WO2015033856A1 - ポリアリーレンスルフィドフィルム及びその製造方法 - Google Patents
ポリアリーレンスルフィドフィルム及びその製造方法 Download PDFInfo
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- WO2015033856A1 WO2015033856A1 PCT/JP2014/072639 JP2014072639W WO2015033856A1 WO 2015033856 A1 WO2015033856 A1 WO 2015033856A1 JP 2014072639 W JP2014072639 W JP 2014072639W WO 2015033856 A1 WO2015033856 A1 WO 2015033856A1
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- polyarylene sulfide
- sulfide resin
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- polyarylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/04—Polysulfides
Definitions
- the present invention relates to a polyarylene sulfide film and a method for producing the same.
- 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. It is attracting attention as a halogen-free material because it is excellent in that it has high flame retardancy without using a halogen-based flame retardant.
- polyphenylene sulfide resins have been produced by, for example, solution polymerization in which p-dichlorobenzene and sodium sulfide, or sodium hydrosulfide and sodium hydroxide are used as raw materials in a polymerization reaction in an organic polar solvent (for example, patents). References 1 and 2).
- polyphenylene sulfide resins are generally produced by this method.
- Patent Document 4 discloses a method of adding a predetermined amount of cyclic polyphenylene sulfide for the purpose of improving molding processability 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.
- a biaxially oriented laminated film in which a base layer part made of a thermoplastic resin and a surface layer part made of a thermoplastic resin containing polyarylene sulfide are laminated (patent) Reference 6).
- the main problem to be solved by the present invention is that the polyarylene sulfide resin can be easily processed while maintaining the original characteristics of the polyarylene sulfide resin, and can be produced with sufficiently suppressed film breakage during film formation.
- Another object of the present invention is to provide a polyarylene sulfide film comprising a composition containing the same and a method for producing the same.
- a polyarylene sulfide film comprising a polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor or a composition containing the same. And found that the above-mentioned problems can be solved by setting the ratio of the non-Newtonian index of the polyarylene sulfide resin and the weight average molecular weight Mw and the peak molecular weight Mtop measured by gel permeation chromatography to predetermined ranges, respectively.
- the present invention has been completed.
- the present invention is a polyarylene sulfide film comprising a polyarylene sulfide resin or a composition containing the same, wherein the polyarylene sulfide resin comprises a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor.
- the polyarylene sulfide resin can be obtained by a method including reacting in a molten mixture containing a diiodo aromatic compound, the elemental sulfur and the polymerization inhibitor, and the polyarylene sulfide resin is 1.1 or more at 300 ° C.
- a polyarylene sulfide film is provided.
- 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.
- the polyarylene sulfide resin obtained by the conventional melt polymerization method has a relatively large amount of gas generated by heating during the molding process.
- the problem of gas generation tends to become prominent due to heating during molding.
- the polyarylene sulfide resin according to the present invention suppresses the amount of gas generated at the time of heating and melting low, it can sufficiently suppress deterioration in film quality caused by gas generation.
- the polyarylene sulfide film according to the present embodiment is a film made of a polyarylene sulfide resin or a composition containing the same.
- the polyarylene sulfide resin used in this embodiment reacts a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the elemental sulfur, and the polymerization inhibitor.
- the diiodo aromatic compound has an aromatic ring and two iodine atoms directly bonded to the aromatic ring.
- diiodo aromatic compounds include, but are not limited to, diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether, and diiododiphenyl sulfone.
- the substitution positions of the two iodine atoms are not particularly limited, but it is preferable that the two substitution positions are located as far as possible in the molecule. Preferred substitution positions are the para position and the 4,4'-position.
- Aromatic rings of diiodo aromatic compounds include phenyl groups, halogen atoms other than iodine atoms, hydroxy groups, nitro groups, amino groups, alkoxy groups having 1 to 6 carbon atoms, carboxy groups, carboxylates, aryl sulfones and aryl ketones. It may be substituted with at least one substituent selected from However, from the viewpoint of crystallinity and heat resistance of the polyarylene sulfide resin, the ratio of the substituted diiodo aromatic compound to the unsubstituted diiodo aromatic compound is preferably in the range of 0.0001 to 5% by mass. The range is preferably 0.001 to 1% by mass.
- the elemental sulfur means a substance (S 8 , S 6 , S 4 , S 2, etc.) composed only of sulfur atoms, and its form is not limited. More specifically, the present invention may be used elemental sulfur which is commercially available as Tsuboneho medicament may be obtained generically, may be used a mixture containing S 8 and S 6 and the like.
- the purity of elemental sulfur is not particularly limited.
- the elemental sulfur may be in the form of particles or powder as long as it is solid at room temperature (23 ° C.).
- the particle size of the elemental sulfur is not particularly limited, but is preferably in the range of 0.001 to 10 mm, more preferably in the range of 0.01 to 5 mm, and still more preferably in the range of 0.01 to 3 mm.
- the polymerization inhibitor can be used without particular limitation as long as it is a compound that inhibits or stops the polymerization reaction in the polymerization reaction of the polyarylene sulfide resin.
- the polymerization inhibitor preferably contains a compound capable of introducing at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group at the end of the main chain of the polyarylene sulfide resin. That is, the polymerization inhibitor is preferably a compound having one or more groups selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a carboxyl group salt.
- the polymerization inhibitor may have the functional group, or the functional group may be generated by a polymerization termination reaction or the like.
- polymerization inhibitor having a hydroxy group or an amino group for example, one or more compounds selected from compounds represented by the following general formula (1) or (2) may be used.
- a monovalent group represented by the following formula (1-1) is introduced as a terminal group of the main chain.
- Y in the formula (1-1) is a hydroxy group, an amino group or the like derived from a polymerization inhibitor.
- a monovalent group represented by the following formula (2-1) is introduced as a terminal group of the main chain.
- a hydroxy group derived from the compound represented by the general formula (1) can be introduced into the polyarylene sulfide resin by, for example, bonding to a carbon atom of a carbonyl group in the formula (2) and a sulfur radical.
- the disulfide bond that is derived from the raw material (single sulfur) in the main chain of the polyarylene sulfide resin is radically cleaved at the melting temperature.
- the generated sulfur radical and the compound represented by the general formula (1) or the compound represented by the general formula (2) are considered to be introduced into the polyarylene sulfide resin.
- the existence of these structural units having a specific structure is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compound represented by the general formula (1) or (2).
- Examples of the compound represented by the general formula (1) include 2-iodophenol and 2-aminoaniline. Examples of the compound represented by the general formula (2) include 2-iodobenzophenone.
- polymerization inhibitor having a carboxyl group for example, one or more compounds selected from the compounds represented by the following general formula (3), (4) or (5) may be used.
- R 1 and R 2 each independently represent a hydrogen atom or a monovalent group represented by the following general formula (a), (b) or (c), and R 1 or At least one of R 2 is a monovalent group represented by the general formula (a), (b) or (c).
- Z represents an iodine atom or a mercapto group
- R 3 represents a monovalent group represented by the following General Formula (a), (b), or (c).
- R 4 is formula (a), represents a monovalent group represented by (b) or (c).
- X in the general formulas (a) to (c) is a hydrogen atom or an alkali metal atom, and is preferably a hydrogen atom from the viewpoint of good reactivity.
- the alkali metal atom include sodium, lithium, potassium, rubidium, and cesium, and sodium is preferable.
- R 10 represents an alkyl group having 1 to 6 carbon atoms.
- R 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 12 represents an alkyl group having 1 to 5 carbon atoms.
- Examples of the compound represented by the general formula (3) include 4,4'-dithiobisbenzoic acid.
- a monovalent group represented by the following formula (6) or (7) is introduced as a terminal group of the main chain.
- the presence of the terminal structural unit of these specific structures is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compound represented by the general formula (3), (4) or (5).
- R 5 represents a monovalent group represented by the general formula (a), (b) or (c)).
- R 6 represents a monovalent group represented by the general formula (a), (b) or (c)).
- a compound having no functional group such as a carboxyl group may be used.
- examples of such compounds include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, 2 At least one compound selected from-(morpholinothio) benzothiazole and N, N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide can be used.
- the polyarylene sulfide resin of the present embodiment is produced by performing melt polymerization in a melt mixture obtained by heating a mixture containing a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, and, if necessary, a catalyst. To do.
- the ratio of the diiodo aromatic compound in the molten mixture is preferably in the range of 0.5 to 2 moles, more preferably in the range of 0.8 to 1.2 moles per mole of elemental sulfur.
- the ratio of the polymerization inhibitor in the mixture is preferably in the range of 0.0001 to 0.1 mol, more preferably in the range of 0.0005 to 0.05 mol, with respect to 1 mol of solid sulfur. .
- the timing of adding the polymerization inhibitor is not particularly limited, but the temperature of the mixture is preferably 200 ° C. to 320 ° C. by heating the mixture containing the diiodo aromatic compound, elemental sulfur and the catalyst to be added as necessary.
- the polymerization inhibitor can be added when the temperature is within the range, more preferably within the range of 250 to 320 ° C.
- the polymerization rate can be adjusted by adding a nitro compound as a catalyst to the molten mixture.
- a nitro compound as a catalyst
- various nitrobenzene derivatives can be usually used.
- the nitrobenzene derivative include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol and 2,6-diiodo-4-nitroamine.
- the amount of the catalyst is usually an amount added as a catalyst, and is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of elemental sulfur, for example.
- the conditions for melt polymerization are appropriately adjusted so that the polymerization reaction proceeds appropriately.
- the temperature of the melt polymerization is preferably 175 ° C. or higher, the melting point of the polyarylene sulfide resin to be formed + 100 ° C. or lower, more preferably 180 to 350 ° C.
- the melt polymerization is carried out with an absolute pressure of preferably 1 [cPa] to 100 [kPa], more preferably 13 [cPa] to 60 [kPa].
- the conditions for melt polymerization need not be constant.
- the temperature is preferably in the range of 175 to 270 ° C., more preferably in the range of 180 to 250 ° C., and the absolute pressure is in the range of 6.7 to 100 [kPa], and then continuously or Polymerization is carried out while raising and lowering the temperature stepwise, and in the latter stage of polymerization, the temperature is preferably 270 ° C. or higher, the melting point of the polyarylene sulfide resin to be produced + 100 ° C. or lower, more preferably 300 to 350 ° C.,
- the polymerization can be carried out at an absolute pressure in the range of 1 [cPa] to 6 [kPa].
- the melting point of the resin means a value measured in accordance with JIS K 7121 using a differential scanning calorimeter (Perkin Elmer DSC device Pyris Diamond).
- the melt polymerization is preferably performed in a non-oxidizing atmosphere from the viewpoint of obtaining a high degree of polymerization while preventing oxidative crosslinking reaction.
- the oxygen concentration in the gas phase is preferably in the range of less than 5% by volume, more preferably in the range of less than 2% by volume, and more preferably the gas phase is substantially free of oxygen.
- the non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen, helium, and argon.
- the melt polymerization can be performed using, for example, a melt kneader equipped with a heating device, a decompression device, and a stirring device.
- a melt kneader equipped with a heating device, a decompression device, and a stirring device.
- the melt kneader include a Banbury mixer, a kneader, a continuous kneader, a single screw extruder, and a twin screw extruder.
- the molten mixture for melt polymerization does not substantially contain a solvent. More specifically, the amount of the solvent contained in the molten mixture is preferably 10 masses with respect to a total of 100 mass parts of the diiodo aromatic compound, elemental sulfur, the polymerization inhibitor, and, if necessary, the catalyst. Part or less, more preferably 5 parts by weight or less, and even more preferably 1 part by weight or less.
- the amount of the solvent may be 0 part by mass or more, 0.01 part by mass or more, or 0.1 part by mass or more.
- the melt mixture (reaction product) after the melt polymerization is cooled to obtain a solid state mixture
- the mixture is heated under reduced pressure or atmospheric pressure in a non-oxidizing atmosphere to further advance the polymerization reaction. Also good. As a result, not only can the molecular weight be increased, but also the generated iodine molecules are sublimated and removed, so the iodine atom concentration in the polyarylene sulfide resin can be kept low.
- the solid state mixture can be obtained by cooling to a temperature of preferably 100 to 260 ° C, more preferably 130 to 250 ° C, and even more preferably 150 to 230 ° C. Heating after cooling to the solid state can be performed under the same temperature and pressure conditions as in melt polymerization.
- the reaction product containing the polyarylene sulfide resin obtained by the melt polymerization step can be directly produced in a melt-kneader to produce a resin composition. It is preferable to prepare a dissolved product by adding a solvent in which the reaction product is dissolved, and to take out the reaction product from the reaction apparatus in the dissolved state because not only the productivity is improved but also the reactivity is improved.
- the addition of the solvent in which the reaction product is dissolved is preferably performed after the melt polymerization, but it may be performed in the later stage of the reaction of the melt polymerization, or as described above, the molten mixture (reaction product) is cooled to form a solid state.
- the polymerization reaction may be further advanced by heating the mixture under pressure, reduced pressure, or atmospheric pressure in a non-oxidizing atmosphere.
- the step of preparing the lysate may be performed in a non-oxidizing atmosphere.
- the temperature for dissolution by heating may be in the range of the melting point of the solvent in which the reaction product dissolves, preferably in the range of 200 to 350 ° C., more preferably in the range of 210 to 250 ° C.
- the amount is preferably in the range of 90 to 1000 parts by mass, and more preferably in the range of 200 to 400 parts by mass with respect to 100 parts by mass of the reaction product containing the sulfur sulfide resin.
- a solvent used as a polymerization reaction solvent in solution polymerization such as a Philips method
- preferable solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and ⁇ -caprolactam.
- Aliphatic cyclic amide compounds such as N-methyl- ⁇ -caprolactam, amide compounds such as hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA), polyethylene
- amide compounds such as hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA)
- polyethylene examples include etherified polyethylene glycol compounds such as glycol dialkyl ether (having a degree of polymerization of 2000 or less and an alkyl group having 1 to 20 carbon atoms), and sulfoxide compounds such as tetramethylene sulfoxide and dimethyl sulfoxide (DMSO). It is done.
- Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4′-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, 2,5- Diphenyloxazole, triphenylmethanol, N, N-diphenylformamide, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, pentachlorophenol, 1-benzyl-2-pyrrolidione, 9- Fluorenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrrolidinone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetate 1,4-d
- the melted product taken out from the reaction apparatus is subjected to post-treatment, and is then melt-kneaded with a resin other than the inorganic filler and polyarylene sulfide resin, which will be described later, and other additives (hereinafter sometimes referred to as other components).
- a resin other than the inorganic filler and polyarylene sulfide resin which will be described later
- other additives hereinafter sometimes referred to as other components.
- the method for post-treatment of the lysate is not particularly limited, and examples thereof include the following methods. (1) The solvent is used as it is or after adding an acid or a base, and then the solvent is distilled off under reduced pressure or normal pressure.
- Solvent such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon, and aliphatic hydrocarbon (soluble in the solvent of the dissolved material and at least A solvent which is a poor solvent for arylene sulfide resins) is added as a precipitating agent to precipitate a solid product containing polyarylene sulfide resin and inorganic salts, and the solid product is filtered, washed and dried. how to.
- Solvent such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon, and aliphatic hydrocarbon (soluble in the solvent of the dissolved material and at least A solvent which is a poor solvent for arylene sulfide resins) is added as a precipitating agent to precipitate a solid product containing polyarylene sulfide resin and inorganic salts, and the solid product is filtered, washed and dried.
- the polyarylene sulfide resin may be dried in a vacuum or in an inert gas atmosphere such as air or nitrogen. May be. It is also possible to oxidatively crosslink the polyarylene sulfide resin by performing heat treatment in an oxidizing atmosphere having an oxygen concentration in the range of 5 to 30% by volume or under reduced pressure conditions.
- Reaction formulas (1) to (5) are, for example, polyphenylene when diphenyl disulfide having a substituent R containing a group represented by general formula (a), (b) or (c) is used as a polymerization inhibitor. It is an example of reaction which sulfide produces
- Reaction formula (1) is a reaction in which the —SS— bond in the polymerization inhibitor undergoes radical cleavage at the melting temperature.
- the sulfur radical generated in the reaction formula (1) attacks the adjacent carbon atom of the terminal iodine atom of the growing main chain, and the iodine atom is detached, so that the polymerization is stopped, In this reaction, a substituent R is introduced at the end of the main chain.
- Reaction formula (3) is a reaction in which a disulfide bond existing in the main chain of the polyarylene sulfide resin derived from the raw material (single sulfur) is radically cleaved at the melting temperature.
- the reaction formula (4) the polymerization is stopped by recombination of the sulfur radical generated in the reaction formula (3) and the sulfur radical generated in the reaction formula (1), and the substituent R is at the end of the main chain.
- the detached iodine atom is in a free state (iodine radical), or iodine molecules are generated by recombination of iodine radicals as in reaction formula (5).
- the reaction product containing polyarylene sulfide resin obtained by melt polymerization contains iodine atoms derived from the raw material. Therefore, the polyarylene sulfide resin is usually used for the preparation of a resin composition in the form of a mixture containing iodine atoms.
- the concentration of iodine atoms in the mixture is, for example, in the range of 0.01 to 10,000 ppm, preferably in the range of 10 to 5000 ppm with respect to the polyarylene sulfide resin. It is also possible to keep the iodine atom concentration low by utilizing the sublimability of iodine molecules.
- the range it is possible to set the range to 900 ppm or less, preferably 100 ppm or less, and further 10 ppm or less. It is. Although it is possible to remove iodine atoms below the detection limit, it is not practical in view of productivity.
- the detection limit is, for example, about 0.01 ppm.
- the polyarylene sulfide resin of the present embodiment obtained by melt polymerization or the reaction product containing the same includes an iodine atom. It can be clearly distinguished from polyarylene sulfides obtained by legal methods.
- the polyarylene sulfide resin obtained by melt polymerization is mainly composed of an arylene sulfide unit composed of an aromatic ring derived from a diiodo aromatic compound and a sulfur atom directly bonded thereto. It includes a main chain and a predetermined substituent R bonded to the end of the main chain.
- the predetermined substituent R is bonded to the aromatic ring at the end of the main chain directly or via a partial structure derived from a polymerization inhibitor.
- the polyphenylene sulfide resin as the polyarylene sulfide resin according to one embodiment is, for example, the following general formula (10):
- the repeating unit represented by the formula (10) has the following formula (10a) bonded at the para position:
- a repeating unit bonded at the para position represented by the formula (10a) is preferable in terms of heat resistance and crystallinity of the resin.
- the polyphenylene sulfide resin according to one embodiment has the following general formula (11):
- R 20 and R 21 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.
- bonded with the aromatic ring represented by these may be included.
- the polyphenylene sulfide resin does not substantially contain the repeating unit of the general formula (11) from the viewpoints of crystallinity and heat resistance. More specifically, the ratio of the repeating unit represented by formula (11) is preferably based on the total of the repeating unit represented by formula (10) and the repeating unit represented by formula (11). The range is 2% by mass or less, and more preferably 0.2% by mass or less.
- the polyarylene sulfide resin of the present embodiment is mainly composed of the above arylene sulfide units, but usually derived from the elemental sulfur of the raw material, the following formula (20):
- a structural unit related to a disulfide bond represented by the formula is also included in the main chain.
- the proportion of the structural unit represented by the formula (20) is preferably 2 with respect to the total of the arylene sulfide unit and the structural site represented by the formula (20).
- the range is 9% by mass or less, and more preferably 1.2% by mass or less.
- Mw / Mtop of the polyarylene sulfide resin according to the present embodiment is in the range of 1.2 to 3.5, preferably in the range of 1.7 to 2.5, more preferably 1.7 or more.
- the range is 2.3 or less, particularly preferably 1.7 or more and 2.2 or less.
- 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 weight average molecular weight of the polyarylene sulfide resin according to this embodiment is preferably in the range of 36,000 to 105,000, and more preferably in the range of 51,000 to 75,000.
- the non-Newtonian index of the polyarylene sulfide resin according to this embodiment is in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4, more preferably 1.2.
- the range is 1.3 or more.
- 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.
- the polyarylene sulfide resin having an Mw / Mtop and a non-Newtonian index in the above specific range includes a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, the diiodo aromatic compound, the elemental sulfur, and the polymerization inhibition.
- a polyarylene sulfide resin can be obtained by increasing the molecular weight to some extent.
- the melting point of the polyarylene sulfide resin according to this embodiment is preferably in the range of 250 to 300 ° C., more preferably in the range of 265 to 300 ° C.
- the melt viscosity (V6) at 300 ° C. of the polyarylene sulfide resin is preferably in the range of 1 to 2000 [Pa ⁇ s], more preferably in the range of 5 to 1700 [Pa ⁇ s].
- 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, more preferably in the range of 75 to 85.
- 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 when the polyarylene sulfide resin according to the present embodiment is heated 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 may further contain one or more inorganic fillers without departing from the spirit of the present invention.
- 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.
- 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.
- thermoplastic resin blended in the polyarylene sulfide resin composition examples 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—).
- 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.
- diamines for obtaining polyamides include aliphatic diamines, aromatic diamines, and alicyclic diamines.
- aliphatic diamine a diamine having 3 to 18 carbon atoms having a straight chain or a side chain is preferable.
- 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.
- aromatic diamine a diamine having 6 to 27 carbon atoms having a phenylene group is preferable.
- 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′-diaminobenzophen
- alicyclic diamine a diamine having 4 to 15 carbon atoms having a cyclohexylene group is preferable.
- suitable alicyclic diamines include 4,4'-diamino-dicyclohexylenemethane, 4,4'-diamino-dicyclohexylenepropane, 4,4'-diamino-3,3'-dimethyl- Examples include dicyclohexylene methane, 1,4-diaminocyclohexane, and piperazine. These can be used alone or in combination of two or more.
- dicarboxylic acid for obtaining the polyamide examples include aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and alicyclic dicarboxylic acid.
- aliphatic dicarboxylic acid a saturated or unsaturated dicarboxylic acid having 2 to 18 carbon atoms is preferable.
- 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.
- the aromatic dicarboxylic acid is preferably a dicarboxylic acid having 8 to 15 carbon atoms having a phenylene group.
- 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 And acid, 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.
- polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range
- the aminocarboxylic acid is preferably an aminocarboxylic acid having 4 to 18 carbon atoms.
- 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.
- lactam for obtaining the polyamide examples include ⁇ -caprolactam, ⁇ -laurolactam, ⁇ -enantolactam, and ⁇ -capryllactam. These can be used alone or in combination of two or more.
- Preferred polyamide raw material combinations include ⁇ -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 / ⁇ -caprolactam, 1,6-hexamethylenediamine / terephthalic acid / adipic acid, 1,9-nonamethylenediamine / terephthalic acid Acids, 1,9-nonamethylenediamine / terephthalic acid / ⁇ -caprolactam, 1,9-nonamethylenediamine / 1,6-hexamethylenediamine / terephthalic acid / adipic acid, and m-xylylenediamine / adipic acid It is done.
- 1,4-tetramethylenediamine / adipic acid nylon 4,6
- 1,6-hexamethylenediamine / terephthalic acid / ⁇ -caprolactam 1,6-hexamethylenediamine / terephthalic acid / adipic acid
- 1,9-nonamethylenediamine / terephthalic acid 1,9-nonamethylenediamine / terephthalic acid / ⁇ -caprolactam
- 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.
- thermoplastic elastomer is often used as the elastomer blended in the polyarylene sulfide resin composition.
- thermoplastic elastomer examples include polyolefin elastomers, fluorine elastomers, and silicone elastomers. In the present specification, the thermoplastic elastomer is classified not as the thermoplastic resin but as an elastomer.
- the elastomer (particularly thermoplastic elastomer) preferably has a functional group capable of reacting with the group represented by the formula (1).
- a functional group capable of reacting with the group represented by the formula (1).
- 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- 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 ⁇ -olefin and a vinyl polymerizable compound having the functional group.
- Examples of the ⁇ -olefin include ⁇ -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 ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid, and the like.
- Other examples include ⁇ , ⁇ -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.
- 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 groups represented are preferable from the viewpoint of improving toughness and impact resistance.
- the elastomer content varies depending on the type and application, it cannot be generally defined. 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 in the range of parts by mass, more preferably in the range of 5 to 45 parts by mass. 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.
- 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.
- the crosslinkable resin include an epoxy resin, a phenol resin, and a urethane resin.
- an aromatic epoxy resin is preferable.
- the aromatic epoxy resin may have a halogen group or a hydroxyl group.
- 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.
- aromatic epoxy resins can be used alone or in combination of two or more.
- 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 capable of reacting with the group represented by the formula (1).
- silane compounds include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ -glycidoxypropylmethyl.
- silane coupling agents such as diethoxysilane and ⁇ -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. .
- 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.
- 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.
- Polyarylene sulfide resin can be obtained in the form of pellets.
- 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 preferably in the range of 250 to 350 ° C., for example, 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.
- 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.
- the polymer is filtered through a filter and discharged from a T-die base into a sheet.
- the sheet-like material is brought into close contact with a cooling drum set so that the surface temperature is in a range of 20 to 70 ° C., and is cooled and solidified, whereby a substantially unoriented film can be obtained.
- the set temperature of the filter part and the die is preferably 0 to 20 ° C. higher than the temperature of the melt part of the melt extruder, more preferably 5 to 15 ° C.
- the unstretched film can be biaxially oriented by further performing biaxial stretching or the like.
- 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.
- an unstretched polyarylene sulfide film is heated with a heated roll group, and the film is stretched using the difference in rotational speed of the rolls.
- 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, the range of 2.8 to 3.2 times is more preferable.
- 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 in the range of Tg to (Tg + 30) ° C. when the glass transition temperature of the polyarylene sulfide resin is Tg, and in the range of (Tg + 5) to (Tg + 20) ° C. More preferably.
- Examples of a 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.
- the stretch 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 from the viewpoint of improving the elongation at break of the film.
- 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.
- 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 ⁇ m.
- 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.
- 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. Further, 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.
- 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 specified 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 ⁇ m or more, and more preferably 150 ⁇ m or more, from the viewpoint of followability during molding.
- the upper limit is preferably in the range of 1000 ⁇ m or less, and more preferably in the range of 500 ⁇ m or less.
- 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.
- a film having a thickness of less than 200 ⁇ m and a thickness of 200 ⁇ m or more is used.
- the distinction between sheets is described.
- the film forming method can be applied to a composition containing the 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.
- 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).
- Non-Newtonian Index 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.
- Mw and Mw / Mtop (molecular weight distribution) The weight average molecular weight Mw and the peak molecular weight Mtop of the polyarylene sulfide resin were measured using gel permeation chromatography under the following measurement conditions. Mw / Mtop was calculated from the obtained Mw and Mtop.
- Measuring device “Tensilon AMF / RTA-100” automatic strength measuring device for film strength made by Orientec Co., Ltd. Sample size: width 10 mm x length 150 mm, sample length 100 mm Pulling speed: 300mm / min
- Processing characteristics The elongation at break of either the longitudinal direction or the width direction of the film at 160 ° C. is 100% or more, and the breaking stress of 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”.
- 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 “ ⁇ ” was designated as “ ⁇ ”, and the case where no film breakage occurred was designated as “ ⁇ ”.
- Synthesis of polyarylene sulfide resin (Synthesis Example 1) 30-part by mass of p-diiodobenzene (Tokyo Kasei Co., Ltd., p-diiodobenzene purity of 98.0% or more), 27.00 parts by mass of solid sulfur (sulfur (powder) manufactured by Kanto Chemical Co., Inc.), 4 , 4′-dithiobisbenzoic acid (4,4′-dithiobisbenzoic acid, Technical Grade, manufactured by Wako Pure Chemical Industries, Ltd.) was heated to 180 ° C. and melted and mixed under nitrogen. Next, the temperature was raised to 220 ° C., and the pressure was reduced to an absolute pressure of 26.6 kPa.
- the obtained molten mixture was melt polymerized for 8 hours by changing the temperature and pressure stepwise so that the absolute pressure was 133 Pa at 320 ° C.
- 200 parts by mass of NMP was added, heated and stirred at 220 ° C., and the resulting dissolved product was filtered.
- 320 parts by mass of NMP was added to the lysate after filtration, and the cake was washed and filtered.
- 1000 parts by mass of ion-exchanged water was added and stirred in an autoclave at 200 ° C. for 10 minutes. Next, the cake was filtered, and 1000 parts by mass of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake.
- the internal pressure was controlled to 0.22 MPa, and Na 2 S ⁇ xH 2 O 1500 parts by mass, NaSH -A liquid mixture of 225 parts by mass of yH 2 O and 425 parts by mass of water (Na 2 S: 11.4 kgol, NaSH: 3.2 kgol, water 50.3 wt%) was added dropwise over 3 hours.
- dehydration was performed simultaneously, water was removed from the system, and p-DCB distilled together with water was continuously returned to the autoclave. The dehydration operation and the operation for returning the p-DCB were performed until the temperature was raised to 240 ° C., and the system was sealed when the temperature was raised.
- the internal temperature was raised to 240 ° C. and held at that temperature for 1 hour to complete the reaction, Cooled to room temperature.
- the amount of water in the reaction system at the end of the reaction was 0.17 (mol / mol) with respect to the total sulfidizing agent used.
- the resulting reaction slurry was heated to 120 ° C. under reduced pressure ( ⁇ 0.08 MPa) to distill off the reaction solvent, and water was poured into the residue and stirred at 80 ° C. for 1 hour, followed by filtration. The cake was stirred again with hot water for 1 hour, washed, and then filtered. This operation was repeated three times, water was further added, the mixture was stirred at 200 ° C. for 1 hour, filtered, and dried with a hot air dryer at 120 ° C. for 10 hours to obtain a white powdery polymer.
- 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.
- a filter set at a temperature of 330 ° C.
- This unstretched film was used in a longitudinal direction of the film at a film temperature of 101 ° C. at a film temperature of 101 ° C. by using a difference in the winding speed of the roll after Yonetsu using a longitudinal stretching machine composed of a plurality of heated roll groups.
- 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).
- 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.
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Abstract
Description
(1)当該溶解物を、そのまま、又は酸若しくは塩基を加えた後、減圧下又は常圧化で溶媒を留去し、次いで溶媒留去後の固形物を水、当該溶解物に用いた溶媒(又は低分子ポリマーに対して同等の溶解度を有する有機溶媒)、アセトン、メチルエチルケトン、及びアルコール類などから選ばれる溶媒で1回又は2回以上洗浄し、更に中和、水洗、濾過及び乾燥する方法。
(2)当該溶解物に水、アセトン、メチルエチルケトン、アルコール、エーテル、ハロゲン化炭化水素、芳香族炭化水素、及び脂肪族炭化水素などの溶媒(当該溶解物の溶媒に可溶であり、且つ少なくともポリアリーレンスルフィド樹脂に対しては貧溶媒である溶媒)を沈降剤として添加して、ポリアリーレンスルフィド樹脂及び無機塩等を含む固体状生成物を沈降させ、固体状生成物を濾別、洗浄及び乾燥する方法。
(3)当該溶解物に、当該溶解物に用いた溶媒(又は低分子ポリマーに対して同等の溶解度を有する有機溶媒)を加えて撹拌した後、濾過して低分子量重合体を除いた後、水、アセトン、メチルエチルケトン、及びアルコールなどから選ばれる溶媒で1回又は2回以上洗浄し、その後中和、水洗、濾過及び乾燥をする方法。
で表される、芳香族環に結合した側鎖としての置換基を有する繰り返し単位を含み得る。ただし、結晶化度及び耐熱性の低下の観点から、ポリフェニレンスルフィド樹脂は、一般式(11)の繰り返し単位を実質的に含まないことが好ましい。より具体的には、式(11)で表される繰り返し単位の割合は、式(10)で表される繰り返し単位と式(11)で表される繰り返し単位との合計に対して、好ましくは2質量%以下の範囲、より好ましくは0.2質量%以下の範囲である。
D=α×Sn
(上記式中、Dはせん断速度を表し、Sはせん断応力を表し、αは定数を表し、nは非ニュートニアン指数を表す。)
1-1.ポリアリーレンスルフィド樹脂の溶融粘度
ポリアリーレンスルフィド樹脂を島津製作所製フローテスター、CFT-500Cを用い、300℃、荷重:1.96×106Pa、L/D=10/1にて、6分間保持した後に溶融粘度を測定した。
ダイアンインスツルメンツ燃焼ガス吸収装置を用い、ポリアリーレンスルフィド樹脂を燃焼させ、発生したガス及び残渣を純水に吸収させた。吸収液中のヨウ素イオンをダイオネクスイオンクロマトグラフで定量した。
白色度(ホットプレスL*値)は、ポリアリーレンスルフィド樹脂を320℃で1.5分間予熱後、320℃で1.5分間、続けて130℃で1.5分間、30kg/cm2の圧力でホットプレスにより加圧成形して円盤状プレートを作製した。これについて、色彩色差計(東京電色株式会社製、Color Ace)を用いて測定した。
ポリアリーレンスルフィド樹脂をキャピラリーレオメーターにて、温度300℃の条件下、直径1mm、長さ40mmのダイスを用いて100~1000(sec-1)の剪断速度に対する剪断応力を測定し、これらの対数プロットした傾きから計算した値である。
ポリアリーレンスルフィド樹脂の重量平均分子量Mw及びピーク分子量Mtopを、ゲル浸透クロマトグラフィーを用いて、下記の測定条件により測定した。得られたMw及びMtopからMw/Mtopを算出した。6種類の単分散ポリスチレンを校正に用いた。 装置:超高温ポリマー分子量分布測定装置(株式会社センシュー科学製「SSC-7000」)
カラム:UT-805L(昭和電工株式会社製)
カラム温度:210℃
溶媒:1-クロロナフタレン
測定方法:UV検出器(360nm)
ガスクロマトグラフ質量分析装置を用いて、ポリアリーレンスルフィド樹脂又は樹脂組成物の所定量のサンプルを325℃で15分間加熱し、そのときの発生ガス量を質量%として定量した。
ASTM-D882に規定された方法に従って、インストロンタイプの引張試験機を用いて測定した。測定は下記の条件で行い、試料数10にて、フィルム長手方向、および幅方向のそれぞれについて平均値をとり、下記式にて50%平均破断応力、50%平均破断伸度を算出した。
50%平均破断応力=(フィルム長手方向における応力の平均値+フィルム幅方向における応力の平均値)/2
50%平均破断伸度=(フィルム長手方向における伸度の平均値+フィルム幅方向における伸度の平均値)/2
測定装置:オリエンテック(株)製フィルム強伸度自動測定装置“テンシロンAMF/RTA-100”
試料サイズ:幅10mm×長さ150mm、試長間100mm
引張り速度:300mm/分
JIS C-2318に規定された方法にしたがって測定した。試料幅10mm、試料長200mmのサンプルをギアオーブンにより150℃、30分間の条件下で熱処理し、試料長の変化から、下記式により熱収縮率を算出した。
熱収縮率(%)=[(熱処理前の長さ-熱処理後の長さ)/熱処理前の長さ]×100
160℃におけるフィルムの長手方向あるいは幅方向のどちらか一方の破断伸度が100%以上であり、かつ、160℃におけるフィルムの長手方向あるいは幅方向のどちらか一方の破断応力が30~80MPaの範囲である場合に限り、加工特性を「○」とし、それ以外の場合を加工特性「×」とした。
製膜時のフィルム破れは、合計時間24時間にわたり連続製膜を行った際、フィルム破れが5回以上起きた場合を「×」、フィルム破れが1回以上5回未満の範囲で起きた場合を「△」、フィルム破れが1回も発生しなかった場合を「○」とした。
(合成例1)
p-ジヨードベンゼン(東京化成株式会社、p-ジヨードベンゼン純度98.0%以上)300.0質量部、固体硫黄(関東化学株式会社製、硫黄(粉末))27.00質量部、4,4’-ジチオビス安息香酸(和光純薬工業株式会社製、4,4’-ジチオビス安息香酸、Technical Grade)1.0質量部を180℃に加熱してそれらを窒素下で溶融、混合した。次に220℃に昇温し、絶対圧26.6kPaまで減圧した。得られた溶融混合物を、320℃で絶対圧133Paとなるように、段階的に温度と圧力変化させて、8時間溶融重合した。反応終了後、NMP200質量部を加えて、220℃で加熱撹拌し、得られた溶解物をろ過した。ろ過後の溶解物にNMP320質量部を加え、ケーキを洗浄ろ過した。得られたNMPを含むケーキにイオン交換水1000質量部を加え、オートクレーブ中で200℃10分間攪拌した。次いでケーキをろ過し、ろ過後のケーキに70℃のイオン交換水1000質量部を加えケーキを洗浄した。得られた含水ケーキにイオン交換水1000質量部を加えて10分間攪拌した。次いでケーキをろ過し、ろ過後のケーキに70℃のイオン交換水1000質量部を加えケーキを洗浄した。この操作をもう一度繰り返した後、ケーキを120℃で4時間乾燥し、PPS樹脂91質量部を得た。
前記「4,4’-ジチオビス安息香酸1.0質量部」の替りに、「4,4’-ジチオビス安息香酸0.60質量部」を用いたこと以外は合成例1と同様にしてPPS樹脂89質量部を得た。
前記「4,4’-ジチオビス安息香酸1.0質量部」の替りに「ジフェニルジスルフィド(住友精化株式会社 DPDS)1.0質量部」を用いたこと以外は合成例1と同様にしてPPS樹脂91質量部を得た。
前記「4,4’-ジチオビス安息香酸1.0質量部」の替りに、「4,4’-ジチオビス安息香酸2.0質量部」を用いたこと以外は合成例1と同様にしてPPS樹脂86質量部を得た。
p-ジヨードベンゼン300.0質量部、2,5-ジヨード安息香酸170.0質量部、固体硫黄27.00質量部、ジフェニルジスルフィド0.60質量部を180℃に加熱してそれらを窒素下で溶融、混合した。以後の操作を合成例1と同様に行い、側鎖にカルボキシ基を有するPPS樹脂95質量部を得た。
前記「4,4’-ジチオビス安息香酸1.0質量部」の替りに、「4,4’-ジチオビス安息香酸0.15質量部」を用いたこと以外は合成例1と同様にしてPPS樹脂93質量部を得た。
温度センサー、冷却塔、滴下槽、滴下ポンプ、留出物分離槽を連結した攪拌翼付チタン製反応釜にパラジクロロベンゼン(以下、「p-DCB」と略記する。)1838質量部(12.5キロモル)、N-メチルピロリドン(以下、「NMP」と略記する。)4958k質量部(50キロモル)、水90質量部(5.0キロモル)を室温で仕込み、攪拌しながら窒素雰囲気下で100℃まで20分かけて昇温し、系を閉じ、さらに220℃まで40分かけて昇温し、その温度で内圧を0.22MPaにコントロールして、Na2S・xH2O 1500質量部、NaSH・yH2O 225質量部、水425質量部の混合液(Na2S:11.4キロモル、NaSH:3.2キロモル、水分50.3質量%)を3時間かけて滴下した。滴下中は同時に脱水操作を行い、水は系外に除去し、水と共に留出するp-DCBは連続的にオートクレーブに戻した。
なお、脱水操作とp-DCBを戻す操作は240℃昇温完了まで行い、昇温完了時に系を密閉した。
その後、そのままの温度圧力で1時間保持した後、1時間かけて、内圧を0.17MPaに下げながら、内温を240℃まで昇温し、その温度で1時間保持して反応を終了し、室温まで冷却した。留出液の分析結果によると、反応終了時の反応系内の水分量は全使用スルフィド化剤に対して0.17(モル/モル)であった。
得られた反応スラリーを減圧下(-0.08MPa)、120℃に加熱することにより反応溶媒を留去し、残査に水を注いで80℃で1時間攪拌した後、濾過した。このケーキを再び湯で1時間攪拌、洗浄した後、濾過した。
この操作を3回繰り返し、さらに水を加え、200℃で1時間攪拌後、濾過し、熱風乾燥機で120℃-10時間乾燥して白色粉末状のポリマーを得た。
合成例1~7で得られた白色粉末状のポリマーをタンブラーを用いて均一に混合した後、2軸混練押出機(TEM-35B、東芝機械)を用いて300℃で溶融混練して、ペレット状のポリマーを得た。得られたペレットを溶融部が320℃に加熱された押出機に供給した。押出機で溶融したポリマーを温度330℃に設定したフィルターでろ過した後、温度310℃に設定した口金から溶融押出して表面温度25℃のキャストドラムに正電荷を印加させながら密着させ冷却固化することで、未延伸フィルムを作製した。
Claims (3)
- ポリアリーレンスルフィド樹脂又はこれを含む組成物からなるポリアリーレンスルフィドフィルムであって、
前記ポリアリーレンスルフィド樹脂が、ジヨード芳香族化合物と、単体硫黄と、重合禁止剤とを、前記ジヨード芳香族化合物、前記単体硫黄及び前記重合禁止剤を含む溶融混合物中で反応させることを含む方法により得ることのできるものであり、
前記ポリアリーレンスルフィド樹脂が、300℃における1.1以上1.5以下の非ニュートニアン指数、及び、1.2以上3.5以下のMw/Mtopを有し、
前記Mw及びMtopはそれぞれゲル浸透クロマトグラフィーにより測定される重量平均分子量及びピーク分子量である、ポリアリーレンスルフィドフィルム。 - 前記ポリアリーレンスルフィド樹脂が、前記重合禁止剤に由来するヒドロキシ基、アミノ基、カルボキシル基及びカルボキシル基の塩からなる群より選ばれる少なくとも一種の基を有する、請求項1記載のポリアリーレンスルフィドフィルム。
- ポリアリーレンスルフィド樹脂又はこれを含む組成物を製膜する工程を有し、
前記ポリアリーレンスルフィド樹脂が、ジヨード芳香族化合物と、単体硫黄と、重合禁止剤とを、前記ジヨード芳香族化合物、前記単体硫黄及び前記重合禁止剤を含む溶融混合物中で反応させることを含む方法により得ることのできるものであり、
前記ポリアリーレンスルフィド樹脂が、300℃における1.1以上1.5以下の非ニュートニアン指数、及び、1.2以上3.5以下のMw/Mtopを有し、
前記Mw及びMtopはそれぞれゲル浸透クロマトグラフィーにより測定される重量平均分子量及びピーク分子量である、ポリアリーレンスルフィドフィルムの製造方法。
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