JP6634682B2 - Polyarylene sulfide resin composition, molded article thereof, and electric vehicle part - Google Patents

Description

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

  An electric vehicle that has attracted attention in recent years has many components that operate at a high voltage, and a resin molded product is used for such an electric vehicle component. As an application of the resin molded product, for example, an ignition coil case for automobiles in which a resin molded product is used as a coil case and an ignition coil is sealed with an epoxy resin composition or the like in the coil case, or an ignition plug and an ignition coil are used. A coil case in an integrated distributorless ignition system (hereinafter sometimes abbreviated as “DLI system”) may be mentioned.

  Such electric vehicle parts are required to have tracking resistance so that they do not easily ignite even under a high voltage. In addition, for example, the above-described coil case desirably has excellent adhesiveness to epoxy resin or 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”) is used. It has been proposed to mold and use it for the above-mentioned automobile parts (for example, see Patent Document 1).
The polyarylene sulfide resin can be produced, for example, by solution polymerization in which a polymerization reaction is carried out in a polar organic solvent using p-dichlorobenzene and sodium sulfide or sodium hydrosulfide and sodium hydroxide as raw materials (for example, Patent References 2 and 3). Currently marketed 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 a purification treatment (Patent Document 4).

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

However, in a composition containing a conventional polyarylene sulfide resin, the amount of gas generated by heating during molding or the like is relatively large. Therefore, 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, the two react, and a tree (a dendritic trace of destruction) is formed. Is also likely to occur, which may lead to a reduction in tracking resistance. In particular, an electric vehicle using a motor as a driving force requires a driving energy equivalent to that of a gasoline engine at the time of starting. Therefore, a lithium-ion secondary battery is provided, and the battery voltage is 100 to 400 V. Driven by high voltages. There are many parts in the automotive field where high safety is required, especially parts for electric vehicles that operate under high voltage and high current, so they are at a higher level than conventional vehicles using lead-acid batteries. Therefore, it is required to prevent the occurrence of fire and the spread of fire in the event of an abnormality, and it is required not only to have excellent flame retardancy, but also to further suppress the tracking phenomenon that causes ignition.
In addition, polyarylene sulfide resin is often used for the case part of electronic control parts of automobiles, and the gap in the case is sealed with epoxy resin or silicone resin, so that the adhesive force with the resin or metal is reduced. As the strength becomes stronger, a peeling point (gap), which is likely to be a starting point of destruction, is less likely to occur, which directly leads to an improvement in the life of the component. Therefore, not only the tracking resistance is improved, but also the adhesion to metal (hereinafter referred to as metal adhesion), It has been an issue to have both strong adhesiveness with epoxy resin and silicone resin (hereinafter referred to as adhesiveness with epoxy resin, etc.).

  Further, although the mechanical properties can be improved by reducing the amount of sodium and the like by improving the purification process of the polyarylene sulfide resin as in Patent Document 4, sodium is promoted by the above-described tree and high humidity and high temperature There is a possibility that the resin composition of Patent Document 4 or a molded product thereof has tracking resistance, mechanical strength, epoxy adhesion, metal, because there is a possibility of adverse effects from the viewpoint of maintaining the strength under the conditions and inhibiting the reaction with the epoxy resin or the like. There is 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 adhesion, metal adhesion, and excellent resin composition or molded product thereof are obtained. It is an object of the present invention to provide a polyarylene sulfide resin composition having cavity balance characteristics, a molded article using the resin composition, and an electric vehicle component including the molded article.

  The cavity balance relates to the uniformity of the degree of filling of each cavity when a plurality of molded products are simultaneously molded 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 as partial filling of the cavities, are liable to occur.

  As a result of various studies, the present inventors have found that a polyarylene sulfide resin obtained by reacting a poly (arylene sulfonium salt) with an aliphatic amide compound and a thermoplastic resin other than the inorganic filler and the polyarylene sulfide resin are used. Blending with at least one other component selected from the group consisting of a resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups (hereinafter, may be simply referred to as “the other component”). Thus, the inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention relates to a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and at least one selected from the group consisting of crosslinkable resins having two or more crosslinkable functional groups. A polyarylene sulfide resin having a structural unit represented by the following general formula (1). Salt) and an aliphatic amide compound to obtain a polyarylene sulfide resin having a structural unit represented by the following general formula (2).
The polyarylene sulfide resin, the infrared absorption spectrum measured by FT-IR ^{spectroscopy,} polyarylene electric car parts, characterized in that it has an absorption peak in the range of 2910cm ^-1 ~2930cm -1 The present invention relates to a sulfide resin composition.

(In the formula, ^{R 1} represents a direct ^bond, -Ar 2 -, ^- Ar 2 -S- or ^-Ar 2 -O- to represent, Ar ¹ and Ar ² may have a functional group as a substituent Represents an arylene group, R ² represents an alkyl group having 1 to 10 carbon atoms or an aryl group which may have an alkyl group having 1 to 10 carbon atoms, and X ⁻ represents an anion.)

(In the formula, ^{R 1} represents a direct ^bond, -Ar 2 -, ^- Ar 2 -S- or ^-Ar 2 -O- to represent, Ar ¹ and Ar ² may have a functional group as a substituent Represents an arylene group.)

According to the present invention, a molded article of a polyarylene sulfide resin composition having excellent properties such as tracking resistance, mechanical strength, epoxy adhesion, metal adhesion, cavity balance, and hot water resistance can be obtained. In addition, by using the above-mentioned polyarylene sulfide resin composition for electric vehicle parts, the amount of gas generated by heating can be suppressed.
In addition, the present invention is superior not only in the amount of gas generated but also in the quality of the gas. According to the present invention, since the terminal of the main chain of the polyarylene sulfide is blocked with an alkyl group, the terminal does not become SH or the like as in the conventional polymerization method. Therefore, thiophenol and chloro compounds are not generated due to the mechanism of polymerization, which leads to improvement of the working environment.
In addition, since the terminal of the main chain of the polyarylene sulfide is an alkyl group, the polarizability is lower than in the case where SH is used as in the conventional polymerization method. Easy to be. This contributes to cost reduction such as introduction of new equipment.
Furthermore, according to the present invention, the sodium content in the resin can be remarkably suppressed, and a molded article excellent in epoxy adhesiveness and hot water resistance can be produced.

FIG. 2 is a diagram showing an infrared absorption spectrum of the PPS resin of Example 1 measured by FT-IR spectroscopy. The peak (arrow) in the figure is derived from the stretching vibration of the methylsulfanyl group (-SMe). FIG. 4 is a diagram illustrating an infrared absorption spectrum of the PPS resin of Comparative Example 1 measured 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 can be obtained by a method including reacting poly (arylene sulfonium salt) with an aliphatic amide compound. According to such a method, a polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with a conventional method such as the Phillips method.
The aliphatic amide compound used in the present embodiment is represented by, for example, a compound represented by the following general formula (10).

In the general formula (10), 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 combine to form a cyclic structure. May be. 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.

  The compound represented by the general formula (10) is considered to function as a so-called dealkylating agent or dearylating agent, for example, as represented by the following reaction formula. That is, the compound can function to sulfide by dealkylating or dearylating an alkyl group or an aryl group bonded to the sulfur atom of the sulfonium salt.

  The aliphatic amide compound has higher miscibility with water and lower compatibility with the polyarylene sulfide resin than the aromatic amide compound, and thus can be easily removed by washing the reaction mixture with water. For this reason, the residual amount of the dealkylating agent or the dearylating agent in the polyarylene sulfide resin can be reduced. As a result, it is possible to suppress the generation of gas during resin processing and the like, to improve the quality of the polyarylene sulfide resin molded product, to improve the working environment, and to improve the mold maintainability. In addition, since aliphatic amide compounds are also excellent in solubility of organic compounds having a relatively low molecular weight, the use of the aliphatic amide compounds can easily remove oligomer components of polyarylene sulfide from a reaction mixture. To As a result, the quality of the obtained polyarylene sulfide resin can be synergistically improved by removing the oligomer component which may contribute to gas generation by the aliphatic amide compound.

Such aliphatic amide compounds include, for example, primary amide compounds such as formamide, secondary amide compounds such as β-lactam, N-methyl-2-pyrrolidone, 2-pyrrolidone, ε-caprolactam, N-methyl- In addition to the compounds represented by the general formula (10) such as tertiary amide compounds such as ε-caprolactam, dimethylformamide, diethylformamide, and dimethylacetamide, tetramethylurea, 1,3-dimethyl-2-imidazolidinonic acid And the like can be used. The aliphatic amide compound preferably contains an aliphatic tertiary amide compound in which R ¹² and R ¹³ are an aliphatic group from the viewpoints of solubility of the poly (arylene sulfonium salt) and water. -Methyl-2-pyrrolidone is particularly preferred.

  The aliphatic amide compound functions as a dealkylating agent or a dearylating agent, and can be used as a reaction solvent because of its excellent solubility in poly (arylene sulfonium salt). Therefore, the amount of the aliphatic amide compound to be used is not particularly limited, but the lower limit is preferably 1.00 equivalent or more based on the total amount of the poly (arylene sulfonium salt), and 1.02 equivalent or less. The above range is more preferable, and the range is more preferably 1.05 equivalent or more. When the amount of the aliphatic amide compound used is 1.00 equivalent or more, the dealkylation or dearylation of the poly (arylene sulfonium salt) can be sufficiently performed. On the other hand, the upper limit is preferably 100 equivalents or less, more preferably 10 equivalents or less. As the reaction solvent, only the aliphatic amide compound may be used, or this may be used in combination with another solvent such as toluene.

  The poly (arylene sulfonium salt) used in the present embodiment has a structural unit represented by the following general formula (1).

Formula (1), ^{R 1} represents a direct ^bond, -Ar 2 -, ^- Ar 2 -S- or ^-Ar 2 -O- to represent, Ar ¹ and Ar ² has a functional group as a substituent R ² represents an alkyl group having 1 to 10 carbon atoms or an aryl group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, and X ⁻ represents Represents an anion.

Here, examples of X ⁻ include anions such as sulfonate, carboxylate, and halogen ion. Ar ¹ and Ar ² may be, for example, an arylene group such as phenylene, naphthylene and biphenylene. Ar ¹ and Ar ² may be the same or different, but are preferably the same.

The mode of bonding of Ar ¹ and Ar ² is not particularly limited, but it is preferable that the bonding is at a distant position in the arylene group. For example, when Ar ¹ and Ar ² are a phenylene group, it is preferably a unit bonded at the para position and a unit bonded at the meta position, and more preferably a unit bonded at the para position. It is preferable that the resin is composed of units bonded at the para position in terms of heat resistance and crystallinity of the resin.

When the arylene group represented by Ar ¹ or Ar ² has a functional group as a substituent, the functional group is preferably a hydroxy group, an amino group, a mercapto group, a carboxy group, or a sulfo group. However, the proportion of the structural unit of the general formula (1) in which Ar ¹ or Ar ² is an arylene group having a substituent is determined from the viewpoint of suppressing a decrease in crystallinity and heat resistance of the polyarylene sulfide resin. It is preferably within a range of 10% by mass or less of the entire sulfonium salt), and more preferably 5% by mass or less.

Examples of R ² include 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, and a decyl group; , Naphthyl, an aryl group having a structure such as biphenyl, and the aryl group further includes 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. And the like may have 1 to 4 alkyl groups having 1 to 10 carbon atoms as substituents on the aromatic ring.

  The poly (arylene sulfonium salt) having the structural unit represented by the general formula (1) can be obtained, for example, by a method of polymerizing aromatic sulfoxide in the presence of an acid.

  The aromatic sulfoxide includes, for example, a compound represented by the following general formula (20). The substitution positions of the two substituents are not particularly limited, but it is preferable that the two substitution positions are located as far as possible in the molecule. A preferred substitution position is the para position.

In the general formula (20), R ² and Ar ¹ are the same as defined in the general formula (1),
³ represents a hydrogen atom, Ar ³ —, Ar ³ —S— or Ar ³ —O—, and Ar ³ represents an aryl group which may have a substituent on a functional group.

Here, examples of Ar ³ include an aryl group having a structure such as phenyl, naphthyl, and biphenyl, and the aryl group is at least one kind selected from a hydroxy group, an amino group, a mercapto group, a carboxy group, and a sulfo group. It may have a functional group as a substituent.

  As the compound represented by the general formula (20), for example, methylphenylsulfoxide, methyl-4- (phenylthio) phenylsulfoxide and the like can be used. Of these compounds, methyl-4- (phenylthio) phenylsulfoxide is preferred. The aromatic sulfoxides may be used alone or in combination of two or more.

  As the acid used when synthesizing the poly (arylene sulfonium salt), any of an organic acid and 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 formic acid, nitric acid, carbonic acid, boric acid, molybdic acid, isopoly acid, and heteropoly acid. Inorganic oxo acids such as acids; sodium hydrogen sulfate, sodium dihydrogen phosphate, proton-remaining heteropolyacid salts, partial salts or partial esters of sulfuric acid such as monomethyl sulfate, trifluoromethane sulfate and the like; formic acid, acetic acid, propionic acid, butanoic acid, succinic acid Mono- 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, ethanesulfonic acid Acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethane Monovalent or polyvalent sulfonic acids such as benzenesulfonic acid and benzenedisulfonic acid; partial metal salts of polyvalent sulfonic acids such as sodium benzenedisulfonic acid; antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tetrachloride Examples thereof include Lewis acids such as tin, zinc chloride, copper chloride, and iron chloride. Among these acids, use of trifluoromethanesulfonic acid or methanesulfonic acid is preferred 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 anhydrides such as acetic anhydride, fluoroacetic anhydride and trifluoroacetic anhydride; and magnesium sulfate anhydride, zeolite, silica gel, calcium chloride and the like. These dehydrating agents may be used alone or in combination of two or more.

  When synthesizing the poly (arylene sulfonium salt), a solvent can be appropriately used. 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; halogen-containing solvents such as methylene chloride and chloroform. Saturated hydrocarbon solvents such as normal hexane, cyclohexane, normal heptane and cycloheptane; amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; sulfur-containing solvents such as sulfolane and DMSO; tetrahydrofuran and dioxane. Ether solvents and the like can be mentioned. These solvents may be used alone or in combination of two or more.

  Conditions for reacting the poly (arylene sulfonium salt) with the aliphatic amide compound according to the present embodiment can be appropriately adjusted so that dealkylation or dearylation proceeds appropriately. The reaction temperature is preferably in the range of 40 to 250C, more preferably 70 to 220C.

  According to the production method of the present embodiment, the residual amount of the dealkylating agent or the dearylating agent in the obtained polyarylene sulfide resin can be reduced. 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. Is more preferable, the range is 700 ppm or less, more preferably 100 ppm or less. When the content is 1000 ppm or less, the substantial effect on the quality of the obtained polyarylene sulfide resin can be reduced. Polyarylene sulfide resin obtained by the production method of the present embodiment, based on the type and content of components such as a mixed dealkylating agent or dearylating agent, based on the polyarylene sulfide resin produced by another method and Can be distinguished.

  The method for producing a polyarylene sulfide resin according to the present 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 residual amount of the dealkylating agent or the dearylating agent contained in the obtained polyarylene sulfide resin can be more reliably reduced.

  The solvent used in the washing step is not particularly limited, but is preferably one that dissolves unreacted substances. Examples of the solvent include water, aqueous hydrochloric acid, aqueous acetic acid, aqueous oxalic acid, aqueous acidic solutions such as aqueous nitric acid, aromatic hydrocarbon solvents such as toluene and xylene, and alcohol solvents such as methanol, ethanol, propanol and isopropyl alcohol. Amide solvents such as dimethylacetamide, N-methyl-2-pyrrolidone, saturated hydrocarbon solvents such as normal hexane, cyclohexane, normal heptane and cycloheptane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; dichloromethane; Examples thereof include a halogen-containing solvent such as chloroform. These solvents may be used alone or in combination of two or more. Among these solvents, water and N-methyl-2-pyrrolidone are preferred from the viewpoint of removing the reaction reagent and the oligomer component of the resin.

  According to the production method of the present embodiment, a polyarylene sulfide resin containing a structural unit represented by the following general formula (2) and having a sulfide group can be obtained.

In the general formula (2), R ¹ and Ar ¹ are the same as those defined in the general formula (1).

  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 device.

  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 400C, more preferably in the range of 150 to 300C. The melting point of the resin indicates a value measured by a DSC device.

  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 article having excellent strength retention (hot water resistance) under high temperature and high humidity and excellent epoxy adhesiveness can be produced.

  Mtop of the polyarylene sulfide resin according to the present 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 indicates the average molecular weight (peak molecular weight) at the point where the detection intensity of the chromatogram measured by gel permeation chromatography is maximum, and Mw indicates the weight average molecular weight.

  The melt viscosity (V6) at 300 ° C. of the polyarylene sulfide resin according to the present embodiment is preferably from 1 to 2000 [Pa · s] from the viewpoint of improving the filling density into a mold and the surface appearance during injection molding. , More preferably in the range of 5 to 1700 [Pa · s]. Here, the melt viscosity (V6) was measured using a flow tester at a temperature of 300 ° C., a load of 1.96 MPa, and an orifice having a ratio of orifice length to orifice diameter (orifice length / orifice diameter) of 10/1. After 6 minutes.

Polyarylene sulfide resin according to the present embodiment, the FT-IR spectrum as measured by FT-IR spectroscopy (IR ^spectrum), which has an absorption peak in the range of 2910cm ^-1 ~2930cm -1 Thus, since the solubility of the low molecular weight component in the solvent is good, the polymer is easily removed by the above-mentioned cleaning 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 a range of 0.2% by mass or less, and preferably in a range of 0.15% by mass or less. Since the amount of gas generated during heating can be suppressed, it is possible to contribute to improvement of the working environment and the like. Further, the contamination of the mold during molding can be suppressed, and the 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 powder fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate 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 fibers and wollastonite fibers, 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 5 to 200 parts by mass, and still more preferably 15 to 150 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. It is in the range of parts by mass. When the content of the inorganic filler is within these ranges, a more excellent effect can be obtained in terms of maintaining the mechanical strength of the molded article.

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

  As the thermoplastic resin blended in the polyarylene sulfide resin composition, for example, polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone, polyethylene , Polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, silicone resin, and liquid crystal polymer (liquid crystal polyester and the like).

  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 the diamine for obtaining the polyamide include an aliphatic diamine, an aromatic diamine, and an alicyclic diamine. As the aliphatic diamine, a diamine having 3 to 18 carbon atoms having a linear or side chain is preferable. Examples of suitable aliphatic diamines include 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, and 1,7-heptamethylenediamine 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanemethylenediamine, 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'-diaminodiphenylsulfide, 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, , 5-Diaminonaphthalene, 1,8-diaminonaphthale 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 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-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, 4,4'-diamino-3,3'-dimethyl- 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 an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an 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 oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, prasillic acid, tetradecane Diacids, pentadecandioic acid, octadecandioic 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 and 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 Acids, diphenylether-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. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as they 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.

  Lactams for obtaining polyamides include, for example, ε-caprolactam, ω-laurolactam, ζ-enantholactam, and η-caprylactam. 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), and 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. Can be Among them, 1,4-tetramethylenediamine / adipic acid (nylon 4,6), 1,6-hexamethylenediamine / terephthalic acid / ε-caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9-nonamethylenediamine / terephthalic acid, 1,9-nonamethylenediamine / terephthalic acid / ε-caprolactam, or 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid Is preferred.

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

  A thermoplastic elastomer is often used as the elastomer to be blended in the polyarylene sulfide resin composition. Examples of the thermoplastic elastomer include a polyolefin-based elastomer, a fluorine-based elastomer, and a silicone-based elastomer. In addition, in this specification, a thermoplastic elastomer is classified into an elastomer instead of the thermoplastic resin.

  The elastomer (particularly a 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. This makes it possible to obtain a resin composition which is particularly excellent in terms of adhesiveness and impact resistance, and which can suppress the amount of gas generated by heating. Examples of such a functional group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, a mercapto group, an isocyanate group, an oxazoline group, and a compound represented by the formula: R (CO) O (CO)-or R (CO) O- 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 copolymerizing an α-olefin with a vinyl polymerizable compound having the above 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) acrylate 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), and glycidyl (meth) acrylate. Among these, an epoxy group, a carboxyl group, and the formula: R (CO) O (CO)-or R (CO) O- (wherein, R represents an alkyl group having 1 to 8 carbon atoms). Ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the groups represented are preferred from the viewpoint of improvement in toughness and impact resistance.

  The content of the elastomer cannot be specified unconditionally because it varies depending on the type and use of the elastomer. For example, the content is preferably in the range of 1 to 300 parts by mass, more preferably 3 to 300 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. The range is from 100 to 100 parts by mass, more preferably from 5 to 45 parts by mass. When the content of the elastomer is in these ranges, more excellent effects can be obtained in terms of securing heat resistance and toughness of the molded article.

  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, a hydroxyl group, or the like. Examples of suitable aromatic epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak Epoxy resin, bisphenol A novolak epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, phenol aralkyl epoxy resin, naphthol novolak epoxy resin, naphthol aralkyl Epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolak 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, in particular, a novolak epoxy resin is preferable, and a cresol novolak epoxy resin is more preferable, from the viewpoint of excellent 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 3 to 100 parts by mass, and still more preferably 5 to 30 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. It is in the range of parts by mass. 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 particularly remarkably obtained.

  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 the polyarylene sulfide resin with other components can be improved, and a resin composition capable of suppressing the amount of gas generated by heating can be obtained. Such silane compounds include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyl Examples include silane coupling agents such as diethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

  The content of the silane compound is, for example, preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. . When the content of the silane compound is in 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 also contains a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and other additives such as 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 compound in the form of pellets by a method of melt-kneading the polyarylene sulfide resin obtained by the above method and the other components. The temperature of the melt-kneading is, for example, preferably in the range of 250 to 350 ° C, and more preferably in the range of 290 to 330 ° C. Melt kneading can be performed using a twin-screw extruder or the like.

  Polyarylene sulfide resin composition according to the present embodiment, alone or in combination with the other components and the like, injection molding, extrusion molding, compression molding and various melt processing methods such as blow molding, heat resistance, It can be processed into a molded product excellent in molding processability, dimensional stability and the like. 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 the present embodiment is used for an electric vehicle component, the amount of gas generated by heating can be reduced. For this reason, the contact between the low molecular weight compound containing a sulfur atom as a gas component and a metal material such as copper can be reduced, and as a result, even when a high voltage is repeatedly applied, the reaction between the two can be suppressed, and the tree can be suppressed. It is possible to improve the tracking resistance by suppressing the occurrence and progress of (dendritic destruction traces).

  As described above, the polyarylene sulfide resin composition of the present invention is particularly useful in the field of electric vehicles requiring high safety, that is, a hybrid vehicle (HV) equipped with a lithium ion secondary battery and powered by an electric motor. , A plug-in hybrid vehicle (PHV), an electric vehicle (EV), a fuel cell vehicle (FCV), and the like. Therefore, specific examples of the 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, There is a case for storing a junction block or the like. The molded product is particularly suitably 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 described below, the following reagents were used.
Methyl phenyl sulfoxide: 98% pure, manufactured by Tokyo Chemical Industry Co., Ltd.
Thioanisole: Wako Pure Chemical Industries, Ltd., purity 99%
Methanesulfonic acid: Wako Pure Chemical Industries, Ltd., Wako Special Grade 60% perchloric acid: Wako Pure Chemical Industries, Ltd., Wako Primary Pyridine: Wako Pure Chemical Industries, Ltd., reagent grade potassium hydrogen carbonate: Sum Kako Pure Chemical Industries, Ltd., reagent grade bromine: Wako Pure Chemical Industries, Ltd., reagent grade trifluoromethanesulfonic acid: Wako Pure Chemical Industries, Ltd., Wako grade quinoline: Wako Pure Chemical Industries, Ltd., Reagent special grade N-methylpyrrolidone: Wako Pure Chemical Industries, Ltd., Wako first grade

1. Evaluation method of monomer 1-1. Identification method ( ¹ H-NMR, ¹³ C-NMR)
It was measured by dissolving it in various heavy solvents using an apparatus of DPX-400 manufactured by BRUKER.

2. Synthesis of monomer (synthesis of methylphenyl [4- (methylthio) phenyl] sulfonium perchlorate)

70.0 [g] of methylphenylsulfoxide and 62.0 [g] of thioanisole were placed in a 3 L three-necked flask, and cooled to 5 ° C. or lower in an ice bath under a nitrogen atmosphere. Methanesulfonic acid 1 [L] was added to the reaction solution while keeping it at 10 ° C. or lower. Thereafter, the ice bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 20 hours. Next, the reaction solution after stirring was put into 2% of a 60% aqueous solution of perchloric acid, and stirred for 1 hour. 1 [L] of water and 1 [L] of dichloromethane were added, and the organic layer was recovered by extraction / separation. Further, the operation of adding 500 [mL] of dichloromethane to the aqueous layer and recovering the organic layer was performed twice. Anhydrous magnesium sulfate was added to the collected organic layer for dehydration. After dehydration, magnesium sulfate was separated by filtration, and the filtrate was concentrated using a rotary evaporator to remove the solvent. Ether was added to the remaining viscous solid for crystallization. The crystal was separated by filtration, and the obtained solid was dried under reduced pressure for 20 hours to obtain 130.0 [g] of methylphenyl [4- (methylthio) phenyl] sulfonium perchlorate (75% yield). Was. ¹ H-NMR measurement confirmed that the target compound was synthesized.
¹ H-NMR (solvent CDCl ₃ ): 2.49, 3.63, 7.40, 7.65, 7.78.7.85 [ppm]

(Synthesis of methyl-4- (phenylthio) phenyl sulfide)

In a 2 L three-necked flask, 100.0 [g] of methylphenyl [4- (methylthio) phenyl] sulfonium perchlorate was added, and 500 [mL] of pyridine was added under a nitrogen atmosphere, followed by stirring for 30 minutes. Thereafter, the temperature was raised to 100 [° C.], and the mixture was stirred for 30 minutes. The reaction solution was poured into 3 [L] of a 10% HCl solution, stirred for 10 minutes, and extracted with dichloromethane / separated liquid to recover an organic layer. Anhydrous magnesium sulfate was added to the collected organic layer for dehydration. Magnesium sulfate was filtered off by filtration, and the filtrate was concentrated with a rotary evaporator to remove the solvent. The target component was recovered by column chromatography using a developing solvent of hexane / chloroform = 3/1 (volume ratio), and the solvent was removed with a rotary evaporator.
The resulting liquid was dried under reduced pressure for 20 hours to obtain 55.5 [g] of methyl 4- (phenylthio) phenyl sulfide (83% yield). ¹ H-NMR measurement confirmed that the target compound was synthesized.
¹ H-NMR (solvent CDCl ₃ ): 2.48, 7.18 to 7.23, 7.28 to 7.31 [ppm]

(Synthesis of methyl 4- (phenylthio) phenylsulfoxide)

A 5-L three-necked flask was charged with 50.0 [g] of methyl 4- (phenylthio) phenyl sulfide, 43.0 [g] of potassium hydrogen carbonate, 390 [mL] of water, and 500 [mL] of dichloromethane for 30 minutes. Stirred. A solution obtained by dissolving 34.5 [g] of bromine in 500 [mL] of dichloromethane was dropped into the reaction vessel over 5 minutes, and stirred for 30 minutes. 1 [L] of a saturated solution of potassium chloride (KCl) and 1 [L] of dichloromethane were added to the reaction solution, and the organic layer was recovered by extraction / separation. An operation of adding 500 [mL] of dichloromethane to the remaining aqueous layer and collecting the organic layer was performed twice. The collected organic layer was washed with water, separated by a liquid separation operation, and dehydrated by adding anhydrous magnesium sulfate. After dehydration, magnesium sulfate was separated by filtration, and the filtrate was concentrated using a rotary evaporator to remove the solvent. Ether was added to the remaining viscous solid for crystallization. The crystal was separated by filtration, and the obtained solid was dried under reduced pressure for 20 hours to obtain 30.5 [g] of methyl 4- (phenylthio) phenylsulfoxide (57% yield). ¹ H-NMR and ¹³ C-NMR measurements confirmed that the target compound was synthesized.
¹ H-NMR (solvent CDCl ₃ ): 2.71, 7.34, 7.39, 7.46, 7.52 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 46.0, 124.5, 128.5, 129.7, 133.0, 133.5, 141.5, 144.3 [ppm]

3. Synthesis of poly (arylene sulfonium salt)

2.0 [g] of methyl 4- (phenylthio) phenylsulfoxide was put into a 500 mL three-necked flask, and cooled in an ice bath under a nitrogen atmosphere. Thereafter, 10 [mL] of trifluoromethanesulfonic acid was slowly dropped. The temperature was raised to room temperature and stirred for 20 hours. Water was added to the reaction solution after stirring, the mixture was stirred for 10 minutes, and then filtered. Thereafter, the solid was washed with water and filtered to collect a solid. The solvent was removed with a rotary evaporator, and the residue was dried under reduced pressure to obtain 2.8 [g] of poly [methyl trifluoromethanesulfonate (4-phenylthiophenyl) sulfonium] (91% yield) as a target substance (91%). PPS-1 in Table 1).
A small amount is collected from the target product obtained for analysis, subjected to ion exchange with an excess of methanesulfonic acid, and then subjected to ¹ H-NMR measurement on a product dissolved in heavy DMSO, whereby the target product is synthesized. It was confirmed.
¹ H-NMR (deuterated DMSO): 3.27, 3.83, 7.66, 8.08 [ppm]

4. Evaluation method of synthesized polyarylene sulfide resin 4-1. Glass transition temperature and melting point Using a DSC apparatus Pyris Diamond manufactured by PerkinElmer, measurement was performed from 40 to 350 ° C under a nitrogen flow of 50 mL / min and a temperature rising condition of 20 ° C / min to determine the glass transition temperature and melting point.
4-2. Infrared absorption spectrum After pressing the obtained PPS resin at 350 ° C., the film is rapidly cooled to produce an amorphous film, and a Fourier transform infrared spectrometer (hereinafter abbreviated as “FT-IR device”) (FTIR-6100 manufactured by FTIR Co., Ltd.). In the infrared absorption spectrum, the presence or absence of absorption at 2,920 cm-1 was measured.
4-3. Melt Viscosity of Polyarylene Sulfide Resin Polyarylene sulfide resin is held at 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10/1 for 6 minutes using a CFT-500C flow tester manufactured by Shimadzu Corporation. After that, the melt viscosity was measured.
4-4. Mw and Mtop (molecular weight distribution)
The weight average molecular weight and peak molecular weight of the polyarylene sulfide resin were measured using gel permeation chromatography under the following measurement conditions. 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 analyzer (“SSC-7000” manufactured by Senshu Kagaku Co., Ltd.)
Column: UT-805L (Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene Measurement method: UV detector (360 nm)
4-5. Generated gas amount A predetermined amount of a polyarylene sulfide resin sample was heated at 325 ° C. for 15 minutes using a gas chromatograph mass spectrometer (GC-2010, manufactured by Shimadzu Corporation), and the amount of gas generated at that time was determined as mass%. did.
4-6. Sodium content About 0.5 g of a sample was weighed into a platinum crucible, and about 2 ml of 97% concentrated sulfuric acid was added thereto, followed by thermal decomposition on a heater. After the decomposition was completed, the residue was dissolved in distilled water after being incinerated in an electric furnace at 500 ° C., and a sample obtained by measuring the amount was quantified using a PerkinElmer Optima 4300 DV.

5. Synthesis of polyarylene sulfide resin (dealkylation or dearylation of poly (arylene sulfonium salt))
(Synthesis example 1: PPS-1)

2.0 [g] of poly [methyl trifluoromethanesulfonate (4-phenylthiophenyl) sulfonium] obtained in the above "Synthesis of poly (arylene sulfonium salt)" is placed in a 100 mL eggplant-shaped flask, and a dealkylating agent or a dealkylating agent is added. 5.5 [mL] (10 equivalents) of N-methyl-2-pyrrolidone as an arylating agent was added, and the mixture was stirred at room temperature for 30 minutes, and then heated to 100 ° C and stirred for 48 hours. After cooling the reaction solution after stirring to room temperature, it was poured into water, and the precipitate was separated by filtration and washed three times with 80 [mL] of water. The obtained solid was dried overnight at 120 ° C. using a hot-air drier to obtain 0.83 [g] of polyphenylene sulfide (73% yield).
The obtained solid was subjected to thermal analysis. As a result, the glass transition temperature (Tg) was 92 ° C. and the melting point was 278 ° C., and thus it was confirmed that a polyphenylene sulfide resin (PPS resin) was formed.
When the infrared absorption spectrum was measured, as shown in FIG. 1, the presence of a peak at 2917 cm ^-1 was recognized.
The melt viscosity of this polymer was 370 Pa · s, Mtop was 52,000, and Mw was 49000.
The amount of generated gas was as small as 0.1 [wt%].
The sodium content was less than 50 ppm.

(Synthesis example 2: PPS-2)
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 to 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 a 47.43 mass% NaSH aqueous solution, and 123.18 g (1.5 mol) of a 48.71 mass% NaOH aqueous solution, and stirred. The temperature was raised to 173 ° C. over 2 hours in a nitrogen atmosphere while distilling 177.98 g of water, and then the kettle was sealed. At that time, p-DCB distilled off by azeotropic distillation was separated by a decanter and returned to the kettle as needed. After completion of the 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., the mixture was 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 obtained slurry was poured into 3 liters of water, stirred at 80 ° C. for 1 hour, and filtered. The cake was again stirred with 3 liters of warm water for 1 hour, washed and filtered. This operation was repeated four times, followed by filtration and drying at 120 ° C. overnight using a hot air drier to obtain 154 g of white powdery PPS.
As a result of a thermal analysis of the obtained solid, it was confirmed that a polyphenylene sulfide resin (PPS resin) had been produced because the glass transition temperature (Tg) was 92 ° C. and the melting point was 277 ° C.
When the infrared absorption spectrum was measured, as shown in FIG. 2, the presence of an absorption peak was not recognized in the range of 2910 cm ^{−1 to} 2930 cm ⁻¹ .
The melt viscosity of this polymer was 220 Pa · s, Mtop was 45,000, and Mw was 44,000.
The amount of generated gas was 0.5% by weight.
The sodium content was 600 ppm.

6. Polyphenylene sulfide resin composition (PPS compound)
<Raw materials>
The following materials were prepared in order to prepare a PPS resin composition.
(Thermoplastic elastomer)
ELA: Copolymer of ethylene / glycidyl methacrylic acid (3% by mass) / methyl acrylate (27% by mass) (“Bond First 7L” manufactured by Sumitomo Chemical Co., Ltd.)
(Silane coupling agent)
Epoxysilane: 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 (length)
-Test result: Average value of the number of tests n = 10

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

[Metal adhesion strength]
Injection and molding of a polyarylene sulfide resin composition of the same dimensions into a 4 × 10 × 49 mm metal piece (SUS304) set in a mold, a tensile test under conditions of a chuck distance of 20 mm and a tensile speed of 1 mm / min. Was carried out, and the metal adhesion strength was measured.

[Epoxy adhesive strength]
A test piece of 3 mm (thickness) x 25 mm (width) x 75 mm (length) is molded, and an epoxy resin (main agent: XNR-5002 (manufactured by Nagase ChemteX)) is cured on the test piece so as to have an adhesion area of 25 mm x 10 mm. Agent: XNH-5002 (manufactured by Nagase ChemteX), main agent / hardener = 100/90 (mass ratio) was applied in a thickness of 40 to 50 μm. After fixing these with clips, they were heated at 130 ° C. for 3 hours, and then gradually cooled to cure the epoxy resin. 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 PPS compound 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, a cylinder temperature of 320 ° C, a mold temperature of 140 ° C, and no holding pressure.

After molding, the filling degree of the cavity (C10) furthest from the primary sprue in the same runner as the cavity (C1) was compared. The degree of filling (% by mass) was determined from the mass ratio of the molded article of the cavity (C10) to the molded article 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: 100-90% by mass A: 89-80% by mass B: 79-70% by mass C: 69-60% by mass D: 59% by mass or less

[Gas generation]
Using a gas chromatograph mass spectrometer (GC-2010, manufactured by Shimadzu Corporation), 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 determined as mass%. .

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

<Compound preparation and evaluation>
After each raw material was uniformly mixed by a tumbler with the composition shown in Table 1, it was melt-kneaded at 300 ° C. using a twin-screw kneading extruder (TEM-35B, Toshiba Machine Co., Ltd.) to obtain a pellet compound. The obtained compound was injection-molded under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 140 ° C., and test pieces used for bending characteristics, metal adhesion strength, cavity balance and hot water resistance test were prepared, and various evaluations were made. . Further, the gas generation amount of the compound was measured. Table 1 shows the results.

  As is evident from the results shown in Table 1, the examples were made of mechanical properties (bending strength, bending elongation at break), metal adhesion strength, epoxy adhesion strength, cavity balance, hot water resistance, gas generation, It was superior to the comparative example in terms of tracking performance.

Claims (5)

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 crosslinkable resins having two or more crosslinkable functional groups, A method for producing a polyarylene sulfide resin composition for electric vehicle parts,
The polyarylene sulfide resin is reacted with a poly (arylene sulfonium salt) having a structural unit represented by the following general formula (1) and an aliphatic amide compound to form a structural unit represented by the following general formula (2) possible to get by a method comprising the steps of obtaining a polyarylene sulfide resin having,
The polyarylene sulfide resin is one having a -S-R ^2, a manufacturing method of an electric vehicle component polyarylene sulfide resin composition.

(In the formula, ^{R 1} represents a direct ^bond, -Ar 2 -, ^- Ar 2 -S- or ^-Ar 2 -O- to represent, Ar ¹ and Ar ² may have a functional group as a substituent Represents an arylene group, R ² represents an alkyl group having 1 to 10 carbon atoms or an aryl group which may have an alkyl group having 1 to 10 carbon atoms, and X ⁻ represents an anion.)

(In the formula, ^{R 1} represents a direct ^bond, -Ar 2 -, ^- Ar 2 -S- or ^-Ar 2 -O- to represent, Ar ¹ and Ar ² may have a functional group as a substituent Represents an arylene group.) The method for producing a polyarylene sulfide resin composition for an electric vehicle component according to claim 1, wherein R ² is a methyl group . The method for producing a polyarylene sulfide resin composition for electric vehicle parts according to claim 1, wherein the aliphatic amide compound contains an aliphatic tertiary amide compound. Molding the produced polyarylene sulfide resin composition by the method according to any one of claims 1 to 3, the manufacturing method of an electric vehicle component molded article. 4. Ru attached with the produced molded article by the method according to the manufacturing method of the electric vehicle parts.

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