Classifications

• • 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
  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
  • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
  • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
  • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
  • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
  • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
  • D06M13/03—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons with unsaturated hydrocarbons, e.g. alkenes, or alkynes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/165—Ethers
  • D06M13/17—Polyoxyalkyleneglycol ethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

• the present invention relates to a treatment agent for carbon fiber precursors and its uses. More specifically, it relates to a treatment agent used in producing carbon fiber precursors, a carbon fiber precursor (hereinafter sometimes referred to as a precursor) using the treatment agent, and a method for producing carbon fiber using the treatment agent.
• a treatment agent used in producing carbon fiber precursors a carbon fiber precursor (hereinafter sometimes referred to as a precursor) using the treatment agent, and a method for producing carbon fiber using the treatment agent.
• carbon fibers are widely used as reinforcing fibers for composite materials with plastics called matrix resins in aerospace, sports, general industrial, and other applications.
• a common method for producing carbon fibers is to first produce a carbon fiber precursor (this production process is sometimes referred to as a spinning process). This carbon fiber precursor is converted into a flame-resistant fiber in an oxidizing atmosphere at 200 to 300°C (this process is sometimes referred to hereinafter as a flame-resistant treatment process), and then carbonized in an inert atmosphere at 300 to 2000°C (this process is sometimes referred to hereinafter as a carbonization treatment process).
• the flame-resistant treatment process and the carbonization treatment process will be collectively referred to as a baking process.
• a baking process In this baking process, fusion between single fibers occurs, which is likely to cause problems such as fluffing and yarn breakage, and has been an obstacle to improving productivity.
• a silicone-based treatment agent is applied to the carbon fiber precursor during production.
• Numerous techniques have been proposed for applying the treatment agent in the form of a water-based emulsion to ensure uniform application. (See Patent Documents 1 and 2.)
• an object of the present invention is to provide a treatment agent for carbon fiber precursors that can suppress deterioration of the carbon fiber precursor when the carbon fiber precursor produced by applying the treatment agent is stored for a long period of time, a carbon fiber precursor using the treatment agent, and a method for producing carbon fiber using the treatment agent.
• a treatment agent for carbon fiber precursors containing a silicone (A) having an amino group and an aromatic compound (B) having a diphenylmethane skeleton and satisfying at least one selected from specific condition 1 and specific condition 2 can inhibit deterioration of carbon fiber precursors produced by applying the treatment agent for carbon fiber precursors when the carbon fiber precursors are stored for long periods of time, leading to the present invention.
• the treating agent for carbon fiber precursors of the present invention includes the following embodiments.
• a treatment agent for carbon fiber precursors comprising a silicone (A) having an amino group and an aromatic compound (B) having a diphenylmethane skeleton, and satisfying at least one of the following conditions 1 and 2:
• Condition 1 The acid value of the treatment agent is 0.1 to 30 mgKOH/g.
• Condition 2 The treating agent contains a Bronsted acid compound (D), and the proportion of the Bronsted acid compound (D) in the nonvolatile components of the treating agent is 0.05 to 10% by weight.
• ⁇ 3> The treating agent for carbon fiber precursors according to ⁇ 1> or ⁇ 2>, wherein the aromatic compound (B) contains an aromatic compound having at least one skeleton selected from a bisphenol A skeleton and a bisphenol F skeleton.
• the aromatic compound (B) contains an aromatic compound having at least one skeleton selected from a bisphenol A skeleton and a bisphenol F skeleton.
• C an aliphatic (poly)oxyalkylene derivative
• D Bronsted acid compound
• ⁇ 6> The treatment agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 5>, which satisfies the conditions 1 and 2.
• ⁇ 7> The treating agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 6>, containing an acetylene-based compound (E).
• ⁇ 8> ⁇ 1> to ⁇ 7>, wherein the proportion of the aromatic compound (B) in the non-volatile content of the treatment agent is 10 to 99% by weight.
• a method for producing a carbon fiber comprising: a flame-resistant treatment step of converting the carbon fiber precursor according to ⁇ 9> into a flame-resistant fiber; and a carbonization treatment step of further carbonizing the flame-resistant fiber.
• the treatment agent for carbon fiber precursors of the present invention can suppress deterioration of carbon fiber precursors even when the carbon fiber precursors produced by applying the treatment agent are stored for a long period of time, and carbon fibers with excellent physical properties can be obtained even when carbon fiber precursors that have been stored for a long period of time are used.
• the carbon fiber precursor and the method for producing carbon fiber of the present invention can provide carbon fiber with excellent physical properties even when using a carbon fiber precursor that has been stored for a long period of time.
• the treatment agent of the present invention contains an amino group-containing silicone (A).
• the amino group-containing silicone (A) is not particularly limited as long as it has an inorganic siloxane bond (—Si—O—Si—) main chain and an organic group having an amino group on the side chain and/or terminal.
• Examples of the amino group-containing silicone (A) include amino-modified silicones and amino polyether-modified silicones, and it is more preferable to include an amino-modified silicone in terms of achieving the effects of the present invention.
• the amino polyether-modified silicone is a silicone having an amino group (including an organic group having an amino group) and a polyether group (including an organic group having a polyoxyalkylene group).
• Known amino-modified silicones and amino polyether-modified silicones can be used.
• the amino group-containing silicone (A) may be used alone or in combination with two or more other silicones.
• the kinematic viscosity of the amino group-containing silicone (A) at 25°C is preferably 50 to 20,000 mm 2 /s from the viewpoints of uniform adhesion to fibers, suppression of scattering of the treatment agent, and imparting sizing properties to fibers.
• the upper limit of the kinematic viscosity is more preferably 15,000 mm 2 /s, even more preferably 12,000 mm 2 /s, particularly preferably 10,000 mm 2 /s, and most preferably 3,000 mm 2 /s.
• the lower limit of the kinematic viscosity is more preferably 100 mm 2 /s, even more preferably 150 mm 2 /s, and particularly preferably 200 mm 2 /s.
• 100 to 15,000 mm 2 /s is more preferable, 150 to 10,000 mm 2 /s is even more preferable, and 200 to 3,000 mm 2 /s is particularly preferable.
• the amino group (including an organic group having an amino group), which is the modified group of the amino group-containing silicone (A), may be bonded to a side chain of the silicone main chain, to an end, or to both. However, from the perspective of protecting the fibers during the flame-retardant treatment process, it is preferable that it be bonded to a side chain (having an amino group on the side chain). Furthermore, the amino group may be a monoamine, diamine, or polyamine type, and both may coexist in one molecule.
• a monoamine or diamine type is preferred, with a diamine type being more preferred.
• the amino equivalent of the amino group-containing silicone (A) is preferably 300 to 10,000 g/mol from the viewpoint of preventing adhesion or fusion between fibers.
• the upper limit of the amino equivalent is more preferably 9,500 g/mol, even more preferably 9,000 g/mol, and particularly preferably 8,000 g/mol.
• the lower limit of the amino equivalent is more preferably 500 g/mol, even more preferably 1,000 g/mol, and particularly preferably 1,500 g/mol.
• 500 to 9,000 g/mol is more preferable, and 1,000 to 8,000 g/mol is even more preferable.
• amino equivalent refers to the mass of the siloxane skeleton per amino group or ammonium group.
• the unit of g/mol is the value converted to per mol of amino group or ammonium group. Therefore, a smaller amino equivalent value indicates a higher ratio of amino groups or ammonium groups in the molecule.
• Amino group-containing silicone (A) may be used in combination with multiple amino group-containing silicones with different amino equivalents and kinematic viscosities (25°C).
• the above amino equivalent refers to the amino equivalent of the entire amino group-containing silicone (A) (mixture)
• the above kinematic viscosity at 25°C refers to the kinematic viscosity of the entire amino group-containing silicone (A) (mixture).
• R1 represents an alkyl group having 1 to 20 carbon atoms.
• R2 represents a group represented by the following general formula (2).
• R3 represents R1 , R2 , or -OR9 ( R9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
• the order of the repeating units bracketed by a and b is not limited, and the bonding pattern may be alternating, block, or random.
• R 1 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.
• R 3 is a group represented by R 1 , R 2 , or -OR 9 , and is preferably R 1.
• Multiple R 9s in formula (1) may be the same or different.
• R9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.
• a is a number from 1 to 10,000, preferably 30 to 5,000, and more preferably 50 to 2,000.
• b is a number from 0 to 1,000, preferably 1 to 500, and more preferably 2 to 100.
• R4 and R6 are each independently an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.
• R5 , R7 , and R8 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.
• c is a number from 0 to 6, preferably 0 to 3, and more preferably 0 to 1.
• the treatment agent of the present invention contains an aromatic compound (B) having a diphenylmethane skeleton (hereinafter sometimes referred to as aromatic compound (B)).
• aromatic compound (B) there are no particular limitations on the aromatic compound (B) as long as it is an aromatic compound having a diphenylmethane skeleton, but in terms of achieving the effects of the present invention, at least one selected from a compound (B-1) having a structure in which an alkylene oxide is added to an aromatic compound having a hydroxyl group and a diphenylmethane skeleton, and an aromatic compound (B-2) having a diphenylmethane skeleton and an ester group is preferred, with the compound (B-1) having a structure in which an alkylene oxide is added to an aromatic compound having a hydroxyl group and a diphenylmethane skeleton being more preferred.
• One or more types of aromatic compounds (B) having a diphenylmethane skeleton may be used.
• the main skeleton of the aromatic compound (B) having a diphenylmethane skeleton can be, for example, diphenylmethane, and more preferably bisphenol.
• bisphenols include bisphenol A, AP, AF, B, BP, C, E, F, G, M, S, P, PH, TMC, and Z. Of these, in terms of improving the bundling ability during flame retardation, at least one selected from the bisphenol A skeleton, bisphenol B skeleton, bisphenol E skeleton, and bisphenol F skeleton is preferred, and at least one selected from the bisphenol A skeleton and bisphenol F skeleton is more preferred.
• the aromatic compound (B) having a diphenylmethane skeleton contains an aromatic compound having an oxyalkylene group.
• the oxyalkylene group contained in the aromatic compound (B) having a diphenylmethane skeleton is preferably at least one selected from an oxyethylene group and an oxypropylene group, with an oxyethylene group or an oxyethyleneoxypropylene group being preferred, and an oxyethylene group being even more preferred.
• the compound (B-1) having a structure in which an alkylene oxide is added to an aromatic compound having a hydroxyl group and a diphenylmethane skeleton is not particularly limited as long as it is a compound other than the aromatic compound (B-2) having a diphenylmethane skeleton and an ester group.
• bisphenol A alkylene oxide adducts bisphenol B alkylene oxide adducts, bisphenol E alkylene oxide adducts, and bisphenol F alkylene oxide adducts are preferred, with bisphenol A ethylene oxide adducts, bisphenol E alkylene oxide adducts, and bisphenol F alkylene oxide adducts being more preferred, and bisphenol A ethylene oxide adduct being even more preferred.
• the number of moles of alkylene oxide added in compound (B-1) having a structure in which alkylene oxide is added to an aromatic compound having a hydroxyl group and a diphenylmethane skeleton is preferably 2 to 60 moles.
• the upper limit of the number of moles added is more preferably 30 moles, even more preferably 18 moles, and particularly preferably 10 moles.
• the lower limit of the number of moles added is more preferably 4 moles, even more preferably 6 moles, and particularly preferably 8 moles. Also, for example, 4 to 18 moles is more preferable, and 6 to 18 moles is particularly preferable.
• the alkylene oxide preferably contains at least one selected from ethylene oxide and propylene oxide, and more preferably contains ethylene oxide.
• the alkylene oxide may be added randomly or in blocks.
• the aromatic compound (B-2) having a diphenylmethane skeleton and an ester group is not particularly limited as long as it has a diphenylmethane skeleton and an ester group, but examples include esters of aromatic compounds having a diphenylmethane skeleton and aliphatic carboxylic acids.
• One or more types of aromatic compounds (B-2) having a diphenylmethane skeleton and an ester group may be used.
• the aliphatic carboxylic acid constituting the aromatic compound (B-2) having a diphenylmethane skeleton and an ester group is not particularly limited, but examples include aliphatic monocarboxylic acids having 4 to 24 carbon atoms and aliphatic polycarboxylic acids having 4 to 24 carbon atoms.
• the aliphatic carboxylic acid may be saturated or unsaturated, and may be linear or branched.
• Examples of aliphatic monocarboxylic acids having 4 to 24 carbon atoms include pentanoic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, octylic acid, decanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, isotridecanoic acid, hexadecanoic acid, octadecanoic acid (stearic acid), isooctadecanoic acid (isostearic acid), hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid (12-hydroxystearic acid), octadecenoic acid, hydroxyoctadecenoic acid, octadecadienoic acid, octadecatrienoic acid, docosanoic acid (behenic acid), tetracosanoic acid, hexacosanoi
• Aliphatic polycarboxylic acids having 4 to 24 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid, with succinic acid and adipic acid being preferred in terms of improving sizing properties during flame retardation.
• aromatic compounds (B-2) having a diphenylmethane skeleton and an ester group include diesters of bisphenol A alkylene oxide adducts and fatty acids, monoesters of bisphenol A alkylene oxide adducts and fatty acids, diesters of bisphenol B alkylene oxide adducts and fatty acids, monoesters of bisphenol B alkylene oxide adducts and fatty acids, diesters of bisphenol E alkylene oxide adducts and fatty acids, monoesters of bisphenol E alkylene oxide adducts and fatty acids, diesters of bisphenol F alkylene oxide adducts and fatty acids, and monoesters of bisphenol F alkylene oxide adducts and fatty acids.
• At least one selected from diesters of bisphenol A alkylene oxide adducts and fatty acids, diesters of bisphenol B alkylene oxide adducts and fatty acids, and diesters of bisphenol F alkylene oxide adducts and fatty acids are preferred, in terms of improving sizing properties during flame retardation.
• the treating agent of the present invention may contain an aliphatic (poly)oxyalkylene derivative (C) (hereinafter, sometimes referred to as the aliphatic derivative (C)).
• the aliphatic derivative (C) is not particularly limited as long as it is an aliphatic compound having a (poly)oxyalkylene group, and examples thereof include an aliphatic alcohol alkylene oxide adduct (C-1) and an aliphatic alkylene oxide adduct (C-2) having an ester group, with the aliphatic alcohol alkylene oxide adduct (C-1) being preferred in terms of emulsion stability.
• One or more types of aliphatic (poly)oxyalkylene derivative (C) may be used.
• the aliphatic derivative (C) is other than the Bronsted acid compound (D) and the acetylene compound (E) described below.
• the aliphatic alcohol alkylene oxide adduct (C-1) includes alkylene oxide adducts of aliphatic alcohols, which do not have an ester group.
• the aliphatic alcohol constituting the aliphatic alcohol alkylene oxide adduct (C-1) is not particularly limited, and examples thereof include aliphatic alcohols having 2 to 24 carbon atoms.
• the aliphatic alcohol may be saturated or unsaturated, straight-chain or branched, and may be a monohydric alcohol or a dihydric or higher alcohol, and from the viewpoint of emulsion stability, monohydric straight-chain saturated aliphatic alcohols and monohydric branched saturated aliphatic alcohols are preferred.
• the aliphatic alcohol alkylene oxide adduct (C-1) may be used alone or in combination.
• the upper limit of the number of carbon atoms of the aliphatic alcohol is preferably 20, more preferably 18, and even more preferably 16.
• the lower limit of the number of carbon atoms is more preferably 4, more preferably 6, and particularly preferably 8.
• 6 to 18 are preferred, and 8 to 16 are more preferred.
• Aliphatic alcohols that constitute the aliphatic alcohol alkylene oxide adduct (C-1) include butyl alcohol, octyl alcohol, nonanol, lauryl alcohol, stearyl alcohol, cetyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol, isododecyl alcohol, isohexadecyl alcohol, isostearyl alcohol, isotetracosanyl alcohol, 12-eicosyl alcohol, vinyl alcohol, butenyl alcohol, hexadecenyl alcohol, oleyl alcohol, eicosenyl alcohol, linear secondary alcohols having 10 to 16 carbon atoms, glycerin, trimethylolpropane, sorbitol, ethylene glycol, propylene glycol, and butylene glycol.
• lauryl alcohol, stearyl alcohol, isododecyl alcohol, isohexadecyl alcohol, isostearyl alcohol, and linear secondary alcohols having 10 to 16 carbon atoms are preferred, with linear secondary alcohols having 10 to 16 carbon atoms being more preferred.
• the number of moles of alkylene oxide added in the aliphatic alcohol alkylene oxide adduct (C-1) is preferably 2 to 50 moles.
• the upper limit of the number of moles added is more preferably 40 moles, even more preferably 30 moles, and particularly preferably 20 moles.
• the lower limit of the number of moles added is more preferably 3 moles, even more preferably 4 moles, and particularly preferably 5 moles.
• 3 to 40 moles is more preferable, and 5 to 20 moles is particularly preferable.
• the alkylene oxide preferably contains at least one selected from ethylene oxide and propylene oxide, and more preferably contains ethylene oxide.
• the alkylene oxide may be added randomly or in blocks.
• ethoxylates examples include polyoxyethylene 1-octylhexyl ether, polyoxyethylene 1-hexyloctyl ether, polyoxyethylene 1-pentylheptyl ether, polyoxyethylene 1-heptylpentyl ether, polyoxyethylene 1-hexylheptyl ether, polyoxyethylene 1-heptylhexyl ether, polyoxyethylene 1-pentylcaptyl ether, polyoxyethylene 1-captylpentyl ether, polyoxyethylene oleyl ether, linear secondary alcohol ethoxylates having 10 to 16 carbon atoms, and oxyethylene-oxypropylene block or random copolymers.
• the aliphatic carboxylic acid constituting the aliphatic alkylene oxide adduct (C-2) having an ester group is not particularly limited, but examples include aliphatic monocarboxylic acids having 4 to 24 carbon atoms and aliphatic polycarboxylic acids having 4 to 24 carbon atoms.
• the aliphatic carboxylic acid may be saturated or unsaturated, and may be linear or branched.
• Aliphatic monocarboxylic acids having 4 to 24 carbon atoms include pentanoic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, octylic acid, decanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, isotridecanoic acid, hexadecanoic acid, octadecanoic acid (stearic acid), isooctadecanoic acid (isostearic acid), hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid (12-hydroxystearic acid), octadecenoic acid, hydroxyoctadecenoic acid, octadecadienoic acid, octadecatrienoic acid, docosanoic acid (behenic acid), tetracosanoic acid, hexacosanoic acid,
• the number of moles of alkylene oxide added in the aliphatic alkylene oxide adduct (C-2) having an ester group is preferably 2 to 50 moles.
• the upper limit of the number of moles added is more preferably 40 moles, even more preferably 30 moles, and particularly preferably 20 moles.
• the lower limit of the number of moles added is more preferably 3 moles, even more preferably 4 moles, and particularly preferably 5 moles. Also, for example, 3 to 40 moles is more preferable, and 5 to 20 moles is particularly preferable.
• the alkylene oxide preferably contains at least one selected from ethylene oxide and propylene oxide, and more preferably contains ethylene oxide.
• the alkylene oxide may be added randomly or in blocks.
• Examples of compounds (C-2-1) having a structure in which an alkylene oxide is added to an aliphatic carboxylic acid include the compounds in which an alkylene oxide is added to the aliphatic carboxylic acids listed above, and from the standpoint of emulsion stability, compounds having a structure in which 1 to 20 moles of ethylene oxide are added to an aliphatic carboxylic acid having 8 to 18 carbon atoms are preferred.
• the polyhydric alcohol constituting the compound (C-2-2) having a structure in which an alkylene oxide is added to an ester compound of an aliphatic carboxylic acid and a polyhydric alcohol is preferably a dihydric, tetrahydric, or tetrahydric alcohol having 2 to 6 carbon atoms, and of these, dihydric, tetrahydric, or trihydric alcohols having 2 to 6 carbon atoms are more preferred.
• polyhydric alcohols include dihydric alcohols such as propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, and 1,6-hexanediol; trihydric alcohols such as glycerin and trimethylolpropane; and tetrahydric or higher alcohols such as pentaerythritol, sorbitan, and sorbitol.
• dihydric alcohols such as propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, and 1,6-hexanediol
• trihydric alcohols such as glycerin and trimethylolpropane
• Examples of compounds (C-2-2) having a structure in which an alkylene oxide is added to an ester compound of an aliphatic carboxylic acid and a polyhydric alcohol include the compounds in which an alkylene oxide is added to the ester compounds of an aliphatic carboxylic acid and a polyhydric alcohol listed above, and from the standpoint of emulsion stability, alkylene oxide adducts of glycerin fatty acid esters and alkylene oxide adducts of sorbitan fatty acid esters are preferred.
• the treatment agent of the present invention preferably contains a Br ⁇ nsted acid compound (D) (hereinafter sometimes referred to as compound (D)) in that it exhibits the effects of the present invention and improves emulsion stability.
• the Br ⁇ nsted acid compound (D) refers to a proton donor, and examples thereof include organic carboxylic acid compounds, inorganic acids, organic sulfonic acid compounds, organic phosphate ester compounds, organic sulfate ester compounds, and organic phosphonic acid compounds.
• the Br ⁇ nsted acid compound (D) is a compound other than the aromatic compound (B) and the acetylene-based compound (E) described below.
• organic carboxylic acid compound is an organic compound that has a carboxyl group in its molecular structure.
• organic carboxylic acid compounds include, but are not limited to, aliphatic monocarboxylic acids, alkyl ether carboxylic acids, aliphatic polycarboxylic acids, aromatic carboxylic acids, aromatic polycarboxylic acids, and amino acids.
• Aliphatic monocarboxylic acids include acetic acid, lactic acid, butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetylic acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, isoeicosalic acid, gadoleic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid, isotetracosanoic acid, nervonic acid, cerotic acid, montanic acid, and
• alkyl ether carboxylic acids include those in which the alkyl group has 8 to 18 carbon atoms and the number of moles of polyoxyalkylene added is 1 to 50.
• alkyl group include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.
• the polyoxyalkylene group include polyoxyethylene, polyoxypropylene, and polyoxyethylene polyoxypropylene groups.
• Aliphatic polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecanedioic acid, and derivatives thereof.
• Aromatic monocarboxylic acids include benzoic acid, cinnamic acid, naphthoic acid, toluic acid, and their derivatives.
• Aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and derivatives thereof.
• Amino acids are compounds that contain both amino and carboxyl groups in their molecular structure, and examples include alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, methionine, proline, glycine, tyrosine, serine, threonine, cysteine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid, and glutamic acid.
• Inorganic acids are acids that contain non-metallic atoms.
• examples of inorganic acids include sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid.
• organic sulfonic acid compounds include alkylbenzene sulfonic acid, polyoxyalkylene alkyl ether sulfonic acid, higher fatty acid amide sulfonic acid, alkyl sulfate monoester, and polyoxyalkylene sulfate monoester.
• organic phosphate ester compounds include alkyl phosphate monoesters, alkyl phosphate diesters, polyoxyalkylene alkyl ether phosphate monoesters, polyoxyalkylene alkyl ether phosphate diesters, polyoxyalkylene alkyl phenyl ether phosphate monoesters, and polyoxyalkylene alkyl phenyl ether phosphate diesters.
• organic sulfate ester compounds include alkyl sulfate esters, polyoxyalkylene alkyl sulfate esters, alkylphenyl sulfate esters, and polyoxyalkylene alkylphenyl sulfate esters.
• Organic phosphonic acid compounds include alkyl phosphonic acids, aromatic phosphonic acids, and polyoxyalkylene alkyl ether phosphonic acids.
• the pKa of the Bronsted acid compound (D) is preferably 0 to 7, more preferably 1 to 6.5, and even more preferably 2 to 6, from the standpoints of preventing corrosion and safety of equipment and suppressing crosslinking over time due to the amino groups of the amino-modified silicone.
• the Br ⁇ nsted acid compound (D) preferably contains at least one selected from an organic carboxylic acid compound, an inorganic acid, and an organic phosphate ester compound, more preferably at least one selected from lactic acid, an alkyl ether carboxylic acid, an organic phosphate ester compound, phosphoric acid, and acetic acid, and even more preferably at least one selected from an alkyl ether carboxylic acid, an organic phosphate ester compound, acetic acid, and phosphoric acid.
• One or more Br ⁇ nsted acid compounds (D) may be used.
• the treating agent of the present invention preferably contains an acetylene compound (E) in that the treating agent is prevented from penetrating into the interior of the fiber structure.
• the acetylene compound refers to a compound having an acetylene group and a hydrophilic group such as a hydroxyl group in its molecular structure.
• the acetylene compound (E) may be used alone or in combination of two or more.
• the acetylene compound (E) is preferably an acetylene surfactant, and more preferably at least one selected from acetylene alcohol (E1), acetylene diol (E2), a compound (E3) in which an alkylene oxide is added to an acetylene alcohol, and a compound (E4) in which an alkylene oxide is added to an acetylene diol.
• acetylene alcohol E1
• acetylene diol E2
• a compound (E3) in which an alkylene oxide is added to an acetylene alcohol and a compound (E4) in which an alkylene oxide is added to an acetylene diol are preferred
• the compound (E4) in which an alkylene oxide is added to an acetylene diol is even more preferred.
• the acetylene alcohol (E1) is a compound having an acetylene group and one hydroxyl group in its molecular structure.
• the acetylene alcohol (E1) is preferably a compound represented by the following general formula (3). (In formula (3), R 10 and R 11 each independently represent an alkyl group having 1 to 8 carbon atoms.)
• Acetylene diol (E2) is a compound having an acetylene group and two hydroxyl groups in its molecular structure.
• the acetylene diol (E2) is preferably a compound represented by the following general formula (4). (In formula (4), R 12 , R 13 , R 14 and R 15 each independently represent an alkyl group having 1 to 8 carbon atoms.)
• the compound (E3) in which an alkylene oxide is added to an acetylene alcohol is a compound in which an alkylene oxide is added to the hydroxyl group of an acetylene alcohol.
• the compound (E3) in which an alkylene oxide is added to an acetylene alcohol is preferably a compound represented by the following general formula (5).
• R 10 and R 11 each independently represent an alkyl group having 1 to 8 carbon atoms.
• R 16 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• AO represents an oxyalkylene group having 2 to 4 carbon atoms.
• n is a number from 1 to 50.
• the compound (E4) in which an alkylene oxide is added to an acetylenic diol is a compound in which an alkylene oxide is added to at least one of the hydroxyl groups of an acetylenic diol.
• the compound (E4) in which an alkylene oxide is added to an acetylene diol is preferably a compound represented by the following general formula (6).
• R 12 , R 13 , R 14 and R 15 each independently represent an alkyl group having 1 to 8 carbon atoms.
• R 16 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Note that, in formula (6), multiple R 16s may be the same or different.
• AO represents an oxyalkylene group having 2 to 4 carbon atoms.
• m and n each independently represent a number from 1 to 50.
• R 10 and R 11 are each independently an alkyl group having 1 to 8 carbon atoms.
• the alkyl group may be linear or may have a branched structure.
• the alkyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 5 carbon atoms.
• R 12 , R 13 , R 14 , and R 15 are each independently an alkyl group having 1 to 8 carbon atoms.
• the alkyl group may be linear or may have a branched structure.
• the alkyl group preferably has 1 to 7 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 5 carbon atoms.
• R 16 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms.
• AO represents an oxyalkylene group having 2 to 4 carbon atoms. That is, it represents an oxyethylene group, an oxypropylene group, or an oxybutylene group.
• As the oxyalkylene group an oxyethylene group or an oxypropylene group is preferred, and an oxyethylene group is more preferred.
• the AO constituting (AO) n or (AO) m may be one type or two or more types. When two or more types are used, the AO may be any of a block adduct, an alternating adduct, or a random adduct.
• n is a number of 1 to 50.
• n is preferably a number of 1 to 45, more preferably a number of 1 to 40, and even more preferably a number of 1 to 35.
• m and n each independently represent a number from 1 to 50.
• m and n each independently represent a number from 1 to 45, more preferably a number from 1 to 40, and even more preferably a number from 1 to 35.
• the HLB of the acetylene compound (E) is preferably 4 to 25.
• the upper limit of the HLB is more preferably 20, and even more preferably 18.
• the lower limit of the HLB is more preferably 5, and even more preferably 6.
• the HLB in the present invention can be experimentally determined using the Atlas method proposed by Griffin et al.
• the acetylene compound (E) is a known compound and can be easily produced by a known method.
• a compound can be obtained by a method called the Reppe reaction, in which acetylene is reacted with a ketone or an aldehyde under pressure in the presence of a catalyst such as an alkali or a metal compound.
• the compound (E3) or the compound (E4) can be obtained by addition polymerization of an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to an acetylenic alcohol (E1) or an acetylenic diol (E2), respectively, in the presence of a catalyst such as an alkali or a metal compound.
• an alkylene oxide e.g., ethylene oxide and/or propylene oxide
• the treating agent for carbon fiber precursors of the present invention contains a silicone (A) having an amino group and an aromatic compound (B) having a diphenylmethane skeleton, and satisfies at least one selected from the following condition 1 and the following condition 2:
• Condition 1 The acid value of the treatment agent is 0.1 to 30 mgKOH/g.
• Condition 2 The treating agent contains a Bronsted acid compound (D), and the proportion of the Bronsted acid compound (D) in the nonvolatile components of the treating agent is 0.05 to 10% by weight.
• the treating agent for carbon fiber precursors of the present invention more preferably satisfies conditions 1 and 2 in terms of further exhibiting the effects of the present invention.
• the treatment agent for carbon fiber precursors of the present invention contains a silicone (A) having an amino group and an aromatic compound (B) having a diphenylmethane skeleton, and satisfies at least one of condition 1 and condition 2, so that when the carbon fiber precursor produced by applying the treatment agent is stored for an extended period of time, deterioration of the carbon fiber precursor can be suppressed.
• the aromatic compound (B) having a diphenylmethane skeleton forms a protective layer on the surface of the carbon fiber precursor, and further because (condition 1) the treatment agent has a specific acid value and/or (condition 2) the proportion of the Bronsted acid (D) in the non-volatile content of the treatment agent is within a specific range, which suppresses crosslinking over time caused by oxidation of the amino group in the silicone (A) having an amino group.
• the acid value of the treatment agent of the present invention is preferably 0.1 to 30 mgKOH/g, as this facilitates suppressing deterioration of the carbon fiber precursor over time and facilitating emulsion stabilization.
• the upper limit of the acid value is more preferred in order of (1) 28 mgKOH/g, (2) 25 mgKOH/g, (3) 20 mgKOH/g, (4) 15 mgKOH/g, and (5) 10 mgKOH/g (the larger the value in parentheses, the more preferred it is).
• the lower limit of the acid value is more preferred in order of (1) 0.2 mgKOH/g, (2) 0.3 mgKOH/g, (3) 0.4 mgKOH/g, (4) 0.5 mgKOH/g, and (5) 0.6 mgKOH/g.
• 0.2 to 28 mgKOH/g is more preferable, 0.3 to 25 mgKOH/g is even more preferable, 0.4 to 20 mgKOH/g is even more preferable, 0.5 to 15 mgKOH/g is particularly preferable, and 0.6 to 10 mgKOH/g is most preferable.
• the acid value of the treatment agent in this invention is measured by the method described in the Examples.
• the proportion of the amino group-containing silicone (A) in the non-volatile content of the treating agent of the present invention is not particularly limited, but is preferably 1 to 90% by weight, from the viewpoints of easily suppressing deterioration over time of the carbon fiber precursor and facilitating emulsion stabilization.
• the upper limit of this proportion is more preferably 88% by weight, even more preferably 85% by weight, and particularly preferably 80% by weight.
• the lower limit of this proportion is more preferably 5% by weight, even more preferably 10% by weight, and particularly preferably 15% by weight.
• 5 to 88% by weight is more preferable, 10 to 85% by weight is even more preferable, and 15 to 80% by weight is particularly preferable.
• the non-volatile content concentration in the present invention is determined by spreading 2.0 to 3.0 g of the treatment agent evenly on an aluminum sheet ( ⁇ 110 mm), drying at 110°C under irradiation with an infrared lamp, accurately weighing the weight of the residue on the aluminum sheet when the fluctuation range of the volatile content over 150 seconds is 0.15%, and calculating the ratio (percentage) of the remaining weight after heating to the weight before heating.
• the non-volatile content in the present invention refers to the residue on the aluminum sheet when the fluctuation range of the volatile content over 150 seconds is 0.15%, which was determined in the same manner as in the non-volatile content concentration measurement procedure.
• the proportion of the aromatic compound (B) having a diphenylmethane skeleton in the non-volatile content of the treatment agent of the present invention is not particularly limited, but is preferably 99% by weight or less, as this facilitates suppression of deterioration over time of the carbon fiber precursor and facilitates emulsion stabilization.
• the upper limit of this proportion is more preferably 95% by weight, even more preferably 90% by weight, and particularly preferably 85% by weight.
• the lower limit of this proportion is more preferably 10% by weight, even more preferably 15% by weight, and particularly preferably 20% by weight.
• 10 to 99% by weight is more preferred, 10 to 90% by weight is even more preferred, 15 to 95% by weight is particularly preferred, and 20 to 85% by weight is most preferred.
• the proportion of the aliphatic (poly)oxyalkylene derivative (C) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but is preferably 1 to 30% by weight, as this facilitates suppression of deterioration over time of the carbon fiber precursor and facilitates emulsion stabilization.
• the upper limit of this proportion is more preferably 25% by weight, even more preferably 20% by weight, and particularly preferably 15% by weight.
• the lower limit of this proportion is more preferably 2% by weight, even more preferably 3% by weight, and particularly preferably 5% by weight.
• 2 to 25% by weight is more preferred, 3 to 20% by weight is even more preferred, and 5 to 15% by weight is particularly preferred.
• the proportion of the Br ⁇ nsted acid compound (D) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but is preferably 0.05 to 10 wt% from the viewpoints of easily suppressing deterioration of the carbon fiber precursor over time and facilitating emulsion stabilization.
• the upper limit of this weight proportion is more preferably 8 wt%, even more preferably 7 wt%, and particularly preferably 5 wt%.
• the lower limit of this weight proportion is more preferably 0.1 wt%, even more preferably 0.15 wt%, and particularly preferably 0.3 wt%.
• 0.1 to 8 wt% is more preferable, 0.15 to 7 wt% is even more preferable, and 0.3 to 5 wt% is particularly preferable.
• the proportion of the acetylene-based compound (E) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but is preferably 0.1 to 10% by weight in order to inhibit the treatment agent from penetrating into the fiber structure.
• the upper limit of this weight proportion is more preferably 8% by weight, even more preferably 7% by weight, and especially preferably 5% by weight.
• the lower limit of this weight proportion is more preferably 0.3% by weight, even more preferably 0.5% by weight, and especially preferably 1% by weight.
• 0.3 to 8% by weight is more preferable, 0.5 to 7% by weight is even more preferable, and 1 to 5% by weight is especially preferable.
• the treatment agent of the present invention preferably further contains another nonionic surfactant as other component (F) in order to enhance emulsion stability.
• the other nonionic surfactant refers to a nonionic surfactant other than the aromatic compound (B) having a diphenylmethane skeleton, the aliphatic (poly)oxyalkylene derivative (C), and the acetylene compound (E).
• nonionic surfactants include sorbitan esters such as sorbitan monopalmitate and sorbitan monooleate; glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate and glycerin monopalmitate; sucrose fatty acid esters; and the like.
• the weight average molecular weight of the other nonionic surfactant is preferably 2000 or less, more preferably 200 to 1800, more preferably 300 to 1500, and even more preferably 500 to 1000.
• One or more types of the other nonionic surfactant may be used.
• the weight proportion of the other nonionic surfactants in the nonvolatile content of the treatment agent is not particularly limited, but from the perspective of emulsion stability, it is preferably 0.1 to 10% by weight.
• the upper limit of this proportion is more preferably 8.5% by weight, even more preferably 7.0% by weight, and especially preferably 5.0% by weight.
• the lower limit of this proportion is more preferably 0.25% by weight, even more preferably 0.4% by weight, and especially preferably 0.5% by weight.
• 0.25 to 8.5% by weight is more preferable, 0.4 to 7.0% by weight is even more preferable, and 0.5 to 5.0% by weight is especially preferable.
• the treatment agent of the present invention may contain surfactants other than the aromatic compound (B) having a diphenylmethane skeleton, the aliphatic (poly)oxyalkylene derivative (C), the Bronsted acid compound (D), the acetylene compound (E), and other nonionic surfactants, as long as the effects of the present invention are not impaired.
• the other surfactants are used as emulsifiers, antistatic agents, etc.
• the other surfactants are not particularly limited, and known surfactants can be appropriately selected from anionic surfactants, cationic surfactants, and amphoteric surfactants and used.
• the other surfactants may be used alone or in combination of two or more.
• Anionic surfactants include ether carboxylates, ether sulfates, sulfosuccinates, (poly)oxyethylene coconut oil fatty acid monoethanolamide sodium sulfate, alkyl group-containing sulfonates, alkyl group-containing phosphate ester salts, fatty acid salts, acylated amino acid salts, and amine-neutralized fatty acids.
• cationic surfactants include lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl ammonium chloride, beef tallow alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, coconut oil alkyl trimethyl ammonium bromide, cetyl trimethyl ammonium methosulfate, and oleyl dimethyl ethyl ammonium ethosulfate.
• alkyl quaternary ammonium salts such as stearoyl ammonium sulfate, dioctyl dimethyl ammonium chloride, dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and octadecyl diethyl methyl ammonium sulfate; acyl amide alkyl quaternary ammonium salts such as N-(2-hydroxyethyl)-N,N-dimethyl-N-stearoyl amide propyl ammonium nitrate, lanolin fatty acid amide propyl ethyl dimethyl ammonium ethosulfate, and lauroyl amide ethyl methyl diethyl ammonium methosulfate; alkyl isoquinolinium salts such as lauryl isoquinolinium chloride; lauryl dimethyl benzyl ammonium benzalkonium salts such as cetylpyridin
• amphoteric surfactants include imidazoline-based amphoteric surfactants such as 2-undecyl-N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt; betaine-based amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaines, amido betaines, and sulfobetaines; and amino acid-based amphoteric surfactants such as N-lauryl glycine, N-lauryl ⁇ -alanine, and N-stearyl ⁇ -alanine.
• imidazoline-based amphoteric surfactants such as 2-undecyl-N,N-(hydroxyethylcarboxymethyl)-2-
• the treating agent for carbon fiber precursors of the present invention may contain other components in addition to the above-mentioned components, provided that the effects of the present invention are not impaired.
• examples of other components include antioxidants such as phenols, amines, sulfurs, phosphorus, and quinones; antistatic agents such as quaternary ammonium salt-type cationic surfactants and amine salt-type cationic surfactants; smoothing agents such as alkyl esters of higher alcohols and waxes; antibacterial agents; preservatives; rust inhibitors; and moisture absorbents.
• the treatment agent of the present invention may also contain one or more low molecular weight silicones.
• low molecular weight silicones include linear or cyclic silicones having 2 to 7 silicon atoms.
• Specific examples of low molecular weight silicones include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.
• These low molecular weight silicones may be substituted with a group represented by the general formula (2) above.
• low molecular weight silicones may be included as a minor component of the amino group-containing silicone (A).
• the content of the low molecular weight silicone in the treating agent of the present invention is preferably 5 parts by weight or less per 100 parts by weight of the amino group-containing silicone (A).
• the treating agent for carbon fiber precursors of the present invention is preferably in a state in which the silicone (A) having an amino group, the aromatic compound (B) having a diphenylmethane skeleton, and, if necessary, the aliphatic (poly)oxyalkylene derivative (C), the Br ⁇ nsted acid compound (D), the acetylene compound (E), and other components (F) are dissolved, solubilized, emulsified, or dispersed in water.
• the weight proportion of water and the weight proportion of nonvolatile matter in the entire carbon fiber precursor treatment agent There are no particular limitations on the weight proportion of water and the weight proportion of nonvolatile matter in the entire carbon fiber precursor treatment agent.
• the weight proportion of water in the entire carbon fiber precursor treatment agent is preferably 0.1 to 99.9 wt %, more preferably 10 to 99.5 wt %, and particularly preferably 50 to 99 wt %.
• the weight proportion (concentration) of nonvolatile matter in the entire carbon fiber precursor treatment agent is preferably 0.01 to 99.9 wt %, more preferably 0.5 to 90 wt %, and particularly preferably 1 to 50 wt %.
• the carbon fiber precursor treatment agent of the present invention can be produced by mixing the components described above.
• the carbon fiber precursor treatment agent of the present invention can be suitably used as a treatment agent for carbon fiber precursors.
• the carbon fiber precursor of the present invention is obtained by adhering the above-mentioned treating agent for carbon fiber precursors to a raw material carbon fiber precursor of the carbon fiber precursor, followed by spinning.
• the method for producing a carbon fiber precursor of the present invention includes a spinning step of adhering the above-mentioned treating agent for carbon fiber precursors to a raw material carbon fiber precursor of the carbon fiber precursor, followed by spinning.
• the method for producing a carbon fiber of the present invention includes a flame-retardant treatment step of converting the carbon fiber precursor having the above-mentioned treatment agent for a carbon fiber precursor attached thereto into a flame-retardant fiber, and a carbonization treatment step of further carbonizing the flame-retardant fiber.
• the above-mentioned flame-resistant treatment step is preferably a flame-resistant treatment step in which a carbon fiber precursor is converted into a flame-resistant fiber in an oxidizing atmosphere at 200 to 300°C
• the carbonization treatment step is preferably a step in which the flame-resistant fiber is further carbonized in an inert atmosphere at 300 to 2000°C.
• the treatment agent for carbon fiber precursor of the present invention is used, so that high-quality carbon fiber can be manufactured even if the carbon fiber precursor manufactured by applying the treatment agent is stored for a long period of time.
• the spinning step is a step of spinning the carbon fiber precursor by adhering a treatment agent for carbon fiber precursors to a raw material carbon fiber precursor of the carbon fiber precursor, and preferably includes an adhering treatment step and a drawing step.
• the adhesion treatment step is a step of adhering a treatment agent for a carbon fiber precursor after spinning the raw carbon fiber precursor of the carbon fiber precursor. That is, in the adhesion treatment step, the treatment agent for a carbon fiber precursor is adhered to the raw carbon fiber precursor of the carbon fiber precursor.
• the high-magnification stretching after the adhesion treatment step is particularly called the "stretching step.”
• the stretching step may be a wet heat stretching method using high-temperature steam, or a dry heat stretching method using a heated roller.
• the stretching ratio in the stretching step is preferably 2 to 20 times the total stretching ratio of the raw carbon fiber precursor immediately after spinning.
• the carbon fiber precursor is preferably composed of acrylic fibers whose main component is polyacrylonitrile, obtained by copolymerizing at least 95 mol% or more of acrylonitrile with 5 mol% or less of a flame retardant-promoting component.
• a vinyl group-containing compound that is copolymerizable with acrylonitrile is preferably used as the flame retardant-promoting component.
• the single fiber fineness of the carbon fiber precursor but in terms of the balance between performance and manufacturing costs, it is preferably 0.1 to 2.0 dtex.
• the number of single fibers that make up the fiber bundle of the carbon fiber precursor but in terms of the balance between performance and manufacturing costs, it is preferably 1,000 to 96,000.
• the carbon fiber precursor treatment agent may be applied to the precursor raw material carbon fiber precursor at any stage in the spinning process, but it is preferable to apply it once before the drawing process. It may be applied at any stage before the drawing process, for example immediately after spinning. It may also be applied again at any stage after the drawing process, for example immediately after the drawing process, or at the winding stage, or immediately before the flame retardant treatment process.
• the application method may be using a roller or the like, or it may be applied by dipping, spraying, etc.
• the application rate of the carbon fiber precursor treatment agent is preferably 0.1 to 5 wt. % of the weight of the carbon fiber precursor, and more preferably 0.3 to 1.5 wt. %, in order to strike a balance between preventing fiber-to-fiber sticking and fusion and preventing degradation of the carbon fiber quality due to tar products of the treatment agent in the carbonization treatment process.
• the application rate of the carbon fiber precursor treatment agent here is defined as the percentage of the weight of the non-volatile components of the carbon fiber precursor treatment agent applied to the carbon fiber precursor weight.
• the flame-resistant treatment process is a process in which a carbon fiber precursor having a carbon fiber precursor treatment agent attached thereto is converted into a flame-resistant fiber in an oxidizing atmosphere at, for example, 200 to 300°C.
• the oxidizing atmosphere is typically an air atmosphere.
• the temperature of the oxidizing atmosphere is preferably 230 to 280°C.
• the carbon fiber precursor after the attachment treatment is heat-treated for, for example, 20 to 100 minutes (preferably 30 to 60 minutes) while applying a tension of, for example, a draw ratio of 0.90 to 1.10 (preferably 0.95 to 1.05).
• This flame-resistant treatment produces a flame-resistant fiber with a flame-resistant structure through intramolecular cyclization and oxygen addition to the rings.
• the carbonization process is a process in which the flame-resistant fiber is further carbonized in an inert atmosphere, for example, at 300 to 2000°C.
• first carbonization process in which the flame-resistant fiber is heat-treated for several minutes in an inert atmosphere, such as nitrogen or argon, in a baking furnace with a temperature gradient from 300 to 800°C while applying a tension of, for example, a draw ratio of 0.95 to 1.15.
• the flame-resistant fiber is heat-treated for several minutes in an inert atmosphere, such as nitrogen or argon, while applying a tension of, for example, a draw ratio of 0.95 to 1.05, in a second carbonization process, thereby carbonizing the flame-resistant fiber.
• an inert atmosphere such as nitrogen or argon
• a tension of, for example, a draw ratio of 0.95 to 1.05 in a second carbonization process, thereby carbonizing the flame-resistant fiber.
• the heat treatment temperature control in the second carbonization process it is preferable to set the maximum temperature to 1000°C or higher (preferably 1000 to 2000°C) while applying a temperature gradient. This maximum temperature is selected and determined appropriately depending on the desired properties of the carbon fiber (tensile strength, modulus of elasticity, etc.).
• a graphitization process can be carried out following the carbonization process.
• the graphitization process is usually carried out in an inert atmosphere such as nitrogen or argon, at a temperature of 2000 to 3000°C, while applying tension to the fiber obtained in the carbonization process.
• the carbon fibers obtained in this manner can be surface treated to increase the adhesive strength with the matrix resin when made into a composite material.
• Gas-phase or liquid-phase treatments can be used as surface treatment methods, and from the standpoint of productivity, liquid-phase treatments using electrolytes such as acids and alkalis are preferred.
• various sizing agents that are highly compatible with the matrix resin can also be applied.
• the carbon fiber precursor after the treatment agent was applied was alkali-fused with potassium hydroxide/sodium butyrate, then dissolved in water and adjusted to pH 1 with hydrochloric acid. Sodium sulfite and ammonium molybdate were added to this to develop color, and colorimetric determination (wavelength 815 m ⁇ ) of silicomolybdenum blue was performed to determine the silicon content.
• the silicon content determined here and the silicon content in the treatment agent previously determined by the same method were used to calculate the application rate (wt%) of the carbon fiber precursor treatment agent.
• ⁇ Acid value of treatment agent> The measurement was carried out in accordance with the neutralization titration method specified in JIS K0070, and the average value of five measurements was taken as the acid value of the treatment agent.
• Carbon fiber precursors were stored under the following two conditions, and carbon fibers were produced using the same, and the number of fluffs was measured by the following method.
• Storage condition 1 stored at room temperature for 7 days
• Storage condition 2 stored at room temperature for 12 months
• the carbon fiber bundle was pulled out from the bobbin without tension, and any fluff was collected until the number of fluffs reached 50.
• the length of the carbon fiber bundle pulled out until 50 fluffs were collected was measured, and the number of fluffs per unit length (pieces/m) was calculated from the measured length of the carbon fiber bundle as the number of fluffs present on the surface of the carbon fiber bundle, and ⁇ and ⁇ were evaluated as pass.
• ⁇ The number of fluffs is less than 3/m, and the fluff is particularly good.
• Good The number of fluffs is 3 or more and less than 10 fluffs/m, and the fluff is small and good.
• ⁇ The number of fluffs is 10 or more per meter, and there is a lot of fluff, which is poor.
• Carbon fibers were produced using carbon fiber precursors stored under the following two conditions, and the tensile properties of the fibers were measured in accordance with the test method for single fibers specified in JIS-R-7606. The average value of 10 measurements was taken as the carbon fiber strength (GPa).
• Storage condition 1 stored at room temperature for 7 days.
• Storage condition 2 stored at room temperature for 12 months.
• ⁇ Inhibition of deterioration of carbon fiber precursor In the evaluation of the fluff and strength of the carbon fiber bundles, the deterioration suppression ability of the carbon fiber precursor was judged according to the following criteria. Pass was marked with ⁇ , and fail was marked with ⁇ . Acceptance criteria: The number of fluffs on the carbon fiber bundle is 0 or more under both storage conditions 1 and 2, and the maintenance rate of carbon fiber strength is 95% or more.
• Example 1 A silicone (A) having an amino group and an aromatic compound (B) having a diphenylmethane skeleton were mixed to obtain the nonvolatile composition of the treatment shown in Table 1.
• the temperature of the mixture during emulsification was adjusted to 60-80°C, and water was added little by little while stirring using a stirring blade at a blade tip speed of 3 m/s to emulsify.
• the Br ⁇ nsted acid compound (D) was dissolved and dispersed, preparing a treatment agent for carbon fiber precursors with a nonvolatile concentration of 30 wt%.
• the weight percentage of the silicone (A) in the nonvolatile content of the treatment agent was 15 wt%
• the weight percentage of the aromatic compound (B) having a phenylmethane skeleton was 84.5 wt%
• the weight percentage of the Br ⁇ nsted acid compound (D) was 0.5 wt%.
• the prepared treatment agent was then further diluted with water to obtain a diluted solution with a nonvolatile concentration of 3.0 wt%.
• the dilution solution was applied to a raw material carbon fiber precursor obtained by copolymerizing 97 mol% acrylonitrile and 3 mol% itaconic acid, so that the non-volatile content of the treatment agent was 1.0 wt%.
• the carbon fiber precursor was then subjected to a drawing process (steam drawing, draw ratio 2.1 times) to produce a carbon fiber precursor (single fiber fineness 0.8 dtex, 24,000 filaments).
• This carbon fiber precursor was flame-resistant treated in a 250°C flame-resistant furnace for 60 minutes, and then calcined in a carbonization furnace with a temperature gradient of 300 to 1400°C under a nitrogen atmosphere to convert it into carbon fiber.
• the results of evaluation of each property value are shown in Table 1.
• Examples 2 to 31, Comparative Examples 1 to 10 The nonvolatile composition was changed as shown in Tables 1 to 4, and when the aliphatic (poly)oxyalkylene derivative (C), the Bronsted acid compound (D), and the acetylene compound (E) were added, they were dissolved and dispersed after emulsification to prepare the treatment agent. Otherwise, treatment agents for carbon fiber precursors, carbon fiber precursors, and carbon fibers were prepared and evaluated in the same manner as in Example 1. The results of evaluating each property value are shown in Tables 1 to 4.
• Aromatic compound having a diphenylmethane skeleton B1: Aromatic compound having a bisphenol A ether diphenylmethane skeleton to which 8 moles of oxyethylene groups have been added
• Aliphatic (poly)oxyalkylene derivative C1 a secondary alkyl ether having 12 to 14 carbon atoms in the alkyl group to which 5 moles of oxyethylene groups have been added.
• Aliphatic (poly)oxyalkylene derivative C2 a secondary alkyl ether having 12 to 14 carbon atoms in the alkyl group to which 9 moles of oxyethylene groups have been added.
• Aliphatic (poly)oxyalkylene derivative C3 a secondary alkyl ether having 12 to 14 carbon atoms in the alkyl group to which 12 moles of oxyethylene groups have been added.
• Acetylenic compound E1 Acetylenic surfactant (manufactured by Nissin Chemical Industry Co., Ltd., trade name Olfine (registered trademark) E1010) Acetylenic compound E2: Acetylenic surfactant (manufactured by Nissin Chemical Industry Co., Ltd., trade name Olfine (registered trademark) EXP-4123) Acetylenic compound E3: Acetylenic surfactant (manufactured by Nissin Chemical Industry Co., Ltd., trade name Surfynol (registered trademark) 104E)
• the treatment agents for carbon fiber precursors in Examples 1 to 31 contained a silicone (A) having an amino group and an aromatic compound (B) having a diphenylmethane skeleton, and satisfied at least one selected from Condition 1 and Condition 2, and therefore were able to suppress deterioration of the carbon fiber precursor over time.
• the treating agents for carbon fiber precursors in Comparative Examples 1 and 4 to 10 were not treating agents for carbon fiber precursors according to the present invention, and therefore could not suppress deterioration of the carbon fiber precursors when the carbon fiber precursors produced by applying the treating agents were stored for a long period of time.
• the treating agents for carbon fiber precursors in Comparative Examples 2 and 3 had poor emulsion stability and did not adhere uniformly to the precursors, so that the carbon fiber precursors could not be produced normally and could not be used as treating agents for carbon fiber precursors.
• the treating agent for carbon fiber precursors of the present invention is a treating agent used in producing treating agents for carbon fiber precursors, and is useful for producing high-quality carbon fibers.
• the treating agent for carbon fiber precursors of the present invention is treated with the treating agent of the present invention, and is useful for producing high-quality carbon fibers. High-quality carbon fibers can be obtained by the carbon fiber production method of the present invention.

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