Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B64—AIRCRAFT; AVIATION; COSMONAUTICS
  • B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
  • B64G1/00—Cosmonautic vehicles
  • B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
  • B64G1/52—Protection, safety or emergency devices; Survival aids
  • B64G1/58—Thermal protection, e.g. heat shields
• • 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
  • D06M13/10—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
  • D06M13/152—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 having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
• • 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
• • 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
  • D06M13/248—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 sulfur
• • 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
  • 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
  • D06M13/322—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 nitrogen
  • D06M13/325—Amines
  • D06M13/335—Amines having an amino group bound to a carbon atom of a six-membered aromatic ring
• • 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
  • D06M15/687—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing atoms other than phosphorus, silicon, sulfur, nitrogen, oxygen or carbon in the main chain

Definitions

• the present invention relates to a treatment agent for carbon fiber precursors (hereinafter sometimes simply referred to as the treatment agent) 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 the 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 fiber is to convert a carbon fiber precursor into a flame-resistant fiber in an oxidizing atmosphere at 200 to 300°C (hereinafter, this may be referred to as the flame-resistant process), and then carbonize it in an inert atmosphere at 300 to 2000°C (hereinafter, this may be referred to as the carbonization process).
• the flame-resistant process and the carbonization process may be collectively referred to as the calcination process.
• the calcination process In order to efficiently perform these calcination processes and improve the physical properties of the carbon fiber, methods have been proposed in which various treatment agents are applied to the carbon fiber precursor (see Patent Documents 1 to 3).
• an object of the present invention is to provide a treatment agent for carbon fiber precursors that can impart suppression of single fiber breakage to carbon fiber precursors in a flame-resistant treatment step, a carbon fiber precursor using the treatment agent, and a method for producing carbon fibers using the carbon fiber precursor.
• the treating agent for carbon fiber precursors of the present invention includes the following embodiments.
• a treatment agent for carbon fiber precursors comprising a smoothing component (A), a radical scavenger (B), and a peroxide decomposer (C)
• the radical scavenger (B) is at least one selected from a phenol-based radical scavenger (B1) and an aromatic amine-based radical scavenger (B2)
• the sulfur-based peroxide decomposer (C1) comprises at least one selected from a sulfur-containing ester compound (C1-1) represented by the following general formula (1) and a sulfur-containing ester compound (C1-2) represented by the following general formula (2):
• a sulfur-containing ester compound (C1-1) represented by the following general formula (1) and a sulfur-containing ester compound (C1-2) represented by the following general formula (2):
• In formula (1), m and n each independently represent an integer of 1 to 4, and R1 and R2 each independently represent a hydrocarbon group having 12 to 32 carbon atoms.
• R3 is a hydrocarbon group having 12 to 32 carbon atoms.
• the sulfur-based peroxide decomposer (C1) contains at least one compound selected from the group consisting of a compound represented by the general formula (1) in which R 1 and R 2 are each independently a hydrocarbon group having 14 to 22 carbon atoms, and a compound represented by the general formula (2) in which
• ⁇ 4> The treatment agent for carbon fiber precursors according to ⁇ 2> or ⁇ 3>, wherein the sulfur-based peroxide decomposer (C1) contains the sulfur-containing ester compound (C1-1) and the sulfur-containing ester compound (C1-2).
• ⁇ 5> ⁇ 4> The treatment agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 4>, wherein a weight ratio ((B)/(C)) of the radical scavenger (B) to the peroxide decomposer (C) is 0.49 or less.
• ⁇ 6> ⁇ 5> The treatment agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 5>, wherein a total proportion of the radical scavenger (B) and the peroxide decomposer (C) in the non-volatile content of the treatment agent for carbon fiber precursors is more than 5.0% by weight.
• ⁇ 7> ⁇ 6> The treatment agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 6>, wherein the smoothing component (A) contains at least one selected from an amino group-containing silicone (A1) and an ester compound (A2).
• ⁇ 8> The treating agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 7>, further comprising a nonionic surfactant (D).
• ⁇ 10> ⁇ 9> A method for producing a carbon fiber, comprising: a flame-resistant step of converting the carbon fiber precursor according to ⁇ 9> into a flame-resistant fiber; and a carbonization step of carbonizing the flame-resistant fiber.
• the treatment agent for carbon fiber precursors of the present invention can impart excellent single-fiber breakage suppression properties to carbon fiber precursors during the flame-resistant treatment process.
• the carbon fiber precursor produced by applying the treatment agent has excellent single-fiber breakage suppression properties during the flame-resistant treatment process, resulting in the production of high-quality carbon fiber.
• the treatment agent of the present invention contains a smoothing component (A).
• a smoothing component used in a treatment agent can be used.
• known smoothing components include silicone compounds, mineral oils, polyolefins, and ester compounds (A2). These smoothing components may be used alone or in combination of two or more.
• the smoothing component (A) preferably contains at least one selected from silicone compounds and ester compounds (A2), and more preferably contains a silicone (A1) having an amino group.
• the silicone compound is not particularly limited as long as it has an inorganic siloxane bond (-Si-O-Si-) main chain and an organic group on the side chain.
• examples include silicone (A1) having an amino group, silicone (A1) having a polyether group, dimethyl silicone, epoxy-modified silicone, amide-modified silicone, alkyl-modified silicone, aralkyl-modified silicone, phenyl-modified silicone, silanol-modified silicone, carbinol-modified silicone, and mercapto-modified silicone.
• the kinematic viscosity of the amino group-containing silicone (A1) 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, and particularly preferably 10,000 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, and 150 to 10,000 mm 2 /s is even more preferable.
• the amino group (including an organic group having an amino group), which is the modified group of the amino group-containing silicone (A1), 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 in 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 (A1) 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 (A1) 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 (A1) (mixture)
• the above kinematic viscosity at 25°C refers to the kinematic viscosity of the entire amino group-containing silicone (A) (mixture).
• the ester compound (A2) is not particularly limited as long as it is a compound having a structure in which an alcohol compound (X) and a carboxylic acid compound (Y) are esterified, but from the viewpoint of sizing ability, at least one selected from an ester of a monohydric alcohol compound and a monocarboxylic acid, an ester of a polyhydric alcohol compound and a monocarboxylic acid, and an ester of a polycarboxylic acid and a monohydric alcohol is preferred, at least one selected from an ester of a polyhydric alcohol compound and a monocarboxylic acid compound, and an ester of a polycarboxylic acid and a monohydric alcohol is more preferred, and an ester of a polyhydric alcohol compound and a monocarboxylic acid compound is even more preferred.
• One or more types of ester compound (A2) may be used.
• the number of ester bonds that the ester compound (A2) has in its molecule is no particular limit to the number of ester bonds that the ester compound (A2) has in its molecule, but from the viewpoint of focusing ability, it is preferable that the number be two or more.
• the upper limit of the number of ester bonds is preferably 10, more preferably 8, and even more preferably 6.
• the lower limit of the number of ester bonds is more preferably 3, even more preferably 4, and particularly preferably 5.
• 2 to 10 is more preferable, and 2 to 8 is even more preferable.
• the molecular weight of the ester compound (A2) is not particularly limited, but from the viewpoint of focusing ability, it is preferably 650 or more.
• the upper limit of the molecular weight is preferably 5000, more preferably 4500, and even more preferably 4000.
• the lower limit of the molecular weight is more preferably 700, even more preferably 750, and particularly preferably 800. Also, for example, 700 to 4500 is more preferable, and 750 to 4000 is even more preferable.
• the molecular weight of the ester compound (A) in the present invention is the sum of the atomic weights of the atoms constituting the compound, calculated using the standard atomic weights published by IUPAC.
• the alcohol compound (X) is not particularly limited as long as it is a compound that can react with the carboxylic acid compound (Y) to form an ester bond, and known compounds can be used.
• the number of carbon atoms in the alcohol (X) is preferably 6 or more and 40 or less from the viewpoint of convergence, and the upper limit of the number of carbon atoms is more preferably 35, even more preferably 30, and particularly preferably 20.
• the lower limit of the number of carbon atoms is more preferably 7, even more preferably 8, and particularly preferably 9.
• the number of carbon atoms is more preferably 6 or more and 35 or less, and even more preferably 6 or more and 20 or less.
• the alcohol compound (X) is not particularly limited, but specific examples include monohydric alcohol compounds such as octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, isocetyl alcohol, oleyl alcohol, and isostearyl alcohol, phenol, alkylene oxide adducts of octyl alcohol, alkylene oxide adducts of 2-ethylhexyl alcohol, alkylene oxide adducts of decyl alcohol, alkylene oxide adducts of lauryl alcohol, and myristyl alcohol.
• monohydric alcohol compounds such as octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, isocetyl alcohol, oleyl alcohol, and isostearyl alcohol, phenol, alkylene oxide adducts of octyl alcohol, alkylene oxide
• alkylene oxide adducts examples include alkylene oxide adducts of ethanol, alkylene oxide adducts of isocetyl alcohol, alkylene oxide adducts of oleyl alcohol, alkylene oxide adducts of isostearyl alcohol, and alkylene oxide adducts of phenol.
• polyhydric alcohol compounds examples include trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, xylitol, mannitol, diglycerin, triglycerin, tetraglycerin, decaglycerin, bisphenol A, alkylene oxide adducts of trimethylolethane, and the like.
• alkylene oxide adducts alkylene oxide adducts, alkylene oxide adducts of trimethylolpropane, alkylene oxide adducts of pentaerythritol, alkylene oxide adducts of sorbitan, alkylene oxide adducts of sorbitol, alkylene oxide adducts of xylitol, alkylene oxide adducts of mannitol, alkylene oxide adducts of diglycerin, alkylene oxide adducts of triglycerin, alkylene oxide adducts of tetraglycerin, alkylene oxide adducts of decaglycerin, alkylene oxide adducts of bisphenol A
• alcohol compounds (X) include adducts, and from the viewpoint of sizing ability, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan
• carboxylic acid compound (Y) there are no particular restrictions on the carboxylic acid compound (Y), but from the standpoint of sizing ability and fuzz suppression, carboxylic acid compounds having 4 to 24 carbon atoms are preferred.
• the upper limit of the carbon number is more preferably 22, even more preferably 20, and particularly preferably 18.
• the lower limit of the carbon number is more preferably 6, even more preferably 8, and particularly preferably 10.
• 6 to 22 is more preferred, and 8 to 20 is even more preferred.
• carboxylic acid compound (Y) There are no particular limitations on the carboxylic acid compound (Y).
• monocarboxylic acids include 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, tuberculostearic acid, arachidic acid, isoeicosalic acid, gadoleic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid, isotetracosa
• polycarboxylic acids include citric acid, isocitric acid, malic acid, and aconitic acid.
• suitable carboxylic acid compounds include oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, phenylmalonic acid, phenylsuccinic acid, ⁇ -phenylglutaric acid, ⁇ -phenyladipic acid, ⁇ -phenyladipic acid, biphenyl-2,2'- or 4,4'-dicarboxylic acid, trimellitic acid, and pyromellitic acid.
• phthalic acid isophthalic acid, terephthalic acid, biphenyl-2,2'- or 4,4'-dicarboxylic acid, trimellitic acid, and pyromellitic acid are preferred, and biphenyl-2,2'- or 4,4'-dicarboxylic acid, trimellitic acid, and pyromellitic acid are more preferred.
• carboxylic acid compound (Y) may be used.
• the ester compound (A2) is not particularly limited as long as it is a compound having an esterified structure between the alcohol compound (X) and the carboxylic acid compound (Y).
• compounds having an esterified structure between an aliphatic alcohol compound and an aromatic carboxylic acid compound and compounds having an esterified structure between an aromatic alcohol compound and an aliphatic carboxylic acid compound are preferred, with aliphatic alcohol compounds and aromatic carboxylic acid compounds being more preferred.
• the compound having an ester structure of an aliphatic alcohol compound and an aromatic carboxylic acid compound is not particularly limited, but examples include trimellitic acid esters, pyromellitic acid esters, phthalic acid esters, and benzoic acid esters, with trimellitic acid esters and pyromellitic acid esters being preferred in terms of focusability.
• the compound having an ester structure of an aromatic alcohol compound and an aliphatic carboxylic acid compound is not particularly limited, but examples include esters of bisphenol A and fatty acids, esters of polyoxyalkylene adducts of bisphenol A and fatty acids, esters of phenol and fatty acids, and esters of naphthol and fatty acids, with esters of bisphenol A and fatty acids and esters of phenol and fatty acids being preferred in terms of sizing ability.
• the method for obtaining the ester compound (A2) is not particularly limited, but commercially available ester compounds can generally be used.
• the sulfur-based peroxide decomposer (C1) is not particularly limited, but examples include sulfur-containing ester compounds, with thiodipropionic acid esters being more preferred in terms of heat generation suppression.
• sulfur-based peroxide decomposers (C1) examples include 2,2-bis ⁇ [3-(dodecylthio)-1-oxopropoxy]methyl ⁇ propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'-thiobispropionate ditridecyl, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.
• n and n each independently represent an integer of 1 to 4, and R1 and R2 each independently represent a hydrocarbon group having 12 to 32 carbon atoms.
• n and n are each independently an integer of 1 to 4, and R3 is a hydrocarbon group having 12 to 32 carbon atoms.
• Nonionic surfactant (D) The treating agent of the present invention preferably contains a nonionic surfactant (D) in terms of emulsifiability and penetration.
• nonionic surfactants include polyoxyalkylene linear alkyl ethers such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, and polyoxyethylene cetyl ether; polyoxyalkylene branched primary alkyl ethers such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether, and polyoxyethylene isostearyl ether; polyoxyalkylene secondary alkyl ethers such as polyoxyethylene 1-hexylhexyl ether, polyoxyethylene 1-octylhexyl ether, polyoxyethylene 1-hexyloctyl ether, polyoxyethylene 1-pentylheptyl ether, and polyoxyethylene 1-
• the treatment agent of the present invention may contain other surfactants.
• examples of other surfactants include anionic surfactants, cationic surfactants, and amphoteric surfactants, and it is preferable to include an anionic surfactant in order to impart uniform sizing properties.
• N-acyl sarcosinic acids such as lauroyl sarcosinic acid (sodium); alkyl phosphonic acids (salts) such as octyl phosphonate (potassium salt); aromatic phosphonic acids (salts) such as phenyl phosphonate (potassium salt); alkyl phosphonic acid alkyl phosphate esters (salts) such as 2-ethylhexyl phosphonate mono 2-ethylhexyl ester (potassium salt); nitrogen-containing alkyl phosphonic acids (salts) such as aminoethyl phosphonic acid (diethanolamine salt); 2-ethylhexyl sulf
• suitable sulfonates include alkyl sulfates (salts) such as polyoxyethylene 2-ethylhexyl ether sulfate (sodium salt); polyoxyalkylene sulfates (s
• cationic surfactants include lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, stearyltrimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, coconut oil alkyltrimethylammonium chloride, beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methosulfate, oleyldimethylethylammonium ethosulfate, dioctyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, octadecyldiethylmethylammonium sulfate, alkyl quaternary ammoni
• alkylethenoxy quaternary ammonium salts such as riethenoxyethyl ammonium chloride and distearyl polyethenoxymethyl ammonium chloride; alkylisoquinolinium salts such as lauryl isoquinolinium chloride; benzalkonium salts such as lauryl dimethyl benzyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride; benzethonium salts such as benzyl dimethyl ⁇ 2-[2-(p-1,1,3,3-tetramethylbutylphenoxy)ethoxy]ethyl ⁇ ammonium chloride; pyridinium salts such as cetyl pyridinium chloride; imidazolinium salts such as oleyl hydroxyethyl imidazolinium ethosulfate and lauryl hydroxyethyl imidazolinium ethosulfate; acyl basic amino acid alkyl esters such as N-cocoyl
• 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 proportion of the amino group-containing silicone (A1) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but from the viewpoint of preventing fusion between fibers, it is preferably 10 to 95% by weight.
• the upper limit of this proportion is more preferably 95% by weight, even more preferably 90% by weight, and particularly preferably 80% 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.
• 15 to 90% by weight is more preferred, and 20 to 80% by weight is particularly preferred.
• the proportion of the phenolic radical scavenger (B1) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but from the viewpoint of suppressing heat generation, it is preferably 0.1 to 30% by weight.
• the upper limit of this proportion is more preferably 30% by weight, even more preferably 25% by weight, and particularly preferably 20% by weight.
• the lower limit of this proportion is more preferably 0.1% by weight, even more preferably 0.5% by weight, and particularly preferably 3.0% by weight.
• 0.5% by weight to 25% by weight is more preferable, and 3.0% by weight to 20% by weight is particularly preferable.
• the proportion of the peroxide decomposer (C) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but from the perspective of suppressing heat generation, it is preferably 0.1 to 60% by weight.
• the upper limit of this proportion is more preferably 60% by weight, even more preferably 55% by weight, and particularly preferably 50% by weight.
• the lower limit of this proportion is more preferably 0.1% by weight, even more preferably 0.5% by weight, and particularly preferably 3.0% by weight.
• 0.5% by weight to 55% by weight is more preferable, and 3.0% by weight to 50% by weight is particularly preferable.
• the proportion of the phosphorus-based peroxide decomposer (C2) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but from the perspective of suppressing heat generation, it is preferably 0.1 to 60% by weight.
• the upper limit of this proportion is more preferably 60% by weight, even more preferably 55% by weight, and particularly preferably 50% by weight.
• the lower limit of this proportion is more preferably 0.1% by weight, even more preferably 0.5% by weight, and particularly preferably 3.0% by weight.
• 0.5% by weight to 55% by weight is more preferable, and 3.0% by weight to 50% by weight is particularly preferable.
• the proportion of the sulfur-containing ester compound (C1-1) in the non-volatile content of the treatment agent of the present invention is not particularly limited, but from the viewpoint of suppressing heat generation, it is preferably 0.1 to 60% by weight.
• the upper limit of this proportion is more preferably 60% by weight, even more preferably 55% by weight, and particularly preferably 50% by weight.
• the lower limit of this proportion is more preferably 0.1% by weight, even more preferably 0.5% by weight, and particularly preferably 3.0% by weight.
• 0.5% by weight to 55% by weight is more preferable, and 3.0% by weight to 50% by weight is particularly preferable.
• the weight ratio of the peroxide decomposer (C) to the smoothing component (A) ((C)/(A)) is not particularly limited, but from the perspective of suppressing heat generation, it is preferably 0.001 to 1.
• the upper limit of this ratio is more preferably 1, even more preferably 0.5, and particularly preferably 0.1.
• the lower limit of this ratio is more preferably 0.001, even more preferably 0.003, and particularly preferably 0.005.
• 0.003 to 0.5 is more preferable, and 0.005 to 0.1 is particularly preferable.
• nonionic surfactant (D) in the nonvolatile content of the treatment agent of the present invention, but from the perspective of imparting uniform sizing properties to the fibers, it is preferably 1 to 50% by weight.
• the upper limit of this proportion is more preferably 50% by weight, even more preferably 40% by weight, and particularly preferably 30% by weight.
• the lower limit of this proportion is more preferably 1% by weight, even more preferably 3% by weight, and particularly preferably 5% by weight.
• 3% by weight to 40% by weight is more preferred, and 5% by weight to 30% by weight is particularly preferred.
• the treating agent for carbon fiber precursors of the present invention is preferably in a state in which the components of the treating agent, including the smoothing component (A), the radical scavenger (B), and the peroxide decomposer (C), are dissolved, solubilized, emulsified, or dispersed in water.
• the weight percentage of water and the weight percentage of nonvolatile matter in the entire carbon fiber precursor treatment agent may be appropriately determined taking into consideration, for example, the transportation costs for transporting the carbon fiber precursor treatment agent of the present invention and the ease of handling due to the emulsion viscosity.
• 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 may be applied to the raw material carbon fiber precursor of the 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-resistant process.
• the application method may be using a roller or the like, or it may be applied by dipping, spraying, etc.
• 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.
• an inert atmosphere such as nitrogen or argon
• 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 with 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 with a draw ratio of 0.95 to 1.05, as compared to the first carbonization process, to perform the second carbonization process, thereby carbonizing the flame-resistant fiber.
• an inert atmosphere such as nitrogen or argon
• the maximum temperature 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.).
• 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 the silicon content was determined by colorimetric quantification (wavelength 815 m ⁇ ) of silicomolybdenum blue.
• 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.
• ⁇ Number of fluffs after flame-proofing process The number of fluffs after the flame-proofing process was determined by counting the number of fluffs of 2 mm or more at the outlet of the flame-proofing furnace when 1,000 m of the carbon fiber precursor was passed using a fluff counting device (manufactured by Toray Engineering Co., Ltd.). The number of fluffs was judged according to the following criteria, with ⁇ and ⁇ representing pass. ⁇ : 5 or less ⁇ : 6 to 10 ⁇ : 11 to 20 ⁇ : 21 or more
• Example 1 A treatment agent for carbon fiber precursors having a nonvolatile content of 20% by weight was prepared by mixing and emulsifying smoothing agent A-1, radical scavenger B-1, peroxide decomposer C-1, nonionic surfactants D-1, D-2, and D-3, and water so as to obtain the nonvolatile content composition of the treatment agent shown in Table 1.
• Examples 2 to 68, Comparative Examples 1 to 26 A treating agent for carbon fiber precursors, a carbon fiber precursor, and a carbon fiber were prepared and evaluated in the same manner as in Example 1, except that the treating agent was prepared so that the non-volatile composition of the treating agent would be as shown in Tables 1 to 7. The results of evaluation of each property value are shown in Tables 1 to 7.
• ⁇ Radical Scavenger (B-1) Triethylene glycol bis 3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate (B-2) Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane (B-3) 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid (B-4) N,N'-diphenyl-p-phenylenediamine (B-5) N-phenyl-2-naphthylamine (B-6) N,N'-diphenylquinone diimine
• C Peroxide Decomposer (C)> (C-1) Thiodipropionic acid diolate (C-2) Thiodipropionic acid monoolate (C-3) Thiodipropionic acid dilaurate (C-4) Thiodipropionic acid monolaurate (C-5) Tris(2,4-di-t-butylphenyl)phosphite (C-6) 2-2'-methylenebis(4,6-di-t-butylphenyl)octylphosphite
• Nonionic surfactant (D)> (D-1) POE (25) hydrogenated castor oil ether (D-2) POE (9) C12-15 secondary alkyl ether (D-3) POE (7) C12-15 secondary alkyl ether POE is polyoxyethylene, and the number in parentheses indicates the number of moles added.
• the carbon fiber precursor treatment agents of Examples 1 to 68 were carbon fiber precursor treatment agents containing a smoothing agent (A), a radical scavenger (B), and a peroxide decomposer (C), where the radical scavenger (B) was at least one selected from a phenol-based radical scavenger (B1) and an aromatic amine-based radical scavenger (B2), and the peroxide decomposer (C) was at least one selected from a sulfur-based peroxide decomposer (C1) and a phosphorus-based peroxide decomposer (C2).
• the carbon fiber precursor treatment agents of Comparative Examples 1 to 26 were not carbon fiber precursor treatment agents according to the present invention, and therefore were unable to impart excellent single-yarn breakage suppression properties to the carbon fiber precursor during the flame-resistant treatment process.
• the treating agent for carbon fiber precursors of the present invention is a treating agent used in producing a treating agent 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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