CN116234956A - Acrylic resin fiber treatment agent and acrylic resin fiber - Google Patents

Acrylic resin fiber treatment agent and acrylic resin fiber Download PDF

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Publication number
CN116234956A
CN116234956A CN202180065334.5A CN202180065334A CN116234956A CN 116234956 A CN116234956 A CN 116234956A CN 202180065334 A CN202180065334 A CN 202180065334A CN 116234956 A CN116234956 A CN 116234956A
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acrylic resin
fiber
agent
carboxylic acid
treating agent
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CN202180065334.5A
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CN116234956B (en
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本田浩气
松永拓也
大岛启一郎
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Takemoto Oil and Fat Co Ltd
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Takemoto Oil and Fat Co Ltd
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    • 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
    • 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
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention aims to inhibit burrs of acrylic resin fibers. The acrylic resin fiber treatment agent contains a carboxylic acid compound having an acid value of 60mgKOH/g or less.

Description

Acrylic resin fiber treatment agent and acrylic resin fiber
Technical Field
The present invention relates to a treating agent for acrylic resin fibers and an acrylic resin fiber.
Background
The carbon fiber is produced, for example, by performing the following steps: a spinning step of spinning an acrylic resin or the like; a drying densification step of drying and densifying the spun fiber; a drawing step of drawing the dry densified fiber to produce a carbon fiber precursor as a synthetic fiber; a refractory treatment step of rendering the carbon fiber precursor refractory; and a carbonization treatment step for carbonizing the refractory fiber.
In order to suppress burrs in the synthetic fiber manufacturing process, a synthetic fiber treating agent is sometimes used.
Patent document 1 discloses an acrylic fiber oil for producing carbon fibers, which contains a modified silicone having a modifying group containing a nitrogen atom and a branched fatty acid. Patent document 2 discloses an amino-modified silicone oil agent composition comprising: silicone oil containing amino-modified polysiloxane, monoester of dicarboxylic acid, emulsifier, and aminocarboxylic acid substance.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-184842
Patent document 2: japanese patent laid-open No. 8-209543
Disclosure of Invention
Problems to be solved by the invention
Further improvement in performance is required for the effect of the acrylic resin fiber treatment agent in suppressing burrs in the step of producing acrylic resin fibers.
The present invention has been made in view of such circumstances, and an object thereof is to provide a treatment agent for acrylic resin fibers, which suitably improves the effect of suppressing burrs in the production process of acrylic resin fibers. Another object is to provide an acrylic resin fiber to which the treatment agent for acrylic resin fiber is attached.
Means for solving the problems
The treating agent for acrylic resin fibers for solving the above problems is characterized by containing a carboxylic acid compound having an acid value of 60mgKOH/g or less.
In the treating agent for acrylic resin fibers, the carboxylic acid compound is preferably a compound having an ester bond in a molecule.
In the treating agent for acrylic resin fibers, the carboxylic acid compound is preferably a compound having 2 or more ester bonds in the molecule.
In the treating agent for acrylic resin fibers, the carboxylic acid compound is preferably a compound having a hydroxyl group in a molecule.
In the acrylic resin fiber treatment agent, the acid value of the carboxylic acid compound is preferably 10 to 50mgKOH/g.
The acrylic resin fiber treatment agent preferably further contains a smoothing agent.
In the acrylic resin fiber treatment agent, the smoothing agent preferably contains an amino-modified silicone.
In the acrylic resin fiber treatment agent, the amino-modified silicone preferably has a kinematic viscosity at 25℃of 50 to 7000mm 2 /s。
The acrylic resin fiber treatment agent preferably further contains a nonionic surfactant.
In this case, the content of the carboxylic acid compound is preferably 0.1 to 15% by mass, based on 100% by mass of the total content of the carboxylic acid compound, the smoothing agent, and the nonionic surfactant in the acrylic resin fiber treating agent.
In the treating agent for acrylic resin fibers, the acrylic resin fibers are preferably carbon fiber precursors.
The acrylic resin fiber for solving the above problems is characterized in that the acrylic resin fiber treating agent is attached thereto.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, burrs of acrylic resin fibers can be suppressed.
Detailed Description
(embodiment 1)
Embodiment 1 in which the treatment agent for acrylic resin fiber of the present invention (hereinafter also simply referred to as the treatment agent) is embodied will be described.
The treatment agent of the present embodiment contains a carboxylic acid compound having an acid value of 60mgKOH/g or less.
By containing the carboxylic acid compound, the burr-suppressing effect of the treating agent can be improved.
Specific examples of the carboxylic acid compound include a pentamer condensate of 12-hydroxystearic acid, a hexamer condensate of castor oil fatty acid, a tridecyl condensate of 12-hydroxystearic acid, a tetramer condensate of 12-hydroxystearic acid, a thirty-polymer condensate of 12-hydroxystearic acid, an ester compound obtained by reacting 10 mol of ethylene oxide adduct of bisphenol A with adipic acid at a molar ratio of 3:4, an ester compound obtained by reacting 15 mol of ethylene oxide adduct of bisphenol A with adipic acid at a molar ratio of 1:1, polyoxyethylene (25 mol) lauryl ether acetic acid, and the like.
The above carboxylic acid compounds may be used alone or in combination of 1 or more than 2.
The carboxylic acid compound may be commercially available or produced by a known method. In the case of production by a known method, for example, the product can be produced by dehydration condensation reaction of a hydroxyl group and a carboxyl group contained in a raw material.
The carboxylic acid compound may be formed into a salt with other alkaline components such as amine and metal in the treating agent.
The acid value of the carboxylic acid compound is preferably 10 to 50mgKOH/g.
By setting the acid value of the carboxylic acid compound to the above-described numerical range, the burr-suppressing effect of the treating agent can be further improved.
The acid value of the carboxylic acid compound can be measured in accordance with JIS K0070.
The carboxylic acid compound is preferably a compound having an ester bond in the molecule.
In the carboxylic acid compound, the number of ester bonds in the molecule is not particularly limited, and for example, it is preferable that the carboxylic acid compound has 2 or more ester bonds in the molecule.
The number of ester bonds can be calculated by the following formula.
Number of ester bonds= (saponification value-acid value)/(acid value)
The saponification value can be measured according to JIS K0070.
The carboxylic acid compound is preferably a compound having a hydroxyl group in the molecule.
The treatment agent of the present embodiment preferably contains a smoothing agent.
Examples of the smoothing agent include silicone and ester.
The silicone used as the smoothing agent is not particularly limited, and examples thereof include dimethyl silicone, phenyl-modified silicone, amino-modified silicone, amide-modified silicone, polyether-modified silicone, amino polyether-modified silicone, alkyl aralkyl-modified silicone, alkyl polyether-modified silicone, ester-modified silicone, epoxy-modified silicone, methanol-modified silicone, mercapto-modified silicone, and the like.
The ester used as the smoothing agent is not particularly limited, and examples thereof include: (1) Ester compounds of aliphatic monoalcohols such as octyl palmitate, oleyl laurate, oleyl oleate and isotetracosyl oleate with aliphatic monocarboxylic acids; (2) Ester compounds of aliphatic polyhydric alcohols such as 1, 6-hexanediol dicaprate, glycerol trioleate, trimethylolpropane trilaurate and pentaerythritol tetraoctanoate with aliphatic monocarboxylic acids; (3) Ester compounds of aliphatic monohydric alcohols and aliphatic polycarboxylic acids such as dioleyl azelate, dioleyl thiodipropionate, diisocetyl thiodipropionate, and diisostearyl thiodipropionate; (4) Ester compounds of an aromatic monoalcohol such as benzyl oleate or benzyl laurate and an aliphatic monocarboxylic acid; (5) Full ester compounds of aliphatic monocarboxylic acids and aromatic polyols such as dilaurate of bisphenol a and dilaurate of alkylene oxide adducts of bisphenol a; (6) Full ester compounds of aliphatic monohydric alcohols such as bis 2-ethylhexyl phthalate, diisostearyl isophthalate, trioctyl trimellitate and aromatic polycarboxylic acids; (7) Natural oils such as coconut oil, rapeseed oil, sunflower seed oil, soybean oil, castor oil, sesame oil, fish oil, and beef tallow. Further, a known smoothing agent used in a treatment agent for synthetic fibers may be used.
Specific examples of the smoothing agent include: kinematic viscosity at 25℃of 650mm 2 Amino-modified silicone with amino equivalent of 1800 g/mol; a kinematic viscosity at 25℃of 90mm 2 Amino modification with amino equivalent weight of 5000g/mol per secondA silicone; the kinematic viscosity at 25℃is 4500mm 2 Amino-modified silicone with amino equivalent weight of 1200 g/mol; a kinematic viscosity at 25℃of 40mm 2 Amino-modified silicone with amino equivalent of 1800 g/mol; a kinematic viscosity at 25℃of 8000mm 2 Amino-modified silicone with amino equivalent of 1000 g/mol; a kinematic viscosity at 25℃of 1700mm 2 S, silicone backbone/polyether side chain = 20/80 (mass ratio), ethylene oxide/propylene oxide = 50/50 (molar ratio) polyether modified silicone; kinematic viscosity at 25℃of 17000mm 2 Epoxy modified silicone with epoxy equivalent of 3800 g/mol; dilauryl esters of ethylene oxide 2 mole adducts of bisphenol a, and the like.
The smoothing agent preferably contains a modified silicone, more preferably an amino modified silicone. Furthermore, the amino-modified silicone preferably has a kinematic viscosity at 25℃of 50 to 7000mm 2 /s。
The smoothing agent may be used alone or in combination of 1 or more than 2.
The treatment agent of the present embodiment preferably contains a nonionic surfactant.
The nonionic surfactant contained in the treating agent of the present embodiment is not particularly limited, and examples thereof include an alcohol or carboxylic acid, an ester compound of a carboxylic acid and a polyol, and an ether-ester compound of an carboxylic acid and an ester compound of a polyol, to which an alkylene oxide is added.
Specific examples of the alcohols used as the raw material of the nonionic surfactant include: (1) Straight-chain alkyl alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosyl alcohol, tricosyl alcohol, tetracosyl alcohol, pentacosyl alcohol, hexacosyl alcohol, heptacosyl alcohol, octacosyl alcohol, nonacosyl alcohol, triacontyl alcohol, and the like; (2) Branched alkyl alcohols such as isopropanol, isobutanol, isohexanol, 2-ethylhexanol, isononanol, isodecanol, isododecanol, isotridecanol, isotetradecanol, isotridecanol, isohexadecanol, isoheptadecanol, isostearyl alcohol, isononadecanol, isoeicosanol, isodi-undecanol, isodocosyl, isotridecanol, isotetracosanol, isoditetradecanol, isooctadecanol, isoicosanol, and isopentadecanol; (3) Straight-chain alkenyl alcohols such as tetradecenol, hexadecenol, heptadecenol, octadecenol, and nonadecenol; (4) Branched alkenyl alcohols such as isocetyl enol and isostearyl enol; (5) cyclic alkyl alcohols such as cyclopentanol and cyclohexanol; (6) Aromatic alcohols such as phenol, nonylphenol, benzyl alcohol, monostyrenated phenol, distyrenated phenol, tristyrenated phenol, and the like.
Specific examples of carboxylic acids used as a raw material of the nonionic surfactant include, for example: (1) Linear alkyl carboxylic acids such as octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, and docosanoic acid; (2) Branched alkyl carboxylic acids such as 2-ethylhexanoic acid, isododecanoic acid, isotridecanoic acid, isotetradecanoic acid, isohexadecanoic acid, and isostearic acid; (3) Linear alkenyl carboxylic acids such as octadecenoic acid, octadecadienoic acid, and octadecatrienoic acid; (4) aromatic carboxylic acids such as benzoic acid.
Specific examples of the alkylene oxide used as a raw material of the nonionic surfactant include ethylene oxide, propylene oxide, and the like. The number of addition moles of the alkylene oxide is preferably 0.1 to 60 moles, more preferably 1 to 40 moles, still more preferably 2 to 30 moles. The number of addition moles of alkylene oxide means the number of moles of alkylene oxide relative to 1 mole of alcohol or carboxylic acid to be charged into the raw material.
Specific examples of the polyhydric alcohol used as a raw material of the nonionic surfactant include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2-methyl-1, 2-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2, 5-hexanediol, 2-methyl-2, 4-pentanediol, 2, 3-dimethyl-2, 3-butanediol, glycerin, 2-methyl-2-hydroxymethyl-1, 3-propanediol, 2-ethyl-2-hydroxymethyl-1, 3-propanediol, trimethylolpropane, sorbitol anhydride, pentaerythritol, sorbitol, and the like.
Specific examples of the nonionic surfactant include 10 mol adducts of ethylene oxide to isodecyl alcohol, 5 mol adducts of ethylene oxide to isostearyl alcohol, 5 mol adducts of ethylene oxide to hexanol, 8 mol adducts of ethylene oxide to tetradecyl alcohol, and the like.
The nonionic surfactant may be used alone or in combination of 1 or more than 2.
The content of the carboxylic acid compound, the smoothing agent, and the nonionic surfactant is not limited. The content of the carboxylic acid compound in the treating agent is preferably 0.1 to 15% by mass, more preferably 0.3 to 13% by mass, based on 100% by mass of the total content of the carboxylic acid compound, the smoothing agent and the nonionic surfactant. By limiting the mixing ratio to this, the burr suppressing effect of the treating agent can be further improved.
(embodiment 2)
Embodiment 2 in which the acrylic resin fiber of the present invention is embodied will be described. The treating agent of embodiment 1 is attached to the acrylic resin fiber of the present embodiment. Specific examples of the acrylic resin fiber are not particularly limited, and examples thereof include polyacrylic fibers such as polyacrylic acid and modified acrylic. As the acrylic resin fiber, a carbon fiber precursor produced from a resin that is subjected to a carbonization treatment step described later to produce a carbon fiber is preferable. As the resin constituting the carbon fiber precursor, an acrylic resin is exemplified.
The amount of the treating agent according to embodiment 1 to be attached to the acrylic resin fibers is not particularly limited, but is preferably 0.1 to 2% by mass, more preferably 0.3 to 1.2% by mass, based on the acrylic resin fibers.
Examples of the form of the treating agent in the case of attaching the treating agent of embodiment 1 to the fibers include an organic solvent solution and an aqueous solution.
As a method for attaching the treating agent to the acrylic resin fiber, for example, the following method can be used: the treatment agent according to embodiment 1 is applied by a known method such as dipping, spraying, rolling, or a yarn feeder oil feeding method using a metering pump, using an aqueous solution containing the treatment agent and water or an aqueous solution obtained by further dilution.
The method for producing the carbon fiber using the treating agent of the present invention and the acrylic resin fiber to which the treating agent is attached will be described.
The method for producing carbon fibers preferably undergoes the following steps 1 to 3.
Step 1: a yarn-making step of making yarns by adhering the treating agent of embodiment 1 to the acrylic resin fibers.
Step 2: a flame-resistant treatment step of converting the acrylic resin fiber obtained in the step 1 into a flame-resistant fiber in an oxidizing atmosphere at 200 to 300 ℃, preferably 230 to 270 ℃.
And step 3: and a carbonization step of carbonizing the refractory fiber obtained in the step 2 in an inert atmosphere at 300 to 2000 ℃, preferably 300 to 1300 ℃.
The yarn-making step preferably further includes a wet spinning step of spinning the resin by dissolving the resin in a solvent, a dry densification step of drying the acrylic resin fiber obtained by the wet spinning to densify the acrylic resin fiber, and a drawing step of drawing the dry densified acrylic resin fiber.
The temperature of the dry densification step is not particularly limited, and the acrylic resin fiber subjected to the wet spinning step is preferably heated at, for example, 70 to 200 ℃. The timing of attaching the treating agent to the acrylic resin fiber is not particularly limited, and is preferably between the wet spinning step and the dry densification step.
The oxidizing atmosphere in the refractory treatment step is not particularly limited, and for example, an air atmosphere may be used.
The inert atmosphere in the carbonization step is not particularly limited, and for example, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or the like can be used.
According to the treating agent and the acrylic resin fiber of the present embodiment, the following effects can be obtained.
(1) The treatment agent of the present embodiment contains a carboxylic acid compound having a predetermined acid value. Therefore, burrs of the acrylic resin fiber can be suppressed. Further, since the heat resistance of the treating agent can be improved, the effect of suppressing welding of the fibers to each other (welding suppressing effect) in the step of refractory treating the acrylic resin fibers can be improved.
(2) The treating agent is attached to the acrylic resin fiber between the wet spinning step and the dry densification step. Since the bundling property of the acrylic resin fibers subjected to the drying densification step and the stretching step can be improved and the bundling property of the refractory fibers subjected to the refractory treatment step can be improved, the occurrence of fiber winding and burrs in the carbon fiber production step can be suppressed. Therefore, the appearance of the carbon fiber can be improved, and the strength of the carbon fiber can be improved.
The above embodiment can be modified as follows. The above-described embodiments and the following modifications can be combined with each other within a range that is not technically contradictory.
In the present embodiment, the treating agent is attached to the acrylic resin fiber between the wet spinning step and the dry densification step, but the present invention is not limited to this embodiment. The treating agent may be attached to the acrylic resin fiber between the dry densification step and the stretching step, or may be attached to the acrylic resin fiber between the stretching step and the refractory treatment step.
In the present embodiment, the acrylic resin fiber treatment agent contains a modified silicone and a nonionic surfactant, but the present invention is not limited to this embodiment. At least any one of the modified silicone and the nonionic surfactant may be omitted.
In the present embodiment, for example, the acrylic resin fiber may be a fiber that has not been subjected to the carbonization treatment step although the flame-resistant treatment step has been performed.
The treating agent of embodiment 1 may be attached to synthetic fibers other than acrylic resin fibers. That is, the treating agent of embodiment 1 may not necessarily be an acrylic resin fiber treating agent, and may be a synthetic fiber treating agent other than an acrylic resin fiber. Specific examples of the synthetic fibers other than the acrylic resin fibers include, for example: (1) Polyester fibers such as polyethylene terephthalate, polypropylene terephthalate and polylactic acid ester; (2) polyamide fibers such as nylon 6 and nylon 66; (3) polyolefin fibers such as polyethylene and polypropylene; (4) cellulose-based fibers; (5) lignin-based fibers, etc. Among them, synthetic fibers that can constitute carbon fibers by undergoing a carbonization treatment process, for example, fibers composed of resins such as polyethylene resins, phenol resins, cellulose resins, lignin resins, pitch, and the like are preferable.
The treatment agent or aqueous solution of the present embodiment may further contain components that are generally used in the treatment agent or aqueous solution, such as a stabilizer, a charge control agent, an antistatic agent, a thickener, an antioxidant, and an ultraviolet absorber, for maintaining the quality of the treatment agent or aqueous solution, within a range that does not impair the effects of the present invention.
Examples
Hereinafter, examples and the like are given for more specifically explaining the constitution and effect of the present invention, but the present invention is not limited to these examples. In the following description of examples and comparative examples,% means% by mass.
Test group 1 (preparation of treatment agent for acrylic fiber)
Example 1
Using the components shown in Table 1, the mixture was placed in a beaker so that the ratio of carboxylic acid compound (A-1) was 5%, smoothing agent (B-1) was 60%, smoothing agent (B-6) was 20%, and nonionic surfactant (C-1) was 15%. They were stirred to mix thoroughly. The 25% aqueous solution of the treatment agent for acrylic resin fiber of example 1 was prepared by slowly adding ion-exchanged water with continuous stirring so as to reach a solid content concentration of 25%.
Examples 2 to 19 and comparative examples 1 to 4
The acrylic resin fiber treatment agents of examples 2 to 19 and comparative examples 1 to 4 were prepared in the same manner as in example 1 using the components shown in table 1.
The types and contents of carboxylic acid compounds, the types and contents of smoothing agents, and the types and contents of surfactants in the treating agents of each example are shown in "(a) carboxylic acid compound" column, "(B) smoothing agent" column, and "(C) nonionic surfactant" column, respectively, of table 1.
TABLE 1
Figure BDA0004141598860000101
The details of the components A-1 to A-8, rA1 to rA-3, B-1 to B-8, and C-1 to C-4 described in the column of the symbols in Table 1 are as follows.
(carboxylic acid compound)
A-1: pentameric condensation compounds of 12-hydroxystearic acid
A-2: hexamer condensate of castor oil fatty acid
A-3: tridecylate condensate of 12-hydroxystearic acid
A-4: tetramer condensation compounds of 12-hydroxystearic acid
A-5: thirty polymer condensation compounds of 12-hydroxystearic acid
A-6: ester compound obtained by reacting 10 mol adduct of ethylene oxide of bisphenol A with adipic acid in a 3:4 mol ratio
A-7: ester compound obtained by reacting ethylene oxide 15 mol adduct of bisphenol A with adipic acid in a molar ratio of 1:1
A-8: polyoxyethylene (25 moles) lauryl ether acetic acid
rA-1: castor oil fatty acid
rA-2: ethylene oxide 12 mole adduct of nonylphenol and monoester of succinic acid
rA-3: isostearic acid
The types, acid numbers, saponification numbers, and numbers of ester bonds in the molecule of the carboxylic acid compounds used in the carboxylic acid compounds are shown in the "(A) carboxylic acid compound" column, "acid number (mgKOH/g)" column, "saponification number (mgKOH/g)" column, and "number of ester bonds in the molecule" column of Table 2, respectively.
TABLE 2
Figure BDA0004141598860000111
(smoothing agent)
B-1: kinematic viscosity at 25℃of 650mm 2 Amino-modified silicone with amino equivalent weight of 1800g/mol per second
B-2: a kinematic viscosity at 25℃of 90mm 2 Amino-modified silicone B-3 with an amino equivalent of 5000 g/mol/s: the kinematic viscosity at 25℃is 4500mm 2 Amino-modified silicone with amino equivalent weight of 1200g/mol per s
B-4: a kinematic viscosity at 25℃of 40mm 2 Amino-modified silicone B-5 with an amino equivalent of 1800 g/mol/s: a kinematic viscosity at 25℃of 8000mm 2 Amino-modified silicone with amino equivalent weight of 1000g/mol per second
B-6: a kinematic viscosity at 25℃of 1700mm 2 S, silicone backbone/polyether side chain=20/80 (mass ratio), ethylene oxide/propylene oxide=50/50 (molar ratio) polyether modified silicone
B-7: kinematic viscosity at 25℃of 17000mm 2 Epoxy modified silicone with epoxy equivalent of 3800g/mol per second
B-8: dilauryl ester of ethylene oxide 2 mole adduct of bisphenol A
(nonionic surfactant)
C-1: ethylene oxide 10 mole adduct of isodecyl alcohol
C-2: ethylene oxide 5 mole adduct of isostearyl alcohol
C-3: ethylene oxide 5 mole adduct of hexanol
C-4: ethylene oxide 8 mole adduct of tetradecanol
Test group 2 (production of acrylic fiber and carbon fiber)
Acrylic resin fibers and carbon fibers were produced using the acrylic resin fiber treatment agent prepared in test group 1.
First, as step 1, an acrylic resin is wet spun. Specifically, a copolymer composed of 95% by mass of acrylonitrile, 3.5% by mass of methyl acrylate, and 1.5% by mass of methacrylic acid and having an intrinsic viscosity of 1.80 was dissolved in Dimethylacetamide (DMAC) to prepare a dope having a polymer concentration of 21.0% by mass and a viscosity of 500 poise at 60 ℃. The dope was discharged at a draft ratio of 0.8 using a spinneret having a pore diameter (inner diameter) of 0.075mm and a pore number of 12,000 in a coagulation bath of a 70 mass% aqueous solution of DMAC maintained at a bath temperature of 35 ℃.
The coagulated filaments were desolventized in a water washing tank and simultaneously drawn to 5 times, whereby an acrylic fiber strand (raw fiber) in a water-swollen state was produced. The acrylic fiber strands were subjected to oil feeding of the treating agent for acrylic resin fibers prepared in test group 1 so that the solid content adhering amount was 1% by mass (no solvent). The oil-feeding of the acrylic resin fiber treatment agent is performed by an impregnation method using a 4% ion-exchange aqueous solution of the acrylic resin fiber treatment agent. Thereafter, the acrylic fiber strand was dried and densified by a heated roll at 130 ℃, and further stretched 1.7 times between heated rolls at 170 ℃, and then wound around a filament tube using a winding device.
Next, as step 2, the filaments were unwound from the wound acrylic resin fibers, subjected to a fire-resistant treatment in an air atmosphere for 1 hour using a fire-resistant furnace having a temperature gradient of 230 to 270 ℃, and then wound around a filament tube, thereby obtaining fire-resistant filaments (fire-resistant fibers).
Next, as step 3, the filaments were unwound from the wound refractory filaments, fired in a carbonization furnace having a temperature gradient of 300 to 1300 ℃ under a nitrogen atmosphere, converted into carbon fibers, and then wound around a filament tube, thereby obtaining carbon fibers.
Test group 3 (evaluation)
The treatment agents of examples 1 to 19 and comparative examples 1 to 4 were evaluated for the presence or absence of burrs of the acrylic resin fibers, the fiber bundling properties of the flame-retardant fibers, and the fiber fusion of the flame-retardant fibers. The procedure of each test is shown below.
(Burr)
In step 1 of test group 2, the number of burrs per 1 hour was measured by a burr counting device provided immediately before a winding device for winding an acrylic fiber, and evaluated according to the following criteria. The results are shown in the "burr" column of table 1.
Evaluation criterion of burrs
Very good: the burr number is 0 to 5
(qualified): the burr number is 6-10
X (bad): the burr number is more than 11
(fire-resistant bundling Property)
The refractory fibers subjected to the refractory treatment in step 2 of test group 2 were visually observed for the bundling state of the refractory fibers before winding, and the fire-resistant bundling property was evaluated according to the following criteria. The results are shown in the column "refractory bundling" in table 1.
Evaluation criterion of fire resistance bundling
Very good: bundling and fixed filament width
(qualified): bundling occurs, but the width of the filament bundle is not fixed
X (bad): space exists in the fiber bundle, and no bundling occurs
(refractory welding)
The refractory fibers subjected to the refractory treatment in step 2 of test group 2 were cut into 10mm lengths and dispersed in an aqueous solution of polyoxyethylene (10) lauryl ether. After stirring for 10 minutes, the dispersion state of the fibers was visually observed, and evaluated according to the following criteria. The results are shown in the column "refractory weld" in Table 1.
Evaluation criterion for refractory fusion
Very good: completely and uniformly dispersed fibers, without the presence of short fiber bundles
(qualified): the fibres being substantially homogeneously dispersed, but in the presence of bundles of short fibres
X (bad): the dispersion state of the fibers is uneven, and a large amount of short fiber bundles exist
From the results of table 1, the heat resistance of the treatment agent for acrylic resin fibers can be improved by the present invention, and the effect of suppressing fusion between fibers can be improved. In addition, the fiber bundling property of the refractory fibers can be improved. In addition, the generation of burrs of the acrylic resin fiber can be suppressed.
The invention also includes the following means.
(additionally, 1)
A treatment agent for synthetic fibers, which is characterized by containing a carboxylic acid compound having an acid value of 60mgKOH/g or less.
(additionally remembered 2)
The treating agent for synthetic fibers according to the supplementary note 1, wherein the carboxylic acid compound is a compound having an ester bond in a molecule.
(additionally, the recording 3)
The treating agent for a synthetic fiber according to any one of supplementary notes 1 and 2, wherein the carboxylic acid compound is a compound having 2 or more ester bonds in the molecule.
(additionally remembered 4)
The treating agent for a synthetic fiber according to any one of supplementary notes 1 to 3, wherein the carboxylic acid compound is a compound having a hydroxyl group in a molecule.
(additionally noted 5)
The treating agent for synthetic fibers according to any one of supplementary notes 1 to 4, wherein the acid value of the carboxylic acid compound is 10 to 50mgKOH/g.
(additionally described 6)
The treatment agent for synthetic fibers according to any one of supplementary notes 1 to 5, further comprising a smoothing agent.
(additionally noted 7)
The synthetic fiber treatment agent according to supplementary note 6, wherein the smoothing agent contains an amino-modified silicone.
(additionally noted 8)
The treatment agent for synthetic fibers according to any one of supplementary note 7, wherein the amino-modified silicone has a kinematic viscosity at 25℃of 50 to 7000mm 2 /s。
(additionally, the mark 9)
The treating agent for a synthetic fiber according to any one of supplementary notes 1 to 8, wherein the treating agent further contains a nonionic surfactant.
(additionally noted 10)
The treating agent for synthetic fibers according to any one of the supplementary notes 6 to 8, wherein,
the treatment agent further comprises a nonionic surfactant,
the content of the carboxylic acid compound is 0.1 to 15 mass% when the total content of the carboxylic acid compound, the smoothing agent and the nonionic surfactant is 100 mass%.
(additionally noted 11)
The treating agent for a synthetic fiber according to any one of supplementary notes 1 to 10, wherein the synthetic fiber is a carbon fiber precursor.
(additional recording 12)
A synthetic fiber, wherein the synthetic fiber is attached with the treating agent for synthetic fiber according to any one of the additional notes 1 to 10.

Claims (12)

1. A treatment agent for acrylic resin fibers, which comprises a carboxylic acid compound having an acid value of 60mgKOH/g or less.
2. The treating agent for acrylic resin fibers according to claim 1, wherein the carboxylic acid compound is a compound having an ester bond in a molecule.
3. The treating agent for acrylic resin fibers according to claim 1 or 2, wherein the carboxylic acid compound is a compound having 2 or more ester bonds in a molecule.
4. The treating agent for acrylic resin fibers according to any one of claims 1 to 3, wherein the carboxylic acid compound is a compound having a hydroxyl group in a molecule.
5. The acrylic resin fiber treatment agent according to any one of claims 1 to 4, wherein the carboxylic acid compound has an acid value of 10mgKOH/g to 50mgKOH/g.
6. The treating agent for acrylic resin fibers according to any one of claims 1 to 5, wherein the treating agent further contains a smoothing agent.
7. The acrylic fiber treatment agent according to claim 6, wherein the smoothing agent contains an amino-modified silicone.
8. The treatment agent for acrylic resin fiber according to claim 7, wherein the amino-modified silicone has a kinematic viscosity of 50mm at 25 °c 2 /s～7000mm 2 /s。
9. The treating agent for acrylic resin fibers according to any one of claims 1 to 8, wherein the treating agent further contains a nonionic surfactant.
10. The treating agent for acrylic resin fibers according to any one of claims 6 to 8, wherein,
the treatment agent further comprises a nonionic surfactant,
the content of the carboxylic acid compound is 0.1 to 15% by mass, based on 100% by mass of the total content of the carboxylic acid compound, the smoothing agent and the nonionic surfactant.
11. The treating agent for acrylic resin fibers according to any one of claims 1 to 10, wherein the acrylic resin fibers are carbon fiber precursors.
12. An acrylic fiber to which the treating agent for acrylic fiber according to any one of claims 1 to 10 is attached.
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