JP2003026920A - Resin mixture and process for producing the mixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin mixture of a polyarylene sulfide resin and an amorphous thermoplastic resin soluble in a polar organic solvent that are strongly bonded to each other by a chemical bond and a process for producing the resin mixture. SOLUTION: The resin mixture in which an amorphous thermoplastic resin is microdispersed in a non-spherical form in a polyarylene sulfide resin is produced by reacting a polyhalogen aromatic compound and a sulfidizing agent in a polar organic solvent to polymerize a polyarylene sulfide resin wherein the polymerization reaction is conducted in the presence of an amorphous thermoplastic resin soluble in the polar organic solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a mixture of a polyarylene sulfide resin and an amorphous thermoplastic resin soluble in a polar organic solvent represented by a polyphenylene ether resin, and a method for producing the same, and particularly to both resins. Relates to a resin mixture in which is strongly bonded by a chemical bond and an efficient method for producing the same.

[0002]

2. Description of the Related Art Polyarylene sulfide resins represented by polyphenylene sulfide resins are engineering plastics excellent in heat resistance, chemical resistance, flame retardancy, mechanical strength, electrical characteristics and dimensional stability. Since it can be molded into various molded products, films, sheets, fibers, etc. by various molding methods such as molding, extrusion molding and compression molding, it is widely used in a wide range of fields such as electric / electronic devices and automobile devices. .

However, the polyarylene sulfide resin does not always have sufficient rigidity at high temperatures, and the amount of burrs generated during molding is relatively large.

On the other hand, an amorphous thermoplastic resin, particularly polyphenylene ether, is a resin excellent in heat resistance, high temperature rigidity and electric insulation, and is a polymer material useful as an engineering plastic, but has a good moldability. It has been problematic that it is bad and that it is inferior in solvent resistance as compared with crystalline polyarylene sulfide resin and the like.

Therefore, many attempts have been made in the past to obtain a mixture of both a polyarylene sulfide resin and a polyphenylene ether resin.
No. 164360 discloses a composition comprising both resins and an epoxy resin, and JP-A No. 64-31862 discloses a composition comprising a modified polyphenylene ether resin, polyphenylene sulfide and an epoxy compound in JP-A-2-36261. JP-A-2-15595 discloses a polymer mixture comprising both resins and a homogeneity improver.
No. 1 discloses a composition comprising a polyphenylene sulfide resin and an epoxy group-containing polyphenylene ether resin, and JP-A-5-78578 discloses a composition in which a polyphenylene sulfide resin is finely dispersed in a polyphenylene sulfide resin matrix. JP-A-4-2119
Japanese Patent Application Laid-Open No. 7-53950 and Japanese Patent Application Laid-Open No. 5-339501 each disclose a method of heat-treating the mixture of both resins.

However, since the above-mentioned conventional techniques are basically based on melt mixing, the contact area of both resins in the obtained composition is limited, and chemical interfacial bonding is performed. Was hard enough.

[0007]

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

Therefore, an object of the present invention is to provide a resin mixture in which a polyarylene sulfide resin and an amorphous thermoplastic resin soluble in a polar organic solvent represented by a polyphenylene ether resin are strongly bound by a chemical bond and the efficiency thereof. To provide a general manufacturing method.

[0009]

In order to achieve the above object, the resin mixture of the present invention comprises a polyarylene sulfide resin containing a non-spherical amorphous thermoplastic resin soluble in a polar organic solvent. It is characterized by being finely dispersed.

In the resin mixture of the present invention, the mixing weight ratio of the polyarylene sulfide to the amorphous thermoplastic resin soluble in the polar organic solvent is 99 to 50: 1.
It is preferably in the range of 50 to 50 and that the amorphous thermoplastic resin soluble in the polar organic solvent is polyphenylene ether.

Further, the method for producing a resin mixture of the present invention having the above-mentioned characteristics is characterized by reacting a polyhalogenated aromatic compound and a sulfidizing agent in a polar organic solvent to polymerize a polyarylene sulfide resin. It is characterized in that the polymerization reaction is carried out in the presence of an amorphous thermoplastic resin soluble in a polar organic solvent.

In the method for producing a resin mixture according to the present invention, the resin mixture is recovered by quenching after the polymerization reaction, the recovery step by quenching is performed by a flash method, and the polymerization reaction or after the polymerization reaction is performed. A preferable condition is to heat-treat the resin mixture obtained by quenching at a temperature of 150 ° C. to 280 ° C.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The resin mixture of the present invention is characterized in that a polymer soluble in a polar organic solvent represented by polyphenylene ether is non-spherically finely dispersed in a polyarylene sulfide resin. .

That is, since all of the above-mentioned conventional techniques are basically based on melt mixing, in the obtained composition, the chemical bond between the polyarylene sulfide resin and the polyphenylene ether is weak, and the polyphenylene ether is weak. While ether is unlikely to exhibit non-spherical dispersion,
In the resin mixture of the present invention, since the polyarylene sulfide resin and the polyphenylene ether are strongly bound to each other by a chemical bond, the polyarylene sulfide resin contains a polymer soluble in a polar organic solvent represented by polyphenylene ether. It will be spherical and will be finely dispersed.

First, both resins used in the present invention will be described.

The polyarylene sulfide resin in the present invention is a homopolymer or copolymer having a repeating unit of the formula-(Ar--S)-as a main constituent unit. Examples of Ar include the units represented by the following formulas (A) to (K), and the like. Among them, the unit represented by the formula (A) is particularly preferable.

[0017]

[Chemical 1] (However, R1 and R2 in the formula are substituents selected from hydrogen, an alkyl group, an alkoxy group and a halogen group, and R1 and R2 may be the same or different.) As long as it is a structural unit, it may contain a small amount of a branching unit or a crosslinking unit represented by the following formulas (L) to (N). The copolymerization amount of these branch units or crosslinking units is preferably in the range of 0 to 5 mol% and more preferably in the range of 1 mol% or less with respect to the-(Ar-S)-unit.

[0018]

[Chemical 2] Further, the polyarylene sulfide resin in the present invention may be a random copolymer containing the above repeating unit, a block copolymer, or a mixture thereof.

Typical examples of these polyarylene sulfide resins include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers and mixtures thereof. Particularly preferred polyarylene sulfide resin is a p-phenylene unit as the main constituent unit of the polymer.

[0020]

[Chemical 3] Examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone containing 90 mol% or more, and polyphenylene sulfide is particularly preferable.

On the other hand, examples of the amorphous thermoplastic resin soluble in the polar organic solvent used in the present invention include polyphenene ether, polyetherimide, polysulfone, polyether sulfone, and polycarbonate. Here, “soluble in a polar organic solvent” means 10
It means at least 5% by weight of dissolution at 0 ° C.

Among them, polyphenylene ether is preferably used. As such polyphenylene ether, the following structural units

[0023]

[Chemical 4] (Wherein R1, R2, R3 and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbon or substituted hydrocarbon group and may be the same or different from each other), The homopolymer and / or copolymer having a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 0.7, preferably 0.20 to 0.60 It is preferably used. Specific examples include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-).
1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), and poly (2,6-dichloro). -1,4-phenylene ether) and the like, and further 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol).
A polyphenylene ether copolymer such as a copolymer with Among them, poly (2,6-dimethyl-
1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1,4) is preferable.
-Phenylene ether) is most preferably used.

The polyphenylene ether is not particularly limited as long as it can be obtained by a known method. For example, it can be easily produced by oxidative polymerization of 2,6-xylenol, for example, using a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 as a catalyst.

Next, a method for producing the polyarylene sulfide used in the present invention will be described. First, the polyhalogenated aromatic compound used in the production method of the present invention,
The contents of the sulfidizing agent, polymerization solvent, molecular weight modifier, branching / crosslinking agent, polymerization aid and polymerization stabilizer will be described. [Polyhalogenated Aromatic Compound] The polyhalogenated aromatic compound used in the present invention means a compound having two or more halogen atoms in one molecule. As a specific example, p
-Dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,
2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,
4-dibromobenzene, 1,4-diiodobenzene,
1,4-dichloronaphthalene, 1,5-dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, 4,
4'-dichlorobiphenyl, 3,5-dichlorobenzoic acid, 4,4'-dichlorodiphenyl ether, 4,4 '
-Dichlorodiphenyl sulfone, and polyhalogenated aromatic compounds such as 4,4'-dichlorodiphenyl ketone, among which p-dichlorobenzene, 4,4'-dichlorodiphenyl sulfone and 4,
4'-Dichlorodiphenylketone, particularly p-dichlorobenzene, is preferably used. It is also possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a p-dihalogenated aromatic compound as a main component.

The amount of polyhalogenated aromatic compound used is
From the viewpoint of obtaining a polyarylene sulfide resin having a viscosity suitable for processing, 0.9 to 2.
The range is 0 mol, preferably 0.95 to 1.5 mol, and more preferably 1.005 to 1.2 mol. [Sulfiding Agent] Examples of the sulfiding agent used in the present invention include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

Specific examples of the alkali metal hydrosulfide include:
Examples thereof include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more kinds thereof, and sodium hydrosulfide is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in anhydrous form.

Further, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. In addition, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide and transferred to a polymerization tank for use.

Alternatively, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. In addition, an alkali metal sulfide can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide and transferred to a polymerization tank for use.

In the present invention, the amount of the sulfidizing agent charged is the residual amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfiding agent occurs before the initiation of the polymerization reaction due to dehydration operation or the like. Shall mean.

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide together with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more of these, and alkaline earth metals are preferable. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Among them, sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but the amount used is 0.95 per mol of the alkali metal hydrosulfide. To 1.20 moles,
The range is preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol. [Polymerization solvent] In the present invention, an organic polar solvent is used as a polymerization solvent. Specific examples include N-methyl-2-pyrrolidone, N-alkylpyrrolidones such as N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolidinium. Examples thereof include aprotic organic solvents represented by non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfone, tetramethylene sulfoxide, and the like, and mixtures thereof. It is preferably used because of its high reaction stability. Among these, especially N-
Methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is preferably used.

The amount of the organic polar solvent used is 2.0 to 10 mol, preferably 2.
25 to 6.0 mol, more preferably 2.5 to 5.5.
A range of moles is selected. [Molecular Weight Modifier, Branching / Crosslinking Agent] In the present invention, a monohalogen compound (not necessarily an aromatic compound) is used in order to form the end of the polyarylene sulfide resin to be formed, or to control the polymerization reaction or the molecular weight. It may be omitted) may be used in combination with the above polyhalogenated aromatic compound. Further, in order to form a branched or crosslinked polymer, a polyhalogen compound of trihalogenation or higher (not necessarily an aromatic compound), an active hydrogen-containing halogenated aromatic compound and a halogenated aromatic nitro compound are used in combination. It is also possible to do so. [Polymerization Aid] In the present invention, a polymerization aid can be used in order to obtain a polyarylene sulfide resin having a high degree of polymerization in a shorter time. Here, the polymerization aid means a substance having an action of increasing the viscosity of the obtained polyarylene sulfide resin. Specific examples of such a polymerization aid include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earth salts. Examples thereof include metal phosphates. These may be used alone or in combination of two or more. Among them, organic carboxylic acid salts and / or water are preferably used.

The above-mentioned alkali metal carboxylate means the general formula R (COOM) n (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group). It is M
Is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium. n is 1
It is an integer of 3. ) Is a compound represented by. The alkali metal carboxylate can also be used as a hydrate, an anhydride or an aqueous solution. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and a mixture thereof. Can be mentioned.

The alkali metal carboxylate is substantially equal to an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates in an organic polar solvent. It may be formed by adding chemical equivalents and reacting. Among the above alkali metal carboxylates, the lithium salt is highly soluble in the reaction system and has a large auxiliary agent effect, but is expensive, and the potassium, rubidium and cesium salts are presumed to have poor solubility in the reaction system. However, sodium acetate, which is inexpensive and has a suitable solubility in the polymerization system, is most preferably used.

When using these polymerization aids, the amount used is
Normally 0.01 with respect to 1 mol of charged alkali metal sulfide
It is in the range of mol to 0.7 mol, and in the sense of obtaining a higher degree of polymerization, the range of 0.1 to 0.6 mol is preferable,
The range of 0.2 to 0.5 mol is more preferable.

The timing of adding these polymerization aids is not particularly specified, and they may be added at the time of the following step described later, at the start of polymerization or at any time during the polymerization, or may be added in a plurality of times. Although it is good, it is more preferable to add it at the start of the previous step or at the start of polymerization because the addition is easy. [Polymerization Stabilizer] In the present invention, a polymerization stabilizer may be used in order to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesired side reactions. One measure of the side reaction is the production of thiophenol, and the addition of a polymerization stabilizer can suppress the production of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferable. The above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, and thus is included in one of the polymerization stabilizers used in the present invention. Further, when the alkali metal hydrosulfide is used as the sulfidizing agent, it is described above that it is particularly preferable to use the alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

These polymerization stabilizers can be used alone or in combination of two or more kinds. The polymerization stabilizer is usually 0.02 to 0.2 mol, preferably 0.03 to 1 mol with respect to 1 mol of the charged alkali metal sulfide.
It is preferably used in a proportion of 0.1 mol, more preferably 0.04 to 0.09 mol. If this ratio is small, the stabilizing effect is insufficient, and if it is too large, it is economically disadvantageous and the polymer yield tends to decrease.

The timing of addition of the polymerization stabilizer is not particularly specified, and it may be added at any time during the pre-process described below, at the start of polymerization, or during the polymerization, or may be added in a plurality of times. However, it is more preferable to add them at the same time at the start of the previous step or at the start of the polymerization from the viewpoint of easy addition.

Next, regarding the method for producing the resin mixture of the present invention, including the method for producing the polyarylene sulfide resin, the preceding step, the polymerization reaction step, the addition of the amorphous thermoplastic resin soluble in the polar organic solvent, The recovery step and the post-treatment step will be specifically described in order. [Previous Step] In the production of the polyarylene sulfide resin of the present invention, the sulfidizing agent is usually used in the form of a hydrate. However, before adding the polyhalogenated aromatic compound, an organic polar solvent and a sulfide are added. It is preferable to raise the temperature of the mixture containing the agent to remove excess water out of the system. In addition, when water is removed too much by this operation, it is preferable to add and supplement the insufficient amount of water.

Further, as described above, as a sulfidizing agent, an alkali metal sulfide prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank. Objects can also be used. This method is not particularly limited, but it is desirable to add an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C., under an inert gas atmosphere. In addition, under normal pressure or reduced pressure, at least 150 ° C or higher, preferably 180
A method of elevating the temperature to ˜260 ° C. and distilling off water is mentioned. A polymerization aid may be added at this stage. Further, in order to accelerate the evaporation of water, the reaction may be carried out by adding toluene or the like.

The amount of water in the polymerization system in the polymerization reaction is
It is preferably 0.5 to 10.0 mol per mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed outside the polymerization system from the amount of water charged in the polymerization system. Also, the water charged is
It may be in any form such as water, an aqueous solution, or water of crystallization. A more preferable range of the water content is 0.75 to 2.5 mol per mol of the sulfidizing agent, and 1.0 to 1.2
The range of 5 mol is more preferable. In order to adjust the water content within this range, it is possible to add water before or during the polymerization. [Polymerization reaction step] In the present invention, a sulfidizing agent and a polyhalogenated aromatic compound are mixed in an organic polar solvent,
The polyarylene sulfide resin is usually produced by reacting within a temperature range of 200 ° C. or higher and lower than 290 ° C. The polymerization reaction is usually performed in a pressure vessel and under pressure.

When the polymerization reaction step is started, the sulfidizing agent and the polyhalogenated aromatic compound are added to the organic polar solvent in an inert gas atmosphere at a temperature range of room temperature to 220 ° C., preferably 100 to 220 ° C. Add. A polymerization aid may be added at this stage. The order of charging these raw materials may be in any order or may be simultaneous.

The mixture is usually heated to a temperature within the range of 200 ° C to 290 ° C. The rate of temperature increase is not particularly limited, but a rate of 0.01 to 5 ° C / min is usually selected, and 0.1 to 3 ° C / min.
The range of minutes is more preferable.

Generally, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is usually performed at that temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.

Before reaching the final temperature, for example, after reacting at 200 ° C. to 245 ° C. for a certain period of time,
The method of raising the temperature to 290 ° C. is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200 ° C. to 245 ° C. is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 to 10 hours.

When carrying out the polymerization in a plurality of steps, 245
It is effective for obtaining a polymer having a higher degree of polymerization that the conversion rate of the polyhalogenated aromatic compound in the system at 40 ° C. reaches 40 mol% or more, preferably 60 mol%.

The conversion rate of the polyhalogenated aromatic compound (abbreviated as PHA here) is a value calculated by the following formula. The PHA residual amount can be usually obtained by a gas chromatographic method.

(A) When the polyhalogenated aromatic compound is added in excess to the alkali metal sulfide in a molar ratio Conversion = [PHA charging amount (mol) -PHA residual amount (mol)] / [PHA charging amount (Mole) -PHA excess (Mole)] (b) In cases other than the above (a) Conversion = [PHA charge (Mole) -PHA residual amount (Mole)] / [PHA charge (Mole)] [Polarity Addition of Amorphous Thermoplastic Resin Soluble in Organic Solvent] When the resin mixture of the present invention is produced, the polyarylene sulfide is polymerized in the presence of the amorphous thermoplastic resin soluble in a polar organic solvent. There is one feature in doing it. The amorphous thermoplastic resin soluble in the polar organic solvent may be added before or after the above-mentioned previous step. Further, it may be added at the same time as the polyhalogenated aromatic compound between the previous step and the polymerization reaction step, or may be added during the polymerization reaction step. The addition amount of the amorphous thermoplastic resin soluble in the polar organic solvent is polyarylene sulfide: amorphous thermoplastic resin soluble in the polar organic solvent = 99 to 50:
A range of 1 to 50 weight ratio is suitable, and polyarylene sulfide: amorphous thermoplastic resin soluble in polar organic solvent =
The range of 95 to 70: 5 to 30 weight ratio is more preferable. [Recovery Step] In the method for producing a resin mixture of the present invention, a solid is recovered from a polymerization reaction product containing a resin mixture, a solvent and the like after completion of polymerization.

That is, in the present invention, it is preferable to carry out the above-mentioned recovery under rapid cooling conditions, and a flash method can be mentioned as a more preferable one of the recovery methods. In the flash method, the polymerization reaction product is flashed from a high-temperature and high-pressure state (usually 250 ° C. or higher, 8 kg / cm ² or higher) into an atmosphere of normal pressure or reduced pressure, and at the same time as solvent recovery, the polymer is recovered in powder form Is the way
The term "flash" as used herein means to eject a polymerization reaction product from a nozzle. The atmosphere for flashing is
Specific examples thereof include nitrogen or steam under normal pressure, and the temperature is usually selected in the range of 30 ° C to 250 ° C.

The flash method is an economical recovery method because it can recover the solid material at the same time as the recovery of the solvent and the recovery time can be relatively short. Further, when the material is slowly cooled, the rate of separation of the amorphous thermoplastic resin soluble in the polar organic solvent may increase during the crystallization process of polyphenylene sulfide, and therefore the quenching recovery method, particularly the flash method is preferable.

In the present invention, the resin mixture thus recovered is washed with warm water of 50 ° C. to 100 ° C. and / or hot water of 100 ° C. to 200 ° C. to remove by-produced salts, residual solvents and oligomers. It is preferable to remove.

The washing with hot water or hot water in the present invention may be either batch type or continuous type.
Ion exchange water and distilled water are preferably used as the type of water used.

The bath ratio in such warm water washing and hot water washing is preferably selected in the range of 2 to 100, more preferably in the range of 4 to 50, and more preferably in the range of 5 to 15 with respect to the dry resin mixture 1 by weight ratio. More preferable.

As the cleaning method, the resin mixture is dipped,
It can be performed by a method such as stirring. [Other post-treatment] Further, in the present invention, in the sense of promoting the binding of the obtained resin mixture, the temperature is 150 to 280 ° C.
Dry heat treatment at the above temperature is also one of the preferable methods.

The temperature of the dry heat treatment is 150 to 280.
C. is preferable, and the range of 180 to 250.degree. C. is more preferable. The atmosphere of the dry heat treatment may be an inert atmosphere such as nitrogen, helium, or vacuum, or an oxidizing atmosphere such as oxygen or air. However, in the sense that the bonding between the resin mixtures is further promoted, an oxidizing atmosphere is used. It is desirable to do it below.
In this case, the oxygen concentration is preferably 1 to 20% by volume, more preferably 2 to 15% by volume. The heat treatment time is 0.
It is preferably 5 to 50 hours, more preferably 1 to 30 hours, still more preferably 1 to 20 hours.

In the resin mixture thus obtained,
The amorphous thermoplastic resin soluble in the polar organic solvent is finely dispersed in the polyarylene sulfide resin matrix, and particularly, it is finely dispersed in a non-spherical shape. The reason why such a non-spherical dispersed form can be taken is that the polyarylene sulfide resin and the amorphous thermoplastic resin soluble in the polar organic solvent are strongly bound to each other, and the interfacial energy between them is lowered. Inferred.

The resin mixture thus obtained has heat resistance,
Its excellent chemical resistance, flame retardancy, electrical properties and mechanical properties make it particularly suitable for extrusion molding applications such as fibers, films, sheets, plates and pipes, as well as for injection molding applications. can do.

The resin mixture obtained in the present invention may be used alone or, if desired, may be used by blending the compounding agents described below. Specific examples of the compounding agent include glass fiber, carbon fiber, potassium whisker titanate,
Fibrous fillers such as zinc oxide whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers, wollastonite, zeolite, sericite, mica, talc, kaolin , Silicates such as clay, pyrophyllite, bentonite, asbestos and alumina silicate, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite , Sulfate such as calcium sulfate, barium sulfate, hydroxide such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, graphite, carbon black and silica, etc. Non-fibrous fillers and the like,
These may be hollow, and it is also possible to use two or more kinds of these fillers in combination. Further, these fillers are isocyanate compounds, organic silane compounds,
Pretreatment with a coupling agent such as an organic titanate-based compound, an organic borane-based compound and an epoxy compound before use is preferable in terms of obtaining more excellent mechanical strength.

Further, the resin mixture obtained in the present invention may be blended with other resins, if desired. The blendable resin is not particularly limited, but specific examples thereof include nylon 6, nylon 66, nylon 61.
0, nylon 11, nylon 12, polyamide resin such as aromatic nylon, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexyl dimethylene terephthalate, polynaphthalene terephthalate, polysulfone, polycarbonate, polyether sulfone, polyether imide, Cyclic olefin copolymer, polyethylene, polypropylene, polytetrafluoroethylene, olefin copolymer having functional groups such as carboxyl group, carboxylic acid ester group, acid anhydride anhydride group and epoxy group, polyolefin elastomer, polyether ester elastomer, poly Examples include ether amide elastomers, polyamide imides, polyacetals and polyimides.

It is also possible to use the resin mixture of the present invention by mixing it with a polyarylene sulfide and / or an amorphous thermoplastic resin soluble in a polar organic solvent, that is, as a compatibilizing agent for both resins. Is.

The resin mixture obtained in the present invention also contains
As desired, polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, plasticizers such as organic phosphorus compounds, talc, kaolin, crystal nucleating agents such as organic phosphorus compounds, polyolefin compounds, silicone compounds, long compounds Release agents such as chain aliphatic ester compounds and long chain aliphatic amide compounds, antioxidants such as hindered phenol compounds and hindered amine compounds, heat stabilizers, calcium stearate, aluminum stearate, lithium stearate, etc. Ordinary additives such as lubricants, UV inhibitors, colorants, flame retardants and foaming agents can be added.

Furthermore, an alkoxysilane compound having at least one functional group selected from epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group and ureido group is added to the resin mixture obtained in the present invention. Addition is effective in improving mechanical strength and toughness. Specific examples of the alkoxysilane compound include γ-glycidoxypropyltrimethoxysilane and γ
-Glycidoxypropyl triethoxy silane, β-
Epoxy group-containing alkoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Mercapto group-containing alkoxysilane compounds such as mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane and other ureido group-containing alkoxys. Silane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ -Isocyanato group-containing alkoxysilane compounds such as isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane, γ- (2
-Aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and other amino group-containing alkoxysilane compounds, and γ-
Examples thereof include hydroxyl group-containing alkoxysilane compounds such as hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane.

The suitable addition amount of the alkoxysilane compound is selected in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin.

The use of the resin mixture obtained in the present invention includes, for example, fibers for bag filters, fibers for canvas for papermaking, films for capacitors, thick plates, extruded pieces such as round bars, sensors, LED lamps and connectors. , Socket, resistor, relay case, switch, coil bobbin, condenser, variable capacitor case, optical pickup,
Oscillator, various terminal boards, transformers, plugs, printed circuit boards,
Tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna,
Electric / electronic parts typified by computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment such as audio / laser disk (registered trademark) / compact disk Household and office electrical product parts represented by parts, 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 such as lighters and typewriters; optical devices such as microscopes, binoculars, cameras and watches; precision machine-related parts; water faucets, mixed faucets, pump parts, pipe joints, water control valves , Relief valve,
Water parts such as hot water temperature sensor, water quantity sensor, water meter housing; optical communication equipment parts such as optical fiber ferrule, optical fiber connector; valve alternator terminal, alternator connector, IC regulator, potentiometer base for light deer, exhaust gas valve, etc. , Various valves for fuel, exhaust system, intake system pipes, 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, 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, detributor, starter switch , Starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, fuse connector, horn terminal, electrical component insulating plate, step motor rotor, lamp socket, lamp reflector, lamp housing, Brake piston, solenoid bobbin, engine oil filter, ignition device case, vehicle speed sensor Chromatography, automobile and vehicle-related parts such as cables liners, and other various uses can be exemplified.

[0067]

EXAMPLES The method of the present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The characteristics of the examples were evaluated by the following methods. [Measurement of Bonding Ratio of Polyarylene Sulfide and Polyphenylene Ether] Sample powder was subjected to Soxhlet extraction for 3 hr with toluene, which is a solvent that dissolves only polyphenylene ether. The bond ratio was determined from the change in the infrared characteristic absorption (polyarylene sulfide; 1900 cm ^-1 , polyphenylene ether; 1300 cm ^-1 ) ratio of each crystalline thermoplastic resin. For measurement of infrared absorption spectrum, Shimadzu FTI
R-8100A was used. The measurement sample was prepared by the KBr tablet method.

The absorbance of infrared absorption of polyarylene sulfide before and after Soxhlet extraction was measured by [PAS] f, [PA
S] a and the infrared absorption of polyphenylene ether before and after Soxhlet extraction is [PPE] f, [PPE]
E] a, the bond ratio was calculated as follows.

Coupling ratio = {([PPE] a / [PAS]
a) / ([PPE] f / [PAS] f)} × 100% [Example 1] 118 g of 47% sodium hydrosulfide in a 1 liter autoclave equipped with a stirrer and a valve at the bottom.
(1.00 mol), 96% sodium hydroxide 44.2 g
(1.06 mol), N-methyl-2-pyrrolidone (NM
P) 199 g (2.01 mol), and ion-exchanged water 1
Charge 50 g, gradually heat to 225 ° C. under nitrogen at atmospheric pressure over about 3 hours, and add 210 g of water and NMP.
After distilling 2 g, the reaction vessel was cooled to 160 ° C. The amount of hydrogen sulfide scattered was 0.02 mol.

Next, p-dichlorobenzene (p-DC
B) 147 g (1.00 mol), NMP 69 g (0.7
0 mol) and poly (2,6-dimethyl-1,4-phenylene ether) (YPX-100 manufactured by Mitsubishi Engineering Corp.)
F) 11.96 g was added and the reaction vessel was sealed under nitrogen gas. Then, while stirring at 400 rpm, 200 ° C
To 274 ° C. at a rate of 0.6 ° C./min, 274
After holding at 50 ° C for 50 minutes, the temperature was raised to 282 ° C. The extraction valve at the bottom of the autoclave was then opened, the contents were flushed into a thick glass container, and a solid containing a mixture of polyphenylene sulfide (PPS) and polyphenylene ether and salts was recovered.

The solid obtained was warmed to 80 ° C. with a bath ratio of 10
Was washed four times. The cake obtained is 120 ° C.
After drying with hot air for 2 hours, vacuum drying was performed at 80 ° C. for 48 hours.

When the binding ratio was determined using this sample, it was 52%. Example 2 The resin mixture obtained in Example 1 was heat-treated in air at 210 ° C. for 20 hours, and the bond ratio was calculated to be 98%.

Further, a film having a thickness of about 100 μm was obtained by hot pressing the resin mixture at 340 ° C. for 4 minutes. Embedding this film in epoxy resin,
A cross section was cut out and the dispersion state of polyphenylene ether in the film was observed with a transmission electron microscope. The result is shown in Figure 1.
Shown in. The white portion in the figure is the polyphenylene ether resin.

As shown in FIG. 1, the polyphenylene ether was finely dispersed in a non-spherical shape. [Comparative Example 1] The same operation as in Example 1 was carried out except that poly (2,6-dimethyl-1,4-phenylene ether) was not added to obtain about 97 g of polyphenylene sulfide.

This polyphenylene sulfide and poly (2,6-dimethyl-1,4-phenylene ether)
(Mitsubishi Enpra Co., Ltd. YPX-100F) at a weight ratio of 90:10 Labo Plastomill (Model 50 manufactured by Toyo Seiki Co., Ltd.)
C150) was used and melt-mixed at 300 ° C. After crushing the obtained mixture, the binding ratio was determined by the above method, and was found to be less than 5%.

The resin mixture was hot pressed at 340 ° C. for 4 minutes to obtain a film having a thickness of about 100 μm.
This film was embedded in an epoxy resin, a cross section was cut out, and the dispersion state of polyphenylene ether in the film was observed with a transmission electron microscope. The results are shown in Fig. 2. The white portion in the figure is the polyphenylene ether resin.

As shown in FIG. 2, the polyphenylene ether was spherical and dispersed. Example 3 118 g of 47% sodium hydrosulfide was added to a 1 liter autoclave equipped with a stirrer and a valve at the bottom.
(1.00 mol), 96% sodium hydroxide 44.2 g
(1.06 mol), N-methyl-2-pyrrolidone (NM
P) 199 g (2.01 mol), and ion-exchanged water 1
Charge 50 g, gradually heat to 225 ° C. under nitrogen at atmospheric pressure over about 3 hours, and add 210 g of water and NMP.
After distilling 2 g, the reaction vessel was cooled to 160 ° C. The amount of hydrogen sulfide scattered was 0.02 mol.

Next, p-dichlorobenzene (p-DC
B) 147 g (1.00 mol), NMP 69 g (0.7
0 mol) and 23.00 g of polyphenylene ether (YPX-100F manufactured by Mitsubishi Engineering Corp.) were added, and the reaction vessel was sealed under nitrogen gas. Then, while stirring at 400 rpm, the temperature was raised from 200 ° C. to 274 ° C. at a rate of 0.6 ° C./min, held at 274 ° C. for 50 minutes, and then raised to 282 ° C. The extraction valve at the bottom of the autoclave was then opened, the contents were flushed into a thick glass container, and a solid containing a mixture of polyphenylene sulfide (PPS) and polyphenylene ether and salts was recovered.

The solid obtained was warmed to 80 ° C. with a bath ratio of 10
Was washed four times. The cake obtained is 120 ° C.
After drying with hot air for 2 hours, vacuum drying was performed at 80 ° C. for 48 hours.

This resin mixture was heat-treated in air at 210 ° C. for 15 hours, and then the binding ratio was determined to be 95%.

[0082]

As described above, according to the present invention,
Polyarylene sulfide resin and an amorphous thermoplastic resin soluble in a polar organic solvent represented by polyphenylene ether resin, a resin mixture strongly bonded by a chemical bond,
It can be obtained by an efficient manufacturing method.

[Brief description of drawings]

1 is a transmission electron micrograph of the resin mixture produced in Example 2. FIG.

2 is a transmission electron micrograph of the resin mixture produced in Comparative Example 1. FIG.

Continued front page    F term (reference) 4J002 AA012 CG002 CH072 CM042                       CN011 CN032 FD010 FD170                       GK01 GM00 GN00 GQ00                 4J030 BA03 BA42 BA43 BA48 BA49                       BB29 BB31 BC08 BD21 BE04                       BF06 BG04 BG25 BG26 BG27                       BG31

Claims (8)

[Claims] 1. A resin mixture comprising a polyarylene sulfide resin, and an amorphous thermoplastic resin soluble in a polar organic solvent, which is non-spherical and finely dispersed. 2. The mixing weight ratio of the polyarylene sulfide: amorphous thermoplastic resin soluble in the polar organic solvent is in the range of 99 to 50: 1 to 50. The resin mixture described. 3. The resin mixture according to claim 1, wherein the amorphous thermoplastic resin soluble in the polar organic solvent is polyphenylene ether. 4. An amorphous thermoplastic resin soluble in a polar organic solvent when the polyarylene sulfide resin is polymerized by reacting a polyhalogenated aromatic compound with a sulfidizing agent in a polar organic solvent. The method for producing a resin mixture according to any one of claims 1 to 3, wherein the method is performed in the presence of 5. The method for producing a resin mixture according to claim 4, wherein the resin mixture is recovered by quenching after the polymerization reaction. 6. The method for producing a resin mixture according to claim 5, wherein the recovering step by quenching is performed by a flash method. 7. The resin mixture obtained by the polymerization reaction or the rapid cooling after the polymerization reaction is heat-treated at a temperature of 150 ° C. to 280 ° C., according to any one of claims 4 to 6. A method for producing a resin mixture. 8. A resin mixture produced by the method according to any one of claims 4 to 7.