Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3833—Polymers with mesogenic groups in the side chain
  • C09K19/3838—Polyesters; Polyester derivatives
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
  • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
  • D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
  • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
  • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
  • C09K2219/01—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of fibres, e.g. fibres after polymerisation of LC precursor
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
  • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]

Definitions

• the present invention relates to a liquid crystal polyester resin composition. Further, the present invention relates to a liquid crystal polyester fiber made of a liquid crystal polyester resin composition and a fiber structure composed of at least a part thereof. The present invention also relates to a melt-molded body obtained by melt-molding a liquid crystal polyester resin composition.
• thermoplastic fibers including (sometimes referred to as fibers) are known.
• Patent Document 1 Japanese Patent Laid-Open No. 1-23003
• Patent Document 2 Japanese Patent Laid-Open No. 2013-237945
• Patent Document 3 Japanese Patent Laid-Open No. 4-732257 describe continuous reinforcing fibers and continuous thermoplastics.
• a composite fiber containing such a continuous reinforcing fiber and a continuous thermoplastic fiber is a prepreg (a tape-like product obtained by applying or coating a thermosetting resin to a tow or a cloth of a reinforcing fiber, which is generally used as a precursor of a fiber-reinforced composite material. It is more flexible than intermediate materials made by melt-impregnating a tow of reinforcing fibers or a fabric with a thermoplastic resin, and various three-dimensional shapes such as tubular and dome-shaped by weaving and knitting. It is easy to form a fabric with a specific deformation.
• a liquid crystal polyester fiber made of liquid crystal polyester, which is a thermoplastic resin having excellent vibration damping property is used. By using it as a reinforcing fiber or a fused fiber, it can be expected that a molded product having excellent vibration damping properties can be obtained.
• liquid crystal polyester fiber is used as a fusion fiber and reinforced with carbon fiber as a member of a structure such as a bicycle, an automobile, a railroad vehicle, an aircraft, etc., which has high impact resistance and a high demand for reducing the scattering of debris due to destruction.
• a molded body having both high impact resistance and vibration damping property has been reported.
• Patent Document 4 Japanese Unexamined Patent Publication No. 2011-84611 states that the total fragrance is substantially insoluble at a temperature of 400 ° C. or higher and is reinforced with high-strength fibers having a breaking strength of 10 cN / dtex or higher.
• Group polyester resin moldings are disclosed. Specifically, the liquid crystal polyester fiber, which is a precursor of the matrix resin, is formed into a bidirectional woven fabric, and then laminated with the bidirectional woven fabric composed of carbon fibers as high-strength fibers, and the temperature is 300 to 370 ° C. A fiber reinforced resin molded body is manufactured by hot pressing under the conditions.
• the present invention solves the above-mentioned problems, and is derived from a liquid crystal polyester resin composition and a resin composition thereof, which can obtain a high-quality molded product without generating bubbles during heating and melting in the production of the molded product. It is an object of the present invention to provide a liquid crystal polyester fiber.
• the inventors of the present invention have a carboxy group at the molecular terminal of the liquid crystal polyester in the thermal decomposition gas generated from the liquid crystal polyester resin composition when heated to a predetermined temperature. It has been found that, if present, a decarbonation reaction occurs at the carboxy group as a trigger. As a result of further research, the resin composition containing the liquid crystal polyester and a specific metal element can reduce the amount of carboxy groups at the molecular ends of the liquid crystal polyester by kneading at the time of melt molding. , It has been found that the bubbles in the obtained melt-molded body can be reduced, and the present invention has been completed.
• the present invention can be configured in the following aspects.
• [Aspect 1] Liquid crystal polyester and at least one metal element selected from the group consisting of metal elements of Groups 8 to 11 of the Periodic Table (preferably at least one metal element selected from the group consisting of copper, cobalt, and palladium).
• Liquid crystal polyester resin composition including.
• the liquid crystal polyester resin composition according to the first or second aspect wherein the total carboxy-terminal amount (total CEG amount) of the liquid crystal polyester is 5.0 meq / kg or less (preferably 4.0 meq / kg or less, more preferably 3).
• a liquid crystal polyester resin composition comprising, or comprising a constituent unit derived from 4-hydroxybenzoic acid, a constituent unit derived from an aromatic dicarboxylic acid and a constituent unit derived from an aromatic diol.
• the liquid crystal polyester contains 50 mol% or more (preferably 53 mol% or more, more preferably) a structural unit derived from 4-hydroxybenzoic acid. Is a liquid crystal polyester resin composition containing 60 mol% or more).
• the metal element is contained as a metal compound, and the melting point of the metal compound is the melting point of the liquid crystal polyester + 30 ° C.
• the metal compound is at least one selected from the group consisting of an organic acid salt, an inorganic acid salt, a halide, a hydroxide, and a metal complex compound.
• a liquid crystal polyester fiber comprising the liquid crystal polyester resin composition according to any one of aspects 1 to 9.
• the liquid crystal polyester fiber has a melting point of 380 ° C. or lower (preferably 250 to 350 ° C., more preferably 260 to 300 ° C.).
• the liquid crystal polyester resin composition according to any one of aspects 1 to 9 or the fiber structure according to aspects 14 or 15 is heated at a temperature equal to or higher than the melting point of the liquid crystal polyester or at a temperature equal to or higher than the melting point of the liquid crystal polyester fiber. A method for manufacturing a melt-molded body.
• liquid crystal polyester resin composition and the liquid crystal polyester fiber of the present invention it is possible to suppress the generation of gas at the time of heating and melting, and it is possible to produce a good quality molded product with few bubbles.
• the liquid crystal polyester contained in the liquid crystal polyester resin composition of the present invention comprises, for example, a repeating structural unit derived from an aromatic diol, an aromatic dicarboxylic acid, an aromatic hydroxycarboxylic acid, etc., as long as the effects of the present invention are not impaired.
• the structural unit derived from the aromatic diol, the aromatic dicarboxylic acid, and the aromatic hydroxycarboxylic acid is not particularly limited in terms of its chemical composition.
• the liquid crystal polyester may contain a structural unit derived from an aromatic diamine, an aromatic hydroxyamine or an aromatic aminocarboxylic acid as long as the effect of the present invention is not impaired.
• a preferable structural unit the example shown in Table 1 can be mentioned.
• m is an integer of 0 to 2
• Y in the formula is independently a hydrogen atom and a halogen atom (for example, a fluorine atom, in the range of 1 to the maximum number of substitutables, respectively.
• alkyl group eg, alkyl group with 1 to 4 carbon atoms such as methyl group, ethy
• More preferable structural units include the structural units shown in Examples (1) to (18) shown in Tables 2, 3 and 4 below.
• the structural unit in the formula is a structural unit capable of exhibiting a plurality of structures, two or more such structural units may be combined and used as the structural unit constituting the polymer.
• n is an integer of 1 or 2
• 2 independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, etc.).
• a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
• an alkyl group for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, etc.
• Alkyl group having 1 to 4 carbon atoms alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), aralkyl group (eg, aralkyl group).
• a benzyl group phenylmethyl group
• a phenethyl group phenylethyl group, etc.
• an aryloxy group for example, a phenoxy group, etc.
• an aralkyloxy group for example, a benzyloxy group, etc.
• a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group is preferable.
• the liquid crystal polyester may preferably be a combination having a naphthalene skeleton as a constituent unit. It is particularly preferable to include both the structural unit (A) derived from hydroxybenzoic acid and the structural unit (B) derived from hydroxynaphthoic acid.
• the structural unit (A) a structural unit derived from 4-hydroxybenzoic acid represented by the following formula (A) can be mentioned, and as the structural unit (B), 6-hydroxy-2-naphthoe represented by the following formula (B) can be mentioned.
• Acid-derived structural units are mentioned, and from the viewpoint of improving melt moldability, the ratio of the structural unit (A) to the structural unit (B) is preferably 9/1 to 1/1, more preferably 7/1 to 1. It may be in the range of 1/1, more preferably 5/1 to 1/1.
• the total of the constituent units of (A) and (B) may be, for example, 65 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% with respect to all the constituent units. It may be% or more.
• liquid crystal polyester in which the constituent unit of (B) is 4 to 45 mol% is particularly preferable.
• the liquid crystal polyester contains a structural unit derived from 4-hydroxybenzoic acid as an aromatic hydroxycarboxylic acid, and may contain a structural unit derived from an aromatic dicarboxylic acid and a structural unit derived from an aromatic diol.
• a structural unit derived from 4-hydroxybenzoic acid as an aromatic hydroxycarboxylic acid
• an aromatic dicarboxylic acid and a structural unit derived from an aromatic diol.
• at least one selected from the group consisting of the following formula (C) and the following formula (D) may be used as the structural unit derived from the aromatic dicarboxylic acid, and the following formula may be used as the structural unit derived from the aromatic diol.
• At least one selected from the group consisting of (E) and the following formula (F) may be used.
• a structural unit (A) derived from 4-hydroxybenzoic acid (formula (A) above), a structural unit (C) derived from terephthalic acid as an aromatic dicarboxylic acid (formula (C) below), and isophthalic acid are preferable.
• the structural unit (D) (the following formula (D)
• the structural unit (E) derived from 4,4'-dihydroxybiphenyl as an aromatic diol (the following formula (E))
• the structural unit derived from hydroquinone the following formula (E)
• F) A liquid crystal polyester or the like containing (the following formula (F)) may be used.
• the liquid crystal polyester may contain a structural unit derived from 4-hydroxybenzoic acid, preferably 50 mol% or more, more preferably 53 mol% or more, still more preferably 60 mol% or more. You may.
• the upper limit of the content of the constituent unit derived from 4-hydroxybenzoic acid in the liquid crystal polyester is not particularly limited, but may be, for example, 90 mol% or less, preferably 88 mol% or less, and more preferably 85 mol%. It may be as follows.
• the melting point of the liquid crystal polyester preferably used in the present invention (hereinafter, may be referred to as Mp 0 ) is preferably in the range of 250 to 380 ° C, more preferably 255 to 370 ° C, still more preferably 260 to 360 ° C. , Even more preferably 260-330 ° C.
• the melting point referred to here is the main absorption peak temperature measured and observed by a differential scanning calorimeter (DSC; “TA3000” manufactured by Metler) in accordance with the JIS K 7121 test method.
• the liquid crystal polyester resin composition may contain 50% by weight or more of liquid crystal polyester, preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, still more preferably 99% by weight. It may be contained in an amount of 9% by weight or more.
• the liquid crystal polyester resin composition may be a resin composition containing other components as long as the effects of the present invention are not impaired, and may be polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyamide, polyphenylene sulfide, or polyether. It may contain a thermoplastic polymer such as an ether ketone or a fluororesin. It may also contain various additives such as titanium oxide, kaolin, silica, barium oxide and other inorganic substances, carbon black, colorants such as dyes and pigments, antioxidants, ultraviolet absorbers and light stabilizers.
• the liquid crystal polyester resin composition of the present invention contains at least one kind of metal element selected from the group consisting of metal elements of Groups 8 to 11 of the Periodic Table. It is preferably at least one kind of metal element selected from the group consisting of metal elements of Group 8 to 11 in the 4th to 6th period of the periodic table, and specifically, iron, ruthenium, osmium, cobalt, rhodium, iridium and nickel. , Platinum, platinum, copper, silver, and at least one metal element selected from the group consisting of gold.
• the above metal element acts as a catalyst for the decarbonation reaction of the aromatic carboxylic acid, it is possible to reduce the amount of the carboxy group at the molecular end by desorbing carbon dioxide at the carboxy group at the molecular end of the liquid crystal polyester. can.
• the metal element contained in the liquid crystal polyester resin composition of the present invention is more preferably selected from the group consisting of copper, cobalt, and palladium from the viewpoint of promoting the decarbonation reaction of the aromatic carboxylic acid and reducing the total amount of CEG. It may be at least one kind of metal element to be used, and more preferably copper.
• the metal element may be contained as a metal compound having a structure in which a metal atom is bonded to a non-metal atom.
• the metal compound include formate, acetate, propionate, butyrate, valerate, capronate, enanthate, caprilate, pelargonate, capricate, laurate, and myristic acid.
• Salt palmitate, stearate, naphthenate, benzoate, oxalate, malonate, succinate, adipate, terephthalate, isophthalate, phthalate, salicylate, tartrate
• Organic acid salts such as salts, citrates, fluoroacetates, chloroacetates, bromoacetates, fluoropropionates, chloropropionates, bromopropionates; inorganic acid salts such as sulfates, carbonates and nitrates. Examples thereof include halides such as fluorides, chlorides, bromides and iodides; hydroxides; oxides; sulfides and the like.
• metal compounds may be used alone or in combination of two or more.
• organic acid salts, inorganic acid salts, halides, and hydroxides are preferable from the viewpoint of having a low melting point and improving dispersibility in the melt-molded body.
• the metal compound is not particularly limited as long as it is a metal compound that acts as a catalyst for the decarbonation reaction of the aromatic carboxylic acid, but may be a metal complex compound in which a metal atom is coordinated to a ligand.
• the ligand is not particularly limited as long as it is a ligand capable of coordinating with a metal atom in a metal compound, but is a nitrogen-based ligand, an oxygen-based ligand, a carbon-based ligand, and a phosphorus-based coordination. Examples include children and sulfur-based ligands.
• an organic acid corresponding to the above-mentioned organic acid salt, an inorganic acid corresponding to the inorganic acid salt, a halogen corresponding to a halide, or the like may be coordinate-bonded with a metal atom as a ligand.
• the nitrogen-based ligand is not particularly limited as long as it is a ligand having a nitrogen atom that can coordinate with the metal atom, and for example, ammine (NH 3 ), aniline, diisopropylamine, triethylamine, triphenylamine, and the like.
• the oxygen-based ligand is not particularly limited as long as it is a ligand having an oxygen atom that can coordinate with the metal atom, and is, for example, dimethyl ether, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-.
• Ether-based ligands such as dimethoxyethane; alcohol-based ligands such as methanol, ethanol, phenol, 1,1'-vinaphthalene-2,2'-diol; carboxylat ( RCOO- ), oxalate (ox -2- ) , Acyl-based ligands such as acetylacetonate (acac); aqua (H 2 O); hydroxydo (OH ⁇ ); oxo (O 2- ) and the like.
• the carbon-based ligand is not particularly limited as long as it is a ligand having a carbon atom that can coordinate with the metal atom, and is, for example, an alkyl-based ligand such as methyl; an aryl-based ligand such as phenyl. Vinyl-based ligands; Alkinyl-based ligands; Calben-based ligands such as N-heterocyclic carben; Alken-based ligands such as ethylene and dibenzylideneacetone (dba); Acetylene, 2-phenylethynylbenzene, etc.
• dba dibenzylideneacetone
• Alkin-based ligands Alkin-based ligands; cyclopentadiene-based ligands such as cyclopentadiene and pentamethylcyclopentadiene; diene-based ligands such as 1,3-butadiene and 1,5-cyclooctadien (cod); benzene and cyclo Cyclic polyene-based ligands such as octatetraene; isocyanide-based ligands such as cyanomethylisocyanide and phenylisocyanide; carbonyl (CO) and the like can be mentioned.
• cyclopentadiene-based ligands such as cyclopentadiene and pentamethylcyclopentadiene
• diene-based ligands such as 1,3-butadiene and 1,5-cyclooctadien (cod)
• benzene and cyclo Cyclic polyene-based ligands such as oc
• the phosphorus-based ligand is not particularly limited as long as it is a ligand having a phosphorus atom that can coordinate with the metal atom, and is, for example, triphenylphosphine, tris (2-methylphenyl) phosphine, tris (2-).
• Methoxyphenyl) phosphine di-tert-butylphenylphosphine, trimethylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, bis (diphenylphosphine) methane (dppm), 1,2-bis (diphenylphosphine) ethane ( dppe), 1,3-bis (diphenylphosphine) propane (dpppp), 2,2'-bis (diphenylphosphine) -1,1'-binaphthyl (BINAP), 2-dicyclohexylphosphino-2', 6 '-Dimethoxybiphenyl (SPhos), 2-dicyclohexylphosphine-2', 4', 6'-triisopropylphosphine (XPhos), 2-dicyclohexylphosphino-2'-methylbiphenyl (MePhos), 2-dicyclohe
• the sulfur-based ligand is not particularly limited as long as it is a ligand having a sulfur atom that can be coordinated to the metal atom, but for example, a thiol-based ligand; a sulfoxide-based coordination such as dimethyl sulfoxide (DMSO). Child; sulfur-containing heteroaromatic ligand such as thiophene, dibenzothiophene, thiopyran; thiocyanide (SCN- ) ; sulfide (S -2- ) and the like.
• the preferred ligand varies depending on the type of metal atom, but in the case of copper, it is preferable that a nitrogen-based ligand is coordinated from the viewpoint of promoting the decarbonation reaction of the aromatic carboxylic acid, and the nitrogen-containing heteroaromatic. It is more preferable that a system ligand or a nitrogen-based chelating ligand is coordinated, and it is further preferable that a nitrogen-containing heteroaromatic chelating ligand is coordinated.
• the chelate ligand is a ligand having a plurality of coordination constellations having two or more loci in the molecule, and the plurality of coordinating loci are in positions where they can be coordinated to one metal atom at the same time. It is a ligand.
• nitrogen-based chelating ligand examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tris (2-aminoethyl) amine, hexamethylenetetramine, bipyridine, terpyridine, phenanthroline, and derivatives thereof.
• the valence of copper in the copper compound may be either 0-valent, 1-valent, or 2-valent, but it may be monovalent or divalent from the viewpoint of avoiding aggregation and localization in melt spinning. It is preferable, and more preferably monovalent from the viewpoint of promoting the decarboxylation reaction of the aromatic carboxylic acid.
• an oxygen-based ligand is coordinated, and an acyl-based ligand is coordinated, from the viewpoint of stability in the atmosphere during use and promotion of the decarbonation reaction of the aromatic carboxylic acid. It is more preferable to do.
• an oxygen-based ligand is coordinated from the viewpoint of stability in the atmosphere during use and promotion of the decarbonation reaction of the aromatic carboxylic acid, and an acyl-based ligand (for example, an acyl-based ligand) is preferable. It is more preferable that a carboxylat (preferably acetato, trifluoroacetato) is coordinated.
• the liquid crystal polyester resin composition of the present invention has, for example, a total content of 1 to 1000 ppm by weight of the metal element from the viewpoint of satisfactorily achieving both promotion of decarbonation reaction of aromatic carboxylic acid and suppression of side reaction. It is preferable, more preferably 3 to 500 wt ppm, still more preferably 5 to 200 ppm by weight, and even more preferably 10 to 100 wt ppm.
• the content of the metal element indicates the ratio of the total weight of the metal element to the weight of the liquid crystal polyester resin composition, and when the metal element is contained as the metal compound described later, the content in terms of metal atom is shown.
• the above-mentioned content of the metal element is the content of the metal element in the components constituting the resin composition itself, excluding the components adhering to the surface of the resin composition (for example, the molded product) such as the coating agent. You may.
• the liquid crystal polyester resin composition of the present invention may contain a polymerization catalyst (for example, alkali metal, alkaline earth metal, etc.) that acts on the polycondensation reaction of liquid crystal polyester, but from the viewpoint of suppressing side reactions, it is alkaline.
• a polymerization catalyst for example, alkali metal, alkaline earth metal, etc.
• the total content of the metal and the alkaline earth metal may be less than 100 wt ppm, preferably 10 wt ppm or less, more preferably 5 wt ppm or less, still more preferably 1 wt ppm or less.
• alkali metals refer to lithium, sodium, potassium, rubidium, cesium, and francium
• alkaline earth metals refer to beryllium, magnesium, calcium, strontium, barium, and radium.
• the metal compound When the metal compound is contained as the above-mentioned metal complex compound, the metal compound may be contained in the resin composition as a metal complex compound in which a ligand is already coordinated and bonded as a form to be mixed with the liquid crystal polyester resin composition. Alternatively, the metal compound and the compound forming the ligand may be separately contained in the resin composition.
• the metal compound may be a compound having a melting point (Mp 0 ) + 30 ° C. or lower of the liquid crystal polyester from the viewpoint of improving dispersibility during melt molding.
• the melting point of the metal compound is preferably Mp 0 + 20 ° C. or lower.
• the melting point of the metal compound is preferably 400 ° C. or lower, more preferably 350 ° C. or lower, from the viewpoint of processability.
• the lower limit of the melting point of the metal compound is not particularly limited, but is preferably 100 ° C. or higher from the viewpoint of handleability in melt molding.
• the liquid crystal polyester resin composition of the present invention may have a melt viscosity of 10 to 100 Pa ⁇ s, preferably 13 to 80 Pa ⁇ s, more preferably 15 to 50 Pa ⁇ s, as measured by the method described in Examples described later. -It may be s. It is possible to reduce the amount of terminal groups to some extent by increasing the degree of polymerization by melt polymerization, solid phase polymerization, etc., but if the degree of polymerization is increased, the viscosity at the time of melting increases and melt molding becomes difficult. There is. Therefore, the liquid crystal polyester resin composition may have a melt viscosity in a range advantageous for melt molding.
• the total carboxy terminal amount (total CEG amount) of the liquid crystal polyester may be 5.0 meq / kg or less.
• the total amount of CEG in the liquid crystal polyester resin composition is a value measured by the method described in Examples described later, and is composed of the amount of carboxy groups present at the molecular ends of the liquid crystal polyester with respect to 1 kg of the liquid crystal polyester resin composition.
• a structural unit derived from a monomer having a carboxy group such as aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid forms the polymer terminal. It may be a carboxy group that remains unreacted in the structural unit existing at the end of the polymer.
• the total amount of CEG of the liquid crystal polyester contained in the liquid crystal polyester resin composition of the present invention is preferably 4.0 meq / kg or less, more preferably 3.0 meq / kg or less, from the viewpoint of suppressing the amount of gas generated during heating and melting. It may be more preferably 2.5 meq / kg or less, and even more preferably 2.0 meq / kg or less.
• the lower limit of the total CEG amount is not particularly limited, but may be, for example, 0.1 meq / kg or more.
• the liquid crystal polyester contained in the liquid crystal polyester resin composition of the present invention has carboxyphenyl (-Ph-COOH (in the formula: other on Ph) among the carboxy groups at the molecular ends, from the viewpoint of suppressing the amount of gas generated during heating. There may be a substituent))
• the amount of CEG for the terminal carboxy group may be 4.0 meq / kg or less, preferably 2.5 meq / kg or less, more preferably 2.0 meq / kg or less, More preferably, it may be 1.5 meq / kg or less.
• the carboxy group at the carboxyphenyl terminal is, for example, a monomer having a carboxyphenyl group such as 4-hydroxybenzoic acid, terephthalic acid, isophthalic acid (optionally, the phenyl of the carboxyphenyl group includes a halogen atom, an alkyl group, an alkoxy group, etc. It may have a substituent such as an aryl group, an aralkyl group, an aryloxy group, an aralkyloxy group), and since it has a chemical structure that easily causes a decarbonization reaction, the carboxy group at the carboxyphenyl terminal is used. It is preferable to reduce the amount of CEG.
• the lower limit of the amount of CEG for the carboxy group at the carboxyphenyl terminal is not particularly limited, but may be, for example, 0.1 meq / kg or more.
• the liquid crystal polyester contained in the liquid crystal polyester resin composition of the present invention has a ratio of the amount of CEG to the carboxy group at the carboxyphenyl terminal of 90% or less with respect to the total amount of CEG from the viewpoint of suppressing the amount of gas generated during heating. It may be preferably 85% or less, more preferably 80% or less.
• the lower limit of the ratio of the CEG amount to the carboxy group at the carboxyphenyl terminal to the total CEG amount is not particularly limited, but may be, for example, 5% or more.
• the liquid crystal polyester contained in the liquid crystal polyester resin composition of the present invention may have a total one-sided end amount of 50 meq / kg or more, preferably 55 meq / kg or more, more preferably 60 meq, from the viewpoint of improving melt moldability. It may be / kg or more. Further, it may be 200 meq / kg or less, preferably 100 meq / kg or less.
• the total amount at one end indicates the number of polymer chains and is used as an index for evaluating the molecular weight. The larger the total amount of one end, the smaller the molecular weight, and the smaller the total amount of one end, the larger the molecular weight.
• the total one-sided terminal amount is the carboxy group terminal derived from hydroxycarboxylic acid with respect to 1 kg of the liquid crystal polyester resin composition.
• the total amount (meq / kg) of the carboxy group derived from hydroxycarboxylic acid with the terminal from which carbon dioxide was desorbed by the decarbonation reaction is divided by the molar ratio of the constituent units derived from hydroxycarboxylic acid in the liquid crystal polyester. It is defined as a numerical value to be determined and is a value measured by the method described in Examples described later.
• the amount of CO 2 gas generated as measured by Examples described later may be 2.0 mmol / kg or less, preferably 1.5 mmol / kg or less, more preferably 1. It may be 0.0 mmol / kg or less.
• the liquid crystal polyester resin composition of the present invention may be produced by polycondensing various monomers in the presence of a specific metal element, or may be produced by polycondensing various monomers with respect to the liquid crystal polyester obtained by polycondensing various monomers. It may be produced by adding a metal element. However, when a specific metal element is added in the early or middle stage of polycondensation, the decarbonation reaction proceeds due to the specific metal element, which inhibits the formation of an ester bond and may not sufficiently increase the degree of polymerization. .. Therefore, it is preferable to add a specific metal element to the already polycondensed liquid crystal polyester so as to act as a catalyst for the decarboxylation reaction.
• the liquid crystal polyester contained in the liquid crystal polyester resin composition of the present invention is preferably a purified liquid crystal polyester.
• a liquid crystal polyester resin composition that has been polycondensed and has a monomer, an acylating agent, etc. remaining is melt-molded as it is, the polycondensation reaction and the decarbonation reaction are selectively selected due to the influence of the residue such as the monomer and the acylating agent. May not be controlled. Therefore, from the viewpoint of adjusting the degree of polymerization for melt moldability, it is preferable to once purify the liquid crystal polyester obtained by polycondensation, remove residual monomers and the like, and then melt mold the liquid crystal polyester resin composition.
• Liquid crystal polyester can be synthesized by a known polycondensation method.
• Various aromatic diols, aromatic dicarboxylic acids, and aromatic hydroxycarboxylic acids may be used as the monomers to be subjected to the polycondensation, and hydroxy group acylated products having these monomer terminals activated, carboxyl group esterified products, and acids may be used.
• Carboxylic acid derivatives such as halides and acid anhydrides may be used.
• the polycondensation may be carried out in the presence of various polymerization catalysts, for example, an organic tin-based catalyst (dialkyltin oxide, etc.), an antimony-based catalyst (antimonite trioxide, etc.), a titanium-based catalyst (titanium dioxide, etc.), and a carboxyl.
• organic tin-based catalyst dialkyltin oxide, etc.
• antimony-based catalyst antimonite trioxide, etc.
• titanium-based catalyst titanium dioxide, etc.
• carboxyl a carboxyl
• alkali metal salts of acids alkaline earth metal salts (potassium acetate, etc.), and Lewis acid salts (BF 3 , etc.).
• a resin composition containing a liquid crystal polyester obtained by polycondensation of various monomers and a specific metal element acting as a catalyst for a decarbonation reaction is melt-kneaded to give aroma in the molecule of the liquid crystal polyester.
• the decarbonation reaction can be allowed to proceed at the terminal of the group carboxylic acid to reduce the total amount of CEG of the liquid crystal polyester.
• a molded product having few bubbles can be obtained by melt-kneading the resin composition in a melt extruder during the process of melt molding to remove carbon dioxide generated by the decarbonization reaction before the molding process.
• the liquid crystal polyester resin composition of the present invention is a mixture of a liquid crystal polyester obtained by polycondensation of various monomers and at least one metal element selected from the group consisting of metal elements of Groups 8 to 11 of the Periodic Table. It may be manufactured by a method including a step of melt-kneading. By melt-kneading the liquid crystal polyester and a specific metal element in advance, the total amount of CEG of the liquid crystal polyester can be reduced to the above range. As described above, the liquid crystal polyester resin composition containing the liquid crystal polyester having a specific total CEG amount may be subjected to melt molding.
• the temperature at which the decarbonation reaction proceeds is lowered by containing a specific metal element together with the liquid crystal polyester obtained by polycondensation of various monomers. It is possible to reduce the total CEG amount of the liquid crystal polyester even at a normal melt-kneading temperature.
• the melt-kneading temperature in the melt-kneading step may be a temperature at which the resin composition can be melt-kneaded, and may be, for example, a melting point (Mp 0 ) or higher of the liquid crystal polyester, which is preferable. May be Mp 0 + 10 ° C. or higher, more preferably Mp 0 + 20 ° C.
• melt-kneading temperature may be 280 ° C. or higher, preferably 290 ° C. or higher, and more preferably 300 ° C. or higher.
• the melt-kneading temperature may be lower than the decomposition temperature of the liquid crystal polyester.
• the metal element in the liquid crystal polyester resin composition may be added in the above-mentioned content, type and form.
• the decarbonation reaction from the polymer terminal is a reaction that substantially proceeds at a temperature as described above, that is, above the normal melt-kneading temperature (for example, above the melting point of the liquid crystal polyester). Since it has generally higher heat resistance and flame retardancy than polyesters that do not exhibit molten liquid crystal properties (for example, polyethylene terephthalate), it can be melt-kneaded without causing deterioration of the resin such as discoloration and main chain decomposition even at such high temperatures. The decarbonation reaction can be efficiently promoted.
• a known method can be used for melt kneading, and for example, a known resin kneader such as a Banbury mixer, a mixing roll machine, a kneader, a single-screw extruder, or a multi-screw extruder (two or more shafts) can be used. ..
• a known resin kneader such as a Banbury mixer, a mixing roll machine, a kneader, a single-screw extruder, or a multi-screw extruder (two or more shafts) can be used. ..
• the melt-kneading time is, for example, the time for the resin to pass through the extruder (residence time in the extruder) when the extruder is used as the resin kneader, and the dispersion of additives and the progress of the decarbonization reaction are sufficient.
• the range is not particularly limited as long as it proceeds to, but may be, for example, 30 seconds to 30 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 8 minutes.
• the degree of vacuum may be 100 kPa or less in absolute pressure, preferably 80 kPa or less, and more preferably 60 kPa or less.
• melt-kneading After melt-kneading, it may be processed into a known shape such as pellet-shaped, chip-shaped, flake-shaped, powder-shaped, etc. used for melt molding. Alternatively, after melt-kneading, the melt-kneaded product may be directly molded into a desired shape to produce a melt-molded product described later.
• the liquid crystal polyester resin composition of the present invention can be processed into a molded product having few bubbles by a known melt molding method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning and the like.
• a known melt molding method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning and the like.
• examples of the melt-molded body include a molded body having a three-dimensional shape, a molded body having various shapes such as a sheet, a film, and a fiber.
• the melt-molded body of the present invention may be a reinforced fiber molded body (fiber-reinforced composite material) containing reinforced fibers.
• the type of the reinforcing fiber is not particularly limited as long as it has a higher melting point than the liquid crystal polyester of the present invention, but for example, glass fiber, carbon fiber, liquid crystal polyester fiber, aramid fiber, polyparaphenylene benzobisoxazole fiber, polyparaphenylene benzo. Included is at least one selected from the group consisting of bisimidazole fibers, polyparaphenylene benzobisthiazole fibers, ceramic fibers, and metal fibers. These reinforcing fibers may be used alone or in combination of two or more.
• the obtained molded body has excellent vibration-damping properties and can be effectively used for applications that generate vibrations such as duct tubes and automobile bumpers. can.
• the film or fiber can be used as an intermediate material for producing a melt-molded body such as a molded body or a sheet having a three-dimensional shape by further melt-molding.
• the method for producing a liquid crystal polyester fiber of the present invention comprises a liquid crystal polyester resin composition containing a liquid crystal polyester and at least one metal element selected from the group consisting of metal elements of Groups 8 to 11 of the Periodic Table in an extruder. It may include at least a step of melt-kneading and a step of discharging the melt-kneaded product from a nozzle and spinning it.
• the reaction time can be secured because it can be retained in the melt-kneaded state for a certain period of time before being supplied to the spinning head. Therefore, in the present invention, the total CEG of the liquid crystal polyester fiber obtained by containing and melt-kneading a specific metal element acting as a catalyst for the decarbonation reaction at the aromatic carboxylic acid terminal of the liquid crystal polyester in the extruder is performed. It is possible to reduce the amount.
• the decarbonization reaction in the melt-kneading step, by incorporating a specific metal element into the resin composition, the decarbonization reaction can be promoted by its catalytic action, and the molecular terminal of the liquid crystal polyester can be controlled. Specifically, even if the above-mentioned liquid crystal polyester resin composition containing a liquid crystal polyester and at least one metal element selected from the group consisting of metal elements of Groups 8 to 11 of the periodic table is melt-kneaded in an extruder. good.
• the liquid crystal polyester resin composition may contain at least one metal element selected from the group consisting of liquid crystal polyester and metal elements of Groups 8 to 11 of the Periodic Table, and the metal elements are described above.
• the content, type, and form may be the same.
• the metal element may be contained as the above-mentioned metal compound, and the metal compound may be the above-mentioned metal complex compound from the viewpoint of promoting the decarbonation reaction.
• the metal compound may have the above-mentioned melting point from the viewpoint of improving the dispersibility in the resin composition and improving the continuous operation of the melt spinning.
• the temperature at which the decarbonization reaction proceeds can be lowered, and the total CEG amount of the liquid crystal polyester fiber is lowered even at a normal kneading temperature.
• the kneading temperature in the extruder in the melt-kneading step may be a temperature such that the viscosity of the liquid crystal polyester resin composition can be adjusted to a viscosity suitable for spinning, and for example, the melting point of the liquid crystal polyester (Mp 0 ). It may be the above, preferably Mp 0 + 10 ° C. or higher, and more preferably Mp 0 + 20 ° C. or higher.
• the kneading temperature in the extruder may be 280 ° C. or higher, preferably 290 ° C. or higher, and more preferably 300 ° C. or higher.
• the kneading temperature in the extruder may be lower than the decomposition temperature of the liquid crystal polyester.
• the time for the resin to pass through the extruder is not particularly limited as long as the dispersion of additives and the progress of the decarboxylation reaction sufficiently proceed, but for example. , 30 seconds to 30 minutes, preferably 1 minute to 10 minutes, more preferably 3 minutes to 8 minutes.
• a known extruder such as a single-screw extruder or a multi-screw extruder (two or more shafts) can be used.
• the degree of vacuum may be 100 kPa or less in absolute pressure, preferably 80 kPa or less, and more preferably 60 kPa or less.
• melt-kneaded product containing a liquid crystal polyester having a reduced total CEG amount
• the melt-kneaded product may be supplied to the spinning head and discharged from a nozzle for melt-spinning.
• Melt spinning can be performed by a known or conventional method, and can be obtained by discharging from a nozzle at a predetermined spinning temperature and winding with a godet roller or the like.
• the liquid crystal polyester fiber of the present invention contains at least one metal element selected from the group consisting of metal elements of Groups 8 to 11 of the Periodic Table. As described above, by melt-spinning using a liquid crystal polyester resin composition containing a specific metal element, the decarbonization reaction of the molecular end of the liquid crystal polyester can be promoted at the time of melt kneading, and the obtained liquid crystal polyester fiber can be obtained. The total amount of CEG can be reduced.
• the metal element in the liquid crystal polyester fiber of the present invention may be contained in the above-mentioned types and forms. Further, the content of the metal element is preferably 1 to 1000 ppm by weight in total, more preferably 3 to 500 wt by weight, from the viewpoint of promoting the decarbonation reaction of the aromatic carboxylic acid and suppressing the side reaction. It may be ppm, more preferably 5 to 200 wt ppm, even more preferably 10 to 100 wt ppm.
• the content of the metal element indicates the ratio of the total weight of the metal element to the weight of the liquid crystal polyester fiber, and when the metal element is contained as the metal compound, the content in terms of metal atom is shown.
• the above-mentioned content of the metal element may be the content of the metal element in the components constituting the fiber itself, excluding the components adhering to the fiber surface such as the oil agent.
• the liquid crystal polyester fiber of the present invention may have a total content of less than 100 wt ppm of alkali metal and alkaline earth metal, preferably 10 wt ppm or less, more preferably 5 wt ppm. It may be ppm or less, more preferably 1 weight ppm or less.
• the above-mentioned contents of the alkali metal and the alkaline earth metal are the contents of the alkali metal and the alkaline earth metal in the components constituting the fiber itself, excluding the components adhering to the fiber surface such as the oil agent. May be good.
• the liquid crystal polyester fiber of the present invention is composed of the above-mentioned liquid crystal polyester resin composition and may contain a component other than the liquid crystal polyester and a specific metal element, but may contain 50% by weight or more of the liquid crystal polyester. It may be contained in an amount of 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, still more preferably 99.9% by weight or more.
• the liquid crystal polyester fiber of the present invention may have a total CEG amount of 5.0 meq / kg or less, preferably 4.0 meq / kg or less, more preferably 3. It may be 0.0 meq / kg or less, more preferably 2.5 meq / kg or less, still more preferably 2.0 meq / kg or less.
• the lower limit of the total CEG amount is not particularly limited, but may be, for example, 0.1 meq / kg or more.
• the total amount of CEG in the liquid crystal polyester fiber is a value measured by the method described in Examples described later, and is the amount of carboxy groups present at the molecular terminal in the molecule constituting the liquid crystal polyester fiber with respect to 1 kg of the liquid crystal polyester fiber. It is composed.
• the liquid crystal polyester fiber of the present invention may have a CEG amount of 4.0 meq / kg or less for the carboxy group at the carboxyphenyl terminal among the carboxy groups at the molecular end. It may be preferably 2.5 meq / kg or less, more preferably 2.0 meq / kg or less, still more preferably 1.5 meq / kg or less.
• the lower limit of the amount of CEG for the carboxy group at the carboxyphenyl terminal is not particularly limited, but may be, for example, 0.1 meq / kg or more.
• the ratio of the CEG amount to the carboxy group at the carboxyphenyl terminal to the total CEG amount may be 90% or less, preferably 85%, from the viewpoint of suppressing the amount of gas generated during heating. Below, it may be more preferably 80% or less.
• the lower limit of the ratio of the CEG amount to the carboxy group at the carboxyphenyl terminal to the total CEG amount is not particularly limited, but may be, for example, 5% or more.
• the liquid crystal polyester fiber of the present invention may have a total end amount of 50.0 meq / kg or more, preferably 55.0 meq / kg or more, and more preferably 60.0 meq / kg or more.
• the total one-sided amount of the liquid crystal polyester fiber is the terminal of the carboxy group derived from hydroxycarboxylic acid and the terminal of the carboxy group derived from hydroxycarboxylic acid from which carbon dioxide is desorbed by the decarbonation reaction with respect to 1 kg of the liquid crystal polyester fiber.
• the upper limit of the total one-sided end amount is not particularly limited, but if the molecular weight is too low, the strength required for processing the fiber may not be obtained. Therefore, for example, it may be 200 meq / kg or less, preferably 100 meq. It may be less than / kg.
• liquid crystal polyester fibers can exhibit extremely high mechanical properties by increasing the molecular weight of the polymer by heat-treating and solid-phase polymerizing the spun yarn obtained by melt-spinning.
• the liquid crystal polyester fiber of the present invention may be a spun yarn or a heat-treated yarn which has been solid-phase polymerized as long as the effect of the present invention is not impaired.
• the liquid crystal polyester fiber of the present invention is preferably a spun yarn when used as a fused fiber. ..
• the liquid crystal polyester fiber of the present invention may have a strength of less than 18 cN / dtex, preferably 2 to 16 cN / dtex, and more preferably 6 to 12 cN / dtex.
• the strength of the liquid crystal polyester fiber means the tensile strength, which is a value measured by the method described in Examples described later.
• the liquid crystal polyester fiber of the present invention may have a melting point of 380 ° C. or lower, preferably 250 to 350 ° C., and more preferably 260 to 300 ° C. from the viewpoint of being used as a fusion fiber.
• the melting point of the liquid crystal polyester fiber is a value measured by the method described in Examples described later.
• the single fiber fineness can be appropriately selected depending on the intended use, for example, the single fiber fineness may be 0.5 to 50 dtex, preferably 1.0 to 35 dtex, and more preferably 1.0 to 35 dtex. It may be 1.0 to 15 dtex, more preferably 1.5 to 10 dtex.
• the liquid crystal polyester fiber of the present invention may be a monofilament or a multifilament.
• the number of filaments can be appropriately selected depending on the intended use, for example, the number of filaments may be 5 to 5000, preferably 10 to 4000, and more preferably 30 to 3000. You may.
• the total fineness of the liquid crystal polyester fiber of the present invention can be appropriately selected depending on the intended use, for example, the total fineness may be 10 to 50,000 dtex, preferably 15 to 30,000 dtex, and more preferably 25 to 10000 dtex. May be good.
• the amount of CO 2 gas generated as measured by the examples described later may be 2.0 mmol / kg or less, preferably 1.5 mmol / kg or less, more preferably 1.0 mmol. It may be less than / kg.
• the liquid crystal polyester fiber of the present invention can be used as a fused fiber for producing a molded product using the liquid crystal polyester fiber as a matrix.
• a fiber structure containing at least a part of the liquid crystal polyester fiber can be used as an intermediate material for producing a melt-molded body.
• the fiber structure containing the liquid crystal polyester fiber of the present invention can be used in any fiber form such as staple fiber, shortcut fiber, filament yarn, spun yarn, string, rope, etc., and the liquid crystal polyester fiber is used. It can also be used as various fabrics such as non-woven fabrics, textiles, and knitted fabrics. Such fibers and fabrics can be produced using liquid crystal polyester fibers by a known method.
• the fiber structure of the present invention may be a combination of a liquid crystal polyester fiber and another fiber as long as the effect of the present invention is not impaired.
• a composite fiber using a liquid crystal polyester fiber and another fiber for example, a mixed fiber in which a liquid crystal polyester fiber and another fiber are mixed
• a composite fabric using a liquid crystal polyester fiber and another fiber for example, a mixed fiber cloth in which a liquid crystal polyester fiber and another fiber are mixed, or a cloth made of a liquid crystal polyester fiber and a cloth made of another fiber.
• Laminates, etc. can be used.
• the fiber structure When the fiber structure is used for producing a reinforced fiber molded body (fiber reinforced composite material), the fiber structure may be a composite fiber or a composite fabric containing the reinforcing fiber as another fiber.
• the reinforcing fiber the reinforcing fiber described above can be used.
• the molded body may be any as long as it can be obtained by molding the fiber structure.
• the molded body may be a molded body obtained by molding the fiber structure and does not contain reinforcing fibers. It may be a reinforcing fiber molded body formed by molding together with reinforcing fibers. Since the fiber structure can be made flexible, it is possible to form various three-dimensional shaped bodies such as a cylinder and a dome by weaving, knitting, or the like.
• the molded body can be obtained by heating and molding the fiber structure at a temperature equal to or higher than the melting point of the liquid crystal polyester fiber.
• the molding method is not particularly limited as long as the liquid crystal polyester fibers are melted and integrated, and a known molding method for a molded product can be used. Since the liquid crystal polyester fiber of the present invention can suppress the generation of bubbles during heat fusion, it is possible to obtain a high-quality molded product.
• the obtained molded body has excellent vibration damping properties and should be effectively used in applications where vibration is generated, such as duct tubes and bumpers of automobiles. Can be done.
• the measurement was performed using the same device and pan as for measuring the melting point of the liquid crystal polyester. However, in order to remove the peak of hydrated water and residual solvent, nitrogen was flowed as a carrier gas at a flow rate of 100 mL / min, the temperature was raised from 25 ° C to 20 ° C / min to 150 ° C, held for 1 minute, and then -20 ° C. After the temperature was lowered to 25 ° C. at / min, the heat absorption peak that appeared at the lowest temperature was measured when the temperature was raised again from 25 ° C. to 20 ° C./min.
• a liquid for analysis was prepared by "microwave decomposition” described below, and the metal element content (weight ppm) was determined by ICP-MS measurement.
• -Microwave decomposition Microwave decomposition was performed using a microwave decomposition device "ETHOS-1" manufactured by Milestone General Co., Ltd. 0.1 g of a liquid crystal polyester resin composition chip sample or a liquid crystal polyester fiber sample was weighed into a quartz insert, and 6 mL of nitric acid (1.42 mol / L) was added. Quartz inserts were placed in a decomposition container containing 5 mL of water and 2 mL of hydrogen peroxide (concentration 30 to 36% by weight), sealed, and microwave-decomposed.
• the volume was adjusted to 50 mL, and the filtrate filtered with a filter having a pore size of 0.45 ⁇ m was used for ICP-MS measurement.
• ICP-MS measurement Using the ICP-MS analyzer "Agient 7900" manufactured by Agilent Technologies, the metal element content of the sample liquid prepared by the above microwave decomposition was analyzed. Under the conditions of carrier gas flow rate of 0.7 L / min and RF output of 1500 W, measurement was performed three times from the same sample solution as compared with XSTC-622 (standard solution manufactured by SPEX), and the content of each metal element was calculated from the average value. Decided.
• the liquid crystal polyester fiber sample was taken out and rinsed twice for 40 minutes with 1 L of ion-exchanged water whose temperature was adjusted to 60 to 90 ° C.
• the liquid crystal polyester fiber sample was taken out and dried at 80 ° C. for 3 hours or more in an air atmosphere using a hot air dryer "DN63HI” manufactured by Yamato Kagaku Co., Ltd. to obtain a liquid crystal polyester fiber sample from which the oil was removed.
• the decomposition products are separated by the HPLC method, and the peak area of the decomposition products having a carboxy group is compared with the calibration line prepared by the HPLC analysis of each standard to obtain the carboxy terminal amount derived from each monomer. (Meq / kg) was quantified.
• the amount of CEG derived from a monovalent carboxylic acid such as 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid can be obtained by quantifying 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid as it is.
• the amount of CEG derived from divalent carboxylic acids such as terephthalic acid, isophthalic acid and 6-naphthalenedicarboxylic acid is terephthalic acid monon-propylamide, isophthalic acid monon-propylamide and 2,6-naphthalenedicarboxylic acid monon-. It is obtained by quantifying a substance such as propylamide in which one carboxy group is amidated. The total of all carboxy-terminal amounts contained in each sample was taken as the total carboxy-terminal amount (total CEG amount) of the sample.
• the total amount of the carboxy-terminal of carboxyphenyl (for example, the carboxy-terminal derived from a monomer having a carboxyphenyl group such as 4-hydroxybenzoic acid, terephthalic acid, and isophthalic acid) contained in each sample is calculated for the carboxy group at the carboxyphenyl terminal.
• the amount of CEG was used.
• the liquid crystal polyester resin composition chip sample or the liquid crystal polyester fiber sample was decomposed with n-propylamine, and the carboxy terminal amount derived from hydroxycarboxylic acid and the terminal derived from hydroxycarboxylic acid were decomposed.
• the total amount (meq / kg) of the terminal amount generated by the decarbonation reaction of the carboxy group of the above was quantified.
• the terminal amount derived from 4-hydroxybenzoic acid is determined by quantifying 4-hydroxybenzoic acid and phenol, and the terminal amount derived from 6-hydroxy-2-naphthoic acid is 6-hydroxy-2-naphthoic acid.
• 2-naphthol is determined by quantification.
• the total terminal amount derived from hydroxycarboxylic acid is divided by the molar ratio of the constituent units derived from hydroxycarboxylic acid in the liquid crystal polyester of the sample. The value obtained was taken as the total terminal amount of the sample.
• melt viscosity Using a melt viscosity measuring device (Capillograph 1C manufactured by Toyo Seiki Co., Ltd.), using a 1.00 mm ⁇ ⁇ 10 mm capillary, the melting point of the liquid crystal polyester is Mp 0 (the melting point of the liquid crystal polyester in the resin composition measured above).
• the melt viscosities (Pa ⁇ s) at a shear rate of 1216 sec -1 were measured under the temperature condition of Mp 0 + 30 ° C.
• total fineness, single fiber fineness Based on JIS L 1013: 2010 8.3.1 A method, liquid crystal polyester fiber is lapped 1m x 100 laps (total 100m) using the measuring instrument "Wrap Reel by Motor Driven” manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd. The weight (g) was multiplied by 100 and measured twice per level, and the average value was taken as the total fineness (dtex) of the obtained liquid crystal polyester fiber. The quotient obtained by dividing this value by the number of filaments was taken as the single fiber fineness (dtex).
• GC gas chromatograph
• a liquid crystal polyester fiber knit fabric was produced using a circular knitting machine (MR-1, diameter 10 cm, 28 gauge) manufactured by Maruzen Sangyo Co., Ltd. This dough was cut into squares with a side of 10 cm, and three pieces were stacked.
• MR-1 circular knitting machine
• Upirex-S, 125S polyimide film
• a SUS304 metal plate with a thickness of 1 mm and a square hole with a side of 10 cm is placed on it to form a square.
• the second polyimide film (same as above) was placed on the metal plate. This was sandwiched from above and below with a flat plate heating press device at a pressure of 0.1 MPa or less, and contact-heated at the melting point of the liquid crystal polyester fiber at + 20 ° C. for 5 minutes. Then, after applying a pressure of 2 MPa for 1 minute, it was opened to the atmosphere and cooled to 100 ° C. or lower to obtain a liquid crystal polyester fiber-derived resin plate as a sample for appearance evaluation. The front and back of a square area with a side of 6 cm in the center of this appearance evaluation sample were observed with a loupe, and the number of bubbles having a major axis of 1 mm or more was counted.
• the resin colored with the pigment was put into the extruder, and the time until the colored resin came out from the tip of the extruder was measured and determined. That is, 5% by weight of graphite powder (AT-No. 20-0.5, particle size 5-11 ⁇ m) manufactured by AS ONE Co., Ltd. is mixed with the resin composition used in each Example and Comparative Example to form a liquid crystal.
• a resin (colored resin) cut after melt-kneading and extrusion at a heater temperature of the melting point of polyester + 20 ° C. was prepared.
• the resin composition used, the melt extrusion temperature, and the discharge amount described in each Example and Comparative Example were used.
• the time from when a small amount of colored resin was added to the time when the colored resin came out from the die was measured and used as the residence time in the extruder of the resin composition. Since the colored resin to be discharged has an increase or decrease in color tone from light to dark to light, the darkest point visually confirmed is set as the discharge time.
• the amount of the colored resin added should be an appropriate amount so that the change in color can be confirmed. However, if the amount is too large, steady melt extrusion cannot be performed. Therefore, the amount of the non-colored resin discharged per 6 seconds (28 g / g / For minutes, it is better to use less than 2.8 g).
• the inside of the reaction vessel is pressurized to about 0.02 to 0.5 MPa with nitrogen, the sample is discharged in a rod shape from the discharge port provided at the bottom of the reaction vessel, and cooled in cooling water. Then, it was cut with a rotary cutter so that the major axis was 5 mm or less.
• a liquid crystal polyester resin ( ⁇ ) (Mp 0 : 281 ° C.) having an ppm or less was obtained.
• a liquid crystal polyester resin ( ⁇ ) (Mp 0 : 315 ° C.) having a total content of alkaline earth metal of 10% by weight or less was obtained.
• Example 1-1 For the chip (granular molded body) of the liquid crystal polyester resin ( ⁇ ) obtained in Reference Example 1, copper acetate (I) (manufactured by Fujifilm Wako Chemical Co., Ltd., melting point 271 ° C.) powder was added as a copper atom as a decarbonation catalyst. It was added to 50 wt ppm (copper element content with respect to the total amount of resin chips and catalyst) in terms of conversion, and mixed well with a shaking device. The blend of the resin chip and the catalyst thus obtained was dried with hot air at 120 ° C.
• copper acetate (I) manufactured by Fujifilm Wako Chemical Co., Ltd., melting point 271 ° C.
• the temperature of the tip die from the extruder outlet was set to 310 ° C.
• the resin is discharged in a rod shape from a circular hole of ⁇ 3 mm at a discharge rate of 28 g / min, and while taking this at a winding speed of 5 m / min, the rod-shaped resin composition is cut with a rotary cutter so that the major axis is 5 mm or less.
• a resin composition chip was obtained in the above.
• the analysis results of the liquid crystal polyester resin composition chip thus obtained are shown in Table 5.
• Example 1-2 Two types of reagents: copper iodide (I) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) and 1,10-phenanthroline (manufactured by Fujifilm Wako Chemical Industries, Ltd.) in the same molar amount as copper (I) iodide.
• copper (I) iodide To 1 mol of copper (I) iodide, add 5 L of acetonitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent), stir in a suspension state for 1 hour, filter, and filter at 100 ° C. The mixture was dried for 3 hours to obtain an orange solid (melting point 300 ° C.).
• a liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1 except that this solid was used as a decarbonation catalyst instead of copper (I) acetate so as to have a copper atom equivalent of 50 ppm by weight.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-3 Except for the addition of copper acetate (II) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako first grade, melting point 115 ° C) as a decarbonation catalyst instead of copper acetate (I) so as to be 50 ppm by weight in terms of copper atom.
• a liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-4 Copper (II) Sulfate pentahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) and 1,10-phenanthroline (Fujifilm Wako Chemical) in double the molar amount of copper (II) sulfate pentahydrate.
• Add 5 L of acetonitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) to 1 mol of copper (II) sulfate pentahydrate, and stir in a suspension state. After 1 hour, it was filtered and dried at 100 ° C. for 3 hours to obtain a blue solid (melting point 294 ° C.).
• a liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1 except that this solid was used as a decarbonation catalyst instead of copper (I) acetate so as to have a copper atom equivalent of 50 ppm by weight.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-5 Cobalt (II) acetate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako special grade, melting point 194 ° C.) as a decarbonation catalyst instead of copper (I) acetate is adjusted to 500 parts by weight in terms of cobalt atom.
• a liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1 except that it was added. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-6 Palladium acetate (II) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako special grade, melting point 205 ° C.) was added as a decarbonation catalyst in place of copper (I) acetate so as to be 500 ppm by weight in terms of palladium atoms.
• a liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-7 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 5 wt ppm in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-8 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 500 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-9 A liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1 except that the resin composition was discharged at a discharge rate of 11.0 g / min. The residence time of the resin composition in the extruder under these melt extrusion conditions was 12 to 13 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-10 Using the liquid crystal polyester resin ( ⁇ ) obtained in Reference Example 2 instead of the liquid crystal polyester resin ( ⁇ ), the temperature of the extruder heater when performing melt extrusion is 360 ° C, and the temperature of the tip die from the extruder outlet is 360.
• a liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1 except that the temperature was set to ° C. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-11 Using the liquid crystal polyester resin ( ⁇ ) obtained in Reference Example 3 instead of the liquid crystal polyester resin ( ⁇ ), the temperature of the extruder heater when performing melt extrusion is 340 ° C, and the temperature of the tip die from the extruder outlet is 350.
• a liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1 except that the temperature was set to ° C. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-12 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 10 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-13 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 20 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-14 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 30 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-15 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 70 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-16 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 100 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-17 Liquid crystal polyester resin composition chip in the same manner as in Example 1-2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 150 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-1 A liquid crystal polyester resin composition chip was obtained in the same manner as in Example 1-1 except that the decarboxylation catalyst was not added. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-2 Same as Example 1-1 except that potassium acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a catalyst instead of copper (I) acetate so as to be 50 wt ppm in terms of potassium atom.
• a liquid crystal polyester resin composition chip was obtained.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1- Example 1-Except that N, N-dimethyl-4-aminopyridine (DMAP) (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) was added as a catalyst in place of copper (I) acetate at a weight ratio of 1 wt%.
• DMAP N, N-dimethyl-4-aminopyridine
• a liquid crystal polyester resin composition chip was obtained in the same manner as in 1.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-4 Same as Example 1-10 except that potassium acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a catalyst instead of copper (I) acetate so as to be 50 wt ppm in terms of potassium atom.
• a liquid crystal polyester resin composition chip was obtained.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Example 1-5 Same as Example 1-11 except that potassium acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a catalyst instead of copper (I) acetate so as to be 50 wt ppm in terms of potassium atom.
• a liquid crystal polyester resin composition chip was obtained.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• Table 5 shows the analysis results of the obtained liquid crystal polyester resin composition chip.
• Examples 1-1 to 1-17 contain a specific metal element, the decarboxylation reaction can be promoted by the catalytic action thereof, and the total amount of CEG can be reduced. There is. Therefore, the liquid crystal polyester compositions of Examples 1-1 to 1-17 can suppress the generation of gas, and the resin plate produced using the same can suppress the generation of bubbles.
• the liquid crystal polyester resin composition of Comparative Example 1-1 does not contain a catalyst, the decarboxylation reaction does not proceed and the total amount of CEG is large. Therefore, the liquid crystal polyester resin composition of Comparative Example 1-1 generates more than three times as much CO 2 gas as that of Examples 1-1 to 1-17 to which a catalyst containing a specific metal element is added. However, even in the resin plate manufactured by using it, more bubbles are generated as compared with these examples.
• Comparative Example 1-3 the organic catalyst used as the polymerization catalyst for synthesizing the liquid crystal polyester was used, and in Comparative Examples 1-2, 1-4 and 1-5, the alkali metal similarly used as the polymerization catalyst was used. Although it is contained, it does not have a catalytic action on the decarbonation reaction, so that all the liquid crystal polyester resin compositions have a large total CEG amount. Therefore, the liquid crystal polyester resin compositions of Comparative Examples 1-2 to 1-5 are three times or more more than those of Examples 1-1 to 1-17 to which a decarboxylation catalyst containing a specific metal element is added. CO 2 gas is generated, and more bubbles are generated in the resin plate manufactured by using the CO 2 gas as compared with these examples.
• Example 2-1 For the chip (granular molded body) of the liquid crystal polyester resin ( ⁇ ) obtained in Reference Example 1, copper acetate (I) (manufactured by Fujifilm Wako Chemical Co., Ltd., melting point 271 ° C.) powder was added as a copper atom as a decarbonation catalyst. It was added to 50 wt ppm (copper element content with respect to the total amount of resin chips and catalyst) in terms of conversion, and mixed well with a shaking device. The blend of the resin chip and the catalyst thus obtained was dried with hot air at 120 ° C.
• copper acetate (I) manufactured by Fujifilm Wako Chemical Co., Ltd., melting point 271 ° C.
• the spinning head is equipped with a spinneret having a hole diameter of 0.125 mm ⁇ , a land length of 0.175 mm, and a number of holes of 50.
• Polyester fiber (spun yarn) was obtained.
• a 2% by weight sodium dodecyl phosphate (Wako Pure Chemical Industries, Ltd., Wako first grade) aqueous solution was applied to the spinning yarn from an oiling guide arranged directly under the spinning cap.
• the amount of this aqueous solution applied was 1.4 g / min, and the adhesion ratio of sodium dodecyl phosphate to the spinning yarn was calculated to be 0.1% by weight.
• the analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-2 Using the orange solid (copper iodide (I), 1,10-phenanthroline, melting point 300 ° C.) described in Example 1-2 as a decarbonation catalyst instead of copper (I) acetate, 50 wt ppm in terms of copper atom.
• a liquid crystal polyester fiber (spun raw yarn) was obtained in the same manner as in Example 2-1 except that it was used so as to be.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• the analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-3 Except for the addition of copper acetate (II) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako first grade, melting point 115 ° C) as a decarbonation catalyst instead of copper acetate (I) so as to be 50 ppm by weight in terms of copper atom.
• a liquid crystal polyester fiber (spun raw yarn) was obtained in the same manner as in Example 2-1. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-4 Using the blue solid (copper sulfate (II), 1,10-phenanthroline, melting point 294 ° C.) described in Example 1-4 as a decarbonation catalyst instead of copper (I) acetate, the amount is reduced to 50 ppm by weight in terms of copper atoms.
• a liquid crystal polyester fiber (spun raw yarn) was obtained in the same manner as in Example 2-1 except that it was used so as to be. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-5 Cobalt (II) acetate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako special grade, melting point 194 ° C.) as a decarbonation catalyst instead of copper (I) acetate so as to have a cobalt atom equivalent of 500 ppm by weight.
• a liquid crystal polyester fiber spun raw yarn was obtained in the same manner as in Example 2-1 except that it was added. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-6 Palladium acetate (II) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako special grade, melting point 205 ° C.) was added as a decarbonation catalyst instead of copper (I) acetate so as to be 500 ppm by weight in terms of palladium atom.
• a liquid crystal polyester fiber (spun raw yarn) was obtained in the same manner as in Example 2-1. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-7 Liquid crystal polyester fiber (spinning source) in the same manner as in Example 2-2, except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 5 parts by weight in terms of copper atoms. Thread) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-8 Liquid crystal polyester fiber (spun yarn) in the same manner as in Example 2 except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 500 ppm by weight in terms of copper atoms. Got The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-9 For the chip (granular molded body) of the liquid crystal polyester resin ( ⁇ ) obtained in Reference Example 1, copper acetate (I) (manufactured by Fujifilm Wako Chemical Co., Ltd., melting point 271 ° C.) powder was added as a copper atom as a decarbonation catalyst. It was added to a conversion of 500 ppm by weight and mixed well with a shaking device. The blend of the resin chip and the polymerization catalyst thus obtained was dried with hot air at 120 ° C. for 4 hours or more, and then heated with a ⁇ 15 mm twin-screw extruder (“KZW15TW-45MG-NH (-700)” manufactured by Technobel Co., Ltd.).
• KZW15TW-45MG-NH (-700) manufactured by Technobel Co., Ltd.
• Melt extrusion was performed at a temperature of 300 ° C., and the resin composition was supplied to the tip die while measuring with a gear pump. At this time, a decompression pump (Dry pump manufactured by Orion Machinery Co., Ltd., "KRF40A-V-01B") is connected from the vent portion in the middle of the twin-screw extruder via a metal pipe, and the resin composition in the twin-screw extruder is not filled. The space was reduced to 60 kPa. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. At this time, the temperature of the tip die from the extruder outlet was set to 310 ° C.
• the resin With the tip die, the resin is discharged in a rod shape from a circular hole of ⁇ 3 mm at a discharge rate of 28 g / min, and while taking this at a winding speed of 5 m / min, the rod-shaped resin composition is cut with a rotary cutter so that the major axis is 5 mm or less.
• a resin composition chip was obtained in the above.
• the resin composition chip thus obtained (mixture equivalent to 500 wt ppm of copper element) and the chip of liquid crystal polyester resin ( ⁇ ) are mixed at a weight ratio of 1: 9, mixed well with a shaking device, and at 120 ° C. for 4 hours. The above was dried with hot air.
• the blend of the two types of chips thus obtained is melt-extruded with a ⁇ 15 mm twin-screw extruder (Technobel Co., Ltd., “KZW15TW-45MG-NH (-700)”) at a heater temperature of 300 ° C. and weighed with a gear pump. While doing so, the resin composition was supplied to the spinning head. At this time, a decompression pump (Dry pump manufactured by Orion Machinery Co., Ltd., "KRF40A-V-01B”) is connected from the vent portion in the middle of the twin-screw extruder via a metal pipe, and the resin composition in the twin-screw extruder is not filled. The space was reduced to 60 kPa.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• the temperature of the spinning head from the extruder outlet at this time was set to 310 ° C.
• the spinning head is equipped with a spinneret having a hole diameter of 0.125 mm ⁇ , a land length of 0.175 mm, and a number of holes of 50.
• a polyester fiber (spun yarn) was obtained.
• a 2% by weight sodium dodecyl phosphate (Wako Pure Chemical Industries, Ltd., Wako first grade) aqueous solution was applied to the spinning yarn from an oiling guide arranged directly under the spinning cap.
• the amount of this aqueous solution applied was 1.4 g / min, and the adhesion ratio of sodium dodecyl phosphate to the spinning yarn was calculated to be 0.1% by weight.
• the analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-10 A liquid crystal polyester fiber (spun yarn) was obtained in the same manner as in Example 2-1 except that a spinneret having a hole diameter of 0.100 mm ⁇ , a land length of 0.140 mm, and a number of holes of 100 was used. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-11 A liquid crystal polyester fiber (spun yarn) was obtained in the same manner as in Example 2-1 except that a spinneret having a hole diameter of 0.150 mm ⁇ , a land length of 0.210 mm, and 20 holes was used. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-12 A spinneret having a hole diameter of 0.125 mm ⁇ , a land length of 0.175 mm, and 20 holes was used, the resin composition was discharged at a discharge rate of 11.0 g / min, and an aqueous solution of sodium dodecyl phosphate was applied from an oiling guide. Liquid crystal polyester fibers (spun yarn) were obtained in the same manner as in Example 2-1 except that the amount was 0.55 g / min. The residence time of the resin composition in the extruder under these melt extrusion conditions was 12 to 13 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-13 Using the liquid crystal polyester resin ( ⁇ ) obtained in Reference Example 2 instead of the liquid crystal polyester resin ( ⁇ ), the temperature of the extruder heater when performing melt extrusion is 360 ° C, and the temperature of the spinning head from the outlet of the extruder is 360. Liquid crystal polyester fibers (spun raw yarn) were obtained in the same manner as in Example 2-1 except that the temperature was set to ° C. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-14 Using the liquid crystal polyester resin ( ⁇ ) obtained in Reference Example 3 instead of the liquid crystal polyester resin ( ⁇ ), the temperature of the extruder heater when performing melt extrusion is 340 ° C, and the temperature of the spinning head from the outlet of the extruder is 350. Liquid crystal polyester fibers (spun raw yarn) were obtained in the same manner as in Example 2-1 except that the temperature was set to ° C. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-15 Liquid crystal polyester fiber (spinning source) in the same manner as in Example 2-2, except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 10 ppm by weight in terms of copper atoms. Thread) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-16 Liquid crystal polyester fiber (spinning source) in the same manner as in Example 2-2, except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 20 ppm by weight in terms of copper atoms. Thread) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-17 Liquid crystal polyester fiber (spinning source) in the same manner as in Example 2-2, except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 30 ppm by weight in terms of copper atoms. Thread) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-18 Liquid crystal polyester fiber (spinning source) in the same manner as in Example 2-2, except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 70 ppm by weight in terms of copper atoms. Thread) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-19 Liquid crystal polyester fiber (spinning source) in the same manner as in Example 2-2, except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 100 ppm by weight in terms of copper atoms. Thread) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-20 Liquid crystal polyester fiber (spinning source) in the same manner as in Example 2-2, except that the weight ratio of adding an orange solid (copper iodide (I), 1,10-phenanthroline) to the resin was 150 ppm by weight in terms of copper atoms. Thread) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-1 Liquid crystal polyester fibers (spun yarn) were obtained in the same manner as in Example 2-1 except that the decarboxylation catalyst was not added. The residence time of the resin in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-2 In the same manner as in Example 2-1 except that potassium acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a catalyst instead of copper (I) acetate so as to be 50 wt ppm in terms of potassium atom. A liquid crystal polyester fiber (spun raw yarn) was obtained. The residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes. The analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2- Example 2-Except that N, N-dimethyl-4-aminopyridine (DMAP) (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) was added as a catalyst in place of copper (I) acetate at a weight ratio of 1 wt%.
• DMAP N, N-dimethyl-4-aminopyridine
• a liquid crystal polyester fiber (spun yarn) was obtained in the same manner as in 1.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• the analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Example 2-4 The same as in Example 2-13 except that potassium acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a catalyst instead of copper (I) acetate so as to be 50 wt ppm in terms of potassium atom.
• a liquid crystal polyester fiber (spun raw yarn) was obtained.
• the residence time of the resin composition in the extruder under these melt extrusion conditions was 5 to 6 minutes.
• the analysis results of the obtained liquid crystal polyester fiber are shown in Table 6.
• Examples 2-1 to 2-20 contain a specific metal element, the decarboxylation reaction can be promoted by the catalytic action thereof, and the total amount of CEG can be reduced. There is. Therefore, the liquid crystal polyester fibers of Examples 2-1 to 2-20 can suppress the generation of gas, and the resin plate produced using the fibers can suppress the generation of bubbles.
• the liquid crystal polyester fiber of Comparative Example 2-1 does not contain a catalyst, the decarboxylation reaction does not proceed and the total amount of CEG is large. Therefore, the liquid crystal polyester fiber of Comparative Example 2-1 generates more than three times as much CO 2 gas as that of Examples 2-1 to 2-20 to which a catalyst containing a specific metal element is added. Even in the resin plate manufactured using it, more bubbles are generated as compared with these examples.
• Comparative Example 2-3 the organic catalyst used as the polymerization catalyst for synthesizing the liquid crystal polyester was used, and in Comparative Examples 2-2, 2-4 and 2-5, the alkali metal similarly used as the polymerization catalyst was used. Although it is contained, since it does not have a catalytic action on the decarbonation reaction, all the liquid crystal polyester fibers have a large total CEG amount. Therefore, the liquid crystal polyester fibers of Comparative Examples 2-2-2-5 have three times or more more CO than those of Examples 2-1 to 2-20 to which a decarboxylation catalyst containing a specific metal element is added. Two gases are generated, and more bubbles are generated in the resin plate manufactured by using the two gases as compared with these examples.
• the liquid crystal polyester resin composition of the present invention can suppress the generation of gas during heating, it is possible to produce a good quality molded product with few bubbles by melt molding.
• the melt molded body include a molded body having a three-dimensional shape, a molded body having various shapes such as a sheet, a film, and a fiber, and the obtained molded body has excellent vibration damping properties, and therefore, for example, a duct tube or an automobile. It is effective for applications that generate vibration such as bumpers.
• liquid crystal polyester fiber of the present invention can suppress the generation of gas during heating, it can be used as a fused fiber for producing a molded product (for example, a fiber reinforced composite material).

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• 2021
  • 2021-11-15 KR KR1020237019766A patent/KR20230101908A/ko active Pending
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• 2023
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