JP6607367B2 - Polyarylene sulfide film and method for producing the same - Google Patents

Description

  The present invention relates to a polyarylene sulfide film and a method for producing the same.

  In recent years, in various fields including the electrical and electronic parts field, there has been an active movement toward low halogen as an environmental measure.

  A polyarylene sulfide resin (hereinafter sometimes abbreviated as “PAS resin”) represented by a polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”) has heat resistance, chemical resistance, electrical insulation, etc. Excellent.

  Paying attention to the excellent characteristics of the PAS resin as described above, various application developments have been attempted.

  Conventionally, a polyphenylene sulfide resin is produced by solution polymerization in which, for example, p-dichlorobenzene and sodium sulfide, or sodium hydrosulfide and sodium hydroxide are used as raw materials in a polymerization reaction in an organic polar solvent (for example, patents). References 1 and 2). Currently commercially available polyphenylene sulfide resins are generally produced by this method.

  However, it is difficult to obtain a high molecular weight body by this method. Considering forming into a film or the like, there are cases where the amount of low molecular weight is large and the processability is not sufficient. As a method for improving this, generally, an elastomer component or the like is added or used in combination. (For example, patent document 3). In addition, since the polyphenylene sulfide resin is a polymer having a high degree of crystallinity, addition of a plasticizer or the like is required to improve processability even when the polymerization conditions are adjusted to obtain a high molecular weight product.

  Patent Document 4 discloses a method of adding a predetermined amount of cyclic polyphenylene sulfide for the purpose of improving moldability and yield. Patent Document 5 discloses a biaxially oriented polyarylene sulfide film composed only of a polyarylene sulfide resin and particles as a composite material that suppresses heat resistance, moldability, and mold contamination.

  On the other hand, in the electric and electronic parts industry, from the viewpoint of environmental protection, the movement of halogen regulation is rapidly expanding, and the regulation (900 ppm or less) is applied to the halogen in the material. As a method for improving this, as a method for obtaining a PAS with a reduced halogen content, for example, a method in which a cyclic arylene sulfide oligomer is heated and subjected to ring-opening polymerization in the presence of a ring-opening polymerization catalyst is disclosed (for example, (See Patent Documents 6 and 7.)

US Pat. No. 2,513,188 US Pat. No. 2,583,941 JP 2006-143793 A JP 2012-233302 A JP 2010-242066 A JP-A-5-163349 JP 2010-126621 A

However, in the above method, it may be difficult to produce a polyarylene sulfide film having good processability while maintaining the original characteristics of the polyarylene sulfide resin such as heat resistance.
Further, the method described in Patent Document 6 has a problem that it is difficult to selectively synthesize cyclic arylene sulfide oligomers, and the method described in Patent Document 7 can somewhat reduce halogen. In a film mainly composed of a resin, it is difficult to satisfy the halogen content regulation value (900 ppm or less).

  Therefore, the main problem to be solved by the present invention is that the amount of halogen is small, it can be easily processed while maintaining the original characteristics of the polyarylene sulfide resin, and the production of the film is sufficiently suppressed during film formation. Another object of the present invention is to provide a polyarylene sulfide resin comprising a polyarylene sulfide resin or a composition containing the same, and a method for producing the same.

  As a result of various studies, the present inventors have found that a polyarylene sulfide film comprising a polyarylene sulfide resin obtained by reacting poly (arylenesulfonium salt) and an aliphatic amide compound or a composition containing the same is a polyarylene sulfide film. The inventors have found that the above-mentioned problems can be solved by synthesizing the polyarylene sulfide resin from a reaction route different from the conventional one, and have completed the present invention.

That is, the present invention comprises reacting a poly (arylenesulfonium salt) having a structural unit represented by the following general formula (1) with an aliphatic amide compound to obtain a structural unit represented by the following general formula (2). with are those which can be obtained by a process comprising the step of obtaining a polyarylene sulfide resin, and, in the infrared absorption spectrum measured by FT-IR ^{spectroscopy,} the absorption peak in the range of 2910cm ^-1 ~2930cm -1 A polyarylene sulfide film is provided.

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

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

According to the present invention, from the polyarylene sulfide resin that can be easily processed while maintaining the original characteristics of the polyarylene sulfide resin and can be produced with sufficiently suppressed occurrence of film breakage during film formation, or a composition containing the same. The polyarylene sulfide film and the manufacturing method thereof can be provided.
In addition, the amount of halogen in the resin can be remarkably suppressed, and it is possible to meet the recent demand for reducing the environmental load. Furthermore, the resin used in the present application also has good processability.
In the conventional polymerization method, the amount of gas generated by heating is relatively large. In particular, the problem of gas generation tends to become prominent during molding. However, since the polyarylene sulfide resin according to the present invention suppresses the amount of gas generated during heating to a low level, it can sufficiently suppress deterioration in film quality caused by gas generation.
Furthermore, the present invention is excellent not only in the amount of the generated gas but also in quality. According to the present invention, since the terminal of the main chain of polyarylene sulfide is blocked with Me, the terminal does not become SH or the like unlike the conventional polymerization method. For this reason, thiophenol, a chloro compound, etc. do not generate | occur | produce on the mechanism of superposition | polymerization, but it leads to the improvement of a working environment.
Furthermore, since the end of the main chain of the polyarylene sulfide is Me, the polarizability is lower than in the case of SH as in the conventional polymerization method, so that components that cause gas generation are removed during the washing process. Cheap. For this reason, it can contribute to cost reduction, such as introduction of new facilities.

It is a figure showing the infrared absorption spectrum which measured the PPS resin of Example 1 by FT-IR spectroscopy. It is a figure showing the infrared absorption spectrum which measured the PPS resin of the comparative example 1 by FT-IR spectroscopy.

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

  The polyarylene sulfide film according to this embodiment is a film made of a polyarylene sulfide resin or a composition containing the same.

  The polyarylene sulfide resin used in the present embodiment can be obtained by a method including reacting poly (arylenesulfonium salt) with an aliphatic amide compound. According to such a method, a polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with conventional methods such as the Philips method.

  The aliphatic amide compound used in the present embodiment is represented by a compound represented by the following general formula (10), for example.

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

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

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

Examples of such aliphatic amide compounds include primary amide compounds such as formamide, secondary amide compounds such as β-lactam, N-methyl-2-pyrrolidone, 2-pyrrolidone, ε-caprolactam, N-methyl- In addition to the compounds represented by the general formula (10) such as tertiary amide compounds such as ε-caprolactam, dimethylformamide, diethylformamide, dimethylacetamide, etc., tetramethylurea, 1,3-dimethyl-2-imidazolidinone acid Urea compounds such as these can be used. The aliphatic amide compound preferably includes an aliphatic tertiary amide compound in which R ¹² and R ¹³ are aliphatic groups from the viewpoint of the solubility of poly (arylenesulfonium salt) and the solubility in water. -Methyl-2-pyrrolidone is particularly preferred.

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

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

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

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

Aspects of binding of Ar ¹ and Ar ² is not particularly limited, in the arylene group is preferably one that binds at positions remote. For example, when Ar ¹ and Ar ² are a phenylene group, a unit bonded at the para position and a unit bonded at the meta position are preferable, and a unit bonded at the para position is more preferable. It is preferable in terms of heat resistance and crystallinity of the resin that it is composed of units bonded at the para position.

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

Examples of R ² include alkyl groups having 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, and phenyl. Aryl groups having a structure such as naphthyl, biphenyl and the like, and the aryl group includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group It may have an alkyl group having 1 to 10 carbon atoms such as 1 to 4 on the aromatic ring as a substituent.

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

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

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

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

  Examples of the compound represented by the general formula (20) include methylphenyl sulfoxide, methyl-4- (phenylthio) phenyl sulfoxide, and the like. Of these compounds, methyl-4- (phenylthio) phenyl sulfoxide is preferred. Aromatic sulfoxides may be used alone or in combination of two or more.

  As the acid used for synthesizing the poly (arylenesulfonium salt), either an organic acid or an inorganic acid can be used. Examples of the acid include non-oxygen acids such as hydrochloric acid, hydrobromic acid, hydrocyanic acid, and tetrafluoroboric acid; sulfuric acid, phosphoric acid, perchloric acid, bromine forged, nitric acid, carbonic acid, boric acid, molybdic acid, isopolyacid, and heteropolyacid. Inorganic oxo acids such as acids; sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropolyacid salts, partial salts or esters of sulfuric acid such as monomethyl sulfuric acid, trifluoromethane sulfuric acid; formic acid, acetic acid, propionic acid, butanoic acid, succinic acid Monovalent or polyvalent carboxylic acids such as acid, benzoic acid and phthalic acid; halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid and trifluoroacetic acid; methanesulfonic acid and ethanesulfone Acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethyl Monovalent or polyvalent sulfonic acids such as sulfonic acid and benzenedisulfonic acid; partial metal salts of polyvalent sulfonic acid such as sodium benzenedisulfonate; antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tetrachloride Examples include Lewis acids such as tin, zinc chloride, copper chloride, and iron chloride. Of these acids, trifluoromethanesulfonic acid and methanesulfonic acid are preferably used from the viewpoint of reactivity. These acids may be used alone or in combination of two or more.

  Since this reaction is a dehydration reaction, a dehydrating agent may be used in combination. Examples of the dehydrating agent include phosphoric anhydrides such as phosphorus oxide and diphosphorus pentoxide; sulfonic acids such as benzenesulfonic anhydride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, and paratoluenesulfonic anhydride. Anhydrides; carboxylic acid anhydrides such as acetic anhydride, fluoroacetic anhydride, and trifluoroacetic anhydride; anhydrous magnesium sulfate, zeolite, silica gel, calcium chloride, and the like. These dehydrating agents may be used alone or in combination of two or more.

  When synthesizing poly (arylenesulfonium salt), a solvent can be appropriately used. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol and isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitrile solvents such as acetonitrile, and 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, etc. Examples include ether solvents. These solvents may be used alone or in combination of two or more.

  The conditions for reacting the poly (arylenesulfonium salt) and the aliphatic amide compound according to this embodiment can be appropriately adjusted so that dealkylation or dearylation proceeds appropriately. The reaction temperature is preferably in the range of 40 to 250 ° C, more preferably in the range of 70 to 220 ° C.

  According to the production method of the present embodiment, it is possible to reduce the remaining amount of the dealkylating agent or dearylating agent in the obtained polyarylene sulfide resin. The residual amount of the dealkylating agent or dearylating agent in the resin is in the range of 1000 ppm or less based on the mass of the resin containing the polyarylene sulfide resin and other components such as the dealkylating agent or the dearylating agent. Preferably, the range is 700 ppm or less, and more preferably 100 ppm or less. By setting it as 1000 ppm or less, the substantial influence with respect to the quality of the polyarylene sulfide resin obtained can be reduced. The polyarylene sulfide resin obtained by the production method of the present embodiment includes a polyarylene sulfide resin produced by another method based on the type and content of components such as a mixed dealkylating agent or dearylating agent. A distinction can be made.

  The method for producing a polyarylene sulfide resin according to this embodiment may further include a step of washing the polyarylene sulfide resin with water, a water-soluble solvent, or a mixed solvent thereof. By including such a washing step, the remaining amount of the dealkylating agent or dearylating agent contained in the obtained polyarylene sulfide resin can be more reliably reduced.

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

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

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

  The glass transition temperature of the polyarylene sulfide resin obtained by the production method of the present embodiment is preferably in the range of 70 to 110 ° C, more preferably in the range of 80 to 95 ° C. The glass transition temperature of the resin indicates a value measured by a DSC apparatus.

  The melting point of the polyarylene sulfide resin obtained by the production method of the present embodiment is preferably in the range of 260 to 300 ° C, more preferably in the range of 270 to 290 ° C. The melting point of the resin indicates a value measured by a DSC apparatus.

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

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

  Mw / Mtop of the polyarylene sulfide resin according to this embodiment is in the range of 0.5 to 3.5, and preferably in the range of 0.7 to 2.5. By setting Mw / Mtop in such a range, the processability of the polyarylene sulfide resin can be improved, and appropriate stretchability and flexibility can be imparted to the resulting film. Mw / Mtop indicates the distribution of the molecular weight to be measured. Normally, when this value is close to 1, it indicates that the molecular weight distribution is narrow, and as this value increases, the molecular weight distribution is broad. The measurement conditions for gel permeation chromatography are the same as those in the examples of the present specification. However, it is possible to change the measurement conditions within a range that does not substantially affect the values of Mw and Mw / Mtop.

The non-Newtonian index of the polyarylene sulfide resin according to the present embodiment is in the range of 0.5 to 2.3, and preferably in the range of 0.9 to 1.8. By setting the non-Newtonian index in such a range, the processability of the polyarylene sulfide resin can be improved. In the present specification, the non-Newtonian index means an index satisfying the following relational expression between the shear rate and the shear stress under the condition of a temperature of 300 ° C. The non-Newtonian index can be an index related to the molecular weight to be measured or the molecular structure such as linear, branched, or crosslinked. Usually, when this value is close to 1, it indicates that the resin molecular structure is linear. It shows that there are many branched and cross-linked structures as the value increases.
D = α × S ⁿ
(In the above formula, D represents shear rate, S represents shear stress, α represents a constant, and n represents a non-Newtonian index.)

Polyarylene sulfide according to the present embodiment, the FT-IR spectrum as measured by FT-IR spectroscopy (IR ^spectrum), which has an absorption peak in the range of 2910cm ^-1 ~2930cm -1, Thereby, since the solubility with respect to the solvent of a low molecular weight component is favorable, it becomes a polymer which is easy to remove | eliminate by the above-mentioned washing | cleaning process, and has little generated gas amount.
The peak is derived from (belongs to) the stretching vibration of a methylsulfanyl group (-SMe).

  The melt viscosity (V6) at 300 ° C. of the polyarylene sulfide resin according to this embodiment is preferably in the range of 1 to 2000 [Pa · s], more preferably in the range of 5 to 1700 [Pa · s]. Here, for the melt viscosity (V6), using a flow tester, an orifice having a temperature of 300 ° C., a load of 1.96 MPa, and a ratio of the orifice length to the orifice diameter (orifice length / orifice diameter) is 10/1. The melt viscosity after holding for 6 minutes.

The whiteness (hot press L value / L ^* value) of the polyarylene sulfide resin according to this embodiment is preferably in the range of 70 to 90, and more preferably in the range of 75 to 85. By setting the L ^* value in such a range, it is possible to obtain a film in which coloring during molding is sufficiently suppressed. The L ^* value is an index related to the whiteness of the measurement target, but can also be an index of oxidative crosslinking. The polyarylene sulfide resin is colored when subjected to a thermal oxidation treatment, and the L ^* value tends to decrease.

  The amount of gas generated during heating of the polyarylene sulfide resin according to the present embodiment can be in the range of 0.2% by mass or less, and preferably in the range of 0.15% by mass or less. By being able to suppress the amount of gas generated during heating, it is possible to further suppress film breakage during film formation and sufficiently suppress deterioration in film quality due to gas generation.

  The composition containing the polyarylene sulfide resin can further contain one or more inorganic fillers without departing from the spirit of the present invention. By blending the inorganic filler, high rigidity and high heat stability can be imparted to the film. Examples of inorganic fillers include powder fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate fillers such as talc and mica, granular fillers such as glass beads, silica beads and glass balloons, and glass fibers. And fibrous fillers such as carbon fiber and wollastonite fiber, and glass flakes. It is particularly preferable that the polyarylene sulfide resin composition contains at least one inorganic filler selected from the group consisting of glass fiber, carbon fiber, carbon black, and calcium carbonate.

  The content of the inorganic filler is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 5 to 200 parts by mass, and still more preferably in the range of 15 to 150 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It is. When the content of the inorganic filler is in these ranges, a more excellent effect can be obtained in terms of tensile properties such as tensile strength when formed into a film.

  The polyarylene sulfide resin composition can contain a resin other than the polyarylene sulfide resin selected from thermoplastic resins, elastomers, and crosslinkable resins without departing from the spirit of the present invention. These resins can be blended in the resin composition together with the inorganic filler.

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

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

  Examples of diamines for obtaining polyamides include aliphatic diamines, aromatic diamines, and alicyclic diamines. As aliphatic diamine, C3-C18 diamine which has a linear or side chain is preferable. Examples of suitable aliphatic diamines include 1,3-trimethylene diamine, 1,4-tetramethylene diamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine. 1,8-octamethylenediamine, 2-methyl-1,8-octanediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanmethylenediamine, 1,12-dodecamethylene Diamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,15-pentadecamethylenediamine, 1,16-hexadecamethylenediamine, 1,17-heptadecamethylenediamine, 1,18 -Octadecamethylenediamine, 2,2,4-trimethylhexamethylenediamine And 2,4,4-trimethyl hexamethylene diamine. These can be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

  As the elastomer blended in the polyarylene sulfide resin composition, a thermoplastic elastomer is often used. Examples of the thermoplastic elastomer include polyolefin elastomers, fluorine elastomers, and silicone elastomers. In the present specification, the thermoplastic elastomer is classified not as the thermoplastic resin but as an elastomer.

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

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

  The crosslinkable resin blended in the polyarylene sulfide resin composition has two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amino group, an amide group, a carboxy group, an acid anhydride group, and an isocyanate group. Examples of the crosslinkable resin include an epoxy resin, a phenol resin, and a urethane resin.

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

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

  The polyarylene sulfide resin composition can contain a silane compound having a functional group. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples include silane coupling agents such as diethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

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

  The polyarylene sulfide resin composition according to this embodiment is a mold release agent, a colorant, a heat stabilizer, a UV stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant, and the like without departing from the spirit of the present invention. Other additives may be included. For example, the content of the additive is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin.

  The polyarylene sulfide resin can be obtained in the form of pellets. In addition, the composition containing the polyarylene sulfide resin can be obtained in the form of, for example, a pellet-like compound by a method of melt-kneading the polyarylene sulfide resin and the other components. The melt kneading temperature is, for example, preferably in the range of 250 to 350 ° C, and more preferably in the range of 290 to 330 ° C. Melting and kneading can be performed using a twin screw extruder or the like.

  The film made of the polyarylene sulfide resin according to the present embodiment can be obtained, for example, by forming the resin using a melt extruder.

  First, the pellet-like polyarylene sulfide resin obtained by the above-described method is charged into a melt extruder heated at a temperature of the melting part in the range of 250 to 350 ° C, preferably in the range of 270 to 330 ° C, and melted. The polymer is filtered through a filter and discharged from the T die die into a film. By making this film-like material adhere to a cooling drum set so that the surface temperature is in the range of 20 to 70 ° C. and cooling and solidifying, an unstretched film in a substantially non-oriented state can be obtained. . The set temperature of the filter part and the die is preferably set to a temperature range that is 0 to 20 ° C. higher than the temperature of the melting part of the melt extruder, and more preferably set to a temperature range that is 5 to 15 ° C. higher.

  The unstretched film can be biaxially oriented by further performing biaxial stretching or the like. As the stretching method, sequential biaxial stretching method (stretching method in which stretching in the longitudinal direction of the film and stretching in the width direction are separately performed), simultaneous biaxial stretching method (method in which stretching in the longitudinal direction and width direction of the film are performed simultaneously) Is mentioned. These stretching methods may be used in appropriate combination.

  In the sequential biaxial stretching method, an unstretched polyarylene sulfide film is heated by a heated roll group, and the film is stretched by utilizing the difference in rotational speed of the rolls. From the viewpoint of improving the thermoformability of the film, the draw ratio is preferably in the range of 2.0 to 4.0 times in the longitudinal direction (MD direction), and is preferably in the range of 2.5 to 3.5 times. More preferably, it is more preferably in the range of 2.8 to 3.2 times. This stretching step may be performed in one step or in two or more steps.

  The temperature in the stretching process in the MD direction is preferably Tg to (Tg + 30) ° C., when the glass transition temperature of the polyarylene sulfide resin is Tg, and (Tg + 5) to (Tg + 20) ° C. More preferably.

  Examples of the stretching method in the width direction (TD direction) after stretching in the MD direction include a method using a transverse stretching machine (tenter). The both ends of the film after MD stretching are sandwiched between clips, guided to a tenter, and stretched in the TD direction. From the viewpoint of improving the elongation at break of the film, the draw ratio is preferably in the range of 2.0 to 4.0 times in the TD direction, and more preferably in the range of 2.5 to 3.5 times.

  The temperature in the stretching process in the TD direction is preferably in the range of Tg to (Tg + 30) ° C., and more preferably in the range of (Tg + 5) to (Tg + 20) ° C.

  With the film stretched in the TD direction, the stretched film is heat-set and relaxed. The heat setting and relaxation treatment is preferably performed at a temperature in the range of 250 to 280 ° C. The total time for heat setting and relaxation treatment is in the range of 1 to 15 seconds, preferably in the range of 5 to 10 seconds, when the film thickness is less than 50 μm. When the thickness of the film exceeds 50 μm, the total time for heat setting and relaxation treatment is in the range of 10 to 40 seconds, preferably in the range of 20 to 30 seconds. The heat setting and relaxation treatment may be performed in one stage, or may be performed in two or more stages.

  Furthermore, the film can be cooled and rolled up to room temperature, if necessary, in the MD direction and TD direction, if necessary, to obtain the desired biaxially oriented polyarylene sulfide film.

  The 50% elongation at break of the polyarylene sulfide film at 160 ° C. in either the MD or TD direction is preferably 100% or more, more preferably 110% or more, and 120 % Or more is more preferable. The 50% average breaking strength in the MD direction of the polyarylene sulfide film at 160 ° C. is preferably in the range of 30 to 80 MPa, more preferably in the range of 40 to 70 MPa, and in the range of 50 to 60 MPa. It is more preferable.

  The polyarylene sulfide film has a breaking elongation in either the MD direction or TD direction of the film at 160 ° C. of 100% or more, and the breaking stress in either the MD direction or TD direction of the film at 160 ° C. Is preferably in the range of 30 to 80 MPa. When the breaking elongation and breaking stress satisfy the above relationship, the occurrence of film breakage during film formation can be further suppressed.

  The breaking elongation and breaking stress indicate values measured using an Instron type tensile tester according to the method defined in ASTM-D882. A more specific method is to perform a tensile test by sandwiching a sample cut out in the tensile direction with a chuck part of an upper and lower tensile tester, and when the film sample breaks, the stress is the elongation at break, Measured as the breaking stress. Measurement is performed at 160 ° C. using an Instron type tensile tester on a film having a sample size of 10 mm width × 150 mm length and 100 mm between test lengths at a tensile speed of 300 mm / min.

  The heat shrinkage ratio of the polyarylene sulfide film is preferably 2.5% or less in the MD direction and 4.0% or less in the TD direction when heat-treated at 150 ° C. for 30 minutes. preferable.

  The thickness of the polyarylene sulfide film is not particularly limited, but the lower limit is preferably 100 μm or more, and more preferably 150 μm or more, from the viewpoint of followability during molding. On the other hand, from the viewpoint of film formability, the upper limit is preferably in the range of 1000 μm or less, and more preferably in the range of 500 μm or less. In the present invention, the “film” is not particularly limited in length and width, and is a flat molded product and includes tapes and ribbons. The planar molded product may be referred to as a sheet depending on the thickness. For example, according to a polymer dictionary edited by the Society of Polymer Science (Asakura Shoten, 1971), a film having a thickness of less than 200 μm and a thickness of 200 μm or more is used. The distinction between sheets is described. However, in general, it is difficult to distinguish between a film and a sheet. Therefore, in the present invention, both are collectively referred to as “film”.

  About the said film forming method, it can apply also to the composition containing the said polyarylene sulfide resin.

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

  The polyarylene sulfide film according to this embodiment also has various performances such as heat resistance and dimensional stability inherent to the polyarylene sulfide resin. Used as a film used in the fields of automotive parts such as electronic parts, lamp reflectors and various electrical parts, interior materials for various buildings, aircraft and automobiles, precision parts such as OA equipment parts, camera parts and watch parts can do. When used in these applications, the polyarylene sulfide film according to this embodiment may be used alone, or may be used in appropriate combination with other films.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
In the examples shown below, the following reagents were used.
Methyl phenyl sulfoxide: Tokyo Chemical Industry Co., Ltd., purity 98%
Thioanisole: Wako Pure Chemical Industries, 99% purity
Methanesulfonic acid: Wako Pure Chemical Industries, Ltd., Wako Special Grade 60% Perchloric acid: Wako Pure Chemical Industries, Ltd., Wako First Grade Pyridine: Wako Pure Chemical Industries, Ltd. Kojun Pharmaceutical Co., Ltd., reagent grade bromine: manufactured by Wako Pure Chemical Industries, Ltd., reagent grade trifluoromethanesulfonic acid: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade quinoline: manufactured by Wako Pure Chemical Industries, Ltd., Reagent special grade N-methylpyrrolidone: Wako Pure Chemical Industries, Ltd., Wako first grade

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

1-2. Analysis of residual halogen content The powder was measured with fluorescent X-rays (ZSX100e manufactured by Rigaku Corporation), and the residual halogen content was analyzed.

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

Methyl phenyl sulfoxide 70.0 [g] and thioanisole 62.0 [g] were placed in a 3 L three-necked flask and cooled to 5 ° C. or lower in an ice bath under a nitrogen atmosphere. Methanesulfonic acid 1 [L] was kept at 10 ° C. or lower and added to the reaction solution. Thereafter, the ice bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 20 hours. Next, the stirred reaction solution was added to a 60% perchloric acid aqueous solution 2 [L] and stirred for 1 hour. Water 1 [L] and dichloromethane 1 [L] were added, and the organic layer was recovered by extraction / separation operation. Furthermore, dichloromethane [500 mL] was added to the aqueous layer, and the operation of recovering the organic layer was performed twice. The collected organic layer was dehydrated by adding anhydrous magnesium sulfate. After dehydration, magnesium sulfate was removed by filtration, and the filtrate was concentrated with a rotary evaporator to remove the solvent. The remaining viscous solid was crystallized by adding ether. The crystalline product was filtered off and the resulting solid was dried under reduced pressure for 20 hours to obtain methyl phenyl [4- (methylthio) phenyl] sulfonium perchlorate 130.0 [g] (yield 75%). It was. It was confirmed by ¹ H-NMR measurement that the target product was synthesized.
¹ H-NMR (solvent CDCl ₃ ): 2.49, 3.63, 7.40, 7.65, 7.78.7.85 [ppm]

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

In a 2 L three-necked flask, 100.0 [g] of methylphenyl perchlorate [4- (methylthio) phenyl] sulfonium was added, and 500 [mL] of pyridine was added and stirred for 30 minutes in a nitrogen atmosphere. Then, it heated up at 100 [degreeC] and stirred for 30 minutes. The reaction solution was poured into 3 [L] of 10% HCl solution, stirred for 10 minutes, and the organic layer was recovered by extraction / separation operation with dichloromethane. The collected organic layer was dehydrated by adding anhydrous magnesium sulfate. Magnesium sulfate was removed by filtration, and the filtrate was concentrated with a rotary evaporator to remove the solvent. The target component was recovered by column chromatography using a developing solvent of hexane / chloroform = 3/1 (volume ratio), and the solvent was removed by a rotary evaporator.
The obtained liquid was dried under reduced pressure for 20 hours to obtain 55.5 [g] (yield 83%) of methyl 4- (phenylthio) phenyl sulfide. It was confirmed by ¹ H-NMR measurement that the target product was synthesized.
¹ H-NMR (solvent CDCl ₃ ): 2.48, 7.18 to 7.23, 7.28 to 7.31 [ppm]

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

In a 5 L three-necked flask, 50.0 [g] methyl 4- (phenylthio) phenyl sulfide, 43.0 [g] potassium hydrogen carbonate, 390 [mL] water, and 500 [mL] dichloromethane were added for 30 minutes. Stir. A solution prepared by dissolving 34.5 [g] of bromine in 500 [mL] of dichloromethane was dropped into the reaction vessel over 5 minutes and stirred for 30 minutes. Potassium chloride (KCl) saturated solution 1 [L] and dichloromethane 1 [L] were added to the reaction solution, and the organic layer was recovered by extraction / separation operation. Dichloromethane 500 [mL] was added to the remaining aqueous layer, and the operation of recovering the organic layer was performed twice. The collected organic layer was washed with water, and the organic layer was collected by a liquid separation operation, and dehydrated by adding anhydrous magnesium sulfate. After dehydration, magnesium sulfate was filtered off, and the filtrate was concentrated with a rotary evaporator to remove the solvent. The remaining viscous solid was crystallized by adding ether. The crystalline product was filtered off and the resulting solid was dried under reduced pressure for 20 hours to obtain 30.5 [g] (yield 57%) of methyl 4- (phenylthio) phenyl sulfoxide. It was confirmed by ¹ H-NMR and ¹³ C-NMR measurements that the target product was synthesized. Further, it was confirmed from the analysis by fluorescent X-ray that the residual halogen amount was outside the detection range.
¹ H-NMR (solvent CDCl ₃ ): 2.71, 7.34, 7.39, 7.46, 7.52 [ppm]
¹³ C-NMR (solvent CDCl ₃ ): 46.0, 124.5, 128.5, 129.7, 133.0, 133.5, 141.5, 144.3 [ppm]

3. Synthesis of poly (arylenesulfonium salt)

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

4). Evaluation method of synthesized polyarylene sulfide resin

4-1. Glass Transition Temperature and Melting Point Using a Perkin Elmer DSC device Pyris Diamond, measurement was performed from 40 to 350 ° C. under a nitrogen flow rate of 50 mL / min and a temperature rising condition of 20 ° C./min to obtain a glass transition temperature and a melting point.

4-2. Infrared absorption spectrum After the obtained PPS resin is pressed at 350 ° C., a film showing an amorphous property is prepared by quenching, and a Fourier transform infrared spectrometer (hereinafter referred to as “FT-IR apparatus”) is used. FTIR-6100 manufactured by KK was used.) In the infrared absorption spectrum, the presence or absence of absorption at 2920 cm −1 was measured.

4-3. Melt viscosity of polyarylene sulfide resin The polyarylene sulfide resin is held for 6 minutes at 300 ° C. under a load of 1.96 × 10 ⁶ Pa and L / D = 10/1 using a flow tester CFT-500C manufactured by Shimadzu Corporation. After that, the melt viscosity was measured.

4-4. Mw and Mtop (Molecular weight distribution)
The weight average molecular weight and peak molecular weight of the polyarylene sulfide resin were measured under the following measurement conditions using gel permeation chromatography. Mw / Mtop was calculated from the obtained Mw and Mtop. Six types of monodisperse polystyrene were used for calibration.
Apparatus: Ultra-high temperature polymer molecular weight distribution measuring apparatus (“SSC-7000” manufactured by Senshu Scientific Co., Ltd.)
Column: UT-805L (made by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene Measurement method: UV detector (360 nm)

4-5. Halogen content The chlorine content in the polymer was determined by absorbing the gas generated by burning the polymer with a Diane Instruments combustion gas absorption device into pure water, and quantifying the chlorine ion in the absorption solution with a Dionex ion chromatograph.

4-6. Color tone L ^* value Whiteness (hot press L ^* value) was determined by preheating the polyarylene sulfide resin at 320 ° C. for 1.5 minutes, then at 320 ° C. for 1.5 minutes, then at 130 ° C. for 1.5 minutes, 30 kg / A disk-shaped plate was produced by pressure molding with a hot press at a pressure of cm ² . About this, it measured using the color difference meter (The Tokyo Denshoku Co., Ltd. make, Color Ace).

4-7. Non-Newtonian index A polyarylene sulfide resin was measured with a capillary rheometer at a temperature of 300 ° C. using a die with a diameter of 1 mm and a length of 40 mm for a shear rate of 100 to 1000 (sec ⁻¹ ). These are values calculated from the slopes of these logarithmic plots.

4-8. Generated Gas Amount Using a gas chromatograph mass spectrometer, a predetermined amount of a sample of polyarylene sulfide resin or resin composition was heated at 325 ° C. for 15 minutes, and the amount of generated gas at that time was determined as mass%.

5. Synthesis of polyarylene sulfide resin (dealkylation or dearylation of poly (arylenesulfonium salt))
Example 1

Poly [methyl trifluoromethanesulfonate (4-phenylthiophenyl) sulfonium] 2.0 [g] obtained in Synthesis Example 1 was placed in a 100 mL eggplant flask, and N-methyl was used as a dealkylating agent or dearylating agent. 2-Pyrrolidone 5.5 [mL] (10 equivalents) was added and stirred at room temperature for 30 minutes, then heated to 100 ° C. and stirred for 48 hours. The reaction solution after stirring was cooled to room temperature, and then poured into water, and the precipitate was filtered off and washed three times with 80 [mL] of water. The obtained solid was dried overnight at 120 ° C. using a hot air dryer to obtain 0.83 [g] (yield 73%) of polyphenylene sulfide.
As a result of conducting a thermal analysis on the obtained solid, it was confirmed that a polyphenylene sulfide resin (PPS resin) was produced because it had a glass transition temperature (Tg) of 92 ° C. and a melting point of 278 ° C.
Further, when the infrared absorption spectrum was measured, the presence of a peak at 2917 [cm ⁻¹ ] was recognized as shown in FIG.
Further, this polymer had a melt viscosity of 370 Pa · s, Mtop of 52000, and Mw of 49000.
In addition, the halogen content was found to be significantly reduced to 50 ppm or less.
The L value was 75, and the non-Newton index was 1.1.
The amount of generated gas was as small as 0.1 [wt%].

(Comparative Example 1)
220.5 g (1.5 mol) of p-dichlorobenzene (hereinafter abbreviated as “p-DCB”) in a 1-liter autoclave of zirconium lining with stirring blades connected with a pressure gauge, a thermometer, a condenser, and a decanter. , 29.7 g (0.3 mol) of NMP, 177.29 g (1.5 mol) of 47.43 wt% aqueous NaOH solution, and 123.18 g (1.5 mol) of 48.71 wt% aqueous NaOH solution were stirred and stirred. Then, the temperature was raised to 173 ° C. over 2 hours under a nitrogen atmosphere to distill 177.98 g of water, and the kettle was sealed. At that time, p-DCB distilled by azeotropic distillation was separated by a decanter and returned to the inside of the kettle as needed. After completion of dehydration, the internal temperature was cooled to 160 ° C., 267.65 g (2.7 mol) of NMP was charged, the temperature was raised to 230 ° C., stirred at 230 ° C. for 5 hours, and then heated to 250 ° C. in 40 minutes. , And stirred at 250 ° C. for 1 hour. After cooling, the resulting slurry was poured into 3 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred with 3 liters of warm water for 1 hour, washed and filtered. This operation was repeated 4 times, and after filtration, it was dried overnight at 120 ° C. using a hot air dryer to obtain 154 g of white powdery PPS.
As a result of conducting a thermal analysis on the obtained solid, it was confirmed that a polyphenylene sulfide resin (PPS resin) was produced because it had a glass transition temperature (Tg) of 92 ° C. and a melting point of 277 ° C.
The measured infrared absorption spectrum, as shown in FIG. ^2, the presence of absorption peak in the range of 2910cm ^-1 ~2930cm -1 did et al observed.
Further, this polymer had a melt viscosity of 220 Pa · s, Mtop of 45000, and Mw of 44,000.
The halogen content was 1700 ppm.
The L value was 77 and the non-Newton index was 1.1.
The amount of generated gas was 0.5 [wt%].

6). Production and Evaluation of Polyarylene Sulfide Film After mixing 30000 parts by weight of the white powdery polymer (PPS resin) obtained in Example 1 and Comparative Example 1 using a tumbler, a twin-screw kneading extruder (TEM-) 35B, Toshiba Machine) and melt-kneaded at 300 ° C. to obtain a pellet-shaped polymer. The obtained pellets were supplied to an extruder whose melting part was heated to 320 ° C. The polymer melted by the extruder is filtered through a filter set at a temperature of 330 ° C., then melt-extruded from a die set at a temperature of 310 ° C., and brought into close contact with a cast drum having a surface temperature of 25 ° C., and solidified by cooling. Thus, an unstretched film was produced.
This unstretched film was heated in a longitudinal stretching machine composed of a plurality of roll groups, and after heating, the difference in the winding speed of the roll was utilized to make a film temperature of 101 ° C. in the film longitudinal direction at a film temperature of 101 ° C. The film was stretched at a double stretch ratio. Thereafter, both ends of the film are gripped with clips and guided to a transverse stretching machine (tenter), stretched in the width direction of the film at a stretching temperature of 101 ° C. and a stretching ratio of 3.3 times, and subsequently at a temperature of 200 ° C. Heat treatment was performed for 4 seconds (first-stage heat treatment), followed by heat treatment at 260 ° C. for 4 seconds (second-stage heat treatment). Subsequently, after 5% relaxation treatment in the transverse direction for 4 seconds in a relaxation treatment zone at 260 ° C., the film edge was removed after cooling to room temperature, and a biaxially oriented polyarylene sulfide film having a thickness of 100 μm was produced.

6-1. Tensile properties (160 ° C, 50% average breaking stress, 160 ° C, 50% average breaking elongation)
According to the method prescribed | regulated to ASTM-D882, it measured using the Instron type tensile tester. The measurement was performed under the following conditions, and with 10 samples, an average value was taken for each of the film longitudinal direction and the width direction, and the 50% average breaking stress and 50% average breaking elongation were calculated by the following formulas.
50% average breaking stress = (average value of stress in the film longitudinal direction + average value of stress in the film width direction) / 2
50% average breaking elongation = (average elongation in the film longitudinal direction + average elongation in the film width direction) / 2
Measuring device: Orientec Co., Ltd. film strong elongation automatic measuring device “Tensilon AMF / RTA-100”
Sample size: width 10 mm ×× length 150 mm, sample length 100 mm
Pulling speed: 300mm / min

6-2. Thermal contraction rate It measured according to the method prescribed | regulated to JISC-2318. A sample having a sample width of 10 mm and a sample length of 200 mm was heat-treated in a gear oven at 150 ° C. for 30 minutes, and the heat shrinkage rate was calculated from the change in the sample length by the following formula.
Thermal shrinkage rate (%) = [(length before heat treatment−length after heat treatment) / length before heat treatment] × 100

6-3. Processing characteristics The elongation at break in either the longitudinal direction or the width direction of the film at 160 ° C. is 100% or more, and the breaking stress in either the longitudinal direction or the width direction of the film at 160 ° C. is 30 to 80 MPa. Only when it was in the range, the processing characteristics were “◯”, and the other cases were processing characteristics “x”.

6-4. Film breakage during film formation Film breakage during film formation is “x” when film breakage occurs 5 times or more when continuous film formation is performed for a total time of 24 hours, and film breakage is 1 time or more and less than 5 times The case where it occurred in the range of “Δ” was designated as “Δ”, and the case where no film breakage occurred was designated as “◯”.

  The obtained biaxially oriented polyarylene sulfide film was evaluated for tensile properties, thermal shrinkage, processing properties, and the like. The evaluation results are shown in Table 1.

  As is apparent from the results shown in Table 1, in Example 1, the film tearing at the time of film formation was suppressed while having the original characteristics of polyarylene sulfide resin such as high tensile properties and a sufficiently small heat shrinkage rate. It was. Moreover, in Example 1, as above-mentioned, it was confirmed that the generated gas amount of polyarylene sulfide resin is suppressed low. Thereby, it turns out that the outstanding film by which the film tear at the time of film forming etc. was suppressed was obtained.

Claims (4)

Having a step of forming a polyarylene sulfide resin or a composition containing the same,
The polyarylene sulfide resin is a poly (arylenesulfonium salt) having a structural unit represented by the following general formula (1):
It can be obtained by a method comprising a step of reacting an aliphatic amide compound to obtain a polyarylene sulfide resin having a structural unit represented by the following general formula (2),
The polyarylene sulfide resin has -S-R ² ;
A method for producing a polyarylene sulfide film.

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

(In the formula, ^{R 1} represents a direct ^bond, -Ar 2 -, ^- Ar 2 -S- or ^-Ar 2 -O- to represent, Ar ¹ and Ar ² may have a functional group as a substituent Represents an arylene group.) The method for producing a polyarylene sulfide film according to claim 1 , wherein the polyarylene sulfide resin has a methylsulfanyl group. The polyarylene sulfide resin, the infrared absorption spectrum measured by FT-IR spectroscopy, and has an absorption peak based on -S-R ^2, the production method of polyarylene sulfide film according to claim 1 . The manufacturing method of the polyarylene sulfide film as described in any one of Claims 1-3 whose said aliphatic amide compound contains an aliphatic tertiary amide compound.

Images