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
  • 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
  • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences

Definitions

• the present invention relates to a treatment agent for carbon fiber precursors and its uses. More specifically, the present invention 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
• ⁇ 6> The treatment agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 5>, wherein the proportion of the silicone (B) having an aryl group in the non-volatile content of the treatment agent is 60% by weight or less.
• the silicone (B) having an aryl group includes a silicone (B1) having a phenyl group.
• ⁇ 8> The treatment agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 7>, wherein the silicone (B) having an aryl group includes at least one selected from methylphenyl silicone and diphenyl silicone.
• ⁇ 9> The treating agent for carbon fiber precursors according to ⁇ 8>, wherein a molar ratio of phenyl groups to methyl groups (phenyl groups:methyl groups) in the methylphenylsilicone and the diphenylsilicone is 1:99 to 90:10.
• ⁇ 10> The treatment agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 9>, wherein the proportion of the silicone having a polyether group in the non-volatile content of the treatment agent is 0 to 10% by weight.
• ⁇ 11> The treating agent for carbon fiber precursors according to any one of ⁇ 1> to ⁇ 10>, wherein the treating agent has a pH of 4 to 8 when diluted with a non-volatile content of 1.0% by weight.
• a method for producing a carbon fiber comprising: a flame-retardant treatment step of converting the carbon fiber precursor according to ⁇ 12> into a flame-retardant fiber; and a carbonization treatment step of further carbonizing the flame-retardant fiber.
• 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 silicone (A) having an amino group may be used alone or in combination with two or more other types.
• the amino group may be any of the monoamine type, diamine type, and polyamine type, and both may coexist in one molecule, but from the viewpoint of uniformly applying the treatment agent to the inside of the fiber bundle in the flame-retardant treatment process and forming a film with the treatment agent to protect the fibers, the monoamine type or diamine type is preferred, and the diamine type is more preferred.
• the amino equivalent of the silicone (A) having an amino group 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.
• the amino equivalent means the mass of the siloxane skeleton per one amino group or ammonium group.
• the unit of g/mol is a value converted per 1 mol of amino group or ammonium group. Therefore, the smaller the amino equivalent value, the higher the ratio of amino group or ammonium group in the molecule.
• the amino group-containing silicone (A) may be used in combination with multiple amino group-containing silicones with different amino equivalents and kinetic viscosities (25°C).
• the above amino equivalent refers to the amino equivalent of the entire amino group-containing silicone (A) (mixture)
• the above kinetic viscosity at 25°C refers to the kinetic viscosity of the entire amino group-containing silicone (A) (mixture).
• R 1 represents an alkyl group having 1 to 20 carbon atoms.
• R 2 represents a group represented by the following general formula (2).
• R 3 represents R 1 , R 2 or -OR 9 (R 9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
• the order of each repeating unit bracketed by a and b is not limited, and the bonding pattern may be alternating, block or random.
• Methylphenyl silicones include silicones having methylphenylsiloxane units ((CH 3 )(C 6 H 5 )SiO 2/2 ) and dimethylsiloxane units ((CH 3 ) 2 SiO 2/2 ), and diphenyl silicones include silicones having diphenylsiloxane units ((C 6 H 5 ) 2 SiO 2/2 ) and dimethylsiloxane units ((CH 3 ) 2 SiO 2/2 ).
• the molar ratio of phenyl groups to methyl groups (phenyl groups:methyl groups) in methylphenylsilicone and diphenylsilicone is not particularly limited, but from the viewpoint of emulsion stability, it is preferably 1:99 to 90:10, more preferably 1:99 to 70:30, even more preferably 1:99 to 50:50, and particularly preferably 1:99 to 30:70.
• Aryl group-containing silicone (B) may be used in combination with multiple aryl group-containing silicones with different kinetic viscosities (25°C).
• the above kinetic viscosity at 25°C refers to the kinetic viscosity of the entire aryl group-containing silicone (B) (mixture).
• the treating agent of the present invention contains an aliphatic (poly)oxyalkylene derivative (C1) (hereinafter sometimes referred to as an aliphatic derivative (C1)).
• the aliphatic derivative (C1) 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 (C1-1) and an aliphatic alkylene oxide adduct (C1-2) having an ester group, with the aliphatic alcohol alkylene oxide adduct (C1-1) being preferred from the viewpoint of emulsion stability.
• the aliphatic (poly)oxyalkylene derivative (C1) may be used alone or in combination of two or more kinds.
• the aliphatic alcohol alkylene oxide adduct (C1-1) includes an alkylene oxide adduct of an aliphatic alcohol, which does not have an ester group.
• the aliphatic alcohol constituting the aliphatic alcohol alkylene oxide adduct (C1-1) is not particularly limited, and examples thereof include aliphatic alcohols having 2 to 24 carbon atoms.
• the aliphatic alcohol may be saturated or unsaturated, may be linear or branched, and may be a monohydric alcohol or a dihydric or higher alcohol, and from the viewpoint of emulsion stability, a monohydric linear saturated aliphatic alcohol or a monohydric branched saturated aliphatic alcohol is preferred.
• the aliphatic alcohol alkylene oxide adduct (C1-1) may be used alone or in combination of two or more kinds.
• the upper limit of the carbon number of the aliphatic alcohol is preferably 20, more preferably 18, and even more preferably 16.
• the lower limit of the carbon number is more preferably 4, more preferably 6, and particularly preferably 8. Also, for example, 6 to 18 is preferable, and 8 to 16 is more preferable.
• the fatty alcohols constituting the fatty alcohol alkylene oxide adduct (C1-1) 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, butylene glycol, etc., and in terms of emulsion stability, lauryl alcohol, stearyl alcohol, isododecyl alcohol, isohexadecyl alcohol, is
• the number of moles of alkylene oxide added in the aliphatic alcohol alkylene oxide adduct (C1-1) 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. 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, more preferably contains ethylene oxide, and the alkylene oxide may be added randomly or in blocks.
• fatty alcohol alkylene oxide adducts include polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene tetradecyl ether, polyoxyethylene cetyl ether, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether, polyoxyethylene 1-hexylhexyl ether, poly Examples include oxyethylene 1-octylhexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentyl heptyl ether, polyoxyethylene 1-heptyl pentyl ether, polyoxyethylene 1-hexyl heptyl ether, polyoxyethylene 1-heptyl hexyl
• Examples of the aliphatic alkylene oxide adduct (C1-2) having an ester group include those having a structure in which an alkylene oxide is added to an aliphatic carboxylic acid (C1-2-1) and those having a structure in which an alkylene oxide is added to an ester compound of an aliphatic carboxylic acid and a polyhydric alcohol (C1-2-2).
• One or more types of aliphatic alkylene oxide adducts having an ester group (C1-2) may be used.
• the number of moles of alkylene oxide added in the aliphatic alkylene oxide adduct (C1-2) 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, more preferably contains ethylene oxide, and the alkylene oxide may be added randomly or in blocks.
• Examples of compounds (C1-2-1) 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 a carboxylic acid having 8 to 18 carbon atoms are preferred.
• the polyhydric alcohol constituting the structure (C1-2-2) in which an alkylene oxide is added to an ester compound of an aliphatic carboxylic acid and a polyhydric alcohol is preferably a dihydric to tetrahydric alcohol having 2 to 6 carbon atoms, and among these, a dihydric to trihydric alcohol having 2 to 6 carbon atoms is more preferable.
• polyhydric alcohol examples 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 structures in which an alkylene oxide is added to an ester compound of an aliphatic carboxylic acid and a polyhydric alcohol (C1-2-2) include compounds in which an alkylene oxide is added to the ester compounds of the 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 treating agent of the present invention may contain an aromatic (poly)oxyalkylene derivative (C2) (hereinafter, sometimes referred to as aromatic derivative (C2)).
• the aromatic derivative (C2) is not particularly limited as long as it is an aromatic compound having a (poly)oxyalkylene group, and examples thereof include an alkylene oxide adduct (C2-1) of an aromatic compound having a hydroxyl group, and an aromatic alkylene oxide adduct (C2-2) having an ester group, among which the alkylene oxide adduct (C2-1) of an aromatic compound having a hydroxyl group is preferred in terms of improving the bundling ability during flame retardancy.
• alkylene oxide adduct (C2-1) of an aromatic compound having a hydroxyl group does not have an ester group.
• the aromatic derivative (C2) preferably contains a compound having a bisphenol skeleton, since it has high heat resistance and can improve the bundling property during flame retardation.
• the aromatic compound having a hydroxyl group constituting the alkylene oxide adduct (C2-1) of an aromatic compound having a hydroxyl group is not particularly limited, and examples thereof include compounds having a bisphenol skeleton, (poly)styrenated phenol, and alkylphenols. From the viewpoint of improving the bundling ability during flame retardation, compounds having a bisphenol skeleton are preferred, and compounds having a bisphenol A skeleton are more preferred.
• the number of moles of alkylene oxide added in the alkylene oxide adduct (C2-1) of an aromatic compound having a hydroxyl group is preferably 2 to 60 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 4 moles, even more preferably 6 moles, and particularly preferably 8 moles.
• 4 to 40 moles is more preferable, and 6 to 30 moles is particularly preferable.
• the alkylene oxide added to the aromatic compound having a hydroxyl group is preferably at least one selected from ethylene oxide and propylene oxide, more preferably includes ethylene oxide, and even more preferably is ethylene oxide.
• 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, citraconic acid, etc., with succinic acid and adipic acid being preferred in terms of emulsion stability.
• aromatic carboxylic acid is not particularly limited, but examples thereof include aromatic polycarboxylic acids having 8 to 40 carbon atoms and aromatic monocarboxylic acids having 7 to 14 carbon atoms.
• aromatic polycarboxylic acids having 8 to 40 carbon atoms include 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, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate, potassium 5-sulfoisophthalate, and derivatives of these dicarboxylic acids, as well as trimellitic acid, pyromellitic acid, and derivatives of these trivalent or higher carboxylic acids. Examples
• the treatment agent of the present invention preferably contains a Bronsted acid compound (D) in that emulsion stability is improved.
• the Bronsted acid compound (D) refers to a proton donor, and examples of the compound include an organic carboxylic acid compound, an inorganic acid, an organic sulfonic acid compound, an organic phosphoric acid ester compound, an organic sulfuric acid ester compound, and an organic phosphonic acid compound.
• 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, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, isoeicosaic 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 acid examples 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 moles.
• alkyl group examples include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
• polyoxyalkylene group examples include polyoxyethylene, polyoxypropylene, and polyoxyethylene polyoxypropylene groups.
• the total proportion of PO units and EO units in the silicone having a polyether group, and the weight ratio of EO units to PO units contained in the silicone having a polyether group refer to the total weight proportion and weight ratio of all PO units and EO units contained in the silicone having a polyether group, and are calculated from the weight ratio of PO units and EO units to the weight of the silicone having a polyether group, which is calculated from the peak area when the silicone having a polyether group is measured by 1H -NMR.
• the proportion of the silicone (A) having an amino group in the non-volatile content of the treatment agent of the present invention is preferably 0.1 to 95% by weight, from the viewpoint of easily suppressing deterioration over time of the carbon fiber precursor and facilitating emulsion stabilization.
• the upper limit of the proportion is more preferably 92% by weight, even more preferably 88% by weight, and particularly preferably 85% by weight.
• the lower limit of the proportion is more preferably 1% by weight, even more preferably 3% by weight, and particularly preferably 5% by weight. Also, for example, 1 to 92% by weight is more preferable, 3 to 88% by weight is even more preferable, and 5 to 85% by weight is particularly preferable.
• the non-volatile content concentration in the present invention is obtained 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, precisely weighing the weight of the residue on the aluminum sheet when the fluctuation range of the volatile content over 150 seconds becomes 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, which has been dried in the same manner as in the non-volatile content concentration measurement procedure, becomes 0.15%.
• the proportion of the aliphatic (poly)oxyalkylene derivative (C1) in the non-volatile content of the treatment agent of the present invention is preferably 1 to 90% by weight, in terms of being able to easily suppress deterioration over time of the carbon fiber precursor and to easily stabilize the emulsion.
• the upper limit of this proportion is more preferably 70% by weight, even more preferably 40% by weight, and particularly preferably 30% by weight.
• the lower limit of this proportion is more preferably 3% by weight, even more preferably 5% by weight, and particularly preferably 7% by weight.
• 3 to 70% by weight is more preferable, 5 to 40% by weight is even more preferable, and 7 to 30% by weight is particularly preferable.
• the weight ratio (B/A) of the silicone (B) having an aryl group to the silicone (A) having an amino group is preferably 1 or less, since this makes it easier to suppress deterioration over time of the carbon fiber precursor and to stabilize the emulsion.
• the upper limit of this ratio is more preferably 0.9, even more preferably 0.7, particularly preferably 0.5, and most preferably 0.48.
• the lower limit of this weight ratio is more preferably 0.005, even more preferably 0.008, and particularly preferably 0.01.
• 0.005 to 0.9 is more preferable
• 0.008 to 0.7 is even more preferable
• 0.01 to 0.5 is particularly preferable
• 0.01 to 0.48 is most preferable.
• the weight ratio (B/C1) of the silicone (B) having an aryl group to the aliphatic (poly)oxyalkylene derivative (C1) is preferably 9 or less, from the viewpoints of easily suppressing deterioration over time of the carbon fiber precursor and stabilizing the emulsion.
• the upper limit of this ratio is more preferably 7, even more preferably 5, particularly preferably 4, and most preferably 1.7.
• the lower limit of this weight ratio is more preferably 0.01, even more preferably 0.05, and particularly preferably 0.1. Also, for example, 0.01 to 7 is more preferable, 0.05 to 5 is even more preferable, 0.1 to 4 is particularly preferable, and 0.1 to 1.7 is most preferable.
• the proportion of the Br ⁇ nsted acid compound (D) in the non-volatile content of the treatment agent of the present invention is preferably 0.05 to 10% by weight, in terms of facilitating emulsion stabilization.
• the upper limit of this weight proportion is more preferably 8.5% by weight, even more preferably 7% by weight, and particularly preferably 5% by weight.
• the lower limit of this weight proportion is more preferably 0.07% by weight, even more preferably 0.08% by weight, and particularly preferably 0.1% by weight. Also, for example, 0.07 to 7% by weight is more preferable, and 0.1 to 5% by weight is even more preferable.
• the proportion of silicone having polyether groups in the non-volatile content of the treatment agent of the present invention is preferably 0 to 10% by weight, since this facilitates emulsion stabilization.
• the upper limit of this weight proportion is more preferably 8.5% by weight, even more preferably 7% by weight, and particularly preferably 5% by weight.
• the lower limit of this weight proportion is more preferably 0.07% by weight, even more preferably 0.08% by weight, and particularly preferably 0.1% by weight. For example, 0.07 to 7% by weight is more preferable, and 0.1 to 5% by weight is even more preferable.
• the treating agent of the present invention preferably further contains another nonionic surfactant as the other component (E) from the viewpoint of enhancing emulsion stability.
• the other nonionic surfactant refers to a nonionic surfactant other than the aliphatic (poly)oxyalkylene derivative (C1) and the aromatic (poly)oxyalkylene derivative (C2).
• Other 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 kinds of the other nonionic surfactant may be used.
• the weight ratio of the other nonionic surfactants to the nonvolatile content of the treatment agent is preferably 0.1 to 10% by weight in terms of emulsion stability.
• the upper limit of this ratio is more preferably 8.5% by weight, even more preferably 7.0% by weight, and particularly preferably 5.0% by weight.
• the lower limit of this ratio is more preferably 0.25% by weight, even more preferably 0.4% by weight, and particularly 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
• 0.5 to 5.0% by weight is particularly preferable.
• the pH of the treatment agent of the present invention when diluted to 1.0% by weight of non-volatile content is preferably 4 to 8 in terms of the long-term storage stability of the treatment agent.
• the upper limit of the pH is more preferably 7, and even more preferably 6.5.
• the lower limit of the content is more preferably 4.5, and even more preferably 5. Also, for example, 4.5 to 6.5 is more preferable, and 5 to 6.5 is even more preferable.
• the pH of the treatment agent of the present invention when diluted to 1.0% non-volatile content is determined by the method described in the Examples.
• Anionic surfactants include ether carboxylates, ether sulfates, sulfosuccinates, sodium (poly)oxyethylene coconut oil fatty acid monoethanolamide sulfate, sulfonates having an alkyl group, phosphates having an alkyl group, 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, oleyl dimethyl ethyl ammonium ethosulfate, alkyl quaternary ammonium salts such as stearoyl dimethyl ammonium sulfate, dioctyl dimethyl ammonium chloride, dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and octt
• 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 dimethylaminoacetate betaine, alkyl betaine, amido betaine, and sulfobetaine; 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-imidazoline
• the carbon fiber precursor treating agent of the present invention may contain other components in addition to the above-mentioned components, so long as 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, higher alcohol ethers, 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 silicone (A) having an amino group and/or the silicone (B) having an aryl group.
• the content of the low molecular weight silicone in the treatment 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) and the aryl group-containing silicone (B).
• the weight ratio of water in the entire carbon fiber precursor treatment agent is preferably 0.1 to 99.9% by weight, more preferably 10 to 99.5% by weight, and particularly preferably 50 to 99% by weight.
• the weight ratio (concentration) of non-volatile matter in the entire carbon fiber precursor treatment agent is preferably 0.01 to 99.9% by weight, more preferably 0.5 to 90% by weight, and particularly preferably 1 to 50% by weight.
• the carbon fiber precursor treatment agent of the present invention can be manufactured by mixing the components described above.
• the above-mentioned flame retardant treatment step is preferably a flame retardant treatment step in which a carbon fiber precursor is converted into a flame retardant fiber in an oxidizing atmosphere at 200 to 300°C, and the carbonization treatment step is preferably a step in which the flame retardant 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, which improves bundling ability and reduces fiber bundle disorder and drawing unevenness, thereby making it possible to produce high-quality carbon fibers.
• the spinning process is a process for spinning the carbon fiber precursor by adhering a treatment agent for carbon fiber precursor to a raw material carbon fiber precursor of the carbon fiber precursor, and preferably includes an adhering treatment process and a drawing process.
• the adhesion treatment step is a step of adhering a treatment agent for carbon fiber precursors after spinning the raw carbon fiber precursor of the carbon fiber precursor. That is, in the adhesion treatment step, the treatment agent for carbon fiber precursors is adhered to the raw carbon fiber precursor of the carbon fiber precursor.
• the high-ratio 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 treatment agent may be applied to the raw carbon fiber precursor at any stage of 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. As for the method of application, it may be applied using a roller or the like, or it may be applied by a dipping method, spraying method, 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 obtaining the effect of preventing adhesion and fusion between fibers and preventing deterioration of the quality of the carbon fiber due to the tarred products of the treatment agent in the carbonization process.
• the application rate of the carbon fiber precursor treatment agent here is defined as the percentage of the weight of the non-volatile content of the carbon fiber precursor treatment agent attached to the weight of the carbon fiber precursor.
• the flame-retardant treatment process is a process in which the carbon fiber precursor to which the carbon fiber precursor treatment agent is attached is converted into a flame-retardant fiber in an oxidizing atmosphere of, for example, 200 to 300°C.
• the oxidizing atmosphere is usually an air atmosphere.
• the temperature of the oxidizing atmosphere is preferably 230 to 280°C.
• the carbon fiber precursor after the attachment process is heat-treated for 20 to 100 minutes (preferably 30 to 60 minutes) while applying a tension of a draw ratio of 0.90 to 1.10 (preferably 0.95 to 1.05).
• intramolecular cyclization and oxygen addition to the rings are carried out to produce a flame-retardant fiber with a flame-retardant structure.
• the carbonization process is a process in which the flame-resistant fiber is further carbonized in an inert atmosphere of, for example, 300 to 2000°C.
• first carbonization process it is preferable to first perform a preliminary carbonization process (first carbonization process) by heat-treating the flame-resistant fiber for several minutes in an inert atmosphere of nitrogen, argon, or the like in a baking furnace having a temperature gradient from 300°C to 800°C while applying a tension of a draw ratio of 0.95 to 1.15 to the flame-resistant fiber.
• the flame-resistant fiber is heat-treated for several minutes in an inert atmosphere of nitrogen, argon, or the like while applying a tension of a draw ratio of 0.95 to 1.05 to the first carbonization process, thereby performing a second carbonization process, and the flame-resistant fiber is carbonized.
• the control of the heat treatment temperature 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 appropriately selected and determined depending on the desired properties of the carbon fiber (tensile strength, elastic modulus, 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, while applying tension to the fiber obtained in the carbonization process, at a temperature of 2000 to 3000°C.
• the carbon fibers obtained in this way can be surface-treated to increase the adhesive strength with the matrix resin when made into a composite material, depending on the purpose.
• Gas-phase or liquid-phase treatment can be used as the surface treatment method, and from the viewpoint of productivity, liquid-phase treatment using an electrolyte such as an acid or alkali is preferred.
• various sizing agents that are highly compatible with the matrix resin can be added to improve the processability and handling of the carbon fibers.
• ⁇ Applying rate of treatment agent> The carbon fiber precursor after the treatment agent was applied was alkali-fused with potassium hydroxide/sodium butyrate, 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 colorimetry (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.
• ⁇ The number of fluff pieces is less than 3 pieces/m, and the number of fluff pieces is particularly 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 the carbon fiber precursors stored under the following two conditions, and the tensile properties of single fibers were measured in accordance with the test method for tensile properties of 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
• Aralkyl-modified silicone b4 kinematic viscosity at 25° C.: 900 mm 2 /s
• the carbon fiber precursor treatment agents of Examples 1 to 42 contained the silicone (A) having an amino group, the silicone (B) having an aryl group, and the aliphatic (poly)oxyalkylene derivative (C1), and therefore were able to suppress deterioration of the carbon fiber precursor over time.
• the carbon fiber precursor treating agents of Comparative Examples 1 to 7 were not the carbon fiber precursor treating agents of the present invention, and therefore could not suppress deterioration of the carbon fiber precursor when the carbon fiber precursor produced by applying the treating agent was stored for a long period of time.
• the carbon fiber precursor treating agents of Comparative Examples 8 to 11 had poor emulsion stability and were not uniformly attached to the precursor, so that the carbon fiber precursor could not be normally produced and could not be used as a carbon fiber precursor treating agent.

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