JP2018035230A - Polyarylene sulfide resin composition, molded article of the same and method for producing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article having higher heat resistance and dimensional stability than those of a polyphenylene sulfide resin, and to provide a resin composition for providing the molded article and a method for producing them.SOLUTION: There are provided a polyarylene sulfide resin composition which contains a polyarylene sulfide resin, and at least one other component selected from the group consisting of an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups, where the polyarylene sulfide resin has a main chain containing a specific constitutional unit containing a bisphenyl skeleton, in the infrared absorption spectrum of the polyarylene sulfide resin, an absorption peak derived from stretching vibration of S=O of a sulfonyl group is not observed; a molded article; and a method for producing them.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyarylene sulfide resin composition, a molded product thereof, and a production method thereof.

  A polyarylene sulfide resin (hereinafter sometimes abbreviated as “PAS resin”) typified by a polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”) is excellent in heat resistance, chemical resistance, etc. Widely used in electronic parts, automobile parts, water heater parts, textiles, film applications, etc.

  Conventionally, a polyphenylene sulfide resin has been produced by solution polymerization in which, for example, p-dichlorobenzene, sodium sulfide or sodium hydrosulfide, and sodium hydroxide are used as raw materials in a polymerization reaction in an organic polar solvent (for example, patents). Reference 1). Currently commercially available polyphenylene sulfide resins are generally produced by this method.

  However, since the method uses dichlorobenzene as a monomer, the halogen concentration remaining in the synthesized resin tends to be high. Further, since it is necessary to carry out the polymerization reaction under a harsh environment of high temperature, high pressure and strong alkali, it was necessary to use a polymerization vessel using expensive, difficult-to-work titanium, chromium or zirconium in the wetted part.

  Therefore, a method for producing a polyarylene sulfide resin without using dichlorobenzene as a polymerization monomer and under mild polymerization conditions is known. For example, Patent Document 2 discloses a solvent-soluble poly (arylenesulfonium salt) as a precursor for synthesizing a polyarylene sulfide resin. A poly (arylenesulfonium salt) is produced by a method of homopolymerizing a sulfoxide having one sulfinyl group such as methylphenylsulfoxide (hereinafter sometimes referred to as “monofunctional sulfoxide”) in the presence of an acid ( For example, see Patent Document 2 and Non-Patent Document 1).

  The polyphenylene sulfide resin is mainly used as a part around an engine of an automobile because of its high heat resistance and dimensional stability based on crystallinity. However, with the recent miniaturization of parts, higher dimensional stability is being demanded, and the development of molded products having heat resistance and dimensional stability that exceed those of polyphenylene sulfide resins is desired.

  Further, in the polymerization reaction shown in Non-Patent Document 1, it is common to use trifluoromethanesulfonic acid as a solvent, but the above acid is highly corrosive, so from the safety and industrial viewpoints, in the polymerization solution There is a need for a production method that lowers the acidity of.

US Pat. No. 3,354,129 Japanese Patent Laid-Open No. 10-182825

JOURNAL OF MACROMOLECULAR SCIENCE Part A-Pure and Applied Chemistry, Volume 40, Issue 4, p. 415-423

  Therefore, the problem to be solved by the present invention is to provide a molded article having heat resistance and dimensional stability exceeding those of polyphenylene sulfide resin, a resin composition for providing the molded article, and a method for producing them. .

  As a result of various studies, the present inventors have found that by using a polyarylene sulfide resin having a biphenyl skeleton, a molded product having crystallinity and high heat resistance, and a resin composition for providing the molded product are provided. As a result, the present invention was completed.

That is, the present invention is selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups, A polyarylene sulfide resin composition containing one other component,
The polyarylene sulfide resin has a main chain containing a structural unit represented by the following general formula (1.1), and in the infrared absorption spectrum of the polyarylene sulfide resin, S═O stretching of the sulfonyl group The present invention relates to a polyarylene sulfide resin composition characterized in that an absorption peak derived from vibration is not observed.

［一般式（１．１）中、Ａｒ^１及びＡｒ^２ｂはそれぞれ独立に、置換基を有していてもよいアリーレン基を表し、２つのＡｒ^１は同一でも異なってもよい。］

[In General Formula (1.1), Ar ¹ and Ar ^2b each independently represent an arylene group which may have a substituent, and two Ar ¹ may be the same or different. ]

  The present invention also relates to a molded article obtained by molding the polyarylene sulfide resin composition described above.

Further, the present invention is selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups, A method for producing a polyarylene sulfide resin composition in which one other component is blended and melt-kneaded,
The polyarylene sulfide resin has a main chain containing a structural unit represented by the following general formula (1.1), and in the infrared absorption spectrum of the polyarylene sulfide resin, S═O stretching of the sulfonyl group The present invention relates to a method for producing a polyarylene sulfide resin composition, wherein an absorption peak derived from vibration is not observed.

［一般式（１．１）中、Ａｒ^１及びＡｒ^２ｂはそれぞれ独立に、置換基を有していてもよいアリーレン基を表し、２つのＡｒ^１は同一でも異なってもよい。］

[In General Formula (1.1), Ar ¹ and Ar ^2b each independently represent an arylene group which may have a substituent, and two Ar ¹ may be the same or different. ]

  The present invention also relates to a method for producing a molded product, characterized in that the polyarylene sulfide resin composition obtained by the production method described above is molded.

  That is, the present invention relates to a molded product obtained by molding the polyarylene sulfide resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for providing the molded article which has the heat resistance and dimensional stability exceeding polyphenylene sulfide resin, the said molded article, and those manufacturing methods can be provided.

It is an infrared absorption spectrum of poly (p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Polymer Synthesis Example 1b. 3 is an infrared absorption spectrum of poly (p-phenylenethio-p, p′-biphenylylene sulfide) obtained in Polymer Synthesis Example 2. FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The polyarylene sulfide resin composition of the present invention comprises:
At least one other component selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. And a polyarylene sulfide resin composition containing,
The polyarylene sulfide resin has a main chain containing a structural unit represented by the following general formula (1.1), and in the infrared absorption spectrum of the polyarylene sulfide resin, S═O stretching of the sulfonyl group An absorption peak derived from vibration is not observed.

［一般式（１．１）中、Ａｒ^１及びＡｒ^２ｂはそれぞれ独立に、置換基を有していてもよいアリーレン基を表し、２つのＡｒ^１は同一でも異なってもよい。］

[In General Formula (1.1), Ar ¹ and Ar ^2b each independently represent an arylene group which may have a substituent, and two Ar ¹ may be the same or different. ]

  The polyarylene sulfide resin according to an embodiment is a polymer having a main chain including a structural unit represented by the following general formula (1.1). The main chain of the polyarylene sulfide resin may be substantially composed only of the structural unit represented by the general formula (1.1). More specifically, the proportion of the structural unit represented by the general formula (1.1) in the main chain of the polyarylene sulfide resin is in the range of 95 to 100% by mass, or in the range of 98 to 100% by mass. May be.

In the formula, Ar ¹ and Ar ^2b each independently represent an arylene group which may have a substituent, and two Ar ¹ may be the same or different.

Aspects of binding of Ar ¹ and ^{Ar 2b} is not particularly limited, Ar ¹ and ^{Ar 2b} is preferably combined with S and Ar ¹ at a distant position in the arylene group. For example, when Ar ¹ and Ar ^2b are phenylene groups, Ar ¹ and Ar ^2b are units bonded at the para position (1,4-phenylene group) or units bonded at the meta position (1,3-phenylene group). ), And more preferably a unit bonded at the para position. In terms of heat resistance and crystallinity of the polyarylene sulfide resin, Ar ¹ and Ar ^2b are preferably composed of units bonded at the para position.

Examples of the substituent that the arylene group represented by Ar ¹ or Ar ^2b may have include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a group, a hydroxy group, an amino group, a mercapto group, an ester group, and a carboxy group.

  In general, in the polyarylene sulfide resin having such a main chain, a small amount of a sulfonyl group which is considered to be derived from a sulfoxide compound described later may remain, but the polyarylene sulfide resin of the present invention is a sulfonyl group. Substantially free of groups. According to the knowledge of the present inventors, a polyarylene sulfide resin having a high melting point can be obtained by substantially eliminating the sulfonyl group. This is presumably because the proportion of the amorphous part due to the remaining sulfonyl group is reduced.

Reflecting that the polyarylene sulfide resin does not substantially contain a sulfonyl group, an absorption peak derived from the S═O stretching vibration of the sulfonyl group is not observed in the infrared absorption spectrum of the polyarylene sulfide resin. An absorption peak derived from S═O stretching vibration of a sulfonyl group is usually observed in a region in the range of wave numbers 1170 to 1140 cm ⁻¹ . In this specification, “absorption peak derived from S═O stretching vibration of sulfonyl group is not observed” means that absorption derived from S═O stretching vibration of sulfonyl group is in a region in the range of wave numbers from 1170 to 1140 cm ^−1. This means that the peak top of is not observed. Here, even when there is a local minimum value or a local maximum value sandwiched between flat portions in the region of wave numbers 1170 to 1140 cm ⁻¹ , the height of the local minimum value or the local maximum value from the flat portion and the wave number A peak whose ratio from the minimum value to the maximum value of the absorption peak observed in the range of 1200 to 1170 cm ⁻¹ is 0.1 or less is not regarded as a peak. The infrared absorption spectrum is measured using, for example, an amorphous film prepared by a method in which a polyarylene sulfide resin is heated and melted on a 400 ° C. hot plate and rapidly cooled, as a measurement sample.

  The mass average molecular weight of the polyarylene sulfide resin according to one embodiment is preferably 8,000 or more, and more preferably 10,000 or more. When the weight average molecular weight is in such a range, the polyarylene sulfide resin can exhibit more excellent heat resistance and mechanical properties. In this specification, “mass average molecular weight” means a value (converted value by standard polystyrene) measured by gel permeation chromatography. The measurement conditions for gel permeation chromatography can be appropriately set within a range that does not substantially affect the measurement value of the mass average molecular weight.

  The glass transition temperature of the polyarylene sulfide resin according to one embodiment is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and in the range of 120 to 180 ° C. Further preferred. The glass transition temperature of the polyarylene sulfide resin can be determined by differential scanning calorimetry (DSC).

  The melting point of the polyarylene sulfide resin according to one embodiment is preferably in the range of 100 to 450 ° C, more preferably in the range of 180 to 420 ° C, and still more preferably in the range of 280 to 400 ° C. More preferably, it is in the range of 330 to 380 ° C. The melting point of the polyarylene sulfide resin can be determined by differential scanning calorimetry (DSC).

The 5% thermal decomposition temperature (T _{5% d} ) of the polyarylene sulfide resin according to an embodiment is preferably in the range of 200 to 800 ° C, more preferably in the range of 300 to 650 ° C, and 350 to More preferably, it is in the range of 600 ° C. The 5% thermal decomposition temperature of the polyarylene sulfide resin indicates a value measured by thermogravimetry / differential thermal analysis (TG-DTA).

<Method for producing polyarylene sulfide resin>
The polyarylene sulfide resin as described above is, for example,
The following general formula (3.1):

で表されるスルホキシド化合物を酸の存在下で重合して、下記一般式（２．１）：

Is polymerized in the presence of an acid, and the following general formula (2.1):

で表される構成単位を含む主鎖を有するポリ（アリーレンスルホニウム塩）を生成させる工程と、
ポリ（アリーレンスルホニウム塩）を脱アルキル化又は脱アリール化して、上記式（１．１）で表される構成単位を含む主鎖を有するポリアリーレンスルフィド樹脂を生成させる工程と、を含む方法により、製造することができる。式（３．１）で表されるスルホキシド化合物を得る方法に関しては後述される。

Producing a poly (arylenesulfonium salt) having a main chain containing a structural unit represented by:
A step of dealkylating or dearylating poly (arylenesulfonium salt) to produce a polyarylene sulfide resin having a main chain containing the structural unit represented by the above formula (1.1). Can be manufactured. A method for obtaining the sulfoxide compound represented by the formula (3.1) will be described later.

Ar ¹ and ^{Ar 2b} in these formulas are defined as Ar ¹ and ^{Ar 2b} in formula (1.1). R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group optionally having an alkyl group having 1 to 10 carbon atoms as a substituent, and X ⁻ represents an anion. . Ar ^2a represents an aryl group which may have a substituent, and this is an aryl group corresponding to Ar ^2b in formula (1.1). The substituent that the aryl group represented by Ar ^2a may have is the same as Ar ^2b .

The R ^1, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, an alkyl group having from 1 to 10 carbon atoms such as a decyl group, In addition, aryl groups having a structure such as phenyl, naphthyl, biphenyl and the like can be mentioned. The aryl group is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group. You may have in the range of 1-4 as a substituent couple | bonded with the ring.

Examples of the anion of X ⁻ include sulfonate, carboxylate, phosphate ion, perchlorate ion, hexafluorophosphate ion, and halogen ion.

  The polymerization reaction of the sulfoxide compound represented by the formula (3.1) can be performed in a reaction solution containing an acid. The acid may be an organic acid or an inorganic acid. Examples of the acid include non-oxygen acids such as hydrochloric acid, hydrobromic acid, hydrocyanic acid, tetrafluoroboric acid; sulfuric acid, phosphoric acid, perchloric acid, bromic acid, nitric acid, carbonic acid, boric acid, molybdic acid, isopolyacid, and heteropolyacid. Inorganic oxo acids such as acids; sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropolyacid salts, partial salts or partial esters of sulfuric acid such as monomethyl sulfate, trifluoromethane sulfate, etc .; formic acid, acetic acid, propionic acid, butanoic acid, succinic acid Monovalent or polyvalent carboxylic acids such as acid, benzoic acid and phthalic acid; halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid and trifluoroacetic acid; methanesulfonic acid and ethanesulfone Acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, benzenedisulfur Monovalent or polyvalent sulfonic acid such as acid; Partial metal salt of polyvalent sulfonic acid such as sodium benzenedisulfonate; Antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride And Lewis acids such as copper chloride and iron chloride. Of these acids, trifluoromethanesulfonic acid and methanesulfonic acid are preferably used from the viewpoint of reactivity, and methanesulfonic acid is more preferable from the viewpoint of easily obtaining a polyarylene resin containing no sulfonyl group. When using trifluoromethanesulfonic acid as an acid, it is preferable to use it with the solvent mentioned later. These acids may be used alone or in combination of two or more.

  The amount of the acid used for the polymerization reaction is preferably in the range of 100 to 2000 parts by mass, more preferably in the range of 200 to 1000 parts by mass with respect to 100 parts by mass of the sulfoxide compound represented by the formula (3.1). is there.

  The polymerization reaction of the sulfoxide compound represented by the formula (3.1) may be performed in the presence of a dehydrating agent together with an acid. The use of a dehydrating agent can also contribute to the production of a polyarylene sulfide resin that does not contain a sulfonyl group. Examples of the dehydrating agent include phosphoric anhydrides such as phosphorus oxide and diphosphorus pentoxide; sulfonic acids such as benzenesulfonic anhydride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, and paratoluenesulfonic anhydride. Examples of the anhydrides include: carboxylic acid anhydrides such as acetic anhydride, fluoroacetic anhydride, and trifluoroacetic anhydride; anhydrous magnesium sulfate, zeolite, silica gel, calcium chloride, and the like. These dehydrating agents may be used alone or in combination of two or more. In order to obtain a polyarylene sulfide resin containing no sulfonyl group, a combination of methanesulfonic acid and diphosphorus pentoxide is particularly preferred.

  The amount of the dehydrating agent used in the polymerization reaction is preferably in the range of 5 to 150 parts by mass, more preferably in the range of 30 to 100 parts by mass with respect to 100 parts by mass of the sulfoxide compound represented by the formula (3.1). It is.

  The reaction solution for the polymerization reaction may contain a solvent. The combined use of an acid and a solvent can also contribute to the production of a polyarylene sulfide resin containing no sulfonyl group. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, and isopropyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitrile solvents such as acetonitrile; dichloromethane (methylene chloride), and chloroform. Halogen solvents; saturated hydrocarbon solvents such as normal hexane, cyclohexane, normal heptane, cycloheptane; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone; sulfur-containing solvents such as sulfolane and DMSO An ether solvent such as tetrahydrofuran and dioxane. These solvents may be used alone or in combination of two or more. When trifluoromethanesulfonic acid is used, a combination of trifluoromethanesulfonic acid and dichloromethane or acetonitrile is preferred in order to obtain a polyarylene sulfide resin not containing a sulfonyl group.

  The amount of the solvent when the acid and the solvent are used in combination in the polymerization reaction is preferably in the range of 50 to 5000 parts by mass and more preferably in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the acid. If the amount of the solvent is within the above range, the acidity during the polymerization reaction is lowered, and the resulting polyarylene sulfide resin is less likely to contain a sulfonyl group.

  The reaction temperature of the polymerization reaction is preferably in the range of -30 to 150 ° C, more preferably in the range of 0 to 100 ° C.

  The reaction of dealkylating or dearylating the poly (arylenesulfonium salt) produced by the polymerization reaction can proceed efficiently in a reaction solution containing a dealkylating agent or a dearylating agent. Examples of dealkylating or dearylating agents include nucleophiles and reducing agents. Examples of the nucleophile include nitrogen-containing aromatic compounds, amine compounds, and amide compounds. Examples of the reducing agent include metal potassium, metal sodium, potassium chloride, sodium chloride, and hydrazine. These compounds may be used alone or in combination of two or more. The amount of the dealkylating agent or dearylating agent may be set so that the reaction proceeds appropriately. Usually, it is 100 to 50,000 parts by mass with respect to 100 parts by mass of poly (arylenesulfonium salt). Set by range.

  Examples of the nitrogen-containing aromatic compound include pyridine, quinoline, and aniline. Of these compounds, pyridine which is a general-purpose compound is preferable.

  Examples of the amine compound include trialkylamine and ammonia.

The amide compound can be an aromatic amide compound or an aliphatic amide compound.
The aliphatic amide compound is represented, for example, by the following general formula (9).

In the general formula (9), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹¹ and R ¹³ are bonded to form a cyclic structure. It may be formed. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

  Aliphatic amide compounds are more miscible in water than aromatic amide compounds and can be easily removed by washing the reaction mixture with water. For this reason, when the aliphatic amide compound is used, the residual amount of the aliphatic amide compound in the polyarylene sulfide resin can be further reduced as compared with the case where the aromatic amide compound is used.

  Use of an aliphatic amide compound as a dealkylating agent or dearylating agent suppresses gas generation during resin processing, improves the quality of the polyarylene sulfide resin molded product, improves the working environment, and further molds This is preferable because the maintainability can be further improved. Since the aliphatic amide compound is excellent in the solubility of the organic compound, the use of the aliphatic amide compound also makes it possible to easily remove the oligomer component of polyarylene sulfide from the reaction mixture. As a result, the quality of the polyarylene sulfide resin obtained can be synergistically improved by removing the oligomer component that may contribute to gas generation with the aliphatic amide compound.

Aliphatic amide compounds include, for example, primary amide compounds such as formamide, secondary amide compounds such as β-lactam, tertiary amide compounds such as N-methyl-2-pyrrolidone, dimethylformamide, diethylformamide, dimethylacetamide, and tetramethylurea. It can be selected from amide compounds. The aliphatic amide compound preferably includes an aliphatic tertiary amide compound in which R ¹² and R ¹³ are aliphatic groups from the viewpoint of the solubility of poly (arylenesulfonium salt) and the solubility in water. Of the tertiary amide compounds, N-methyl-2-pyrrolidone is preferred.

  In addition to functioning as a dealkylating agent or dearylating agent, the aliphatic amide compound can also be used as a reaction solvent because of its excellent solubility. Only an aliphatic amide compound may be used as the reaction solvent, or another solvent such as toluene may be used in combination.

The reaction temperature of dealkylation or dearylation of poly (arylenesulfonium salt) can be appropriately adjusted so that the reaction proceeds appropriately. For example, the reaction temperature is in the range of 50 to 250 ° C or 80 to 230 ° C. It may be a range.

  The method for producing a polyarylene sulfide resin further includes a step of washing the polyarylene sulfide resin produced by dealkylation or dearylation of poly (arylenesulfonium salt) with water, a water-soluble solvent or a mixed solvent thereof. But you can. By this washing step, the remaining amount of the dealkylating agent or dearylating agent contained in the polyarylene sulfide resin can be more reliably reduced. This tendency is particularly remarkable when the dealkylating agent or dearylating agent is an aliphatic amide compound.

  The residual amount of the dealkylating agent or dearylating agent in the polyarylene sulfide resin is based on the total mass of the resin including the polyarylene sulfide resin and other components such as the dealkylating agent or the dearylating agent. Preferably it is 1000 ppm or less, More preferably, it is 700 ppm or less, More preferably, it is 100 ppm or less. When the residual amount of the dealkylating agent or dearylating agent in the resin is 1000 ppm or less, the substantial influence on the quality of the polyarylene sulfide resin can be further reduced.

  The solvent used in the washing step is not particularly limited, but is preferably a solvent that dissolves unreacted substances. Examples of the solvent include acidic aqueous solutions such as water, hydrochloric acid, acetic acid aqueous solution, oxalic acid aqueous solution and nitric acid aqueous solution; aromatic hydrocarbon solvents such as toluene and xylene; alcoholic solvents such as methanol, ethanol, propanol and isopropyl alcohol; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dioxane; Amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; Dichloromethane, chloroform and the like And halogen-containing solvents. These solvents may be used alone or in combination of two or more. Of these solvents, water or N-methyl-2-pyrrolidone is preferable from the viewpoint of removing the reaction reagent and the oligomer component of the resin.

  If necessary, the polyarylene sulfide resin as the reaction product may be subjected to a base treatment by contact with an aqueous solution containing a basic compound. By the base treatment, a hydroxy group or a carboxy group present in the molecular structure of the polyarylene sulfide resin can be converted into a metal salt.

  Examples of the basic compound used for the base treatment include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; sodium carbonate Potassium carbonate; sodium phosphate.

<Method for Producing Sulphoxide Compound Represented by Formula (3.1)>
(Method 1)
The sulfoxide compound represented by the formula (3.1) is, for example,
The following general formula (5.1):

で表されるジアリールジスルフィドと下記一般式（６．１）：

And a diaryl disulfide represented by the following general formula (6.1):

で表されるスルフィド化合物との反応によって、下記一般式（４．１）：

By the reaction with the sulfide compound represented by the following general formula (4.1):

で表されるスルフィド化合物を生成させる工程と、
式（４．１）で表されるスルフィド化合物を酸化して式（３．１）で表されるスルホキシド化合物を生成させる工程と、を含む方法により得ることができる。

A step of producing a sulfide compound represented by:
And oxidizing the sulfide compound represented by the formula (4.1) to produce a sulfoxide compound represented by the formula (3.1).

(Method 2)
Alternatively, the sulfoxide compound represented by the formula (3.1) is
The following general formula (6.1):

で表されるスルフィド化合物を酸化して下記一般式（８．１）：

The sulfide compound represented by the following general formula (8.1):

で表されるスルホキシド化合物を生成させる工程と、
式（８．１）で表されるスルホキシド化合物と下記一般式（５．１）：

A step of producing a sulfoxide compound represented by:
The sulfoxide compound represented by the formula (8.1) and the following general formula (5.1):

で表されるジアリールジスルフィドとの反応によって式（３．１）で表されるスルホキシド化合物を生成させる工程と、を含む方法により得ることもできる。

And a step of producing a sulfoxide compound represented by the formula (3.1) by reaction with a diaryl disulfide represented by formula (3.1).

In these formulas, Ar ¹ , Ar ^2a , and R ¹ are defined in the same manner as in formula (3.1). Two Ar ^2a in the formula (5.1) may be the same or different. Y ¹ represents a halogen atom.
Y ¹ may be a chlorine atom, a bromine atom, or an iodine atom, and is preferably a bromine atom.

  In Method 1, the reaction of the diaryl disulfide represented by the formula (5.1) and the sulfide compound represented by the formula (6.1) can be performed in a suitable solvent. The solvent used for this reaction can be appropriately selected from those described above. The reaction temperature may be, for example, in the range of −100 to 100 ° C., or in the range of −78 to 10 ° C.

  Specific examples of the diaryl disulfide represented by the formula (5.1) include unsubstituted diaryl disulfides such as diphenyl disulfide and dinaphthyl disulfide; bis (2-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, bis Examples include diaryl disulfides having a substituent such as (2-carboxyphenyl) disulfide; diaryl disulfides having a heterocyclic ring such as 2,2′-dibenzothiazolyl disulfide, and the like.

  The sulfide compound represented by the formula (6.1) is, for example, the following general formula (7.1):

で表される芳香族化合物と、式：Ｒ^１Ｙ^２で表されるハロゲン化炭化水素とを、硫黄の存在下で反応させることで得ることができる。Ｒ^１としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の炭素原子数１〜１０の範囲のアルキル基、並びに、フェニル、ナフチル、ビフェニル等の構造を有するアリール基が挙げられる。当該アリール基は、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の炭素原子数１〜１０の範囲のアルキル基を、芳香環に結合した置換基として１〜４個の範囲で有していてもよい。またＹ^２としては塩素原子、臭素原子、又はヨウ素原子であってもよく、Ｒ^１とＹ^２の組み合わせは上記記載の中から適宜選択できる。式（７．１）中、Ａｒ^１は式（６．１）のＡｒ^１と同様に定義される。Ｙ^１及びＹ^２は、ハロゲン原子を表し、Ｙ^１とＹ^２は互いに同一でも異なっていてもよい。

Can be obtained by reacting a halogenated hydrocarbon represented by the formula: R ¹ Y ² in the presence of sulfur. The R ^1, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, an alkyl group having from 1 to 10 carbon atoms such as a decyl group, In addition, aryl groups having a structure such as phenyl, naphthyl, biphenyl and the like can be mentioned. The aryl group is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group. You may have in the range of 1-4 as a substituent couple | bonded with the ring. Y ² may be a chlorine atom, a bromine atom, or an iodine atom, and the combination of R ¹ and Y ² can be appropriately selected from the above description. Wherein (7.1), Ar ¹ is defined as in Ar ¹ of formula (6.1). Y ¹ and Y ² represent a halogen atom, and Y ¹ and Y ² may be the same as or different from each other.

  Examples of the aromatic compound represented by the formula (7.1) include 4-bromo-4′-iodobiphenyl, 4,4′-dibromobiphenyl, 4,4′-dibromobinaphthyl, and 10,10′-dibromo. Unsubstituted aromatic compounds such as -9,9'-bianthracene; aromatics having substituents such as 4,4'-dibromo-2-biphenylamine and 4,4'-dibromo-2,2'-biphenyldiamine Compound, etc. can be mentioned.

  The reaction of the sulfide compound represented by the formula (6.1) and the halogenated hydrocarbon can be performed in a reaction solution containing a solvent selected from the solvents described above.

  The sulfide compound represented by the formula (4.1) can be oxidized in a reaction solution containing an oxidizing agent. The oxidizing agent is not particularly limited, but is selected from, for example, potassium permanganate, oxygen, ozone, organic peroxide, hydrogen peroxide, nitric acid, m-chloroperoxybenzoic acid, oxone (registered trademark), and osmium tetroxide. Can do. This reaction can be performed in an appropriately selected solvent. What is necessary is just to set reaction temperature suitably, For example, the range of -20-100 degreeC or the range of 0-70 degreeC may be sufficient.

  Each reaction constituting Method 2 can be performed in the same manner as each elementary reaction constituting Method 1. For example, the oxidation reaction of the sulfide compound represented by the formula (6.1) can be performed in the presence of an oxidizing agent under the same conditions as the sulfide compound represented by the formula (4.1).

  The halogen content of the polyarylene sulfide resin of the present invention is preferably 900 ppm or less, and more preferably 500 ppm or less.

  The sodium content of the polyarylene sulfide resin of the present invention is preferably 100 ppm or less, and more preferably 50 ppm or less. By using a polyarylene sulfide resin having a sodium content in such a range, a molded article having excellent chemical resistance can be produced.

  The amount of gas generated during heating of the polyarylene sulfide resin of the present invention can be in the range of 0.2% by mass or less, and preferably in the range of 0.15% by mass or less. By suppressing the amount of gas generated during heating, it is possible to contribute to the improvement of the working environment. Furthermore, mold contamination can be suppressed during molding, and productivity is improved.

  The polyarylene sulfide resin composition according to the present invention can contain the above-mentioned polyarylene sulfide resin and one or more inorganic fillers. By containing the inorganic filler, a composition having high rigidity and high heat stability can be obtained. Examples of inorganic fillers include powdery fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate-like fillers such as talc and mica, granular fillers such as glass beads, silica beads and glass balloons, and glass fibers. And fibrous fillers such as carbon fiber and wollastonite fiber, and glass flakes. It is particularly preferable that the polyarylene sulfide resin composition contains at least one inorganic filler selected from the group consisting of glass fiber, carbon fiber, carbon black, and calcium carbonate.

  The content of the inorganic filler is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 5 to 200 parts by mass, and still more preferably in the range of 15 to 150 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It is. When the content of the inorganic filler is in these ranges, a more excellent effect can be obtained in terms of maintaining the mechanical strength of the molded product.

  The polyarylene sulfide resin composition according to the present invention can contain the polyarylene sulfide resin described above and a resin other than the polyarylene sulfide resin selected from thermoplastic resins, elastomers, and crosslinkable resins. These resins can be blended in the resin composition together with the inorganic filler.

  Examples of the thermoplastic resin that can be blended in the polyarylene sulfide resin composition include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, and polyethylene. , Polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymer (liquid crystal polyester, etc.).

  Polyamide is a polymer having an amide bond (—NHCO—). Examples of the polyamide resin include (i) a polymer obtained from polycondensation of diamine and dicarboxylic acid, (ii) a polymer obtained from polycondensation of aminocarboxylic acid, and (iii) a polymer obtained from ring-opening polymerization of lactam. Is mentioned. Polyamides can be used alone or in combination of two or more.

  Examples of diamines for obtaining polyamides include aliphatic diamines, aromatic diamines, and alicyclic diamines. As the aliphatic diamine, a diamine having 3 to 18 carbon atoms having a straight chain or a side chain is preferable. Examples of suitable aliphatic diamines include 1,3-trimethylene diamine, 1,4-tetramethylene diamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine. 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanmethylenediamine, 1,12-dodecamethylene Diamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18 -Octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine And 2,4,4-trimethyl hexamethylene diamine. These can be used alone or in combination of two or more.

As the aromatic diamine, a diamine having a phenylene group and having 6 to 27 carbon atoms is preferable. Examples of suitable aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 3,4-diaminodiphenyl ether, 4,4′- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-di (m-aminophenoxy) Diphenylsulfone, 4,4′-di (p-aminophenoxy) diphenylsulfone, benzidine, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 1 , 5-Diaminonaphthalene, 1,8-diaminonaphthalene 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-diamino-3,3′-diethyl -5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 2,4-diaminotoluene, and 2,2'-dimethylbenzidine.
These can be used alone or in combination of two or more.

  The alicyclic diamine is preferably a diamine having a cyclohexylene group and having 4 to 15 carbon atoms. Examples of suitable alicyclic diamines include 4,4'-diamino-dicyclohexylene methane, 4,4'-diamino-dicyclohexylene propane, 4,4'-diamino-3,3'-dimethyl- Examples include dicyclohexylenemethane, 1,4-diaminocyclohexane, and piperazine. These can be used alone or in combination of two or more.

  Examples of the dicarboxylic acid for obtaining the polyamide include aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and alicyclic dicarboxylic acid.

  As the aliphatic dicarboxylic acid, a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms is preferable. Examples of suitable aliphatic dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, placillic acid, tetradecane Examples include diacids, pentadecanedioic acid, octadecanedioic acid, maleic acid, and fumaric acid. These can be used alone or in combination of two or more.

  As the aromatic dicarboxylic acid, dicarboxylic acids having a phenylene group and having 8 to 15 carbon atoms are preferable. Examples of suitable aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, methyl terephthalic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid. Examples include acids, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. . These can be used alone or in combination of two or more. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range that can be melt-molded.

  As the aminocarboxylic acid, an aminocarboxylic acid having 4 to 18 carbon atoms is preferable. Examples of suitable aminocarboxylic acids include 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid, 14-aminotetradecanoic acid, 16-aminohexadecanoic acid, and 18-aminooctadecanoic acid. These can be used alone or in combination of two or more.

  Examples of the lactam for obtaining the polyamide include ε-caprolactam, ω-laurolactam, ζ-enantolactam, and η-capryllactam. These can be used alone or in combination of two or more.

  Preferred combinations of polyamide raw materials include ε-caprolactam (nylon 6), 1,6-hexamethylenediamine / adipic acid (nylon 6,6), 1,4-tetramethylenediamine / adipic acid (nylon 4,6) 1,6-hexamethylenediamine / terephthalic acid, 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9-nonamethylenediamine / terephthalic acid Acids, 1,9-nonamethylenediamine / terephthalic acid / ε-caprolactam, 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid, and m-xylylenediamine / adipic acid It is done. Among these, 1,4-tetramethylenediamine / adipic acid (nylon 4,6), 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, Obtained from 1,9-nonamethylenediamine / terephthalic acid, 1,9-nonamethylenediamine / terephthalic acid / ε-caprolactam, or 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid More preferred are amide resins.

  The content of the thermoplastic resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, and still more preferably in the range of 5 to 45 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It is. When the content of the thermoplastic resin other than the polyarylene sulfide resin is within these ranges, the effect of further improving the heat resistance, chemical resistance and mechanical properties can be obtained.

  Examples of the elastomer that can be contained in the polyarylene sulfide resin composition of the present invention include thermoplastic elastomers. Examples of the thermoplastic elastomer include polyolefin elastomers, fluorine elastomers, and silicone elastomers. In the present specification, the thermoplastic elastomer is classified not as the thermoplastic resin but as an elastomer.

  The elastomer (especially thermoplastic elastomer) preferably has a functional group capable of reacting with a hydroxy group or an amino group. Thereby, it is possible to obtain a resin composition that is particularly excellent in terms of adhesion and impact resistance. Such functional groups include epoxy groups, carboxy groups, isocyanate groups, oxazoline groups, and the formula: R (CO) O (CO)-or R (CO) O- (wherein R is from 1 to 8 carbon atoms). Represents an alkyl group in the range of 2). The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having the functional group. Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, and butene-1. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid, and the like. Other examples include α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters and acid anhydrides thereof), glycidyl (meth) acrylates, and the like. Among these, an epoxy group, a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms). The ethylene-propylene copolymer and the ethylene-butene copolymer having at least one functional group selected from the group consisting of groups represented by formula (1) are preferred from the viewpoint of improving toughness and impact resistance.

  Since the elastomer content varies depending on the type and application, it cannot be defined unconditionally. For example, it is preferably in the range of 1 to 300 parts by mass, more preferably 3 to 100 parts per 100 parts by mass of the polyarylene sulfide resin. It is the range of a mass part, More preferably, it is the range of 5-45 mass part. When the content of the elastomer is within these ranges, a more excellent effect can be obtained in terms of ensuring the heat resistance and toughness of the molded product.

Examples of the crosslinkable resin that can be contained in the polyarylene sulfide resin composition according to the present invention include those having two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amino group, an amide group, a carboxy group, an acid anhydride group, and an isocyanate group. Examples of the crosslinkable resin include an epoxy resin, a phenol resin, and a urethane resin.

  As the epoxy resin, an aromatic epoxy resin is preferable. The aromatic epoxy resin may have a halogen group or a hydroxyl group. Examples of suitable aromatic epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolacs. Type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl Type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon Le formaldehyde resin-modified phenol resin type epoxy resins, and biphenyl novolac-type epoxy resin. These aromatic epoxy resins can be used alone or in combination of two or more. Among these aromatic epoxy resins, a novolak type epoxy resin is preferable and a cresol novolak type epoxy resin is more preferable because it is excellent in compatibility with other resin components.

  The content of the crosslinkable resin is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 3 to 100 parts by mass, and still more preferably in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It is. When the content of the crosslinkable resin is in these ranges, the effect of improving the rigidity and heat resistance of the molded product can be obtained particularly remarkably.

  The polyarylene sulfide resin composition of the present invention can contain the above-described polyarylene sulfide resin and a silane compound having a functional group capable of reacting with a hydroxy group or an amino group. Examples of the silane compound include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples include silane coupling agents such as diethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

  The content of the silane compound is, for example, preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. . When the content of the silane compound is within these ranges, an effect of improving the compatibility between the polyarylene sulfide resin and the other components can be obtained.

  The polyarylene sulfide resin composition of the present invention may contain other additives such as a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant. For example, the content of the additive is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin.

  The production method of the polyarylene sulfide resin composition of the present invention is not particularly limited, and has a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more crosslinkable functional groups. After at least one other component selected from the group consisting of a crosslinkable resin is put into a ribbon blender, a Henschel mixer, a V blender, etc. in various forms such as powder, pellets, strips, etc., dry blended, A temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably a melting point + 10 ° C. or higher, is charged into a known melt kneader such as a Banbury mixer, a mixing roll, a single or twin screw extruder and a kneader. Temperature range, more preferably (the melting point + 10 ° C.) to (the melting point + 100 ° C.) Comprising temperature range, more preferably it can be produced through the steps of melt-kneading at a temperature range of between (melting point + 20 ° C.) ~ (melting point + 50 ° C.). Addition and mixing of each component to the melt kneader may be performed simultaneously or may be performed separately.

  The melt kneader is preferably a biaxial kneader / extruder from the viewpoint of dispersibility and productivity. For example, the resin component discharge rate is in the range of 5 to 500 kg / hr, and the screw rotation speed is 50 to 500 (rpm). It is preferable to perform melt kneading while appropriately adjusting the range of the above, and melt kneading under the condition that the ratio (discharge amount / screw rotation number) is in the range of 0.02 to 5 (kg / hr / rpm). Is more preferable. In addition, for example, when adding a fibrous filler or additive, instead of the top feeder of the biaxial kneading extruder, it can also be fed into the extruder from a side feeder, and shape retention and dispersibility can be achieved. It is also possible to improve. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin charging part to the side feeder with respect to the total screw length of the twin-screw kneading extruder is in the range of 0.1 to 0.9. In particular, a range of 0.3 to 0.7 is particularly preferable.

  The polyarylene sulfide resin composition of the present invention thus obtained comprises the polyarylene sulfide resin as an essential component, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more crosslinkable properties. It is a melt-kneaded product obtained by blending at least one other component selected from the group consisting of a crosslinkable resin having a functional group so as to have the above content, and after the melt-kneading, pellets are obtained by a known method, After processing into a form such as a chip, granule, powder, etc., it is preferably subjected to preliminary drying in a temperature range of 100 to 150 ° C., if necessary, and used for various moldings.

  The polyarylene sulfide resin composition of the present invention produced by the above production method has a polyarylene sulfide resin as a matrix (sea component), and in the matrix, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, At least one other component selected from the group consisting of an elastomer and a crosslinkable resin having two or more crosslinkable functional groups, or a morphology having a sea-island structure in which components derived therefrom are dispersed in an island shape is formed. It is preferable.

  The polyarylene sulfide resin composition of the present invention can be used for various types of melt molding such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. It is suitable for injection molding because of its excellent mold release properties. When molding by injection molding, various molding conditions are not particularly limited, and can be molded by a general method. For example, in an injection molding machine, the resin temperature is a temperature range above the melting point of the polyarylene sulfide resin, preferably (the melting point + 10 ° C.) or more, more preferably (the melting point + 10 ° C.) to (the melting point + 100 ° C.). After the step of melting the polyarylene sulfide resin composition in a temperature range of, preferably (the melting point + 20 ° C.) to (the melting point + 50 ° C.), it is injected into the mold from the resin discharge port. What is necessary is just to shape | mold. At that time, the mold temperature may be set to a known temperature range, for example, a temperature range of room temperature (23 ° C.) to 300 ° C., preferably a temperature range of 120 to 200 ° C.

  The polyarylene sulfide resin composition of the present invention has excellent swelling resistance against petroleums such as gasoline, and oils such as engine oil and ATF oil. The degree of swelling of the polyarylene sulfide resin composition of the present invention is preferably in the range of 1.5% or less, and more preferably in the range of 1.0% or less. However, the degree of swelling was determined by measuring the weight of the molded product when immersed in a drug (methanol / isooctane / toluene = 15 / 42.5 / 42.5 (volume ratio)) and allowed to stand at 80 ° C. for 2000 hours. Thus, the weight increase rate after immersion is evaluated with respect to the weight before immersion.

  The polyarylene sulfide resin composition of the present invention can suppress swelling into petroleums such as gasoline, various oils, and drugs, and assures dimensional stability and sealability as a container as parts in contact with drugs. This is preferable. As a result, it can be used for a long period of several years, and it is also preferable from the viewpoint of durability life and miniaturization and thinning, such as reduction of parts replacement frequency and thickness.

  As an embodiment of the polyarylene sulfide resin composition of the present invention, it can be used alone or in combination with materials such as the above-mentioned other components by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. Can be processed into a molded product having excellent properties, molding processability, dimensional stability, and the like. Since the polyarylene sulfide resin composition of the present invention generates a small amount of gas when heated, it enables easy production of a high-quality molded product.

  The polyarylene sulfide resin composition of the present invention combines, for example, the above-described polyarylene sulfide resin and an inorganic filler having high thermal conductivity (hereinafter referred to as high thermal conductivity inorganic filler). Therefore, it can be processed into a molded product having excellent thermal conductivity. Examples of the high thermal conductive inorganic filler include those having a thermal conductivity in the range of 20 or more [W / m · K], such as aluminum oxide, beryllium oxide, magnesium oxide, aluminum nitride or silicon nitride, Silicon carbide, boron nitride, zinc oxide, zinc sulfide and the like can be mentioned, and these can be used alone or in combination of two or more. At that time, since it exhibits excellent thermal conductivity, the proportion of the high thermal conductive inorganic filler in the composition is such that the molded product exhibits high thermal conductivity, so that 100 parts by mass of the polyarylene sulfide resin, It is preferably in the range of 10 parts by mass or more, and preferably in the range of 300 parts by mass or less because the moldability and the molded product exhibit high mechanical strength.

  In addition, the polyarylene sulfide resin composition of the present invention is suitable for use around water including, for example, a pipe for fluid having excellent cold-heat shock resistance by combining the above-described polyarylene sulfide resin and the above-described thermoplastic elastomer. It can be processed into a molded product.

  Examples of fluid piping include pipes, lining pipes, cap nuts, pipe joints (elbow, header, cheese, reducer, joint, coupler, etc.), various valves, flow meters, gaskets (seal, packing) And various parts (fluid pipes) attached to the pipe for conveying the fluid. In addition, as water use, other materials suitable for water use such as toilet related parts, water heater related parts, pump related parts, bath related parts and the like. In particular, the opening and closing parts such as valves and plugs are generally subject to high stress loads, and are greatly damaged by acidic or alkaline cleaning agents and the temperature difference between cold air and hot water, especially in winter, which makes it difficult to use for a long time. Therefore, the composition of the present invention is particularly useful in the field of the opening / closing component.

  Furthermore, when the polyarylene sulfide resin composition of the present invention is used for electric vehicle parts, the amount of gas generated by heating can be reduced. Therefore, a low molecular weight compound containing a sulfur atom as a gas component and a metal material such as copper (conductive) As a result, even when a high voltage is repeatedly applied, the reaction between the two can be suppressed, and the occurrence and progress of trees (dendritic destruction traces) can be suppressed. It is also possible to improve tracking performance. As a result, it can be used not only for parts mounted on automobiles (hereinafter referred to as automobile parts) such as electrical / electronic parts such as connectors, printed circuit boards and sealing molded products, lamp reflectors and various electrical equipment parts, etc. Electric vehicle field where high safety is required, that is, a hybrid vehicle (HV), a plug-in hybrid vehicle (PHV), an electric vehicle (EV), and a fuel having a lithium ion secondary battery and using an electric motor as a power source Cases for storing power modules, converters, capacitors, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, junction blocks, etc. in battery cars (FCV) etc., especially ignition coil cases for DLI systems, etc. Preferably used as That.

  In addition, since the polyarylene sulfide resin composition of the present invention also has various performances such as heat resistance and dimensional stability inherent to the polyarylene sulfide resin, for example, a gasket material for a secondary battery such as lithium ion, Used to obtain precision parts that require dimensional stability, such as interior materials for various buildings, aircraft and automobiles, OA equipment parts, camera parts and watch parts, for example, by injection molding, compression molding, and insert molding. it can. In addition, the polyarylene sulfide resin composition according to this embodiment is widely useful as a material for various molding processes such as extrusion molding and pultrusion molding for composites, sheets and pipes, and a material for fibers or films. is there.

  In the present invention, a range of “1 to 10” represents a range of 1 or more and 10 or less.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Production example of polyarylene sulfide resin]

1. Evaluation method 1-1. Identification method (NMR measurement)
The compound was dissolved in various heavy solvents with a BRUKER DPX-400 apparatus, and various NMR was measured.

1-2. Identification method (mass spectrometry)
The molecular weight of the compound was measured using MS-700T manufactured by JEOL.

1-3. Identification method (elemental analysis)
The ratio of the elements constituting the compound was measured using MT-5 manufactured by Yanaco.

1-4. Infrared absorption spectrum The infrared absorption spectrum was measured using "FT / IR-6100" manufactured by JASCO Corporation. An amorphous film produced by heating and melting the synthesized resin with a hot plate at 400 ° C. and rapidly cooling was used as a measurement sample.

1-5. Glass transition temperature (Tg)
Using a Perkin Elmer DSC device Pyris Diamond, the glass transition temperature was determined by measuring the temperature up to 40 to 400 ° C. under a nitrogen flow rate of 50 mL / min under a temperature rising condition of 20 ° C./min.

1-6. Melting point (Tm)
Using a Perkin Elmer DSC apparatus Pyris Diamond, measurement was performed in a nitrogen flow of 50 mL / min under a temperature rising condition of 20 ° C./min up to a range of 40 to 400 ° C. to obtain a melting point.

1-7.5% thermal decomposition temperature (T _{5% d} )
Using a TG-DTA apparatus (Rigaku TG-8120 Co., Ltd.), measurement was conducted at a rate of temperature increase of 20 ° C./min under a nitrogen flow of 20 mL / min to measure a 5% weight loss temperature.

1-8. Mass average molecular weight Mass average molecular weight was measured using a high temperature gel permeation chromatograph (GPC) SSC-7000 manufactured by Senshu Scientific. The average molecular weight was calculated in terms of standard polystyrene.
Solvent: 1-chloronaphthalene inlet: 250 ° C
Temperature: 210 ° C
Detector: UV detector (360 nm)
Sample concentration: 1 g / L
Flow rate: 0.7 mL / min

2. Monomer Synthesis In the examples shown below, the following reagents were used.
4-Bromo-4'-iodobiphenyl: Tokyo Chemical Industry Co., Ltd., purity> 98%
Iodomethane: Kanto Chemical Co., Ltd., special grade copper iodide: Kanto Chemical Co., Inc., purity> 99%
Sulfur: Kanto Chemical Co., Ltd. Potassium carbonate: Nacalai Tesque Co., Ltd., Nacalai standard special grade N, N-dimethylformamide (dehydrated): Kanto Chemical Co., Ltd., special grade Sodium borohydride: Kanto Chemical Co., Ltd. Celite: Wako Pure Chemical Industries, Ltd. , No. 503
n-Butyl bromide: Tokyo Chemical Industry Co., Ltd., purity> 98%
tert-Butyllithium (n-pentane solution) 1.6 mol / L: Kanto Chemical Co., Inc. Tetrahydrofuran (dehydration): Kanto Chemical Co., Ltd. Diphenyl disulfide: Kanto Chemical Co., Ltd., special grade Ammonium chloride: Nacalai Tesque Co., Ltd., Nacalai Standard Special Grade Nitric acid (1.38): Wako Pure Chemical Industries, Ltd., reagent grade, content in the range of 60-61%, density 1.38 g / mL
Dichloromethane: Kanto Chemical Co., Ltd., special grade Methanesulfonic acid: Wako Pure Chemical Industries, Ltd., Wako special grade Diphosphorus pentoxide: Wako Pure Chemical Industries, Ltd., Wako special grade

(Monomer Synthesis Example 1a)
Synthesis of 4-bromo-4 '-(methylthio) biphenyl

In a three-necked flask, 100 parts by mass of 4-bromo-4′-iodobiphenyl, 10 parts by mass of copper iodide, 300 parts by mass of sulfur, and 1,700 parts by mass of potassium carbonate were placed, and the atmosphere in the flask was replaced with nitrogen. After adding 20,000 parts by mass of N, N-dimethylformamide (dehydrated) to the flask, the mixture was stirred at 100 ° C. for 17 hours. Then, 400 mass parts of sodium borohydride was added at 0 degreeC, and it stirred at 50 degreeC for 6 hours. Then, 900 mass parts of iodomethane was added at 0 degreeC, and it stirred at 25 degreeC for 20 hours. After stirring, the reaction solution was poured into 10% hydrochloric acid to stop the reaction. After filtration through celite, extraction with dichloromethane, and liquid separation, the organic layer was dehydrated over anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator and dried under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using hexane as a developing solvent. The solution containing the separated target product was collected, the solvent was removed with a rotary evaporator, and dried under reduced pressure to obtain 4-bromo-4 ′-(methylthio) biphenyl in 43% yield. ^The product was confirmed by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (solvent CDCl ₃ ): 2.52, 7.32, 7.43, 7.48, 7.54 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 15.9, 121.5, 127.0, 127.4, 128.5, 132.0, 136.8, 138.4, 139.6 [ppm]

(Monomer Synthesis Example 1b)
Synthesis of 4-methylthio-4 '-(phenylthio) biphenyl

4-Bromo-4 ′-(methylthio) biphenyl 100 parts by mass and tetrahydrofuran (dehydrated) 4000 parts by mass were added to a nitrogen-substituted three-necked flask. 400 mass parts of t-butyllithium was added to the reaction solution under -78 degreeC, and it stirred for 1 hour. Subsequently, 100 parts by mass of diphenyl disulfide was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Thereafter, the reaction solution was poured into an aqueous ammonium chloride solution to stop the reaction. After extraction with diethyl ether and liquid separation, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator and dried under reduced pressure to obtain a crude product. The crude product is separated by column chromatography using hexane as a developing solvent, the solution containing the target product is recovered, and the solvent is removed by a rotary evaporator to obtain 4-methylthio-4 ′-(phenylthio) biphenyl in a yield of 73. %. ^The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 2.52, 7.24-7.28, 7.30-7.34, 7.39, 7.50 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 15.9, 127.0, 127.3, 127.4, 127.6, 129.4, 131.3, 131.5, 135.0, 135.8, 137.1, 138.1, 139.4 [ppm]
EI-MS: m / z 308 (M ⁺ )
Elemental analysis (calculated value): C 73.98 (73.70), H 5.23 (5.23)

(Monomer Synthesis Example 1c)
Synthesis of 4-methylsulfinyl-4 '-(phenylthio) biphenyl

In an eggplant flask, 100 parts by mass of 4-methylthio-4 ′-(phenylthio) biphenyl and 2000 parts by mass of dichloromethane were added, and 40 parts by mass of nitric acid was added. The reaction solution was stirred at 25 ° C. for 3 hours and neutralized with a saturated aqueous potassium carbonate solution to stop the reaction. Then, after extraction with dichloromethane and liquid separation, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator and dried under reduced pressure to obtain a crude product. The crude product is separated by column chromatography using chloroform as a developing solvent, the solution containing the target product is recovered, the solvent is removed with a rotary evaporator, and the residue is dried under reduced pressure to give 4-methylsulfinyl-4 ′-(phenylthio). ) Biphenyl was obtained in 72% yield. ^The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 2.77, 7.30, 7.35, 7.39, 7.43, 7.52, 7.71 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 44.1, 124.3, 127.7, 128.0, 128.0, 129.5, 130.9, 132.0, 135.0, 136.9, 143.4, 144.8 [ppm]
EI-MS: m / z 324 (M ^<+> )
Elemental analysis (calculated value): C 70.33 (70.19), H 4.97 (4.98)

(Monomer Synthesis Example 2a)
Synthesis of 4-n-butylthio-4 ′-(phenylthio) biphenyl

4-Bromo-4 ′-(n-butylthio) biphenyl was obtained in a yield of 72% by performing the same operation as in Monomer Synthesis Example 1a except that 700 parts by mass of n-butyl bromide was used instead of iodomethane. Thereafter, 100 parts by mass of 4-bromo-4 ′-(n-butylthio) biphenyl and 4,000 parts by mass of tetrahydrofuran (dehydrated) were added to a nitrogen-substituted three-necked flask. To the reaction solution, 400 parts by mass of t-butyllithium was added at −78 ° C., and the mixture was stirred for 1 hour. Subsequently, 100 parts by mass of diphenyl disulfide was added to the reaction solution, followed by stirring at 25 ° C. for 3 hours. Thereafter, the reaction solution was poured into an aqueous ammonium chloride solution to stop the reaction. After extraction with diethyl ether and liquid separation, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtering the dehydrated reaction solution, the solvent was removed from the filtrate with a rotary evaporator, and the crude product was obtained by drying under reduced pressure. The crude product was separated by column chromatography using hexane as a developing solvent, and a solution containing the target product was recovered. The solvent was removed with a rotary evaporator and dried under reduced pressure to obtain 4-n-butylthio-4 ′-(phenylthio) biphenyl in a yield of 72%. ^The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 0.94, 1.47, 1.67, 2.96, 7.24-7.28, 7.31, 7.34-7.40, 7.49, 7.51 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 13.8, 22.1, 31.3, 33.2, 127.3, 127.4, 127.7, 129.0, 129.4, 131.3, 131.4, 135.7, 136.7, 137.6, 139.3 [ppm]
EI-MS: m / z 350 (M ⁺ )
Elemental analysis (calculated value): C 75.21 (75.38), H 6.35 (6.33)

(Monomer Synthesis Example 2b)
Synthesis of 4-n-butylsulfinyl-4 ′-(phenylthio) biphenyl

4-n-butyl was prepared in the same manner as in Monomer Synthesis Example 1c except that 4-n-butylthio-4 ′-(phenylthio) biphenyl was used instead of 4-methylthio-4 ′-(phenylthio) biphenyl. Sulfinyl-4 ′-(phenylthio) biphenyl was obtained in a yield of 85%. ^The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 0.93, 1.42-1.50, 1.59-1.78, 2.83, 7.29-7.43, 7.53, 7.69 [ ppm]
¹³ C-NMR (solvent CDCl ₃ ): 13.8, 22.0, 24.3, 57.2, 124.7, 127.6, 127.8, 128.0, 129.5, 130.9, 131.8, 135.0, 136.7, 138.3, 143.0, 143.1 [ppm]
EI-MS: m / z 366 (M ^<+> )
Elemental analysis (calculated values): C 72.09 (72.12), H 6.05 (6.10)

(Polymer synthesis example 1a)
Synthesis of poly {methyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium}

To a separable flask, 100 parts by mass of 4-methylsulfinyl-4 ′-(phenylthio) biphenyl and 50 parts by mass of diphosphorus pentoxide were added, and 500 parts by mass of methanesulfonic acid was added dropwise at 0 ° C. The reaction solution was stirred at 25 ° C. for 20 hours, and then poured into acetone to stop the reaction. The precipitated solid was removed by filtration and washed with acetone. Thereafter, the washed solid was dried under reduced pressure to obtain poly {methyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} at a yield of 93%. ^The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent DMSO-d ₆ ): 3.84, 7.63, 7.87, 8.04, 8.15 [ppm]

(Polymer synthesis example 1b)
Synthesis of poly (p-phenylenethio-p, p'-biphenylylene sulfide)

  100 parts by mass of the obtained poly {methyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} and 2000 parts by mass of N-methyl-2-pyrrolidone were added to the flask. The reaction solution was stirred at 25 ° C. for 30 minutes and then stirred at 120 ° C. for 20 hours. The reaction solution was poured into water to stop the reaction, and the precipitate was filtered off. Subsequently, the precipitate was washed with chloroform, NMP, and water, and the resulting solid was dried under reduced pressure to obtain poly (p-phenylenethio-p, p′-biphenylylene sulfide) at a yield of 43%. (Hereinafter sometimes referred to as PAS-1).

As a result of thermal analysis of the obtained poly (p-phenylenethio-p, p′-biphenylylene sulfide), the glass transition temperature (Tg) was 164 ° C., the melting point was 347 ° C., and the 5% thermal decomposition temperature (T _{5 % D} ) was 507 ° C. FIG. 1 shows an infrared absorption spectrum of the obtained poly (p-phenylenethio-p, p′-biphenylylene sulfide). In the infrared absorption spectrum of FIG. 1, no absorption peak derived from the S═O stretching vibration of the sulfonyl group was observed in the vicinity of the wave number of 1160 cm ⁻¹ . This indicates that the obtained poly (p-phenylenethio-p, p′-biphenylylene sulfide) has substantially no sulfonyl group.

(Polymer synthesis example 2)
Synthesis of poly {n-butyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} and poly (p-phenylenethio-p, p′-biphenylylene sulfide)

The same procedure as in Polymer Synthesis Example 1a was performed, except that 4-n-butylsulfinyl-4 ′-(phenylthio) biphenyl was used instead of 4-methylsulfinyl-4 ′-(phenylthio) biphenyl. N-butyl 4- [4- (phenylthio) phenyl] phenylsulfonium sulfonate was obtained with a yield of 95%. ^The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent DMSO-d ₆ ): 0.81, 1.40, 1.54, 4.31, 7.40, 7.82, 7.99, 8.04, 8.15 [ppm]

  The same procedure as in Polymer Synthesis Example 1b was performed except that the obtained poly {n-butyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} was used, so that poly (p-phenylenethio- p, p′-biphenylylene sulfide) was obtained in a yield of 56% (hereinafter sometimes referred to as PAS-2).

As a result of thermal analysis of the obtained poly (p-phenylenethio-p, p′-biphenylylene sulfide), the glass transition temperature (Tg) was 159 ° C., the melting point was 348 ° C., and the 5% thermal decomposition temperature (T _{5 % D} ) was 507 ° C. FIG. 2 shows an infrared absorption spectrum of the obtained poly (p-phenylenethio-p, p′-biphenylylene sulfide). In the infrared absorption spectrum of FIG. 2, an absorption peak derived from S═O stretching vibration of the sulfonyl group was not observed in the vicinity of the wave number of 1160 cm ⁻¹ .

[Comparative synthesis example]
220.5 g (1.5 mol) of p-dichlorobenzene (hereinafter abbreviated as “p-DCB”) in a 1-liter autoclave of zirconium lining with stirring blades connected with a pressure gauge, a thermometer, a condenser, and a decanter. , 29.7 g (0.3 mol) of NMP, 177.29 g (1.5 mol) of 47.43 wt% aqueous NaOH solution, and 123.18 g (1.5 mol) of 48.71 wt% aqueous NaOH solution were stirred and stirred. Then, the temperature was raised to 173 ° C. over 2 hours under a nitrogen atmosphere to distill 177.98 g of water, and the kettle was sealed. At that time, p-DCB distilled by azeotropic distillation was separated by a decanter and returned to the inside of the kettle as needed. After completion of dehydration, the internal temperature was cooled to 160 ° C., 267.65 g (2.7 mol) of NMP was charged, the temperature was raised to 230 ° C., stirred at 230 ° C. for 5 hours, and then heated to 250 ° C. in 40 minutes. , And stirred at 250 ° C. for 1 hour. After cooling, the resulting slurry was poured into 3 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred with 3 liters of warm water for 1 hour, washed and filtered. This operation was repeated 4 times, and after filtration, dried at 120 ° C. overnight using a hot air dryer to obtain 154 g of white powdery PPS (indicated as PAS-3 in Table 1).
As a result of thermal analysis of the obtained solid, it was confirmed that polyphenylene sulfide was formed since it had a glass transition temperature (Tg) of 92 ° C. and a melting point of 277 ° C.

Examples 1-4, Comparative Example 1
[Polyarylene sulfide resin composition (PAS composite)]
<Raw material>
In order to prepare the polyarylene sulfide resin composition, the following materials were prepared.

(Filler / Additive)
・ Epoxysilane: γ-glycidoxypropyltrimethoxysilane ・ GF: Glass fiber chopped strand (fiber diameter 10 μm, length 3 mm)
Elastomer: Sumitomo Chemical, Bond First 7L
CF: pitch-based carbon fiber, tensile elastic modulus 560 GPa
CaCO ₃ (calcium carbonate): “Caltex 5” (powder, average particle size 1.2 μm), manufactured by Maruo Calcium Co., Ltd.

<Evaluation method>
[Swelling characteristics by immersion test]
-Test piece: 1 mm (thickness) x 60 mm (width) x 60 mm (long)
-Immersion solution: methanol / isooctane / toluene = 15 / 42.5 / 42.5 (volume ratio)
Immersion conditions: 80 ° C. × 2000 hours Test result: The weight before and after immersion was measured at n = 3, the weight increase rate was calculated from the following formula, and the average value was used as the test result of the swelling property.
(Weight increase rate) = ((weight after immersion) − (weight before immersion)) / (weight before immersion) × 100

[Gas generation amount]
Using a gas chromatograph mass spectrometer (manufactured by Shimadzu Corporation, GC-2010), a predetermined amount of a sample of the polyarylene sulfide resin composition was heated at 325 ° C. for 15 minutes, and the amount of gas generated at that time was quantified as mass%. .

<Production and evaluation of compound>
After each raw material is uniformly mixed using a tumbler with the composition shown in Table 1, each barrel temperature range of 6 zones is 370 to 410 ° C. using a twin-screw kneading extruder (TEM-35B, Toshiba Machine). The mixture was melt-kneaded so as to satisfy the above range to obtain a pellet-like compound. The obtained compound was injection-molded under the conditions of the mold temperature: 200 ° C. with each cylinder temperature in the three zones in the range of 370 to 410 ° C., bending properties, Charpy impact strength, acid resistance test, alkali resistance test or Test pieces used for the hot water resistance test were prepared and subjected to various evaluations. Further, the amount of generated gas was measured for the PAS compound. The evaluation results are shown in Table 1.

  As is clear from the results shown in Table 1, the swelling degree (weight increase rate before and after immersion) of Examples 1 to 4 using the PAS resins of Polymer Synthesis Examples 1 and 2 is the same as that of the PAS resin of Comparative Synthesis Example. Not only is it significantly smaller than that of Comparative Example 1 used, and it is clear that the swelling resistance is excellent, and the amount of generated gas is significantly higher than that of Comparative Example 1 using the PAS resin of Comparative Synthesis Example. It became clear that it could be reduced. Although the reason is not a fixed theory, it is thought to be derived from a biphenyl skeleton having crystallinity and high heat resistance.

Claims (5)

At least one other component selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. And a polyarylene sulfide resin composition containing,
The polyarylene sulfide resin has a main chain containing a structural unit represented by the following general formula (1.1), and in the infrared absorption spectrum of the polyarylene sulfide resin, S═O stretching of the sulfonyl group A polyarylene sulfide resin composition characterized in that an absorption peak derived from vibration is not observed.

[In General Formula (1.1), Ar ¹ and Ar ^2b each independently represent an arylene group which may have a substituent, and two Ar ¹ may be the same or different. ]   A molded article obtained by molding the polyarylene sulfide resin composition according to claim 1.   High heat conductive material application, secondary battery gasket material application, water supply application, electric / electronic component application, automotive parts application including electric automobile parts, interior material application, precision parts application, film or fiber application Item 3. A molded article according to Item 2. At least one other component selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. And a method for producing a polyarylene sulfide resin composition that is blended and melt kneaded,
The polyarylene sulfide resin has a main chain containing a structural unit represented by the following general formula (1.1), and in the infrared absorption spectrum of the polyarylene sulfide resin, S═O stretching of the sulfonyl group A method for producing a polyarylene sulfide resin composition, wherein an absorption peak due to vibration is not observed.

[In General Formula (1.1), Ar ¹ and Ar ^2b each independently represent an arylene group which may have a substituent, and two Ar ¹ may be the same or different. ]   A method for producing a molded article, comprising molding the polyarylene sulfide resin composition obtained by the production method according to claim 4.

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