 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.

[0031]

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(Where R ¹ is hydrogen or a lower alkyl group, X is a group selected from —COOR ² , —CN, or an aromatic group. R ² is 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 such an olefin-based copolymer are the same as described above.

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.

The olefin-based copolymer may be 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 viewpoints of the effects on the desired effects, polymerizability, gelation, heat resistance, fluidity, strength and the like. 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.

(B) 'α-olefin and α, β-
An epoxy group-containing olefin copolymer obtained by copolymerizing an unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer is particularly preferably used. Particularly preferred copolymers include copolymers having a copolymerization ratio of 52 to 95% by weight of α-olefin and α, β-unsaturated carboxylic acid, based on the total amount of α-olefin and α, β-unsaturated carboxylic acid alkyl ester. 5 to 48% by weight of an acid alkyl ester,
(B) ′ In the epoxy group-containing olefin-based copolymer, the epoxy group-containing vinyl monomer is 0.5 to 99.5% by weight based on the total amount of the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester, 85 to 99.5% by weight. 15% by weight of an epoxy group-containing olefin copolymer. More preferably, the copolymerization ratio is from 60 to 85% by weight of the α-olefin and from 15 to 40% by weight of the α, β-unsaturated carboxylic acid alkyl ester based on the total of the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester. % And (b) ′
Α-olefin and α, β-unsaturated carboxylic acid alkyl ester in epoxy group-containing olefin copolymer in total 85
Epoxy group-containing olefin-based copolymers in which the epoxy group-containing vinyl monomer is 0.5 to 15% by weight with respect to ９９99.5% by weight.

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

Further, (b) ′ another monomer component of the epoxy group-containing olefin copolymer which is particularly preferable,
As the α, β-unsaturated carboxylic acid alkyl ester,
An unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid and methacrylic acid, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acrylic N-butyl acrylate, t-butyl acrylate, isobutyl acrylate, hexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methacrylic Examples thereof include isobutyl acrylate and hexyl methacrylate. Of these, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, and n-butyl methacrylate are preferably used. Also, two or more of these can be used simultaneously.

The epoxy group-containing vinyl monomer which is a particularly preferred monomer component of the (b) 'epoxy group-containing olefin copolymer includes glycidyl esters and glycidyl ethers of α, β-unsaturated acids. ,
In particular, glycidyl esters of α, β-unsaturated acids represented by the following general formula

[0040]

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

In another preferred embodiment of the epoxy group-containing olefin (co) polymer of 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-mentioned 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 (b) 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 or more and 7% by weight or less, 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, as the olefin (co) polymer (b), an epoxy group-containing olefin copolymer is an essential component, but other olefin (co) polymers may be used in combination. .

Examples of such other olefin (co) polymers include ethylene-propylene copolymers and ethylene-propylene copolymers.
Butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer and other ethylene and α-olefin copolymers, polyethylene, polypropylene, polystyrene, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene Copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SI
S), polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS) ), The above α-
An olefin copolymer composed of an olefin and the above-mentioned α, β-unsaturated carboxylic acid alkyl ester can be exemplified. In addition, these olefin-based (co) polymers may be added to maleic anhydride, succinic anhydride, fumaric anhydride and other acid anhydrides, carboxylic acids such as acrylic acid, methacrylic acid and vinyl acetate and their Na, Zn, K Olefin-based copolymers in which salts of Ca, Mg, and the like are copolymerized.

In the present invention, when an olefin (co) polymer other than the epoxy group-containing olefin copolymer is used, its amount is not more than 75% by weight of the total amount of (b) the olefin (co) polymer. Preferably 50% by weight
The following ranges are particularly preferred. If the amount of the olefin (co) polymer other than the epoxy group-containing olefin copolymer is too large, the weld strength decreases, which is not preferable.

In the present invention, (b) an olefin (co)
When the content of the polymer is set to 5 to 15 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin (a),
It is very important to obtain high cylindrical weld strength,
A range of from 13 to 13 parts by weight is particularly preferred. Outside the above range, the strength of the cylindrical weld is reduced, which is not preferable.

Next, (c) an inorganic filler, which is another essential component in the present invention, will be described.

As a specific example of the inorganic filler in the present invention, a fibrous filler and a non-fibrous filler can be used, and it is preferable to use both of them in order to simultaneously obtain high general strength and cylindrical weld strength.

The fibrous filler in the present invention is
Defined as having a length / diameter ratio of 20 or greater.

The fibrous filler that can be used in the present invention includes glass fibers, carbon fibers, metal fibers and the like. On the other hand, as non-fibrous fillers, silicates such as walasteinite, zeolite, sericite, mica, talc, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide Metal compounds such as titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide; Examples thereof include glass beads, ceramic beads, boron nitride, silicon carbide, graphite, carbon black, and silica. Among them, glass beads, milled fibers (short glass fibers), and glassy fillers such as glass powder are particularly preferable.

These may be hollow, and it is also possible to use two or more of these fillers in combination. In addition, when these fillers are pre-treated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, more excellent mechanical strength can be obtained. Preferred in meaning.

The amount of the inorganic filler (c) is as follows:
The range of (c) the inorganic filler is 20 to 90 parts by weight, and the range of 30 to 60 parts by weight is particularly preferable, based on 100 parts by weight of the (a) polyphenylene sulfide resin. (C)
If the amount of the inorganic filler is too large, the fluidity and the weld strength are impaired.

In the present invention, the combined use of a fibrous filler and a non-fibrous filler is preferable in order to simultaneously obtain high general strength, rigidity and cylindrical weld strength. When these are used in combination, the weight ratio of fiber filler / non-fibrous filler is preferably in the range of 1/3 to 3/1.

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

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

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

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

[0066]

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[0067]

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As the polyfunctional epoxy compound (e) having two or more epoxy groups in one molecule, the above-mentioned (b) epoxy group-containing olefin copolymer is excluded.

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

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

The method for preparing the PPS resin composition of the present invention is not particularly limited, but the mixture of the raw materials is supplied to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. 280-3
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 resin composition of the present invention is a composition excellent in the strength of a weld portion formed on a side surface of a cylindrical injection molded product.

Therefore, it is useful for an injection molded article having a cylindrical portion, and particularly useful for an injection molded article having a cylindrical portion used in an environment where the inside is pressurized to 1 atm or more. is there. Specific applications include pump parts, pipe joints, water flow control valves, relief valve hot water temperature sensors, water flow sensors, water meter housings, and the like.

The composition of the present invention can be applied to applications other than those described above. Examples of such applications include sensors, LED lamps, connectors, sockets, resistors,
Relay case, switch, coil bobbin, capacitor, variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, semiconductor, Liquid crystal, FDD carriage, FDD chassis, motor brush holder, motor insulator, parabolic antenna, electric and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, Audio components such as audio components, audio laser disks (registered trademark) and compact discs, lighting components, refrigerator components, air conditioner components, typewriter components, word processor components, etc. Home and office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, washing jigs, cleaning parts, motor parts, lighters, typewriters, and other mechanical-related parts: microscopes, Optical instruments such as binoculars, cameras, clocks, etc., precision machinery-related parts; water faucet tops, mixing faucets, any water supply parts; valve alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, Various valves such as exhaust gas valves, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensorー, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller , Turbine vanes, parts related to wiper motors, 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, insulation of electrical components Board, step motor rotor, lamp socket, lamp reflector, lamp housing,
Examples include automobile / vehicle-related parts such as a brake piston, a solenoid bobbin, an engine oil filter, an ignition device case, a vehicle speed sensor, a cable liner, and other various uses.

[0075]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, the test piece weld strength and the cylindrical weld strength were evaluated by the following methods.

[Test piece weld strength] Injection molding machine (resin setting temperature: 280 ° C. below hopper to 320 ° C. at tip)
Was used to inject a resin composition from both ends of an ASTM No. 1 dumbbell piece having a gate at both ends to obtain a test piece having a weld at the center. Using this test piece, a tensile test was performed at a distance between chucks of 114 mm and a strain rate of 5 mm / min, and the breaking strength was taken as the test piece weld strength.

[Cylindrical Weld Strength] Using an injection molding machine (resin setting temperature: 280 ° C. under the hopper to 320 ° C. at the tip), the outer diameter is 25 mm, the inner diameter is 20 mm, and the height is 30 shown in FIG.
A cylindrical molded piece 1 having a diameter of 2 mm was injection molded at a two-point gate at pin gate positions a and b. Next, the eight-piece metal piece 2 shown in FIG.
Was inserted into the cylindrical shaped piece (1) and mounted, and then a conical metal rod 3 was inserted into the eight-piece metal piece 2 and set therein. The metal bar 3 was pressed at a speed of 3 mm / min using a tensile tester (Autograph AG-2000C, manufactured by Shimadzu Corporation) to perform a compression test. Destruction is side weld part 4,
5 occurred. The breaking strength at that time was defined as cylindrical weld strength.

[Bending Strength] An injection molding machine (SG-75 HIPRO) manufactured by Sumitomo-Nestal Co., Ltd. was prepared by subjecting a PPS resin pellet to a cylinder temperature of 280 ° C. (lower side of the hopper) to 320 ° C. (nozzle side) and a mold temperature of 140 ° C. Injection molding was performed using MIII) to obtain a rectangular parallelepiped specimen of 127 mm × 12.7 mm × 6.35 mm. Using this test piece, in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, using a Tensilon RTA-1T tester manufactured by Orientec, 12.7 mm × 127 m
The test piece was placed in a direction in which the surface of m was in contact with the fulcrum, and a bending test was performed with a distance between the fulcrums of 100 mm and a crosshead of 3 mm.

(A) PPS resin a1: Linear PPS resin, melt viscosity 50 Pa · s (31
0 ° C., shear rate 1000 / sec), ash content 0.05% by weight a2: linear PPS resin, melt viscosity 250 Pa · s (3
(10 ° C., shear rate 1000 / sec), ash content 0.08% by weight a3: a1 was oxidatively crosslinked at 210 ° C. in an air atmosphere. Melt viscosity 100 Pa · s (310 ° C, shear rate 1
000 / sec).

(B) Epoxy-containing olefin copolymer b1: Ethylene / methyl acrylate / glycidyl methacrylate = 64/30/6 (% by weight) copolymer. b2: ethylene / n-butyl acrylate / glycidyl methacrylate = 79/15/6 (% by weight) copolymer. b3: ethylene / methyl acrylate / glycidyl methacrylate = 38.7 / 59 / 2.3 (wt%) copolymer. b4: ethylene / glycidyl methacrylate = 88/1
2 (% by weight) copolymer. b5: ethylene / butene-1 = 92/8% by weight copolymer.

(C) Inorganic filler c1: Glass fiber (TN107GH manufactured by NEC Corporation)
C2: Glass beads (EGB7 manufactured by Toshiba Barrodini)
31B2, spherical) c3: Calcium carbonate (KSS100 manufactured by Kanehira Mining Co., Ltd.)
0, amorphous) (d) Alkoxysilane compound d1: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane d2: γ- (2-ureidoethyl) aminopropyltrimethoxysilane (e) Epoxy in one molecule Polyfunctional epoxy compound having two or more groups e1: ortho-cresol novolak glycidyl ether compound SUMI-EPOXY ESCN195HH (manufactured by Sumitomo Chemical Co., Ltd.).

Comparative Examples 1-3 and Examples 1-2 After (a) PPS resin, (b) olefin copolymer and (c) filler were dry-blended at the ratios shown in Table 1, the cylinder temperature was 280 ° C. (Hopper side) ~ 32
The mixture was melt-kneaded with a twin-screw extruder set at 0 ° C (tip side), pelletized with a strand cutter, and dried at 120 ° C overnight. Using such pellets, test piece weld strength, cylindrical weld strength, and bending strength were measured. Table 1 shows the results.

From the results, it can be seen that the test piece weld strength and the cylindrical weld strength have different dependences on the (b) olefin copolymer addition amount. That is, the test piece weld strength decreases as the (b) olefin copolymer addition amount increases, but the cylindrical weld strength shows a maximum value in a certain (b) olefin copolymer addition area.

Examples 3 to 12 and Comparative Example 4 After dry-blending (a) a PPS resin, (b) an olefin-based copolymer, and (c) a filler in the proportions shown in Table 1, a cylinder temperature of 280 ° C. (a hopper) Side) ~ 32
The mixture was melt-kneaded with a twin-screw extruder set at 0 ° C (tip side), pelletized with a strand cutter, and dried at 120 ° C overnight. Using such pellets, test piece weld strength, cylindrical weld strength, and bending strength were measured. The results are shown in Tables 1 and 2.

[0085]

[Table 1]

[0086]

[Table 2]

As can be seen from the results of Example 3, the combined use of glass fiber / glass beads is clearly effective in improving the cylindrical weld strength.

From Examples 4 to 6, it can be seen that the addition of the compounds indicated by d1 to d3 is also effective in improving the cylindrical weld strength.

[0089]

As described above, the present invention provides a polyphenylene sulfide resin composition having an extremely high weld strength, particularly an extremely high weld strength formed on the side surface of a cylindrical portion, and an injection molded article thereof.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an evaluation sample used for measuring a cylindrical weld strength in Examples.

[Explanation of symbols]

1. 2. cylindrical shaped piece, 2.8 divided metal piece (wedge-shaped hole in the center), 3. metal rod; 4. weld part; Weld part a. Pin gate position, b. Pin gate position

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/5415 C08K 5/5415 7/04 7/04 // (C08L 81/02 (C08L 81/02 23 : 00 23:00 33:06 33:06 101: 06 101: 06 63:00) 63:00) B29K 83:00 B29K 83:00 F term (reference) 4F071 AA04X AA14X AA33X AA42 AA62 AA76 AD01 AE17 AF14 AH07 AH12 AH17 BA01 BB05 BC05 4F206 AA34 AM36 JA07 4J002 AA05X BB00X BG02X CD00Y CN011 EX037 EX067 EX077 FA046 FD016 GL00 GM00 GN00 GQ00 4J100 AA00P AL00R AL02R AL03R AL04R AL10Q CA05 JA28 JA43

Claims (12)

[Claims] 1. A polyphenylene sulfide resin (a)
(B) 5 parts by weight of the olefin-based (co) polymer
A polyphenylene sulfide resin composition comprising 20 to 90 parts by weight of (c) an inorganic filler, and (b) an olefin (co) polymer,
(B) Polyphenylene comprising, as an essential component, an epoxy group-containing olefin copolymer obtained by copolymerizing an α-olefin, an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer. Sulfide resin composition. (B) ′ The copolymerization ratio of the epoxy group-containing olefin copolymer is from 52 to 95% by weight of α-olefin and α, β-unsaturated carboxylic acid alkyl ester in total. And α, β-unsaturated carboxylic acid alkyl ester in an amount of from 5 to 48% by weight, and (b) ′ in the epoxy group olefin-based copolymer of α-olefin and α, β-unsaturated carboxylic acid alkyl ester. 8 in total
2. The polyphenylene sulfide according to claim 1, further comprising an epoxy group-containing olefin-based copolymer in an amount of 0.5 to 15% by weight based on 5 to 99.5% by weight of the epoxy group-containing vinyl monomer. Resin composition. 3. The polyphenylene sulfide resin composition according to claim 1, wherein (c) at least one of a fibrous filler and a non-fibrous filler is contained as the inorganic filler. (C) as an inorganic filler, at least one kind of each of a fibrous filler and a non-fibrous filler is contained;
And the fibrous filler / non-fibrous filler weight ratio is 1 /
The polyphenylene sulfide resin composition according to claim 3, wherein the ratio is 3 to 3/1. 5. A non-fibrous inorganic filler which is a glassy non-fibrous inorganic filler.
The polyphenylene sulfide resin composition according to any one of the above. 6. The polyphenylene sulfide resin composition according to claim 1, wherein (a) a substantially linear polyphenylene sulfide resin is used as the polyphenylene sulfide resin. 7. A method according to claim 1, wherein (a) a polyphenylene sulfide resin having a melt viscosity (310 ° C., shear rate 1,000 / sec) of 100 to 400 Pa · s is used as the polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to the above. 8. An alkoxysilane compound selected from (d) an epoxy group, an amino group, a ureide group and an isocyanate group, and (a) a polyphenylene sulfide resin
The polyphenylene sulfide resin composition according to any one of claims 1 to 7, wherein the polyphenylene sulfide resin composition is added in an amount of 0.1 to 5 parts by weight based on parts by weight. 9. The method according to claim 1, wherein (e) a polyfunctional epoxy compound having two or more epoxy groups in one molecule is compounded in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin (a). The polyphenylene sulfide resin composition according to any one of claims 1 to 8. 10. (a) Polyphenylene sulfide resin 1
A polyphenylene sulfide resin composition comprising (b) 5 to 15 parts by weight of an olefin (co) polymer and (c) 20 to 90 parts by weight of an inorganic filler with respect to 00 parts by weight; A polyphenylene sulfide resin composition for an injection-molded article having a cylindrical portion, which contains at least one olefin copolymer containing an epoxy group as the olefin (co) polymer. 11. The polyphenylene sulfide resin composition according to claim 1, which is for an injection molded article having a cylindrical portion. 12. A molded article having a cylindrical portion, obtained by injection molding the polyphenylene sulfide resin composition according to claim 10.