JP6816408B2 - Polyarylene sulfide resin composition and its molded product - Google Patents

Description

The present invention relates to a polyarylene sulfide resin and a method for producing the same, and poly (arylene sulfonium salt) and a method for producing the same.

Polyphenylene sulfide resin (hereinafter sometimes abbreviated as "PAS resin") represented by polyphenylene sulfide resin (hereinafter sometimes abbreviated as "PPS resin") has excellent heat resistance, chemical resistance and the like, and is electrically charged. It is widely used in electronic parts, automobile parts, water heater parts, textiles, film applications, etc.

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

However, since this method uses dichlorobenzene as a monomer, the halogen concentration remaining in the resin after synthesis tends to be high. In addition, since it is necessary to carry out the polymerization reaction in a harsh environment of high temperature and high pressure and strong alkali, it is necessary to use a polymerization container using expensive and difficult-to-process titanium, chromium or zirconium for the wetted part.

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

In the case of the method for producing a polyarylene sulfide resin by homopolymerization of monofunctional sulfoxide, the structural unit of the resin is determined by the structure of the monofunctional sulfoxide as a raw material. Therefore, when changing the structural unit of the polyarylene sulfide resin according to the purpose of use or the like, it is often the case that the design of the monofunctional sulfoxide as a raw material is started. However, the options for monofunctional sulfoxides that can be used are limited, and the range in which the constituent units of the polyarylene sulfide resin can be changed is substantially very limited.

Furthermore, since the polyarylene sulfide resin produced by these production methods does not have a highly reactive functional group at the terminal, it has poor reactivity with other resins other than the polyarylene sulfide resin, and its functionality as a resin is impaired. It was enough.

Various sulfoxides of 1,4-bis (methylsulfinyl) benzene, which are sulfoxides having two sulfinyl groups (hereinafter, may be referred to as "bifunctional sulfoxides"), in the presence of diphosphorus pentoxide and trifluoromethanesulfonic acid. Non-Patent Document 1 discloses a method for reacting with an aromatic compound. According to this method, it is possible to produce various polyarylene sulfide resins having a sulfide group by changing the aromatic compound. However, it is difficult to obtain a resin having a sufficiently high molecular weight by this method. Further, the polyarylene sulfide resin produced by these production methods has poor reactivity with other resins because it does not have a highly reactive functional group at the terminal. Therefore, the resin composition containing the polyarylene sulfide resin has insufficient mechanical strength, particularly cold and thermal impact resistance.

U.S. Pat. No. 3,354,129 Japanese Unexamined Patent Publication No. 10-182825

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

Therefore, the problem to be solved by the present invention is a machine using a polyarylene sulfide resin having a high degree of freedom in designing a structural unit, a sufficiently high molecular weight, and a highly reactive functional group. A resin composition that can be a molded product having excellent target strength, particularly cold and thermal impact resistance, and a molded product having excellent mechanical strength, particularly cold and thermal impact resistance, obtained by molding the resin composition, and a method for producing them. Is to provide.

As a result of various studies, the present inventors conducted a step of obtaining a poly (arylene sulfonium salt) having a specific functional group at the terminal, and dealkylated or dearylled the poly (arylene sulfonium salt) to polyallylen sulfide. It has been found that a polyarylene sulfide resin having a specific functional group at the terminal becomes a resin composition that can be a molded product having excellent mechanical strength, particularly cold and thermal impact resistance, by a step of obtaining a resin and a production method including the above. , The present invention has been completed.

That is, the present invention is selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups, at least. A polyelastomer sulfide resin composition containing one other component.
The polyarylene sulfide resin
From a group consisting of a main chain containing a structural unit represented by the following general formula (1-1) or the following general formula (2-1) and a carboxy group, a hydroxy group and an amino group bonded to the end of the main chain. A polyarylene sulfide resin composition comprising a terminal group containing at least one functional group selected.

〔式中、Ｒ^２ｂは、直接結合、−Ａｒ^４ｂ−、−Ｓ−Ａｒ^４ｂ−、−Ｏ−Ａｒ^４ｂ−、−ＣＯ−Ａｒ^４ｂ−、−ＳＯ_２−Ａｒ^４ｂ−又は−Ｃ（ＣＦ_３）_２−Ａｒ^４ｂ−を表し、Ａｒ^１、Ａｒ^２、Ａｒ^３ｂ及びＡｒ^４ｂは、それぞれ独立に、置換基を有していてもよいアリーレン基を表し、Ｚは、直接結合、−Ｓ−、−Ｏ−、−ＣＯ−、−ＳＯ_２−又は−Ｃ（ＣＦ_３）_２−を表す。
ただし、一般式（１−１）において、Ａｒ^１、Ａｒ^２及びＡｒ^３ｂが１，４−フェニレン基で、Ｒ^２ｂが直接結合であるとき、Ｚは、直接結合、−ＣＯ−、−ＳＯ_２−又は−Ｃ（ＣＦ_３）_２−であり、Ａｒ^１、Ａｒ^２及びＡｒ^３ｂが１，４−フェニレン基で、Ｒ^２ｂが−Ａｒ^４ｂ−で、Ａｒ^４ｂが１，４−フェニレン基であるとき、Ｚは、−Ｓ−、−Ｏ−、−ＣＯ−、−ＳＯ_２−又は−Ｃ（ＣＦ_３）_２−である。〕に関する。

^{Wherein, R 2b} is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or -C (CF ₃ ) ₂ -Ar ^4b - ^{represents, Ar 1, Ar 2, Ar} 3b and ^{Ar 4b} each independently represent an arylene group which may have a substituent, Z is a direct bond, -S-, Represents -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- .
However, in the general formula (1-1), 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} - a ^and, in Ar 1, Ar ² and ^{Ar 3b} is 1,4-phenylene ^{group, R 2b} is ^{-Ar 4b} - a, ^{Ar 4b} is a 1,4-phenylene group When Z is -S-, -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- . ] Regarding.

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

According to the present invention, a polyarylene sulfide resin having a high degree of freedom in designing a structural unit, a sufficiently high molecular weight, and a highly reactive functional group is used to provide mechanical strength, particularly cold and thermal impact resistance. It is possible to provide a resin composition that can be an excellent molded product, a molded product that is excellent in mechanical strength, particularly cold and thermal impact resistance, obtained by molding the resin composition, and a method for producing the same.

6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 1b by an infrared absorption spectrum. The arrow (position of 1708 cm ^-1 ) is the absorption peak of the C = O expansion and contraction vibration of the carboxy group. 6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 2 by an infrared absorption spectrum. The arrows (positions in the range of 3551 cm- ¹ and 3500-3300 cm- ¹ ) are absorption peaks of the OH stretching vibration of the hydroxy group. 6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 3 by an infrared absorption spectrum. The arrow (position of 3365 cm ^-1 ) is the absorption peak of the NH expansion and contraction vibration of the amino group. 6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 4 by an infrared absorption spectrum. The arrow (position of 3552 cm ^-1 ) is the absorption peak of the free OH stretching vibration of the hydroxy group. 6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 4 by an infrared absorption spectrum. The arrow (position of 1687 cm ^-1 ) is the absorption peak of the C = O expansion and contraction vibration of the carboxy group. 6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 5 by an infrared absorption spectrum. The arrow (position of 3555 cm ^-1 ) is the absorption peak of the free OH stretching vibration of the hydroxy group. 6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 5 by an infrared absorption spectrum. The arrows (3433 cm- ¹ and 3377 cm- ¹ positions) are the absorption peaks of the NH stretching vibration of the amino group. 6 is a chart obtained by measuring the poly (p-phenylene sulfide) obtained in Polymer Synthesis Example 6 by an infrared absorption spectrum. The arrow (position of 1707 cm ^-1 ) is the absorption peak of the C = O expansion and contraction vibration of the carboxy group. 6 is a chart obtained by measuring the poly (p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Polymer Synthesis Example 7b by an infrared absorption spectrum. The arrow (position of 3567 cm ^-1 ) is the absorption peak of the free OH stretching vibration of the hydroxy group. 6 is a chart obtained by measuring the poly (p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Polymer Synthesis Example 7b by an infrared absorption spectrum. The arrow (position of 1681 cm ^-1 ) is the absorption peak of C = O expansion and contraction vibration of the carboxy group. 6 is a chart obtained by measuring the poly (p-phenylenethio-p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Polymer Synthesis Example 8b by an infrared absorption spectrum. The arrow (position of 3454 cm ^-1 ) is the absorption peak of the OH stretching vibration of the hydroxy group. 6 is a chart obtained by measuring the poly (p-phenylenethio-p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Polymer Synthesis Example 8b by an infrared absorption spectrum. The arrow (position of 1684 cm ^-1 ) is the absorption peak of C = O expansion and contraction vibration of the carboxy group.

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

The polyarylene sulfide resin composition according to the present embodiment is
At least one other component selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. A polyarylene sulfide resin composition containing
The polyarylene sulfide resin
From a group consisting of a main chain containing a structural unit represented by the following general formula (1-1) or the following general formula (2-1) and a carboxy group, a hydroxy group and an amino group bonded to the end of the main chain. It is characterized by having a terminal group containing at least one selected functional group.

〔式中、Ｒ^２ｂは、直接結合、−Ａｒ^４ｂ−、−Ｓ−Ａｒ^４ｂ−、−Ｏ−Ａｒ^４ｂ−、−ＣＯ−Ａｒ^４ｂ−、−ＳＯ_２−Ａｒ^４ｂ−又は−Ｃ（ＣＦ_３）_２−Ａｒ^４ｂ−を表し、Ａｒ^１、Ａｒ^２、Ａｒ^３ｂ及びＡｒ^４ｂは、それぞれ独立に、置換基を有していてもよいアリーレン基を表し、Ｚは、直接結合、−Ｓ−、−Ｏ−、−ＣＯ−、−ＳＯ_２−又は−Ｃ（ＣＦ_３）_２−を表す。
ただし、一般式（１−１）において、Ａｒ^１、Ａｒ^２及びＡｒ^３ｂが１，４−フェニレン基で、Ｒ^２ｂが直接結合であるとき、Ｚは、直接結合、−ＣＯ−、−ＳＯ_２−又は−Ｃ（ＣＦ_３）_２−であり、Ａｒ^１、Ａｒ^２及びＡｒ^３ｂが１，４−フェニレン基で、Ｒ^２ｂが−Ａｒ^４ｂ−で、Ａｒ^４ｂが１，４−フェニレン基であるとき、Ｚは、−Ｓ−、−Ｏ−、−ＣＯ−、−ＳＯ_２−又は−Ｃ（ＣＦ_３）_２−である。〕。

^{Wherein, R 2b} is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or -C (CF ₃ ) ₂ -Ar ^4b - ^{represents, Ar 1, Ar 2, Ar} 3b and ^{Ar 4b} each independently represent an arylene group which may have a substituent, Z is a direct bond, -S-, Represents -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- .
However, in the general formula (1-1), 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} - a ^and, in Ar 1, Ar ² and ^{Ar 3b} is 1,4-phenylene ^{group, R 2b} is ^{-Ar 4b} - a, ^{Ar 4b} is a 1,4-phenylene group When Z is -S-, -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- . ].

This polyarylene sulfide resin is a poly (arylene sulfonium) having a terminal group containing at least one functional group (hereinafter sometimes referred to as "specific functional group") selected from the group consisting of a carboxy group, a hydroxy group and an amino group. It is obtained by a production method including a step of obtaining a salt) and a step of dealkylating or dearylting the poly (arylene sulfonium salt) to obtain a polyarylene sulfide resin.

In the present specification, the term "hydroxy group" or "carboxy group" refers to not only a hydroxy group or a carboxy group but also a hydroxy group or a carboxy group deprotonated to become an anion, a hydroxy group or a carboxy group. It also includes those in which protons have been ion-exchanged. Hydroxy groups or carboxy groups not only easily deprotonate in polar solvents such as aqueous solutions to form anions, but also have alkali metals such as lithium, sodium and potassium, or alkaline earth such as calcium and magnesium. This is because an ion-exchanged product with a strong base containing a metal or the like is easily formed.

Poly (allylen sulfonium salt) and production method The poly (arylene sulfonium salt) according to one embodiment has a main chain containing a structural unit represented by the following general formula (1-2) or a general formula (2-2). It has a main chain containing the structural unit represented, and a terminal group containing a specific functional group bonded to the end of the main chain. Even if the main chain of poly (arylene sulfonium salt) is substantially composed of only the structural units represented by the following general formula (1-2) or the structural units represented by the general formula (2-2). Good. The terminal group containing the specific functional group is often directly bonded to the structural unit represented by the formula (1-2) or (2-2).

In the general formula (1-2) or (2-2), R ¹ may have an alkyl group in the range of 1 to 10 carbon atoms or an alkyl group in the range of 1 to 10 carbon atoms. represents a ^{group, R 2b} is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or -C (CF ₃ ) ₂ -Ar ^4b - ^{represents, Ar 1, Ar 2, Ar} 3b and ^{Ar 4b} each independently represent an arylene group which may have a substituent, Z is a direct bond, -S-, -O -, - CO -, - SO 2 - or -C _{(CF 3) 2} - represents, X ^- represents an anion.

The structural unit represented by the general formula (2-2) may be the structural unit represented by the following general formula (5-2).

In the formula, R ¹ and X ⁻ are defined in the same manner as in the formula (1-2), and Ar ⁷ , Ar ⁸ and Ar ^9b each independently represent a phenylene group which may have a substituent. That is, when Ar ⁷ , Ar ⁸ and Ar ^9b are 1,4-phenylene groups in the formula (5-2), respectively, Ar ¹ is a 4,4'-biphenylene group in the formula (2-2), and R ^This corresponds to the case where ^2b is −S—Ar ^4b− and Ar ^4b is a 1,4-phenylene group.

The poly (arylene sulfonium salt) according to one embodiment is, for example, the sulfoxide represented by the following general formula (1-3) and the following general formula (1) in the presence of (a) an aromatic compound having a specific functional group. Step of reacting with the aromatic compound represented by -4) (hereinafter referred to as step (a)),
Or
(B) It has a step (hereinafter referred to as step (b)) of (single) polymerizing an aromatic sulfoxide represented by the following general formula (2-3) in the presence of an aromatic compound having a specific functional group. Obtained by the manufacturing method.

The sulfoxide used in the step (a) is a compound represented by the following general formula (1-3) and has two sulfinyl groups.

In the general formula ^(1-3), R ^1, Ar 1, Ar ² and Z are each a ^{R 1,} Ar 1, Ar ² and Z in the above general formula (1-2) or (2-2) It is defined in the same way.

The sulfoxide represented by the general formula (1-3) can be obtained, for example, by oxidizing the compound represented by the following general formula (1-5) by reacting it with an oxidizing agent or the like.

In the general formula (1-5), R ¹ , Ar ¹ , Ar ² and Z are the same as those of the general formula (1-2) or (2-2) above, R ¹ , Ar ¹ , Ar ² and Z. Defined.

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, m-chloroperoxybenzoic acid, oxone (registered trademark), osminium tetraoxide and the like can be used.

The compound represented by the general formula (1-5) (sulfide compound) is a halogen represented by Y using a compound represented by the following general formula (1-6) and dimethyl disulfide or the like, if necessary. It can be synthesized by subjecting an atom to a methylthio group or the like in a substitution reaction.

In the general formula (1-6), Y represents a halogen atom, and Ar ¹ , Ar ² and Z are defined in the same manner as in the general formula (1-2) or (2-2). Y is, for example, a chlorine atom, a bromine atom, an iodine atom, or the like, and is preferably a chlorine atom.

In the compounds represented by the general formulas (1-3), (1-5) or (1-6), Ar ¹ and Ar ² may be an arylene group such as phenylene, naphthylene or biphenylene, for example. Ar ¹ and Ar ² may be the same or different, but are preferably the same.

The mode of bonding Ar ¹ and Ar ² is not particularly limited, but it is preferable that Ar ¹ and Ar ² are bonded to Y and Z at a distant position in the arylene group. For example, when Ar ¹ and Ar ² are phenylene groups, Ar ¹ and Ar ² are units bonded at the para position (1,4-phenylene group) and units bonded at the meta position (1,3-phenylene group). Is preferable, and a unit that binds at the para position is more preferable. In terms of heat resistance and crystallinity of the obtained resin, Ar ¹ and Ar ² are preferably composed of units that are bonded at the para position.

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

Examples of the compound represented by the general formula (1-3) 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 Examples thereof include 3,3-hexafluoropropane. These compounds can be used alone or in combination.

Examples of R ¹ include alkyl groups in the range of 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. In addition, an aryl group having a structure such as phenyl, naphthyl, biphenyl and the like can be mentioned. Further, the aryl group includes an alkyl group having an number of carbon atoms in the range of 1 to 10, 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. It may have 1 to 4 substituents bonded to the aromatic ring.

The aromatic compound used in the step (a) is represented by, for example, the following general formula (1-4).

In the general formula (1-4), R ^2a is a hydrogen atom, an alkyl group in the range of 1 to 10 carbon atoms, -Ar ^4a , -S-Ar ^4a , -O-Ar ^4a , -CO-Ar ^4a , It represents −SO _2- Ar ^4a or −C (CF ₃ ) _2- Ar ^4a , where Ar ^3a and Ar ^4a each independently represent an aryl group which may have a substituent. When R ^2a is an alkyl group in the range of 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, and a nonyl group. A decyl group and the like can be mentioned. When the aryl group represented by Ar ^3a or Ar ^4a has a substituent, the substituent is preferably an alkyl group (methyl group or the like), a hydroxy group, an amino group, a mercapto group, a carboxy group or a sulfo group. .. Examples of Ar ^3a and Ar ^4a include aryl groups having a structure such as phenyl, naphthyl, and biphenyl. The aryl group is an alkyl group or hydroxy group having a carbon atom number in the range of 1 to 10, 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. , Amino group, mercapto group, carboxy group and sulfo group may have at least one substituent. Ar ^3a and Ar ^4a may be the same or different, but are preferably the same.

Examples of the compound represented by the general formula (1-4) include benzene, toluene, biphenyl, diphenyl sulfide, diphenyl ether, benzophenone, diphenyl sulfone, hexafluoro-2,2-diphenyl propane and the like. Of these compounds, biphenyl, diphenyl sulfide or diphenyl ether is preferable from the viewpoint of crystallinity. Diphenyl sulfide is preferable from the viewpoint of obtaining a polyarylene sulfide resin as a higher molecular weight substance. Diphenyl sulfide has a low melting point and can function as a solvent by itself, which is preferable from the viewpoint of controlling the reaction temperature and the like. Diphenyl ether is preferable from the viewpoint of lowering the melting point of the polyarylene sulfide resin. Benzophenone is preferable from the viewpoint of improving the heat resistance of the polyarylene sulfide resin. From the viewpoint of obtaining an amorphous polyarylene sulfide resin, diphenylsulfone or hexafluoro-2,2-diphenylpropane is preferable. By making the polyarylene sulfide resin amorphous, it is possible to improve the molding processability and transparency of the polyarylene sulfide resin.

The aromatic sulfoxide used in the step (b) is a compound represented by the following general formula (2-3), and has a sulfinyl group and an aromatic ring.

In the general formula (2-3), R ¹ and Ar ¹ are defined in the same manner as the above general formula (1-2) or (2-2) R ¹ and Ar ^1, and R ^2a is the above general formula. It is defined in the same way as R ^{2a in} equation (1-4).

In the step (b), as the aromatic sulfoxide of the formula (2-3), the structural unit represented by the formula (5-2) is used by using the aromatic sulfoxide represented by the following general formula (5-3). (Aromatic sulfonium salt) having the above can be obtained.

一般式（５−３）中、Ｒ^１は、式（２-３）と同様に定義される。Ａｒ^７及びＡｒ^８は、式（５−２）と同様に定義される。Ａｒ^９ａは、置換基を有していてもよいフェニル基を表す。

In the general formula (5-3), R ¹ is defined in the same manner as in the general formula (2-3). Ar ⁷ and Ar ⁸ are defined in the same manner as in equation (5-2). Ar ^9a represents a phenyl group which may have a substituent.

The aromatic sulfoxide represented by the general formula (2-3) can be obtained, for example, by oxidizing the compound represented by the following general formula (2-4) by reacting it with an oxidizing agent or the like.

In the general formula (2-4), ^{R 1} and Ar ¹ are defined as for ^{R 1} and Ar ¹ in the general formula (1-2) or ^{(2-2), R 2a} is the general It is defined in the same way as R ^{2a in} equation (1-4).

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), osminium tetraoxide and the like can be used.

The compound represented by the general formula (2-4) (sulfide compound) is a halogen represented by Y using a compound represented by the following general formula (2-5) and dimethyl disulfide or the like, if necessary. It can be synthesized by subjecting an atom to a methylthio group or the like in a substitution reaction.

In the general formula (2-5), Y is defined as Y in the above general formula (1-6), Ar ¹ is a Ar ¹ in the general formula (1-2) or (2-2) Similarly ^{defined, R 2a} is as defined for ^{R 2a} of the general formula (1-4).

As the aromatic sulfoxide represented by the general formula (2-3), for example, methylphenylsulfoxide, methyl-4- (phenylthio) phenylsulfoxide and the like can be used. Of these compounds, methyl-4- (phenylthio) phenylsulfoxide is preferred. Aromatic sulfoxides may be used alone or in combination of two or more.

The poly (arylene sulfonium salt) according to one embodiment is obtained by reacting sulfoxide in the presence of an aromatic compound having a specific functional group (hereinafter, may be referred to as "terminal denaturing agent").

The aromatic compound having such a specific functional group is not particularly limited as long as it does not deviate from the gist of the present invention, and may have a specific functional group directly bonded to the aromatic ring, or may have an aromatic. It may have a specific functional group bonded to a divalent organic group substituting the group ring.

More specifically, preferable aromatic compounds having a specific functional group include the following general formulas (3-1a), (3-2a), (3-3a), (3-4a), (3-5a). Alternatively, an aromatic compound represented by (3-6a) can be mentioned.

式中、Ｒ^３は直接結合又は炭素原子数１〜１０の範囲のアルキレン基を表し、Ａｒ^５ａは、アリール基を表す。

In the formula, R ³ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^5a represents an aryl group.

The alkylene group in the range of 1 to 10 carbon atoms as R ³ may be linear or branched. Examples of the alkylene group include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3. -Propene, 2,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,4-butylene, 1,10-decylene and the like can be mentioned. Examples of Ar ^5a include aryl groups having a structure such as phenyl, naphthyl, and biphenyl.

Specific examples of the aromatic compounds represented by (3-1a), (3-2a), (3-3a), (3-4a), (3-5a) or (3-6a) are benzoic acid. , Phenylpropionic acid, phenylhexanoic acid, phenylisobutyric acid, phenylmalonic acid, phenol, N-phenylglycine, N-benzyliminodiacetic acid, and aniline.

Preferred aromatic compounds having a specific functional group include aromatic compounds represented by the following general formulas (4-1a), (4-2a), (4-3a) or (4-4a).

式中、Ｒ^４は、直接結合又は炭素原子数１〜１０の範囲のアルキレン基を表し、Ａｒ^６ａは、アリール基を表す。

In the formula, R ⁴ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^6a represents an aryl group.

The alkylene group in the range of 1 to 10 carbon atoms as R ⁴ may be linear or branched. Examples of the alkylene group include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3. -Propene, 2,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,4-butylene, 1,10-decylene and the like can be mentioned. Examples of Ar ^6a include aryl groups having structures such as phenyl, naphthyl, and biphenyl.

The aromatic compound represented by the general formula (4-1a), (4-2a), (4-3a) or (4-4a) may be, for example, a compound represented by the following chemical formula. In the formula, R ⁴ is defined in the same manner as in the formula (4-1a) and the like.

In the reaction of the step (a), the sulfoxide represented by the general formula (1-3) is reacted with the aromatic compound represented by the general formula (1-4) to form a poly (arylene sulfonium salt). After obtaining the product, an aromatic compound having a specific functional group can be added to the reaction system for reaction. The step is to react the sulfoxide represented by the general formula (1-3) with the aromatic compound represented by the general formula (1-4) in the presence of an aromatic compound having a specific functional group. It is preferable because it is excellent in further simplification of.

Similarly, in the reaction of the step (b), after reacting the aromatic sulfoxide represented by the general formula (2-3) to obtain a poly (arylene sulfonium salt), an aromatic compound having a specific functional group is obtained. Can also be added to the reaction system for reaction. It is preferable to react the aromatic sulfoxide represented by the general formula (2-3) in the presence of an aromatic compound having a specific functional group from the viewpoint of further simplifying the process.

The reaction of step (a) or step (b) is preferably carried out in the presence of an acid. The acid may be either an organic acid or an inorganic acid. Acids include, for example, non-oxygenic acids such as hydrochloric acid, hydrobromic acid, blue acid, tetrafluoroboric acid; sulfuric acid, phosphoric acid, perchloric acid, bromic acid, nitrate, carbonic acid, boric acid, molybdic acid, isopolyic acid, heteropoly. Inorganic oxo acids such as acids; partial salts or esters of sulfuric acids such as sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropolyate, monomethyl sulfate, trifluoromethane sulfate; formic acid, acetic acid, propionic acid, butanoic acid, succinic acid Monovalent or polyvalent carboxylic acids such as acids, benzoic acids and phthalates; halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid and trifluoroacetic acid; methanesulfonic acid and ethanesulfone. Monovalent or polyvalent sulfonic acid such as acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, benzenedisulfonic acid; partial metal salt of polyvalent sulfonic acid such as sodium benzenedisulfonic acid; Examples thereof include antimony chloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride, Lewis acid such as iron chloride and the like. 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 the reaction in step (a) or step (b) is a dehydration reaction, a dehydrating agent may be used in combination. Examples of the dehydrating agent include phosphate 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 anhydrous acetic acid, anhydrous fluoroacetic anhydride, anhydrous trifluoroacetic anhydride; anhydrous magnesium sulfate, zeolite, silica gel, calcium chloride and the like can be mentioned. These dehydrating agents may be used alone or in combination of two or more.

A solvent can be appropriately used for the reaction of the step (a) or the step (b). 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, cycloheptane; amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; sulfur-containing solvents such as sulfolane and DMSO; tetrahydrofuran, dioxane and the like Examples include ether solvents and the like. These solvents may be used alone or in combination of two or more.

The conditions of the reaction of step (a) or step (b) 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 (arylene sulfonium salt) obtained in the above step (a) has a main chain containing a structural unit represented by the following general formula (1-2) and a terminal containing a specific functional group bonded to the end of the main chain. Has a group.

In the general formula (1-2), R ¹ represents an alkyl group in the range of 1 to 10 carbon atoms or an aryl group which may have an alkyl group in the range of 1 to 10 carbon atoms, and R ^2b. is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or ^{_{-C (CF 3) 2 -Ar 4b}} - Ar ¹ , Ar ² , Ar ^3b and Ar ^4b each independently represent an arylene group which may have a substituent, and Z represents a direct bond, -S-, -O-, -CO. -, - SO ₂ - or -C _{(CF 3) 2} - represents, X ^- represents an anion.

Ar ^3b and Ar ^4b may be, for example, an arylene group such as phenylene, naphthylene, and biphenylene. Ar ^3b and Ar ^4b 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 (1-2), 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 − is preferable. Ar ^1, Ar ² and ^{Ar 3b} is 1,4-phenylene ^{group, R 2b} is ^{-Ar 4b} - a, when ^{Ar 4b} is 1,4-phenylene group, Z is, -S -, - O -, - It is preferably CO-, -SO _2- or -C (CF ₃ ) _2- .

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

When the arylene group represented by Ar ^3b or Ar ^4b has a substituent, the substituents are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl. It is preferably an alkyl group, a hydroxy group, an amino group, a mercapto group, a carboxy group or a sulfo group in the range of 1 to 10 carbon atoms such as a group. However, the ratio of the structural units of the general formula (1-2) in which Ar ¹ , Ar ² , Ar ^3b and Ar ^4b are arylene groups having substituents reduces the crystallinity and heat resistance of the polyarylene sulfide resin. From the viewpoint of further suppression, it is preferably in the range of 10% by mass or less of the whole poly (arylene sulfonium salt), and more preferably 5% by mass or less.

The constituent units of the poly (arylene sulfonium salt) are represented by, for example, sulfoxide represented by the general formula (1-3) and the general formula (1-4) according to the purpose of use of the polyarylene sulfide resin and the like. It can be appropriately selected by changing the combination with the aromatic compound.

On the other hand, the poly (arylene sulfonium salt) obtained in the above step (b) has a main chain containing a structural unit represented by the following general formula (2-2) and a specific functional group bonded to the end of the main chain. Has a terminal group, including.

In the general formula (2-2), R ¹ represents an alkyl group in the range of 1 to 10 carbon atoms or an aryl group which may have an alkyl group in the range of 1 to 10 carbon atoms, and R ^2b. is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or ^{_{-C (CF 3) 2 -Ar 4b}} - , Ar ¹ and Ar ^4b each independently represent an arylene group which may have a substituent, and X ⁻ represents an anion.

In the general formula ^{(2-2), R 1, R} 2b, Ar 1 and X ^{- is, R} 1, ^R 2b in formula (1-2), Ar ¹ and X ^- to be defined as well.

Further, the aromatic compound represented by the general formula (3-1a), (3-2a), (3-3a), (3-4a), (3-5a) or (3-6a) is used as a raw material. The poly (arylene sulfonium salt) produced using the following general formulas (3-1b), (3-2b), (3-3b), (3-4b), (3-5b) or (3-6b) ) Can have a terminal group.

In the formula, R ³ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^5b represents an aryl group.

Poly (allylen sulfonium salt) produced by using the aromatic compound represented by the general formula (4-1a), (4-2a), (4-3a) or (4-4a) as a raw material is as follows. It can have a terminal group represented by the general formula (4-1b), (4-2b), (4-3b) or (4-4b).

式中、Ｒ^４は、直接結合又は炭素原子数１〜１０の範囲のアルキレン基を表し、Ａｒ^６ｂは、アリール基を表す。

In the formula, R ⁴ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^6b represents an aryl group.

The aryl groups of Ar ^5b and Ar ^6b may also contain an arylene group in which a substituent is attached to the aryl group.

Examples of the terminal group represented by the general formula (4-1b), (4-2b), (4-3b) or (4-4b) include a group represented by the following chemical formula. In the formula, R ⁴ is defined in the same manner as in the formula (4-1a) and the like.

Polyarylene Sulfide Resin and Production Method The polyarylene sulfide resin according to one embodiment mainly contains a structural unit represented by the general formula (1-1) or a structural unit represented by the general formula (2-1). It has a chain and a terminal group attached to the end of the main chain and containing at least one functional group (specific functional group) selected from the group consisting of a carboxy group, a hydroxy group and an amino group.

In the general formula (1-1) or ^{(2-1), R 2b} represents a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO ₂ −Ar ^4b − or −C (CF ₃ ) ₂ −Ar ^4b −, and Ar ¹ , Ar ² , Ar ^3b and Ar ^4b each independently represent an arylene group which may have a substituent. , Z represent direct binding, -S-, -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- .

The structural unit represented by the formula (2-1) may be the structural unit represented by the following general formula (5-1).

式中、Ａｒ^７、Ａｒ^８及びＡｒ^９ｂは、それぞれ独立に、置換基を有していてもよいフェニレン基を表す。すなわち、式（５−１）においてＡｒ^７、Ａｒ^８及びＡｒ^９ｂがそれぞれ１，４−フェニレン基であるとき、式（２−１）において、Ａｒ^１が４，４’−ビフェニレン基で、Ｒ^２ｂが−Ｓ−Ａｒ^４ｂ−で、Ａｒ^４ｂが１，４−フェニレン基に相当する。

In the formula, Ar ⁷ , Ar ⁸ and Ar ^9b each independently represent a phenylene group which may have a substituent. That is, when Ar ⁷ , Ar ⁸ and Ar ^9b are 1,4-phenylene groups in the formula (5-1), respectively, Ar ¹ is a 4,4'-biphenylene group in the formula (2-1), and R ^2b is −S—Ar ^4b− , and Ar ^4b corresponds to a 1,4-phenylene group.

The polyarylene sulfide resin according to one embodiment includes a main chain containing a structural unit represented by the following general formula (1-2) or a structural unit represented by the following general formula (2-2), and a terminal of the main chain. It is obtained by a production method having a step of dealkylating or dearyllating a poly (arylene sulfonium salt) having a terminal group containing a specific functional group bonded to.

In the general formula (1-2) or (2-2), R ¹ may have an alkyl group in the range of 1 to 10 carbon atoms or an alkyl group in the range of 1 to 10 carbon atoms. represents a ^{group, R 2b} is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or -C (CF ₃ ) ₂ -Ar ^4b - ^{represents, Ar 1, Ar 2, Ar} 3b and ^{Ar 4b} each independently represent an arylene group which may have a substituent, Z is a direct bond, -S-, -O -, - CO -, - SO 2 - or -C _{(CF 3) 2} - represents, X ^- represents an anion.

The polyarylene sulfide resin having a main chain containing a structural unit represented by the general formula (5-1) is, for example, a poly (arylene) having a main chain containing a structural unit represented by the general formula (5-2). The sulfonium salt) is obtained by having a step of dealkylating or dearyllating.

The dealkylation or dearyllation of the poly (arylene sulfonium salt) is considered to proceed as represented by, for example, the following reaction formula.

A dealkylating agent or a dearylting agent can be used in such a step. Dealkylating or dearylting agents include nucleophiles or reducing agents. As the nucleophile, a nitrogen-containing aromatic compound, an amine compound, an amide compound and 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 nitrogen-containing aromatic compound include pyridine, quinoline, and aniline. Of these compounds, pyridine, which is a general-purpose compound, is preferable.

Examples of the amine compound include trialkylamine and ammonia.

As the amide compound, an aromatic amide compound and an aliphatic amide compound can be used. The aliphatic amide compound is represented by, for example, a compound represented by the following general formula (4).

In the general formula (4), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group in the range of 1 to 10 carbon atoms, and R ¹¹ and R ¹³ are bonded to form a cyclic structure. It may be formed. Examples of the alkyl group in the range of 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, a decyl group and the like.

The compound represented by the general formula (4) is, for example, dealkylated or dealkylated from an alkyl group or an aryl group bonded to the sulfur atom of the sulfonium salt as represented by the following reaction formula (1) or (2). It is believed to function as a dealkylating or dearylting agent that dearyllates.

(Reaction formula 1)

(Reaction formula 2)

Further, the aliphatic amide compound has higher miscibility with water than the aromatic amide compound, and can be easily removed by washing the reaction mixture with water. Therefore, when the aliphatic amide compound is used, the residual amount of the aliphatic amide compound in the polyarylene sulfide resin can be further reduced as compared with the case where the aromatic amide compound is used.

Using the aliphatic amide compound as a dealkylating agent or a dearylling agent in this way suppresses gas generation during resin processing, etc., improves the quality of polyarylene sulfide resin molded products, improves the working environment, and further. Is preferable because the maintainability of the mold can be further improved. Moreover, since the aliphatic amide compound is also excellent in the solubility of the organic compound, the use of the aliphatic amide compound also makes it possible to easily remove the oligomer component of polyarylene sulfide from the reaction mixture. As a result, the quality of the obtained polyarylene sulfide resin can be synergistically improved by removing the oligomer component, which can contribute to gas generation, with the aliphatic amide compound.

Examples of such an aliphatic amide compound include a primary amide compound such as formamide, a secondary amide compound such as β-lactam, N-methyl-2-pyrrolidone, dimethylformamide, diethylformamide, dimethylacetamide, and tetramethylurea. A tertiary amide compound or the like can be used. The aliphatic amide compound preferably contains an aliphatic tertiary amide compound in which R ¹² and R ¹³ are aliphatic groups, from the viewpoint of solubility of poly (arylene sulfonium salt) and solubility in water. Among the amide compounds, N-methyl-2-pyrrolidone is preferable.

The aliphatic amide compound functions as a dealkylating agent or a dearylling agent, and 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 (arylene sulfonium salt), and 1.02 equivalents. The above range is more preferable, and the range of 1.05 equivalent or more is further preferable. When the amount of the aliphatic amide compound used is 1.00 equivalent or more, the poly (arylene sulfonium salt) can be more sufficiently dealkylated or dearylled. On the other hand, the upper limit is preferably 100 equivalents or less, and more preferably 10 equivalents or less. Only the aliphatic amide compound may be used as the reaction solvent, or this may be used in combination with another solvent such as toluene.

The conditions for reacting the poly (arylene sulfonium salt) according to the present embodiment with the aliphatic amide compound can be appropriately adjusted so that dealkylation or dearyllation proceeds appropriately. The reaction temperature is preferably in the range of 50 to 250 ° C, more preferably in the range of 80 to 230 ° C.

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 cleaning step, the residual amount of the dealkylating agent or the dearylling agent contained in the obtained polyarylene sulfide resin can be more reliably reduced. This tendency becomes more remarkable when an aliphatic amide compound is used as the dealkylating agent or the dearylling agent.

By going through the washing step, it is possible to more reliably reduce the residual amount of the dealkylating agent or the dearylling agent in the obtained polyarylene sulfide resin. The residual amount of the dealkylating agent or dearylling 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 dearylting agent. It is preferably in the range of 700 ppm or less, and further preferably in the range of 100 ppm or less. By setting the residual amount of the dealkylating agent or the dearylling agent in the resin to 1000 ppm or less, the substantial influence on the quality of the obtained polyarylene sulfide resin can be further reduced.

The solvent used in such a washing step is not particularly limited, but preferably one that dissolves an unreacted product. Examples of the solvent include acidic aqueous solutions such as water, hydrochloric acid, acetic acid aqueous solution, oxalic acid aqueous solution and nitrate aqueous solution; aromatic hydrocarbon solvents such as toluene and xylene; 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; ether solvents such as tetrahydrofuran and dioxane; amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; dichloromethane, chloroform and the like Halogen-containing solvent and the like can be mentioned. These solvents may be used alone or in combination of two or more. Of these solvents, water or N-methyl-2-pyrrolidone is preferable from the viewpoint of removing the reaction reagent and the oligomer component of the resin.

The reaction product obtained through the above washing step is base-treated with an aqueous solution containing a basic compound, if necessary, to remove a hydroxy group or a carboxy group existing in the molecular structure of the polyarylene sulfide resin as a metal salt. May be replaced with.

The temperature condition of the base treatment may be in the range of 5 to 100 ° C., and the temperature is particularly in the range of 15 to 80 ° C. from the viewpoint of increasing the amount of the terminal metal salt in the polyarylene sulfide resin and preventing the decrease in molecular weight. Is preferable. The pH during the base treatment step is preferably controlled in the range of 3.0 to 10.0 after the base treatment step, and is 6.0 from the viewpoint of increasing the terminal metal salt content in the polyarylene sulfide resin. It is more preferable that the control is in the range of ~ 8.0. Examples of the pH measuring method include a method of measuring the pH of the filtrate obtained by filtering the slurry when an acid is added to the slurry, with respect to the polyarylene sulfide resin which is the solid content after filtration. In the case of base treatment, a method of measuring the pH of a washing filtrate in which all the filtrates obtained by repeating washing using an aqueous solution having a predetermined base concentration is mixed can be mentioned.

The basic compound used for the base treatment is preferably a compound showing strong basicity in an aqueous solution, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; calcium hydroxide. , Alkaline earth metal hydroxides such as magnesium hydroxide; sodium carbonate; calcium carbonate; sodium phosphate and the like may be used.

The polyarylene sulfide resin obtained by the production method according to one embodiment using the poly (arylene sulfonium salt) obtained in the above step (a) has a structural unit represented by the following general formula (1-1). It has a main chain containing the main chain and a terminal group containing a specific functional group attached to the end of the main chain.

In the general formula (1-1), R ^2b , Ar ¹ , Ar ² , Ar ^3b and Z are as already defined. In the general formula (1-1), 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 − is preferable. When, and ^{Ar 4b} is 1,4-phenylene group, Z ^{is, -S - - Ar 1, Ar} 2 and ^{Ar 3b} is 1,4-phenylene group, ^{R 2b} is ^{-Ar 4b,} - O -, - It is preferably CO-, -SO _2- or -C (CF ₃ ) _2- .

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

When the arylene group represented by Ar ¹ , Ar ² , Ar ^3b and Ar ^4b has a substituent, the substituent is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group. It is preferably an alkyl group, a hydroxy group, an amino group, a mercapto group, a carboxy group or a sulfo group in the range of 1 to 10 carbon atoms such as a group, a nonyl group and a decyl group. However, the ratio of the structural units of the general formula (1-1) in which Ar ¹ , Ar ² , Ar ³ and Ar ^4b are allylene groups having substituents reduces the crystallinity and heat resistance of the polyarylene sulfide resin. From the viewpoint of further suppression, it is preferably in the range of 10% by mass or less of the entire polyarylene sulfide resin, and more preferably 5% by mass or less.

The structural unit of the polyarylene sulfide resin is, for example, a sulfoxide represented by the general formula (1-3) and an aromatic compound represented by the general formula (1-4) according to the purpose of use of the resin and the like. By changing the combination with, it can be appropriately selected.

The glass transition temperature of the polyarylene sulfide resin represented by the general formula (1-1) is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 170 ° C. The glass transition temperature of the resin indicates a value measured by a DSC device.

The melting point of the polyarylene sulfide resin represented by the general formula (1-1) is preferably in the range of 100 to 400 ° C, more preferably in the range of 150 to 370 ° C. The melting point of the resin indicates a value measured by a DSC device.

On the other hand, the polyarylene sulfide resin obtained by the production method according to one embodiment using the poly (arylene sulfonium salt) obtained in the above step (b) has a configuration represented by the following general formula (2-1). It has a main chain containing a unit and a terminal group containing a specific functional group attached to the end of the main chain.

In the general formula (2-1), R ^2b and Ar ¹ are as already defined.

The glass transition temperature of the polyarylene sulfide resin represented by the general formula (2-1) is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 170 ° C. The glass transition temperature of the resin indicates a value measured by a DSC device.

The melting point of the polyarylene sulfide resin represented by the general formula (2-1) is preferably in the range of 100 to 400 ° C, more preferably in the range of 150 to 370 ° C. The melting point of the resin indicates a value measured by a DSC device.

The terminal group containing the specific functional group of the polyarylene sulfide resin is the following general formula (3-1b), (3-2b), (3-3b), (3-4b), (3-5b) or (3-5b). It is preferably a group represented by 6b). The polyarylene sulfide resin having these terminal groups has good compatibility with other resins such as a silane coupling agent or an epoxy resin at the time of producing the resin composition. It is also possible to impart excellent adhesion to different materials to the member obtained from the resin composition.

式中、Ｒ^３は直接結合又は炭素原子数１〜１０の範囲のアルキレン基を表し、Ａｒ^５ｂは、アリール基を表す。

In the formula, R ³ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^5b represents an aryl group.

The terminal group containing the specific functional group of the polyarylene sulfide group may be a group represented by the following general formulas (4-1b), (4-2b), (4-3b) or (4-4b). .. The polyarylene sulfide resin having these terminal groups also has good compatibility with other resins such as a silane coupling agent or an epoxy resin at the time of producing the resin composition. It is possible to impart excellent adhesion to different materials to the member obtained from the resin composition.

式中、Ｒ^４は、直接結合又は炭素原子数１〜１０の範囲のアルキレン基を表し、Ａｒ^６ｂは、アリール基を表す。

In the formula, R ⁴ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^6b represents an aryl group.

The aryl groups of Ar ^5b and Ar ^6b may also contain an arylene group in which a substituent is attached to the aryl group.

Examples of the terminal group represented by the general formula (4-1b), (4-2b), (4-3b) or (4-4b) include a group represented by the following chemical formula. In the formula, R ⁴ is defined in the same manner as in the formula (4-1a) and the like.

The halogen content of the polyarylene sulfide resin according to the present embodiment is preferably 900 ppm or less, more preferably 500 ppm or less.

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

The Mw (mass average molecular weight) of the polyarylene sulfide resin according to the present embodiment is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 80,000.

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, 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 and the like. Furthermore, dirt on the mold can be suppressed during molding, and productivity is improved.

The polyarylene sulfide resin composition according to the present invention can contain the above-mentioned polyarylene sulfide resin and one or more kinds of inorganic fillers. By containing the inorganic filler, a composition having high rigidity and high heat resistance 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. , 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 further preferably in the range of 15 to 150 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. Is. When the content of the inorganic filler is in these ranges, a better effect can be obtained in terms of maintaining the mechanical strength of the molded product.

The polyarylene sulfide resin composition according to the present invention can contain the above-mentioned polyarylene sulfide resin and a resin other than the polyarylene sulfide resin selected from the thermoplastic resin, the elastomer, and the crosslinkable resin. These resins can also 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, polysulphon, polyethersulfone, polyetheretherketone, polyetherketone, and polyethylene. , Polypropylene, polytetrafluorinated ethylene, polydifluorinated ethylene, 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 by polycondensation of diamine and dicarboxylic acid, (ii) a polymer obtained by polycondensation of aminocarboxylic acid, and (iii) a polymer obtained by ring-opening polymerization of lactam. Can be mentioned. Polyamides can be used alone or in combination of two or more.

Examples of diamines for obtaining polyamides include aliphatic diamines, aromatic diamines, and alicyclic diamines. As the aliphatic diamine, a diamine having a linear or side chain and having a carbon atom number in the range of 3 to 18 is preferable. Examples of suitable aliphatic diamines are 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine. , 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylene Diamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexamethylenediamine, 1,17-heptadecamethylenediamine, 1,18 − Octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine. These can be used alone or in combination of two or more.

As the aromatic diamine, a diamine having a phenylene group and having a carbon atom number in the range of 6 to 27 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'-diaminodiphenylsulphon, 4,4'-diaminodiphenylsulphon, 4,4'-diaminodiphenylsulfide, 4,4'-di (m-aminophenoxy) Diphenyl sulphon, 4,4'-di (p-aminophenoxy) diphenyl sulphon, 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 Included are 2,2'-dimethylbenzidine. These can be used alone or in combination of two or more.

As the alicyclic diamine, a diamine having a cyclohexylene group and having a carbon atom number in the range of 4 to 15 is preferable. Examples of suitable alicyclic diamines are 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, 4,4'-diamino-3,3'-dimethyl-. Included are dicyclohexylene methane, 1,4-diaminocyclohexane, and piperazine. These can be used alone or in combination of two or more.

Examples of the dicarboxylic acid for obtaining a 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 in the range of 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, undecanedioic acid, dodecanedioic acid, placeric acid, tetradecane. Examples include diacid, 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 a phenylene group and having a carbon atom number in the range of 8 to 15 is preferable. Examples of suitable aromatic dicarboxylic acids are isophthalic acid, terephthalic acid, methylterephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid. Examples thereof include acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulphon-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 within a range that can be melt-molded.

As the aminocarboxylic acid, an aminocarboxylic acid having a carbon atom number in the range of 4 to 18 is preferable. Examples of suitable aminocarboxylic acids are 4-aminobutyric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12 Included are −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 a polyamide include ε-caprolactam, ω-laurolactam, ζ-enantractum, and η-caprilactam. 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. Be 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 The rearmid resin to be obtained is more preferable.

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

Examples of the elastomer that can be contained in the polyarylene sulfide resin composition of the present invention include thermoplastic elastomers. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. In addition, in this specification, a thermoplastic elastomer is classified into an elastomer instead of the thermoplastic resin.

Elastomers (particularly thermoplastic elastomers) preferably have a functional group capable of reacting with a hydroxy or amino group. As a result, a resin composition particularly excellent in terms of adhesiveness, impact resistance and the like can be obtained. Examples of the functional group include an epoxy group, a carboxy group, an isocyanate group, an oxazoline group, and a formula: R (CO) O (CO)-or R (CO) O- (in the formula, R has 1 to 8 carbon atoms. Represents an alkyl group in the range of.). The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerizing an α-olefin with the vinyl polymerizable compound having the functional group. Examples of the α-olefin include α-olefins having a carbon atom number of 2 to 8 such as ethylene, propylene and butene-1. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid and the like. Other examples thereof include α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters and their acid anhydrides, etc.), and glycidyl (meth) acrylates. Among these, an epoxy group, a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O- (in the formula, R represents an alkyl group in the range of 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 groups represented by) are preferable from the viewpoint of improving toughness and impact resistance.

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

Examples of the crosslinkable resin that can be contained in the polyarylene sulfide resin composition according to the present invention include those having two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amino group, an amide group, a carboxy group, an acid anhydride group, and an isocyanate group. Examples of the crosslinkable resin include epoxy resin, phenol resin, and 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, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, and cresol novolac. 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 novolac type epoxy resin, naphthol aralkyl Examples thereof include type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, 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 novolac type epoxy resin is preferable, and a cresol novolac type epoxy resin is more preferable, because it is excellent in compatibility with other resin components.

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

The polyarylene sulfide resin composition of the present invention can contain the above-mentioned polyarylene sulfide resin and a silane compound having a functional group capable of reacting with a hydroxy group or an amino group. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples thereof 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, and 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 in these ranges, the effect of improving the compatibility between the polyarylene sulfide resin and the other components can be obtained.

The polyarylene sulfide resin composition of the present invention may contain other additives such as a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive, a flame retardant and a lubricant. 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, for example.

The method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited, and has a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more crosslinkable functional groups. At least one other component selected from the group consisting of crosslinkable resins is put into a ribbon blender, a Henschel mixer, a V blender, etc. in various forms such as powder, pellets, and strips, and then dry-blended. A temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably (the melting point + 10 ° C.), is placed in a known melt kneader such as a Banbury mixer, a mixing roll, a single-screw or twin-screw extruder, and a kneader. Manufactured through a step of melt-kneading in the above temperature range, more preferably (the melting point + 10 ° C. to the melting point + 100 ° C.), and further preferably (the melting point + 20 to the melting point + 50 ° C.). can do. Each component may be added to and mixed with the melt kneader at the same time, or may be divided.

As the melt kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. For example, a resin component discharge amount in the range of 5 to 500 (kg / hr) and a screw rotation speed of 50 to 500 (rpm) are preferable. It is preferable to melt-knead while appropriately adjusting the range of, and melt-knead under the condition that the ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). Is even more preferable. Further, for example, when a fibrous filler or an additive is added, it can be charged into the extruder from the side feeder instead of the top feeder of the twin-screw kneading extruder, and shape retention and dispersibility can be improved. It can be improved, which is preferable. The position of the side feeder is preferably in the range of 0.1 to 0.9 in the ratio of the distance from the extruder resin input portion to the side feeder with respect to the total length of the screw of the twin-screw kneading extruder. Above all, the range of 0.3 to 0.7 is particularly preferable.

The polyarylene sulfide resin composition of the present invention thus obtained comprises a polyarylene sulfide resin which is an essential component, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more crosslinkable properties. It is a melt-kneaded product obtained by blending at least one other component selected from the group consisting of a crosslinkable resin having a functional group so as to have the above-mentioned content, and after the melt-kneading, pellets are prepared by a known method. It is preferable that the product is processed into a form of chips, granules, powder, or the like, and then pre-dried in a temperature range of 100 to 150 ° C., if necessary, for various moldings.

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

The polyarylene sulfide resin composition of the present invention can be used for various melt molding such as injection molding, compression molding, composite, extrusion molding of sheets, pipes and the like, drawing molding, blow molding, transfer molding and the like. It is suitable for injection molding because it has excellent releasability. When molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a general method. For example, in an injection molding machine, the resin temperature is in a temperature range equal to or higher than the melting point of the polyarylene sulfide resin, preferably (the melting point + 10 ° C.) or higher, more preferably (the melting point + 10 ° C.) to (the melting point + 100 ° C.). After undergoing the step of melting the polyarylene sulfide resin composition in the temperature range of (the melting point + 20 ° C.) to (the melting point + 50 ° C.), the resin is injected into the mold from the resin discharge port. It may be molded. At that time, the mold temperature may also be set in a known temperature range, for example, a temperature range of room temperature (23 ° C.) to 300 ° C., preferably a temperature range of 120 to 200 ° C.

The polyarylene sulfide resin composition according to the present embodiment has heat resistance by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding, alone or in combination with materials such as the other components. It can be processed into a molded product with excellent moldability and dimensional stability. The polyarylene sulfide resin composition according to the present embodiment enables easy production of high-quality molded products because the amount of gas generated when heated is small.

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

Further, the polyarylene sulfide resin composition of the present invention is used for water circulation including, for example, a fluid piping having excellent cold thermal impact resistance by combining the above-mentioned polyarylene sulfide resin and the above-mentioned thermoplastic elastomer. It can be processed into a molded product.

Examples of fluid piping include pipes, lining pipes, bag nuts, pipe joints (elbows, headers, cheese, reducers, joints, couplers, etc.), various valves, flow meters, gaskets (seals, packings). , Etc., and various parts (fluid piping) attached to the piping for transporting the fluid. In addition, as water-related applications, it is a material suitable for water-related applications such as toilet-related parts, water heater-related parts, pump-related parts, and bath-related parts. In particular, opening and closing parts such as valves and plugs are generally constantly subject to high stress loads, and are severely damaged by acidic or alkaline cleaning agents and the temperature difference between cold air and hot water, especially in winter, resulting in difficulty in long-term use. Therefore, the composition of the present invention is particularly useful in the field of this opening / closing part.

Furthermore, when the polyarylene sulfide resin composition of the present invention is used for electric vehicle parts, the amount of gas generated by heating can be reduced, so that a low molecular weight compound containing a sulfur atom, which is a gas component, and a metal material such as copper (conductive). Contact with (sexual material) can be reduced, and as a result, the reaction between the two can be suppressed even when a high voltage is repeatedly applied, and the generation and progression of trees (dendritic destruction traces) can be suppressed to withstand It is also possible to improve the tracking property. As a result, it can be used not only for electric / electronic parts such as connectors, printed boards and sealed molded products, and parts mounted on automobiles such as lamp reflectors and various electrical component parts (hereinafter referred to as automobile parts), and above all. The field of electric vehicles that require high safety, that is, hybrid vehicles (HVs), plug-in hybrid vehicles (PHVs), electric vehicles (EVs), fuels equipped with lithium-ion secondary batteries and powered by electric motors. Cases for storing power modules, converters, capacitors, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, junction blocks, etc. in battery vehicles (FCVs), especially cases for ignition coils of DLI systems, etc. It is preferably used as.

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

In the present invention, the range of "1 to 10" means a range of 1 or more and 10 or less.

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

[Production example of polyarylene sulfide resin]
1. 1. Evaluation method 1-1. Identification method (various NMR)
The compound was dissolved in various deuterated solvents by the apparatus of DPX-400 manufactured by BRUKER, and various NMR measurements were performed.
1-2, 3. Melting point (Tm) and glass transition temperature (Tg)
Using a PerkinElmer DSC device, Pyris Diamond, measurements were taken in the range of 40 to 350 ° C. under a nitrogen flow of 50 mL / min and a temperature rise condition of 20 ° C./min to determine the melting point. The resins obtained in Polymer Synthesis Examples 7 and 8 were measured in the range of 40 to 400 ° C. under a nitrogen flow of 50 mL / min and a temperature rise condition of 20 ° C./min to determine the melting point and glass transition temperature (Tg). I asked.

1-4. Mass Average Molecular Weight The mass average molecular weight was measured using a high temperature gel permeation chromatograph (GPC) SSC-7000 manufactured by Senshu Kagaku. The average molecular weight was calculated in terms of standard polystyrene.
Solvent: 1-chloronaphthalene inlet: 250 ° C
Temperature: 210 ° C
Detector: UV detector (360 nm)
Sample concentration: 1 g / L
Flow velocity: 0.7 mL / min

1-5. Infrared absorption spectrum measurement
Infrared absorption spectrum measurement was measured using "FT / IR-6100" manufactured by JASCO Corporation. An amorphous film prepared by heating the synthesized resin on a hot plate at 330 ° C. to melt it and quenching it was used as a measurement sample. Regarding the resins obtained in Polymer Synthesis Examples 7 and 8, an amorphous film prepared by heating on a hot plate at 400 ° C. to melt and quenching was used as a measurement sample.

2. 2. Monomer Synthesis In the examples shown below, the following reagents were used.
・ Methylphenyl sulfoxide: Wako Pure Chemical Industries, Ltd. ・ Thioanisole: Wako Pure Chemical Industries, Ltd., purity 99%
・ Methane sulfonic acid: Wako Pure Chemical Industries, Ltd., Wako special grade ・ 60% perchloric acid: Wako Pure Chemical Industries, Ltd., reagent special grade ・ Ppyridine: Wako Pure Chemical Industries, Ltd., reagent special grade ・ dichloromethane: Kanto Chemical Co., Ltd., Special grade / chloroform: Kanto Chemical Industries, Ltd., special grade n-hexane: Kanto Chemical Co., Ltd., special grade / ethyl acetate: Kanto Chemical Industries, Ltd., special grade / potassium hydrogen carbonate: Wako Pure Chemical Industries, Ltd., reagent special grade / sodium hydroxide: Kanto Chemical Co., Ltd., special grade ・ Bromine: Wako Pure Chemical Industries, Ltd., reagent special grade ・ Bis [4- (methylthio) phenyl] sulfide: Sigma Aldrich Product number S203815-25MG
-Nitric acid (1.38): manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent, content range of 60 to 61%, density 1.38 g / mL
・ 4,4'-Bis-methylsulfanyl-biphenyl: Sigma-Aldrich Product No. S203807-25MG
4-Bromo-4'-iodobiphenyl: Tokyo Chemical Industry Co., Ltd., purity> 98%
・ Iodomethane: Kanto Chemical Co., Inc., special grade ・ Copper iodide: Kanto Chemical Co., Inc., purity> 99%
・ Sulfur: Kanto Chemical Co., Inc. ・ Potassium carbonate: Nacalai Tesque Co., Ltd., Nakarai standard special grade ・ N, N-dimethylformamide (dehydration): Kanto Chemical Co., Ltd., special grade ・ Sodium borohydride: Kanto Chemical Co., Inc. ・ Celite: Japanese Kojunyaku Kogyo Co., Ltd., No. 503
・ Turt-butyl lithium (n-pentane solution) 1.6 mol / L: Kanto Chemical Co., Inc. ・ tetrahydrofuran (dehydration): Kanto Chemical Co., Inc. ・ Diphenyl disulfide: Kanto Chemical Co., Inc., special grade ・ Ammonium chloride: Nacalai Tesque Co., Ltd., Nacalai Tesque Special Grade ・ Phosphorus Oxide (V) (2 phosphorus pentaoxide): Wako Pure Chemical Industries, Ltd., Wako Special Grade ・ N-Methyl-2-pyrrolidone (NMP): Kanto Chemical Co., Inc., Special Grade ・ Phenylpropionic Acid: Tokyo Kasei Kogyo Co., Ltd., purity> 98%
・ Phenol: Tokyo Chemical Industry Co., Ltd., purity> 98%
・ Aniline: Tokyo Chemical Industry Co., Ltd., purity> 98%
・ Diphenyl sulfide: Wako Pure Chemical Industries, Ltd., Wako special grade ・ Salicylic acid: Kanto Chemical Co., Ltd., special grade ・ m-aminophenol: Wako Pure Chemical Industries, Ltd., Wako first grade

(Monomer Synthesis Example 1)
Synthesis of Methylphenyl Perchlorate [4- (Methylthio) Phenyl] Sulfonium

120 parts by mass of thioanisole was placed in a three-necked flask with respect to 100 parts by mass of methylphenylsulfoxide, and the mixture was placed in a nitrogen atmosphere and cooled to 5 ° C. or lower in an ice bath. While keeping 2000 parts by mass of methanesulfonic acid at 10 ° C. or lower, the mixture was added to the reaction solution, then the ice bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 20 hours. Then, the reaction solution was put into 2000 parts by mass of a 60% perchloric acid aqueous solution and stirred for 1 hour. 1000 parts by mass of water and 1000 parts by mass of dichloromethane were added, and the mixture was extracted / separated to recover the organic layer. Further, 500 parts by mass of dichloromethane was added to the aqueous layer, and the operation of recovering the organic layer was performed twice. Anhydrous magnesium sulfate was added to the recovered organic layer for dehydration, and the solvent was removed from the solution filtered by filtration using a rotary evaporator. Then, diethyl ether was added to the remaining solid for recrystallization, and the solid filtered by filtration was dried under reduced pressure for 20 hours to obtain a yield of methylphenyl [4- (methylthio) phenyl] sulfonium perchlorate to 75%. I got it. ¹ It was confirmed by ¹ H-NMR that a product was formed.
^{1 1} H-NMR (solvent CDCl ₃ ): 2.49, 3.63, 7.40, 7.65, 7.78, 7.85 [ppm]

(Monomer Synthesis Example 2)
Synthesis of methyl 4- (phenylthio) phenyl sulfide

100 parts by mass of methylphenyl [4- (methylthio) phenyl] sulfonium perchlorate was placed in a three-necked flask, and the mixture was placed in a nitrogen atmosphere, 500 parts by mass of pyridine was added, and the mixture was stirred for 30 minutes. Then, the reaction solution was heated to 100 ° C. and stirred for 30 minutes. The reaction solution was added to 3000 parts by mass of a 10% HCl solution and stirred for 10 minutes. Then, the organic layer was recovered by extraction / separation with dichloromethane, dehydrated by adding anhydrous magnesium sulfate, and the solvent was removed from the solution filtered by filtration with a rotary evaporator. The target product was separated by column chromatography using hexane / chloroform = 3/1 as the developing solvent. After removing the solvent from the separated solution containing the target product with a rotary evaporator, the solution was dried under reduced pressure for 20 hours to obtain methyl 4- (phenylthio) phenylsulfide in a yield of 83%. ¹ It was confirmed by ¹ H-NMR that a product was formed.
^{1 1} H-NMR (solvent CDCl ₃ ): 2.48, 7.18 to 7.23, 7.28 to 7.31 [ppm]

(Monomer Synthesis Example 3)
Synthesis of Methyl 4- (Phenylthio) Phenyl Sulfoxide

To 100 parts by mass of methyl 4- (phenylthio) phenylsulfide, 86 parts by mass of potassium hydrogen carbonate, 800 parts by mass of water, and 1000 parts by mass of dichloromethane were placed in a three-necked flask and stirred for 30 minutes. A solution prepared by dissolving 69 parts by mass of bromine in 1000 parts by mass of dichloromethane was added dropwise to the reaction vessel over 5 minutes, and the mixture was stirred for 30 minutes. 1 liter of KCl saturated solution and 1 liter of girolomethane were added to the reaction solution, and the organic layer was recovered by extraction / separation. 1000 parts by mass of dichloromethane was added to the remaining aqueous layer, and the operation of recovering the organic layer was performed twice. The recovered organic layer was washed with water / separated, dehydrated by adding anhydrous magnesium sulfate, and the solvent was removed from the solution filtered by filtration with a rotary evaporator. Diethyl ether was added to the remaining solid for recrystallization, and the solid filtered by filtration was dried under reduced pressure for 20 hours to obtain methyl 4- (phenylthio) phenylsulfoxide in a yield of 57%. It was confirmed by ^{1 1} H-NMR and ¹³ C-NMR that the product was formed.
^{1 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]

(Monomer Synthesis Example 4)
Synthesis of bis [4- (methylsulfinyl) phenyl] sulfide

In a three-necked flask, 2,500 parts by mass of dichloromethane was added to 100 parts by mass of bis [4- (methylthio) phenyl] sulfide to dissolve it, and the mixture was cooled in an ice bath. 80 parts by mass of nitric acid (1.38) was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 72 hours. The reaction solution was neutralized with an aqueous potassium carbonate solution, and an extraction / separation operation was performed with dichloromethane to recover the organic layer. The organic layer was dehydrated with anhydrous magnesium sulfate. The dehydrated organic layer was filtered, the solvent was removed with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The desired product was separated by column chromatography using ethyl acetate as a developing solvent. After removing the solvent from the solution containing the separated target product with a rotary evaporator, the solution was dried under reduced pressure to obtain bis [4- (methylsulfinyl) phenyl] sulfide in a yield of 30%. ¹ It was confirmed by ¹ H-NMR measurement that the target product was obtained.
^{1 1} H-NMR (solvent CDCl ₃ ): 2.75, 7.49, 7.61 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 44.0, 124.6, 131.6, 138.7, 145.1 [ppm]

３つ口フラスコに、４,４’-ビス−メチルスルファニル−ビフェニル１００質量部に対し、クロロホルム１０，０００質量部を加えて４０℃に加温した。液温４０℃に維持しながら、反応溶液に硝酸（１．３８）１２８質量部を少しずつ滴下し、その後４０℃で２４時間攪拌した。反応溶液を水酸化ナトリウム水溶液で中和し、固体が析出し、クロロホルムにて抽出／分液操作を行い、有機層と固体層を回収した。回収した有機層と固体層をロータリーエバポレーターで溶媒を除去し、減圧乾燥することで粗生成物を得た。粗生成物を５００質量部の水で３回洗浄し、固体分を回収した。更に得た固体分を３つ口フラスコに入れ、その固体分の８０倍の塩化メチレンを加えて１時間還流した。その溶液を３時間掛けて除冷して室温に戻し、３日間室温下に置くことで結晶化させた。結晶固体をろ過にて分離し、減圧乾燥することでビス［４−（メチルスルフィニル）］ビフェニルを収率２０％にて得た。^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲ測定により目的物が得られたことを確認した。
^１Ｈ−ＮＭＲ（溶媒ＣＤＣｌ_３）：２．７９，７．７６［ｐｐｍ］
^１３Ｃ−ＮＭＲ（溶媒ＣＤＣｌ_３）：４４．０、１２４．２、１２８．２、１４２．６、１４５．５［ｐｐｍ］ (Monomer Synthesis Example 5)
Synthesis of bis [4- (methylsulfinyl)] biphenyl

To a three-necked flask, 10,000 parts by mass of chloroform was added to 100 parts by mass of 4,4'-bis-methylsulfanyl-biphenyl and heated to 40 ° C. While maintaining the liquid temperature at 40 ° C., 128 parts by mass of nitric acid (1.38) was added dropwise to the reaction solution, and then the mixture was stirred at 40 ° C. for 24 hours. The reaction solution was neutralized with an aqueous sodium hydroxide solution, a solid was precipitated, and an extraction / separation operation was performed with chloroform to recover the organic layer and the solid layer. The recovered organic layer and solid layer were subjected to solvent removal with a rotary evaporator and dried under reduced pressure to obtain a crude product. The crude product was washed 3 times with 500 parts by mass of water to recover the solid content. Further, the obtained solid content was placed in a three-necked flask, 80 times as much methylene chloride as the solid content was added, and the mixture was refluxed for 1 hour. The solution was cooled over 3 hours, returned to room temperature, and allowed to stand at room temperature for 3 days to crystallize. The crystalline solid was separated by filtration and dried under reduced pressure to give bis [4- (methylsulfinyl)] biphenyl in a yield of 20%. It was confirmed that the target product was obtained by ¹ H-NMR and ¹³ C-NMR measurements.
^{1 1} H-NMR (solvent CDCl ₃ ): 2.79, 7.76 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 44.0, 124.2, 128.2, 142.6, 145.5 [ppm]

(Monomer Synthesis Example 6)
Synthesis of 4-bromo-4'-(methylthio) biphenyl

100 parts by mass of 4-bromo-4'-iodobiphenyl, 10 parts by mass of copper iodide, 300 parts by mass of sulfur, and 1,700 parts by mass of potassium carbonate were placed in a three-necked flask, and the inside of the flask was replaced with nitrogen. After adding 20,000 parts by mass of N, N-dimethylformamide (dehydrated) to the flask, the mixture was stirred at 100 ° C. for 17 hours. Then, 400 parts by mass of sodium borohydride was added at 0 ° C., and the mixture was stirred at 50 ° C. for 6 hours. Subsequently, 900 parts by mass of iodomethane was added at 0 ° C., and the mixture was stirred at 25 ° C. for 20 hours. After stirring, the reaction solution was poured into 10% hydrochloric acid to stop the reaction, and after filtration through Celite, extraction with dichloromethane and liquid separation, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using hexane as a developing solvent. The solution containing the separated target product was recovered, the solvent was removed with a rotary evaporator, and the mixture was dried under reduced pressure to obtain 4-bromo-4'-(methylthio) biphenyl in a yield of 43%. ^The product was confirmed by ^{1 1} H-NMR and ¹³ C-NMR.
^{1 1} H-NMR (solvent CDCl ₃ ): 2.52, 7.32, 7.43, 7.48, 7.54 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 15.9, 121.5, 127.0, 127.4, 128.5, 132.0, 136.8, 138.4, 139.6 [ppm]

(Monomer Synthesis Example 7)
Synthesis of 4-methylthio-4'-(phenylthio) biphenyl

To a nitrogen-substituted three-necked flask, 100 parts by mass of 4-bromo-4'-(methylthio) biphenyl and 4000 parts by mass of tetrahydrofuran (dehydrated) were added. At −78 ° C., 400 parts by mass of tert-butyllithium (n-pentane solution 1.6 mol / L) was added to the reaction solution, and the mixture was stirred for 1 hour. Subsequently, 100 parts by mass of diphenyl disulfide was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Then, the reaction solution was poured into an aqueous ammonium chloride solution to stop the reaction, and after extraction and separation with diethyl ether, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using hexane as a developing solvent, the solution containing the target product was recovered, and the solvent was removed with a rotary evaporator to obtain 4-methylthio-4'-(phenylthio) biphenyl in a yield of 73. Obtained in%. ^The product was confirmed by ^{1 1} H-NMR and ¹³ C-NMR.
^{1 1} H-NMR (solvent CDCl ₃ ): 2.52, 7.24-7.28, 7.30-7.34, 7.39, 7.50 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 15.9, 127.0, 127.3, 127.4, 127.6, 129.4, 131.3, 131.5, 135.0, 135.8, 137.1, 138.1, 139.4 [ppm]

(Monomer Synthesis Example 8)
Synthesis of 4-methylsulfinyl-4'-(phenylthio) biphenyl

100 parts by mass of 4-methylthio-4'-(phenylthio) biphenyl and 2000 parts by mass of dichloromethane were placed in an eggplant flask, and 40 parts by mass of nitric acid was added. The reaction solution was stirred at 25 ° C. for 3 hours, neutralized with saturated aqueous potassium carbonate solution, and the reaction was stopped. Then, after extraction with dichloromethane and liquid separation, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The crude product is separated by column chromatography using chloroform as a developing solvent, the solution containing the target product is recovered, the solvent is removed with a rotary evaporator, and the mixture is dried under reduced pressure to 4-methylsulfinyl-4'-(phenylthio). ) Biphenyl was obtained in a yield of 72%. ^The product was confirmed by ^{1 1} H-NMR and ¹³ C-NMR.
^{1 1} H-NMR (solvent CDCl ₃ ): 2.77, 7.30, 7.35, 7.39, 7.43, 7.52, 7.71 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 44.1, 124.3, 127.7, 128.0, 128.0, 129.5, 130.9, 132.0, 135.0, 136.9, 143.4, 144.8 [ppm]

3. 3. Synthesis of terminally modified polysulfonium salt and PAS resin (Polymer synthesis example 1a)

In a separable flask, add 3 parts by mass of phenylpropionic acid to 100 parts by mass of methyl 4- (phenylthio) phenylsulfoxide, and add 800 parts by mass of methanesulfonic acid and 70 parts by mass of diphosphorus pentoxide while cooling to 10 ° C or lower. The mixture was further stirred for 20 hours. The reaction solution was poured into 10,000 parts by mass of acetone, and the precipitated solid was collected by filtration and washed twice with 600 parts by mass of acetone. The obtained solid was dried under reduced pressure to obtain poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium] in a yield of 97%. It was confirmed by ^{1 1} H-NMR and ¹³ C-NMR that the product was formed.
^{1 1} H-NMR (solvent DMSO-d ₆ ): 3.77, 7.59, 8.03 [ppm]
¹³ C-NMR (solvent DMSO-d ₆ ): 27.1, 127.1, 131.7, 132.9, 140.8 [ppm]

(Polymer Synthesis Example 1b)

To 100 parts by mass of poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium], 800 parts by mass of N-methyl-2-pyrrolidone was added to the eggplant flask and dissolved. This was stirred at 70 ° C. for 8 hours, and the precipitated solid was collected by filtration. The obtained solid was charged into an autoclave, 800 parts by mass of N-methyl-2-pyrrolidone was added, and the mixture was stirred at 230 ° C. for 1 hour. The solid was collected by filtration and washed twice with 1000 parts by mass of water at 70 ° C. The recovered solid was dried at 120 ° C. for 4 hours to obtain the desired poly (p-phenylene sulfide) (hereinafter, may be referred to as PAS-1) in a yield of 72%.

The mass average molecular weight of the obtained resin (PAS-1) was measured and found to be 25,000. As a result of thermal analysis, the glass transition temperature (Tg) was 100 ° C. and the melting point was 274 ° C. When the infrared absorption spectrum was measured, as shown in FIG. 1, the presence of an absorption peak of C = O stretching vibration of the carboxy group was observed at the position of 1708 cm ^-1 .

(Polymer Synthesis Example 2a)
In (Polymer Synthesis Example 1a), the same procedure was carried out except that 2 parts by mass of phenol was used instead of phenylpropionic acid, and a yield of 100 poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium] was obtained. Obtained in%. Then, the same operation as in (Polymer Synthesis Example 1b) was carried out to obtain poly (p-phenylene sulfide) (hereinafter, may be referred to as PAS-2) in a yield of 47%.

The weight average molecular weight of the obtained resin (PAS-2) was measured and found to be 14,000. As a result of thermal analysis, the glass transition temperature (Tg) was 87 ° C. and the melting point was 277 ° C. When the infrared absorption spectrum was measured, as shown in FIG. 2, the presence of absorption peaks of free OH expansion and contraction vibrations of hydroxy groups was observed at positions in the range of 3551 cm ^-1 and 3500 to 3300 cm ^-1 .

(Polymer Synthesis Example 3)
In (Polymer Synthesis Example 1a), the same operation was carried out except that 2 parts by mass of aniline was used instead of phenylpropionic acid, and a yield of 100 poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium] was obtained. Obtained in%. Then, the same operation as in (Polymer Synthesis Example 1b) was carried out to obtain poly (p-phenylene sulfide) (hereinafter, may be referred to as PAS-3) in a yield of 48%.

The mass average molecular weight of the obtained resin (PAS-3) was measured and found to be 36,000. As a result of thermal analysis, the glass transition temperature (Tg) was 97 ° C. and the melting point was 264 ° C. When the infrared absorption spectrum was measured, as shown in FIG. 3, the presence of an absorption peak of the NH stretching vibration of the amino group was observed at the position of 3365 cm ^-1 .

(Polymer Synthesis Example 4)
In (Polymer Synthesis Example 1a), the same operation was carried out except that 3 parts by mass of salicylic acid was used instead of phenylpropionic acid, and the yield of poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium] was 98. Obtained in%. Then, the same operation as in (Polymer Synthesis Example 1b) was carried out to obtain poly (p-phenylene sulfide) (hereinafter, may be referred to as PAS-4) in a yield of 58%.

The mass average molecular weight of the obtained resin (PAS-4) was measured and found to be 14,000. As a result of thermal analysis, the glass transition temperature (Tg) was 88 ° C. and the melting point was 277 ° C. Was measured infrared absorption spectrum, as shown in FIG. 4, the absorption peak of free O-H stretching vibration of hydroxyl groups was observed at the position of 3552cm ^-1, as shown in FIG. 5, the position of 1687Cm ^-1 The presence of an absorption peak of C = O expansion and contraction vibration of the carboxy group was observed.

(Polymer Synthesis Example 5)
In (Polymer Synthesis Example 1a), the same operation was carried out except that 2 parts by mass of m-aminophenol was used instead of phenylpropionic acid to obtain poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium]. It was obtained in a yield of 97%. Then, the same operation as in (Polymer Synthesis Example 1b) was carried out to obtain poly (p-phenylene sulfide) (hereinafter, may be referred to as PAS-5) in a yield of 72%.
The mass average molecular weight of the obtained resin (PAS-5) was measured and found to be 25,000. As a result of thermal analysis, the glass transition temperature (Tg) was 91 ° C. and the melting point was 275 ° C. Was measured infrared absorption spectrum, as shown in FIG. 6, the absorption peak of free O-H stretching vibration of hydroxyl groups was observed at the position of 3555cm ^-1, as shown in FIG. 7, 3433cm ^-1 and 3377cm The presence of an absorption peak of the NH expansion and contraction vibration of the amino group was observed at the position of ^-1 .

(Polymer Synthesis Example 6)

Put 100 parts by mass of bis [4- (methylsulfinyl) phenyl] sulfide in a separable flask, put it in a nitrogen atmosphere, and add 60 parts by mass of diphenylsulfide, 100 parts by mass of diphosphorus pentoxide, and 2.5 parts by mass of phenylpropionic acid. It was. After cooling the reaction solution in an ice bath, 750 parts by mass of methanesulfonic acid was slowly added dropwise. Then, the reaction solution was heated to room temperature and stirred for 20 hours. The reaction solution was poured into 10,000 parts by mass of acetone, and the precipitated solid was collected by filtration and washed twice with 600 parts by mass of acetone. The obtained solid was dried under reduced pressure to obtain poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium] in a yield of 99%. Then, the same operation as in (Polymer Synthesis Example 1b) was carried out to obtain poly (p-phenylene sulfide) (hereinafter, may be referred to as PAS-6) in a yield of 48%.

The mass average molecular weight of the obtained resin (PAS-6) was measured and found to be 22,000. As a result of thermal analysis, the glass transition temperature (Tg) was 92 ° C. and the melting point was 275 ° C. Further, when the infrared absorption spectrum was measured, as shown in FIG. 8, the presence of an absorption peak of C = O expansion and contraction vibration of the carboxy group was observed at the position of 1707 cm ^-1 .

(Polymer Synthesis Example 7a)

セパラブルフラスコに、４−メチルスルフィニル−４’−（フェニルチオ）ビフェニル１００質量部に対し、サリチル酸３質量部を入れ、１０℃以下に冷却しながらメタンスルホン酸５００質量部及び五酸化二リン５０質量部を加え２０時間攪拌した。反応溶液をアセトン１００００質量部に投入し、析出した固体をろ過にて回収し、これをアセトン６００質量部にて２回洗浄した。得られた固体を減圧乾燥することで、ポリ｛メタンスルホン酸メチル４−［４−（フェニルチオ）フェニル］フェニルスルホニウム}を収率９５％にて得た。
^１Ｈ−ＮＭＲ（溶媒ＤＭＳＯ−ｄ_６）：３．８４、７．６３、７．８６、８．０４、８．１４［ｐｐｍ］

In a separable flask, add 3 parts by mass of salicylic acid to 100 parts by mass of 4-methylsulfinyl-4'-(phenylthio) biphenyl, and cool to 10 ° C or lower with 500 parts by mass of methanesulfonic acid and 50 parts by mass of diphosphorus pentoxide. The parts were added and the mixture was stirred for 20 hours. The reaction solution was poured into 10000 parts by mass of acetone, and the precipitated solid was recovered by filtration, and this was washed twice with 600 parts by mass of acetone. The obtained solid was dried under reduced pressure to obtain poly {methyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} in a yield of 95%.
^{1 1} H-NMR (solvent DMSO-d ₆ ): 3.84, 7.63, 7.86, 8.04, 8.14 [ppm]

(Polymer Synthesis Example 7b)

In an eggplant flask, 100 parts by mass of poly {methyl 4- [4- (phenylthio) phenyl] phenylsulfonium} of methanesulfonate was dissolved in 800 parts by mass of N-methyl-2-pyrrolidone. This was stirred at 70 ° C. for 8 hours, and the precipitated solid was collected by filtration. The obtained solid was charged into an autoclave, 800 parts by mass of N-methyl-2-pyrrolidone was added, and the mixture was stirred at 230 ° C. for 1 hour. The solid was collected by filtration and washed twice with 1000 parts by mass of water at 70 ° C. Then, the washed solid is dried at 120 ° C. for 4 hours to obtain a poly (p-phenylenethio-p, p'-biphenylylene sulfide) (hereinafter, may be referred to as PAS-7) in a yield of 45. Obtained in%.

The mass average molecular weight of the obtained resin (PAS-7) was measured and found to be 10,000. As a result of thermal analysis, the glass transition temperature (Tg) was 155 ° C and the melting point was 372 ° C. Was measured infrared absorption spectrum, as shown in FIG. 9, the absorption peak of free O-H stretching vibration of hydroxyl groups was observed at the position of 3567cm ^-1, as shown in FIG. 10, the position of 1681Cm ^-1 The presence of an absorption peak of C = O expansion and contraction vibration of the carboxy group was observed.

(Polymer Synthesis Example 8a)

To a separable flask, 66 parts by mass of diphenylsulfide, 130 parts by mass of diphosphorus pentoxide, and 2 parts by mass of salicylic acid were added to 100 parts by mass of bis [4- (methylsulfinyl)] biphenyl under a nitrogen atmosphere. After cooling the reaction solution in an ice bath, 1300 parts by mass of methanesulfonic acid was slowly added dropwise. The reaction solution was heated to room temperature and stirred for 20 hours. The reaction solution was poured into 10,000 parts by mass of acetone, and the precipitated solid was collected by filtration and washed twice with 600 parts by mass of acetone. The obtained solid was dried under reduced pressure to obtain poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium-4'-thiomethyl (biphenyl)] sulfonium in a yield of 98%.

(Polymer Synthesis Example 8b)
In an eggplant flask, 100 parts by mass of poly [methyl methanesulfonate (4-phenylthiophenyl) sulfonium-4'-thiomethyl (biphenyl)] sulfonium was dissolved in 800 parts by mass of N-methyl-2-pyrrolidone. This was stirred at 70 ° C. for 8 hours, and the precipitated solid was collected by filtration. The obtained solid was charged into an autoclave, 800 parts by mass of N-methyl-2-pyrrolidone was added, and the mixture was stirred at 230 ° C. for 1 hour. The solid was collected by filtration and washed twice with 1000 parts by mass of water at 70 ° C. Then, the washed solid is dried at 120 ° C. for 4 hours to obtain poly (p-phenylenethio-p-phenylenethio-p, p'-biphenylylene sulfide) (hereinafter, referred to as PAS-8). ) Was obtained in a yield of 70%.

The mass average molecular weight of the obtained resin (PAS-8) was measured and found to be 18,000. As a result of thermal analysis, the glass transition temperature (Tg) was 122 ° C. and the melting point was 330 ° C. Further, when the infrared absorption spectrum was measured, as shown in FIG. 11, an absorption peak of the OH expansion and contraction vibration of the hydroxy group was observed at the position of 3454 cm ^-1 , and as shown in FIG. 12, 1684 cm ^-1 was observed. The presence of an absorption peak of C = O expansion and contraction vibration of the carboxy group was observed at the position.

(Comparative Synthesis Example 1)
220.5 g (1.5 mol) of p-dichlorobenzene (hereinafter abbreviated as "p-DCB") in a 1-liter autoclave of a zirconium lining with a stirring blade connected to a pressure gauge, a thermometer, a condenser, and a decanter. , NMP 29.7 g (0.3 mol), 47.43 mass% NaSH aqueous solution 177.29 g (1.5 mol), and 48.71 mass% NaOH aqueous solution 123.18 g (1.5 mol) were charged and stirred. While in a nitrogen atmosphere up to 173 ° C 2
The temperature was raised over time to distill out 177.98 g of water, and then the kettle was sealed. At that time, the p-DCB distilled by azeotrope was separated by a decanter and returned to the kettle at any time. After the dehydration is completed, the internal temperature is cooled to 160 ° C., 267.65 g (2.7 mol) of NMP is charged, the temperature is raised to 230 ° C., the mixture is stirred at 230 ° C. for 5 hours, and then the temperature is raised to 250 ° C. in 40 minutes. , 250 ° C. for 1 hour. After cooling, the obtained slurry was poured into 3 liters of water and stirred at 80 ° C. for 1 hour, and then.
It was filtered. The cake was again stirred with 3 liters of warm water for 1 hour, washed and then filtered.
This operation was repeated 4 times, and after filtration, it was dried overnight at 120 ° C. using a hot air dryer to obtain 154 g of white powdery PPS (hereinafter, may be referred to as PAS-9).

The mass average molecular weight of the obtained resin (PAS-9) was measured and found to be 44,000. As a result of thermal analysis, the glass transition temperature (Tg) was 92 ° C. and the melting point was 277 ° C. From this, it was confirmed that polyphenylene sulfide was produced.

Examples 1-11, Comparative Examples 1-4
[Production Example of Polyarylene Sulfide Resin Composition (PAS Compound)]
<Raw materials>
The following materials were prepared to prepare the polyarylene sulfide resin composition.

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

<Evaluation method>
[Crack resistance under cold impact]
A steel insert block member having a length of 25 mm, a width of 40 mm, and a thickness of 10 mm is connected with the midpoints of the vertical sides of the member, and has a diameter of 3.55 mm on a straight line parallel to the horizontal side of the member. Prepare an insert block member having the diameter centers of two through holes parallel to each other and having the centers of the diameters of the through holes arranged 20 mm apart from each other about the midpoint of the straight line. The insert block member is held inside the injection molding die by using the two through holes and the two steel columnar pins installed inside the injection molding die. An injection molding die designed so that the entire outer periphery of the insert block member is covered with a polyphenylene sulfide resin composition having a wall thickness of 1 mm after installation and injection molding of pellets of the polyarylene sulfide resin composition is performed. The pellet of the polyarylene sulfide resin composition was injection-molded using the product to obtain a molded product. Using the obtained molded product of the polyarylene sulfide resin composition containing the insert block member, in a vapor phase type thermal shock tester, "1 cycle; -40 ° C./0.5 hours to 150 ° C./ A thermal cycle test of "0.5 hours" was carried out and the number of cycles in which cracks occurred was recorded. The number of measurement samples: n = 5, and the average value was evaluated according to the following criteria.

Cracks occur in the range of less than 10 cycles ... Rank "E"
Cracks occur in the range of 10 or more and less than 100 cycles ... Rank "D"
Cracks occur in the range of 100 or more and less than 200 cycles ... Rank "C"
Cracks occur in the range of 200 or more and less than 500 cycles ... Rank "B"
Range of 500 cycles or more ... Rank "A"

[Adhesive strength of PAS resin composition with epoxy resin]
The obtained pellets were placed in a cylinder temperature range of 290 to 320 ° C., and in Examples 7 and 8 in a range of 360 to 410 ° C., and supplied to a Sumitomo-Nestal injection molding machine (SG75-HIPRO / MIII). Injection molding was performed using a mold for molding an ATM No. 1 dumbbell piece whose temperature was adjusted to 140 ° C. and 200 ° C. for Example 8 to obtain an ATM No. 1 dumbbell piece. The obtained ASTM No. 1 dumbbell piece was divided into two equal parts from the center, and a spacer (thickness: 1.8 to 2.2 mm, opening: 5 mm × 10 mm) was prepared so that the contact area with the epoxy adhesive was 50 mm ^2. ) Is divided into two equal parts, sandwiched between two pieces of ASTM No. 1 dumbbell, fixed with a clip, and then epoxy resin (two-component epoxy resin manufactured by Nagase ChemteX Corporation, main agent: XNR5002, curing agent: XNH5002, As for the compounding ratio, the main agent: curing agent = 100: 90) was injected, and the mixture was heated in a hot air dryer set at 135 ° C. for 3 hours to cure and adhere. After cooling at 23 ° C for 1 day, remove the spacer, and measure the tensile breaking strength using the obtained test piece at a strain rate of 1 mm / min, a distance between fulcrums of 80 mm, and a tensile tester manufactured by Instron at 23 ° C. Then, the value divided by the adhesive area was taken as the epoxy adhesive strength.

<Preparation and evaluation of compound>
After uniformly mixing each raw material with the compounding composition shown in Table 1 using a tumbler, the range of each barrel temperature in 6 zones using a twin-screw kneading extruder (TEM-35B, Toshiba Machine Co., Ltd.) is set to Example 7. Pellet-like compounds were obtained by melt-kneading at 290 to 350 ° C. for other than 8 and 360 to 410 ° C. for Examples 7 and 8. The evaluation results are shown in Tables 1 to 3.

表１〜３に示される結果から明らかなように、ポリマー合成例１〜８のＰＡＳ樹脂を用いた実施例１〜１１の冷熱衝撃下における耐クラック性は、比較合成例のＰＡＳ樹脂を用いた比較例１〜４に比して優れることが明らかとなった。また更にエポキシ接着性の点でも、比較合成例１のＰＡＳ樹脂を用いた比較例１〜４のものに比べ、実施例１〜１１のものが優れることが明らかとなった。その理由は、確定した理論ではないものの、官能基をポリマー末端に有する効果により、エラストマーやフィラー等との密着性が改良されたことによるものと考えられる。

As is clear from the results shown in Tables 1 to 3, the crack resistance of Examples 1 to 11 using the PAS resin of Polymer Synthesis Examples 1 to 8 under cold impact was determined by using the PAS resin of Comparative Synthesis Example. It was clarified that it was superior to Comparative Examples 1 to 4. Further, it was clarified that the ones of Examples 1 to 11 are superior to those of Comparative Examples 1 to 4 using the PAS resin of Comparative Synthesis Example 1 in terms of epoxy adhesiveness. Although the theory is not fixed, it is considered that the reason is that the adhesion to the elastomer, the filler, etc. is improved by the effect of having the functional group at the polymer terminal.

Claims (5)

At least one other component selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. A polyarylene sulfide resin composition containing
The polyarylene sulfide resin
From a group consisting of a main chain containing a structural unit represented by the following general formula (1-1) or the following general formula (2-1) and a carboxy group, a hydroxy group and an amino group bonded to the end of the main chain. Having a terminal group containing at least one functional group of choice ,
The terminal group is the following general formula (3-1b), (3-2b), (3-3b), (3-4b), (4-1b), (4-2b), (4-3b) or Being a group represented by (4-4b),
A polyarylene sulfide resin composition comprising.

^{Wherein, R 2b} is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or -C (CF ₃ ) ₂ -Ar ^4b - ^{represents, Ar 1, Ar 2, Ar} 3b and ^{Ar 4b} each independently represent an arylene group which may have a substituent, Z is a direct bond, -S-, Represents -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- .
However, in the general formula (1-1), 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} - a ^and, in Ar 1, Ar ² and ^{Ar 3b} is 1,4-phenylene ^{group, R 2b} is ^{-Ar 4b} - a, ^{Ar 4b} is a 1,4-phenylene group When Z is -S-, -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- . ]

[In the formula, R ³ represents an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^5b represents an arylene group. ]

[In the formula, R ⁴ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^6b represents an arylene group. ] A molded product obtained by molding the polyarylene sulfide resin composition according to claim 1 . High thermal conductivity material use, secondary battery gasket material use, water supply use, electric / electronic parts use, automobile parts including electric automobile parts, interior material use, precision parts use, film or textile use, claim Item 2. The molded product according to Item 2 . At least one other component selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups. This is a method for producing a polyarylene sulfide resin composition in which and is blended and melt-kneaded.
The polyarylene sulfide resin
From a group consisting of a main chain containing a structural unit represented by the following general formula (1-1) or the following general formula (2-1) and a carboxy group, a hydroxy group and an amino group bonded to the end of the main chain. Having a terminal group containing at least one functional group of choice ,
The terminal group is the following general formula (3-1b), (3-2b), (3-3b), (3-4b), (4-1b), (4-2b), (4-3b) or Being a group represented by (4-4b),
A method for producing a polyarylene sulfide resin composition.

^{Wherein, R 2b} is a direct ^{bond, -Ar 4b -, - S-} Ar 4b -, - O-Ar 4b -, - CO-Ar 4b -, - SO 2 -Ar 4b - or -C (CF ₃ ) ₂ -Ar ^4b - ^{represents, Ar 1, Ar 2, Ar} 3b and ^{Ar 4b} each independently represent an arylene group which may have a substituent, Z is a direct bond, -S-, Represents -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- .
However, in the general formula (1-1), 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} - a ^and, in Ar 1, Ar ² and ^{Ar 3b} is 1,4-phenylene ^{group, R 2b} is ^{-Ar 4b} - a, ^{Ar 4b} is a 1,4-phenylene group When Z is -S-, -O-, -CO-, -SO _2- or -C (CF ₃ ) _2- . ]

[In the formula, R ³ represents an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^5b represents an arylene group. ]

[In the formula, R ⁴ represents a direct bond or an alkylene group in the range of 1 to 10 carbon atoms, and Ar ^6b represents an arylene group. ] A method for producing a molded product, which comprises molding the polyarylene sulfide resin composition obtained by the production method according to claim 4 .

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