JP2023019242A - Polyarylene sulfide resin composition - Google Patents

Abstract

To provide a resin composition which has a low chlorine content, and hardly causes deterioration of tensile strength even by subjected to long-term hot water treatment when formed into a molded article.SOLUTION: A polyarylene sulfide resin composition is obtained by compounding a polyarylene sulfide resin having a specific amount of an amino group content with a filler and alkoxysilane having a specific functional group.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition which, when formed into a molded product, does not easily cause a decrease in tensile strength even after long-term hot water treatment. Specifically, the present invention provides a polyarylene sulfide resin composition comprising a polyarylene sulfide resin having an amino group content within a specific range, a filler, and an alkoxysilane having a specific functional group blended therein.

Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin has properties suitable as an engineering plastic, such as excellent heat resistance, chemical resistance, and electrical insulation. For this reason, it is widely used in electrical and electronic parts, communication equipment parts, automobile materials, etc., but it has low adhesiveness to different materials such as resins other than PAS resin, fillers, metals, etc. Composite materials have a problem of low strength. Furthermore, it is pointed out that long-term hot water treatment and long-term dry heat treatment further reduce the strength and toughness of the composite material. In particular, in line with the recent market demands for fuel efficiency, weight reduction, and cost reduction of automobiles, the strength is increased by improving the adhesiveness with different materials, and the strength and toughness are maintained even after long-term hot water treatment and long-term dry heat treatment. There is a demand for an excellent material that does not cause a decrease in the

On the other hand, an improvement method has been reported in which other compounds are added to the PAS resin to enhance adhesion to different materials and maintain strength and toughness. For example, Patent Document 1 discloses a PAS resin composition obtained by blending a PAS resin, a glass fiber, and a polyamide. Patent Document 2 discloses a PAS resin composition obtained by blending a PAS resin and polyvinylpyrrolidone. Patent Document 3 discloses a PAS resin composition obtained by blending a PAS resin and a phenol resin.

However, the above-mentioned PAS resin does not greatly improve the low adhesiveness to different materials, and the problem remains that it is difficult to meet market demands.

Therefore, several methods have been reported for improving PAS resins in order to achieve higher strength. For example, in Patent Document 4, sodium hydrosulfide and paradichlorobenzene are added under specific conditions in the presence of NMP solvent for the purpose of exhibiting high dielectric constant and low dielectric loss tangent, excellent moldability, and improving impact resistance. A polyphenylene sulfide resin is disclosed in which a certain amount of carboxyl groups are introduced at the terminals by reacting with.

JP 2019-137868 A JP 2018-199250 A JP 2018-161768 A JP 2012-177015 A

However, in the PAS resin described in Patent Document 4, while a PAS resin having a relatively high molecular weight can be obtained, the functional group content is insufficient, and the strength is reduced by applying long-term hot water treatment or long-term dry heat treatment. extremely low.

Thus, it is difficult for the PAS resins described in Patent Documents 1 to 4 to achieve both a high functional group content and a high molecular weight. There was a problem that it could not be adopted for parts and automobile parts.

As a result of intensive studies by the present inventors in order to solve the above problems, a polyarylene sulfide resin composition obtained by blending a filler and a specific alkoxysilane with a polyarylene sulfide resin having a specific amount of amino group content. The inventors have found that the product has excellent mechanical strength after long-term hydrothermal treatment, leading to the present invention.
That is, the present invention is as follows.
1. 3 to 150 parts by weight of a filler and 0.1 part of an alkoxysilane having at least one functional group selected from an amino group, an acid anhydride group, a carboxyl group, and an isocyanate group per 100 parts by weight of a polyarylene sulfide resin. A polyarylene sulfide resin composition containing up to 10 parts by weight, wherein the amino group content of the polyarylene sulfide resin is 60 to 600 μmol/g.
2. 2. The polyarylene sulfide according to 1, wherein the alkoxysilane having at least one functional group selected from an amino group, an acid anhydride group, a carboxyl group, and an isocyanate group is an alkoxysilane having an isocyanate group. Resin composition.
3. 3. The polyarylene sulfide resin composition according to 1 or 2, wherein the polyarylene sulfide resin has a weight average molecular weight of 35,000 or more.
4. 4. The polyarylene sulfide resin composition according to any one of 1 to 3, wherein the polyarylene sulfide resin has a chlorine content of 1500 ppm or less.
5. 5. The polyarylene according to any one of 1 to 4, wherein the filler is provided with a sizing agent having at least one functional group selected from an amino group, an epoxy group, an isocyanate group, and a carboxyl group. A sulfide resin composition.
6. A molded article made of the polyarylene sulfide resin composition according to any one of 1 to 5.

According to the present invention, it is possible to obtain a polyarylene sulfide resin composition which has a low chlorine content, is excellent in tensile strength, and does not easily deteriorate in tensile strength even after long-term hot water treatment. These characteristics comply with the environmental regulations of each country represented by the RoHS directive and REACH regulations, and are particularly effective for applications such as components through which high-temperature fluids flow, cooling modules for automobiles, and cooling pipes.

PAS in the present invention is a homopolymer or copolymer having a repeating unit of the formula -(Ar-S)- as a main structural unit, preferably containing 80 mol% or more of the repeating unit. Ar includes units represented by the following formulas (A) to (K), among which formula (A) is particularly preferred.

(R1 and R2 are substituents selected from hydrogen, alkyl groups, alkoxy groups and halogen groups, and R1 and R2 may be the same or different.)

As long as this repeating unit is the main structural unit, it can contain a small amount of branching units or cross-linking units represented by the following formulas (L) to (N). The amount of copolymerization of these branching units or cross-linking units is preferably in the range of 0 to 1 mol % with respect to 1 mol of —(Ar—S)— units.

Moreover, the PAS in the present invention may be a random copolymer, a block copolymer, or a mixture thereof containing the repeating unit.

Representative examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers, block copolymers and mixtures thereof. A particularly preferred PAS is the p-phenylene sulfide unit shown below as the main structural unit of the polymer.

of 80 mol % or more, particularly 90 mol % or more of polyphenylene sulfide.

The method for producing the PAS resin of the present invention is described below.

First, the contents of the dihalogenated aromatic compound, the sulfidating agent, the polymerization solvent, the compound for introducing an amino group into PAS, the branching/crosslinking agent, the polymerization aid, and the polymerization stabilizer used in the production method will be described.

[Dihalogenated Aromatic Compound]
A dihalogenated aromatic compound means a compound having two halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodine. Benzene, 1-methoxy-2,5-dichlorobenzene and the like can be mentioned, and p-dichlorobenzene is preferably used. Two or more different dihalogenated aromatic compounds may be combined to form a copolymer, but p-dihalogenated aromatic compound is preferably the main component.

The amount of the dihalogenated aromatic compound used is 90 mol to 120 mol, preferably 95 mol to 110 mol, more preferably 99 mol to 105 mol, per 100 mol of the sulfidating agent, from the viewpoint of obtaining a PAS resin having a viscosity suitable for processing. mol, more preferably a range of 100.5 to 103 mol can be exemplified.

[Sulfidation agent]
Sulfidating agents include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, with sodium sulfide being preferred. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in anhydrous form.

Specific examples of alkali metal hydrosulfides include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in anhydrous form.

Alkali metal sulfides prepared in situ in the reaction system from alkali metal hydrosulfides and alkali metal hydroxides can also be used. Alternatively, 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. Alternatively, 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.

The amount of the charged sulfidating agent means the remaining amount obtained by subtracting the loss from the actual charged amount when a part of the sulfiding agent is lost before the start of the polymerization reaction due to dehydration or the like.

An alkali metal hydroxide and/or an alkaline earth metal hydroxide can be used together with the sulfidating agent. Specific examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more thereof. Specific examples of metal hydroxides include calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Among them, sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as the sulfidating agent, it is particularly preferable to use an alkali metal hydroxide at the same time. 0.20 mol, preferably 1.00 mol to 1.15 mol, more preferably 1.005 mol to 1.100 mol.

[Polymerization solvent]
It is preferable to use an organic polar solvent as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidine non-, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric acid triamide, dimethylsulfone, tetramethylene sulfoxide, and aprotic organic solvents, and mixtures thereof. These polymerization solvents are preferably used due to their high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

The organic polar solvent is used in an amount of 20 to 1000 mol, preferably 225 to 600 mol, more preferably 250 to 550 mol per 100 mol of the sulfidation agent.

[Method for introducing amino group into PAS]
In the present invention, the amino group content of the PAS to be blended is essentially 60 μmol/g, preferably 70 μmol/g or more, more preferably 80 μmol/g. The upper limit of the amino group content is not particularly limited, but from the viewpoint of compatibility with high molecular weight, it is essential to be 600 μmol/g or less, preferably 400 μmol/g or less, and 300 μmol/g or less. is more preferable, and 150 μmol/g or less is even more preferable.

The amino group content introduced into the PAS resin here is measured by FT-IR (IR-810 type infrared spectrophotometer manufactured by JASCO Corporation) of the amorphous film of the PAS resin, and the benzene ring-derived This value is obtained by comparing the absorption at around 3380 cm ^-1 originating from the amino group with the absorption at around 1,900 cm ^-1 .

A method for introducing an amino group into PPS is not particularly limited, and can be introduced by a known method. In order to achieve the amino group content described above, for example, a method of copolymerizing a halo compound having an amino group, a method of copolymerizing a thiol compound having an amino group or a phenol compound having an amino group, a method of copolymerizing a PAS A preferred example is a method of melt-kneading a resin and a thiol compound having an amino group.

Preferred examples of halo compounds having an amino group include 2,5-dichloroaniline, 3,5-dichloroaniline and 4-chloroaniline.

Preferred examples of thiol compounds having an amino group include 4-aminothiophenol, 3-aminothiophenol and 2-aminothiophenol.

Preferred examples of phenol compounds having an amino group include 4-aminophenol, 3-aminophenol and 2-aminophenol.
Among these, amino group introduction using 4-aminothiophenol is preferable from the viewpoint of high reactivity, high molecular weight, and reduction of chlorine content.

[Branching/crosslinking agent]
In the present invention, a substantially linear PAS resin having a high functional group content and a high molecular weight can be obtained. Polyhalogen compounds (not necessarily aromatic compounds) can be used. Among them, polyhalogenated aromatic compounds are preferred, and specific examples include 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 1,4 ,6-trichloronaphthalene, among which 1,3,5-trichlorobenzene and 1,2,4-trichlorobenzene are preferred.

[Polymerization aid]
In order to obtain a PAS resin having a relatively high degree of polymerization in a shorter time, it is also one of preferred embodiments to use a polymerization aid. The term "polymerization aid" as used herein means a substance having the effect of increasing the viscosity of the resulting PAS resin. Specific examples of such polymerization aids include organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earth metal salts. metal phosphates and the like.

These may be used alone or in combination of two or more. Among them, organic carboxylates, alkali metal chlorides, and water are preferable, and more preferable organic carboxylates are alkali metal carboxylates, and alkali metal chlorides are lithium chloride.

The alkali metal carboxylate has the general formula R(COOM) _n (wherein R is an alkyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms). M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, n is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrous or aqueous solutions. Specific examples of alkali metal carboxylates include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. can be mentioned.

The alkali metal carboxylate is obtained by adding 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 approximately equivalent chemical equivalents to react them. may be formed by Among the above alkali metal carboxylates, the lithium salt is highly soluble in the reaction system and has a large auxiliary effect, but is expensive. On the other hand, potassium, rubidium and cesium salts are considered to have insufficient solubility in the reaction system, so sodium acetate, which is inexpensive and has moderate solubility in the polymerization system, is most preferably used.

In the present invention, the amount of the polymerization aid added is preferably in the range of 1 mol to 1500 mol per 100 mol of the charged sulfidating agent.

In the present invention, an alkali metal carboxylate is preferably used as the polymerization aid, and sodium acetate is more preferably used. In this case, from the viewpoint of obtaining a higher degree of polymerization, the amount of the alkali metal carboxylate used is preferably in the range of 1 mol to 200 mol, more preferably in the range of 10 mol to 100 mol, per 100 mol of the charged sulfidating agent. Preferably, the range of 20 to 50 mol is more preferred.

When water is used as a polymerization aid, the amount added is preferably in the range of 30 mol to 1,500 mol per 100 mol of the sulfidating agent charged, and in the sense of obtaining a higher degree of polymerization, the range is 60 mol to 1,000 mol. More preferably, the range of 100 mol to 500 mol is even more preferable.

Of course, it is possible to use two or more of these polymerization aids in combination. For example, if an alkali metal carboxylate and water are used in combination, it is possible to increase the molecular weight with a smaller amount of the alkali metal carboxylate and water.

The timing of addition of these polymerization auxiliaries is not particularly specified, and they may be added at any time during the pre-process described later, at the start of polymerization, or during polymerization, or may be added in multiple portions. When an alkali metal carboxylate is used as a polymerization aid, it is more preferable to add it simultaneously with other additives at the time of starting the pre-process or at the time of starting the polymerization from the viewpoint of ease of addition. Further, when water is used as a polymerization aid, it is effective to add it during the polymerization reaction after charging the polyhalogenated aromatic compound.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One indication of side reactions is the production of thiophenol. The addition of a polymerization stabilizer can suppress the formation of thiophenol. Specific examples of polymerization stabilizers 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 preferred. The above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, and is included in one of the polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as the sulfidation agent, it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also serve as polymerization stabilizers.

These polymerization stabilizers may be used alone or in combination of two or more. The polymerization stabilizer is usually 0.02 mol to 0.2 mol, preferably 0.03 mol to 0.1 mol, more preferably 0.04 mol to 0.09 mol, per 1 mol of charged alkali metal sulfide. It is preferred to use molar proportions. If this proportion is too small, the stabilizing effect is insufficient, and conversely, if it is too large, it is economically disadvantageous and tends to reduce the yield of the polymer.

The timing of adding the polymerization stabilizer is not particularly specified. It is more preferable from the point that it is easy to add at the time of starting the pre-process or at the time of starting the polymerization.

Next, a preferred method for producing the PAS resin of the present invention will be specifically described in order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process, but it is of course not limited to this method. .

[pre-process]
In the method for producing a PAS resin, the sulfidation agent is usually used in the form of a hydrate. Before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidation agent is heated. , it is preferable to remove excess water out of the system.

Further, as described above, a sulfidating agent prepared from an alkali metal hydrosulfide and an alkali metal hydroxide either in situ in the reaction system or in a tank separate from the polymerization tank can also be used. can be done. Although this method is not particularly limited, it is desirable to add an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent in an inert gas atmosphere at a temperature range of room temperature to 150°C, preferably room temperature to 100°C. In addition, there is a method in which the temperature is raised to at least 150° C. or higher, preferably 180° C. to 260° C., under normal pressure or reduced pressure to distill off water. A polymerization aid may be added at this stage. In addition, toluene or the like may be added to carry out the reaction in order to accelerate the distillation of water.

In the polymerization reaction, the amount of water in the polymerization system is preferably 0.3 mol to 10.0 mol per 1 mol of the charged sulfidating agent. Here, the amount of water in the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water fed into the polymerization system. Moreover, the water to be charged may be in any form such as water, an aqueous solution, or water of crystallization.

[Polymerization reaction step]
A PAS resin is produced by reacting a sulfidating agent and a dihalogenated aromatic compound in an organic polar solvent within a temperature range of 200°C or higher and lower than 290°C.

When starting the polymerization reaction step, an organic polar solvent, a sulfidation agent and a dihalogenated aromatic compound are mixed at a temperature range of room temperature to 240°C, preferably 100°C to 230°C, preferably in an inert gas atmosphere. do. A polymerization aid may be added at this stage.

In the present invention, when a halo compound having an amino group, a thiol compound having an amino group, or a phenolic compound having an amino group is added as a copolymerization component for the purpose of introducing an amino group into PAS, they are added in the polymerization reaction step. . These raw materials may be added in any order, or may be added at the same time.

This mixture is usually heated to a temperature in the range of 200°C to less than 290°C. Although there is no particular limitation on the rate of temperature increase, a rate of 0.01°C/min to 5°C/min is usually selected, and a range of 0.1°C/min to 3°C/min is more preferable.

Generally, the temperature is finally raised to a temperature of 250° C. to less than 290° C., and the reaction is normally carried out at that temperature for 0.25 hours to 50 hours, preferably 0.5 hours to 20 hours.

A method in which the temperature is raised to 270° C. to less than 290° C. after reacting at 200° C. to 260° C. for a certain period of time before reaching the final temperature is effective in obtaining a higher degree of polymerization. In this case, the reaction time at 200° C. to 260° C. is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 hours to 10 hours.

In order to obtain a polymer with a higher degree of polymerization, it may be effective to carry out polymerization in multiple stages. When the polymerization is carried out in multiple stages, it is effective that the conversion rate of the polyhalogenated aromatic compound in the system at 245° C. reaches 40 mol % or more, preferably 60 mol %.

The conversion rate of the polyhalogenated aromatic compound (hereinafter abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When the polyhalogenated aromatic compound is added in excess molar ratio to the alkali metal sulfide Conversion rate = [PHA charge amount (mol) - PHA residual amount (mol)] / [PHA charge amount (mol) -PHA excess amount (mol)]
(B) In cases other than the above (A) Conversion rate = [PHA charge amount (mol) - PHA residual amount (mol)] / [PHA charge amount (mol)

[Recovery process]
In the method for producing a PAS resin, solid matter is recovered from the polymerization reaction product containing the polymer, solvent, etc. after completion of the polymerization. As for the recovery method, any known method may be adopted.

For example, after completion of the polymerization reaction, a method of recovering the particulate polymer by slow cooling may be used. The slow cooling rate at this time is not particularly limited, but it is usually about 0.1° C./min to 3° C./min. It is not necessary to cool slowly at the same rate in all steps of the slow cooling process, and slowly cool at a rate of 0.1° C./min to 1° C./min until the polymer particles crystallize and precipitate, and then at a rate of 1° C./min or more. method may be adopted.

It is also one of the preferred methods to carry out the above recovery under rapid cooling conditions. Among these recovery methods, a preferred method is the flash method. 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 the polymer is powdered and recovered at the same time as the solvent is recovered. The method. The term "flash" as used herein means ejecting the polymerization reactant from a nozzle. The flashing atmosphere is specifically nitrogen or water vapor under normal pressure, and the temperature is usually selected in the range of 150°C to 250°C.

[Post-treatment process]
After the PAS resin is produced through the polymerization and recovery steps, it may be subjected to acid treatment, hot water treatment, washing with an organic solvent, alkali metal or alkaline earth metal treatment.

When acid treatment is performed, it is as follows. The acid used for the acid treatment of the PAS resin is not particularly limited as long as it does not decompose the PAS resin, and includes acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used. On the other hand, substances such as nitric acid that decompose and deteriorate the PAS resin are not preferable.

The method of acid treatment includes, for example, a method of immersing the PAS resin in an acid or an aqueous solution of an acid, which can be stirred or heated if necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PAS resin powder in an acetic acid aqueous solution of pH 4 heated to 80° C. to 200° C. and stirring for 30 minutes. The pH after the treatment may be 4 or higher, for example, about pH 4-8. In order to remove the acid or salt remaining from the acid-treated PAS resin, it is preferable to wash the PAS resin several times with water or hot water. The water used for washing is preferably distilled water or deionized water so as not to impair the preferable chemical modification effect of the PAS resin by acid treatment.

The case of performing hot water treatment is as follows. In the hot water treatment of the PAS resin, the temperature of hot water is preferably 100° C. or higher, more preferably 120° C. or higher, still more preferably 150° C. or higher, and particularly preferably 170° C. or higher. If the temperature is less than 100° C., the desired chemical modification effect of the PAS resin is small, which is not preferable.

The water used is preferably distilled water or deionized water in order to exhibit the desired chemical modification effect of the PAS resin by hot water washing. There are no particular restrictions on the operation of the hydrothermal treatment. A predetermined amount of PAS resin is put into a predetermined amount of water, heated and stirred in a pressure vessel, or a continuous hot water treatment is performed. As for the ratio of PAS resin and water, it is preferable that the amount of water is large, but usually a bath ratio (the weight of washing liquid to the weight of dry PAS) of 200 g or less of PAS resin per 1 liter of water is selected.

In addition, since the decomposition of the terminal group is undesirable, it is desirable to set the treatment atmosphere to an inert atmosphere in order to avoid this. In addition, the PAS resin after this hydrothermal treatment operation is preferably washed several times with warm water to remove residual components.

When washing with an organic solvent, it is as follows. The organic solvent used for washing the PAS resin is not particularly limited as long as it does not decompose the PAS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphorasamide, nitrogen-containing polar solvents such as piperazinones, dimethylsulfoxide, dimethylsulfone, sulfoxides such as sulfolane, Sulfone-based solvents, ketone-based solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone, ether-based solvents such as dimethyl ether, dipropyl ether, dioxane, and tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, and monochloroethane. Halogenated solvents such as , dichloroethane, tetrachloroethane, perchlorethane, and chlorobenzene, alcohols and phenols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol Aromatic hydrocarbon solvents such as benzene, toluene, and xylene are examples of organic solvents used for washing the PAS resin. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferred. These organic solvents are used singly or in combination of two or more.

As a method of washing with an organic solvent, for example, there is a method of immersing the PAS resin in an organic solvent, and if necessary, it is possible to appropriately stir or heat. There are no particular restrictions on the washing temperature when washing the PAS resin with an organic solvent, and any temperature from room temperature to about 300° C. can be selected. There is a tendency that the higher the washing temperature, the higher the washing efficiency. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Also, the cleaning time is not particularly limited. Although it depends on the cleaning conditions, in the case of batch cleaning, a sufficient effect can be obtained by cleaning for 5 minutes or more. It is also possible to wash continuously. In the post-treatment step, it is preferable to perform any one of acid treatment, hot water treatment, and washing with an organic solvent, and it is preferable to use two or more treatments in combination from the viewpoint of removing impurities.

Examples of the method of treating with an alkali metal or alkaline earth metal include a method of adding an alkali metal salt or an alkaline earth metal salt before, during, or after the pre-process, a method of adding an alkali metal salt or an alkaline earth metal salt before, during, or after the pre-process, before, during, or during the polymerization process. Examples include a method of adding an alkali metal salt or alkaline earth metal salt to the polymerization reactor afterward, or a method of adding an alkali metal salt or alkaline earth metal salt at the beginning, middle or end of the washing process. Among them, the easiest method includes a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with warm or hot water. Alkali metals and alkaline earth metals are preferably introduced into PAS in the form of alkali metal ions and alkaline earth metal ions such as acetates, hydroxides and carbonates. Further, it is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water or the like. When the alkali metal or alkaline earth metal is introduced, the concentration of the alkali metal ion or alkaline earth metal ion is preferably 0.001 mmol or more, more preferably 0.01 mmol or more, relative to 1 g of PAS. The temperature is preferably 50°C or higher, more preferably 75°C or higher, and particularly preferably 90°C or higher. Although there is no particular upper limit temperature, 280° C. or less is usually preferable from the viewpoint of operability. The bath ratio (washing liquid weight to dry PAS weight) is preferably 0.5 or more, more preferably 3 or more, and even more preferably 5 or more.

[Thermal oxidation cross-linking treatment]
The PAS resin in the present invention is subjected to a thermal oxidation cross-linking treatment by heating in an oxygen atmosphere after the completion of polymerization or heating with the addition of a cross-linking agent such as a peroxide to increase the molecular weight while maintaining the amino group content. is preferred.

The lower limit of the temperature for thermal oxidation crosslinking is preferably 160° C. or higher, more preferably 180° C. or higher, and still more preferably 200° C. or higher. The upper limit of the temperature for thermal oxidation cross-linking is preferably 250° C. or lower, more preferably 230° C. or lower, because the amino group may be decomposed.

Also, the oxygen concentration is desirably 5% by volume or less, more preferably 2% by volume or less. The lower limit of the treatment time is preferably 0.5 hours or more, preferably 1 hour or more, and the upper limit of the treatment time is preferably 10 hours or less, more preferably 5 hours or less. , more preferably 3 hours or less. By setting these conditions, it is possible to increase the molecular weight of PAS while suppressing a decrease in amino group content, and to obtain a PAS resin composition having particularly excellent tensile strength.

The apparatus for heat treatment may be a conventional hot air dryer or a heating apparatus with a rotating or stirring blade. For efficient and uniform treatment, it is preferable to use a rotary heating device or a heating device with stirring blades.

[Features of PAS resin]
In the present invention, a polyarylene sulfide resin composition is obtained by blending a filler and a specific alkoxysilane with a polyarylene sulfide resin having a specific amount of amino group content. Molded articles using the PAS resin composition of the present invention have a low chlorine content, high tensile strength, and are less prone to decrease in tensile strength after long-term hot water treatment.

In the present invention, from the viewpoint of obtaining a PAS resin that is excellent in tensile strength and whose tensile strength is unlikely to decrease after long-term hot water treatment, it is essential that the amino group content of the PAS resin to be blended is 60 μmol/g or more. It is preferably 70 μmol/g or more, more preferably 80 μmol/g or more. If the functional group content of the obtained PAS resin is less than 60 μmol/g, it is not preferable because sufficient adhesiveness to different materials cannot be obtained. The upper limit of the amino group content is not particularly limited, but from the viewpoint of compatibility with high molecular weight, it is essential to be 600 μmol/g or less, preferably 400 μmol/g or less, and 300 μmol/g or less. is more preferable, and 150 μmol/g or less is even more preferable.

The amino group content introduced into the PAS resin here is measured by FT-IR (IR-810 type infrared spectrophotometer manufactured by JASCO Corporation) of the amorphous film of the PAS resin, and the benzene ring-derived It can be determined by comparing the absorption at around 3380 cm ^-1 derived from the amino group with the absorption at around 1,900 cm ^-1 .

In the present invention, the PAS resin preferably has a weight average molecular weight of 35,000 or more, more preferably 40,000 or more, and even more preferably 45,000 or more, from the viewpoint of obtaining a resin composition having excellent tensile strength. If the weight-average molecular weight of the PAS resin is less than 30,000, the strength and toughness of the PAS resin may be significantly impaired during molding, which is undesirable. There is no particular upper limit to the weight average molecular weight of the PAS resin.

The weight-average molecular weight referred to herein is a value measured by gel permeation chromatography (GPC) using 1-chloronaphthalene as an eluent at a column temperature of 210° C. and converted to a polystyrene standard.

In the present invention, the chlorine content of the PAS resin is preferably 1500 ppm or less, more preferably 1300 ppm or less, and even more preferably 1200 ppm or less from the viewpoint of recent environmental regulations. Although there is no particular lower limit to the chlorine content of the PAS resin, it is usually at least 50 ppm. When the chlorine content of PAS exceeds 1500 ppm, it becomes difficult to comply with the environmental regulations of each country, which is not preferable. As a method for reducing the chlorine content of PAS, a method of copolymerizing a thiol compound having an amino group or a phenol compound having an amino group is preferable in order to obtain a structure in which chlorine is not introduced at the polymer terminal, and has an amino group. More preferably, a thiol compound is copolymerized. In addition, in the post-treatment step, it is preferable to carry out hot water treatment in addition to washing with water several times in order to completely remove sodium chloride that is a by-product of polymerization. In the hot water treatment of the PAS resin, the temperature of hot water is preferably 100° C. or higher, more preferably 120° C. or higher, still more preferably 150° C. or higher, and particularly preferably 170° C. or higher.

[Characteristics of PAS resin composition]
The PAS resin obtained in the present invention can be preferably used as a PAS resin composition obtained by melt-kneading with a filler. The filler referred to here includes glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, Fibrous fillers such as ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina silicate, etc. silicates, silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, iron oxide and other metal compounds, calcium carbonate, magnesium carbonate, carbonates such as dolomite, calcium sulfate, barium sulfate and other sulfates, calcium hydroxide , magnesium hydroxide, hydroxides such as aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and non-fibrous fillers such as silica and graphite are used, among which glass Fibrous fillers such as fibers, carbon fibers, ceramic fibers and aramid fibers are preferred, and glass fibers are more preferred.

The lower limit of the amount of the filler compounded is essentially 3 parts by weight or more, preferably 30 parts by weight or more, and more preferably 60 parts by weight or more, relative to 100 parts by weight of PAS. The upper limit is essentially 150 parts by weight or less, preferably 100 parts by weight or less, more preferably 80 parts by weight or less, relative to 100 parts by weight of PAS. If the amount of filler compounded is less than 30 parts by weight with respect to 100 parts by weight of PAS, the tensile strength and dimensional accuracy of a molded product may be significantly lowered, which is not preferable. If the amount of filler compounded exceeds 150 parts by weight per 100 parts by weight of PAS, the flowability of the resulting PAS resin composition is significantly lowered, which is not preferred.

A sizing agent having at least one functional group selected from an amino group, an epoxy group, an isocyanate group, and a carboxyl group is preferably added to the filler to be blended in the present invention. The method of applying the sizing agent to the filler is not particularly limited, but examples include a method of applying the sizing agent to the filler. Sizing agents include urethane resins, amino resins, alkoxysilane compounds, and the like. These may be used singly or in combination of two or more. Among them, a method of applying a sizing agent containing a primary amine or isocyanate to the filler is preferred. Epoxy resins, polyethylene glycol, polyesters, emulsifiers, surfactants and the like may also be used in combination as necessary.

Amino resins include urea resins, melamine resins, benzoguanamine resins, glycoluril resins, etc., and those having an amino group, a methylol group or an alkoxymethyl group, and further having an imino group can also be used. These can be used alone or in combination of two or more, and are preferably used in the form of a water dispersion such as an emulsion or dispersion, and water-soluble amino resins that are readily soluble in water are preferably used.

The sizing agent adhesion amount is preferably 0.05 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass, relative to the filler. When the amount of the sizing agent attached is 0.05% by mass or more, the effect of improving the mechanical properties of the PAS resin composition appears, and at the same time, problems such as fluff and thread breakage can be suppressed. An adhesion amount of 20% by mass or less is preferable because the sizing agent volatilizes when the PAS resin composition is melted and the working environment is not deteriorated due to gas generation.

In the present invention, when the PAS resin and the filler are melt-kneaded, an alkoxysilane having at least one functional group selected from the group consisting of an amino group, an acid anhydride group, a carboxyl group, and an isocyanate group is blended. Melt-kneading is essential.

The alkoxysilane referred to here is preferably a silane coupling agent. Specific examples include N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino propyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylethyldimethoxysilane, and the like can be preferably exemplified. Among them, alkoxysilanes having at least one functional group selected from an isocyanate group and an amino group are more preferred, and alkoxysilanes having an isocyanate group are even more preferred. The upper limit of the amount of the alkoxysilane compounded is essentially 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and more preferably 0.3 parts by weight or more, relative to 100 parts by weight of the PAS resin. preferable. The lower limit is essentially 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 1 part by weight or less, relative to 100 parts by weight of the PAS resin composition. If the amount of the alkoxysilane is less than 0.1 part by weight, the resulting PAS resin composition has low tensile strength, which is not preferable because of practical problems. If the amount of the alkoxysilane is more than 10 parts by weight, the melt viscosity is significantly increased, which is undesirable from the viewpoint of molding.

The PAS resin composition obtained by the above method is characterized by excellent tensile strength, excellent tensile strength after hydrolysis resistance test, and excellent strength retention after hydrolysis resistance test. In the present invention, the tensile strength is a JIS K7161-2 1A type test piece obtained by injection molding, using an AG-20kNx universal testing machine, a tensile speed of 5 mm / min, an ambient temperature of 23 ° C., a relative humidity of 50%. It is a value obtained according to ISO527-1 (2012) under the conditions of. In the present invention, the lower limit of tensile strength is preferably 150 MPa or higher, more preferably 170 MPa or higher, and even more preferably 180 MPa or higher. If the tensile strength is less than 150 MPa, it is not practical as a molded product, which is undesirable. Although there is no upper limit to the tensile strength in the present invention, it is usually less than 500 MPa.

Moreover, in the present invention, the tensile strength after the hydrolysis resistance test can be determined as follows. A JIS K7161-2 1A type test piece obtained by injection molding is put in an autoclave, and a solution obtained by mixing Toyota Super Long Life Coolant and deionized water at a weight ratio of 1: 1 is added to the test piece. Pour until submerged. After that, the autoclave is treated for 500 hours in a dryer heated to 150°C. After sufficiently cooling, remove the test piece from the autoclave, remove the moisture, and then use an AG-20kNx universal testing machine at a tensile speed of 5 mm / min, an ambient temperature of 23 ° C., and a relative humidity of 50%, according to ISO527-1. The tensile strength is measured and taken as the tensile strength after the hydrolysis resistance test. The lower limit of the tensile strength after the hydrolysis resistance test is preferably 130 MPa or more, more preferably 140 MPa or more. If the tensile strength after the hydrolysis resistance test is less than 120 MPa, it is not preferable because it may crack when used for a long time in an environment immersed in water. Although there is no upper limit for the tensile strength after the hydrolysis resistance test, it is usually less than 300 MPa.

In the present invention, the strength retention rate after the hydrolysis resistance test is determined according to the following formula.

Strength retention after hydrolysis resistance test (%) = Tensile strength after hydrolysis resistance test (MPa) / Tensile strength before hydrolysis resistance test (MPa) x 100 (%)
The lower limit of the strength retention rate after the hydrolysis resistance test is preferably 70% or more, more preferably 75% or more. If the strength retention rate after the hydrolysis resistance test is less than 70%, it is not preferable because it may crack when used for a long time in an environment immersed in water. Although the upper limit of the strength retention rate after the hydrolysis resistance test is not particularly limited, it is usually less than 120%.

[Use of PAS resin]
The PAS resin obtained in the present invention is preferably used for applications that require adhesion to different materials such as resins other than PAS resins, fillers, and metals, and is preferably used for applications that require adhesion to fillers. It is more preferably used in applications where adhesion to glass fibers is required. The filler as used herein includes the same fillers as those added to the PPS resin when it is melt-kneaded. In addition, in order to introduce many functional groups on the surface of the filler, it can be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. preferable.

In the present invention, the adhesion to the filler can be improved by forming a covalent bond between the PAS resin and the filler. Covalent bonds formed between the PAS resin and the filler include ether bonds, urethane bonds, ester bonds, amide bonds, esteramide bonds, imide bonds and urea bonds. Among them, a urea bond formed by reaction between an amino group of PAS and an alkoxysilane having an isocyanate group is preferred.

As a method for mixing the PAS resin obtained in the present invention with a filler, production in a molten state, production in a solution state, or the like can be used, but production in a molten state is preferably used from the viewpoint of simplicity. For production in a molten state, melt-kneading by an extruder, melt-kneading by a kneader, or the like can be used. From the viewpoint of productivity, melt-kneading by an extruder that can be continuously produced is preferably used. For melt-kneading by an extruder, one or more extruders such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder such as a four-screw extruder, and a twin-screw single-screw composite extruder can be used. From the viewpoint of improving properties, reactivity and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and melt-kneading by a twin-screw extruder is most preferable.

The PAS resin composition obtained by the present invention is excellent in heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties, and is used not only for injection molding, injection compression molding and blow molding, but also for extrusion molding. It can be formed into extrudates such as sheets, films, fibers and pipes.

Applications of the PAS resin composition of the present invention include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, and transformers. , plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc.・Electronic parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioners Household and office electrical product parts represented by parts, typewriter parts, word processor parts; Machine-related parts such as lighters: Microscopes, binoculars, cameras, clocks and other optical instruments, and precision machine-related parts; Water faucet tops, mixing faucets, pump parts, pipe joints, water control valves, relief valves , water temperature sensor, water level sensor, water meter housing, etc.; valve alternator terminal, alternator connector, IC regulator, potentiometer base for light day, various valves such as exhaust gas valve, fuel related, exhaust system, intake Various system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow Meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust tributor, starter switch, starter relay, wire for transmission Harness, window washer nozzle, air conditioner panel switch board, fuel related Electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, vehicle speed sensors, cable liners, Automobile/vehicle-related parts such as engine control unit cases, engine driver unit cases, condenser cases, motor insulating materials, hybrid car control system parts cases, and other various uses can be exemplified. Among others, it is particularly suitable for applications such as automobile cooling modules, automobile piping, housing piping, water heater parts, etc., which may come into contact with hot water or cooling water for a long period of time.

As a method for producing a PAS film using the PAS resin obtained by the present invention, a known melt film-forming method can be employed. A method in which the film is extruded from a film die and cooled on a cooling drum, or a biaxial stretching method in which the film thus prepared is stretched lengthwise and crosswise with a roller-type longitudinal stretching device and a transverse stretching device called a tenter. etc., but it is not particularly limited to this.

The PAS film obtained in this way has excellent mechanical properties, electrical properties, and heat resistance, and is suitable for various applications such as dielectric films for film capacitors and chip capacitors, and release films. can do.

As a method for producing PAS fibers using the PAS resin obtained by the present invention, a known melt spinning method can be applied. Then, the polymer is extruded from a spinneret through a streamline changer and a filter layer installed at the tip of the extruder, and then cooled, drawn, and heat-set. It is not limited.

The PAS monofilaments or short fibers thus obtained can be suitably used for various applications such as paper dryer campuses, net conveyors, and bag filters.

EXAMPLES Hereinafter, the method of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited only to these examples. In addition, various measuring methods are as follows.

[Polymer Weight Average Molecular Weight]
The weight average molecular weight (Mw) of the polymer was calculated in terms of polystyrene by gel permeation chromatography (GPC). GPC measurement conditions are shown below.
Device: SSC-7100 (Senshu Science)
Column name: GPC3506 (Senshu Kagaku)
Eluent: 1-chloronaphthalene Detector: Differential refractive index detector Column temperature: 210°C
Pre-temperature bath temperature: 250°C
Pump thermostat temperature: 50°C
Detector temperature: 210°C
Flow rate: 1.0mL/min
Sample injection volume: 300 μL (slurry: about 0.2% by weight).

[Amino group content]
The functional group content of the PAS resin was measured as follows depending on the type of functional group.

The amino group content introduced into the PAS resin is measured by FT-IR (IR-810 type infrared spectrophotometer manufactured by JASCO Corporation) of the amorphous film of the PAS resin, and 1,900 cm derived from the benzene ring ^. It was obtained by comparing the absorption around 3380 cm ⁻¹ derived from the amino group with the absorption around ¹ .

[injection molding]
The PAS resin composition was molded into a JIS K7161-2 1A type test piece using an injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries under the conditions of a resin temperature of 310°C and a mold temperature of 140°C.

[Tensile strength]
A JIS K7161-2 1A type test piece obtained by injection molding is used with an AG-20kNx universal testing machine at a tensile speed of 5 mm/min, an ambient temperature of 23 ° C., and a relative humidity of 50%. Tensile according to ISO527-1. The intensity was measured and the average value of 5 measurements was obtained.

[Chlorine content]
Using an automatic sample combustion apparatus AQF-100 manufactured by Dia Instruments, 1 to 2 mg of polymer is burned at a final temperature of 1000 ° C., the generated gas component is absorbed in 10 mL of water containing a dilute oxidant, and the absorption liquid is carbonated. An ion chromatography system ICS1500 manufactured by DIONEX Co., Ltd. using a sodium/sodium hydrogencarbonate mixed aqueous solution as a mobile phase was used to measure the total amount of chlorine in the polymer.

[Tensile strength after hydrolysis resistance test]
A JIS K7161-2 1A type test piece obtained by injection molding is put in an autoclave, and a solution obtained by mixing Toyota Super Long Life Coolant (product number 08889-01005) and ion-exchanged water at a weight ratio of 1:1 manufactured by Toyota Motor Co., Ltd. , was poured in until the specimen was fully immersed. After that, the autoclave was treated with a dryer heated to 150° C. for 500 hours. After sufficiently cooling, remove the test piece from the autoclave, remove the moisture, and then use an AG-20kNx universal testing machine at a tensile speed of 5 mm / min, an ambient temperature of 23 ° C., and a relative humidity of 50%, according to ISO527-1. The tensile strength was measured and the average value of five measurements was obtained to determine the tensile strength after the hydrolysis resistance test.

[Strength retention after hydrolysis resistance test]
The strength retention after the hydrolysis resistance test was determined according to the following formula.

Strength retention after hydrolysis resistance test (%) = Tensile strength after hydrolysis resistance test (MPa) / Tensile strength before hydrolysis resistance test (MPa) x 100 (%)
The following compounds were used for each compound used in the examples.

[Reference Example 1] Filler Filler-1: Glass fiber (Nippon Electric Glass "T760H").

[Reference Example 2] Alkoxysilane Alkoxysilane-1:2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (“KBM303” manufactured by Shin-Etsu Silicone Co., Ltd.)
Alkoxysilane-2:3-aminopropyltriethoxysilane (“KBE903” manufactured by Shin-Etsu Silicone Co., Ltd.)
Alkoxysilane-3:3-isocyanatopropyltriethoxysilane (“KBE9007” manufactured by Shin-Etsu Silicone Co., Ltd.).

[Synthesis Example 1]
8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.08 kg (73.89 mol) of 96% sodium hydroxide, N-methyl-2 were added to a 70 liter autoclave equipped with a stirrer and bottom plug valve. - Pyrrolidone (NMP) 14.57 kg (147.00 mol), sodium acetate 1.89 kg (23.10 mol) and ion-exchanged water 5.65 kg were charged, and heated to 225 ° C. over about 3 hours while passing nitrogen at normal pressure. It was gradually heated, and when 9.99 kg of water and 0.28 kg of NMP were distilled off, heating was terminated and cooling was started. Since the amount of hydrogen sulfide scattered at this point was 1.40 mol, the inorganic sulfidating agent in the system after this step was 68.60 mol.

After that, it is cooled to 200° C., p-dichlorobenzene (p-DCB) 10.24 kg (69.64 mol), 4-aminothiophenol 0.089 kg (0.71 mol), NMP 5.55 kg (56.00 mol) ) was added, the reaction vessel was sealed under nitrogen gas, and the temperature was raised from 200° C. to 218° C. at a rate of 1.0° C./min while stirring at 240 rpm. Then, the temperature was raised from 218°C to 234°C at a rate of 0.6°C/min, from 234°C to 240°C at a rate of 0.04°C/min, and from 240°C to 276°C at a rate of 0.8°C/min. °C.

Then, 1.01 g (56.00 mol) of ion-exchanged water was pressurized into the reaction vessel and reacted at 276° C. for 60 minutes. The vessel was flushed over 15 minutes and stirred briefly at 250° C. to remove most of the NMP.

The obtained recovered product and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75° C. for 15 minutes, and filtered through a filter to obtain a cake. The resulting cake was washed with ion-exchanged water at 75°C for 15 minutes and filtered three times. After that, the cake and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, and the interior of the autoclave was purged with nitrogen. The temperature was raised to 195°C. The autoclave was then cooled and the contents unloaded. The contents were filtered with a filter to obtain a cake. The obtained cake was dried at 120° C. for 4 hours under a nitrogen stream to obtain dry PAS. This PAS had a weight average molecular weight of 39,000, a chlorine content of 1,300 ppm, and an amino group content of 95 μmol/g. All of the charged 4-aminothiophenol reacted and did not remain in the polymerization reaction product.

[Synthesis Example 2]
The amino group-containing PAS obtained in Synthesis Example 1 was placed in a heating apparatus with a stirrer and having a volume of 100 L, and subjected to thermal oxidation treatment at 220° C. and an oxygen concentration of 2% for 2 hours. The obtained PAS had a weight average molecular weight of 45,000, a chlorine content of 1,200 ppm, and an amino group content of 90 μmol/g.

[Synthesis Example 3]
After the temperature was raised to 276° C., polymerization and washing were carried out in the same manner as in Synthesis Example 1, except that ion-exchanged water was not injected into the reaction vessel. The obtained PAS had a weight average molecular weight of 31000, a chlorine content of 1400 ppm and an amino group content of 95 μmol/g. All of the charged 4-aminothiophenol reacted and did not remain in the polymerization reaction product.

[Synthesis Example 4]
8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 were added to a 70 liter autoclave equipped with an agitator and bottom plug valve. -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 1.89 kg (23.10 mol), and ion-exchanged water 10.5 kg were charged, and heated to 245°C over about 3 hours while passing nitrogen under normal pressure. After 14.78 kg of water and 0.28 kg of NMP were distilled off, the reactor was cooled to 200°C. The amount of water remaining in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per 1 mol of the charged alkali metal sulfide.

After cooling to 200° C., 10.45 kg (71.07 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm to 0.000. The temperature was raised from 200°C to 270°C at a rate of 6°C/min. After reacting at 270°C for 100 minutes, the bottom plug valve of the autoclave was opened, and the contents were flushed into a container with a stirrer over 15 minutes while pressurizing with nitrogen, and stirred for a while at 250°C to remove most of the NMP. bottom.

The resulting solid matter and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70° C. for 30 minutes, and suction-filtered through a glass filter. Then, 76 liters of deionized water heated to 70° C. was poured into a glass filter and suction filtered to obtain a cake.

The resulting cake and 90 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, and acetic acid was added to adjust the pH to 7. After purging the inside of the autoclave with nitrogen, the temperature was raised to 192° C. and held for 30 minutes. The autoclave was then cooled and the contents were discharged.

After the content was suction-filtered through a glass filter, 76 liters of ion-exchanged water at 70° C. was poured thereinto and suction-filtration was performed to obtain a cake. Dry PPS was obtained by drying the resulting cake at 120° C. under a nitrogen stream. This PAS had a weight average molecular weight of 45,000, a chlorine content of 3,000 ppm, and an amino group content of 0 μmol/g.

[Synthesis Example 5]
The compounded amount of 96% sodium hydroxide was changed to 3.02 kg (72.45 mol), then the compounded amount of 4-aminothiophenol was changed to 0.044 kg (0.35 mol), p-dichlorobenzene (p -DCB) was changed to 10.19 kg (69.29 mol), polymerization and washing were carried out in the same manner as in Synthesis Example 1. The obtained PAS had a weight average molecular weight of 38,000, a chlorine content of 1,800 ppm, and an amino group content of 46 μmol/g. All of the charged 4-aminothiophenol reacted and did not remain in the polymerization reaction product.

[Examples 1 to 4, Comparative Examples 1 to 4]
For 100 parts by weight of PAS obtained in each synthesis example as shown in Table 1, an alkoxysilane having at least one functional group selected from an amino group, an acid anhydride group, a carboxyl group, and an isocyanate group is added in advance to Table 1. After dry blending at the indicated ratio, a TEX30α type twin-screw extruder equipped with a vacuum vent (manufactured by Japan Steel Works, Ltd.: L / D = 30, out of 11 cylinder blocks, two places in contact with the tip of the die were heated to 300 ° C. , and other 9 locations were set to 280° C. (Tc: cylinder temperature) and melt-kneaded. Further, glass fibers were fed at the ratio shown in Table 1 from the side feeder of the twin-screw extruder. The gut obtained by melt-kneading was pelletized by a strand cutter and dried at 130° C. overnight. The obtained pellets were subjected to injection molding, and the obtained molded articles were evaluated for tensile strength, tensile strength after the hydrolysis resistance test, and tensile strength retention after the hydrolysis resistance test. The results were as shown in Table 1.

The results of the above examples and comparative examples will be compared and explained.

In Examples 1 to 4, 3 to 200 parts by weight of a filler, an amino group, an acid anhydride group, a carboxyl group, and an isocyanate group are added to 100 parts by weight of a polyarylene sulfide resin having an amino group content of 60 to 600 μmol/g. By blending 0.1 to 10 parts by weight of alkoxysilane having at least one functional group selected from, a PAS resin composition having excellent initial strength and excellent tensile strength after the hydrolysis resistance test was obtained.

In Examples 2 to 4, by using alkoxysilanes having isocyanate groups, PAS resin compositions having excellent tensile strength after the hydrolysis resistance test were obtained.

In Examples 2 and 3, by blending PAS having a weight average molecular weight of 35000 or more and using an alkoxysilane having an isocyanate group, the initial strength is further improved, and the tensile strength after the hydrolysis resistance test is excellent. A PAS resin composition was obtained.

On the other hand, in Comparative Example 1, 3 to 200 parts by weight of a filler was mixed with 100 parts by weight of a polyarylene sulfide resin having an amino group content of 60 to 600 μmol/g. , a carboxyl group, and an isocyanate group, a PAS resin composition having a low tensile strength after the hydrolysis resistance test was obtained.

Comparative Examples 2 to 4 have a weight average molecular weight of 35000 or more, but the PAS resin having a low tensile strength after the hydrolysis resistance test by blending a polyarylene sulfide resin having an amino group content of less than 60 μmol / g. A composition was obtained.

Claims (6)

3 to 150 parts by weight of a filler and 0.1 part of an alkoxysilane having at least one functional group selected from an amino group, an acid anhydride group, a carboxyl group, and an isocyanate group per 100 parts by weight of a polyarylene sulfide resin. A polyarylene sulfide resin composition containing up to 10 parts by weight, wherein the amino group content of the polyarylene sulfide resin is 60 to 600 μmol/g. The alkoxysilane having at least one functional group selected from the amino group, acid anhydride group, carboxyl group, and isocyanate group is an alkoxysilane having an isocyanate group, the poly according to claim 1 Arylene sulfide resin composition. 3. The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide resin has a weight average molecular weight of 35,000 or more. 4. The polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide resin has a chlorine content of 1500 ppm or less. 5. The filler according to any one of claims 1 to 4, wherein the filler is provided with a sizing agent having at least one functional group selected from an amino group, an epoxy group, an isocyanate group, and a carboxyl group. A polyarylene sulfide resin composition. A molded article comprising the polyarylene sulfide resin composition according to any one of claims 1 to 5.