JP2000319511A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin composition which has excellent mechanical strengths, especially excellent breaking toughness, excellent flexural strength, and so on. SOLUTION: A polyarylene sulfide comprises the mixture of (A) a polyarylene sulfide having an intrinsic viscosity of <=0.25 with (B) a polyarylene sulfide which has an intrinsic viscosity of >=0.30 and a mol.wt. distribution of <=10 measured by gel permeation chromatography. A polyarylene sulfide resin composition comprises the polyarylene sulfide and an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyarylene sulfide (hereinafter referred to as "PAS") and a resin composition using the same. More specifically, a PAS obtained by mixing two kinds of PAS having different intrinsic viscosities, and a resin composition of such a PAS and an inorganic filler such as glass fiber, which can be broken without lowering fluidity. The present invention relates to a resin composition having improved mechanical strength such as toughness and bending strength.

[0002]

2. Description of the Related Art PAS typified by polyphenylene sulfide has been used for automobiles, electric and electronic parts, etc. by utilizing its excellent heat resistance, flame retardancy, rigidity, solvent resistance, and electric insulation. However, for use in parts used in harsh environments such as around automobile engines, even conventional resin compositions in which PAS is compounded with glass fibers or the like still have insufficient mechanical strength.

[0003] In this case, PAS, which is usually available means
Even if the mechanical strength is increased by the method of increasing the molecular weight of, the fluidity is reduced and the moldability is deteriorated. Therefore,
There has been a demand for the development of a technique for increasing the mechanical strength without lowering the fluidity.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a PAS having excellent mechanical strength, in particular, fracture toughness and bending strength without lowering fluidity, and a resin composition comprising such a PAS and an inorganic filler. The purpose is to provide things.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been accomplished based on this finding, finding that PAS obtained by mixing two kinds of PAS having different intrinsic viscosities is particularly effective for the above purpose. It is. That is, the present invention has the following gist. [1] (A) polyarylene sulfide having an intrinsic viscosity η _inh (dl / g) of 0.25 or less, and (B) an intrinsic viscosity η
_inh (dl / g) is 0.30 or more and gel permeer
A polyarylene sulfide comprising a mixture with a polyarylene sulfide having a molecular weight distribution of 10 or less as determined by chromatography.

[2] The polyarylene sulfide according to the above [1], wherein the molecular weight distribution of the polyarylene sulfide (B) determined by gel permeation chromatography is 5 or less. [3] The polyarylene sulfide according to any of the above [1] or [2], wherein the polyarylene sulfide of (B) is a linear polyarylene sulfide.

[4] The polyarylene sulfide (A) having a molecular weight distribution of 5 or less as determined by gel permeation chromatography,
The polyarylene sulfide according to any one of [3]. [5] The polyarylene sulfide according to any one of the above [1] to [4], wherein the polyarylene sulfide of (A) is a linear polyarylene sulfide.

[6] The polyarylene according to any one of [1] to [5], wherein the polyarylene sulfides of (A) and (B) each have a chloroform-soluble content of 0.5% by weight or less. Sulfide. [7] A polyarylene sulfide resin composition obtained by blending an inorganic filler with the mixed polyarylene sulfide according to any of the above [1] to [6].

[8] An automobile part or an electric / electronic part obtained by injection molding the polyarylene sulfide or the polyarylene sulfide resin composition according to any one of the above [1] to [7].

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [PAS] Novel PAS of the present invention
Is (A) P having an intrinsic viscosity η _inh (dl / g) of 0.25 or less.
This is a PAS comprising a mixture of AS and the PAS of (B) described in detail below. (PAS as Component (B)) The PAS as component (B) in the PAS of the present invention has an intrinsic viscosity η _inh (dl / g) of 0.30 or more, preferably 0.35 or more, In addition, the molecular weight distribution determined by gel permeation chromatography (hereinafter abbreviated as "GPC") is 10 or less, preferably 5 or less, particularly preferably 3.5.
The following must be used:

The PAS obtained by mixing the PAS of (B) and the PAS of (A) satisfying the above requirements shows a necking phenomenon in a load-elongation curve in a fracture toughness test described later, It has the characteristic of having ductile fracture. This is considered to have the effect of increasing mechanical strength such as fracture toughness and Izonet impact strength. Further, when a PAS having a molecular weight distribution determined by GPC of 5 or less, particularly 3.5 or less is used, the effect is even more remarkable.

Here, the intrinsic viscosity η _inh (dl / g) is 0.30
If it is less than 7, the improvement of the toughness of the PAS mixed with the PAS of (A) is not recognized, and the object cannot be achieved. Further, when the molecular weight distribution determined by GPC exceeds 10, no improvement effect such as fracture toughness of PAS mixed with (A) is exhibited. Here, the molecular weight distribution determined by GPC means a weight average molecular weight (hereinafter abbreviated as “Mw”) and a number average molecular weight (hereinafter “Mw”) determined by GPC.
n ") (Mw / Mn). This Mw
Is from 200,000 to 200,000, especially from 20,000 to 100,000, and Mn is preferably from 0.5 to 50,000, more preferably from 30,000 to 30,000. Property can be sufficiently secured.

Next, the PAS of (B) may be a linear type, a branched type, a semi-linear type, or a cross-linked type.
Since a linear PAS generally has better mechanical strength than other types of PAS, it is often preferable to use a linear PAS. Further, the PAS of (B) is preferably a PAS having a chloroform-soluble content of 0.5 or less, more preferably 0.4 or less, especially 0.35 or less. If the chloroform-soluble content exceeds 0.5, the mechanical strength may decrease. (PAS as Component (A)) In the PAS of the present invention, as described above, the PAS as Component (A) has the object of the present invention if the intrinsic viscosity η _inh (dl / g) is 0.25 or less. The effect of improving the fracture toughness of PAS mixed with PAS of (B) is recognized. This intrinsic viscosity η _{in h} (dl /
g) is more preferably 0.23 or less.

The PAS of (A) preferably has a molecular weight distribution determined by GPC of 5 or less, more preferably 3.5 or less. Thereby, the fracture toughness is further improved. Further, the PAS of (A) may be a linear type, a branched type, a semi-linear type, or a cross-linked type. However, it is often preferable to use a linear type PAS as described in (B) above. ) Is the same as in the case of the PAS.

Further, the PAS of (A) has a chloroform-soluble content similar to that of the above-mentioned PAS of (B).
It is preferably at most 0.5% by weight, more preferably at most 0.4% by weight, particularly preferably at most 0.35% by weight. (Mixing ratio of PAS of component (A) and PAS of component (B)) The mixing ratio of (A) and (B) of the PAS of the present invention is not particularly limited, and the PAS of the present invention can be mixed at an arbitrary ratio to obtain an effect. Can be obtained. However, the PAS of (A): the PAS of (B) (weight ratio) is 95-5: 5-95, and more preferably 90-10: 1.
It is preferably from 0 to 90, particularly preferably from 90 to 50:10 to 50.

(Chemical Structure of PAS) The PAS of the present invention comprises:
Both (A) and (B) have the structural formula [-Ar-S-]
(Where Ar is an arylene group and S is sulfur). A polymer containing at least 70 mol% of a repeating unit represented by the following chemical formula (I):

[0017]

Embedded image

(Wherein R is an alkyl group having 6 or less carbon atoms,
A substituent selected from an alkoxy group, a phenyl group, a carboxyl group or a metal salt thereof, a nitro group, and a halogen atom such as fluorine, chlorine, and bromine, and m is an integer of 0 to 4. ) Is a polyarylene sulfide having 70 mol% or more of the repeating unit represented by the formula (1). If the content of the repeating unit is less than 70 mol%, the original crystalline component characteristic of a crystalline polymer is small, and the mechanical strength may be insufficient.

Furthermore, a homopolymer or a copolymer may be used. As the copolymerization structural unit, a metaphenylene sulfide unit, an orthophenylene sulfide unit, pp ′
-Diphenylene ketone sulfide unit, pp'-diphenylene sulfone sulfide, pp'-biphenylene sulfide unit, pp'-diphenylene methylene sulfide unit, pp'-diphenylene cumenyl sulfide unit, naphthyl And sulfide units.

Further, the PAS of the present invention needs to be a polymer having a substantially linear structure. However, as long as the performance is not hindered, a monomer having three or more functional groups as a part of the monomer is used. It may be a polymer having a branched structure or a crosslinked structure polymerized by using a small amount. Further, it may be used by blending it with the polymer having a substantially linear structure. [Production method of PAS] PAS of (A) and (B) of the present invention
Can be produced by the following method. That is, it is characterized in that the polymerization is carried out by introducing a fixed ratio of a raw material sulfur source and an alkali metal hydroxide such as lithium hydroxide in the polymerization step. In the polymerization step of this method, the starting dihalogenated aromatic compound is preferably polymerized by two-stage or multi-stage polymerization in which a part of a required amount is charged. In that case, the amount of water is controlled in the step of further polymerizing (main polymerization) the prepolymer obtained in the first-stage polymerization (preliminary polymerization),
To produce the PAS of (B), without adding water,
It is particularly preferable that the PAS production of (A) is performed by adding an appropriate amount of water. The specific method is shown below. (I) First method In a method for producing a PAS, a sulfur compound and a dihalogenated aromatic compound are charged into a mixture containing lithium hydroxide and a solid substance of non-lithium hydroxide in an aprotic organic solvent. (A) charging a liquid or gaseous sulfur compound into a mixture containing lithium hydroxide and a solid substance of non-lithium hydroxide in an aprotic organic solvent;
A step of directly reacting lithium hydroxide with a sulfur compound,
(B) separating a non-lithium hydroxide solid substance;
(C) a step of adjusting the sulfur content in the reaction solution, and (d) lithium hydroxide having a concentration of 21 to 100 of lithium sulfide in the reaction solution.
(E) a step of introducing a dihalogenated aromatic compound into the reaction solution to perform polycondensation, and (f) a step of containing a by-product lithium chloride.
A step of introducing an alkali metal hydroxide or an alkaline earth metal hydroxide into the AS production reaction solution, causing lithium ions to react with hydroxide ions, and recovering lithium ions as lithium hydroxide as a reaction product thereof. And a method for producing a PAS.

Hereinafter, each step will be described in order. (1) Step of Injecting Sulfur Compound (Step (a)) In the present invention, lithium hydroxide and non-hydroxylated compound are introduced into an aprotic organic solvent such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). A liquid or gaseous sulfur compound, for example, hydrogen sulfide gas is blown into a mixture containing a solid substance of lithium (for example, sodium chloride),
Lithium hydroxide is directly reacted with a sulfur compound. By this reaction, the lithium hydroxide is modified into thiolithium (LiSH) soluble in NMP, and a solid non-lithium hydroxide (eg, sodium chloride) unnecessary for NMP can be separated. It is necessary to keep the temperature in the system during this reaction at less than 150 ° C. If the temperature exceeds 150 ° C., thiolithium (LiSH) soluble in NMP further increases lithium sulfide (Li) unnecessary for NMP.
_{This is because} it is denatured to 2S) and the above-mentioned solid non-lithium hydroxide (eg, sodium chloride) unnecessary for NMP cannot be separated.

The amount of the sulfur compound to be added is selected from the range of 0.5 to 2 times mol of lithium hydroxide as sulfur atom. If it is less than 0.5 mole, lithium hydroxide partially remains, and if it exceeds 2 moles, the reaction has already reached saturation, which results in excessive addition of a highly toxic sulfur compound, which is not preferable. As the sulfur compound, hydrogen sulfide gas is preferable, and when blowing this hydrogen sulfide gas,
It may be normal pressure or pressurized. Usually, the blowing time is
It takes about 10 to 180 minutes. The blowing speed is usually about 10 to 1000 cc / min. Further, as a blowing method, for example, a general method of bubbling into a mixture containing a solid state of lithium hydroxide and non-lithium hydroxide (eg, sodium chloride) in NMP can be used while stirring.

As the aprotic organic solvent, generally, aprotic polar organic compounds (for example, amide compounds, lactam compounds, urea compounds, organic sulfur compounds,
Cyclic organic phosphorus compounds), and these can be used as a single solvent or a mixed solvent. As specific compound names, N, N-dimethylformamide, N, N-diethylformamide, N, N
N-dimethylacetamide and the like can be mentioned.

Examples of the lactan compound include N-alkylcaprolactams such as caprolactam, N-methylcaprolactan and N-ethylcaprolactane;
Examples thereof include 2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, and N-isopropyl-2-pyrrolidone. As the urea compound, tetramethyl urea,
N, N'-dimethylethylene urea and the like can be mentioned.

As the organic sulfur compound, dimethyl sulfoxide, diethyl sulfoxide, diphenyl sulfone,
1-methyl-1-oxosulfolane and the like can be mentioned. As the cyclic organic phosphorus compound, 1-methyl-1-
Oxophosphorane, 1-n-propyl-1-oxophosphorane, 1-phenyl-1-oxophosphorane and the like can be mentioned.

Among the aprotic organic solvents, N-alkylcaprolactam and N-alkylpyrrolidone are preferred, and N-methyl-2-pyrrolidone is more preferred. Further, the non-lithium hydroxide solid used in the present invention refers to a solid other than lithium hydroxide, for example, an alkali metal chloride such as sodium chloride, calcium chloride, maugnesium chloride, barium chloride, or an alkaline earth metal. Metal chloride and the like. Non-lithium hydroxide solids that can be separated in the above step include alkali metal chlorides such as sodium chloride and alkaline earth metal chlorides.

(2) Separation of Solid Non-Lithium Hydroxide (Step (b)) By adding a sulfur compound in the above step, lithium hydroxide unnecessary for NMP is dissolved in thiolithium (LiSH) which is soluble in NMP. ), It is possible to separate the solid state of non-lithium hydroxide (eg, sodium chloride) unnecessary for NMP. For this separation, a known method such as filtration using a glass filter G4 or centrifugation can be used. At the time of separation, the temperature in the system is usually 20 to 15
0 ° C. (3) Adjustment of Sulfur Content (Step (c)) In this step, excess sulfur content is removed from the reaction liquid after the separation of the non-lithium hydroxide (eg, sodium chloride) solid by hydrogen sulfide removal. At the same time, water produced as a by-product of the blowing of the hydrogen sulfide is eliminated.

That is, in order to react with the dichloroaromatic compound in the next polymerization step, the sulfur / lithium atomic ratio in the system is preferably reduced to 1/2 or less, more preferably adjusted to 1/2. . When it is larger than 1/2, the reaction hardly proceeds. Also, the presence of water in the polymerization process has the effect of promoting the reaction rather than the presence of a small amount in the former stage of oligomer formation, and it effectively functions as a phase separation agent in the later stage of polymerization. Excessive presence in both the latter and subsequent stages has the disadvantage that the oligomer is eliminated from the NMP by water (in the NMP) and the reaction is suppressed. Therefore, water is preferably 10 to 200% based on lithium hydroxide.

As a method for adjusting the sulfur content and water, a method in which the reaction solution in the system is heated and subjected to nitrogen bubbling or the like to remove it is effective. Usually, the reaction solution is
By heating to 00 ° C, thiolithium (LiSH) soluble in NMP becomes Lithium sulfide (Li ₂ S) insoluble in NMP.
This is because hydrogen sulfide is generated.

(4) Step of adding and adjusting lithium hydroxide (step (d)) In this step, lithium hydroxide is added in an amount of 21 to 100 mol based on lithium sulfide (Li ₂ S) generated in the reaction solution. %
Adjust so that it exists at the ratio of Therefore, lithium hydroxide is added to the raw material dichloroaromatic compound required for polycondensation and lithium sulfide (Li ₂ S) as a necessary direct sulfur source, and the lithium sulfide (Li ₂ S) is added to the lithium sulfide (Li ₂ S) by 21 to 100. Mol%, preferably 24-88 mol%, more preferably 2
It must be present in a proportion of 6 to 60 mol%. 2
If the amount is less than 1 mol%, it is difficult to make the chloroform-soluble component of the obtained PAS less than 0.5% by weight, and the balance between fluidity and mechanical strength is poor. There is no improvement in balance.

In the production method of the present invention, it is the most important part, the cause of which is unknown, but in the presence of excess lithium hydroxide, a large amount of aromatic-SLi is easily produced in the presence of excess lithium hydroxide, and it is difficult to produce the polymer. It is inferred that the production of low molecular weight components was suppressed as a result of the production of aromatic-SH being suppressed. (5) Polycondensation, post-treatment (step (e)) In this step, a dichloroaromatic compound is charged into a reaction solution containing lithium sulfide and lithium hydroxide prepared in advance,
Polycondensation is performed, and the obtained polymer is separated and washed to obtain PAS.

The dichloroaromatic compound used in the present invention includes p-dichlorobenzene, p-dibromobenzene,
2,5-dichlorotoluene, 2,5-dibromotoluene, 2,5-dichloro-tert-butylbenzene,
2,5-dibromo-tert-butylbenzene, 2,5
-Dichlorobiphenyl and the like, and among them, those containing 50 mol% or more of p-dichlorobenzene and p-dibromobenzene can be suitably used.

Further, a comonomer or a branching agent may be copolymerized as long as the effects of the present invention are not impaired. Examples of the comonomer include 2,3-dichlorophenol, 2,3-dibromophenol, 2,4-dichlorophenol, 2,4-dibromophenol, 2,5-dichlorophenol,
5-dibromophenol, 2,4-dichloroaniline,
2,4-dibromoaniline, 2,5-dichloroaniline, 2,5-dibromoaniline, 3,3′-dichloro-
4,4'-diaminobiphenyl, 3,3'-dibromo-
4,4'-diaminobiphenyl, 3,3'-dichloro-
4,4′-dihydroxybiphenyl, 3,3′-dibromo-4,4′-dihydroxybiphenyl, di (3-chloro-4amino) phenylmethane, m-dichlorobenzene, m-dibromobenzene, o-dichlorobenzene, o
-Dibromobenzene, 4,4'-dichlorodiphenylether, 4,4'-dichlorodiphenylrufone and the like. Moreover, as a branching agent, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,2
3-trichlorobenzene and the like.

These comonomers and branching agents may be used alone or in combination of two or more. As a reaction vessel, for example, a 1-liter stainless steel autoclave (a paddle blade is provided as a stirring blade, and the number of rotations is 300 to 700 rpm)
Can be mentioned. The polymerization temperature is 220 to 2
60 ° C. is preferable, and the polymerization time is preferably 1 to 6 hours. As the input amount of the dichloroaromatic compound, dichloroaromatic compound / sulfur present in the system = 0.9 to 1.2
(Molar ratio), more preferably 0.95 to 1.
05 (molar ratio) is preferred. If the molar ratio is smaller than 0.9, the molecular weight does not elongate, and if it is larger than 1.2, the molecular weight does not elongate.

The polymerization reaction may be one-stage polymerization, or may be two-stage polymerization in which preliminary polymerization is performed in the first stage and the molecular weight is increased in the second stage, or multi-stage polymerization in which the reaction is performed in multiple stages. Among them, two-stage polymerization, which is convenient for production of various grades, is preferred. The polymerization temperature, time and other polymerization conditions are as follows: relatively low temperature in the first stage at 190 to 240 ° C. and polymerization time of about 2 to 10 hours; second stage in the second stage at a relatively high temperature at 240 to 270 ° C .;
About an hour. In addition, there are cases where the water is used properly in the former stage and the latter stage, for example, in the treatment of water described above.

The post-processing may be performed by a method generally used. For example, after cooling, the precipitate can be separated by centrifugation, filtration, or the like, and the obtained polymer can be purified by heating or repeating washing with an organic solvent, water, or the like at room temperature. Such washing may be carried out while the polymer remains in a solid state or in a liquid state and subjected to melt washing.

(6) Step of recovering lithium ions (step (f)) In this step, a PAS production reaction solution containing lithium chloride (dissolved in NMP) by-produced in the polycondensation step (after removing the polymer) And an alkali metal hydroxide or an alkaline earth metal hydroxide is added thereto, and lithium ions are reacted with hydroxide ions to be recovered as lithium hydroxide.

The alkali metal hydroxide or alkaline earth metal hydroxide used here includes sodium hydroxide, potassium hydroxide, magnesium hydroxide and the like. Among them, sodium hydroxide is preferable. The input amount is such that the hydroxyl group is 0.9 to 1.1 mol, preferably 0.95 to 1.05 mol per 1 mol of lithium ion. If the amount is less than 0.9 mol, lithium recovery loss may occur. If the amount exceeds 1.1 mol, the purity of the PAS produced in connection with the subsequent operation may decrease. The reaction temperature in this case is not particularly limited, but when the alkali metal hydroxide or the alkaline earth metal hydroxide is charged in the form of an aqueous solution, the reaction temperature is room temperature to 230 ° C, preferably 65 to 150 ° C, When charged in a solid state, the temperature is 60 to 230 ° C, preferably 90 to 150 ° C. When the reaction temperature is low, the dissolution temperature is low, and the reaction rate becomes extremely slow. If the reaction temperature is high, it will be higher than the boiling point of NMP and must be carried out under pressure, which is disadvantageous in terms of process. The reaction time is not particularly limited.

(II) Second Method This is a method for producing PAS in which lithium disulfide and lithium hydroxide are added to a dihaloaromatic compound in the presence of an aprotic organic solvent to carry out a one-stage or multistage polycondensation reaction. The input amount of lithium oxide is 21 to
A method for producing PAS, characterized in that the ratio is 100 mol%.

In the second method, lithium sulfide is used instead of hydrogen sulfide as the sulfur source in the first method, and the so-called lithium cycle is performed outside the system. Other raw materials and reaction conditions are the same as in the first method. That is, in the presence of NMP and other aprotic organic solvents, lithium disulfide is added to the dihalo-aromatic compound and dichloroaromatic compound / lithium sulfide is added to 0.9 to 1.2.
(Molar ratio), and lithium hydroxide corresponding to the lithium sulfide is supplied at a rate of 21 to 100 mol%. The reaction is preferably a two-stage method. In the former stage, a part of the raw materials and others are charged and prepolymerized, and in the latter stage, the remaining raw materials and other water are charged in a ratio of water / lithium sulfide of 0.1 to 2.5 (molar ratio). To a high molecular weight. The reaction conditions were as follows:
The polymerization time is 240 to 270 ° C. in the latter stage, 2 to 10 hours in the former stage, and 1 to 3 hours in the latter stage.

In the latter stage, as the polycondensation reaction proceeds, lithium chloride is produced and dissolves in NMP, but in the presence of water (water is dissolved in NMP), the lithium chloride concentration increases. Phase separation occurs in the polymer reaction liquid phase, and a lithium chloride-NMP phase / polymer-NMP liquid phase is generated, and the polymerization of the polymer further proceeds. After completion of the reaction, the resulting polymer may be post-treated by a method generally used. For example, the precipitate can be separated by centrifugation, filtration or the like after cooling, and the obtained polymer can be purified by repeating washing with an organic solvent or water at room temperature or at room temperature.

[PAS Resin Composition] The PAS resin composition of the present invention comprises PAS composed of the above-mentioned components (A) and (B) and an inorganic filler, and preferably contains PAS in an amount of 30 to 80% by weight, more preferably 50 to 70% by weight, particularly preferably 55 to 65% by weight, the inorganic filler is preferably 70 to 20% by weight.
% By weight, more preferably 30 to 50% by weight, particularly preferably 45 to 35% by weight.

When the amount of the inorganic filler is more than 70% by weight, the fluidity is reduced. When the amount is less than 20% by weight, the dimensional stability may be deteriorated. In this case, it is preferable that a coupling agent is present in the resin composition.If the coupling agent has been previously subjected to a coupling treatment with an inorganic filler, the amount of addition may be adjusted according to the degree of the treatment. Well, if it is sufficient, it is not necessary to add it, and if it is completely untreated, 0.1 to 100 parts by weight of PAS resin is used.
What is necessary is just to add 3.0 weight part. At this time, if the amount of the coupling agent added is more than 3.0 parts by weight, the effect of increasing the amount cannot be expected, and if it is less than 0.1 parts by weight, the mechanical strength may be reduced.

As the inorganic filler used in the present invention, glass fiber, carbon fiber, aramid fiber, potassium titanate whisker, silicon carbide whisker, mica ceramic fiber,
Wustonite, mica, talc, silica, alumina,
Kaolin, clay, silica alumina, carbon black, calcium carbonate, titanium oxide, lithium carbonate, molybdenum disulfide, graphite, iron oxide, glass beads, calcium phosphate, calcium sulfate, magnesium carbonate, magnesium phosphate, silicon nitride, hydrotalcite, etc. Can be mentioned. These inorganic fillers can be used alone or in combination of two or more. Among these, glass fiber, carbon fiber, potassium titanate whisker, mica, silica, and calcium carbonate are preferred in terms of performance and economy, and glass fiber is particularly preferred.

The glass fiber used in the present invention is not particularly limited, and may be any of alkali glass, low alkali glass and non-alkali glass. The fiber length is preferably 0.1 to 8 mm, more preferably 0.1 to 8 mm. The diameter is 3 to 6 mm, and the fiber diameter is preferably 0.1 to 30 μm, more preferably 0.5 to 25 μm. Fiber length is 0.1mm
If it is smaller, the reinforcing effect is low, and if it is larger than 8 mm, the fluidity decreases. Further, when the fiber diameter is smaller than 0.1 μm, the fluidity decreases, and when the fiber diameter is larger than 30 μm, the strength decreases. Furthermore, as a form of glass fiber,
There is no particular limitation, and examples thereof include various types such as roving, milled fiber, and chopped strand. These glass fibers can be used alone or in combination of two or more.

In order to increase the affinity for the resin, glass silane coupling agents such as amino silane, epoxy silane, vinyl silane, methacryl silane and the like, tetramethyl orthotitanate, tetraethyl ortho It may be surface-treated with titanate, a titanate coupling agent, a chromium complex compound, or a boron compound.

As described above, these coupling agents may be separately added and used instead of surface-treating the glass fiber. The resin composition of the present invention may contain additives such as a weathering agent, an ultraviolet absorber, an antioxidant, a lubricant, an antistatic agent, and a flame retardant as long as the effects of the present invention are not impaired. As described above, PAS and an inorganic filler are blended at a predetermined blending ratio, and can be kneaded by a ribbon tumbler, Henschel mixer, Banbury mixer, drum tumbler, single screw extruder, or the like. A suitable kneading temperature is usually 280 to 320 ° C. [Applications] The PAS and PAS resin composition of the present invention are excellent in the balance between fluidity and mechanical strength, have a thin and complex shape, and are required to have high-strength material performance at high temperatures, particularly in engines. Around, radiator parts, caps,
It can be suitably used for hose clips, wiring connectors and electric / electronic parts.

[0048]

EXAMPLES The present invention will be described in further detail with reference to Examples. The test method used in the examples is as follows. [Intrinsic viscosity] 0.04 g ± 0.001 g of sample was α-
The polymer was dissolved in 10 cc of chloronaphthalene at 235 ° C. for 15 minutes, and the relative viscosity between the viscosity obtained in a thermostat at 206 ° C. and the viscosity of α-chloronaphthalene in which the polymer was not dissolved was measured. As the intrinsic viscosity η _ihr , a value represented by the following equation was used. η _ihr = ln (relative viscosity) / polymer concentration [dl / g]

[Molecular weight distribution by GPC (gel permeation chromatography)] Polymer sample 9.
3 mg is previously dissolved at 240 ° C. in an α-chloronaphthalene solvent (4 cc). Next, the mixture is filtered and allowed to cool to form a slurry. Using an ultra-high temperature GPC apparatus (column open: manufactured by Senshu-Kagaku Co., Ltd.), the column temperature of α-chloronaphthalene solvent (for liquid chromatography: manufactured by Wako Pure Chemical Industries, Ltd.) was measured.
10 ° C, sample concentration 0.23%, solvent flow rate 1ml / min
Was measured. Other measurement conditions are as follows.

GPC column: TSK-GEL GMHHR-M (S), manufactured by Tosoh Corporation 30 cm × 2 UV detection wavelength: 360 nm Injection amount: 250 μl From the obtained elution curve, Mw and Mn were corrected by fluorescence PS conversion. I asked. This ratio of Mw and Mn (Mw / Mn)
Was taken as the molecular weight distribution. [Chloroform-soluble component] A powdery substance obtained by polymerization is cooled with liquid nitrogen, crushed and sieved with a 9-mesh sieve, and the obtained sample is treated with chloroform as a solvent.
The extract was filtered at 40 ° C. or higher to remove the solvent, and the solid was converted into a chloroform-soluble component. The cylindrical filter paper used was ADVANTEC 84 (28 ×
(100 mm), a 9 g sample was soxhlet extracted. Expressed as a weight ratio (%) to PAS. [Zero Shear Viscosity (η ₀ )] A powdery polymer and a blend sample were subjected to a desktop test press (Shindo Metal Industry Co., Ltd.).
Thus, a sheet having a thickness of 1 m / m was produced. Using this sheet, the frequency dependence of the melt viscosity (η) under a nitrogen atmosphere and a temperature of 320 ° C. was measured using RMS800 manufactured by Rheometrics. Frequency is 0.1 to 100 rad / s
ec.

From the frequency dependence curve of the melt viscosity (η),
The zero shear viscosity (η ₀ ) of the polymer (neat polymer) was calculated from the following Ferry's equation. 1 / η (ω) = 1 / η ₀ + Bσ (ω) where B is a constant, σ is a shear stress, and ω is a frequency.

[Method for Preparing Test Pieces for Evaluation of Fracture Toughness, etc.] (1) Pelletized powdery polymer (neat polymer) was heated to a temperature of 300 using a 20 mmφ single screw extruder (manufactured by Tanabe Plastics Co., Ltd.).
The mixture was melt-kneaded at 〜320 ° C. and a rotation speed of 80 rpm to form a pellet.

(2) Injection molding The pelletized sample was injection molded using an in-line screw type injection molding machine (J750EP, manufactured by Nippon Steel Corporation), and was 127 mm long, 12.7 mm wide and 3 mm thick. .
A strip-shaped test piece measuring 2 mm was produced. The molding conditions are a cylinder temperature of 320 ° C. and a mold temperature of 135 ° C.

[Evaluation Method for Fracture Toughness, etc.] Autograph (Model IS5000, manufactured by Shimadzu Corporation: span interval: 40)
mm, crosshead speed 1 mm / min)
Fracture toughness was measured by a point bending test. The test piece used for the evaluation was injection-molded 127 mm long and 12.7 m wide.
m, a 3.2 mm-thick strip-shaped test piece was cut with its center at the center, and was cut to 60 mm × 12.7 mm × 3.2 m.
m, and the central part is "the fracture toughness of plastic"
(Kunio Narusawa, Sigma Publishing Co., Ltd., 1993) 5
A U-notch was formed by the method described on page 9 and a 0.1 mm pre-crack was formed at the tip of the U-notch with a razor blade to obtain a test piece.

A specimen having a U-notch and a pre-crack was subjected to a three-point bending test using a test piece to determine the load at the time of breaking. Further, the notch depth of the test piece after the fracture was read with a microscope, and the fracture toughness value (K _1C ) was calculated from the equation (3).
Further, from the load-displacement curve obtained when performing the three-point bending test, the maximum load at break σMax (N) and the fracture energy-value (J) obtained from the area of the load-displacement curve were calculated.

K _1C = PS / BW ^3/2 f (a / W) (3) where P is the maximum load (N) and S is the span interval (m
m), B is the sample thickness (mm), W is the sample height (m
m) and a represent notch + pre-crack (mm). f (a /
W) is “Fracture Mechanics”
(Written by TL Anderson, published by CRC Press) Single described on Page 2, Chapter 63
It was determined in accordance with the Edge Notched Bend method.

[PA of (A) used in Examples and Comparative Examples]
S: Polymer-A] In a 10-liter autoclave, 10 mol (459.5 g) of lithium sulfide, 10 mol (1470 g) of p-dichlorobenzene, 2.0 mol (83.93 g) of lithium hydroxide-hydrate and NMP (N-methyl-2-pyrrolidone) 4.3 liters and 1.5 moles of water (27.02 g) were added and reacted at 200 ° C. for 5 hours.
After cooling to room temperature, a prepolymer was obtained.

To the prepolymer, 0.2 liter of NMP and 0.8 mol (14.4 g) of water were added and reacted at 260 ° C. for 3 hours. After cooling to 100 ° C., the liquid phase was separated to obtain a precipitated polymer. The obtained polymer is washed with deionized water
Washed times. The polymer was placed again in a 10 liter autoclave, 5 liters of NMP and 30 cc of acetic acid were added, and the polymer was washed at 150 ° C. for 1 hour. After cooling, the solid polymer is ion-exchanged with cold water, and the electric conductivity of the water is 10 μS / c.
m or less. After washing, 120 ° C for 24 hours
And vacuum dried.

The intrinsic viscosity ([η] ihr) of the obtained polymer (polymer powder) was 0.22. The molecular weight distribution by GPC was 2.82. In addition, fracture toughness value (Kc) using a strip-shaped test piece obtained by injection molding.
Was 2.70 MPam ^1/2 . Table 1 shows these results.
It was shown to.

[PAS of (B) used in Examples: Polymer B] In the production of Polymer A, the amount of NMP added to the prepolymer was 0.2 to 0.7 L and the amount of water was 0.1 to 0.7 L. Polymer A was used except that it was changed from 8 moles to 0 moles.
The same reaction as described above was performed. The intrinsic viscosity of the obtained polymer was 0.38, and the molecular weight distribution by GPC was 3.5.
Further, the fracture toughness value (Kc) using a strip-shaped test piece obtained by injection molding was 4.39 MPam ^1/2 . The results are shown in Table 1. [PAS: Polymer C used in Comparative Example] LD-10 manufactured by Toprene was used. The intrinsic viscosity of this polymer is 0.2
5, The molecular weight distribution by GPC was 10.5. Table 1
The results are shown in FIG.

Example 1 After 90 parts by weight of polymer A and 10 parts by weight of polymer B were mixed, the mixture was pelletized and injection-molded by the above-mentioned method to obtain a fracture toughness. The value Kc, the maximum load σ (N) in the three-point bending test, and the breaking energy value (J) were measured.

The fracture toughness value was 3.46. This value is unexpectedly higher than the calculated fracture toughness value (predicted value) of 2.85 in the case where the fracture energy values of 2.70 and 4.39 for each of the polymers A and B alone are assumed to be additive. Is a high value. The maximum load in the three-point bending test was 274 N, and the breaking energy was 71.2 J. These are shown in Table 2.

Example 2 The same experiment as in Example 1 was carried out using 70 parts by weight of polymer A and 30 parts by weight of polymer B. The fracture toughness value was 3.87. This value is unexpectedly higher than the fracture toughness value (predicted value) 3.20 obtained by calculating the fracture energy value of each of the polymers A and B alone. The maximum load in the three-point bending test is 3
11N and breaking energy was 87.9J. These are shown in Table 2.

Comparative Example 1 The same experiment as in Example 1 was conducted by mixing 90 parts by weight of Polymer A and 10 parts by weight of Polymer C. The fracture toughness value was 2.41. This value is unexpectedly lower than the fracture toughness value (predicted value) of 2.75 obtained by calculating the fracture energy value of each of the polymers A and C alone. The maximum load in the three-point bending test was 179 N, and the breaking energy was 29.2 J.
These are shown in Table 2.

Comparative Example 2 The same experiment as in Example 1 was conducted by mixing 70 parts by weight of polymer A and 30 parts by weight of polymer C. The fracture toughness value was 2.93, the maximum load in a three-point bending test was 217 N, and the fracture energy was 42.
It was 5J. Table 2 shows the results.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

According to the present invention, (A) intrinsic viscosity η _inh (dl / g)
And a (B) intrinsic viscosity η _inh (dl
/ g) is a mixture of PAS having a molecular weight distribution determined by GPC of not less than 0.30 and not more than 10.
S is a PAS having extremely excellent mechanical strength such as fracture toughness, maximum load in a three-point bending test, and fracture energy. The degree is higher than the value calculated on the premise of additivity from the fracture toughness values of the individual PASs (A) and (B) which are the materials of the mixture, and shows an unexpected effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29L 31:30 31:34 (72) Inventor Masaya Okamoto 1-1, Anesaki Beach, Ichihara City, Chiba Prefecture (72) Invention Person Tohru Bando 1280 Kamiizumi, Kamiizumi, Sodegaura-shi, Chiba Pref. BF09 BG04 BG27

Claims (8)

[Claims] (A) An intrinsic viscosity η _inh (dl / g) of 0.25
The following polyarylene sulfide and (B) an intrinsic viscosity [η] _inh (dl / g) of 0.30 or more and a gel particle
A polyarylene sulfide comprising a mixture with a polyarylene sulfide having a molecular weight distribution of not more than 10 as determined by luminescence chromatography. 2. The polyarylene sulfide according to claim 1, wherein the molecular weight distribution of the polyarylene sulfide (B) determined by gel permeation chromatography is 5 or less. 3. The polyarylene sulfide according to claim 1, wherein the polyarylene sulfide of (B) is a linear polyarylene sulfide. 4. The polyarylene sulfide according to claim 1, wherein the molecular weight distribution of the polyarylene sulfide (A) determined by gel permeation chromatography is 5 or less. 5. The polyarylene sulfide according to claim 1, wherein the polyarylene sulfide of (A) is a linear polyarylene sulfide. 6. The polyarylene sulfide according to claim 1, wherein each of the polyarylene sulfides (A) and (B) has a chloroform-soluble content of 0.5% by weight or less. 7. A polyarylene sulfide resin composition comprising the mixed polyarylene sulfide according to claim 1 and an inorganic filler. 8. An automobile part or an electric / electronic part obtained by injection molding the polyarylene sulfide or the polyarylene sulfide resin composition according to claim 1.