JP2001261831A - Production method for polyarylene sulfide resin, and polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyarylene sulfide resin which is excellent in strength and toughness, decreased in the amount of deposits left on a metal mold when injection molded, and is advantageous in term of cost, and to provide a polyarylene sulfide resin composition based on the resin. SOLUTION: This production method comprises treating a polyarylene sulfide resin having an ash content of 0.2 wt.% or lower at a temp. of 100 deg.C or higher under a reduced pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyarylene sulfide resin and a polyarylene sulfide resin composition, and more particularly, to a method for efficiently producing a polyarylene sulfide resin having less adhesion to a mold during injection molding. Method, and with less mold deposits during injection molding, excellent toughness and strength, textile applications, film applications, injection molding applications, extrusion applications, blow molding applications,
The present invention relates to a polyarylene sulfide resin composition widely applicable to various uses such as tube and pipe molding.

[0002]

2. Description of the Related Art Polyarylene sulfide resin represented by polyphenylene sulfide has heat resistance, chemical resistance,
It is an engineering plastic with excellent flame retardancy, electrical properties and mechanical properties, and is widely used in various applications such as fibers, films, injection molding and extrusion molding.

[0003] However, polyarylene sulfide resin is sometimes insufficient in toughness in comparison with other crystalline engineering plastics such as nylon and polybutylene terephthalate, and its improvement has been studied so far. .

[0004] That is, as a conventional example of a means for improving the toughness of a polyarylene sulfide resin, (1). A method of blending an olefin resin or an elastomer having a functional group such as an epoxy group or an acid anhydride group (for example,
JP-A-153343, JP-A-62-153344, JP-A-62-169854, JP-A-62-1
72056) and (2). A method of adding an organic additive having an epoxy group, an amino group, an isocyanate group and the like (for example, JP-A-63-251430,
JP-A-3-124453, JP-A-4-723554
Publication No.) and the like.

However, in each of the above-mentioned prior arts, the effect of improving the toughness and strength of the polyphenylene sulfide resin is still not sufficient, and there remains a problem that a large amount of metal adheres during injection molding.

On the other hand, many methods for improving various characteristics by heat-treating a polyphenylene sulfide resin have been proposed in the past. For example, US Pat. A method of performing a heat treatment under an atmosphere, and Japanese Patent Application Laid-Open No. 3-41152 discloses a method of performing a heat treatment of a polyphenylene sulfide resin under an inert gas atmosphere.
Each is disclosed. But with these methods,
The toughness and strength of the polyphenylene sulfide resin could not be sufficiently improved.

Japanese Patent Application Laid-Open No. H11-323130 discloses a method of heat treating a polyphenylene sulfide resin under reduced pressure. This method aims at improving the film forming property of the polyphenylene sulfide resin. There is no mention of improvement in toughness and strength.

[0008]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above.

Therefore, an object of the present invention is to provide a method for efficiently producing a polyarylene sulfide resin having a small amount of mold adherence during injection molding, and a method of reducing the amount of mold adherence during injection molding and improving toughness and strength. An object of the present invention is to provide an excellent polyarylene sulfide resin composition.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, a polyarylene sulfide resin having an ash content (metal content) of a specific amount or less has been obtained. Only when performing high-temperature decompression treatment at a temperature, it is possible to obtain a polyarylene sulfide resin that meets the above-described object, and by blending a specific compounding agent into the polyarylene sulfide resin obtained by such a method, The present inventors have found that the object can be effectively achieved, and arrived at the present invention.

That is, according to the present invention, the ash content is 0.2% by weight.
The following polyarylene sulfide resin was added under reduced pressure to 10
An object of the present invention is to provide a method for producing a polyarylene sulfide resin, which comprises performing a high-temperature decompression treatment at a temperature of 0 ° C. or higher.

Further, the method for producing a polyarylene sulfide resin according to the present invention is a method for producing a polyarylene sulfide resin having an ash content of 0.2% by weight or less and an alkaline earth metal ion content of 100 ppm or less under reduced pressure. It is more preferable to perform high-temperature decompression treatment at a temperature of not less than ℃ in order to achieve the object.

Further, in the method for producing a polyarylene sulfide resin according to the present invention, it is preferable that the polyarylene sulfide resin is a powder or granules, and that the polyarylene sulfide resin is a powder or granules, The polyarylene sulfide resin having a particle size of 1000 μm or less, the step (1) of polymerizing a polyhalo compound and a sulfur source in an aprotic polar organic solvent at a temperature of 240 ° C. or more, and (2) the obtained polyarylene sulfide resin The polymer is obtained by a polymerization method including a step of extracting an arylene sulfide resin from a pressurized state of 240 ° C. or more under normal pressure and recovering a polymer, and performing the high-temperature decompression treatment under a reduced pressure of 6.665 kPa (50 mmHg) or less. Lower one
Performing at a temperature of 20 ° C. or higher for 0.5 to 100 hours is a preferable condition.

The polyarylene sulfide resin composition of the present invention comprises (B) an epoxy group and (B) an epoxy group, based on 100 parts by weight of the polyarylene sulfide resin obtained by the above method.
A compound having at least one type of functional group selected from an amino group, an isocyanate group and an acid anhydride group is added in an amount of 0.05%.
５０50 parts by weight.

Further, the polyarylene sulfide resin composition of the present invention is based on (C) an epoxy group, an amino group, an isocyanate group and an acid anhydride based on 100 parts by weight of the (A) polyarylene sulfide resin obtained by the above method. It is also characterized in that 10 to 400 parts by weight of a filler surface-treated with a compound having at least one kind of functional group selected from the group consisting of the same is blended.

Further, the polyarylene sulfide resin composition of the present invention comprises (A) 5 to 95% by weight of the polyarylene sulfide resin obtained by the above method, and (D) a thermoplastic resin other than the polyarylene sulfide resin. (Excluding those contained in the above (B)) (95 to 5% by weight).

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The polyarylene sulfide resin used in the present invention refers to a repeating unit represented by the following structural formula:
A polymer containing at least 90 mol%, more preferably at least 90 mol%,

[0019]

Embedded image If the content of the repeating unit is less than 70 mol%, heat resistance tends to be impaired. In the polyarylene sulfide resin, less than 30 mol% of the repeating unit can be constituted by a repeating unit having the following structural formula.

[0020]

Embedded image The melt viscosity of the polyarylene sulfide resin used in the present invention is not particularly limited as long as melt kneading is possible,
Usually, a material having a viscosity of 2 to 2,000 Pa · sec (310 ° C., a shear rate of 1,000 / sec) is used.
Those having a range of 0 Pa · sec are more preferably used.

The polyarylene sulfide resin is as follows:
A generally known method, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, JP-B-52-12240, and JP-A-61-73.
It can be produced according to a method for obtaining a polymer having a relatively large molecular weight described in JP-A No. 32, and the like.

In the present invention, the polyarylene sulfide resin which is subjected to high-temperature decompression treatment at a temperature of 100 ° C. or more under reduced pressure can obtain excellent effects of improving toughness and strength and reducing adhesion to a mold by such treatment. In the above, the ash content needs to be 0.2% by weight or less,
%, More preferably 0.10% by weight or less.
The content is more preferably not more than 0.07% by weight, and still more preferably not more than 0.07% by weight. The polyarylene sulfide resin having an ash content exceeding the above range was added under reduced pressure to 100
Even if the high-temperature decompression treatment is performed at a temperature of not less than ° C., the desired effects of the present invention cannot be sufficiently obtained.

Here, the ash content refers to the amount of the inorganic component in the polyarylene sulfide resin obtained by the following method.

(1) 5 to 6 g of a polyarylene sulfide resin is weighed in a platinum dish calcined and cooled at 583 ° C.

(2) Pre-baking the polyarylene sulfide resin together with a platinum dish at 450 to 500 ° C.

(3) A pre-fired polyarylene sulfide resin sample together with a platinum dish is placed in a muffle furnace set at 583 ° C. and fired for about 6 hours until completely incinerated.

(4) After cooling in a desiccator, weigh it.

The ash content is calculated by the formula (5): ash content (% by weight) = (weight of ash (g) / sample weight (g)) × 100.

As a method of reducing the ash content in the polyarylene sulfide resin, a method of washing the polyarylene sulfide resin with an organic solvent, a method of washing with hot water, a method of treating with an acidic solution, and a method of combining these are used. Among them, a method of treating with an acidic solution is most preferable.

As a specific method for washing the polyarylene sulfide resin with an organic solvent, the following method can be exemplified. That is, the organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the polyarylene sulfide resin, for example, N-methylpyrrolidone, dimethylformamide, a nitrogen-containing polar solvent such as dimethylacetamide, dimethyl Sulfoxides, sulfoxide-sulfone solvents such as dimethyl sulfone, acetone, methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, ether solvents such as tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, Halogen solvents such as dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol Propylene glycol, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, and benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. Also,
These organic solvents are used in one kind or in a mixture of two or more kinds.

As a method of washing with an organic solvent, there is a method of immersing a polyarylene sulfide resin in an organic solvent, and it is also possible to agitate or heat as appropriate, if necessary. The washing temperature for washing the polyarylene sulfide resin with an organic solvent is not particularly limited, and an arbitrary 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 is usually obtained at a cleaning temperature of normal temperature to 150 ° C. The polyarylene sulfide resin that has been subjected to the organic solvent washing is preferably washed several times with water or hot water in order to remove the remaining organic solvent.

As a specific method for treating the polyarylene sulfide 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 preferable chemical modification effect of the polyarylene sulfide resin by hot water washing. The operation of the hot water treatment is usually performed by charging a predetermined amount of polyarylene sulfide resin into a predetermined amount of water, and heating and stirring the mixture at normal pressure or in a pressure vessel. The proportion of the polyarylene sulfide resin and water is preferably as high as possible, but usually a bath ratio of 200 g or less of the polyarylene sulfide resin per liter of water is selected.

As a specific method for treating the polyarylene sulfide resin with an acid, the following method can be exemplified. That is, there is a method of immersing the polyarylene sulfide 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 a function of decomposing the polyarylene sulfide resin.Halo substitution such as aliphatic saturated monocarboxylic acid such as formic acid, acetic acid, propionic acid, and butyric acid, chloroacetic acid, and dichloroacetic acid. Aliphatic unsaturated 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,
Dicarboxylic acids such as phthalic acid and fumaric acid, and sulfuric acid,
Inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid are exemplified. Among these acids, acetic acid and hydrochloric acid are more preferably used. The acid-treated polyarylene sulfide resin is preferably washed several times with water or hot water in order to remove residual acids or salts. 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 polyarylene sulfide resin by the acid treatment is not impaired.

When hard water containing an alkaline earth metal is used as the washing water, for example, the alkaline earth metal is incorporated into the polyarylene sulfide resin. Even if the polyarylene sulfide resin containing such an alkaline earth metal is subjected to a high-temperature decompression treatment, the effects intended by the present invention may not be sufficiently exhibited, so that the alkaline earth metal in the polyarylene sulfide resin may be insufficient. The ion content is desirably 100 ppm or less, and 50 ppm or less.
It is more desirable that:

When the polyarylene sulfide resin is subjected to molding, a method of once melting and pelletizing is often employed. Even if such a polyarylene sulfide resin in the form of a pellet is subjected to high-temperature decompression treatment at a temperature of 100 ° C. or more under reduced pressure, the effects of the present invention can be obtained to some extent, but a more excellent effect of improving toughness and strength, and reducing adhesion of molds. In order to obtain the effect, it is preferable that the polyarylene sulfide resin subjected to high-temperature decompression treatment at a temperature of 100 ° C. or more under reduced pressure has a powder or granular shape.

Further, the weight average particle diameter of the polyarylene sulfide resin powder or granules is preferably 1,000 μm or less, more preferably 700 μm or less.

In the present invention, the weight average particle diameter is defined as
This is a value measured using a vibrating sieve using six types of sieves of 20 to 330 mesh.

Further, as a polyarylene sulfide resin which is subjected to high-temperature decompression treatment at a temperature of 100 ° C. or more under reduced pressure,
It is effective to use a polyarylene sulfide resin obtained by a polymerization method including the following steps (1) and (2).

(1) a step of polymerizing a polyhalo compound and a sulfur source in an aprotic polar organic solvent at a temperature of 240 ° C. or more; and (2) a step of subjecting the obtained polyarylene sulfide resin to a pressurized state of 240 ° C. or more. And recovering the polymer by extracting the polymer under normal pressure.

By applying such a method, a polyarylene sulfide resin having a relatively small particle diameter can be obtained. Also, the polyarylene sulfide resin produced by such a method is gradually cooled after polymerization,
Compared to a polyarylene sulfide resin produced by growing particles, the cooling step time is shortened, which is advantageous in terms of production cost, but tends to increase the content of low molecular weight components such as oligomers. However, many of them are removed by performing the high-temperature decompression treatment of the present invention. Therefore, by combining the above-described production process and high-temperature decompression treatment, it is possible to produce a polyarylene sulfide resin resin with little adhesion to a mold and excellent toughness and strength when a resin composition is formed, at low cost. .

Next, the high temperature decompression treatment of the polyarylene sulfide resin resin in which the ash content and the alkaline earth metal content are reduced in the present invention will be described.

As the depressurizing conditions of the high-temperature depressurizing treatment, the internal pressure of the depressurizing vessel is set at 6.665 kPa (50) in order to obtain a more excellent effect of improving toughness and strength and an effect of reducing the adhesion of the mold.
mmHg) or less, preferably 2.666 kPa (20 m
mHg) or less, more preferably 1.333 kPa (1
0 mmHg) or less, still more preferably 0.6665 k
It is desirable that the pressure be Pa (5 mmHg) or less.

The temperature condition of the high-temperature decompression treatment depends on the degree of decompression, but it must be at least 100 ° C., preferably in the range of 120 to 250 ° C.,
A range of 30 ° C. is more preferred, above 200 ° C.
A range up to ° C is even more preferred.

The processing time of the high-temperature decompression treatment depends on the degree of decompression and the temperature, but is preferably in the range of 0.5 to 100 hours, more preferably in the range of 1 to 70 hours, and more preferably in the range of 1 to 24 hours.
A time range is even more preferred.

The high-temperature decompression apparatus is not particularly limited, but a rotary or high-temperature decompression apparatus equipped with a stirring blade is preferably used.

Thus, by subjecting a polyarylene sulfide resin satisfying the above ash condition to a high-temperature decompression treatment under the above conditions, it is possible to obtain a polyarylene sulfide resin in which the amount of metal deposits during injection molding is extremely reduced.

Next, the polyarylene sulfide resin composition of the present invention will be described.

With respect to (A) the polyarylene sulfide resin obtained by the above-mentioned production method, (B) an epoxy group,
Polyarylene sulfide which is superior in toughness and strength and has reduced adhesion to a mold during injection molding by blending a compound having at least one functional group selected from an amino group, an isocyanate group and an acid anhydride group. A resin composition can be obtained.

Such a compound (B) having at least one functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group contains at least one of the above functional groups in one molecule. There is no particular limitation as long as it has a compound.

The amount of the compound (B) having at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group and an acid anhydride depends on the kind of the additive. Resin 100
The range of 0.05 to 50 parts by weight is selected with respect to parts by weight.

Specific examples of the compound (B) having at least one functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group include (a)
Epoxy group, acid anhydride group-containing olefin polymer,
(B) an organic silane compound containing an epoxy group, an amino group and an isocyanate group; (c) a polyfunctional epoxy compound having two or more epoxy groups in one molecule (excluding those contained in (a) and (b)) , (D) a polyisocyanate compound, and (e) others.

Specific examples of (a) an olefin polymer containing an epoxy group and an acid anhydride group include the following compounds.

As the olefin polymer having an epoxy group, 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 is subjected to epoxy oxidation. And the like.

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.

As specific examples of such α-olefin,
Ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, decene-1 and octene-1
And the like, and two or more of these can be used simultaneously. Among them, ethylene is particularly preferably used.

On the other hand, the glycidyl ester of an α, β-unsaturated acid is represented by the general formula

[0057]

Embedded image (Where R represents a hydrogen atom or a lower alkyl group)
And specific examples thereof include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably 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
It is preferably in the range of 0.5 to 40% by weight, especially 3 to 30% by weight.

In the present invention, as the epoxy group-containing olefin-based polymer, α-olefin and α, β-
In addition to the glycidyl ester of an unsaturated acid, an epoxy group-containing olefin copolymer containing a monomer represented by the following general formula as a copolymer component is also preferably used.

[0061]

Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Is a group selected from a —COOR ² group, a —CN group and an aromatic group. R ² represents an alkyl group having 1 to 10 carbon atoms. Specific examples of the monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, Α, such as t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate;
β-unsaturated carboxylic acid alkyl ester, acrylonitrile, styrene, α-methylstyrene, styrene in which the aromatic ring is substituted with an alkyl group, acrylonitrile-styrene copolymer, and the like. Can also.

The olefin copolymer comprises an α-olefin, a glycidyl ester of an α, β-unsaturated acid,
Any of random, alternating, block and graft copolymerization modes of the above monomers may be used. For example, a random copolymer of an α-olefin and a glycidyl ester of an α, β-unsaturated acid may be used. May be a copolymer in which two or more copolymerization modes are combined, such as a copolymer obtained by graft copolymerization.

The copolymerization ratio of the olefin copolymer depends on the desired effect, polymerizability, gelation,
Glycidyl ester of α-olefin / α, β-unsaturated acid = 6 from the viewpoint of heat resistance, fluidity, influence on strength, etc.
A range of 0 to 99% by weight / 40 to 1% by weight is preferably selected. Further, the copolymerization ratio of the above-mentioned monomer is 9% in total of glycidyl ester of α-olefin and α, β-unsaturated acid.
A range in which the amount of the monomer is 5 to 60% by weight based on 5 to 40% by weight is preferably selected.

Further, as another preferred embodiment of the epoxy group-containing olefin 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-
An aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as A, (A-B-) _4- Si, or ABABA. Further, the partially hydrogenated block copolymer is obtained by hydrogenating the above 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 a conjugated diene compound containing 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 (the monomer component increases or decreases along the molecular chain), may be partially block-shaped or any combination thereof, and may be a polymer block mainly composed of an aromatic vinyl compound; When there are two or more polymer blocks each containing a conjugated diene compound as a main component,
Each polymer block may have the same structure or different structures.

The aromatic vinyl compound constituting the block copolymer is, for example, one or two of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, 1,1-diphenylethylene and the like. The above can be selected, and among them, styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene and 2,3-dimethyl-
One or more kinds are selected from 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 5 to 5.
A range of 65% is preferred, especially preferred is 10-50%
Range.

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 method include JP-B-42-8704 and JP-B-43-6-6.
Although the method described in JP-A-636 can be adopted, it was synthesized using a titanium-based hydrogenation catalyst exhibiting particularly excellent performance in weather resistance and heat deterioration resistance of the obtained hydrogenated block copolymer. Hydrogenated block copolymers are most preferred. For example, JP-A-59-133203 and JP-A-6-133203
According to the method described in JP-A-0-79005, a hydrogenated block copolymer is synthesized by hydrogenating a block copolymer having the above structure in the presence of a titanium-based hydrogenation catalyst in an inert solvent. can do. At this time, 0 to 99 of the aliphatic double bond based on the conjugated diene compound of the aromatic vinyl compound-conjugated diene compound block copolymer.
% Hydrogenated, preferably from 0 to 70% hydrogenated. These block copolymers and partially hydrogenated block copolymers are already on the market and can be easily obtained.

Next, the epoxidized diene-based block copolymer usable in the present invention is a conjugated diene compound obtained by reacting an epoxidizing agent with a block copolymer having the above-mentioned structure or a partially hydrogenated block copolymer. Epoxidized aliphatic double bond based on The epoxidized diene-based block copolymer that can be 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. Can be obtained. To obtain a catalytic effect by using a mixture of formic acid, peracetic acid, and perbenzoic acid with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. Can be. 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-based 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, and It can be performed by a direct desolvation method or the like.

The degree of epoxidation of the epoxidized diene 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, particularly preferably 1.0% by weight. It is preferably at least 5% by weight. When the oxirane oxygen concentration is in the above range, the impact resistance and appearance properties of the polyarylene sulfide resin composition are good, delamination is suppressed, and stable heat resistance is obtained, which is preferable.

Examples of other functional group-containing olefin polymers which can be used in the present invention include polyethylene, polypropylene, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer and the like. And α-olefin copolymer,
Polystyrene, ethylene-propylene copolymer, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer ( SIS), polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-ethylene / butylene-styrene block copolymer (SEB)
S), polystyrene-based (co) polymers such as styrene-ethylene-propylene-styrene block copolymer (SEPS) and the ethylene-α-olefin-based copolymer described above, and maleic anhydride and succinic anhydride. Olefin-based copolymers obtained by copolymerizing an acid anhydride such as an anhydride and fumaric anhydride. Specific examples thereof include an ethylene-maleic anhydride copolymer and an ethylene-butene-maleic anhydride copolymer. Polymer, ethylene-propylene-maleic anhydride copolymer, ethylene-hexene-maleic anhydride copolymer, ethylene-octene-maleic anhydride copolymer, propylene-maleic anhydride copolymer or anhydride Maleic acid-modified SBS, SIS, SEBS, S
EPS, ethylene-ethyl acrylate copolymer and the like can be exemplified.

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

Compounding when the above-mentioned (a) olefin polymer containing an epoxy group and an acid anhydride group is used as a compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group. The quantity is
For 100 parts by weight of polyarylene sulfide resin, 1
A range of ~ 50 parts by weight is selected, with a range of 5-30 parts by weight being more preferred.

Next, specific examples of (b) an organic silane compound containing an epoxy group, an amino group and an isocyanate group include:
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,
Epoxy-containing alkoxysilane compounds such as 4-epoxycyclohexyl) ethyltrimethoxysilane;
Ureido group-containing alkoxysilane compounds such as ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanato Propyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane Such as isocyanato group-containing alkoxysilane compounds, γ
Examples include amino-containing alkoxysilane compounds such as-(2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane.

As the compound having at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group and an acid anhydride group, (b) a composition in the case of using an organic silane compound containing an epoxy group, an amino group and an isocyanate group. The amount is selected from the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin.
A range of 5 to 5 parts by weight is more preferred.

Specific examples of (c) 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, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, their halogen-substituted and alkyl-substituted products, butanediol, ethylene glycol, erythrit, novolak, glycerin, polyoxyalkylene, etc. Glycidyl ethers synthesized from compounds containing two or more hydroxyl groups in the molecule and epichlorohydrin, glycidyl esters such as glycidyl phthalate, aniline, diaminodiphenylmethane, metaxylenediamine, 1,3-bisaminimethyl Glycidylamine resins such as glycidylamine synthesized from primary or secondary amines such as cyclohexane and epichlorohydrin, epoxidized soybean oil, vinylcyclohexyl Examples include non-glycidyl epoxy resins such as sendioxide and dicyclopentadienedioxide. Among them, polyfunctional phenol type epoxy resins are preferable, and orthocresol novolac glycidyl ether is particularly preferable.

As the compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group, (c) a polyfunctional epoxy compound having two or more epoxy groups in one molecule is used. The blending amount in the case is selected from the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin,
A range of 5 to 5 parts by weight is more preferred.

Further, specific examples of the polyisocyanate compound (d) include 2,4-TDI (2,4-tolylene diisocyanate), 2,6-TDI (2,6-tolylene diisocyanate), and MDI (diphenylmethane). −
4,4'-diisocyanate, polymethylene polyphenyl polyisocyanate and the like can be exemplified.

When the polyisocyanate compound (d) is used as the compound having at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group and an acid anhydride group, the compounding amount is 100 parts by weight of a polyarylene sulfide resin. The range of 0.05 to 10 parts by weight is selected with respect to parts, and the range of 0.05 to 5 parts by weight is more preferable.

Examples of the above (e) other compounds include silicone oils modified with epoxy groups, amino groups, isocyanate groups, and acid anhydride groups, polysiloxane rubbers, polyphenylene oxide resins, fluororubbers, and fluororesins.

The compound having at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group and an acid anhydride group may be used in combination of two or more.

Further, (C) a compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group is added to (A) the polyarylene sulfide resin obtained by the above-mentioned production method. By blending the filler surface-treated with the above, it is possible to obtain a polyarylene sulfide resin composition which is more excellent in toughness and strength and which has reduced adhesion to a mold during injection molding.

Examples of the surface treating agent for the filler (C) include the above-mentioned (b) an organic silane compound containing an epoxy group, an amino group, and an isocyanate group, and (c) a polysilane having two or more epoxy groups in one molecule. Functional epoxy compounds (excluding those contained in (a) and (b)), and (e)
In addition to the polyisocyanate compound, an organic titanate compound and an organic borane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group can be exemplified. These may be used in combination of two or more.

The fillers treated with these surface treatment agents include glass fiber, carbon fiber, potassium whisker, titanate whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, Fibrous fillers such as asbestos fiber, masonry fiber, metal fiber, walasteinite, zeolite, sericite,
Mica, talc, kaolin, clay, pyrophyllite, bentonite, asbestos, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide,
Metal compounds such as zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide Materials, glass beads, ceramic beads, non-fibrous fillers such as boron nitride, silicon carbide, graphite, carbon black, dolomite and silica. These may be hollow, and furthermore, two kinds of these fillers may be used. These can be used together.

The amount of the filler (C) surface-treated with a compound having at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group and an acid anhydride is determined by the amount of the polyarylene sulfide resin A range of 10 to 400 parts by weight is selected with respect to parts by weight.

Further, (A) a polyarylene sulfide resin obtained by the above-mentioned production method and (D) a thermoplastic resin other than the polyarylene sulfide resin (provided that (B) the epoxy group, amino group, isocyanate group and acid group) A resin composition obtained by mixing a compound having at least one functional group selected from anhydride groups (excluding those contained in a compound having at least one functional group) is also useful.

At this time, (D) a thermoplastic resin other than the polyarylene sulfide resin and (B) a compound having at least one kind of functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group are used. It is desirable to use them together.

(A) a polyarylene sulfide resin,
(D) The blending ratio of the thermoplastic resin other than the polyarylene sulfide resin is in the range of (A) 95 to 5% by weight of the polyarylene sulfide resin and (D) 5 to 95% by weight of the thermoplastic resin other than the polyarylene sulfide resin. Selected,
(A) 95 to 50% by weight of a polyarylene sulfide resin, (D) a range of 5 to 50% by weight of a thermoplastic resin other than the polyarylene sulfide resin, and (A) 95 to 70% by weight of a polyarylene sulfide resin, D)
Thermoplastic resins other than polyarylene sulfide resin
A range of 30% by weight is more preferred.

Specific examples of the thermoplastic resin (D) other than the polyarylene sulfide resin include polyphenylene oxide, polysulfone, polyethylene tetrafluoride, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, and polyetherketone. , Polythioetherketone, polyetheretherketone, phenolic resin, nylon 6, nylon 6
6, nylon 610, nylon 11, nylon 12, aromatic nylon, polybutylene terephthalate, polyethylene terephthalate, polycyclylhexyl dimethylene terephthalate, ABS resin, polyamide elastomer, polyester elastomer, and polyalkylene oxide.

In the polyarylene sulfide resin composition of the present invention, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds, talc, and the like, as long as the effects of the present invention are not impaired. Crystal nucleating agents such as kaolin, organic phosphorus compounds, polyetherketone, polyetheretherketone, release agents such as polyolefin compounds, silicone compounds, long-chain aliphatic ester compounds, long-chain aliphatic amide compounds, and hinders Dophenolic compounds,
Antioxidants such as hindered amine compounds, heat stabilizers, lubricants such as calcium stearate, aluminum stearate, lithium stearate, UV inhibitors,
Conventional additives such as colorants, flame retardants and blowing agents can be added.

The method for preparing the polyarylene sulfide resin composition of the present invention is not particularly limited, and the mixture of the raw materials is mixed with a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. And kneading at a temperature of 280 to 380 ° C. as a typical example. There is no particular limitation on the mixing order of the raw materials, and a method in which all the raw materials are blended and then melt-kneaded according to the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are further blended and melt-kneaded Or a method of mixing some of the raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading with a single-screw or twin-screw extruder. Also, for the small amount of additive components,
After kneading other components by the above method and pelletizing,
Of course, it is also possible to add before molding and to provide for molding.

The polyarylene sulfide resin and the polyarylene sulfide resin composition obtained by the present invention are:
It can be applied to various applications such as film applications, fiber applications, injection molding applications, extrusion molding applications, blow molding applications, tube and pipe molding applications. It is particularly suitable for injection molding applications because the amount of mold deposits during injection molding is reduced.

Specific examples of uses of the molded article obtained from the polyarylene sulfide resin and the polyarylene sulfide resin composition of the present invention include sensors, LED lamps, connectors, sockets, resistors, relay cases,
Switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD Carriage, FDD chassis, motor brush holder,
Electric and electronic components such as motor insulators, parabolic antennas, and computer-related components; V
TR parts, TV parts, irons, hair dryers,
Rice cooker parts, microwave parts, acoustic parts, audio equipment
Home and office electrical product parts such as audio equipment parts such as laser disk (registered trademark) and compact disk, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc .; office computer related parts, telephone related Parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, machine-related parts represented by lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machinery-related Parts; tap faucet, mixing faucet,
Pump parts, pipe joints, water control valves, relief valves, hot water temperature sensors, water flow sensors, water supply parts such as water meter housings; valve alternator terminals, alternator connectors, IC regulators,
Potentiometer base for light drier, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, Exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, radiator motor Brush holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter Switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector, lamp housing,
Examples thereof include automobile / vehicle-related parts such as brake pistons, solenoid bobbins, engine oil filters, ignition device cases, vehicle speed sensors, cable liners, and various other uses.

[0096]

EXAMPLES 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 bending strength,
The following methods were used to evaluate the Izod impact strength and the adhesion of the mold during injection molding. [Bending strength] It was evaluated according to ASTM D790. [Notched Izod Impact Strength] ASTM D256
It evaluated according to. [Measurement of Deposits on Mold During Injection Molding] As the mold, an ASTM No. 1 test piece having gates at both ends and forming a weld portion (a portion where the molten resin abuts from both sides) in the center was used. The mold was set in an injection molding machine (resin set temperature 330 ° C., mold temperature 130 ° C.), and firstly oil on the mold surface was sufficiently wiped off with a gauze impregnated with an organic solvent. Next, a predetermined material was molded for 100 to 500 shots, and then components adhering to the mold surface near the weld portion were wiped off with gauze impregnated with an organic solvent. Adhered components were extracted from the gauze by chloroform-Soxhlet extraction and analyzed by gas chromatography (column: DB-5).
(Manufactured by J & W), temperature rise profile: initial temperature 80 ° C,
Heating rate 0.6 ° C / min, final temperature 300 ° C, holding time at 300 ° C for 60 minutes, injection temperature: 300 ° C,
From the comparison of the detector: FID, carrier gas: helium) and the total peak intensity, a relative comparison of the amount of attached matter was performed.

First, the following materials (A) to (D) were prepared. (A) Polyarylene sulfide resin PPS / a1: 6.005 kg (25 mol) of sodium sulfide / 9-hydrate, 0.656 kg (8 mol) of sodium acetate and N-methyl- 2-pyrrolidone (hereinafter abbreviated as NMP) 5k
g, and the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled off. Next, the reaction vessel is
After cooling to 80 ° C., 3.734 of 1,4-dichlorobenzene
kg (25.4 mol) and 3.7 kg of NMP were added, the mixture was sealed under nitrogen, heated to 272 ° C, and reacted at 272 ° C for 2 hours. Thereafter, the reaction solution at 272 ° C. was flashed (released to normal pressure) while being heated and kept at 250 ° C. with a cooling condenser to obtain a mixed powder of polyarylene sulfide and salts. This was slurried with 15 liters of ion-exchanged water at 70 ° C. and filtered with a centrifuge. An appropriate amount of the obtained cake, 15 liters of ion-exchanged water and glacial acetic acid (so that the pH of the washing liquid after washing becomes 3.7) is charged into an autoclave equipped with a stirrer, sealed under nitrogen gas, and heated to 190 ° C. The temperature was raised, and after reaching 190 ° C., it was cooled to 70 ° C. The obtained slurry was filtered with a centrifuge, washed with ion exchanged water at 80 ° C.
Drying with hot air at 80 ° C for 2 hours and 80 ° C for 24 hours PPS / a
2.57 kg was obtained.

The resulting PPS / a1 has a viscosity of 50 Pa
・ Sec (320 ° C., shear rate 1000 / s), ash content: ash content: 0.05% by weight, alkaline earth metal content: 5 p
pm or less, and the weight average particle diameter was 400 μm. PPS / a2: Into an autoclave equipped with a stirrer equipped with a valve at the bottom, 6.005 kg (25 mol) of sodium sulfide / 9-hydrate, 0.656 kg (8 mol) of sodium acetate and 5 kg of NMP were charged, and 205 g of NMP was gradually added while passing nitrogen.
The temperature was raised to ℃, and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.734 kg (25.4 mol) of 1,4-dichlorobenzene and 3.7 NMP were added.
Add kg, seal under nitrogen, raise the temperature to 272 ° C,
The reaction was performed at 272 ° C. for 2 hours. Thereafter, the reaction solution at 272 ° C. was flashed (released to normal pressure) while being heated and kept at 250 ° C. with a cooling condenser to obtain a mixed powder of PPS and salts. This is placed in 70 ° C. ion-exchanged water 15
Slurried in liters and filtered in a centrifuge. An appropriate amount of the obtained cake, 15 liters of ion-exchanged water and glacial acetic acid (so that the pH of the washing solution after washing becomes 5.5)
Charged in an autoclave equipped with a stirrer, sealed under nitrogen gas, heated to 190 ° C and heated to 190 ° C,
Cooled down. The obtained slurry was filtered with a centrifugal separator, washed with ion-exchanged water at 80 ° C, and dried with hot air at 120 ° C for 2 hours and at 80 ° C for 24 hours to obtain 2.57 kg of PPS / a2.

The viscosity of the obtained PPS / a2 is 63 Pa
・ Sec (320 ° C., shear rate 1000 / s), ash content: ash content: 0.15% by weight, alkaline earth metal content: 5 p
pm or less, and the weight average particle diameter was 400 μm. PPS / a3: In an autoclave equipped with a stirrer equipped with a valve at the bottom, 6.005 kg (25 mol) of sodium sulfide / 9-hydrate, 0.656 kg (8 mol) of sodium acetate and 5 kg of NMP were charged, and 205 g of NMP was gradually added while passing nitrogen.
The temperature was raised to ℃, and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.734 kg (25.4 mol) of 1,4-dichlorobenzene and 3.7 NMP were added.
Add kg, seal under nitrogen, raise the temperature to 272 ° C,
The reaction was performed at 272 ° C. for 2 hours. Thereafter, the reaction solution at 272 ° C. was flashed (released to normal pressure) while being heated and kept at 250 ° C. with a cooling condenser to obtain a mixed powder of PPS and salts. This is placed in 70 ° C. ion-exchanged water 15
Slurried in liters and filtered in a centrifuge. The resulting cake and 15 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, sealed under nitrogen gas, and
The temperature was raised to 0 ° C., cooled to 70 ° C. after reaching 190 ° C. The resulting slurry was filtered with a centrifuge,
Wash with ion-exchanged water at 0 ° C, 80 ° C for 2 hours,
Dry with hot air at 24 ° C for 32.57 kg PPS / a
Obtained.

The viscosity of the obtained PPS / a3 is 80 Pa ·
sec (320 ° C., shear rate 1000 / s), ash content: ash content: 0.38 wt%, alkaline earth metal content: 5 pp
m or less, and the weight average particle diameter was 400 μm. PPS / a4: In an autoclave equipped with a stirrer equipped with a valve at the bottom, 6.005 kg (25 mol) of sodium sulfide / 9-hydrate, 0.656 kg (8 mol) of sodium acetate, and 5 kg of NMP were charged, and 205 g of NMP was gradually added while passing nitrogen.
The temperature was raised to ℃, and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.734 kg (25.4 mol) of 1,4-dichlorobenzene and 3.7 NMP were added.
Add kg, seal under nitrogen, raise the temperature to 272 ° C,
The reaction was performed at 272 ° C. for 2 hours. Thereafter, the reaction solution at 272 ° C. was flashed (released to normal pressure) while being heated and kept at 250 ° C. with a cooling condenser to obtain a mixed powder of PPS and salts. This is placed in 70 ° C. ion-exchanged water 15
Slurried in liters and filtered in a centrifuge. The resulting cake, 15 liters of ion-exchanged water and appropriate amounts of glacial acetic acid and calcium acetate (so that the pH of the washing solution after washing becomes 5.5 and the calcium content becomes 100 ppm or more) are charged into an autoclave equipped with a stirrer, The vessel was sealed under nitrogen gas, heated to 190 ° C., heated to 190 ° C., and cooled to 70 ° C. after reaching 190 ° C. The obtained slurry was filtered with a centrifugal separator, and this was washed with ion exchanged water at 80 ° C.
Hot air drying at 0 ° C for 2 hours and 80 ° C for 24 hours
2.57 kg of a4 was obtained.

The viscosity of the obtained PPS / a4 is 65 Pa ·
sec (320 ° C., shear rate 1000 / s), ash content: ash content: 0.16% by weight, alkaline earth metal content: 150
ppm, weight average particle diameter: 400 μm. PPS / a5: In an autoclave equipped with a stirrer equipped with a valve at the bottom, 6.005 kg (25 mol) of sodium sulfide / 9-hydrate, 0.656 kg (8 mol) of sodium acetate and 5 kg of NMP were charged, and 205 g of NMP was gradually added while passing nitrogen.
The temperature was raised to ℃, and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.734 kg (25.4 mol) of 1,4-dichlorobenzene and 3.7 NMP were added.
Add kg, seal under nitrogen, raise the temperature to 272 ° C,
The reaction was performed at 272 ° C. for 2 hours. 25 minutes of water over 30 minutes
After the mole injection, the mixture was gradually cooled to 200 ° C. at a rate of 0.4 ° C./min. The reaction solution was slurried with 15 liters of ion-exchanged water at 70 ° C., and the operation of filtering with a centrifuge was repeated 5 times. This was washed with ion-exchanged water at 80 ° C. and dried with hot air at 120 ° C. for 2 hours and at 80 ° C. for 24 hours to obtain 2.57 kg of PPS / a5.

The viscosity of the obtained PPS / a5 is 50 Pa ·
sec (320 ° C., shear rate 1000 / s), ash content: ash content: 0.06% by weight, alkaline earth metal content: 5 pp
m or less, and the weight average particle diameter was 1200 μm. (B) Compound having at least one functional group selected from epoxy group, amino group, isocyanate group and acid anhydride group b1: ethylene / methyl acrylate / glycidyl methacrylate = 64/30/6 (% by weight) ) Copolymers. b2: maleic anhydride of ethylene propylene rubber
5% by weight graft copolymer b3: ortho-cresol novolac glycidyl ether compound [SUMI-EPOXY ESCN195HH
(Manufactured by Sumitomo Chemical Co., Ltd.)] b4: γ- (2-aminoethyl) aminopropylmethyldimethoxysilane b5: polymethylene polyphenyl polyisocyanate [“Millionate” M manufactured by Nippon Polyurethane Industry Co., Ltd.
R] (C) filler c1: glass fiber (E glass, fiber diameter 10 μm, fiber length 3 mm), γ-glycidoxypropyltrimethoxysilane treatment c2: glass fiber (E glass, fiber diameter 10 μm, fiber length 3 mm, Untreated (D) Thermoplastic resin other than polyarylene sulfide resin d1: Nylon 6 (manufactured by Toray Industries, Inc., CM1010) [Example 1, Comparative Example 1] For PPS / a1, 0.1
A high-temperature decompression treatment was performed at a temperature of 210 ° C. for 5 hours under a reduced pressure of 333 kPa.

The PPS / a1 subjected to the high temperature decompression treatment
(Example 1) and PPS /
a1 (Comparative Example 1) was subjected to injection molding to evaluate the amount of deposits on the mold.

The results were compared with each other by assuming that the total peak area intensity in gas chromatographic measurement of the deposits on the mold of Comparative Example 1 was 100%. As a result, the result was 55% in Example 1. It was found that deposits were significantly reduced. [Examples 2 to 4, Comparative Examples 2 to 4] PPS / a1 to PPS
0.1333 k for each polymer of / a5
Under a reduced pressure of Pa, a high-temperature reduced pressure treatment was performed at a temperature of 210 ° C. for 5 hours.

20 parts by weight of the ethylene / methyl acrylate / glycidyl methacrylate copolymer (b1) was dry blended with 80 parts by weight of each of the PPSs subjected to the high-temperature decompression treatment, and pre-mixed for 2 minutes by a tumbler. The mixture was melt-kneaded with a twin-screw extruder set at a temperature of 300 ° C., pelletized with a strand cutter, and dried at 120 ° C. overnight. Using these pellets, test specimens of Izod impact strength and bending strength were injection molded, and Izod impact strength and bending strength were evaluated. Table 1 shows the results.

The PPS which has not been subjected to the high temperature decompression treatment
Comparative Example 2 was a resin composition in which (b1) 20 parts by weight of an epoxy group-containing olefin copolymer was blended with 80 parts by weight of / a1.

[0108]

[Table 1] As is clear from the comparison between Example 2 and Comparative Example 2, a resin composition having significantly improved bending strength and impact strength can be obtained by performing high-temperature decompression treatment.

When PPS / a3 having a large ash content (Comparative Example 3) and PPS / a4 having a large calcium content (Comparative Example 4) are used, the effect of the high-temperature decompression treatment on the strength is clearly reduced. . [Examples 5 to 8 and Comparative Examples 5 to 7] Seven types of PPS polymers were prepared by changing PPS / a1 under the conditions of high-temperature decompression treatment as shown in Table 2.

The processing conditions of Comparative Example 7 were set to a normal pressure nitrogen atmosphere.

20 parts by weight of the ethylene / methyl acrylate / glycidyl methacrylate copolymer (b1) was dry blended with 80 parts by weight of each of the PPS polymers thus obtained, and preliminarily mixed for 2 minutes in a tumbler. Melt kneading with a twin screw extruder set at a cylinder temperature of 300 ° C., and pelletizing with a strand cutter,
This was dried at 120 ° C. overnight. Using these pellets, test specimens of Izod impact strength and bending strength were injection molded, and Izod impact strength and bending strength were evaluated. Table 2 shows the results.

[0112]

[Table 2] As can be seen from Comparative Example 4 from the results in Table 2, when the treatment temperature is 80 ° C. (Comparative Example 5), the effects intended by the present invention are hardly obtained. Further, under the processing conditions under pressure (Comparative Example 6) and under a nitrogen atmosphere (Comparative Example 7), a sufficient strength improving effect cannot be obtained. [Examples 9 to 11, Comparative Examples 8 to 10] PPS / a1 to P
0.133 for each polymer of PS / a5
A high-temperature decompression treatment was performed at a temperature of 210 ° C. under a reduced pressure of 3 kPa for 5 hours.

The PPS which has not been subjected to the high temperature decompression treatment
The case where / a1 was used was taken as Comparative Example 8.

The six types of PPS prepared as described above
For each 60 parts by weight of the polymer, (c1) 40 parts by weight of glass fiber (E glass, fiber diameter 10 μm, fiber length 3 mm) treated with γ-glycidoxypropyltrimethoxysilane was dry-blended, and the mixture was tumbled with a tumbler. After pre-mixing for 2 minutes, the mixture was melt-kneaded with a twin-screw extruder set at a cylinder temperature of 320 ° C., pelletized with a strand cutter, and dried at 120 ° C. overnight. Each of these pellets was subjected to injection molding to evaluate the amount of deposits on the mold.

Table 3 shows the results of the relative comparison, with the total peak area intensity of the deposits on the mold of Comparative Example 8 measured by gas chromatography as 100%.

[0116]

[Table 3] From the results in Table 3, it can be seen that the use of PPS subjected to high-temperature decompression treatment clearly reduces the amount of deposits on the mold during injection molding of the resin composition. [Examples 12 to 14, Comparative Example 11] Four types of PPS polymers were prepared by changing PPS / a1 under the conditions of high-temperature decompression treatment as shown in Table 4.

The processing conditions of Comparative Example 11 were set in a nitrogen atmosphere at normal pressure.

The four types of PPS prepared as described above
For each 60 parts by weight of the polymer, (c1) 40 parts by weight of glass fiber (E glass, fiber diameter 10 μm, fiber length 3 mm) treated with γ-glycidoxypropyltrimethoxysilane was dry-blended, and the mixture was tumbled with a tumbler. After pre-mixing for 2 minutes, the mixture was melt-kneaded with a twin-screw extruder set at a cylinder temperature of 320 ° C., pelletized with a strand cutter, and dried at 120 ° C. overnight. Each of these pellets was subjected to injection molding to evaluate the amount of deposits on the mold.

The results were obtained by measuring the total peak area intensity of the deposits on the mold of Comparative Example 8 by gas chromatography as 100%.
Table 4 shows the results of relative comparison as%.

[0120]

[Table 4] From the results in Table 4, it can be seen that the use of PPS subjected to high-temperature decompression treatment clearly reduces the amount of deposits on the mold during injection molding of the resin composition. However, in the heat treatment under a nitrogen atmosphere at normal pressure (Comparative Example 11), the effect of the resin composition to reduce the adhesion of the resin composition to the mold is small. [Examples 15 to 20, Comparative Examples 12 to 18] PPS / a1
Was subjected to a high-temperature decompression treatment at 210 ° C. for 5 hours under a reduced pressure of 0.1333 kPa.

For each of the PPS subjected to the high-temperature decompression treatment and the PPS not subjected to the high-temperature decompression treatment, the respective blending agents shown in Tables 5 and 6 were dry-blended at the ratios shown in Tables 5 and 6, respectively. Then in the tumbler 2
After pre-mixing for 300 minutes, cylinder temperature 300-320
The mixture was melt-kneaded with a twin-screw extruder set at a temperature of ° C, pelletized with a strand cutter, and dried at 120 ° C overnight. Using these pellets, test specimens of Izod impact strength and bending strength were injection molded, and Izod impact strength and bending strength were evaluated. The results are shown in Tables 5 and 6.

[0122]

[Table 5]

[0123]

[Table 6] As is clear from the results in Tables 5 and 6, by using PPS subjected to high-temperature decompression treatment, a resin composition having significantly improved bending strength and impact strength can be obtained.

[0124]

As described above, according to the production method of the present invention, it is possible to efficiently produce a polyarylene sulfide resin having a small amount of adhesion to a mold during injection molding.

Further, the resin composition using the polyarylene sulfide resin obtained by the production method of the present invention has excellent strength and toughness, reduces the amount of adherence to the mold at the time of injection molding, and reduces cost. It is an advantageous resin composition, and can be widely applied to various uses such as fiber use, film use, injection molding use, extrusion molding use, blow molding use, and tube / pipe molding use.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 101/06 C08L 101/06 F term (reference) 4J002 BB012 BD153 BG072 BH002 BN002 BN153 BP012 CD042 CD043 CD052 CD062 CD122 CD182 CD192 CD202 CF053 CF063 CF073 CG003 CH013 CH073 CK022 CL013 CL033 CL063 CL064 CM043 CN011 CN033 CP052 DA016 DA026 DA036 DB006 DE076 DE096 DE106 DE146 DE186 DG056 DJ006 DJ026 DJ036 BD046 DJ056 DK006 DL006 DM006 FA044 BA046 FB FB 014 FB 016 FB FB FB 016 FB FB FB FB FB FB FB FB FB FB FB CB FB BG30 BG31

Claims (9)

[Claims] 1. A method for producing a polyarylene sulfide resin, comprising subjecting a polyarylene sulfide resin having an ash content of 0.2% by weight or less to a high-temperature decompression treatment at a temperature of 100 ° C. or more under reduced pressure. 2. A polyarylene sulfide resin having an ash content of 0.2% by weight or less and an alkaline earth metal ion content of 100 ppm or less is subjected to high-temperature decompression treatment at a temperature of 100 ° C. or more under reduced pressure. The method for producing a polyarylene sulfide resin according to claim 1. 3. The polyarylene sulfide resin,
The method for producing a polyarylene sulfide resin according to claim 1, wherein the method is a powder or granules. 4. The polyarylene sulfide resin,
A powder or a granule having a weight average particle diameter of 100
The method for producing a polyarylene sulfide resin according to any one of claims 1 to 3, wherein the thickness is 0 µm or less. 5. The polyarylene sulfide resin,
The method for producing a polyarylene sulfide resin according to any one of claims 1 to 4, which is obtained by a polymerization method including the following steps (1) and (2). (1) a step of polymerizing a polyhalo compound and a sulfur source in an aprotic polar organic solvent at a temperature of 240 ° C. or more, and (2) a step of converting the obtained polyarylene sulfide resin to 24
A step of extracting the polymer from a pressurized state of 0 ° C. or more under normal pressure to recover the polymer. 6. The high-temperature decompression treatment is performed at 6.665 kPa.
The method for producing a polyarylene sulfide resin according to any one of claims 1 to 5, wherein the reaction is performed at a temperature of 120 ° C or higher under a reduced pressure of (50 mmHg) or lower for 0.5 to 100 hours. 7. A polyarylene sulfide resin (A) obtained by the method according to any one of claims 1 to 6.
(B) 0.05 to 50 parts by weight of (B) a compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group and an acid anhydride group. Polyarylene sulfide resin composition. 8. An epoxy group, an amino group, an isocyanate group and an acid (C) based on 100 parts by weight of the polyarylene sulfide resin (A) obtained by the method according to any one of claims 1 to 6. A polyarylene sulfide resin composition comprising 10 to 400 parts by weight of a filler surface-treated with a compound having at least one functional group selected from anhydride groups. 9. A thermoplastic resin other than (A) 5 to 95% by weight of the polyarylene sulfide resin obtained by the method according to claim 1 and (D) a polyarylene sulfide resin. (Excluding those contained in the above (B)) 95 to 5% by weight of the polyarylene sulfide resin composition.