JP7199123B1 - Carbon fiber precursor treatment agent and carbon fiber precursor - Google Patents

Abstract

An object of the present invention is to realize a carbon fiber precursor treatment agent and a carbon fiber precursor capable of improving productivity of carbon fibers and obtaining high-strength carbon fibers. SOLUTION: An ionic compound (A) containing no halogen atom in its composition formula, a monoalcohol derivative (B), a silicone (C), and an ester compound (D) having a bisphenol skeleton in the molecule. contains. [Selection figure] None

Description

The present invention relates to a carbon fiber precursor treatment agent and a carbon fiber precursor.

As a method for producing carbon fibers, a method of spinning a fibrous material and then firing the material is widely used, and this fibrous material is called a carbon fiber precursor. As the carbon fiber precursor, a fiber material such as a polymer having a carbon fiber precursor treatment agent attached to the surface thereof may be used. Such a treating agent is used for the purpose of improving the handleability of the carbon fiber precursor in various steps of manufacturing carbon fibers.

As a treatment agent of this kind, for example, Japanese Patent Application Laid-Open No. 2002-266239 (Patent Document 1) discloses an oil agent composition for producing a carbon fiber precursor acrylic fiber containing a bisphenol A derivative as a main component. Using a material can prevent deterioration of runnability, processability, and carbon fiber quality.

Further, Japanese Patent Application Laid-Open No. 2016-56497 (Patent Document 2) discloses a carbon fiber precursor acrylic fiber oil agent containing a hydroxybenzoic acid ester having a specific structure, an amino-modified silicone, and a specific organic compound. ing. By using the oil agent, the carbon fiber precursor acrylic fiber bundle and mechanical A carbon fiber bundle having excellent physical properties can be obtained with high productivity. In addition, emulsification can be easily performed even when the amount of emulsifier used is small.

JP-A-2002-266239 JP 2016-56497 A

However, the techniques of Patent Literatures 1 and 2 have room for further improvement in terms of achieving both an improvement in the productivity of carbon fibers and an improvement in the performance of the obtained carbon fibers.

Therefore, it is desired to realize a carbon fiber precursor treatment agent and a carbon fiber precursor capable of improving the productivity of carbon fibers and obtaining high-strength carbon fibers.

The carbon fiber precursor treatment agent according to the present invention comprises an ionic compound (A) containing no halogen atom in the composition formula, a monoalcohol derivative (B), silicone (C), and a bisphenol skeleton in the molecule. and an amine derivative (E) , wherein the ionic compound (A) contains an aliphatic hydrocarbon group having 8 to 17 carbon atoms in the molecule, a phosphorus atom and sulfur and at least one of the atoms, and the monoalcohol derivative (B) is selected from aliphatic alcohols having 12 to 15 carbon atoms and tristyrenated phenols. It is an alkylene oxide adduct of a monoalcohol with a total of 7 mol or more and 33 mol or less added, and the ester compound (D) is added with a total of 2 mol or more and 10 mol or less of ethylene oxide and propylene oxide per 1 mol of bisphenol A. and a diester of an alkylene oxide adduct of bisphenol A and a saturated fatty acid having 8 to 18 carbon atoms .

Further, a carbon fiber precursor according to the present invention is characterized in that the above treating agent for carbon fiber precursor is adhered thereto.

According to these configurations, it is possible to suppress the generation of scum adhering to the roller when manufacturing carbon fibers. In addition, when the carbon fiber precursor is wound around the yarn tube, it is difficult for the twill to fall off or the winding to collapse. Furthermore, rust is less likely to occur in manufacturing equipment than when conventional processing agents are used. These features can improve carbon fiber productivity. Moreover, according to these configurations, the strength of the obtained carbon fiber can be improved. Thus, according to the present invention, it is possible to improve the productivity of carbon fibers and obtain high-strength carbon fibers.

Preferred embodiments of the present invention are described below. However, the scope of the present invention is not limited by the preferred embodiments described below.

In one aspect of the carbon fiber precursor treatment agent according to the present invention, the silicone (C) preferably contains an amino-modified silicone.

This configuration can further improve the strength of the carbon fiber.

As one aspect, the carbon fiber precursor treatment agent according to the present invention includes the ionic compound (A), the monoalcohol derivative (B), the silicone (C), the ester compound (D), and the amine derivative. Assuming that the total content of (E) is 100 parts by mass, the content of the ionic compound (A) is preferably 0.1 parts by mass or more and less than 15 parts by mass.

According to this configuration, the productivity and strength of the carbon fiber can be further enhanced.

As one aspect, the carbon fiber precursor treatment agent according to the present invention includes the ionic compound (A), the monoalcohol derivative (B), the silicone (C), the ester compound (D), and the amine derivative. Taking the total content of (E) as 100 parts by mass, the content of the silicone (C) is preferably 1 part by mass or more and less than 30 parts by mass.

According to this configuration, the generation of scum can be further suppressed.

Further features and advantages of the invention will become clearer from the following description of exemplary and non-limiting embodiments.

Embodiments of the carbon fiber precursor treatment agent and the carbon fiber precursor according to the present invention will be described.

[Construction of treatment agent for carbon fiber precursor]
The carbon fiber precursor treatment agent according to this embodiment contains an ionic compound (A), a monoalcohol derivative (B), a silicone (C), and an ester compound (D). Moreover, the carbon fiber precursor treatment agent according to the present embodiment preferably further contains an amine derivative (E). In the following description, the ionic compound (A), monoalcohol derivative (B), silicone (C), ester compound (D), and amine derivative (E) are the main components of the carbon fiber precursor treatment agent. It says.

In the following description, the total content of the main components means the ionic compound (A), monoalcohol derivative (B), silicone (C ), and the total content of the ester compound (D), and when the carbon fiber precursor treatment agent contains the amine derivative (E), the ionic compound (A), the monoalcohol derivative (B), the silicone (C ), ester compound (D), and amine derivative (E). When the content of each component is indicated by a numerical value in units of parts by mass, the numerical value represents the content of the component based on the total content of the main components being 100 parts by mass.

The carbon fiber precursor treatment agent according to the present embodiment includes, for example, an ionic compound (A), a monoalcohol derivative (B), a silicone (C), an ester compound (D), and other optionally added constituents. The ingredients are weighed in predetermined amounts, uniformly mixed in a glass container, and then ion-exchanged water or the like is added to emulsify. In addition, a dilution solvent such as water may be further added to adjust the solid content concentration.

In the present embodiment, the halogen atom content in the carbon fiber precursor treating agent may be 1000 ppm or less with respect to the carbon fiber precursor treating agent.

(Ionic compound)
The ionic compound (A) is an ionic compound having no halogen atom in its composition formula. Here, the ionic compound is a compound in which a cation and an anion are bound by an ionic bond. That is, an ionic compound containing no halogen atoms in its composition formula is a compound in which cations and anions containing no halogen atoms are linked by ionic bonds. The ionic compound (A) may be an ionic compound containing phosphorus (P) or sulfur (S) in its composition formula. Also, the ionic compound (A) may be one type of ionic compound or a mixture of a plurality of types of ionic compounds. However, in the latter case, all of the plurality of types of ionic compounds must be ionic compounds that do not contain halogen atoms in their compositional formulas.

The cations constituting the ionic compound (A) can be metal ions, substituted or unsubstituted ammonium ions, substituted or unsubstituted phosphonium ions, substituted or unsubstituted imidazolinium ions, and the like. The cations are, for example, sodium ion, potassium ion, magnesium ion, calcium ion, strontium ion, barium ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, trimethyloctylammonium ion, trimethyldecylammonium ion, lauryl trimethylammonium ion, tetramethylammonium ion, tetrabutylammonium ion, tetramethylphosphonium ion, tetrabutylphosphonium ion, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H -imidazolinium ion, and 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium.

Anions constituting the ionic compound (A) can be anions derived from organic acids such as carboxylic acid, sulfonic acid and phosphonic acid, inorganic acid ions, and the like. Examples of the anion include octylate ion, oleate ion, carbonate ion, sulfate ion, methyl sulfate ion, ethyl sulfate ion, alkylsulfonate ion having 12 to 15 carbon atoms, dodecylbenzenesulfonate ion, and methylphosphate ion. , dimethyl phosphate ion, ethyl phosphate ion, diethyl phosphate ion, octyl phosphate ion, dioctyl phosphate ion, dodecyl phosphate ion, and didodecyl phosphate ion.

Accordingly, the ionic compound (A) includes lithium octylate, sodium octylate, potassium octylate, magnesium octylate, calcium octylate, strontium octylate, barium octylate, and monoethanolammonium octylate. salt, diethanolammonium octylate, triethanolammonium octylate, trimethyloctylammonium octylate, trimethyldecylammonium octylate, lauryltrimethylammonium octylate, tetramethylammonium octylate, tetrabutylammonium octylate, Octylic acid tetramethylphosphonium salt, octylic acid tetrabutylphosphonium salt, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium octylate, octylic acid 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, lithium oleate salt, sodium oleate salt, potassium oleate salt, magnesium oleate salt, calcium oleate, strontium oleate, barium oleate, monoethanolammonium oleate, diethanolammonium oleate, triethanolammonium oleate, trimethyloctylammonium oleate, trimethyldecylammonium oleate , lauryltrimethylammonium oleate, tetramethylammonium oleate, tetrabutylammonium oleate, tetramethylphosphonium oleate, tetrabutylphosphonium oleate, 1-ethyl-2-(heptadecenyl)-4 oleate, 5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, monocarbonate ethanolammonium salt, diethanolammonium carbonate, triethanolammonium carbonate, trimethyloctylammonium carbonate, trimethyldecylammonium carbonate, lauryltrimethylammonium carbonate, tetramethylammonium carbonate, tetrabutylammonium carbonate, tetramethylphosphonium carbonate , tetrabutylphosphoni carbonate salt, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium carbonate, 1-ethyl-2-(heptadecyl)-4,5 carbonate -dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, monoethanol sulfate ammonium salt, diethanolammonium sulfate, triethanolammonium sulfate, trimethyloctylammonium sulfate, trimethyldecylammonium sulfate, lauryltrimethylammonium sulfate, tetramethylammonium sulfate, tetrabutylammonium sulfate, tetramethylphosphonium sulfate, Tetrabutylphosphonium sulfate, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium sulfate, 1-ethyl-2-(heptadecyl)-sulfate 4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, lithium methyl sulfate, sodium methyl sulfate, potassium methyl sulfate, magnesium methyl sulfate, calcium methyl sulfate, strontium methyl sulfate salt, barium methylsulfate, monoethanolammonium methylsulfate, diethanolammonium methylsulfate, triethanolammonium methylsulfate, trimethyloctylammonium methylsulfate, trimethyldecylammonium methylsulfate, lauryltrimethylammonium methylsulfate, methylsulfate Tetramethylammonium salt, tetrabutylammonium methylsulfate, tetramethylphosphonium methylsulfate, tetrabutylphosphonium methylsulfate, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxy ethyl)-1H-imidazolinium salt, methyl sulfate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, ethyl sulfate lithium salt, ethyl Sodium sulfate, potassium ethylsulfate, magnesium ethylsulfate, calcium ethylsulfate, strontium ethylsulfate, barium ethylsulfate, monoethanolammonium ethylsulfate, diethanolammonium ethylsulfate , ethylsulfate triethanolammonium salt, ethylsulfate trimethyloctylammonium salt, ethylsulfate trimethyldecylammonium salt, ethylsulfate lauryltrimethylammonium salt, ethylsulfate tetramethylammonium salt, ethylsulfate tetrabutylammonium salt, ethylsulfate tetramethylphosphonium salt, Ethyl sulfate tetrabutylphosphonium salt, Ethyl sulfate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, Ethyl sulfate 1-ethyl-2-( heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, lithium salt of alkylsulfonate having 12 to 15 carbon atoms, sodium salt of alkylsulfonate having 12 to 15 carbon atoms , alkylsulfonic acid potassium salt having 12 to 15 carbon atoms, magnesium salt of alkylsulfonic acid having 12 to 15 carbon atoms, calcium salt of alkylsulfonic acid having 12 to 15 carbon atoms, alkylsulfonic acid having 12 to 15 carbon atoms strontium salt, barium salt of alkylsulfonate having 12 to 15 carbon atoms, monoethanolammonium alkylsulfonate having 12 to 15 carbon atoms, diethanolammonium alkylsulfonate having 12 to 15 carbon atoms, and diethanolammonium salt of alkylsulfonate having 12 to 15 carbon atoms The following alkylsulfonic acid triethanolammonium salt, alkylsulfonic acid trimethyloctylammonium salt having 12 to 15 carbon atoms, alkylsulfonic acid trimethyldecylammonium salt having 12 to 15 carbon atoms, and alkylsulfonic acid having 12 to 15 carbon atoms lauryltrimethylammonium salt, alkylsulfonic acid tetramethylammonium salt having 12 to 15 carbon atoms, tetrabutylammonium alkylsulfonic acid having 12 to 15 carbon atoms, tetramethylphosphonium alkylsulfonic acid having 12 to 15 carbon atoms, tetrabutylphosphonium salt of alkylsulfonate having 12 to 15 carbon atoms, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-alkylsulfonate having 12 to 15 carbon atoms 1H-imidazolinium salts, 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salts of alkylsulfonates having 12 to 15 carbon atoms, dodecyl Lithium benzenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, magnesium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, strontium dodecylbenzenesulfonate, barium dodecylbenzenesulfonate, dodecylbenzene Sulfonic acid monoethanolammonium salt, dodecylbenzenesulfonic acid diethanolammonium salt, dodecylbenzenesulfonic acid triethanolammonium salt, dodecylbenzenesulfonic acid trimethyloctylammonium salt, dodecylbenzenesulfonic acid trimethyldecylammonium salt, dodecylbenzenesulfonic acid lauryltrimethylammonium salt , dodecylbenzenesulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt, dodecylbenzenesulfonic acid tetramethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid 1-ethyl-2-(heptadecenyl) -4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl dodecylbenzenesulfonate) )-1H-imidazolinium salt, methyl phosphate lithium salt, methyl phosphate sodium salt, methyl phosphate potassium salt, methyl phosphate magnesium salt, methyl phosphate calcium salt, methyl phosphate strontium salt, methyl phosphate barium salt, methyl phosphate monoethanolammonium salt , methylphosphate diethanolammonium salt, methylphosphate triethanolammonium salt, methylphosphate trimethyloctylammonium salt, methylphosphate trimethyldecylammonium salt, methylphosphate lauryltrimethylammonium salt, methylphosphate tetramethylammonium salt, methylphosphate tetrabutylammonium salt, methyl phosphate tetramethylphosphonium salt, methyl phosphate tetrabutylphosphonium salt, methyl phosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, methyl phosphate 1 -ethyl-2-(heptadecyl)-4 ,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, dimethyl phosphate lithium salt, dimethyl phosphate sodium salt, dimethyl phosphate potassium salt, dimethyl phosphate magnesium salt, dimethyl phosphate calcium salt, dimethyl phosphate strontium salt , dimethylphosphate barium salt, dimethylphosphate monoethanolammonium salt, dimethylphosphate diethanolammonium salt, dimethylphosphate triethanolammonium salt, dimethylphosphate trimethyloctylammonium salt, dimethylphosphate trimethyldecylammonium salt, dimethylphosphate lauryltrimethylammonium salt, dimethylphosphate tetra methylammonium salt, dimethylphosphate tetrabutylammonium salt, dimethylphosphate tetramethylphosphonium salt, dimethylphosphate tetrabutylphosphonium salt, dimethylphosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl )-1H-imidazolinium salt, dimethyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, ethyl phosphate lithium salt, ethyl phosphate sodium salt, ethyl phosphate potassium salt, ethyl phosphate magnesium salt, ethyl phosphate calcium salt, ethyl phosphate strontium salt, ethyl phosphate barium salt, ethyl phosphate monoethanol ammonium salt, ethyl phosphate diethanol ammonium salt, ethyl phosphate triethanol ammonium salt, ethyl phosphate trimethyloctyl ammonium salt, ethyl phosphate trimethyldecyl ammonium salt, ethyl phosphate lauryl trimethyl ammonium salt, ethyl phosphate tetramethyl ammonium salt, ethyl phosphate tetrabutyl ammonium salt, ethyl phosphate tetramethyl phosphonium salt, ethyl phosphate tetrabutyl phosphonium salt, ethyl phosphate 1 -ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, ethyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3 - (2-ha hydroxyethyl)-1H-imidazolinium salt, diethyl phosphate lithium salt, diethyl phosphate sodium salt, diethyl phosphate potassium salt, diethyl phosphate magnesium salt, diethyl phosphate calcium salt, diethyl phosphate strobe

diethylphosphate barium salt, diethylphosphate monoethanolammonium salt, diethylphosphate diethanolammonium salt, diethylphosphate triethanolammonium salt, diethylphosphate trimethyloctylammonium salt, diethylphosphate trimethyldecylammonium salt, diethylphosphate lauryltrimethylammonium salt, diethyl phosphate Phosphate tetramethylammonium salt, diethylphosphate tetrabutylammonium salt, diethylphosphate tetramethylphosphonium salt, diethylphosphate tetrabutylphosphonium salt, diethylphosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2- hydroxyethyl)-1H-imidazolinium salt, diethyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, octylphosphate lithium salt, octylphosphate sodium salt, octylphosphate potassium salt, octylphosphate magnesium salt, octylphosphate calcium salt, octylphosphate strontium salt, octylphosphate barium salt, octylphosphate monoethanolammonium salt, octylphosphate diethanolammonium salt, octylphosphate triethanolammonium salt, Octyl phosphate trimethyloctyl ammonium salt, octyl phosphate trimethyldecylammonium salt, octyl phosphate lauryl trimethyl ammonium salt, octyl phosphate tetramethyl ammonium salt, octyl phosphate tetrabutyl ammonium salt, octyl phosphate tetramethyl phosphonium salt, octyl phosphate tetrabutyl phosphonium salt, octyl phosphate Phosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, octyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro -3-(2-hydroxyethyl)-1H-imidazolinium salt, dioctyl phosphate lithium salt, dioctyl phosphate sodium salt, dioctyl phosphate potassium salt, dioctyl phosphate magnesium salt, dioctyl phosphate calcium salt, dioctyl phosphate dioctylphosphate strontium salt, dioctylphosphate barium salt, dioctylphosphate monoethanolammonium salt, dioctylphosphate diethanolammonium salt, dioctylphosphate triethanolammonium salt, dioctylphosphate trimethyloctylammonium salt, dioctylphosphate trimethyldecylammonium salt, dioctylphosphate lauryltrimethylammonium salt , dioctylphosphate tetramethylammonium salt, dioctylphosphate tetrabutylammonium salt, dioctylphosphate tetramethylphosphonium salt, dioctylphosphate tetrabutylphosphonium salt, dioctylphosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-( 2-hydroxyethyl)-1H-imidazolinium salt, dioctyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, dodecyl phosphate lithium salt, dodecylphosphate sodium salt, dodecylphosphate potassium salt, dodecylphosphate magnesium salt, dodecylphosphate calcium salt, dodecylphosphate strontium salt, dodecylphosphate barium salt, dodecylphosphate monoethanolammonium salt, dodecylphosphate diethanolammonium salt, dodecylphosphate triethanolammonium salt salt, dodecylphosphate trimethyloctylammonium salt, dodecylphosphate trimethyldecylammonium salt, dodecylphosphate lauryltrimethylammonium salt, dodecylphosphate tetramethylammonium salt, dodecylphosphate tetrabutylammonium salt, dodecylphosphate tetramethylphosphonium salt, dodecylphosphate tetrabutylphosphonium salt , dodecyl phosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, dodecyl phosphate 1-ethyl-2-(heptadecyl)-4,5 -dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, didodecyl phosphate lithium salt, didodecyl phosphate sodium salt, didodecyl phosphate potassium salt, didodecyl phosphate magnesium salt , didodecylphosphate calcium salt, didodecylphosphate strontium salt, didodecylphosphate barium salt, didodecylphosphate monoethanolammonium salt, didodecylphosphate diethanolammonium salt, didodecylphosphate triethanolammonium salt, didodecylphosphate trimethyloctylammonium salt, didodecyl phosphate trimethyldecyl ammonium salt, didodecyl phosphate lauryl trimethyl ammonium salt, didodecyl phosphate tetramethyl ammonium salt, didodecyl phosphate tetrabutyl ammonium salt, didodecyl phosphate tetramethyl phosphonium salt, didodecyl phosphate tetrabutyl phosphonium salt, didodecyl Phosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt and didodecyl phosphate 1-ethyl-2-(heptadecyl)-4,5 - dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salts.

The ionic compound (A) includes monoethanolammonium sulfate, diethanolammonium sulfate, triethanolammonium sulfate, trimethyloctylammonium sulfate, trimethyldecylammonium sulfate, lauryltrimethylammonium sulfate, tetramethylammonium sulfate, and sulfuric acid. tetrabutylammonium salt, tetramethylphosphonium sulfate, tetrabutylphosphonium sulfate, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium sulfate, 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium sulfate, monoethanolammonium methylsulfate, diethanolammonium methylsulfate, triethanol methylsulfate ammonium salt, trimethyloctylammonium methylsulfate, trimethyldecylammonium methylsulfate, lauryltrimethylammonium methylsulfate, tetramethylammonium methylsulfate, tetrabutylammonium methylsulfate, tetramethylphosphonium methylsulfate, tetrabutylphosphonium methylsulfate salts, 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium methylsulfate, 1-ethyl-2-(heptadecyl)-4 methylsulfate, 5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, monoethanolammonium ethylsulfate, diethanolammonium ethylsulfate, triethanolammonium ethylsulfate, trimethyloctylammonium ethylsulfate, trimethyl ethylsulfate Decylammonium salt, lauryltrimethylammonium ethylsulfate, tetramethylammonium ethylsulfate, tetrabutylammonium ethylsulfate, tetramethylphosphonium ethylsulfate, tetrabutylphosphonium ethylsulfate, 1-ethyl-2-(heptadecenyl) ethylsulfate -4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-ethyl sulfate 1H-imidazolinium salt, alkylsulfonic acid monoethanolammonium salt having 12 to 15 carbon atoms, alkylsulfonic acid having 12 to 15 carbon atoms acid diethanolammonium salt, alkylsulfonic acid triethanolammonium salt having 12 to 15 carbon atoms, trimethyloctylammonium alkylsulfonic acid having 12 to 15 carbon atoms, trimethyldecylammonium alkylsulfonic acid having 12 to 15 carbon atoms , lauryltrimethylammonium alkylsulfonate having 12 to 15 carbon atoms, tetramethylammonium alkylsulfonate having 12 to 15 carbon atoms, tetrabutylammonium alkylsulfonate having 12 to 15 carbon atoms, 12 or more carbon atoms tetramethylphosphonium alkylsulfonate of 15 or less, tetrabutylphosphonium alkylsulfonate of 12 to 15 carbon atoms, 1-ethyl-2-(heptadecenyl)-4,5-alkylsulfonate of 12 to 15 carbon atoms Dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxy)alkylsulfonate having 12 to 15 carbon atoms Ethyl)-1H-imidazolinium salt, dodecylbenzenesulfonic acid monoethanolammonium salt, dodecylbenzenesulfonic acid diethanolammonium salt, dodecylbenzenesulfonic acid triethanolammonium salt, dodecylbenzenesulfonic acid trimethyloctylammonium salt, dodecylbenzenesulfonic acid trimethyloctyl ammonium salt Decyl ammonium salt, lauryltrimethylammonium dodecylbenzenesulfonate, tetramethylammonium dodecylbenzenesulfonate, tetrabutylammonium dodecylbenzenesulfonate, tetramethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, dodecyl 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium benzenesulfonate, 1-ethyl-2-(heptadecyl)-4 dodecylbenzenesulfonate ,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, methyl phosphate monoethanolammonium salt, methyl phosphate diethanol ammonium salt, methyl phosphate triethanol ammonium salt, methyl phosphate trimethyloctylammonium salt, methyl phosphate Trimethyldecylammonium salt , methyl phosphate lauryltrimethylammonium salt, methyl phosphate tetramethylammonium salt, methyl phosphate tetrabutylammonium salt, methyl phosphate tetramethylphosphonium salt, methyl phosphate tetrabutylphosphonium salt, methyl phosphate 1-ethyl-2-(heptadecenyl)-4, 5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, methyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazo Phosphate, dimethylphosphate monoethanolammonium salt, dimethylphosphate diethanolammonium salt, dimethylphosphate triethanolammonium salt, dimethylphosphate trimethyloctylammonium salt, dimethylphosphate trimethyldecylammonium salt, dimethylphosphate lauryltrimethylammonium salt, dimethylphosphate tetramethylammonium salt salt, dimethylphosphate tetrabutylammonium salt, dimethylphosphate tetramethylphosphonium salt, dimethylphosphate tetrabutylphosphonium salt, dimethylphosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)- 1H-imidazolinium salt, dimethyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, ethyl phosphate monoethanolammonium salt, ethyl phosphate Diethanolammonium salt, Ethylphosphate triethanolammonium salt, Ethylphosphate trimethyloctylammonium salt, Ethylphosphate trimethyldecylammonium salt, Ethylphosphate lauryltrimethylammonium salt, Ethylphosphate tetramethylammonium salt, Ethylphosphate tetrabutylammonium salt, Ethylphosphate tetramethyl phosphonium salts, ethyl phosphate tetrabutylphosphonium salts, ethyl phosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salts, ethyl phosphate 1-ethyl- 2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolini salt, diethylphosphate monoethanolammonium salt, diethylphosphate diethanolammonium salt, diethylphosphate triethanolammonium salt, diethylphosphate trimethyloctylammonium salt, diethylphosphate trimethyldecylammonium salt, diethylphosphate lauryltrimethylammonium salt, diethylphosphate tetramethylammonium salt , diethyl phosphate tetrabutylammonium salt, diethyl phosphate tetramethylphosphonium salt, diethyl phosphate tetrabutylphosphonium salt, diethyl phosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H - imidazolinium salt, diethyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, octylphosphate monoethanolammonium salt, octylphosphate diethanol ammonium salt, octylphosphate triethanolammonium salt, octylphosphate trimethyloctylammonium salt, octylphosphate trimethyldecylammonium salt, octylphosphate lauryltrimethylammonium salt, octylphosphate tetramethylammonium salt, octylphosphate tetrabutylammonium salt, octylphosphate tetramethylphosphonium salt, octylphosphate tetrabutylphosphonium salt, octylphosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, octylphosphate 1-ethyl-2 -(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, dioctylphosphate monoethanolammonium salt, dioctylphosphate diethanolammonium salt, dioctylphosphate triethanolammonium salt, dioctylphosphate trimethyl octylammonium salt, dioctylphosphate trimethyldecylammonium salt, dioctylphosphate lauryltrimethylammonium salt, dioctylphosphate tetramethylammonium salt, dioctylphosphate tetrabutylammonium salt, dioctylphosphate tetramethylphosphonate dioctylphosphate tetrabutylphosphonium salt, dioctylphosphate 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, dioctylphosphate 1-ethyl- 2-(heptadecyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, dodecylphosphate monoethanolammonium salt, dodecylphosphate diethanolammonium salt, dodecylphosphate triethanolammonium salt, dodecylphosphate trimethyloctylammonium salt, dodecylphosphate trimethyldecylammonium salt, dodecylphosphate lauryltrimethylammonium salt, dodecylphosphate tetramethylammonium salt, dodecylphosphate tetrabutylammonium salt, dodecylphosphate tetramethylphosphonium salt, dodecylphosphate tetrabutylphosphonium salt, dodecylphosphate 1 -ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt, dodecyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3 -(2-hydroxyethyl)-1H-imidazolinium salt, didodecylphosphate monoethanolammonium salt, didodecylphosphate diethanolammonium salt, didodecylphosphate triethanolammonium salt, didodecylphosphate trimethyloctylammonium salt, didodecylphosphate trimethyl Decylammonium salt, didodecylphosphate lauryltrimethylammonium salt, didodecylphosphate tetramethylammonium salt, didodecylphosphate tetrabutylammonium salt, didodecylphosphate tetramethylphosphonium salt, didodecylphosphate tetrabutylphosphonium salt, didodecylphosphate 1-ethyl -2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium salt and didodecyl phosphate 1-ethyl-2-(heptadecyl)-4,5-dihydro-3 -(2-Hydroxyethyl)-1H-imidazolinium salts.

The content of the ionic compound (A) is preferably 0.1 parts by mass or more and less than 15 parts by mass based on 100 parts by mass of the total content of the main components of the treatment agent for carbon fiber precursors. When the ionic compound (A) is a mixture of multiple types of ionic compounds, the content of the ionic compound (A) refers to the total content of each ionic compound. The content of the ionic compound (A) is more preferably 1 part by mass or more. Moreover, the content of the ionic compound (A) is more preferably 14 parts by mass or less.

(Monoalcohol derivative)
The monoalcohol derivative (B) contained in the carbon fiber precursor treatment agent according to the present embodiment is not limited as long as it is a monoalcohol derivative as the term suggests. Moreover, the monoalcohol derivative (B) may be one kind of monoalcohol derivative or a mixture of a plurality of kinds of monoalcohol derivatives.

Here, monoalcohols can be substituted or unsubstituted aliphatic monoalcohols, substituted or unsubstituted aromatic alcohols, and the like. In addition, when the said monoalcohol has a hydrocarbon group, the said hydrocarbon group may be linear, and may be branched. Also, the monoalcohol may have an unsaturated bond, a cyclic structure, or both.

The monoalcohol derivative (B) may be an alkylene oxide adduct of the above monoalcohol, an alkoxy-blocked alkylene oxide adduct, or the like. When the monoalcohol derivative (B) is an alkylene oxide adduct of a monoalcohol, the number of alkylene oxide additions can be, for example, 1 mol or more and 50 mol or less on average. Non-limiting examples of the monoalcohol derivative (B) include a compound obtained by adding 9 moles of ethylene oxide to 1 mole of dodecyl alcohol, a compound obtained by adding 12 moles of ethylene oxide to 1 mole of isododecyl alcohol, and tetradecyl alcohol. A compound obtained by adding 7 mol of ethylene oxide to 1 mol of ethylene oxide, a compound obtained by adding 15 mol of ethylene oxide to 1 mol of pentadecyl alcohol, and 15 mol of ethylene oxide and 18 mol of propylene oxide to 1 mol of tetradecyl alcohol. a compound sequentially added in order, a compound in which 9 mol of ethylene oxide is added to 1 mol of secondary tridecyl alcohol, a compound in which 2 mol of ethylene oxide and 6 mol of propylene oxide are randomly added to 1 mol of dodecyl alcohol, and , a compound in which 15 mol of ethylene oxide and 9 mol of propylene oxide are randomly added to 1 mol of tristyrenated phenol.

The content of the monoalcohol derivative (B) may be 5 parts by mass or more and 60 parts by mass or less when the total content of the main components of the carbon fiber precursor treatment agent is 100 parts by mass. In addition, when the monoalcohol derivative (B) is a mixture of a plurality of types of monoalcohol derivatives, the content of the monoalcohol derivative (B) refers to the total content of each monoalcohol derivative.

(silicone)
The type of silicone (C) contained in the carbon fiber precursor treatment agent according to the present embodiment is not limited. However, if the silicone (C) contains an amino-modified silicone, the strength of the obtained carbon fiber can be improved, which is preferable. Silicone (C) may be one type of silicone, or may be a mixture of multiple types of silicones.

Non-limiting examples of silicone (C) include monoamine-type amino-modified silicone, diamine-type amino-modified silicone, dimethyl silicone, polyether-modified silicone, and the like. In addition, the kinematic viscosity of silicone (C) determined by a Canon Fenske viscometer at 25° C. may be 50 mm ² /sec or more and 5000 mm ² /sec or less. Also, the amino functional group equivalent weight determined by the method of total amine value with perchloric acid of silicone (C) may be 500 g/mol or more and 10000 g/mol or less.

The content of silicone (C) is preferably 1 part by mass or more and less than 30 parts by mass based on 100 parts by mass of the total content of the main components of the treatment agent for carbon fiber precursors. When the content of the silicone (C) is within the above range, scum is less likely to occur in the drying and densification step during the production of the carbon fiber precursor. In addition, when silicone (C) is a mixture of multiple types of silicones, the content of silicone (C) refers to the total content of each silicone. More preferably, the content of silicone (C) is 2 parts by mass or more. Moreover, the content of silicone (C) is more preferably 28 parts by mass or less.

(Ester compound)
Ester compound (D) is an ester compound having a bisphenol skeleton in the molecule. In other words, the ester compound (D) is a compound having a bisphenol skeleton derived from a substituted or unsubstituted bisphenol and at least one carboxylic acid residue connected to the bisphenol skeleton via an ester bond. . The ester compound (D) may be one type of ester compound, or may be a mixture of a plurality of types of ester compounds that satisfy the above conditions.

The bisphenol skeleton includes bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z, It can be a partial structure corresponding to bisphenol such as The bisphenol skeleton is preferably a partial structure corresponding to bisphenol selected from the group consisting of bisphenol A and bisphenol F.

Carboxylic acid residues include saturated fatty acids such as octylic acid, lauric acid, and stearic acid, unsaturated fatty acids such as oleic acid and linoleic acid, cyclic carboxylic acids such as cyclohexanecarboxylic acid, and aromatic carboxylic acids such as benzoic acid. It can be the corresponding carboxylic acid residue. The carboxylic acid residue is preferably a carboxylic acid residue corresponding to an acid selected from the group consisting of saturated fatty acids such as octylic acid, lauric acid and stearic acid, and unsaturated fatty acids such as oleic acid and linoleic acid. It is more preferably a carboxylic acid residue corresponding to an acid selected from the group consisting of saturated fatty acids such as , octylic acid, lauric acid and stearic acid. In addition, the carboxylic acid residue may have a substituent.

In the ester compound (D), the bisphenol skeleton and the carboxylic acid residue may be directly ester-bonded, or another partial structure may be interposed between the bisphenol skeleton and the carboxylic acid residue. Such other partial structures are exemplified by alkylene oxide and the like.

Non-limiting examples of the ester compound (D) include a diester of 4 mol ethylene oxide adduct of bisphenol A and lauric acid, a diester of 2 mol ethylene oxide adduct of bisphenol A and octylic acid, and ethylene of bisphenol A. Diesters of 2 mol oxide adducts and lauric acid, monoesters of 10 mol ethylene oxide adducts of bisphenol A and lauric acid, diesters of 2 mol propylene oxide adducts of bisphenol A and lauric acid, and bisphenol A A diester of stearic acid and a compound to which 2 mol of ethylene oxide and 2 mol of propylene oxide are sequentially added is exemplified.

The content of the ester compound (D) may be 10 parts by mass or more and 70 parts by mass or less when the total content of the main components of the carbon fiber precursor treatment agent is 100 parts by mass. In addition, when an ester compound (D) is a mixture of multiple types of ester compounds, content of an ester compound (D) means the sum total of content of each ester compound.

(amine derivative)
If the carbon fiber precursor treatment agent according to the present embodiment contains the amine derivative (E), it is preferable because the windability can be improved when the carbon fiber precursor is wound around a thread tube. The amine derivative (E) is not limited as long as it is an amine derivative as the term suggests. Moreover, the amine derivative (E) may be one type of amine derivative or a mixture of a plurality of types of amine derivatives.

Amine derivative (E) can be, for example, an alkylamine compound. The alkyl group of the alkylamine compound may have from 4 to 20 carbon atoms, and may be saturated or unsaturated, substituted or unsubstituted.

Also, the amine derivative (E) may be an alkylene oxide adduct of the alkylamine compound described above. When the amine derivative (E) is an alkylene oxide adduct of an alkylamine compound, the alkylene oxide may be one or more alkylene oxides selected from known alkylene oxides such as ethylene oxide and propylene oxide. Also, the number of alkylene oxides to be added may be 1 mol or more and 30 mol or less per molecule of the alkylamine compound. When multiple types of alkylene oxides are added, the number of alkylene oxides added means the total number of each type of alkylene oxide added.

Non-limiting examples of the amine derivative (E) include a compound in which 4 mol of ethylene oxide is added to 1 mol of dodecylamine, a compound in which 8 mol of ethylene oxide is added to 1 mol of dodecylamine, and 1 mol of octadecylamine. A compound to which 15 mol of ethylene oxide was added, a compound to which 5 mol of ethylene oxide and 3 mol of propylene oxide were randomly added to 1 mol of dodecylamine, and 8 mol of ethylene oxide and propylene oxide to 1 mol of octadecylamine. A compound in which 5 moles are sequentially added is exemplified.

The content of the amine derivative (E) may be 1 part by mass or more and 40 parts by mass or less when the total content of the main components of the carbon fiber precursor treatment agent is 100 parts by mass. When the amine derivative (E) is a mixture of multiple types of amine derivatives, the content of the amine derivative (E) refers to the total content of each amine derivative.

(other ingredients)
The carbon fiber precursor treatment agent according to the present embodiment includes the ionic compound (A), the monoalcohol derivative (B), the silicone (C), the ester compound (D), and the amine derivative (E). may contain ingredients. Such other ingredients include tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, acetic acid, lactic acid, oleoyl sarcosinate, lauroyl sarcosinate, malic acid. , phosphoric acid, phosphate ester, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H,5H)-trione and the like are exemplified. In addition, the carbon fiber precursor treatment agent according to the present embodiment may contain antiseptic agents, antistatic agents, antioxidants, ultraviolet absorbers, antifoaming agents (modified silicone, etc.), and the like.

The content of the other components is a value (so-called external value) where the total content of the main components of the carbon fiber precursor treatment agent is 100 parts by mass, and is 0.1 parts by mass or more and 10 parts by mass or less. Possible. In addition, when there are multiple types of other components, the content of the other components refers to the total content of each component.

[Carbon fiber precursor]
In the carbon fiber precursor according to the present embodiment, a fiber material generally used as a carbon fiber precursor is added with a carbon fiber precursor treatment agent (hereinafter, sometimes simply referred to as "treatment agent") according to the present embodiment. It is an attached aspect. The fiber material referred to here is a fibrous material that becomes carbon fiber through a baking process, and includes polyacrylic fiber, polyamide fiber, polyester fiber, polyolefin fiber, cellulose fiber, lignin fiber, and phenolic resin. , and pitch, etc., or a combination thereof.

As a method for attaching the treatment agent to the fiber material, a method commonly used in the art for attaching this type of treatment agent to the fiber material can be applied. That is, an immersion oiling method, a spray oiling method, a roller oiling method, a guide oiling method, and the like can be employed. In applying each method, the treatment agent can be appropriately diluted with a solvent such as water.

In the carbon fiber precursor according to this embodiment, the amount of the treatment agent attached is not particularly limited. For example, it is preferable that 0.3% by mass or more and 3% by mass or less of the treatment agent is adhered to the entire carbon fiber precursor to which the treatment agent is adhered.

[Other embodiments]
Containing an ionic compound (A) containing no halogen atoms in the composition formula, a monoalcohol derivative (B), a silicone (C), and an ester compound (D) having a bisphenol skeleton in the molecule The characteristic carbon fiber precursor treatment agent is mentioned as a reference example of the present invention.

In the above reference example, the total content of the ionic compound (A), the monoalcohol derivative (B), the silicone (C), and the ester compound (D) is 100 parts by mass, and the ionic compound ( The content of A) may be 0.1 parts by mass or more and less than 15 parts by mass. In this case, it is easy to further increase the productivity and strength of the carbon fiber.

In the above reference example, the total content of the ionic compound (A), the monoalcohol derivative (B), the silicone (C), and the ester compound (D) is 100 parts by mass, and the silicone (C) may be 1 part by mass or more and less than 30 parts by mass. In this case, the generation of scum can be further suppressed.

The above reference examples may further contain an amine derivative (E). In this case, the windability of the carbon fiber precursor can be further improved.

Regarding other configurations, it should be understood that the embodiments disclosed in this specification are examples in all respects, and that the scope of the present invention is not limited by them. Those skilled in the art will easily understand that modifications can be made as appropriate without departing from the scope of the present invention. Therefore, other embodiments modified without departing from the gist of the present invention are naturally included in the scope of the present invention.

The present invention is further illustrated by the following examples. It should be noted that the following examples do not limit the present invention.

[Preparation of treatment agent for carbon fiber precursor]
By the following method, the carbon fiber precursor treatment agents of Examples 1 to 12, Reference Examples 1 to 4, and Comparative Examples 1 to 4 shown in Tables 1 and 2 were obtained.

(1) Reagent (ionic compound)
As ionic compounds, the following ionic compounds A-1 to A-8 and a-1 were used. Of these, the ionic compounds A-1 to A-8 correspond to the ionic compound (A) in the above embodiment, but the ionic compound a-1 does not.
A-1: 1-ethyl-2-(heptadecenyl)-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium ethyl sulfate A-2: 1-ethyl-2-(heptadecyl )-4,5-dihydro-3-(2-hydroxyethyl)-1H-imidazolinium methyl sulfate A-3: trimethyloctylammonium dimethyl phosphate A-4: trimethyldecylammonium dimethyl phosphate A-5: dodecylbenzene Sulfonic acid tetrabutylphosphonium salt A-6: Alkyl sulfonic acid tetrabutylphosphonium salt having 12 to 15 carbon atoms A-7: Dodecylbenzenesulfonic acid tetrabutylammonium salt A-8: Dodecylbenzenesulfonic acid triethanolamine salt a-1 : Lauryltrimethylammonium chloride

(Monoalcohol derivative)
As monoalcohol derivatives, the following monoalcohol derivatives B-1 to B-8 were used. All of the monoalcohol derivatives B-1 to B-8 correspond to the monoalcohol derivative (B) in the above embodiments.
B-1: A compound in which 9 mol of ethylene oxide is added to 1 mol of dodecyl alcohol B-2: A compound in which 12 mol of ethylene oxide is added to 1 mol of isododecyl alcohol B-3: Per 1 mol of tetradecyl alcohol B-4: Compound in which 15 mol of ethylene oxide is added to 1 mol of pentadecyl alcohol B-5: 15 mol of ethylene oxide and 18 mol of propylene oxide to 1 mol of tetradecyl alcohol is sequentially added in this order B-6: A compound in which 9 mol of ethylene oxide is added to 1 mol of secondary tridecyl alcohol B-7: 2 mol of ethylene oxide and 6 mol of propylene oxide to 1 mol of dodecyl alcohol is randomly added B-8: A compound in which 15 mol of ethylene oxide and 9 mol of propylene oxide are randomly added to 1 mol of tristyrenated phenol

(silicone)
Silicones C-1 to C-6 below were used as silicones. Silicones C-1 to C-6 all correspond to the silicone (C) in the above embodiments.
C-1: Kinematic viscosity: 250 mm ² /s, functional group equivalent weight: 7600 g/mol, diamine-type amino-modified silicone C-2: Kinematic viscosity: 1300 mm ² /s, functional group equivalent weight: 1700 g/mol, diamine-type amino-modified silicone C-3: Kinematic viscosity: 1700 mm ² /s, functional group equivalent weight: 3800 g/mol, monoamine-type amino-modified silicone C-4: Kinematic viscosity: 80 mm ² /s, functional group equivalent weight: 4000 g/mol, diamine-type amino-modified silicone C-5: Dimethyl silicone with kinematic viscosity of 350 mm ² /s C-6: Polyether with kinematic viscosity of 1700 mm ² /s, ethylene oxide/propylene oxide = 40/60, silicone/polyether weight ratio = 20/80 modified silicone

(Ester compound)
As ester compounds, the following ester compounds D-1 to D-6 were used. All of the ester compounds D-1 to D-6 correspond to the ester compound (D) in the above embodiments.
D-1: Diester of 4 mol ethylene oxide adduct of bisphenol A and lauric acid D-2: Diester of 2 mol ethylene oxide adduct of bisphenol A and octylic acid D-3: 2 mol ethylene oxide adduct of bisphenol A Diester of product and lauric acid D-4: Monoester of 10 mol adduct of ethylene oxide of bisphenol A and lauric acid D-5: Diester of 2 mol of propylene oxide adduct of bisphenol A and lauric acid D-6: Diester of stearic acid and a compound obtained by sequentially adding 2 mol of ethylene oxide and 2 mol of propylene oxide to bisphenol A

(amine derivative)
As amine derivatives, the following amine compounds E-1 to E-5 were used. All of the amine derivatives E-1 to E-5 correspond to the amine derivative (E) in the above embodiments.
E-1: A compound in which 4 mol of ethylene oxide is added to 1 mol of dodecylamine E-2: A compound in which 8 mol of ethylene oxide is added to 1 mol of dodecylamine E-3: Ethylene to 1 mol of octadecylamine Compound to which 15 mol of oxide was added E-4: Compound in which 5 mol of ethylene oxide and 3 mol of propylene oxide were randomly added to 1 mol of dodecylamine E-5: 8 mol of ethylene oxide and propylene to 1 mol of octadecylamine Compound to which 5 moles of oxide are sequentially added

(other ingredients)
As other components, the following components F-1 to F-3 were used. The contents of other components shown in Tables 1 and 2 are values (so-called external values) based on the total content of the main components of the treatment agent being 100 parts by mass.
F-1: tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane F-2: acetic acid F-3: lactic acid

(2) Preparation of carbon fiber precursor treatment agent (preparation of Example 1)
14 parts by mass of the ionic compound A-1, 20 parts by mass of the monoalcohol derivative B-1, 10 parts by mass of the monoalcohol derivative B-2, 21 parts by mass of the silicone C-1, and 30 parts by mass of the ester compound D-1 and 5 parts by mass of the amine compound E-1 were weighed and put into a beaker. After thoroughly mixing the above components, 300 parts by mass of ion-exchanged water was gradually added while stirring to prepare the carbon fiber precursor treatment agent of Example 1.

(Preparation of other examples, reference examples, and comparative examples)
Except for changing the type of ionic compound, the presence and type of monoalcohol derivative, the presence and type of silicone, the presence and type of ester compound, the presence and type of amine derivative, and the presence and type of other components, except for changing the Treatment agents for carbon fiber precursors of Examples 2 to 12, Reference Examples 1 to 4, and Comparative Examples 1 to 4 were prepared in the same procedure and under the same conditions as in Example 1. Preparation conditions for all examples, including Example 1, are shown in Tables 1 and 2 below.

[Evaluation of treatment agent for carbon fiber precursor]
(1) Preparation of carbon fiber (1-1) Preparation of fiber material A copolymer consisting of 95% by mass of acrylonitrile, 3.5% by mass of methyl acrylate, and 1.5% by mass of methacrylic acid, having an intrinsic viscosity of 1.80, A spinning stock solution was prepared by dissolving in dimethylacetamide (DMAC), having a polymer concentration of 21.0% by weight and a viscosity of 500 poise at 60°C. The spinning stock solution was discharged from a spinneret with a hole diameter (inner diameter) of 0.075 mm and 12,000 holes into a coagulation bath of 70% by mass aqueous solution of DMAC maintained at a spinning bath temperature of 35° C. at a draft ratio of 0.8. The coagulated yarn was desolvated in a water washing bath and at the same time, stretched 5 times to prepare a water-swollen acrylic fiber strand (an example of a fiber material).

(1-2) Preparation of Carbon Fiber Precursor The prepared acrylic fiber strand was dipped in a 4% ion-exchange aqueous solution of the carbon fiber precursor treatment agent of each example, reference example, and comparative example by an immersion method. , oil was supplied so that the amount of the treating agent adhered was 1% by mass (not including the solvent). After that, the acrylic fiber strand to which the treatment agent has adhered is dried and densified with a heating roller at 150°C, further stretched by 1.7 times between heating rollers at 170°C, and then wound around a yarn tube. to obtain a carbon fiber precursor.

(1-3) Production of carbon fiber A thread is unwound from the carbon fiber precursor of each example, reference example, and comparative example, and placed in an air atmosphere in a flameproofing furnace having a temperature gradient of 230 to 270 ° C. After being flame-resistant treated for 1 hour, it was wound around a yarn tube to obtain a flame-resistant yarn. Further, the flame-resistant yarn is unwound, calcined in a nitrogen atmosphere in a carbonization furnace with a temperature gradient of 300 to 1300° C., converted to carbon fiber, and wound around a yarn tube to obtain carbon fiber. rice field.

(2) Evaluation of amount of scum generated For each of the examples, reference examples, and comparative examples, the carbon fibers were continuously produced according to the procedure in (1) above, and the amount of scum deposited on the rollers in the drying and densification process was measured. Observation was made for presence and degree. They were classified into the following three levels according to the observation results.
A: There was little scum accumulation, and continuous operation was possible without cleaning for two weeks or more without stopping the operation due to yarn breakage or the like.
B: Although scum deposits were slightly observed, continuous operation was possible without cleaning for 1 week or more and less than 2 weeks without stopping the operation due to thread breakage or the like.
C: A large amount of scum accumulated, and it became necessary to stop the operation due to thread breakage, etc., and cleaning was required in less than one week.

(3) Evaluation of windability The examples, reference examples, and comparative examples were classified into the following three levels according to the state of work when winding the carbon fiber precursor around a thread tube.
A: It was possible to wind 200 kg or more without causing twill drop and winding collapse.
B: It was possible to wind 150 kg or more and less than 200 kg without causing twill drop and winding collapse.
C: Twill drop or winding collapse occurred before the winding amount reached 150 kg.

(4) Evaluation of Strength The tensile strength of the carbon fibers of Examples, Reference Examples, and Comparative Examples was measured according to JIS R 7606:2000. It was classified into the following three levels according to the measured value of tensile strength.
A: Tensile strength 4.0 GPa or more B: Tensile strength 3.5 GPa or more and less than 4.0 GPa C: Tensile strength less than 3.5 GPa

(5) Evaluation of Antirust Property The treatment agents of Examples, Reference Examples, and Comparative Examples were diluted with ion-exchanged water to prepare samples having a non-volatile content of 20%. 15 g of the sample was placed in a petri dish having a diameter of about 10 cm, a knitting needle made of iron was placed therein, the sample was sealed, and the condition of the knitting needle was observed after standing at 25° C. for one week. It was classified into the following two levels according to the observation results.
+: No rust was observed on the knitting needle.
-: Rust was observed on the knitting needle.

〔result〕
Tables 1 and 2 show the types and contents of the reagents used, the amount of scum generated, the windability, the strength, and the rust resistance for each of the examples, reference examples, and comparative examples. Indicated.

Table 1: Evaluation results of treatment agent for carbon fiber precursor (Example)

Table 2: Evaluation results of carbon fiber precursor treatment agent (comparative example)

INDUSTRIAL APPLICABILITY The present invention can be used, for example, in the production of carbon fibers.

Claims (5)

an ionic compound (A) containing no halogen atoms in the composition formula;
a monoalcohol derivative (B);
silicone (C);
an ester compound (D) having a bisphenol skeleton in the molecule;
and an amine derivative (E) ,
The ionic compound (A) has an aliphatic hydrocarbon group having 8 to 17 carbon atoms and at least one of a phosphorus atom and a sulfur atom in the molecule,
The monoalcohol derivative (B) is added with a total of 7 mol or more and 33 mol or less of ethylene oxide and propylene oxide per 1 mol of alcohol selected from aliphatic alcohols having 12 to 15 carbon atoms and tristyrenated phenol. , is an alkylene oxide adduct of a monoalcohol,
The ester compound (D) is an alkylene oxide adduct of bisphenol A in which ethylene oxide and propylene oxide are added in total of 2 to 10 mol per 1 mol of bisphenol A, and a saturated fatty acid having 8 to 18 carbon atoms. A treatment agent for a carbon fiber precursor, which is a diester of The treating agent for carbon fiber precursors according to claim 1, wherein the silicone (C) contains an amino-modified silicone. With the total content of the ionic compound (A), the monoalcohol derivative (B), the silicone (C), the ester compound (D), and the amine derivative (E) being 100 parts by mass,
The carbon fiber precursor treatment agent according to claim 1 or 2, wherein the content of the ionic compound (A) is 0.1 parts by mass or more and less than 15 parts by mass. With the total content of the ionic compound (A), the monoalcohol derivative (B), the silicone (C), the ester compound (D), and the amine derivative (E) being 100 parts by mass,
The carbon fiber precursor treatment agent according to claim 1 or 2, wherein the content of the silicone (C) is 1 part by mass or more and less than 30 parts by mass. A carbon fiber precursor to which the treatment agent for carbon fiber precursor according to claim 1 is adhered.