Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions 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; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions 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; Compositions of polysulfones; Compositions of derivatives of such polymers

Definitions

• the present invention relates to a polyarylene sulfide resin composition and a molded product thereof.
• a polyarylene sulfide resin (hereinafter sometimes abbreviated as “PAS resin”) typified by a polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”) is highly flame retardant without using a halogen-based flame retardant. As a result, it has attracted attention as a halogen-free material.
• the polyphenylene sulfide resin can be produced, for example, by solution polymerization in which p-dichlorobenzene and sodium sulfide, or sodium hydrosulfide and sodium hydroxide are used as raw materials in a polymerization reaction in an organic polar solvent (for example, Patent Documents). 1 and 2).
• Patent Documents for example, Patent Documents 1 and 2.
• Currently commercially available polyphenylene sulfide resins are generally produced by this method.
• the polymerization product obtained by this method generally contains a by-product such as sodium chloride and an organic polar solvent, a purification treatment for removing them is required. Even if purification treatment is performed, it is often difficult to sufficiently remove chlorine atoms in the resin.
• a method for producing a polyarylene sulfide resin As another method for producing a polyarylene sulfide resin, a method is known in which a diiodo aromatic compound and elemental sulfur are melt polymerized without using a chlorine atom-containing raw material and a polar solvent (Patent Documents 3, 4, and 5). reference). Although the polyarylene sulfide resin obtained by this method contains an iodine atom, the iodine atom is relatively easily and sufficiently obtained by heating the polymerization reaction product or the reaction soul after the polymerization reaction under reduced pressure to sublimate the iodine. To a low concentration. That is, according to this melt polymerization method, it is expected that a polyarylene sulfide resin substantially free of chlorine atoms and having a sufficiently reduced halogen atom concentration can be easily produced.
• the polyarylene sulfide resin obtained by the above-described melt polymerization method has a relatively large amount of gas generated by heating at the time of molding or the like, and further improvement is required in this respect.
• a resin composition prepared by mixing polyarylene sulfide resin with other materials such as an inorganic filler, various thermoplastic resins, and elastomers the problem of gas generation tended to be remarkable. If the amount of gas generated is large, problems such as deterioration of the quality of the molded product may occur. Therefore, it is practically very important as a molding material to suppress gas generation.
• the main problem to be solved by the present invention is to suppress the amount of gas generated by heating in a resin composition containing a polyarylene sulfide resin by a method of melt polymerization of a diiodo aromatic compound and elemental sulfur. is there.
• the present inventors have solved the above problem by using a polymerization inhibitor having a specific functional group in a method for producing a polyarylene sulfide resin that is melt-polymerized with a diiodo aromatic compound and elemental sulfur.
• the present inventors have found that this can be done and have completed the present invention.
• the present invention is selected from the group consisting of a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a crosslinkable resin having two or more crosslinkable functional groups
• the present invention relates to a polyarylene sulfide resin composition containing one type of other component (hereinafter sometimes simply referred to as “the other component”).
• the polyarylene sulfide resin includes a diiodo aromatic compound, elemental sulfur, and the following general formula (1):
• X represents a hydrogen atom or an alkali metal atom.
• a polymerization inhibitor having a group represented by formula (1) can be obtained by a method comprising reacting in a molten mixture containing the diiodo aromatic compound, the elemental sulfur and the polymerization inhibitor.
• the polyarylene sulfide resin composition according to the present invention may be substantially free of chlorine atoms and sufficiently reduced in the concentration of halogen atoms. Furthermore, the polyarylene sulfide resin composition according to the present invention comprises a polyarylene sulfide resin, an inorganic filler, a thermoplastic resin, an elastomer, and another component selected from a crosslinkable resin having two or more crosslinkable functional groups. Based on the combination, excellent characteristics can be exhibited in terms of mechanical properties, acid resistance, alkali resistance, hot water resistance, and cavity balance.
• the cavity balance is related to the uniformity of the filling degree of each cavity when a plurality of molded articles are molded simultaneously by injection molding using a mold having a plurality of cavities. If the cavity balance of the molding material is not sufficient, there is a tendency that molding defects such that some of the cavities are not sufficiently filled tend to occur.
• the polyarylene sulfide resin composition according to this embodiment contains a polyarylene sulfide resin such as a polyphenylene sulfide resin.
• This polyarylene sulfide resin includes a diiodo aromatic compound, elemental sulfur, and the following general formula (1):
• X represents a hydrogen atom or an alkali metal atom. It is obtained by a method comprising reacting a diiodo aromatic compound, elemental sulfur and a polymerization inhibitor in a molten mixture containing a polymerization inhibitor having a group represented by the formula:
• 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.
• substitution positions of two iodine atoms are not particularly limited, 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. More preferably, it is in the range of 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 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.
• polymerization inhibitor As a polymerization inhibitor having a group represented by the formula (1) (hereinafter sometimes simply referred to as “polymerization inhibitor”), it has one or more groups represented by the general formula (1), And if it is a compound which prohibits or stops the said polymerization reaction in the polymerization reaction of polyarylene sulfide resin, it can use without a restriction
• polymerization inhibitor examples 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, directly or via other partial structures in the conjugated aromatic ring And a compound having a group represented by the general formula (1) bonded together. If necessary, a compound having no group represented by the formula (1) may be used in combination as a polymerization inhibitor.
• X in the formula (1) is a hydrogen atom or an alkali metal atom, but a hydrogen atom is preferable from the viewpoint of good reactivity.
• alkali metal atom include sodium, lithium, potassium, rubidium, and cesium, and sodium is preferable.
• the polymerization inhibitor preferably contains one or more compounds selected from the compounds represented by the following general formula (2), (3) or (4).
• 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), R 1 or R At least one of 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 represents a monovalent group represented by the general formula (a), (b) or (c).
• X in the formulas (a) to (c) is synonymous with X in the formula (1), including preferred embodiments thereof.
• 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, and R 12 represents an alkyl group having 1 to 5 carbon atoms.
• 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 proportion 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, 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 and the melting point of the polyarylene sulfide resin to be produced is + 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 less than 5% by volume, more preferably 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 optionally the catalyst. Part or less, more preferably 5 parts by weight or less, and still 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, but the reaction product contains the reaction product. It is preferable to prepare a dissolved product by adding a solvent in which the product is dissolved, and 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. It is preferable to carry out with.
• the mixing ratio of the solvent in which the reaction product is used for preparing the dissolved product is preferably 90 to 1000 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the reaction product containing the polyarylene sulfide resin.
• the range is 200 to 400 parts by mass.
• 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). .
• 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 preferably post-treated and then melt-kneaded with the other components to prepare a resin composition because the reactivity becomes better.
• 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. (Or an organic solvent having an equivalent solubility in a low molecular weight polymer), a method of washing once or more with a solvent selected from acetone, methyl ethyl ketone, and alcohols, and further neutralizing, washing with water, filtering and drying .
• 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.
• a reaction in which a polyarylene sulfide resin having a group represented by the general formula (1) at the terminal is generated by melt polymerization is exemplified below.
• Reaction formulas (1) to (5) are examples of reactions in which polyphenylene sulfide is formed using diphenyl disulfide having a substituent R containing a group represented by general formula (1) as a polymerization inhibitor.
• 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,
• a group represented by the formula (1) is introduced at the end of the main chain.
• Reaction formula (3) is a reaction in which a disulfide bond present 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 group represented by the formula (1) Is a reaction introduced 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 polyarylene sulfide resin of the present embodiment obtained by melt polymerization or the reaction product containing the same includes an iodine atom, so that, for example, a solution weight of a dichloroaromatic compound such as a Philips method in an organic polar solvent is used. 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.
• a main chain and a group of the general formula (1) bonded to an end of the main chain.
• the group of the general formula (1) 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):
• 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). It is 2 mass% or less, More preferably, it is 0.2 mass% or less.
• the polyarylene sulfide resin according to the present embodiment has, for example, a monovalent group represented by the following general formula (6) or (7) as a structural unit at the end of the main chain.
• the existence of the terminal structural unit of the specific structure is characteristic of the polyarylene sulfide resin obtained by melt polymerization according to the present embodiment.
• 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)).
• 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.
• 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 polyarylene sulfide resin composition according to the present embodiment can contain one or more inorganic fillers.
• inorganic fillers include powdery fillers such as carbon black, calcium carbonate, silica and titanium oxide, plate-like fillers such as talc and mica, granular fillers such as glass beads, silica beads and glass balloons, and glass fibers. And fibrous fillers such as carbon fiber and wollastonite fiber, and glass flakes. It is particularly preferable that the polyarylene sulfide resin composition contains at least one inorganic filler selected from the group consisting of glass fiber, carbon fiber, carbon black, and calcium carbonate.
• the content of the inorganic filler is preferably in the range of 1 to 300 parts by mass, more preferably in the range of 5 to 200 parts by mass, and still more preferably 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 maintaining the mechanical strength of the molded product.
• the polyarylene sulfide resin composition according to this embodiment may contain a resin other than the polyarylene sulfide resin selected from thermoplastic resins, elastomers, and crosslinkable resins. These resins can be blended in the resin composition together with the inorganic filler.
• 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.
• the aromatic diamine is preferably a diamine having 6 to 27 carbon atoms having a phenylene group.
• 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
• 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.
• aromatic dicarboxylic acid a dicarboxylic acid having 8 to 15 carbon atoms having a phenylene group is preferable.
• 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
• 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 a hydroxy group or an amino group.
• a functional group capable of reacting with a hydroxy group or an amino group.
• Such functional groups include epoxy groups, carboxy groups, isocyanate groups, oxazoline groups, and the formula: R (CO) O (CO)-or R (CO) O- (wherein R is from 1 to 8 carbon atoms)
• R (CO) O (CO)-or R (CO) O- wherein R is from 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 ensuring the heat resistance and toughness of the molded product.
• the crosslinkable resin blended in the polyarylene sulfide resin composition has two or more crosslinkable functional groups.
• 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 in these ranges, the effect of improving the rigidity and heat resistance of the molded product can be obtained particularly remarkably.
• the polyarylene sulfide resin composition can contain a silane compound having a functional group capable of reacting with 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 the present embodiment may contain other additives such as a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant. Good.
• the content of the additive is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin, for example.
• the polyarylene sulfide resin composition can be obtained, for example, in the form of a pellet-like compound by a method of melt-kneading the polyarylene sulfide resin obtained by the above method 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 polyarylene sulfide resin composition according to the present embodiment can be used alone or in combination with materials such as the above-mentioned other components, by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding, It can be processed into a molded product having excellent molding processability and dimensional stability. Since the polyarylene sulfide resin composition according to the present embodiment generates a small amount of gas when heated, it enables easy production of a high-quality molded product.
• the polyarylene sulfide resin composition according to the present embodiment also has various performances such as heat resistance and dimensional stability inherent to the polyarylene sulfide resin, for example, a connector, a printed circuit board, a sealed molded product, etc.
• Automotive parts such as electric / 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, for example, injection molding and compression It can be used to obtain by molding.
• the polyarylene sulfide resin composition according to the present embodiment is widely useful as a material for various molding processes such as extrusion molding and pultrusion molding for composites, sheets and pipes, and as a material for fibers or films. is there.
• PPS resin melting point Using a Perkin Elmer DSC, the temperature of the PPS resin sample was raised from 50 ° C to 350 ° C at 20 ° C / min, and the peak temperature of the endothermic peak when the polymer melted was taken as the melting point.
• Ratio of disulfide bonds in PPS resin Using a fluorescent X-ray analyzer ZSX100e manufactured by Rigaku Denki Kogyo Co., Ltd., the total amount of sulfur atoms (total amount of sulfur) was measured, and the ratio of disulfide bonds in the PPS resin was calculated based on the following formula. Asked.
• Acid Resistance Test / Alkaline Resistance Test With the bending stress applied to the test piece so as to obtain a predetermined bending strain, the test piece was immersed in the test solution, and the time until the test piece broke was examined. A cutting notch was provided at the center of the test piece.
• Acid resistance test solution St. Paul stock solution (trade name, surfactant containing hydrochloric acid and surfactant, manufactured by Dainippon Insect Chrysanthemum) ⁇ Alkali resistance test solution ...
• Domest stock solution (trade name, alkaline detergent containing sodium hypochlorite, sodium hydroxide and surfactant, manufactured by Japan Lever)
• Test piece 1.6 mm (thickness) x 12.7 mm (width) x 127 mm (long) ⁇
• Cavity Balance Using a washer mold having 40 cavities, the PPS compound was injection molded under the lowest molding conditions as long as the cavity (C1) closest to the primary sprue was completely filled.
• the molding conditions were a 75-ton molding machine, a cylinder temperature of 320 ° C, a mold temperature of 140 ° C, and no holding pressure.
• the degree of filling of the cavity (C10) farthest from the primary sprue in the same runner as the cavity (C1) after molding was compared.
• the degree of filling (% by mass) was determined from the mass ratio of the molded product of the cavity (C10) to the molded product of the cavity (C1). It can be said that the higher the degree of filling of the cavity (C10), the better the cavity balance.
• the cavity balance of each composition was determined according to the following criteria. AA: 100 to 90% by mass range A: 89 to 80% by mass range B: 79 to 70% by mass range C: 69 to 60% by mass range D: 59% by mass or less range
• melt polymerization was performed for 8 hours while heating the obtained molten mixture by changing the temperature and pressure stepwise so that the inside pressure was 320 ° C. and the absolute pressure was 133 Pa.
• 200 g of NMP was added, and the mixture was heated and stirred at 220 ° C., and the resulting dissolved product was filtered.
• 320 g of NMP was added to the lysate after filtration, and cake washing filtration was performed. 1 L of ion-exchanged water was added to the obtained cake containing NMP, and the mixture was stirred in an autoclave at 200 ° C. for 10 minutes.
• the cake was filtered, and 1 L of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. 1 L of ion-exchanged water was added to the obtained water-containing cake and stirred for 10 minutes. Next, the cake was filtered, and 1 L of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. After repeating this operation once more, the cake was dried at 120 ° C. for 4 hours to obtain 91 g of PPS resin.
• the obtained PPS resin had an iodine content of 200 ppm and a disulfide bond ratio of 0.2% by mass.
• Polyphenylene sulfide resin composition (PPS compound) 3-1.
• Raw materials In order to prepare the PPS resin composition the following materials were prepared.
• PA6T aromatic polyamide obtained by reacting terephthalic acid 65 mol%, isophthalic acid 25 mol%, and adipic acid 10 mol% as essential monomer components (melting point 310 ° C., Tg 120 ° C.)
• PA9T Polyamide obtained by reacting nonanediamine and terephthalic acid (Kuraray Co., Ltd., “Genesta N1000A”)
• PA46 Polyamide 46 (DSM Japan Engineering Plastics Co., Ltd., “S
• PAR aromatic polyester synthesized by the following method 3,3 ', 5,5'-tetramethyl-1,1'-biphenyl-4,4'-diol in a polymerization apparatus equipped with a stirring blade and a nitrogen inlet 2.42 kg (10.0 mol) and 50 g of metacresol were dissolved in 30 L of deoxygenated water containing 1.0 kg of sodium hydroxide to obtain an aqueous solution. Separately, 64 g of tetrabutylammonium bromide, 1.62 kg (8.0 mol) of isophthalic acid chloride, and 0.41 kg (2.0 mol) of terephthalic acid chloride were dissolved in 5 L of dichloromethane to obtain an organic solution.
• the organic solution was added while stirring the aqueous solution under a nitrogen stream, and stirring was continued at 25 ° C. for 30 minutes, and then the aqueous solution phase was removed.
• the organic solution phase containing the product was washed repeatedly with distilled water, poured into an acetone bath to obtain a precipitate, and further washed with acetone to obtain an aromatic polyester. Thereafter, it was vacuum-dried under a reduced pressure of about 10 Pa at 200 ° C. for 3 hours in a vacuum dryer to obtain 3.2 kg of aromatic polyester.
• LCP Thermotropic liquid crystal polyester resin synthesized by the following method: Hydroquinone 55.1 g (0.5 mol), 4,4′-dihydroxybiphenyl 93.1 g (0.5 mol), terephthalic acid 116.3 g (0. 7 mol), 6,6-dicarboxynaphthalene (64.9 g, 0.3 mol), p-hydroxybenzoic acid (621.5 g, 4.5 mol) and acetic anhydride (612.5 g, 6 mol) were cooled and stirred. The mixture was charged into a reaction vessel equipped with a machine and heated with stirring under a nitrogen gas atmosphere, and refluxed at 170 ° C. for 60 minutes.
• the reaction vessel was gradually raised to 370 ° C. over 4 hours, and the reaction system was depressurized to 25 kPa at 370 ° C. Furthermore, the polymerization was carried out by reducing the pressure to 0.5 to 1 kPa over 2 hours while removing acetic acid as a by-product at that temperature. Subsequently, polymerization was performed at 370 ° C. for 1 hour. While acetic acid generated as a by-product was removed during this time, polymerization was performed under strong stirring, and then the system was gradually cooled, and the liquid crystal polyester resin obtained at 200 ° C. was taken out of the system.
• Epoxysilane ⁇ -glycidoxypropyltrimethoxysilane (crosslinkable resin)
• Epoxy resin Cresol novolac type epoxy resin (manufactured by DIC Corporation, “Epiclon N-695”, epoxy equivalent 214 g / eq, softening point 94 ° C.)
• GF Glass fiber chopped strand (fiber diameter 10 ⁇ m, length 3 mm)
• CF pitch-based carbon fiber, tensile elastic modulus 560 GPa
• Carbon black graphitized carbon blackCaCO 3 (calcium carbonate): “Caltex 5” manufactured by Maruo Calcium Co., Ltd. (powder, average particle size 1.2 ⁇ m)
• the PPS resin of Synthesis Example 1 has a generated gas amount of a resin composition obtained by blending with an inorganic filler and various types of resins. It was confirmed that it was significantly reduced as compared with. Furthermore, the resin composition obtained using the PPS resin of Synthesis Example 1 was excellent in terms of mechanical properties (bending, impact), acid resistance, alkali resistance, hot water resistance, and cavity balance.

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