JP2016147959A - Polyarylene sulfide resin composition and molded article of the same, and electric automobile part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin composition which can suppress an amount of gas to be generated by heating, and has excellent tracking resistance, mechanical strength, metal adhesiveness, and cavity balance characteristics in the resin composition or a molded article of the same; a molded article using the resin composition; and electric automobile parts having the molded article.SOLUTION: A polyarylene sulfide resin composition for electric automobile parts contains a polyarylene sulfide resin, an inorganic filler, and at least one component other than the polyarylene sulfide resin selected from the group consisting of a thermoplastic resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. A method for producing a polyarylene sulfide resin includes a step of obtaining poly(arylene sulfonium salt) by reaction of sulfoxide and an aromatic compound; and a step of obtaining a polyarylene sulfide resin by dealkylation or dearylation of the poly(arylene sulfonium salt).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyarylene sulfide resin composition, a molded product thereof, and an electric vehicle part.

  An electric vehicle attracting attention in recent years has many components that operate at a high voltage, and resin molded products are used for such electric vehicle components. Examples of the use of the resin molded product include an automobile ignition coil case in which a resin molded product is used as a coil case and the ignition coil is sealed with an epoxy resin composition in the coil case, or an ignition plug and an ignition coil. Examples thereof include a coil case in an integrated distributorless ignition system (hereinafter sometimes abbreviated as “DLI system”).

  Such electric vehicle parts are required to have tracking resistance so as not to ignite even under high voltage. Further, for example, the coil case as described above is desirably excellent in adhesiveness with an epoxy resin or a metal.

On the other hand, for example, a resin composition containing a polyarylene sulfide resin (hereinafter sometimes abbreviated as “PAS resin”) represented by a polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”). It has been proposed to be molded and used for the automobile parts as described above (see, for example, Patent Document 1).
The polyarylene sulfide resin can be produced, for example, by solution polymerization in which p-dichlorobenzene and 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). References 2 and 3). Currently commercially available polyphenylene sulfide resins are generally produced by this method.
However, since the polymerization product obtained by this method generally contains by-products such as sodium chloride and oligomers, a purification treatment for removing these is required. Attempts have been made to reduce by-products by devising the purification process (Patent Document 4).

JP 2000-103964 A US Pat. No. 2,513,188 US Pat. No. 2,583,941 JP 2010-77347 A

However, a composition containing a conventional polyarylene sulfide resin has a relatively large amount of gas generated by heating such as during molding. For this reason, when a low molecular weight compound containing a sulfur atom, which is a gas component, and a metal material such as copper come into contact with each other, a high voltage is repeatedly applied to cause the two to react, and a tree (dendritic fracture trace) There is also a high possibility that the tracking resistance will be lowered. In particular, an electric vehicle using a motor for driving force requires driving energy equivalent to that of a gasoline engine when starting, so a lithium ion secondary battery is provided, the battery voltage is 100 to 400 V, and a booster circuit is installed, 650 V. Driven by high voltage. In automotive parts where high safety is required, especially in parts for electric vehicles, there are many parts that operate under high voltage and high current, so it is even higher than conventional automobiles that use lead-acid batteries. In addition, there is a need for fire prevention performance and fire spread prevention performance at the time of abnormality, and it has been required not only to have excellent flame retardancy but also to further suppress the tracking phenomenon that causes fire.
In addition, polyarylene sulfide resin is often used in the case part of electronic control parts for automobiles, and since the voids in the case are sealed with epoxy resin, silicone resin, etc., the adhesion between these resins and metals is low. The stronger it is, the less likely it is to have a peeling point (void) that tends to be the starting point of destruction, which directly leads to an improvement in the life of the part. Therefore, not only the tracking resistance is improved, but also the adhesion with metal (hereinafter referred to as metal adhesion), It has been a challenge to combine strong adhesion with epoxy resins and silicone resins (hereinafter referred to as adhesion such as epoxy resins).

  Moreover, although the mechanical characteristics can be improved by reducing the amount of sodium and the like by improving the purification process of the polyarylene sulfide resin as described in Patent Document 4, sodium is promoted by the above-described tree, high humidity and high temperature. In the resin composition of Patent Document 4 or its molded product, tracking resistance, mechanical strength, epoxy adhesion, metal, etc. may be adversely affected from the standpoint of maintaining the strength below and inhibiting the reaction with the epoxy resin, etc. There was still room for improvement in properties such as adhesion and cavity balance.

  Therefore, the problem to be solved by the present invention is that the amount of gas generated by heating can be suppressed, and excellent tracking resistance, hot water resistance, mechanical strength, epoxy adhesiveness, metal adhesion, resin composition or molded product thereof, An object of the present invention is to provide a polyarylene sulfide resin composition having a cavity balance characteristic, a molded article using the resin composition, and an electric vehicle part including the molded article.

  The cavity balance is related to the uniformity of the filling degree of each cavity when a plurality of molded products are molded simultaneously by injection molding using a mold having a plurality of cavities. If the cavity balance of the molding material is not sufficient, there is a tendency that molding defects such that some of the cavities are not sufficiently filled tend to occur.

  As a result of various studies, the present inventors have reacted sulfoxide with an aromatic compound to obtain poly (arylenesulfonium salt), and dealkylated or dearylated the poly (arylenesulfonium salt). A polyarylene sulfide resin obtained by a method including a step of obtaining 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 The present inventors have found that the above-mentioned problems can be solved by blending with at least one other component selected from the group consisting of the following (hereinafter sometimes simply referred to as “the other component”), and have completed the present invention. .

That is, the present invention is at least one selected from the group consisting of polyarylene sulfide resins, inorganic fillers, thermoplastic resins other than polyarylene sulfide resins, elastomers, and crosslinkable resins having two or more crosslinkable functional groups. And a polyarylene sulfide resin comprising a sulfoxide represented by the following general formula (1) and the following general formula (2): Reacting the aromatic compound represented to obtain a poly (arylenesulfonium salt) having a structural unit represented by the following general formula (10);
Dealkylating or dearylating the poly (arylenesulfonium salt) to obtain a polyarylene sulfide resin having a structural unit represented by the following general formula (20);
Can be obtained by a method comprising
The polyarylene sulfide resin, the infrared absorption spectrum measured by FT-IR ^{spectroscopy, and} has an absorption peak in the range of 2910cm ^-1 ~2930cm -1, electric automobile parts polyarylene sulfide resin composition About.

(In Formula (1), (2), (10) or (20), R ¹ is an aryl optionally having an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. R ^2a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, —Ar ⁴ , —S—Ar ⁴ , —O—Ar ⁴ , —CO—Ar ⁴ , —SO ₂ —Ar ⁴ or It represents ^{_{-C (CF 3) 2 -Ar 4}} , R 2b is a direct ^{bond, -Ar 6 -, - S-} Ar 6 -, - O-Ar 6 -, - CO-Ar 6 -, - SO 2 - Ar ⁶ — or —C (CF ₃ ) ₂ —Ar ⁶ — is represented, Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ each independently represent an arylene group which may have a substituent, Ar ^3a and Ar ⁴ each independently represent an aryl group which may have a substituent, Z is a direct bond, - -, - O -, - CO -, - SO 2 - or -C _{(CF 3) 2} - represents, X ^- represents an anion).

According to the present invention, a molded article of a polyarylene sulfide resin composition excellent in properties such as tracking resistance, mechanical strength, epoxy adhesion, metal adhesion, cavity balance, hot water resistance and the like can be obtained. Moreover, the gas generation amount by heating can be suppressed by using the said polyarylene sulfide resin composition for electric vehicle components.
In addition, the present invention is excellent not only in the amount of gas generated but also in quality. According to the present invention, since the terminal of the main chain of polyarylene sulfide is blocked with an alkyl group, the terminal does not become SH or the like unlike the conventional polymerization method. For this reason, thiophenol, a chloro compound, etc. do not generate | occur | produce on the mechanism of superposition | polymerization, It leads to the improvement of a working environment.
In addition, since the polyarylene sulfide main chain ends are alkyl groups, the polarizability is lower than in the case of SH as in the conventional polymerization method, so that components that cause gas generation during the cleaning process are removed. Easy to be. For this reason, it contributes to cost reduction, such as introduction of new facilities.
Furthermore, according to this invention, the sodium content in resin can be suppressed notably and the molded article excellent in epoxy adhesiveness and hot water resistance can be produced.

It is a figure showing the infrared absorption spectrum which measured the PAS resin of the synthesis example 1 by FT-IR spectroscopy. The peak (arrow) in the figure is derived from the stretching vibration of the methylsulfanyl group (-SMe). It is a figure showing the infrared absorption spectrum which measured the PAS resin of the synthesis example 2 by FT-IR spectroscopy. The peak (arrow) in the figure is derived from the stretching vibration of the methylsulfanyl group (-SMe). It is a figure showing the infrared absorption spectrum which measured the PAS resin of the synthesis example 3 by FT-IR spectroscopy. The peak (arrow) in the figure is derived from the stretching vibration of the methylsulfanyl group (-SMe). It is a figure showing the infrared absorption spectrum which measured the PAS resin of the comparative synthesis example by FT-IR spectroscopy.

  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 used in the present embodiment comprises a step of reacting a sulfoxide and an aromatic compound to obtain a poly (arylenesulfonium salt), a dealkylation or dearylation of the poly (arylenesulfonium salt), And obtaining a polyarylene sulfide resin. According to such a method, a polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with conventional methods such as the Philips method.

  The sulfoxide used in the present embodiment is a compound represented by the following general formula (1), and has two sulfinyl groups.

In General Formula (1), R ¹ represents an aryl group which may have an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and Ar ¹ and Ar ² are each represented by Independently, it represents an arylene group which may have a substituent, and Z represents a direct bond, —S—, —O—, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —. In the general formula (1), when Z is —S—, R ¹ is an alkyl group having 2 to 10 carbon atoms or an aryl group optionally having an alkyl group having 2 to 10 carbon atoms. There may be.

  The sulfoxide represented by the general formula (1) can be obtained, for example, by oxidizing the compound represented by the following general formula (3) by reacting with an oxidizing agent or the like.

In the general formula ^(3), R ^1, Ar 1, Ar ² and Z are defined above for the ^{R 1,} Ar 1, Ar ² and Z in the general formula (1).

  The oxidizing agent is not particularly limited, and various oxidizing agents can be used. As the oxidizing agent, for example, potassium permanganate, oxygen, ozone, organic peroxide, hydrogen peroxide, nitric acid, meta-chloroperoxybenzoic acid, oxone (registered trademark), osmium tetroxide and the like can be used.

  If necessary, the compound represented by the general formula (3) may be substituted with a halogen atom represented by Y and a sulfide group using a compound represented by the following general formula (4) and dimethyl disulfide. By doing so, a sulfide compound can be synthesized.

In the general formula (4), Y represents a halogen ^atom, Ar 1, Ar ² and Z are defined above for the ^Ar 1, Ar ² and Z in the general formula (1). Y is, for example, a chlorine atom, a bromine atom, an iodine atom or the like, and is preferably a chlorine atom.

In the compound represented by the general formula (1), (3) or (4), Ar ¹ and Ar ² may be an arylene group such as phenylene, naphthylene, biphenylene and the like. Ar ¹ and Ar ² may be the same or different, but are preferably the same.

Aspects of binding of Ar ¹ and Ar ² is not particularly limited, in the arylene group is preferably one that binds at positions remote. For example, when Ar ¹ and Ar ² are phenylene groups, they are preferably a unit bonded at the para position (1,4-phenylene group) and a unit bonded at the meta position (1,3-phenylene group). More preferred are units bonded at the position. It is preferable in terms of heat resistance and crystallinity of the resulting resin to be composed of units bonded at the para position.

When the arylene group represented by Ar ¹ or Ar ² has a substituent, the substituent is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. It is preferably an alkyl group having 1 to 10 carbon atoms such as a group, a hydroxy group, an amino group, a mercapto group, a carboxyl group or a sulfo group.

  Examples of the compound represented by the general formula (1) include 4,4′-bis (methylsulfinyl) biphenyl, bis [4- (methylsulfinyl) phenyl] ether, and bis [4- (methylsulfinyl) phenyl] sulfide. Bis [4- (methylsulfinyl) phenyl] sulfone, bis [4- (methylsulfinyl) phenyl] ketone, 2,2-bis [4- (methylsulfinyl) phenyl] -1,1,1,3,3, Examples include 3-hexafluoropropane. These compounds can be used alone or in combination.

Examples of R ¹ include alkyl groups 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, and a decyl group. Aryl groups having a structure such as naphthyl, biphenyl and the like, and the aryl group includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group It may have an alkyl group having 1 to 10 carbon atoms such as 1 to 4 on the aromatic ring as a substituent.

  The aromatic compound used in this embodiment is represented by the following general formula (2), for example.

In General Formula (2), R ^2a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, —Ar ⁴ , —S—Ar ⁴ , —O—Ar ⁴ , —CO—Ar ⁴ , —SO ₂ —. Ar ⁴ or —C (CF ₃ ) ₂ —Ar ⁴ is represented, and Ar ^3a and Ar ⁴ each independently represent an aryl group which may have a substituent. When R ^2a is an alkyl group having 1 to 10 carbon atoms, examples thereof 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. It is done. When the aryl group represented by Ar ^3a or Ar ⁴ has a substituent, the substituent is preferably an alkyl group (such as a methyl group), a hydroxy group, an amino group, a mercapto group, a carboxyl group, or a sulfo group. . Ar ^3a and Ar ⁴ include, for example, an aryl group having a structure such as phenyl, naphthyl, or biphenyl, and the aryl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. , An octyl group, a nonyl group, a decyl group or the like, and an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an amino group, a mercapto group, a carboxy group, and a sulfo group. Good. Ar ^3a and Ar ⁴ may be the same or different, but are preferably the same.

  Examples of the compound represented by the general formula (2) include benzene, toluene, biphenyl, diphenyl sulfide, diphenyl ether, benzophenone, diphenyl sulfone, hexafluoro-2,2-diphenylpropane, and the like. Of these compounds, biphenyl, diphenyl sulfide or diphenyl ether is preferred from the viewpoint of crystallinity. From the viewpoint of obtaining a polyarylene sulfide resin as a higher molecular weight, diphenyl sulfide is preferable. Diphenyl sulfide also has a low melting point and can itself function as a solvent, and is preferable from the viewpoint of controlling the reaction temperature. From the viewpoint of reducing the melting point of the polyarylene sulfide resin, diphenyl ether is preferred. From the viewpoint of improving the heat resistance of the polyarylene sulfide resin, benzophenone is preferable. From the viewpoint of obtaining an amorphous polyarylene sulfide resin, diphenyl sulfone or hexafluoro-2,2-diphenylpropane is preferable. By making it amorphous, it is possible to improve the molding processability and transparency of the polyarylene sulfide resin.

  The reaction between the sulfoxide and the aromatic compound is preferably performed in the presence of an acid. As the acid, either an organic acid or an inorganic acid can be used. Examples of the acid include non-oxygen acids such as hydrochloric acid, hydrobromic acid, hydrocyanic acid, and tetrafluoroboric acid; sulfuric acid, phosphoric acid, perchloric acid, bromine forged, 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 esters of sulfuric acid such as monomethyl sulfuric acid, trifluoromethane sulfuric acid; 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, trifluoromethyl Monovalent or polyvalent sulfonic acids such as sulfonic acid and benzenedisulfonic acid; partial metal salts of polyvalent sulfonic acid such as sodium benzenedisulfonate; antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tetrachloride Examples include Lewis acids such as tin, zinc chloride, copper chloride, and iron chloride. Of these acids, trifluoromethanesulfonic acid and methanesulfonic acid are preferably used from the viewpoint of reactivity. These acids may be used alone or in combination of two or more.

  Since this reaction is a dehydration reaction, a dehydrating agent may be used in combination. 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. Anhydrides; 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.

  A solvent can be appropriately used for the reaction between the sulfoxide and the aromatic compound. 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, and halogen-containing solvents such as methylene chloride and chloroform. Solvents, saturated hydrocarbon solvents such as normal hexane, cyclohexane, normal heptane, cycloheptane, amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, sulfur-containing solvents such as sulfolane and DMSO, tetrahydrofuran, dioxane, etc. And ether-based solvents. These solvents may be used alone or in combination of two or more.

  In the step of obtaining a poly (arylenesulfonium salt) by reacting a mixture containing a sulfoxide and an aromatic compound, the conditions can be appropriately adjusted so that the reaction proceeds appropriately. The reaction temperature is preferably in the range of −30 to 150 ° C., more preferably in the range of 0 to 100 ° C.

  The poly (arylenesulfonium salt) obtained by the above process has a structural unit represented by the following general formula (10).

In the general formula ^{(10), R 2b} represents a direct ^{bond, -Ar 6 -, - S-} Ar 6 -, - O-Ar 6 -, - CO-Ar 6 -, - SO 2 -Ar 6 - or -C (CF ₃ ) ₂ —Ar ⁶ —, Ar ^3b and Ar ⁶ each independently represent an arylene group which may have a substituent, X ⁻ represents an anion, Ar ¹ , Ar ² , R ¹ and Z are defined above for the ^{Ar 1,} Ar 2, ^{R 1} and Z in the general formula (1). Ar ^3b and Ar ⁶ may be, for example, an arylene group such as phenylene, naphthylene, and biphenylene. Ar ^3b and Ar ⁶ may be the same or different, but are preferably the same. Examples of X ⁻ representing an anion include anions such as sulfonate, carboxylate, and halogen ion. In the general formula (10), when Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups and R ^2b is a direct bond, Z is a direct bond, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —, Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups, R ^2b is —Ar ⁶ —, and Ar ⁶ is 1,4-phenylene group. Sometimes Z may be —S—, —O—, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —.

In the structural unit represented by the general formula (10), the bonding mode of Ar ^3b and Ar ⁶ is not particularly limited, and Ar ¹ and Ar ^{2 in the} general formulas (1), (3), and (4) Similar considerations can be applied to the combination aspect of.

When the arylene group represented by Ar ^3b or Ar ⁶ has a substituent, the substituent is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl It is preferably an alkyl group having 1 to 10 carbon atoms such as a group, a hydroxy group, an amino group, a mercapto group, a carboxyl group or a sulfo group. However, the proportion of the structural unit of the general formula (10) in which Ar ¹ , Ar ² , Ar ^3b, and Ar ⁶ are arylene groups having a substituent suppresses a decrease in crystallinity and heat resistance of the polyarylene sulfide resin. From the viewpoint, it is preferably in the range of 10% by mass or less, more preferably 5% by mass or less, based on the whole poly (arylenesulfonium salt).

  The structural unit possessed by the poly (arylenesulfonium salt) includes, for example, a sulfoxide represented by the general formula (1) and an aromatic represented by the general formula (2) in accordance with the purpose of using the polyarylene sulfide resin. It can select suitably by changing the combination with a compound.

  The method for producing a polyarylene sulfide resin according to this embodiment includes a step of dealkylating or dearylating poly (arylenesulfonium salt). The dealkylation or dearylation of poly (arylenesulfonium salt) is considered to proceed, for example, as represented by the following reaction formula.

  In this step, a dealkylating agent or a dearylating agent can be used. The dealkylating agent or dearylating agent includes a nucleophile or a reducing agent. As the nucleophilic agent, a nitrogen-containing aromatic compound, an amine compound, an amide compound, or the like can be used. As the reducing agent, metallic potassium, metallic sodium, potassium chloride, sodium chloride, hydrazine and the like can be used. These compounds may be used alone or in combination of two or more.

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

  Examples of the amine compound include trialkylamine and ammonia.

  As the amide compound, an aromatic amide compound or an aliphatic amide compound can be used. The aliphatic amide compound is represented, for example, by a compound represented by the following general formula (30).

In General Formula (30), 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. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

  The compound represented by the general formula (30) is, for example, dealkylated by dealkylating or dearylating an alkyl group or aryl group bonded to a sulfur atom of a sulfonium salt as represented by the following reaction formula: It is thought to function as a de- or dearylating agent.

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

  As described above, when the aliphatic amide compound is used as a dealkylating agent or a dearylating agent, it suppresses gas generation during resin processing, improves the quality of the polyarylene sulfide resin molded product, improves the working environment, and It is preferable because the maintainability of the mold can be improved. In addition, since the aliphatic amide compound is also excellent in the solubility of the organic compound, the use of the aliphatic amide compound makes it possible to easily remove the oligomer component of polyarylene sulfide from the reaction mixture. As a result, it is possible to synergistically improve the quality of the polyarylene sulfide resin obtained by removing the oligomer component, which may contribute to gas generation, with the aliphatic amide compound.

Examples of such aliphatic amide compounds include primary amide compounds such as formamide, secondary amide compounds such as β-lactam, N-methyl-2-pyrrolidone, dimethylformamide, diethylformamide, dimethylacetamide, and tetramethylurea. A tertiary amide compound such as can be used. 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 solubility of poly (arylenesulfonium salt) and solubility in water. Among the amide compounds, N-methyl-2-pyrrolidone is preferable.

  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. Therefore, the amount of the aliphatic amide compound used is not particularly limited, but the lower limit is preferably in the range of 1.00 equivalents or more with respect to the total amount of poly (arylenesulfonium salt), and 1.02 equivalents. The above range is more preferable, and the range of 1.05 equivalents or more is more preferable. If the amount of the aliphatic amide compound used is 1.00 equivalent or more, the poly (arylenesulfonium salt) can be sufficiently dealkylated or dearylated. On the other hand, the upper limit is preferably 100 equivalents or less, and more preferably 10 equivalents or less. Only an aliphatic amide compound may be used as the reaction solvent, or another solvent such as toluene may be used in combination.

  The conditions for reacting the poly (arylenesulfonium salt) and the aliphatic amide compound according to this embodiment can be appropriately adjusted so that dealkylation or dearylation proceeds appropriately. The reaction temperature is preferably in the range of 50 to 250 ° C, more preferably in the range of 80 to 220 ° C.

  The method for producing a polyarylene sulfide resin according to this embodiment may further include a step of washing the polyarylene sulfide resin with water, a water-soluble solvent, or a mixed solvent thereof. By including such a washing step, the remaining amount of the dealkylating agent or dearylating agent contained in the obtained polyarylene sulfide resin can be more reliably reduced. This tendency becomes remarkable when an aliphatic amide compound is used as a dealkylating agent or a dearylating agent.

  By passing through the washing step, it is possible to more reliably reduce the remaining amount of the dealkylating agent or dearylating agent in the polyarylene sulfide resin obtained. The residual amount of the dealkylating agent or dearylating agent in the resin is in the range of 1000 ppm or less based on the mass of the resin containing the polyarylene sulfide resin and other components such as the dealkylating agent or the dearylating agent. Preferably, the range is 700 ppm or less, and more preferably 100 ppm or less. By setting it as 1000 ppm or less, the substantial influence with respect to the quality of the polyarylene sulfide resin obtained can be 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, aqueous hydrochloric acid, aqueous acetic acid, aqueous oxalic acid, and aqueous nitric acid, aromatic hydrocarbon solvents such as toluene and xylene, and alcohols such as methanol, ethanol, propanol, and isopropyl alcohol. Solvents, 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 And halogen-containing solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, water and N-methylpyrrolidone are preferred from the viewpoint of removal of the reaction reagent and removal of the oligomer component of the resin.

  The polyarylene sulfide resin obtained by the production method according to this embodiment has a structural unit represented by the following general formula (20).

In the general formula ^{(20), R 2b, Ar} 1, Ar 2, Ar 3b and Z, ^R 2b in the formula ^(10), is similarly defined as ^{Ar 1,} Ar 2, Ar ^3b and Z. In the general formula (20), when Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups and R ^2b is a direct bond, Z is a direct bond, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —, Ar ¹ , Ar ² and Ar ^3b are 1,4-phenylene groups, R ^2b is —Ar ⁶ —, and Ar ⁶ is 1,4-phenylene group. Sometimes Z may be —S—, —O—, —CO—, —SO ₂ — or —C (CF ₃ ) ₂ —.

In the structural unit represented by the general formula (20), the bonding mode of Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ is not particularly limited, and the general formulas (1), (3) and (4) The same idea as that of the bonding mode of Ar ¹ and Ar ² can be applied.

When the arylene group represented by Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ has a substituent, the substituent is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl It is preferably a C1-C10 alkyl group such as a group, nonyl group, decyl group, etc., a hydroxy group, an amino group, a mercapto group, a carboxyl group, or a sulfo group. However, the ratio of the structural unit of the general formula (20) in which Ar ¹ , Ar ² , Ar ^3, and Ar ⁶ are arylene groups having a substituent suppresses a decrease in crystallinity and heat resistance of the polyarylene sulfide resin. From the viewpoint, the range is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total polyarylene sulfide resin.

  The structural unit possessed by the polyarylene sulfide resin is, for example, a combination of a sulfoxide represented by the general formula (1) and an aromatic compound represented by the general formula (2) in accordance with the purpose of use of the resin. By changing, it can select suitably.

  The glass transition temperature of the polyarylene sulfide resin obtained by the production method of the present embodiment is preferably in the range of 50 to 250 ° C, more preferably in the range of 80 to 180 ° C. The glass transition temperature of the resin indicates a value measured by a DSC apparatus.

  The melting point of the polyarylene sulfide resin obtained by the production method of the present embodiment is preferably in the range of 100 to 400 ° C, and more preferably in the range of 150 to 300 ° C. The melting point of the resin indicates a value measured by a DSC apparatus.

  The sodium content of the polyarylene sulfide resin according to this embodiment is preferably 300 ppm or less, and more preferably 100 ppm or less. By using a polyarylene sulfide resin having a sodium content in such a range, a molded product excellent in strength retention (hot water resistance), epoxy adhesion, and the like under high temperature and high humidity can be produced.

  The Mtop of the polyarylene sulfide resin according to this embodiment is preferably 5,000 to 100,000, and more preferably 10,000 to 80,000. Mw is also in the same range. In this specification, Mtop represents the average molecular weight (peak molecular weight) at the point where the detection intensity of the chromatogram measured by gel permeation chromatography is maximized, and Mw represents the weight average molecular weight.

  The melt viscosity (V6) at the melting point + 20 ° C. of the polyarylene sulfide resin according to this embodiment is preferably 1 to 2000 [Pa · s] from the viewpoint of improving the filling density into the mold and the surface appearance during injection molding. ], More preferably 5 to 1700 [Pa · s]. Here, the melt viscosity (V6) is measured using a flow tester with a temperature: melting point + 20 ° C., load 1.96 MPa, and an orifice length / orifice diameter ratio (orifice length / orifice diameter) of 10/1. Means melt viscosity after use and hold for 6 minutes.

Polyarylene sulfide resin according to the present embodiment, the FT-IR spectrum as measured by FT-IR spectroscopy (infrared absorption ^spectrum), which has an absorption peak in the range of 2910cm ^-1 ~2930cm -1 As a result, since the solubility of the low molecular weight component in the solvent is good, the polymer is easily removed by the above-described washing process and the amount of generated gas is small.

  The amount of gas generated during heating of the polyarylene sulfide resin according to the present embodiment 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 embodiment can contain one or more inorganic fillers. By blending the inorganic filler, a composition having high rigidity and high heat stability can be obtained. Examples of the inorganic filler 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 15 to 150 parts with respect to 100 parts by mass of the polyarylene sulfide resin. It is the range of mass parts. 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 embodiment can contain 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 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 aliphatic diamine, C3-C18 diamine which has a linear or 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 6 to 27 carbon atoms having a phenylene group 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.

  As the alicyclic diamine, a diamine having 4 to 15 carbon atoms having a cyclohexylene group is preferable. 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, a dicarboxylic acid having 8 to 15 carbon atoms having a phenylene group is 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 weight, more preferably in the range of 3 to 100 parts by weight, still more preferably 5 to 45 parts with respect to 100 parts by weight of the polyarylene sulfide resin. It is the range of mass parts. 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.

  As the elastomer blended in the polyarylene sulfide resin composition, a thermoplastic elastomer is often used. 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 (particularly thermoplastic elastomer) preferably has a functional group capable of reacting with at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group. Thereby, it is possible to obtain a resin composition that is particularly excellent in terms of adhesiveness and impact resistance and that can suppress the amount of gas generated by heating. Such functional groups include epoxy groups, amino groups, hydroxyl groups, carboxyl groups, mercapto groups, isocyanate groups, oxazoline groups, and the formula: R (CO) O (CO)-or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms.). 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. As for alpha olefin, C2-C8 alpha olefins, such as ethylene, propylene, and butene-1, are mentioned, for example. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids and alkyl esters thereof such as (meth) acrylic acid and (meth) acrylic acid esters, 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 carboxyl group, and a formula: R (CO) O (CO)-or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms). An ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the represented groups 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 by mass of the polyarylene sulfide resin. It is the range of -100 mass parts, More preferably, it is the range of 5-45 mass parts. 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.

  The crosslinkable resin blended in the polyarylene sulfide resin composition has 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 carboxyl 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, further preferably 5 to 30 parts per 100 parts by mass of the polyarylene sulfide resin. It is the range of mass parts. 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 can contain a silane compound having a functional group capable of reacting with at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group. Thereby, the compatibility of polyarylene sulfide resin and another component can be improved, and the resin composition which can suppress the gas generation amount by a heating can be obtained. Examples of such silane compounds 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 according to the present embodiment 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. Good. 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 polyarylene sulfide resin composition can be obtained, for example, in the form of a pellet compound by a method of melt-kneading the polyarylene sulfide resin obtained by the above method and the other components. For example, the melting and kneading temperature is preferably in the range of melting point to melting point + 100 ° C., and more preferably in the range of melting point to melting point + 70 ° C. Melting and kneading can be performed using a twin screw extruder or the like.

  The polyarylene sulfide resin composition according to the present embodiment 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, It can be processed into a molded product having excellent molding processability and dimensional stability. Since the polyarylene sulfide resin composition according to the present embodiment generates a small amount of gas when heated, it enables easy production of a high-quality molded product.

  When the polyarylene sulfide resin composition according to this embodiment is used for electric vehicle parts, the amount of gas generated by heating can be reduced. For this reason, the contact between a low molecular weight compound containing a sulfur atom, which is a gas component, and a metal material such as copper can be reduced. As a result, even when a high voltage is repeatedly applied, the reaction between the two can be suppressed. It is possible to improve the tracking resistance by suppressing the occurrence and development of (dendritic fracture traces).

  As described above, the polyarylene sulfide resin composition of the present invention is an electric vehicle field in which particularly high safety is required, that is, a hybrid vehicle (HV) including a lithium ion secondary battery and using an electric motor as a power source. It can be suitably used for plug-in hybrid vehicles (PHV), electric vehicles (EV), fuel cell vehicles (FCV), and the like. Therefore, specific examples of electric vehicle parts obtained by molding the polyarylene sulfide resin composition of the present invention include, for example, power modules, converters, capacitors, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, Examples include cases that store junction blocks and the like. The molded article is particularly preferably used as a case for an ignition coil of a DLI system.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
In the examples shown below, the following reagents were used.
Bis [4- (methylthio) phenyl] sulfide: manufactured by Sigma-Aldrich, product number S203815-25MG
Nitric acid (1.38): manufactured by Wako Pure Chemical Industries, Ltd., reagent grade, content 60-61%, density 1.38 g / mL
Diphenyl sulfide: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade diphenyl ether: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade biphenyl: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade trifluoromethanesulfonic acid: Wako Pure Chemical Industries ( Co., Ltd., Wako Special Grade Methanesulfonic Acid: Wako Pure Chemical Industries, Ltd., Wako Special Grade Phosphorus Oxide (V): Wako Pure Chemical Industries, Ltd., Wako First Grade Pyridine: Wako Pure Chemical Industries, Ltd., Reagent special grade N-methylpyrrolidone: Wako Pure Chemical Industries, Ltd., Wako first grade

<Evaluation method>
1. Monomer Evaluation Method 1-1. Identification method ( ¹ H-NMR, ¹³ C-NMR)
Measurement was conducted by dissolving in various heavy solvents using a DPX-400 apparatus manufactured by BRUKER.

2. Monomer synthesis

In a 10 L three-necked flask, 20.0 [g] of bis [4- (methylthio) phenyl] sulfide and 5 [L] of dichloromethane were added and dissolved, and cooled in an ice bath. Nitric acid (1.38) 14 [mL] was added dropwise little by little, and the mixture was stirred at room temperature for 72 hours. The mixture was neutralized with an aqueous potassium carbonate solution and extracted / separated with dichloromethane to recover the organic layer. The organic layer was dried over anhydrous magnesium sulfate. After filtration, the solvent was removed with a rotary evaporator and dried under reduced pressure to obtain a crude product. Separation by column chromatography using ethyl acetate as a developing solvent, the target product is recovered, the solvent is removed by a rotary evaporator, and dried under reduced pressure to obtain 6.7 g of bis [4- (methylsulfinyl) phenyl] sulfide. 30%). It was confirmed that the target product was obtained by ¹ H-NMR measurement.
¹ H-NMR (solvent CDCl ₃ ): 2.75, 7.49, 7.61 [ppm]

3. 3. Evaluation method of synthesized polyarylene sulfide resin 3-1. Glass Transition Temperature and Melting Point Using a Perkin Elmer DSC device Pyris Diamond, measurement was performed from 40 to 400 ° C. under a nitrogen flow rate of 50 mL / min and a temperature rising condition of 20 ° C./min to obtain a glass transition temperature and a melting point.
3-2. Infrared absorption spectrum The obtained PPS resin is pressed at a melting point of + 50 ° C. and then rapidly cooled to prepare an amorphous film, which is abbreviated as a Fourier transform infrared spectrometer (hereinafter referred to as “FT-IR apparatus”). FTIR-6100 manufactured by JASCO Corporation was used).
3-3. Melt viscosity of polyarylene sulfide resin Using polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500C, at a temperature of melting point + 20 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10/1 The melt viscosity was measured after holding for 6 minutes.
3-4. Mw and Mtop (Molecular weight distribution)
The weight average molecular weight and peak molecular weight of the polyarylene sulfide resin were measured under the following measurement conditions using gel permeation chromatography. Mw / Mtop was calculated from the obtained Mw and Mtop. Six types of monodisperse polystyrene were used for calibration.
Apparatus: Ultra-high temperature polymer molecular weight distribution measuring apparatus (“SSC-7000” manufactured by Senshu Scientific Co., Ltd.)
Column: UT-805L (made by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene Measurement method: UV detector (360 nm)
3-5. Generated gas amount Using a gas chromatograph mass spectrometer (manufactured by Shimadzu Corporation, GC-2010), a predetermined amount of a sample of polyarylene sulfide resin is heated at 325 ° C. for 15 minutes, and the amount of generated gas is determined as mass%. did.
3-6. About 0.5 g of a sample was weighed in a platinum crucible made of sodium, and about 2 ml of 97% concentrated sulfuric acid was added thereto, followed by thermal decomposition on a heater. After completion of the decomposition, the residue was incinerated in an electric furnace at 500 ° C., and the residue was dissolved in distilled water. The sample was quantified with an Optima 4300 DV manufactured by PerkinElmer.

4). Synthesis synthesis example 1 of polyarylene sulfide resin

In a 500 mL separable flask, 0.932 [g] of bis [4- (methylsulfinyl) phenyl] sulfide is placed, put under a nitrogen atmosphere, 0.560 [g] of diphenyl sulfide is added, and phosphorus oxide is further added to 1 [g]. Was added. After cooling in an ice bath, methanesulfonic acid 5 [mL] was slowly added dropwise. The mixture was warmed to room temperature and stirred for 20 hours. The reaction solution was put into water, stirred for 10 minutes, filtered, washed with water and filtered to collect a solid. The solvent was removed with a rotary evaporator and dried under reduced pressure to obtain 2.25 [g] (99% yield) of poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium].
A small amount of the sample was collected for analysis, and ¹ H-NMR measurement was performed on the sample dissolved in heavy DMSO to confirm that the target product was synthesized.
¹ H-NMR (solvent weight DMSO): 3.27, 3.93, 7.76, 8.19 [ppm]

  Poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium] 2.00 [g] is placed in a 100 mL eggplant flask, pyridine 100 [mL] is added, and the mixture is stirred at room temperature for 30 minutes, and then heated to 110 ° C. And stirred for 20 hours. The reaction solution was cooled to room temperature and then poured into water, and the precipitate was filtered off and washed with chloroform, NMP and water. After washing, the solid was dried under reduced pressure to obtain 0.60 [g] (yield 56%) of polyphenylene sulfide (indicated as PPS-1 in Table 1).

As a result of conducting a thermal analysis on the obtained resin, the glass transition temperature (Tg) was 93 ° C. and the melting point was 273 ° C.
When an infrared absorption spectrum was measured, the presence of an absorption peak was observed at a position of 2917 cm ⁻¹ as shown in FIG.
The melt viscosity of this polymer was 1430 Pa · s, Mtop was 57000, and Mw was 60000.
The amount of generated gas was as small as 0.1 [wt%].
The sodium content was 50 ppm or less.

Synthesis example 2

In a 500 mL separable flask, 0.932 [g] of bis [4- (methylsulfinyl) phenyl] sulfide was placed, put under a nitrogen atmosphere, and 0.511 [g] of diphenyl ether was added. After cooling in an ice bath, trifluoromethanesulfonic acid 7.5 [mL] was slowly added dropwise. The mixture was warmed to room temperature and stirred for 20 hours. The reaction solution was put into water, stirred for 10 minutes, filtered, washed with water and filtered to collect a solid. By removing the solvent with a rotary evaporator and drying under reduced pressure, poly [trifluoromethanesulfonic acid methyl (4-phenyloxyphenyl) sulfonium-4′-methyl (4-phenylthiophenyl) sulfonium] 2.19 [g] ( Yield 98%).
A small amount of the sample was collected for analysis, and after ion exchange with an excess of methanesulfonic acid, ¹ H-NMR measurement was performed on what was dissolved in heavy acetic acid to confirm that the target product was synthesized. .
¹ H-NMR (solvent biacetic acid): 3.17, 3.92, 7.61, 7.87, 8.08, 8.18 [ppm]

Poly [trifluoromethanesulfonic acid methyl (4-phenyloxyphenyl) sulfonium-4′-methyl (4-phenylthiophenyl) sulfonium] 2.00 [g] is placed in a 100 mL eggplant flask, and pyridine 100 [mL] is added. The mixture was stirred at room temperature for 30 minutes, heated to 110 ° C., and stirred for 20 hours. The reaction solution was cooled to room temperature and then poured into water, and the precipitate was filtered off and washed with chloroform, NMP and water. After washing, the solid was dried under reduced pressure to obtain 0.54 [g] (yield 48%) of poly [(phenylene ether)-(phenylene sulfide)] (indicated as PPS-2 in Table 1).
As a result of thermal analysis of the obtained resin, it had a glass transition temperature (Tg) of 96 ° C. and a melting point of 229 ° C.
When an infrared absorption spectrum was measured, the presence of an absorption peak was observed at a position of 2918 cm ⁻¹ as shown in FIG.
This polymer had a melt viscosity of 100 Pa · s, Mtop of 10,000, and Mw of 12,000.
The amount of generated gas was as small as 0.05 [wt%].
The sodium content was 50 ppm or less.

Synthesis example 3

Instead of diphenyl ether, poly [trifluoromethylsulfonic acid methyl (4-phenylthiophenyl) sulfonium-4′-methyl (4-biphenyl) was synthesized in the same manner as in Synthesis Example 2 except that biphenyl 0.463 [g] was used. ) Sulfonium] 2.08 [g] (yield 95%).
A small amount of the sample was taken for analysis, and after ion exchange with an excess of methanesulfonic acid, ¹ H-NMR measurement was performed on what was dissolved in deuterated acetonitrile to confirm that the target product was synthesized. .
¹ H-NMR (deuterated acetonitrile): 3.32, 3.58, 7.45, 7.66, 7.78, 7.95 [ppm]

Poly [methyl trifluoromethanesulfonate (4-phenylthiophenyl) sulfonium-4′-methyl (4-biphenyl) sulfonium] 1.80 [g] was placed in a 100 mL eggplant flask, pyridine 100 [mL] was added, and room temperature was added. After stirring for 30 minutes, the temperature was raised to 110 ° C. and stirred for 20 hours. The reaction solution was cooled to room temperature and then poured into water, and the precipitate was filtered off and washed with chloroform, NMP and water. After washing, the solid was dried under reduced pressure to obtain 0.87 [g] (yield 88%) in poly [(phenylene sulfide)-(biphenylene sulfide)] (indicated as PPS-3 in Table 1).
As a result of thermal analysis of the obtained resin, the glass transition temperature (Tg) was 127 ° C. and the melting point was 325 ° C.
When an infrared absorption spectrum was measured, the presence of an absorption peak was observed at a position of 2917 cm ⁻¹ as shown in FIG.
The melt viscosity of this polymer was 330 Pa · s, Mtop was 16000, and Mw was 18000.
The amount of generated gas was as small as 0.1 [wt%].
The sodium content was 50 ppm or less.

Comparative Synthesis Example 220.5 g 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. 5 mol), 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 While stirring, 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 PPS-4 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.
Was measured infrared absorption spectrum, as shown in FIG. ^4, the presence of absorption peak in the range of 2910cm ^-1 ~2930cm -1 did et al observed.
The melt viscosity of this polymer was 220 Pa · s, Mtop was 45000, and Mw was 44000.
The amount of generated gas was 0.5 [wt%].
The sodium content was 600 ppm.

5. Polyarylene sulfide resin composition (compound)
<Raw material>
In order to prepare the polyarylene sulfide resin composition, the following materials were prepared.
(Thermoplastic elastomer)
ELA: Copolymer of ethylene / glycidyl methacrylic acid (3% by mass) / methyl acrylate (27% by mass) (manufactured by Sumitomo Chemical Co., Ltd., “Bond First 7L”)
(Silane coupling agent)
Epoxy silane: 3-glycidyloxypropyltrimethoxysilane (inorganic filler)
GF: Glass fiber chopped strand (fiber diameter 10 μm, length 3 mm)

<Evaluation method>
[Bending characteristics]
-Compliance test method: ASTM D-790
-Test piece: 3.2 mm (thickness) x 12.7 mm (width) x 127 mm (long)
・ Test results: Average number of tests n = 10

[Heat resistant water]
The test piece was immersed in hot water at 95 ° C., and the change with time in bending strength was examined.
-Test piece: 3.2 mm (thickness) x 12.7 mm (width) x 127 mm (long)
Test method for bending strength: ASTM D-790
・ Evaluation item: Retention ratio with respect to initial strength of bending strength after 1000 hours and 3000 hours ・ Test result: Average value of number of tests n = 5

[Metal adhesion strength]
A 4 × 10 × 49 mm metal piece (SUS304) set in a mold was injected and molded with a polyarylene sulfide resin composition of the same size, and was subjected to a tensile test under the conditions of 20 mm between chucks and 1 mm / min tensile speed. The metal adhesion strength was measured.

[Epoxy bond strength]
A test piece of 3 mm (thickness) x 25 mm (width) x 75 mm (length) was molded, and an epoxy resin (main agent: XNR-5002 (manufactured by Nagase ChemteX)) and cured so that the adhesion area was 25 mm x 10 mm on the test piece Agent: XNH-5002 (manufactured by Nagase ChemteX), main agent / curing agent = 100/90 (mass ratio) was applied in a thickness of 40 to 50 μm. After fixing these with clips, the epoxy resin was cured by heating at 130 ° C. for 3 hours and further cooling. Thereafter, the tensile shear strength was measured at a tensile speed of 5 mm / min, and the actual load was recorded.

[Cavity balance]
Using a washer mold having 40 cavities, the polyarylene sulfide resin composition was injection molded under the minimum molding conditions as long as the cavity (C1) closest to the primary sprue was completely filled. . The molding conditions were a 75-ton molding machine, cylinder temperature: melting point + 40 ° C., mold temperature: glass transition temperature + 50 ° C., and no holding pressure.

The degree of filling of the cavity (C10) farthest from the primary sprue in the same runner as the cavity (C1) after molding was compared. The degree of filling (% by mass) was determined from the mass ratio of the molded product of the cavity (C10) to the molded product of the cavity (C1). It can be said that the higher the degree of filling of the cavity (C10), the better the cavity balance. Based on the degree of filling, the cavity balance of each composition was determined according to the following criteria.
AA: 100 to 90% by mass range A: 89 to 80% by mass range B: 79 to 70% by mass range C: 69 to 60% by mass range D: 59% by mass or less range

[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%. .

[Tracking resistance]
A test piece of 2 mm (thickness) × 50 mm (width) × 100 mm (long) was molded, measured along the resin flow direction by a method according to ASTM D3638, the breakdown voltage and the number of drops were plotted, and 50 drops The voltage was read.

<Production and evaluation of compound>
Each raw material was uniformly mixed by a tumbler with the composition shown in Table 1, and then melt-kneaded at a melting point + 30 ° C. using a twin-screw kneading extruder (TEM-35B, Toshiba Machine) to obtain a pellet-like compound. . The resulting compound is injection-molded under the conditions of cylinder temperature: melting point + 20 ° C., mold temperature: mold temperature: glass transition temperature + 50 ° C., and used for bending properties, metal adhesion strength, cavity balance and hot water resistance test. Pieces were prepared and subjected to various evaluations. Moreover, the amount of gas generation was measured about the compound. The results are shown in Table 1.

  As is apparent from the results shown in Table 1, Examples 1, 2 and 3 are mechanical properties (bending strength, bending elongation at break), metal adhesion strength, epoxy adhesion strength, cavity balance. It was superior to the comparative example in terms of hot water resistance, chemical resistance, gas generation amount, and tracking resistance.

Claims (3)

Polyarylene sulfide resin,
An inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and at least one other component selected from the group consisting of a crosslinkable resin having two or more crosslinkable functional groups, A polyarylene sulfide resin composition for electric vehicle parts,
The polyarylene sulfide resin reacts with a sulfoxide represented by the following general formula (1) and an aromatic compound represented by the following general formula (2) to form a structural unit represented by the following general formula (10). Obtaining a poly (arylenesulfonium salt) having:
Dealkylating or dearylating the poly (arylenesulfonium salt) to obtain a polyarylene sulfide resin having a structural unit represented by the following general formula (20);
Can be obtained by a method comprising
The polyarylene sulfide resin, the infrared absorption spectrum measured by FT-IR ^{spectroscopy, and} has an absorption peak in the range of 2910cm ^-1 ~2930cm -1, electric automobile parts polyarylene sulfide resin composition .

(In Formula (1), (2), (10) or (20), R ¹ is an aryl optionally having an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. R ^2a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, —Ar ⁴ , —S—Ar ⁴ , —O—Ar ⁴ , —CO—Ar ⁴ , —SO ₂ —Ar ⁴ or It represents ^{_{-C (CF 3) 2 -Ar 4}} , R 2b is a direct ^{bond, -Ar 6 -, - S-} Ar 6 -, - O-Ar 6 -, - CO-Ar 6 -, - SO 2 - Ar ⁶ — or —C (CF ₃ ) ₂ —Ar ⁶ — is represented, Ar ¹ , Ar ² , Ar ^3b and Ar ⁶ each independently represent an arylene group which may have a substituent, Ar ^3a and Ar ⁴ each independently represent an aryl group which may have a substituent, Z is a direct bond, - -, - O -, - CO -, - SO 2 - or -C _{(CF 3) 2} - represents, X ^- represents an anion).   The molded article for electric vehicle parts obtained by shape | molding the polyarylene sulfide resin composition of Claim 1.   An electric vehicle part comprising the molded article according to claim 2.

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