JP5968685B2 - Oil agent for carbon fiber precursor acrylic fiber, oil agent composition for carbon fiber precursor acrylic fiber, and oil agent treatment liquid for carbon fiber precursor acrylic fiber - Google Patents

Description

  The present invention relates to an oil agent for carbon fiber precursor acrylic fiber, an oil agent composition for carbon fiber precursor acrylic fiber, and an oil agent treatment liquid for carbon fiber precursor acrylic fiber.

  Conventionally, as a method for producing a carbon fiber bundle, a carbon fiber precursor acrylic fiber bundle (hereinafter, also referred to as “precursor fiber bundle”) made of acrylic fiber or the like is heat-treated in an oxidizing atmosphere at 200 to 400 ° C. Thus, there is known a method for obtaining a carbon fiber bundle by converting into a flame-resistant fiber bundle (flame-proofing process) and subsequently carbonizing in an inert atmosphere at 1000 ° C. or higher (carbonization process). Carbon fiber bundles obtained by this method are widely used industrially as reinforcing fibers for composite materials because of their excellent mechanical properties.

  However, in the method for producing a carbon fiber bundle, fusion occurs between single fibers in a flameproofing process in which the precursor fiber bundle is converted into a flameproofed fiber bundle, and the flameproofing process and the subsequent carbonization process (hereinafter referred to as flameproofing). The process and the carbonization process are collectively referred to as “firing process”.) In some cases, process failures such as fluff and bundle breakage may occur. As a method for preventing the fusion between single fibers, a method of applying an oil agent composition to the surface of the precursor fiber bundle (oil agent treatment) is known, and many oil agent compositions have been studied.

As an oil agent composition, a silicone oil agent mainly composed of silicone having an effect of preventing fusion between single fibers has been generally used.
However, the silicone-based oil agent undergoes a crosslinking reaction to increase in viscosity due to heating, and its adhesive is easily deposited on the surface of the fiber transport roller and guide used in the precursor fiber bundle manufacturing process and flameproofing process. It was. For this reason, the precursor fiber bundle and the flame-resistant fiber bundle may cause a decrease in operability such as wrapping or catching on the fiber conveyance roller or guide.

In addition, the precursor fiber bundle with the silicone-based oil agent has a problem that it tends to produce silicon compounds such as silicon oxide, silicon carbide, and silicon nitride in the firing process, which lowers industrial productivity and product quality. Was.
In recent years, due to the growing demand for carbon fiber, there is an increasing demand for larger production facilities and improved production efficiency. However, industrial productivity decline due to the formation of silicon compounds in the above firing process must be solved. One.

Therefore, for the purpose of reducing the silicon content of the precursor fiber bundle that has been treated with an oil agent, an oil agent composition having a reduced silicone content or no silicone has been proposed. For example, an oil agent composition containing 40 to 100% by mass of an emulsifier containing 50 to 100% by mass of a polycyclic aromatic compound to reduce the silicone content has been proposed (see Patent Document 1).
Moreover, the oil agent composition which combined the heat-resistant resin and silicone which are 80 mass% or more after heating for 2 hours at 250 degreeC in the air is proposed (refer patent document 2).
Furthermore, an oil agent composition (see Patent Documents 3 and 4) in which a bisphenol A aromatic compound and an amino-modified silicone are combined, or an oil agent composition containing a fatty acid ester of an alkylene oxide adduct of bisphenol A as a main component (patent) Document 5) has been proposed.
Moreover, the oil agent composition which reduced silicone content by using the ester compound which has 3 or more ester groups in a molecule | numerator is proposed (refer patent document 6).
Furthermore, by using together an ester compound having three or more ester groups in the molecule and a water-soluble amide compound, both the prevention of fusion between fibers and stable operability are achieved while reducing the silicone content. It is reported that it can be made (refer patent document 7).
In addition, an oil agent composition containing 10% by mass or more of a compound having a reactive functional group and not containing a silicone compound or containing a silicone compound is proposed in a range of 2% by mass or less in terms of silicon mass. (See Patent Document 8).
Furthermore, an oil composition comprising 0.2 to 20% by weight of an acrylic polymer having an aminoalkylene group in the side chain, 60 to 90% by weight of a specific ester compound, and 10 to 40% by weight of a surfactant is proposed. (See Patent Document 9).

JP 2005-264384 A JP 2000-199183 A JP 2003-55881 A JP 2004-149937 A International Publication No. 97/009474 International Publication No. 07/0666517 JP 2010-24582 A JP 2005-264361 A JP 2010-53467 A

However, in the oil agent composition described in Patent Document 1, the stability of the emulsion is increased due to a large content of the emulsifier. It was not suitable for manufacturing with high production efficiency. Furthermore, there is a problem that it is difficult to obtain a carbon fiber bundle excellent in mechanical properties.
The oil composition described in Patent Document 2 uses a bisphenol A-based aromatic ester as a heat-resistant resin, so the heat resistance is very high, but the effect of preventing fusion between single fibers is not sufficient. . Furthermore, there is a problem that it is difficult to stably obtain a carbon fiber bundle excellent in mechanical properties.

Moreover, also in the oil agent composition of patent documents 3-5, the carbon fiber bundle excellent in the mechanical physical property was not able to be manufactured stably.
Furthermore, in the case of the oil agent composition described in Patent Document 6, it is difficult to maintain the convergence in the flame resistance process only with an ester compound having three or more ester groups in the molecule. Therefore, a silicone compound is an essential component, and generation of a silicon compound that is a problem in the firing process is inevitable.
In addition, even in the oil composition described in Patent Document 7 containing a water-soluble amide compound, stable operation and product quality could not be maintained in a system substantially free of silicone.
Moreover, although the oil agent composition of patent document 8 can improve oil agent adhesiveness by raising the viscosity of the oil agent composition in 100-145 degreeC, since the viscosity is high, it is the precursor fiber after oil agent processing There was a problem that the bundle adhered to the fiber transport roller in the spinning process, causing a process failure such as winding of the fiber bundle.
Furthermore, although the oil agent composition described in Patent Document 9 can prevent fusion where single fiber substrates adhere to each other in the flameproofing step, the oil component is present as an adhesive between the single fibers, and thus, sticking is unavoidable. In addition, due to this sticking, the diffusion of oxygen into the fiber bundle in the flameproofing process is hindered, so that the flameproofing process is not performed uniformly, and there is a problem that it becomes an obstacle such as fluff or bundle breakage in the subsequent carbonization process. It was.

As described above, an oil composition with a reduced silicone content or an oil composition containing only a non-silicone component has a lower anti-fusing property and a convergence property of an oil-treated precursor fiber bundle than a silicone-based oil agent. Or the mechanical properties of the obtained carbon fiber bundle tend to be inferior. Therefore, it has been difficult to stably obtain a high-quality carbon fiber bundle.
On the other hand, as described above, in the case of the silicone-based oil agent, there has been a problem of a decrease in operability due to an increase in viscosity and a decrease in industrial productivity due to generation of a silicon compound.
In other words, problems of lowering the operability and industrial productivity due to the silicone-based oil agent, reducing the silicone content, or preventing fusion by the oil agent composition containing only the non-silicone component, the convergence property of the precursor fiber bundle, The problem of the deterioration of the mechanical properties of the carbon fiber bundle is in an integrated relationship, and the prior art cannot solve both of these problems.

  An object of the present invention is to effectively prevent fusion between single fibers in the production process of carbon fiber bundles, suppress deterioration in operability, and have good converging properties, and a carbon fiber precursor acrylic fiber bundle and mechanical properties. To provide a carbon fiber precursor acrylic fiber oil agent, a carbon fiber precursor acrylic fiber oil agent composition, and a carbon fiber precursor acrylic fiber oil agent treatment liquid capable of obtaining an excellent carbon fiber bundle with high productivity. is there.

  As a result of intensive studies, the present inventors have used, as an oil agent, two or more compounds selected from the group consisting of the following groups A, B, C, D, E, and F, which are non-silicone components. The present inventors have found that the problems of the silicone-based oil described above and the problems of the oil composition with a reduced silicone content or a non-silicone component only can be solved, and the present invention has been completed.

That is, the carbon fiber precursor acrylic fiber oil agent of the present invention is characterized by containing two or more compounds selected from the group consisting of A, B, C, D, E, and F below.
A: Compound A obtained by reaction of hydroxybenzoic acid with a monovalent aliphatic alcohol having 8 to 20 carbon atoms.
B: Compound B obtained by reacting cyclohexanedicarboxylic acid with a monovalent aliphatic alcohol having 8 to 22 carbon atoms.
C: a cyclohexanedicarboxylic acid, a monovalent aliphatic alcohol having 8 to 22 carbon atoms, a polyhydric alcohol having 2 to 10 carbon atoms and / or a polyoxyalkylene glycol having 2 to 4 carbon atoms in an oxyalkylene group Compound C obtained by reaction.
D: Compound D obtained by reaction of cyclohexanedimethanol and / or cyclohexanediol with a fatty acid having 8 to 22 carbon atoms.
E: Compound E obtained by reaction of cyclohexanedimethanol and / or cyclohexanediol, a fatty acid having 8 to 22 carbon atoms and dimer acid.
F: One or more compounds selected from the group consisting of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = isocyanate, monovalent aliphatic alcohols having 8 to 22 carbon atoms and polyoxyalkylene ether compounds thereof Compound F obtained by reaction with

  The compound A is preferably represented by the following formula (1a).

In formula (1a), R ^1a is a hydrocarbon group having 8 to 20 carbon atoms.

  The compound B is preferably represented by the following formula (1b).

In formula (1b), R ^1b and R ^2b are each independently a hydrocarbon group having 8 to 22 carbon atoms.

  The compound C is preferably represented by the following formula (2b).

In Formula (2b), R ^3b and R ^5b are each independently a hydrocarbon group having 8 to 22 carbon atoms, and R ^4b is a hydrocarbon group having 2 to 10 carbon atoms or an oxyalkylene group having 2 carbon atoms. It is a residue obtained by removing two hydroxyl groups from polyoxyalkylene glycol which is ˜4.

  The compound D is preferably represented by the following formula (1c).

In formula (1c), R ^1c and R ^2c are each independently a hydrocarbon group having 7 to 21 carbon atoms, and nc is each independently 0 or 1.

  The compound E is preferably represented by the following formula (2c).

In formula (2c), R ^3c and R ^5c are each independently a hydrocarbon group having 7 to 21 carbon atoms, R ^4c is a hydrocarbon group having 30 to 38 carbon atoms, and mc is independently , 0 or 1.

  The compound F is preferably represented by the following formula (1d).

In formula (1d), R ^1d and R ^4d are each independently a hydrocarbon group having 8 to 22 carbon atoms, R ^2d and R ^3d are each independently a hydrocarbon group having 2 to 4 carbon atoms, nd and md mean the average number of moles added, and are each independently a number from 0 to 5.

The oil agent for carbon fiber precursor acrylic fiber of the present invention preferably contains at least the compound A and / or the compound F.
Moreover, the oil agent composition for carbon fiber precursor acrylic fibers of this invention contains the said oil agent for carbon fiber precursor acrylic fibers, and a nonionic surfactant, It is characterized by the above-mentioned.
Here, it is preferable to contain 20 to 150 parts by mass of the nonionic surfactant with respect to 100 parts by mass of the carbon fiber precursor acrylic fiber oil.
Furthermore, it is preferable to contain 1-5 mass parts of antioxidant with respect to 100 mass parts of said oil agents for carbon fiber precursor acrylic fibers.
Moreover, the oil agent treatment liquid for carbon fiber precursor acrylic fibers of the present invention is characterized in that the oil agent composition for carbon fiber precursor acrylic fibers is dispersed in water.

  According to the present invention, a carbon fiber precursor acrylic fiber bundle and mechanical properties that effectively prevent fusion between single fibers in the carbon fiber bundle manufacturing process, suppress deterioration in operability, and have good convergence. The carbon fiber precursor acrylic fiber oil agent, the carbon fiber precursor acrylic fiber oil agent composition, and the carbon fiber precursor acrylic fiber oil agent treatment liquid capable of obtaining an excellent carbon fiber bundle with high productivity can be provided.

Hereinafter, the present invention will be described in detail.
[Oil agent for carbon fiber precursor acrylic fiber]
The carbon fiber precursor acrylic fiber oil agent of the present invention (hereinafter also simply referred to as “oil agent”) is selected from the group consisting of groups A, B, C, D, E, and F described below. It contains the above compounds and is applied to a carbon fiber precursor acrylic fiber bundle that is made of acrylic fiber and is not yet treated with an oil. Here, “two or more compounds” means that a compound is selected from two or more different groups. In addition, one compound may be selected from one group (group), and two or more compounds may be selected.
Hereinafter, in this specification, the carbon fiber precursor acrylic fiber bundle before the oil agent treatment is referred to as “precursor fiber bundle”.

<Group A>
The compound A included in the group A is a compound obtained by a condensation reaction of hydroxybenzoic acid and a monovalent aliphatic alcohol having 8 to 20 carbon atoms (hereinafter also referred to as “hydroxybenzoic acid ester”).

Hydroxybenzoic acid ester has sufficient heat resistance in the flameproofing process, fixability to the precursor fiber bundle due to hydrogen bonding of hydroxyl groups, and the alkyl and the chain between the fiber and the transport roller or bar. It is possible to maintain smoothness between them and reduce damage to the fiber bundle.
Hydroxybenzoic acid ester is a carbon that has a good mechanical property because it easily adheres uniformly to the precursor fiber bundle because it uses a nonionic surfactant, which will be described later, and is stably dispersed in moisture by an emulsification method. This is effective for producing a carbon fiber precursor acrylic fiber bundle for obtaining a fiber bundle.

  The hydroxybenzoic acid used as the raw material for the hydroxybenzoic acid ester may be any of 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid, but has heat resistance and is imparted to the precursor fiber bundle. 4-hydroxybenzoic acid is preferable because it is favorable in terms of smoothness between the fiber bundle and the transport roller, bar, and the like. Further, the carboxyl group of benzoic acid may be an ester with a short-chain alcohol having 1 to 3 carbon atoms. Examples of the short-chain alcohol having 1 to 3 carbon atoms include methanol, ethanol, normal, and isopropanol.

As an alcohol used as a raw material for the hydroxybenzoic acid ester, one or more alcohols selected from monovalent aliphatic alcohols are used.
The carbon number of the monovalent aliphatic alcohol is 8-20. If the number of carbon atoms is 8 or more, the thermal stability of the hydroxybenzoic acid ester can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, if the number of carbon atoms is 20 or less, the viscosity of the hydroxybenzoic acid ester does not become too high and it is difficult to solidify, so an emulsion of an oil agent composition containing the hydroxybenzoic acid ester that is an oil agent can be easily prepared. It adheres uniformly to the precursor fiber bundle.
11-20 are preferable and, as for carbon number of monovalent | monohydric aliphatic alcohol, 14-20 are more preferable.

Examples of the monovalent aliphatic alcohol having 8 to 20 carbon atoms include octanol, 2-ethylhexanol, nonanol, isononyl alcohol, decanol, isodecanol, isotridecanol, tetradecanol, hexadecanol, stearyl alcohol, Alkyl alcohols such as stearyl alcohol and octyldodecanol; octenyl alcohol, nonenyl alcohol, decenyl alcohol, 2-ethyldecenyl alcohol, undecenyl alcohol, dodecenyl alcohol, tetradecenyl alcohol, penta Alkenyl alcohols such as decenyl alcohol, hexadecenyl alcohol, heptadecenyl alcohol, octadecenyl alcohol (oleyl alcohol), nonadecenyl alcohol, icocenyl alcohol; Alkynyl such as nyl alcohol, nonynyl alcohol, decynyl alcohol, undecynyl alcohol, dodecynyl alcohol, tridecynyl alcohol, tetradecynyl alcohol, hexadecynyl alcohol, octadecynyl alcohol, nonadecynyl alcohol, eicosinyl alcohol Examples include alcohol. Above all, ease of preparation of the oil treatment liquid described later, handling that the process is difficult to occur such as fiber winding around the transport roller when attached to the fiber transport roller in the spinning process, and has the desired heat resistance. Octadecenyl alcohol (oleyl alcohol) is preferable from the balance of process passability and performance.
These aliphatic alcohols may be used alone or in combination of two or more.

  As the hydroxybenzoic acid ester, a compound having a structure represented by the following formula (1a) is preferable.

In formula (1a), R ^1a is a hydrocarbon group having 8 to 20 carbon atoms. If the hydrocarbon group has 8 or more carbon atoms, the thermal stability of the hydroxybenzoic acid ester can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, if the carbon number of the hydrocarbon group is 20 or less, the viscosity of the hydroxybenzoic acid ester does not become too high and it is difficult to solidify. The oil agent adheres uniformly to the precursor fiber bundle. As for carbon number of a hydrocarbon group, 11-20 are preferred.

The compound having the structure represented by the formula (1a) is a hydroxybenzoic acid ester obtained by a condensation reaction between hydroxybenzoic acid and a monovalent aliphatic alcohol having 8 to 20 carbon atoms.
Therefore, R ^1a in formula (1a) is derived from a monovalent aliphatic alcohol having 8 to 20 carbon atoms. R ^1a may be any of an alkyl group having 8 to 20 carbon atoms, an alkenyl group, and an alkynyl group, and may be linear or branched. R ^1a is preferably 11 to 20, and more preferably 14 to 20.
Examples of the alkyl group include n- and iso-octyl group, 2-ethylhexyl group, n- and iso-nonyl group, n- and iso-decyl group, n- and iso-undecyl group, n- and iso-dodecyl group. N- and iso-tridecyl group, n- and iso-tetradecyl group, n- and iso-hexadecyl group, n- and iso-heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.
Examples of the alkenyl group include octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group and the like.
Examples of the alkynyl group include 1- and 2-octynyl groups, 1- and 2-noninyl groups, 1- and 2-decynyl groups, 1- and 2-undecynyl groups, 1- and 2-dodecynyl groups, 1- and 2 -Tridecynyl group, 1- and 2-tetradecynyl group, 1- and 2-hexadecynyl group, 1- and 2-octadecynyl group, 1- and 2-nonadecynyl group, 1- and 2-eicosinyl group and the like can be mentioned.

Hydroxybenzoic acid ester is obtained by condensation reaction of hydroxybenzoic acid and monovalent aliphatic alcohol having 8 to 20 carbon atoms in the presence of a non-catalyst or a known esterification catalyst such as a tin compound and a titanium compound. Can be obtained. The condensation reaction is preferably performed in an inert gas atmosphere. The reaction temperature is preferably 160 to 250 ° C, more preferably 180 to 230 ° C.
The molar ratio of hydroxybenzoic acid and alcohol component to be subjected to the condensation reaction is preferably 0.9 to 1.3 mol of monovalent aliphatic alcohol having 8 to 20 carbon atoms with respect to 1 mol of hydroxybenzoic acid. 0-1.2 mol is more preferable. In addition, when using an esterification catalyst, after a condensation reaction, it is preferable from a viewpoint of strand strength to inactivate a catalyst and to remove with an adsorbent.

<Groups B and C>
Compound B included in Group B is a compound obtained by a condensation reaction of cyclohexanedicarboxylic acid as a carboxylic acid component and a monovalent aliphatic alcohol having 8 to 22 carbon atoms as an alcohol component (hereinafter referred to as “cyclohexanedicarboxylic acid”). Also referred to as “ester B”.
On the other hand, compound C contained in group C includes cyclohexanedicarboxylic acid as the carboxylic acid component, monovalent aliphatic alcohol having 8 to 22 carbon atoms, polyhydric alcohol having 2 to 10 carbon atoms and / or alcohol component. Alternatively, it is a compound obtained by a condensation reaction with a polyoxyalkylene glycol having 2 to 4 carbon atoms in an oxyalkylene group (hereinafter also referred to as “cyclohexanedicarboxylic acid ester C”).
Hereinafter, Compound B and Compound C are collectively referred to as “cyclohexane dicarboxylic acid ester”.

Cyclohexanedicarboxylic acid ester has sufficient heat resistance in the flameproofing process, and also has excellent thermal decomposability because it does not have an aromatic ring. At the same time, it is easily discharged out of the system and is unlikely to cause process failure or quality degradation.
In addition, cyclohexanedicarboxylic acid ester is a non-ionic surfactant described later and is easily dispersed in moisture by an emulsification method. It is effective for producing a carbon fiber precursor acrylic fiber bundle for obtaining a bundle.

The cyclohexanedicarboxylic acid may be any of 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Cyclohexanedicarboxylic acid is preferred.
Cyclohexanedicarboxylic acid may be an acid anhydride or an ester with a short-chain alcohol having 1 to 3 carbon atoms. Examples of the short-chain alcohol having 1 to 3 carbon atoms include methanol, ethanol, normal, and isopropanol.

As the alcohol used as a raw material for the cyclohexanedicarboxylic acid ester, one or more alcohols selected from the group consisting of monovalent aliphatic alcohols, polyhydric alcohols, and polyoxyalkylene glycols are used.
The carbon number of the monovalent aliphatic alcohol is 8-22. If the number of carbon atoms is 8 or more, the thermal stability of the cyclohexanedicarboxylic acid ester can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, if the number of carbon atoms is 22 or less, the viscosity of the cyclohexanedicarboxylic acid ester does not become too high and is difficult to solidify. It adheres uniformly to the precursor fiber bundle.
12-22 are preferable from said viewpoint, and, as for carbon number of monovalent | monohydric aliphatic alcohol, 15-22 are more preferable.

Examples of the monovalent aliphatic alcohol having 8 to 22 carbon atoms include octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, heptadecanol, octadecanol, and nonadecanol. Alkyl alcohols such as eicosanol, heneicosanol and docosanol; octenyl alcohol, nonenyl alcohol, decenyl alcohol, undecenyl alcohol, dodecenyl alcohol, tetradecenyl alcohol, pentadecenyl alcohol, Hexadecenyl alcohol, heptadecenyl alcohol, octadecenyl alcohol, nonadecenyl alcohol, icocenyl alcohol, henycocenyl alcohol, dococenyl alcohol, oleyl alcohol Alkenyl alcohol such as alcohol, gadryl alcohol, 2-ethyldecenyl alcohol; octynyl alcohol, noninyl alcohol, decynyl alcohol, undecynyl alcohol, dodecynyl alcohol, tridecynyl alcohol, tetradecynyl alcohol, hexa Alkynyl alcohols such as decynyl alcohol, stearinyl alcohol, nonadecynyl alcohol, eicosinyl alcohol, heicosinyl alcohol, docosinyl alcohol and the like can be mentioned. Above all, ease of preparation of the oil treatment liquid described later, handling that the process is difficult to occur such as fiber winding around the transport roller when attached to the fiber transport roller in the spinning process, and has the desired heat resistance. Oleyl alcohol is preferable from the balance of process passability and performance.
These aliphatic alcohols may be used alone or in combination of two or more.

The carbon number of the polyhydric alcohol is 2-10. If the number of carbon atoms is 2 or more, the thermal stability of the cyclohexanedicarboxylic acid ester can be maintained satisfactorily, so that a sufficient fusion prevention effect can be obtained in the flameproofing step. On the other hand, if the number of carbon atoms is 10 or less, the viscosity of the cyclohexanedicarboxylic acid ester does not become too high and is difficult to solidify. It adheres uniformly to the precursor fiber bundle.
5-10 are preferable from said viewpoint, and, as for carbon number of a polyhydric alcohol, 5-8 are more preferable.

The polyhydric alcohol having 2 to 10 carbon atoms may be an aliphatic alcohol or an aromatic alcohol, and may be a saturated alcohol or an unsaturated alcohol.
Examples of such polyhydric alcohols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol, 2- Methyl-1,8-octanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2-ethyl-1,6-hexanediol, 2,4-dimethyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 1,3-butanediol, 2-ethyl-1,3-hexanediol, 2-buty Dihydric alcohols such as 2-ethyl-1,3-propanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; trimethylolethane, trimethylolpropane, hexanetriol, Although trihydric alcohols, such as glycerol, are mentioned, a dihydric alcohol is preferable from a viewpoint of making an oil agent composition low viscosity and making an oil agent adhere to a precursor fiber bundle uniformly.

The polyoxyalkylene glycol has a repeating unit having 2 to 4 carbon atoms in the oxyalkylene group and has two hydroxyl groups. It is preferable to have a hydroxyl group at both ends.
If the number of carbon atoms in the oxyalkylene group is 2 or more, the thermal stability of the cyclohexanedicarboxylic acid ester can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, if the number of carbon atoms of the oxyalkylene group is 4 or less, the viscosity of the cyclohexanedicarboxylic acid ester does not become too high and it is difficult to solidify, so an emulsion of an oil agent composition containing the cyclohexanedicarboxylic acid ester that is an oil agent is easily prepared. The oil agent can be uniformly attached to the precursor fiber bundle.

Examples of the polyoxyalkylene glycol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxybutylene glycol and the like. The average number of moles of oxyalkylene groups is preferably from 1 to 15, more preferably from 1 to 10, and even more preferably from 2 to 8 from the viewpoint of lowering the viscosity of the oil composition and uniformly attaching the oil to fibers.
Both the polyhydric alcohol having 2 to 10 carbon atoms and the polyoxyalkylene glycol having 2 to 4 carbon atoms in the oxyalkylene group may be used, or one of them may be used.

  The cyclohexanedicarboxylic acid ester B is preferably a compound having a structure represented by the following formula (1b), and the cyclohexanedicarboxylic acid ester C is preferably a compound having a structure represented by the following formula (2b).

In formula (1b), R ^1b and R ^2b are each independently a hydrocarbon group having 8 to 22 carbon atoms. If the hydrocarbon group has 8 or more carbon atoms, the thermal stability of the cyclohexanedicarboxylic acid ester B can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, if the number of carbon atoms of the hydrocarbon group is 22 or less, the viscosity of cyclohexanedicarboxylic acid ester B does not become too high and is difficult to solidify. The oil agent is uniformly attached to the precursor fiber bundle. From the above viewpoint, the number of carbon atoms of the hydrocarbon group is independently 12 to 22, and more preferably 15 to 22.
R ^1b and R ^2b may have the same structure or may have independent structures.

The compound having the structure represented by the formula (1b) is a cyclohexanedicarboxylic acid ester obtained by a condensation reaction between cyclohexanedicarboxylic acid and a monovalent aliphatic alcohol having 8 to 22 carbon atoms. Therefore, R ^1b and R ^2b in formula (1b) are derived from an aliphatic alcohol. R ^1b and R ^2b may be any of an alkyl group having 8 to 22 carbon atoms, an alkenyl group, and an alkynyl group, and may be linear or branched.
Examples of the alkyl group include n- and iso-octyl group, 2-ethylhexyl group, n- and iso-nonyl group, n- and iso-decyl group, n- and iso-undecyl group, n- and iso-dodecyl group. , N- and iso-tridecyl group, n- and iso-tetradecyl group, n- and iso-hexadecyl group, n- and iso-heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl, docosyl group, etc. It is done.
Examples of the alkenyl group include octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, heicocosenyl group, dococenyl group, oleyl group , A gadrel group, a 2-ethyldecenyl group, and the like.
Examples of the alkynyl group include 1- and 2-octynyl groups, 1- and 2-noninyl groups, 1- and 2-decynyl groups, 1- and 2-undecynyl groups, 1- and 2-dodecynyl groups, 1- and 2 -Tridecynyl group, 1- and 2-tetradecynyl group, 1- and 2-hexadecynyl group, 1- and 2-stearinyl group, 1- and 2-nonadecynyl group, 1- and 2-eicosinyl group, 1- and 2-henicosinyl group Groups, and 1- and 2-docosinyl groups and the like.

Cyclohexanedicarboxylic acid ester B is a condensation reaction between cyclohexanedicarboxylic acid and a monovalent aliphatic alcohol having 8 to 22 carbon atoms in the presence of no catalyst or a known esterification catalyst such as a tin compound or a titanium compound. Can be obtained at The condensation reaction is preferably performed in an inert gas atmosphere.
The reaction temperature is preferably 160 to 250 ° C, more preferably 180 to 230 ° C.
The molar ratio of the carboxylic acid component and the alcohol component to be subjected to the condensation reaction is preferably 1.8 to 2.2 mol of monovalent aliphatic alcohol having 8 to 22 carbon atoms with respect to 1 mol of cyclohexanedicarboxylic acid. 9-2.1 mol is more preferable.
In addition, when using an esterification catalyst, after a condensation reaction, it is preferable from a viewpoint of strand strength to inactivate a catalyst and to remove with an adsorbent.

On the other hand, in the formula (2b), R ^3b and R ^5b are each independently a hydrocarbon group having 8 to 22 carbon atoms, and R ^4b is a carbon number of a hydrocarbon group or oxyalkylene group having 2 to 10 carbon atoms. Is a divalent residue obtained by removing two hydroxyl groups from a polyoxyalkylene glycol having 2 to 4.
In the case of R ^3b and R ^5b , if the hydrocarbon group has 8 or more carbon atoms, the thermal stability of the cyclohexanedicarboxylic acid ester C can be maintained satisfactorily. It is done. On the other hand, if the number of carbon atoms of the hydrocarbon group is 22 or less, the viscosity of cyclohexanedicarboxylic acid ester C does not become too high and is difficult to solidify. The oil agent is uniformly attached to the precursor fiber bundle. The hydrocarbon groups of R ^3b and R ^5b each independently have 12 to 22 carbon atoms, and more preferably 15 to 22 carbon atoms.
R ^3b and R ^5b may have the same structure or may have independent structures.

In the case of R ^4b , if the hydrocarbon group has 2 or more carbon atoms or the oxyalkylene group has 2 or more carbon atoms, it is esterified with a carboxylic acid added to the cyclohexyl ring, and a bridge is formed between the cyclohexyl rings. As a result, it becomes easy to obtain a material having high thermal stability. On the other hand, if the carbon number of the hydrocarbon group is 10 or less, or the carbon number of the oxyalkylene group is 4 or less, the viscosity of the cyclohexanedicarboxylic acid ester C does not become too high and is difficult to solidify. An emulsion of the oil agent composition containing the ester C can be easily prepared, and the oil agent can be uniformly attached to the precursor fiber bundle.
When R ^4b is a hydrocarbon group, the number of carbon atoms is preferably 5 to 10, and in the case of a residue obtained by removing two hydroxyl groups from polyalkylene glycol, the number of carbon atoms of the oxyalkylene group is preferably 4.

A compound having a structure represented by the formula (2b) is a condensation reaction of cyclohexanedicarboxylic acid, a monovalent aliphatic alcohol having 8 to 22 carbon atoms and a polyhydric alcohol having 2 to 10 carbon atoms, or cyclohexanedicarboxylic acid and And a cyclohexanedicarboxylic acid ester obtained by a condensation reaction of a monovalent aliphatic alcohol having 8 to 22 carbon atoms and a polyoxyalkylene glycol having 2 to 4 carbon atoms of an oxyalkylene group. Therefore, R ^3b and R ^5b in formula (2b) are derived from an aliphatic alcohol. R ^3b and R ^5b may be any of an alkyl group, an alkenyl group, and an alkynyl group, and may be linear or branched. Examples of the alkyl group, alkenyl group, and alkynyl group include the alkyl group, alkenyl group, and alkynyl group exemplified above in the description of R ^1b and R ^2b in formula (1b).
R ^3b and R ^5b may have the same structure or may have independent structures.

On the other hand, R ^4b is derived from a polyhydric alcohol having 2 to 10 carbon atoms or a polyoxyalkylene glycol having 2 to 4 carbon atoms of an oxyalkylene group.
If R ^4b is derived from a polyhydric alcohol having 2 to 10 carbon atoms, R ^4b is preferably a divalent hydrocarbon group of a linear or branched, saturated or unsaturated, specifically, an alkyl group And a substituent obtained by removing one hydrogen from an arbitrary carbon atom of an alkenyl group or an alkynyl group. As above-mentioned, 5-10 are preferable and, as for carbon number, 5-8 are more preferable.
Examples of the alkyl group include ethyl group, propyl group, butyl group, pentyl group, hexyl group, n- and iso-heptyl group, n- and iso-octyl group, 2-ethylhexyl group, n- and iso-nonyl group, Examples include n- and iso-decyl groups.
Examples of the alkenyl group include ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group and the like.
Examples of the alkynyl group include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, noninyl group, decynyl group and the like.
On the other hand, when R ^4b is derived from polyoxyalkylene glycol, R ^4b is a divalent residue obtained by removing two hydroxyl groups from polyoxyalkylene glycol, and specifically, — (OA) _pb-1 — Represented by A- (wherein OA represents an oxyalkylene group having 2 to 4 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and pb represents an average number of moles). 1-15 are preferable, as for pb, 1-10 are more preferable, and 2-8 are still more preferable.
Examples of the oxyalkylene group include an oxyethylene group, an oxypropylene group, an oxytetramethylene group, and an oxybutylene group.

The conditions for the condensation reaction of cyclohexanedicarboxylic acid ester C are the same as those described above.
From the viewpoint of suppressing side reactions, the molar ratio of the carboxylic acid component and the alcohol component used for the condensation reaction is 0.8 to 1 monovalent aliphatic alcohol having 8 to 22 carbon atoms with respect to 1 mol of cyclohexanedicarboxylic acid. It is preferable to use 0.2 to 0.6 moles of polyhydric alcohol and / or polyoxyalkylene glycol having 2 to 10 carbon atoms and / or polyoxyalkylene glycol. It is more preferable to use 0.3 to 0.55 mol of polyhydric alcohol and / or polyoxyalkylene glycol having 9 to 1.4 mol and 2 to 10 carbon atoms, and monovalent aliphatic having 8 to 22 carbon atoms. More preferably, 0.9 to 1.2 mol of alcohol and 0.4 to 0.55 mol of polyhydric alcohol and / or polyoxyalkylene glycol having 2 to 10 carbon atoms are used.
Moreover, in the alcohol component to be subjected to the condensation reaction, the total molar ratio of the monovalent aliphatic alcohol having 8 to 22 carbon atoms, the polyhydric alcohol having 2 to 10 carbon atoms and the polyoxyalkylene glycol is 8 to 22 carbon atoms. The total of 0.1 to 0.6 mol of the polyhydric alcohol having 2 to 10 carbon atoms and the polyoxyalkylene glycol is preferable with respect to 1 mol of the monovalent aliphatic alcohol. More preferred is 0.4 to 0.6 mol.

When a compound is selected from the groups B and C, cyclohexanedicarboxylic acid having a structure represented by the above formula (2b) in that it does not scatter in the flameproofing process and tends to remain stably on the surface of the precursor fiber bundle. Acid esters are particularly preferred.
The number of cyclohexyl rings in one molecule is preferably 1 or 2 because of its low viscosity when it is used as an oil composition, easy dispersion in water, and good stability of the emulsion.

<Groups D and E>
The compound D included in the group D is a compound obtained by a condensation reaction of cyclohexanedimethanol and / or cyclohexanediol and a fatty acid having 8 to 22 carbon atoms, that is, cyclohexanedimethanol ester or cyclohexanediol ester (hereinafter, these are generically named) (Also referred to as “ester (I)”).
On the other hand, the compound E included in the group E is a compound obtained by a condensation reaction between cyclohexanedimethanol and / or cyclohexanediol, a fatty acid having 8 to 22 carbon atoms, and a dimer acid, that is, cyclohexanedimethanol ester or cyclohexanediol ester. (Hereinafter, these are collectively referred to as “ester (II)”).

Esters (I) and (II) are non-ionic surfactants, which will be described later, and are easily dispersed in moisture by the emulsification method, so that they easily adhere uniformly to the precursor fiber bundle and have good mechanical properties. This is effective for producing a carbon fiber precursor acrylic fiber bundle for obtaining a carbon fiber bundle having the same.
In addition, since these esters (I) and esters (II) are aliphatic esters, they are also excellent in thermal decomposability, are easily depolymerized in the carbonization process, and are easily discharged out of the system together with the gas flowing in the furnace. Less likely to cause quality degradation.

The ester (I) is obtained by a condensation reaction between cyclohexanedimethanol and / or cyclohexanediol and a fatty acid having 8 to 22 carbon atoms.
Cyclohexanedimethanol may be 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, or 1,4-cyclohexanedimethanol, but 1,4-cyclohexanedimethanol is 1,4-cyclohexanedimethanol in terms of ease of synthesis and heat resistance. Cyclohexanedimethanol is preferred.
On the other hand, as cyclohexanediol, any of 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol may be used, but 1,4-cyclohexanediol is easy in synthesis and heat resistant. Is preferred.

Carbon number of the fatty acid used as the raw material of ester (I) is 8-22. That is, the hydrocarbon group portion of the fatty acid has 7 to 21 carbon atoms.
If the hydrocarbon group has 7 or more carbon atoms, the thermal stability of the ester (I) can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, when the carbon number of the hydrocarbon group is 21 or less, the viscosity of the ester (I) does not become too high, and an emulsion of the oil agent composition containing the ester (I) that is an oil agent can be easily prepared. It adheres uniformly to the body fiber bundle.
The number of carbon atoms of the hydrocarbon group is preferably 11 to 21 and more preferably 15 to 21 from the above viewpoint. That is, a fatty acid having 12 to 22 carbon atoms is preferable, and a fatty acid having 16 to 22 carbon atoms is more preferable.
The fatty acid having 8 to 22 carbon atoms may be an ester with a short chain alcohol having 1 to 3 carbon atoms. Examples of the short-chain alcohol having 1 to 3 carbon atoms include methanol, ethanol, normal, and isopropanol.

Examples of the fatty acid having 8 to 22 carbon atoms include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vacenoic acid, linoleic acid, Linolenic acid, tuberculostearic acid, arachidic acid, arachidonic acid, behenic acid and the like can be mentioned. Among them, it becomes easy to disperse in water during the preparation of an oil agent treatment liquid described later, and it is difficult to cause a process failure in which fibers are wound around a transport roller that may occur when adhering to a fiber transport roller in a spinning process, and has a desired heat resistance. Oleic acid is preferred from the balance of handling properties, processability, and performance.
These fatty acids may be used alone or in combination of two or more.

  As the ester (I), a compound having a structure represented by the following formula (1c) is preferable.

In formula (1c), R ^1c and R ^2c are each independently a hydrocarbon group having 7 to 21 carbon atoms. If the hydrocarbon group has 7 or more carbon atoms, the thermal stability of the ester (I) can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, when the carbon number of the hydrocarbon group is 21 or less, the viscosity of the ester (I) does not become too high, and an emulsion of the oil agent composition containing the ester (I) that is an oil agent can be easily prepared. It adheres uniformly to the body fiber bundle. From the above viewpoint, the number of carbon atoms of the hydrocarbon group of R ^1c and R ^2c is preferably 11 to 21 and more preferably 15 to 21.
R ^1c and R ^2c may have the same structure or may have independent structures.

R ^1c and R ^2c are derived from a hydrocarbon group of a fatty acid, and may be any of an alkyl group, an alkenyl group, and an alkynyl group, and may be linear or branched.
Examples of the alkyl group include n- and iso-heptyl groups, n- and iso-octyl groups, 2-ethylhexyl groups, n- and iso-nonyl groups, n- and iso-decyl groups, n- and iso-undecyl groups. N- and iso-dodecyl group, n- and iso-tridecyl group, n- and iso-tetradecyl group, n- and iso-hexadecyl group, n- and iso-heptadecyl group, stearyl group, nonadecyl group, eicosyl group, And heneicosyl group and the like.
Examples of alkenyl groups include heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, oleyl, gadryl, and 2 -An ethyl decenyl group etc. are mentioned.
Examples of the alkynyl group include 1- and 2-dodecynyl group, 1- and 2-tridecynyl group, 1- and 2-tetradecynyl group, 1- and 2-hexadecynyl group, 1- and 2-stearinyl group, 1- and 2 -Nonadecynyl group, 1- and 2-eicosinyl group, etc. are mentioned.

In formula (1c), nc is each independently 0 or 1.
When 1,4-cyclohexanedimethanol is used as a raw material for ester (I), nc is 1, and when 1,4-cyclohexanediol is used, nc is 0.

The ester (I) is obtained by subjecting cyclohexanedimethanol and / or cyclohexanediol and a fatty acid having 8 to 22 carbon atoms to a condensation reaction in the presence of a non-catalyst or a known esterification catalyst such as a tin compound or a titanium compound. Can be obtained. The condensation reaction is preferably performed in an inert gas atmosphere.
The reaction temperature is preferably 160 to 250 ° C, more preferably 180 to 230 ° C.
The molar ratio of the carboxylic acid component and the alcohol component to be subjected to the condensation reaction is preferably 1.8 to 2.2 mol of a fatty acid having 8 to 22 carbon atoms with respect to 1 mol in total of cyclohexanedimethanol and cyclohexanediol. 9-2.1 mol is more preferable.
In addition, when using an esterification catalyst, after a condensation reaction, it is preferable from a viewpoint of strand strength to inactivate a catalyst and to remove with an adsorbent.

On the other hand, ester (II) is obtained by a condensation reaction of cyclohexanedimethanol and / or cyclohexanediol, a fatty acid having 8 to 22 carbon atoms, and dimer acid.
Examples of cyclohexanedimethanol and cyclohexanediol include cyclohexanedimethanol and cyclohexanediol exemplified above in the description of ester (I).

Carbon number of the fatty acid used as the raw material of ester (II) is 8-22. That is, the hydrocarbon group portion of the fatty acid has 7 to 21 carbon atoms.
If the hydrocarbon group has 7 or more carbon atoms, the thermal stability of the ester (II) can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, if the hydrocarbon group has 21 or less carbon atoms, the viscosity of the ester (II) does not become too high, and an emulsion of an oil agent composition containing the ester (II) as an oil agent can be easily prepared. It adheres uniformly to the body fiber bundle.
The number of carbon atoms of the hydrocarbon group is preferably 11 to 21 and more preferably 15 to 21 from the above viewpoint. That is, a fatty acid having 12 to 22 carbon atoms is preferable, and a fatty acid having 16 to 22 carbon atoms is more preferable.
Examples of the fatty acid having 8 to 22 carbon atoms include the fatty acids exemplified above in the description of the ester (I).

Dimer acid is a dimerized unsaturated fatty acid.
As the dimer acid, a dicarboxylic acid having 32 to 40 carbon atoms (HOOC—R ^{4c ′} —COOH) obtained by dimerizing an unsaturated fatty acid having 16 to 20 carbon atoms is preferable.
In this case, R ^{4c ′} is a hydrocarbon group having 30 to 38 carbon atoms. If the number of carbon atoms of the hydrocarbon group is 30 or more, the thermal stability of the ester (II) can be maintained satisfactorily, so that a sufficient anti-fusion effect can be obtained in the flameproofing step. On the other hand, if the hydrocarbon group has 38 or less carbon atoms, the viscosity of the ester (II) does not become too high, and an emulsion of an oil agent composition containing the ester (II) as an oil agent can be easily prepared. It adheres uniformly to the body fiber bundle.
From these viewpoints, R ^{4c ′} preferably has 30 to 38 carbon atoms, and preferably 34. That is, the dimer acid is preferably a dicarboxylic acid having 32 to 40 carbon atoms, and more preferably 36 dicarboxylic acid.
As described above, the fatty acid and dimer acid having 8 to 22 carbon atoms may be an ester with a short chain alcohol having 1 to 3 carbon atoms.

Specific examples of R ^{4c ′} include a divalent substituent obtained by removing two hydrogen atoms from any carbon atom of an alkane, alkene, or alkyne having 30 to 38 carbon atoms. Examples of such a divalent substituent include a substituent obtained by removing one hydrogen from any carbon atom of an alkyl group, alkenyl group, or alkynyl group having 30 to 38 carbon atoms.

  As the ester (II), a compound having a structure represented by the following formula (2c) is preferable.

In formula (2c), R ^3c and R ^5c are each independently a hydrocarbon group having 7 to 21 carbon atoms, and R ^4c is a hydrocarbon group having 30 to 38 carbon atoms. If the carbon number of the hydrocarbon group of R ^3c and R ^5c is 7 or more and the number of carbon atoms of the hydrocarbon group of R ^4c is 30 or more, the thermal stability of the ester (II) can be maintained satisfactorily. A sufficient anti-fusing effect can be obtained in the process. On the other hand, if the carbon number of the hydrocarbon group of R ^3c and R ^5c is 21 or less and the carbon number of the hydrocarbon group of R ^4c is 38 or less, the viscosity of the ester (II) does not become too high, and the ester which is an oil agent An oil composition emulsion containing (II) can be easily prepared, and the oil agent uniformly adheres to the precursor fiber bundle.
The number of carbon atoms of the hydrocarbon group of R ^3c and R ^5c is preferably independently 11 to 21, more preferably 15 to 21, and the number of carbon atoms of the hydrocarbon group of R ^4c is preferably 34.

R ^3c and R ^5c are derived from a hydrocarbon group of a fatty acid, and ^{may be} any of an alkyl group, an alkenyl group, and an alkynyl group, and may be linear or branched. Examples of the alkyl group, alkenyl group, and alkynyl group include the alkyl group, alkenyl group, and alkynyl group exemplified above in the description of R ^1c and R ^2c of the compound represented by the formula (1c).
R ^3c and R ^{5c may} have the same structure or may have independent structures.

On the other hand, R ^4c is a divalent substituent obtained by removing two hydrogen atoms from an arbitrary carbon atom of an alkane, alkene, or alkyne, derived from a hydrocarbon group of dimer acid. R ^4c may be linear or branched.
Examples of R ^4c include the same divalent substituent as R ^{4c ′} exemplified above in the description of dimer acid.

In formula (2c), mc is independently 0 or 1.
When 1,4-cyclohexanedimethanol is used as a raw material for the ester (II), mc is 1, and when 1,4-cyclohexanediol is used, mc is 0.

The conditions for the condensation reaction of ester (II) are the same as for ester (I).
The molar ratio of the carboxylic acid component and the alcohol component used for the condensation reaction is a fatty acid having 8 to 22 carbon atoms with respect to a total of 1 mol of cyclohexanedimethanol and cyclohexanediol from the viewpoint of suppressing side reactions and reducing the viscosity. It is preferable to use 0.8 to 1.6 mol of dimer acid and 0.2 to 0.6 mol of dimer acid, 0.9 to 1.4 mol of fatty acid having 8 to 22 carbon atoms, and 0. It is more preferable to use 3 to 0.55 mol, and it is more preferable to use 1.0 to 1.4 mol of fatty acid having 8 to 22 carbon atoms and 0.3 to 0.5 mol of dimer acid.
Moreover, in the carboxylic acid component to be subjected to the condensation reaction, the molar ratio of the fatty acid having 8 to 22 carbon atoms and the dimer acid is such that the dimer acid is 0.1 to 0.6 with respect to 1 mole of the fatty acid having 8 to 22 carbon atoms. Mol is preferable, 0.1 to 0.5 mol is more preferable, and 0.2 to 0.4 mol is still more preferable.

  When a compound is selected from the groups D and E, a cyclohexanedimethanol ester having a structure represented by the above formula (2c) is particularly preferable in that a carbon fiber bundle excellent in mechanical properties is easily obtained.

<Group F>
The compound F included in the group F includes 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = isocyanate (isophorone diisocyanate), a monovalent aliphatic alcohol having 8 to 22 carbon atoms, and a polyoxyalkylene ether compound thereof. A compound obtained by reaction with one or more compounds selected from the group consisting of (hereinafter also referred to as “isophorone diisocyanate-aliphatic alcohol adduct”).

The isophorone diisocyanate-aliphatic alcohol adduct has sufficient heat resistance in the flameproofing process and is also excellent in thermal decomposability because it does not have an aromatic ring, and has a low molecular weight in the carbonization process. It is easy to be discharged out of the system together with the in-furnace gas, and is unlikely to cause process failure or quality deterioration.
In addition, isophorone diisocyanate-aliphatic alcohol adducts use nonionic surfactants, which will be described later, and are easily dispersed in moisture by an emulsification method. It is effective in the production of a carbon fiber precursor acrylic fiber bundle for obtaining a carbon fiber bundle having the following.

As alcohol used as the raw material of the isophorone diisocyanate-aliphatic alcohol adduct, one or more monovalent aliphatic alcohols are used.
The carbon number of the monovalent aliphatic alcohol is 8-22. If the number of carbon atoms is 8 or more, the thermal stability of the isophorone diisocyanate-aliphatic alcohol adduct can be maintained satisfactorily, so that a sufficient anti-fusing effect can be obtained in the flameproofing step. On the other hand, if the number of carbon atoms is 22 or less, the viscosity of the isophorone diisocyanate-aliphatic alcohol adduct does not become too high and is difficult to solidify. An emulsion can be easily prepared, and an oil agent adheres uniformly to a precursor fiber bundle.
11-22 are preferable and, as for carbon number of monovalent | monohydric aliphatic alcohol, 15-22 are more preferable.

Examples of the monovalent aliphatic alcohol having 8 to 22 carbon atoms include octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, heptadecanol, octadecanol, and nonadecanol. Alkyl alcohols such as eicosanol, heneicosanol and docosanol; octenyl alcohol, nonenyl alcohol, decenyl alcohol, undecenyl alcohol, dodecenyl alcohol, tetradecenyl alcohol, pentadecenyl alcohol, Hexadecenyl alcohol, heptadecenyl alcohol, octadecenyl alcohol (oleyl alcohol), nonadecenyl alcohol, icocenyl alcohol, heenicocenyl alcohol, dococenyl alcohol Calk, alkenyl alcohols such as 2-ethyldecenyl alcohol; octynyl alcohol, noninyl alcohol, decynyl alcohol, undecynyl alcohol, dodecynyl alcohol, tridecynyl alcohol, tetradecynyl alcohol, hexadecynyl alcohol, octa Alkynyl alcohols such as decynyl alcohol, nonadecynyl alcohol, eicosinyl alcohol, heicosinyl alcohol, docosinyl alcohol and the like can be mentioned. Above all, ease of preparation of the oil treatment liquid described later, handling that the process is difficult to occur such as fiber winding around the transport roller when attached to the fiber transport roller in the spinning process, and has the desired heat resistance. Octadecenyl alcohol (oleyl alcohol) is preferable from the balance of process passability and performance.
These aliphatic alcohols may be used alone or in combination of two or more.

The aliphatic alcohol used as a raw material of the isophorone diisocyanate-aliphatic alcohol adduct may be a polyoxyalkylene ether compound obtained by adding an alkylene oxide to the above-described monovalent aliphatic alcohol having 8 to 22 carbon atoms.
A monovalent aliphatic alcohol having 8 to 22 carbon atoms can maintain good thermal stability when it is finally used as an oil agent if it has 8 or more carbon atoms. Preventive effect is obtained. On the other hand, if the number of carbon atoms is 22 or less, the viscosity of the oil agent does not become too high and is difficult to solidify, so an emulsion of the oil agent composition containing the oil agent can be easily prepared, and the oil agent uniformly adheres to the precursor fiber bundle. . 11-22 are preferable and, as for carbon number of aliphatic alcohol, 15-22 are more preferable.

Alkylene oxide contributes to the hydrophilicity of the oil and the affinity with the fibers when applied to the precursor fiber bundle.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, and ethylene oxide and propylene oxide are preferable.
The average number of moles of alkylene oxide added is determined by the balance with the number of carbons of the aliphatic alcohol. When the number of carbons of the aliphatic alcohol is in the above preferred range, the amount of addition of alkylene oxide is 0-5. Mole is preferable, and 0 to 3 mol is more preferable.

  Examples of such polyoxyalkylene ethers include polyoxyethylene 4-mol adducts of octanol (hereinafter referred to as “POE (4) octyl ether”), POE (3) dodecyl ether, and polyoxypropylene of dodecanol. 3 mol adducts (hereinafter referred to as “POP (3) dodecyl ether”), polyoxyalkylene alkyl ethers such as POE (2) octadecyl ether, POP (1) octadecyl ether; POE (2) dode Polyoxyalkylene alkenyl ethers such as senyl ether, POP (2) dodecenyl ether, POE (2) octadecenyl ether, POP (1) octadecenyl ether; POE (2) dodecynyl ether, POE (2) Octadecynyl ether, POP (1) octade Such as polyoxyalkylene ethers of such vinyl ether and the like. The number in parentheses is the average number of moles added.

  As the isophorone diisocyanate-aliphatic alcohol adduct, a compound having a structure represented by the following formula (1d) is preferable.

In formula (1d), R ^1d and R ^4d are each independently a hydrocarbon group having 8 to 22 carbon atoms. R ^2d and R ^3d are each independently a hydrocarbon group having 2 to 4 carbon atoms. nd and md mean the average number of added moles, and are each independently 0 to 5, preferably 0 to 3.
If R ^1d and R ^4d have 8 or more carbon atoms, the thermal stability of the isophorone diisocyanate-aliphatic alcohol adduct can be maintained satisfactorily, so that a sufficient anti-fusing effect can be obtained in the flameproofing step. On the other hand, if the carbon number of the hydrocarbon group is 22 or less, the viscosity of the isophorone diisocyanate-aliphatic alcohol adduct does not become too high and is difficult to solidify, so that the oil agent contains an isophorone diisocyanate-aliphatic alcohol adduct that is an oil agent. An emulsion of the composition can be easily prepared, and the oil agent uniformly adheres to the precursor fiber bundle. 11-22 are preferable and, as for carbon number of a hydrocarbon group, 15-22 are more preferable.

The compound having the structure represented by the above formula (1d) is an isophorone diisocyanate-aliphatic alcohol adduct obtained by reacting isophorone diisocyanate with a monovalent aliphatic alcohol having 8 to 22 carbon atoms or a polyoxyalkylene ether thereof. is there.
Therefore, R ^1d and R ^4d in formula (1d) are derived from a monovalent aliphatic alcohol having 8 to 22 carbon atoms, and may be any of an alkyl group, alkenyl group, and alkynyl group having 8 to 22 carbon atoms, It may be linear or branched.
Examples of the alkyl group include n- and iso-octyl group, 2-ethylhexyl group, n- and iso-nonyl group, n- and iso-decyl group, n- and iso-undecyl group, n- and iso-dodecyl group. , N- and iso-tridecyl group, n- and iso-tetradecyl group, n- and iso-hexadecyl group, n- and iso-heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl, docosyl group, etc. It is done.
Examples of the alkenyl group include an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an icocenyl group, a heicocosenyl group, a dococenyl group, and a gadorail group. And 2-ethyldecenyl group and the like.
Examples of the alkynyl group include 1- and 2-octynyl groups, 1- and 2-noninyl groups, 1- and 2-decynyl groups, 1- and 2-undecynyl groups, 1- and 2-dodecynyl groups, 1- and 2 -Tridecynyl group, 1- and 2-tetradecynyl group, 1- and 2-hexadecynyl group, 1- and 2-octadecynyl group, 1- and 2-nonadecynyl group, 1- and 2-eicosinyl group, 1- and 2-henicosinyl Groups, and 1- and 2-docosinyl groups and the like.
R ^1d and R ^4d may have the same structure or may have independent structures.

On the other hand, —R ^2d O— and —R ^3d O— in formula (1d) are derived from the alkylene oxide of the polyoxyalkylene ether, and nd and md are derived from the added mole number of the alkylene oxide.
R ^2d and R ^3d are alkylene groups having 2 to 4 carbon atoms. Specifically, they are an ethylene group, a propylene group, and a butylene group. Preferably they are an ethylene group and a propylene group. R ^2d and R ^3d may have the same structure or may have independent structures.
As described above, nd and md indicate the addition amount of alkylene oxide. The polyalkylene oxide structure is not an essential structure, that is, nd and md may be 0. When introduced for the purpose of improving hydrophilicity and affinity with fibers, nd and md can each be added up to 5 mol.

Isophorone diisocyanate-aliphatic alcohol adduct includes 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = isocyanate (isophorone diisocyanate), monovalent aliphatic alcohol having 8 to 22 carbon atoms and polyoxyalkylene ether thereof. It can be obtained by reacting one or more compounds selected from the group consisting of compounds in the presence of no catalyst or a known urethane-bonded catalyst. The reaction is preferably performed in an inert gas atmosphere. The reaction temperature is preferably 70 to 150 ° C, more preferably 80 to 130 ° C.
The molar ratio of the isophorone diisocyanate to be used for the reaction to one or more compounds selected from the group consisting of monovalent aliphatic alcohols having 8 to 22 carbon atoms and polyoxyalkylene ether compounds thereof is 1 mol of isophorone diisocyanate. The compound is preferably 1.8 to 2.2 mol, more preferably 1.9 to 2.1 mol.

<Combination>
The oil agent of the present invention contains two or more compounds selected from the group consisting of the aforementioned groups A, B, C, D, E, and F, and among these, the compound A and / or group selected from the group A It is preferable from the viewpoint of the strand strength of the obtained carbon fiber bundle that the compound F selected from F is included as an essential component. More preferable combinations include Compound A and Compound B, Compound A and Compound C, Compound A and Compound E, Compound A and Compound F, Compound F and Compound B, Compound F and Compound B from the viewpoint of the strand strength of the carbon fiber bundle. C, the combination containing the compound F and the compound D, the compound F and the compound E is mentioned.
Further, the oil agent of the present invention preferably contains Group C in that it is stable and easily remains on the surface of the precursor fiber bundle without scattering in the flameproofing step, and a carbon fiber bundle having excellent mechanical properties is obtained. It is preferable that the group E is included because it is easy to be formed.
From these viewpoints, it is more preferable to include two or more compounds selected from the group consisting of groups A, C, E, and F. Again, this means that the compound is selected from two or more different groups.
When the oil agent of the present invention contains two kinds of compounds, the mass ratio of the two kinds of selected compounds is preferably 1/3 to 3/1 from the viewpoint of the strand strength of the obtained carbon fiber bundle, and is preferably 1/2 to 2/1 is more preferable.
The oil agent of the present invention preferably contains 2 to 4 compounds, and more preferably contains 2 to 3 compounds.

<Usage form of oil agent>
The oil agent of the present invention is mixed with a surfactant or the like to form an oil agent composition, and is preferably applied to the precursor fiber bundle in a form in which the oil agent composition is dispersed in water. Can be applied to fiber bundles.

[Oil agent composition for carbon fiber precursor acrylic fiber]
The oil agent composition for acrylic fibers for carbon fiber precursor of the present invention (hereinafter also simply referred to as “oil agent composition”) contains the above-described oil agent of the present invention and a nonionic surfactant.
20-150 mass parts is preferable with respect to 100 mass parts of oil agents, and, as for content of a nonionic surfactant, 20-100 mass parts is more preferable. If content of a nonionic surfactant is 20 mass parts or more, it will be easy to emulsify and stability of an emulsion will become favorable. On the other hand, if content of a nonionic surfactant is 150 mass parts or less, it can suppress that the convergence property of the precursor fiber bundle to which the oil agent composition adheres falls. In addition, the mechanical properties of the carbon fiber bundle obtained by firing the precursor fiber bundle are unlikely to decrease.

Various known substances can be used as the nonionic surfactant. For example, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, aliphatic ethylene oxide adduct, polyhydric alcohol aliphatic ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, aliphatic amide ethylene oxide adduct, fat and oil Polyethylene glycol type nonionic surfactants such as ethylene oxide adduct and polypropylene glycol ethylene oxide adduct; aliphatic ester of glycerol, aliphatic ester of pentaerythritol, aliphatic ester of sorbitol, aliphatic ester of sorbitan, Examples thereof include polyhydric alcohol type nonionic surfactants such as aliphatic esters of sugars, alkyl ethers of polyhydric alcohols, and fatty acid amides of alkanolamines.
These nonionic surfactants may be used alone or in combination of two or more.

  As the nonionic surfactant, a block copolymer type polyether composed of a propylene oxide (PO) unit and an ethylene oxide (EO) unit represented by the following formula (1e) and / or represented by the following formula (2e) Polyoxyethylene alkyl ethers comprising EO units are particularly preferred.

In formula (1e), R ^1e and R ^2e are each independently a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. The hydrocarbon group may be linear or branched.
R ^1e and R ^2e are determined in consideration of the balance with EO and PO, and other components of the oil composition, but a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms Preferably, it is a hydrogen atom.

In formula (1e), x and z represent the average added mole number of EO, and y represents the average added mole number of PO.
x, y, and z are each independently 1 to 500, preferably 20 to 300.
Moreover, it is preferable that ratio (x + z: y) of the sum of x and z and y is 90: 10-60: 40.

Further, the block copolymer type polyether preferably has a number average molecular weight of 3000 to 20000. If the number average molecular weight is within the above range, it is possible to have both thermal stability and dispersibility in water required for an oil composition.
Further, the block copolymer type polyether preferably has a kinematic viscosity at 100 ° C. of 300 to 15000 mm ² / s. If the kinematic viscosity is within the above range, the permeation of the oil composition into excess fibers is prevented, and in the drying step after application to the precursor fiber bundle, the single fiber is fed to the transport roller or the like due to the viscosity of the oil composition. Process failure such as wrapping around is less likely to occur.

  The kinematic viscosity of the block copolymer type polyether is a value measured in accordance with “Viscosity of liquid—Measurement method” defined in JIS-Z-8803, or ASTM D 445-46T. It can be measured using a Ubbelohde viscometer.

On the other hand, in the formula (2e), R ^3e is a hydrocarbon group having 10 to 20 carbon atoms. When the number of carbon atoms is less than 10, the thermal stability of the oil composition is likely to be lowered, and appropriate lipophilicity is hardly exhibited. On the other hand, when carbon number exceeds 20, the viscosity of an oil agent composition may become high, or an oil agent composition may solidify, and operativity may fall. In addition, the balance with the hydrophilic group is deteriorated, and the emulsification performance may be lowered.

The hydrocarbon group for R ^3e is preferably a saturated hydrocarbon group such as a saturated chain hydrocarbon group or a saturated cyclic hydrocarbon group, specifically a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, Examples include pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
Among these, in order to efficiently emulsify the oil agent composition, a dodecyl group is particularly preferable in terms of imparting an appropriate lipophilicity that is easily adapted to other oil agent composition components.

In formula (2e), r shows the average addition mole number of EO, is 3-20, 5-15 are preferable and 5-10 are more preferable. When r is less than 3, it becomes difficult to become familiar with water, and it becomes difficult to obtain emulsification performance. On the other hand, when r exceeds 20, the viscosity increases, and when used as a constituent component of the oil composition, the fiber separation property of the precursor fiber bundle to which the obtained oil composition is attached tends to be lowered.
Note that R ^3e is an element involved in the lipophilicity of the oil composition, and r is an element involved in the hydrophilicity of the oil composition. Therefore, the value of r is appropriately determined ^depending on the combination with R ^3e .

  As the nonionic surfactant, a commercially available product can be used. For example, “New Pole PE-128” manufactured by Sanyo Chemical Industries, Ltd. as the nonionic surfactant represented by the formula (1e); As the nonionic surfactant represented by (2e), “Emulgen 109P” manufactured by Kao Corporation is suitable.

The oil composition of the present invention preferably further contains an antioxidant.
1-5 mass parts is preferable with respect to 100 mass parts of oil agents, and, as for content of antioxidant, 1-3 mass parts is more preferable. When the content of the antioxidant is 1 part by mass or more, the antioxidant effect is sufficiently obtained. On the other hand, if content of antioxidant is 5 mass parts or less, antioxidant will become easy to disperse | distribute uniformly in an oil agent composition.

Various known substances can be used as the antioxidant, and phenol-based and sulfur-based antioxidants are preferable.
Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, 4,4′-butylidenebis- (6-t-butyl-3-methylphenol), 2,2′- Methylene bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene bis- (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methyl) Eniru) propionate], tris (3,5-di -t- butyl-4-hydroxybenzyl) isocyanurate.
Specific examples of the sulfur-based antioxidant include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, and ditridecyl thiodipropionate.
These antioxidants may be used alone or in combination of two or more.

Furthermore, the oil agent composition of the present invention may contain an antistatic agent as necessary for the purpose of improving its properties.
A known substance can be used as the antistatic agent. Antistatic agents are roughly classified into ionic types and nonionic types, and ionic types include anionic, cationic and amphoteric, and nonionic types include polyethylene glycol type and polyhydric alcohol type. From the viewpoint of antistatic, ionic type is preferable, among them aliphatic sulfonate, higher alcohol sulfate ester salt, higher alcohol ethylene oxide adduct sulfate ester, higher alcohol phosphate ester salt, higher alcohol ethylene oxide adduct sulfate phosphate ester salt, Quaternary ammonium salt type cationic surfactants, betaine type amphoteric surfactants, higher alcohol ethylene oxide adducts polyethylene glycol fatty acid esters, polyhydric alcohol fatty acid esters and the like are preferably used.
These antistatic agents may be used alone or in combination of two or more.

Further, the oil agent composition of the present invention is an antifoaming agent for the purpose of improving the stability of the process, the stability of the oil agent composition, and the adhesion characteristics depending on the equipment and use environment for adhering to the precursor fiber bundle. Further, additives such as preservatives, antibacterial agents and penetrants may be contained.
In addition, the oil agent composition of this invention may contain well-known oil agents (for example, aliphatic ester, amino modified silicone, etc.) other than the oil agent of this invention within the range which does not impair the effect of this invention. However, in consideration of suppressing the formation of silicon compounds, it is preferable not to contain a silicone-based oil such as amino-modified silicone. In the total oil agent, the content of the oil agent of the present invention is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.

The oil composition of the present invention described above includes a specific hydroxybenzoic acid ester (compound A), a specific cyclohexanedicarboxylic acid ester (compounds B and C), a specific cyclohexanedimethanol ester and / or a cyclohexanediol ester (compound D). , E), containing the oil agent of the present invention containing two or more compounds selected from the group consisting of specific isophorone diisocyanate-aliphatic alcohol adducts (compound F), thereby maintaining the convergence in the flameproofing step. Meanwhile, fusion between single fibers can be effectively prevented. In addition, since generation of silicon compounds and scattering of silicon degradation products can be suppressed, operability and process passability are remarkably improved, and industrial productivity can be maintained. Therefore, it is possible to obtain a carbon fiber bundle having excellent mechanical properties by a stable continuous operation.
Thus, according to the oil agent and oil agent composition of the present invention, there are problems of conventional oil agent compositions mainly composed of silicone, and problems of oil agent compositions in which the silicone content is reduced or only non-silicone components are included. Can be solved together.

The oil agent composition of the present invention is preferably applied to the precursor fiber bundle in a form dispersed in water.
Hereinafter, an example of a method for producing a carbon fiber precursor acrylic fiber bundle by treating a precursor fiber bundle with an oil using the oil composition of the present invention will be described.

<Method for producing carbon fiber precursor acrylic fiber bundle>
The carbon fiber precursor acrylic fiber bundle is obtained by, for example, applying the oil agent composition of the present invention to a precursor fiber bundle in a water-swollen state (oil agent treatment), and then drying and densifying the precursor fiber bundle treated with the oil agent. can get.

As the precursor fiber bundle used in the present invention, an acrylic fiber bundle spun by a known technique can be used. Specifically, an acrylic fiber bundle obtained by spinning an acrylonitrile polymer can be used.
The acrylonitrile-based polymer is a polymer obtained by polymerizing acrylonitrile as a main monomer. The acrylonitrile-based polymer may be a homopolymer obtained only from acrylonitrile, or may be an acrylonitrile-based copolymer in which other monomers are used in addition to the main component acrylonitrile.

  The content of the acrylonitrile unit in the acrylonitrile-based copolymer is 96.0 to 98.5% by mass to prevent heat fusion of the fiber in the firing step, heat resistance of the copolymer, stability of the spinning dope, And more preferable from the viewpoint of the quality of the carbon fiber. When the acrylonitrile unit is 96% by mass or more, it is preferable because excellent quality and performance of the carbon fiber can be maintained without inducing the thermal fusion of the fiber in the firing step when converting to the carbon fiber. In addition, the heat resistance of the copolymer itself is not lowered, and adhesion between single fibers can be avoided in spinning the precursor fiber or in a process such as fiber drying or drawing with a heating roller or pressurized steam. On the other hand, when the acrylonitrile unit is 98.5% by mass or less, the solubility in the solvent is not lowered, the stability of the spinning stock solution can be maintained, and the precipitation solidification property of the copolymer is not increased. This is preferable because stable production of body fibers is possible.

As a monomer other than acrylonitrile in the case of using a copolymer, it can be appropriately selected from vinyl monomers copolymerizable with acrylonitrile, and acrylic acid or methacrylic acid having an action of promoting flameproofing reaction. , Itaconic acid, or an alkali metal salt or ammonium salt thereof, or a monomer such as acrylamide is preferable because flame resistance can be promoted.
As the vinyl monomer copolymerizable with acrylonitrile, carboxyl group-containing vinyl monomers such as acrylic acid, methacrylic acid and itaconic acid are more preferable. The content of the carboxyl group-containing vinyl monomer unit in the acrylonitrile copolymer is preferably 0.5 to 2.0% by mass.
These vinyl monomers may be used alone or in combination of two or more.

  At the time of spinning, an acrylonitrile-based polymer is dissolved in a solvent to obtain a spinning dope. The solvent used here can be appropriately selected from known solvents such as organic solvents such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, and aqueous inorganic compounds such as zinc chloride and sodium thiocyanate. Among these, dimethylacetamide, dimethylsulfoxide and dimethylformamide having a high coagulation rate are preferable from the viewpoint of improving productivity, and dimethylacetamide is more preferable.

Further, in order to obtain a dense coagulated yarn, it is preferable to prepare the spinning dope so that the polymer concentration of the spinning dope becomes a certain level or more. Specifically, it is preferably prepared so that the polymer concentration in the spinning dope is 17% by mass or more, and more preferably 19% by mass or more.
Since the spinning dope requires proper viscosity and fluidity, the polymer concentration is preferably within a range not exceeding 25% by mass.

  As the spinning method, known methods such as a wet spinning method in which the above-described spinning solution is directly spun into a coagulation bath, a dry spinning method in which the solution is coagulated in air, and a dry and wet spinning method in which the solution is once coagulated in the air and then coagulated in the bath. A spinning method can be appropriately employed, but a wet spinning method or a dry-wet spinning method is preferable for obtaining a carbon fiber bundle having higher performance.

The spinning shaping by the wet spinning method or the dry and wet spinning method can be performed by spinning the spinning solution into a coagulation bath from a nozzle having a hole having a circular cross section. As the coagulation bath, it is preferable to use an aqueous solution containing a solvent used in the spinning dope from the viewpoint of easy solvent recovery.
When an aqueous solution containing a solvent is used as the coagulation bath, the solvent concentration in the aqueous solution is such that there is no void and a dense structure can be formed to obtain a high-performance carbon fiber bundle, and stretchability can be ensured and productivity is excellent. From 50 to 85 mass%, the temperature of the coagulation bath is preferably 10 to 60 ° C.

A coagulated yarn obtained by dissolving a polymer or copolymer in a solvent and discharging into a coagulation bath as a spinning dope into a fiber can be stretched in a coagulation bath or in a stretching bath. . Alternatively, it may be partially stretched in the air and then stretched in a bath, and the precursor fiber bundle in a water-swelled state can be obtained by washing with water before or after stretching or simultaneously with stretching.
Stretching in the bath is usually carried out in a water bath at 50 to 98 ° C. by dividing it into multiple stages once or twice, and the coagulated yarn so that the total ratio of in-air stretching and stretching in the bath becomes 2 to 10 times. It is preferable from the viewpoint of the performance of the obtained carbon fiber bundle.

For the application of the oil agent to the precursor fiber bundle, the oil agent treatment liquid for the carbon fiber precursor acrylic fiber (hereinafter simply referred to as “oil agent treatment liquid”) in which the oil agent composition containing the oil agent of the present invention is dispersed in water. It is preferable to use the notation. The average particle size of the emulsified particles at the time of dispersion is preferably 0.01 to 0.3 μm.
If the average particle diameter of the emulsified particles is within the above range, the oil agent can be more uniformly applied to the surface of the precursor fiber bundle.
In addition, the average particle diameter of the emulsified particles in the oil treatment liquid can be measured using a laser diffraction / scattering particle size distribution analyzer (“LA-910” manufactured by Horiba, Ltd.).

The oil agent treatment liquid can be prepared, for example, as follows.
The oil agent of the present invention and a nonionic surfactant are mixed to obtain an oil agent composition, and water is added while stirring this to obtain an emulsion (aqueous emulsion) in which the oil agent composition is dispersed in water.
When the antioxidant is contained, it is preferable to dissolve the antioxidant in the oil beforehand.
Each component can be mixed or dispersed in water using a propeller, a homomixer, a homogenizer, or the like. In particular, when preparing an aqueous emulsion using an oil composition having a high viscosity, it is preferable to use an ultra-high pressure homogenizer that can be pressurized to 150 MPa or more.

  2-40 mass% is preferable, as for the density | concentration of the oil agent composition in an aqueous emulsion, 10-30 mass% is more preferable, and 20-30 mass% is especially preferable. When the concentration of the oil agent composition is 2% by mass or more, a necessary amount of the oil agent is easily applied to the precursor fiber bundle in the water-swelled state. On the other hand, when the concentration of the oil composition is 40% by mass or less, the stability of the aqueous emulsion is excellent.

The obtained aqueous emulsion can be used as it is as an oil treatment liquid, but it is preferable to use a solution obtained by further diluting the aqueous emulsion until a predetermined concentration is obtained.
The “predetermined concentration” is adjusted according to the state of the precursor fiber bundle during the oil agent treatment.

Application of the oil agent to the precursor fiber bundle can be performed by attaching an oil agent treatment liquid to the precursor fiber bundle in a water-swollen state after stretching in the bath described above.
When washing is performed after stretching in the bath, the oil agent treatment liquid can be adhered to the fiber bundle in a water-swelled state obtained after stretching and washing in the bath.

As a method of attaching the oil treatment liquid to the precursor fiber bundle in the water-swelled state, the lower part of the roller is immersed in the oil treatment liquid, and the precursor fiber bundle is brought into contact with the upper part of the roller. The guide adhesion method in which the oil agent treatment liquid is discharged from the guide and the precursor fiber bundle is brought into contact with the guide surface, the spray adhesion method in which a predetermined amount of the oil agent treatment liquid is sprayed onto the precursor fiber bundle from the nozzle, and the oil agent treatment liquid A known method such as a dip attachment method in which the precursor fiber bundle is dipped in and then squeezed with a roller or the like to remove the excess oil agent treatment liquid can be used.
Among these methods, from the viewpoint of uniform adhesion, the dip adhesion method in which the oil agent treatment liquid is sufficiently infiltrated into the precursor fiber bundle and the excess treatment liquid is removed is preferable. In order to adhere more uniformly, it is also effective to make the oil agent treatment step into two or more multi-stages and repeatedly apply them.

The precursor fiber bundle to which the oil agent is applied is dried and densified in a subsequent drying step.
The temperature for drying and densification needs to be performed at a temperature exceeding the glass transition temperature of the fiber, but may be substantially different depending on the dry state from the water-containing state. For example, it is preferable to perform dense drying by a method using a heating roller having a temperature of about 100 to 200 ° C. At this time, the number of heating rollers may be one or plural.

The densely dried precursor fiber bundle is preferably subjected to pressurized steam drawing by a heating roller. By the pressurized steam drawing treatment, the denseness and orientation degree of the obtained carbon fiber precursor acrylic fiber bundle can be further increased.
Here, pressurized steam stretching is a method of stretching in a pressurized steam atmosphere. Since the pressurized steam drawing can be drawn at a high magnification, stable spinning can be performed at a higher speed, and at the same time, it contributes to improving the denseness and orientation degree of the resulting fiber.

  In the pressurized steam stretching process, it is preferable to control the temperature of the heating roller immediately before the pressurized steam stretching apparatus to 120 to 190 ° C., and the variation rate of the steam pressure in the pressurized steam stretching to 0.5% or less. By controlling the variation rate of the temperature of the heating roller and the water vapor pressure in this way, it is possible to suppress the variation of the draw ratio made on the fiber bundle and the variation of the tow fineness generated thereby. When the temperature of the heating roller is less than 120 ° C., the temperature of the precursor fiber bundle is not sufficiently increased, and the drawability tends to be lowered.

  The pressure of water vapor in the pressurized steam stretching is preferably 200 kPa · g (gauge pressure, the same shall apply hereinafter) or more so that the stretching by the heating roller and the characteristics of the pressurized steam stretching method appear clearly. The water vapor pressure is preferably adjusted as appropriate in consideration of the treatment time, but if the pressure is high, leakage of water vapor may increase. Therefore, it is preferably about 600 kPa · g or less industrially.

  The carbon fiber precursor acrylic fiber bundle obtained through the drying densification treatment and the secondary stretching treatment with a heating roller is passed through a roller at room temperature, cooled to room temperature, and then wound around a bobbin with a winder or transferred to a can. Rarely stored.

In the carbon fiber precursor acrylic fiber bundle thus obtained, the oil agent composition is preferably attached in an amount of 0.3 to 2.0% by mass, more preferably 0.6 to 1% with respect to the dry fiber mass. 0.5% by mass. In order to fully express the original function of the oil composition, the amount of the oil composition to be deposited is preferably 0.3% by mass or more. From the viewpoint of suppressing the cause of adhesion between the oil agent composition, the amount of the oil composition is preferably 2.0% by mass or less.
Here, “dry fiber mass” refers to the dry fiber mass of the precursor fiber bundle after the dry densification treatment.

The adhesion amount of the oil composition is determined as follows.
In accordance with the Soxhlet extraction method using methyl ethyl ketone, the methyl ethyl ketone heated and vaporized at 90 ° C. was brought into contact with the carbon fiber precursor acrylic fiber bundle for 8 hours while being refluxed to extract the oil composition and dried at 105 ° C. for 2 hours before extraction. The mass W _{1 of} the carbon fiber precursor acrylic fiber bundle and the mass W ₂ of the carbon fiber precursor acrylic fiber bundle dried at 105 ° C. for 2 hours after extraction were measured, respectively, and the adhesion amount of the oil composition by the following formula (i) Ask for.
Adhesion amount (mass%) of oil agent composition = (W ₁ −W ₂ ) / W ₁ × 100 (i)

  Further, the carbon fiber precursor acrylic fiber bundle preferably has 1000 to 300,000 filaments, more preferably 3000 to 200000, and further preferably 12000 to 100000. When the number of filaments is less than 1000, production efficiency tends to deteriorate. On the other hand, if the number of filaments is more than 300,000, it may be difficult to obtain a uniform carbon fiber precursor acrylic fiber bundle.

  In addition, the larger the single fiber fineness of the carbon fiber precursor acrylic fiber bundle, the larger the fiber diameter of the resulting carbon fiber bundle, which suppresses buckling deformation under compressive stress when used as a reinforcing fiber for composite materials. Therefore, it is preferable that the single fiber fineness is larger from the viewpoint of improving the compressive strength. However, as the single fiber fineness is larger, firing spots are generated in the flameproofing step described later, which is not preferable from the viewpoint of uniformity. In view of these factors, the single fiber fineness of the carbon fiber precursor acrylic fiber bundle is preferably 0.6 to 3 dTex, more preferably 0.7 to 2.5 dTex, and still more preferably 0.8 to 2. 0.0 dTex.

The carbon fiber precursor acrylic fiber bundle is transferred to a firing step, subjected to flame resistance, carbonization, and graphitization and surface treatment as necessary to form a carbon fiber bundle.
In the flameproofing step, the carbon fiber precursor acrylic fiber bundle is heat-treated in an oxidizing atmosphere to be converted into a flameproof fiber bundle.
As flameproofing conditions, heating is performed in an oxidizing atmosphere under tension of 200 to 300 ° C. until the density is preferably 1.28 to 1.42 g / cm ³ , more preferably 1.29 to 1.40 g / cm ^3. It is good to do. When the density is less than 1.28 g / cm ³ , adhesion between single fibers is likely to occur in the next carbonization step, and yarn breakage occurs in the carbonization step. Moreover, in order to make a density larger than 1.42 g / cm < ³ >, a flameproofing process becomes long and is unpreferable from the surface of economical efficiency. As the atmosphere, a known oxidizing atmosphere such as air, oxygen, and nitrogen dioxide can be adopted, but air is preferable from the viewpoint of economy.

  The apparatus for performing the flameproofing treatment is not particularly limited, but a conventionally known hot air circulating furnace or a method of contacting with a heated solid surface can be employed. Usually, in a flameproofing furnace (hot-air circulating furnace), the carbon fiber precursor acrylic fiber bundle that has entered the flameproofing furnace is once taken out of the flameproofing furnace, and then turned by a folding roll disposed outside the flameproofing furnace. A method of turning back and repeatedly passing through the flameproofing furnace is employed. Moreover, in the method of making it contact with the heating solid surface, the method of making it contact intermittently is taken.

The flame resistant fiber bundle is continuously led to the carbonization process.
In the carbonization step, the flame-resistant fiber bundle is carbonized under an inert atmosphere to obtain a carbon fiber bundle.
Carbonization is performed in an inert atmosphere with a maximum temperature of 1000 ° C. or higher. The gas forming the inert atmosphere may be any inert gas such as nitrogen, argon, helium, etc., but nitrogen is preferably used from the economical aspect.
In the initial stage of the carbonization process, that is, at a processing temperature of 300 to 400 ° C., the polyacrylonitrile copolymer that is a component of the fiber is cut and crosslinked. In this temperature range, it is preferable to increase the fiber temperature gently at a temperature increase rate of 300 ° C./min or less in order to improve the mechanical properties of the finally obtained carbon fiber bundle.
Further, at a treatment temperature of 400 to 900 ° C., the polyacrylonitrile copolymer is thermally decomposed, and a carbon structure is gradually constructed. In the stage of constructing the carbon structure, regular orientation of the carbon structure is promoted, and therefore, it is preferable to perform the treatment while stretching under tension. Therefore, in order to control the temperature gradient and stretching (tension) at 900 ° C. or lower, it is more preferable to install a pre-process (pre-carbonization process) separately from the final carbonization process.

  When the treatment temperature is 900 ° C. or higher, the remaining nitrogen atoms are desorbed and the carbonaceous structure develops, so that the entire fiber contracts. Even in such a heat treatment in a high temperature region, it is preferable to perform the treatment under tension in order to develop good mechanical properties of the final carbon fiber.

The carbon fiber bundle thus obtained may be subjected to graphitization treatment as necessary. The graphitization treatment further increases the elasticity of the carbon fiber bundle.
The graphitization is preferably carried out in an inert atmosphere having a maximum temperature of 2000 ° C. or higher while extending in the range of 3 to 15%. When the elongation is less than 3%, it is difficult to obtain a highly elastic carbon fiber bundle (graphitized fiber bundle) having sufficient mechanical properties. This is because when a carbon fiber bundle having a predetermined elastic modulus is to be obtained, a higher processing temperature is required for a condition with a lower elongation rate. On the other hand, when the elongation rate exceeds 15%, the difference in the effect of promoting the growth of the carbon structure due to elongation becomes large between the surface layer and the inside, thereby forming a non-uniform carbon fiber bundle and lowering the physical properties.

The carbon fiber bundle after the firing step is preferably subjected to a surface treatment so as to suit the final use.
Although there is no restriction | limiting in the method of surface treatment, The method of electrolytic oxidation in an electrolyte solution is preferable. In the electrolytic oxidation, oxygen is generated on the surface of the carbon fiber bundle to introduce oxygen-containing functional groups on the surface, thereby performing surface modification treatment.
As the electrolyte, acids such as sulfuric acid, hydrochloric acid and nitric acid and salts thereof can be used.
As conditions for electrolytic oxidation, the temperature of the electrolytic solution is preferably room temperature or lower, the electrolyte concentration is 1 to 15% by mass, and the amount of electricity is 100 coulomb / g or lower.

The carbon fiber precursor acrylic fiber bundle obtained by the above-described method is excellent in convergence because the oil agent of the present invention is adhered thereto. Furthermore, since fusion between single fibers can be prevented in the firing process, and generation of silicon compounds and scattering of silicone degradation products can be suppressed, operability and process passability are significantly improved, and industrial productivity can be maintained. . Therefore, a carbon fiber bundle having excellent mechanical properties can be obtained with high productivity.
Moreover, the carbon fiber bundle obtained by firing this carbon fiber precursor acrylic fiber bundle is excellent in mechanical properties, high quality, and suitable as a reinforcing fiber used in fiber reinforced resin composite materials used in various structural materials. It is.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these.
Each component used in this example, various measurement methods, and evaluation methods are as follows.

[component]
<Hydroxybenzoic acid ester>
A-1: ester compound composed of 4-hydroxybenzoic acid and oleyl alcohol (molar ratio 1.0: 1.0) (an ester having the structure of the above formula (1a), wherein R ^1a is an octadecenyl group (oleyl group) Compound)

(Synthesis method of A-1)
In a 1 L four-necked flask, 207 g (1.5 mol) of 4-hydroxybenzoic acid, 486 g (1.8 mol) of oleyl alcohol, and 0.69 g (0.1% by mass) of tin octylate as a catalyst were weighed. Then, under nitrogen blowing, an esterification reaction was performed at 200 ° C. for 6 hours and further at 220 ° C. for 5 hours.
Then, excess alcohol was removed while blowing steam under a reduced pressure of 230 ° C. and 666.61 Pa, cooled to 70-80 ° C., 0.43 g of 85 mass% phosphoric acid was added, and stirring was continued for 30 minutes, followed by filtration. To obtain A-1.

<Cyclohexanedicarboxylic acid ester>
B-1: ester compound composed of 1,4-cyclohexanedicarboxylic acid and oleyl alcohol (molar ratio 1.0: 2.0) (in the structure of the above formula (1b), R ^1b and R ^2b are both oleyl groups) Some ester compounds)
An ester compound composed of C-1: 1,4-cyclohexanedicarboxylic acid, oleyl alcohol, and 3-methyl 1,5-pentanediol (molar ratio 2.0: 2.0: 1.0) (formula (2b)) Ester compound in which R ^3b and R ^5b are both oleyl groups and R ^4b is —CH ₂ CH ₂ CHCH ₃ CH ₂ CH ₂ —

(Method for synthesizing B-1 and C-1)
B-1;
In a 1 L four-necked flask, 180 g (0.9 mol) of methyl 1,4-cyclohexanedicarboxylate (manufactured by Ogura Synthetic Co., Ltd.) and 486 g of oleyl alcohol (manufactured by Shin Nippon Chemical Co., Ltd., trade name: Rica Coal 90B) (1.8 mol) and 0.33 g of dibutyltin oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst were weighed and subjected to methanol removal reaction at 200 to 205 ° C. under nitrogen blowing. The amount of methanol distilled at this time was 57 g.
Then, it cooled to 70-80 degreeC, 85 mass% phosphoric acid (made by Wako Pure Chemical Industries Ltd.) 0.34g was added, stirring was continued for 30 minutes, it confirmed that the reaction system became cloudy, and also adsorbent (Kyowa). (Chemical Industry Co., Ltd., trade name: KYOWARD 600S) 1.1 g was added and stirred for 30 minutes, followed by filtration to obtain B-1.

C-1;
In a 1 L four-necked flask, 240 g (1.2 mol) of methyl 1,4-cyclohexanedicarboxylate (manufactured by Kokura Synthesis Co., Ltd.) and 324 g of oleyl alcohol (manufactured by Shin Nippon Chemical Co., Ltd., trade name: Rica Coal 90B) (1.2 mol), 70.8 g (0.6 mol) of 3-methyl-1,5-pentanediol (manufactured by Wako Pure Chemical Industries, Ltd.) and dibutyltin oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst ) 0.32 g was weighed and subjected to demethanol reaction at 200 to 205 ° C. under nitrogen blowing. The amount of methanol distilled at this time was 76 g.
Thereafter, the mixture was cooled to 70 to 80 ° C., 0.33 g of 85% by mass phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and stirring was continued for 30 minutes to confirm that the reaction system became cloudy. (Chemical Industry Co., Ltd., trade name: KYOWARD 600S) 1.1 g was added and stirred for 30 minutes, followed by filtration to obtain C-1.
In addition, although B-1 and C-1 mentioned above were synthesize | combined by the transesterification method by a demethanol reaction, they can also be obtained by esterification reaction from 1, 4- cyclohexanedicarboxylic acid and alcohol.

<Cyclohexanedimethanol ester / cyclohexanediol ester>
D-1: ester compound composed of 1,4-cyclohexanedimethanol and oleic acid (molar ratio 1.0: 2.0) (in the structure of the above formula (1c), R ^1c and R ^2c are both carbon atoms) Ester compound having 17 alkenyl groups (heptadecenyl group) and nc 1)
E-1: ester compound composed of 1,4-cyclohexanedimethanol, oleic acid, and dimer acid obtained by dimerizing oleic acid (molar ratio 1.0: 1.25: 0.375) (formula (2c R ^3c and R ^5c are both alkenyl groups having 17 carbon atoms (heptadecenyl group), and R ^4c is one hydrogen atom from the carbon atom of an alkenyl group having 34 carbon atoms (tetratriacontenyl group). Ester compound which is a substituted substituent and mc is 1)
D-2: ester compound composed of 1,4-cyclohexanedimethanol, oleic acid and caprylic acid (molar ratio 1.0: 0.5: 1.5) (in the structure of the above formula (1c), R ^1c is An ester compound which is a mixture of an alkenyl group having 17 carbon atoms (heptadecenyl group) and an alkyl group having 7 carbon atoms (n-heptyl group), R ^2c is a mixture of heptadecenyl group and n-heptyl group, and nc is 1 )

(Synthesis method of D-1, D-2, E-1)
D-1;
In a 1 L four-necked flask, 144 g (1.0 mol) of 1,4-cyclohexanedimethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 580 g of oleic acid (trade name: LUNAC OA, manufactured by Kao Corporation) 0.05) and 0.35 g of dibutyltin oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst were weighed and subjected to dehydration esterification reaction at 220 to 230 ° C. under nitrogen blowing. The reaction was continued until the acid value of the reaction system became 10 mgKOH / g or less.
Then, it cools to 70-80 degreeC, 85 mass% phosphoric acid (made by Wako Pure Chemical Industries Ltd.) 0.36g is added, stirring is continued for 30 minutes, It confirms that the reaction system became cloudy, and also adsorbent ( After adding 1.3 g of Kyowa Chemical Industry Co., Ltd. (trade name: KYOWARD 600S) and stirring for 30 minutes, filtration was performed to obtain Compound D-1.

D-2;
144 g (1.0 mol) of 1,4-cyclohexanedimethanol (manufactured by Wako Pure Chemical Industries, Ltd.), 145 g (0.5 mol) of oleic acid (trade name: Lunac OA, manufactured by Kao Corporation), and caprylic acid 216 g (1.5 mol) (trade name: Octanoic acid, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.35 g of dibutyltin oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst were weighed, and D- D-2 was obtained under the same conditions as in 1.

E-1;
In a 1 L four-necked flask, 144 g (1.0 mol) of 1,4-cyclohexanedimethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 350 g of oleic acid (trade name: LUNAC OA, manufactured by Kao Corporation) .25 mol), dimer acid (manufactured by Sigma Aldrich Japan Co., Ltd.) 213.8 g (0.375 mol) and 0.35 g of dibutyltin oxide (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst were weighed and blown with nitrogen E-1 was obtained under the same conditions as for D-1.

<Isophorone diisocyanate-aliphatic alcohol adduct>
F-1: 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = compound composed of isocyanate and oleyl alcohol (molar ratio 1.0: 2.0) (in the structure of the above formula (1d), R ^1d And R ^4d are both octadecenyl group (oleyl group), and both nd and md are 0)

(Method for synthesizing F-1)
In a 3 L four-necked flask, 1970 g (7.2 mol) of oleyl alcohol was weighed and stirred under a nitrogen atmosphere, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = isocyanate 800 g (3.6 mol). ) Was added dropwise at room temperature using a dropping funnel. Thereafter, the mixture was reacted at 100 ° C. for 10 hours to obtain F-1.

<Aromatic ester>
K-1: Triisodecyl trimellitate (trade name: Trimex T-10, manufactured by Kao Corporation)
-K-2: Polyoxyethylene bisphenol A lauric acid ester (product name: EXCEPARL BP-DL, manufactured by Kao Corporation)

<Chain aliphatic ester>
G-1: Pentaerythritol tetrastearate (Tokyo Chemical Industry Co., Ltd., product code: P0739)

<Non-ionic surfactant>
H-1: PO / EO block copolymer polyether (Sanyo Kasei Kogyo Co., Ltd.) having the structure of the above formula (1e), wherein ^x≈75 , ^y≈30 , ^z≈75, and R ^1e and R ^2e are both hydrogen atoms Product name: New Pole PE-68)
H-2: Polyoxyethylene lauryl ether having the structure of the above formula (2e), r≈9 and R ^3e being a lauryl group (Wako Pure Chemical Industries, Ltd., trade name: Nikkor BL-9EX)
H-3: polyoxyethylene lauryl ether having a structure of the above formula (2e), r≈7 and R ^3e being a lauryl group (Japan Emulsion Co., Ltd., trade name: EMALEX 707)

<Amino-modified silicone>
I-1: primary side chain amino-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-865)
I-2: Amino-modified silicone at both ends (Shin-Etsu Chemical Co., Ltd., trade name: KF-8012)

<Antistatic agent>
・ J-1: Dialkylethylmethylammonium etosulphate (manufactured by Lion Akzo Co., Ltd., trade name: Arcard 2HT-50ES)
J-2: Lauryltrimethylammonium chloride (Kao Corporation, trade name: Cotamin 24P)
J-3: N-ethyl N, N-dimethyl-9-octadecene-1-aminium (ethyl sulfate) anion (Hangzu Sage Chemical Co., Ltd.)

[Measurement / Evaluation]
<Measurement of oil adhesion amount>
After drying the carbon fiber precursor acrylic fiber bundle at 105 ° C. for 1 hour, the carbon fiber precursor acrylic fiber bundle was brought into contact with the carbon fiber precursor acrylic fiber bundle for 8 hours while refluxing the methyl ethyl ketone heated and vaporized to 90 ° C. in accordance with the Soxhlet extraction method using methyl ethyl ketone. Then, the attached oil agent composition was subjected to solvent extraction. Methyl ethyl ketone may be used in an amount sufficient to extract the oil composition attached to the carbon fiber precursor acrylic fiber bundle.
The mass W _{1 of} the carbon fiber precursor acrylic fiber bundle dried at 105 ° C. for 2 hours before extraction and the mass W ₂ of the carbon fiber precursor acrylic fiber bundle dried at 105 ° C. for 2 hours after extraction were measured, respectively. The adhesion amount of the oil composition was determined from (i). In addition, the measurement of oil agent adhesion amount confirms that the oil agent composition is provided to the precursor fiber bundle in an appropriate range in which the effect is expressed.

<Evaluation of convergence>
Observe the condition of the carbon fiber precursor acrylic fiber bundle on the final roller in the manufacturing process of the carbon fiber precursor acrylic fiber bundle, i.e., the roller immediately before winding the fiber bundle on the bobbin. The convergence was evaluated. The evaluation of convergence is to evaluate the quality of the carbon fiber precursor acrylic fiber bundle in consideration of the productivity of the carbon fiber precursor acrylic fiber bundle and the handling property in the subsequent carbonization step.
A: Converging, the tow width is constant, and it does not contact the adjacent fiber bundle.
B: Converged, but tow width is not constant or tow width is wide.
C: There is a space in the fiber bundle and it is not focused.

<Evaluation of operability>
When the carbon fiber precursor acrylic fiber bundle was continuously produced for 24 hours, the operability was evaluated based on the frequency with which the single fiber was wound around and removed from the transport roller. The evaluation criteria were as follows. In addition, the evaluation of operability is an index serving as a standard for stable production of the carbon fiber precursor acrylic fiber bundle.
A: The number of removals (times / 24 hours) is 1 or less.
B: The number of removals (times / 24 hours) is 2 to 5 times.
C: The number of removals (times / 24 hours) is 6 times or more.

<Measurement of the number of fusions between single fibers>
A carbon fiber bundle is cut into a length of 3 mm, dispersed in acetone, stirred for 10 minutes, and the total number of single fibers and the number of single fibers fused (number of fusions) are counted. The number of fusions per 100 pieces was calculated and evaluated according to the following evaluation criteria. The measurement of the number of fusions between single fibers evaluates the quality of the carbon fiber bundle.
A: The number of fusions (pieces / 100 pieces) is 1 or less.
C: The number of fusions (pieces / 100 pieces) is more than one.

<Measurement of strand strength>
Start production of carbon fiber bundles, sample carbon fiber bundles in a steady state, and measure strand strength of carbon fiber bundles according to the epoxy resin impregnated strand method specified in JIS-R-7608 did. The number of measurements was 10 times, and the average value was used as an evaluation target.

<Measurement of Si scattering amount>
The amount of silicon-derived silicon compound scattered in the flameproofing process was determined by measuring the silicon (Si) content of the carbon fiber precursor acrylic fiber bundle and the flameproofed fiber bundle obtained by flameproofing it by ICP emission spectrometry. The change in the amount of Si calculated from the above was taken as the amount of Si scattered in the flameproofing process (Si scattering amount) and used as an evaluation index.
Specifically, 50 mg of a sample obtained by finely pulverizing the carbon fiber precursor acrylic fiber bundle and the flameproof fiber bundle with a scissors was weighed into a sealed crucible, and 0.25 g of powdered NaOH and KOH were added to the muffle furnace. And then thermally decomposed at 210 ° C. for 150 minutes. This was dissolved in distilled water, and a constant volume of 100 mL was used as a measurement sample. The Si content of each measurement sample was determined by ICP emission analysis, and the amount of Si scattering was determined by the following formula (ii). As the ICP emission analyzer, “IRIS Advantage AP” manufactured by Thermo Electron Co., Ltd. was used.
Si scattering amount (mg / kg) = Si content of carbon fiber precursor acrylic fiber bundle−Si content of flameproof fiber bundle (ii)

[Example 1]
<Preparation of oil agent composition and oil treatment liquid>
The ester compound (A-1) and the ester compound (B-1) were mixed and stirred to prepare an oil agent. Nonionic surfactants (H-1, H-3) were added thereto, and mixed and stirred to prepare an oil agent composition.
After sufficiently stirring, ion-exchanged water was further added so that the concentration of the oil composition was 30% by mass and emulsified with a homomixer. The average particle size of the micelles in this state was measured using a laser diffraction / scattering particle size distribution analyzer (trade name: LA-910, manufactured by Horiba, Ltd.), and was about 3.0 μm.
Then, it further disperse | distributed until the average particle diameter of the micelle became 0.3 micrometer or less with the high voltage | pressure homogenizer, and obtained the aqueous emulsion (emulsion) of the oil agent composition. The obtained aqueous emulsion was further diluted with ion-exchanged water to prepare an oil agent treatment liquid having an oil agent composition concentration of 1.3% by mass.
Table 1 shows the types and amounts (% by mass) of the components in the oil composition.

<Manufacture of carbon fiber precursor acrylic fiber bundle>
The precursor fiber bundle to which the oil agent is adhered was prepared by the following method. An acrylonitrile copolymer (composition ratio: acrylonitrile / acrylamide / methacrylic acid = 96.5 / 2.7 / 0.8 (mass ratio)) is dispersed in dimethylacetamide at a ratio of 21 mass%, heated and dissolved to spin. A stock solution was prepared and discharged from a spinning nozzle having a pore diameter (diameter) of 50 μm and a pore number of 50000 into a coagulation bath at 38 ° C. filled with an aqueous dimethylacetamide solution having a concentration of 67% by mass to obtain a coagulated yarn. The coagulated yarn was desolvated in a water washing tank and stretched 3 times to obtain a precursor fiber bundle in a water swollen state.
A precursor fiber bundle in a water-swelled state was introduced into an oil agent treatment tank filled with the oil agent treatment liquid obtained earlier, and an oil agent was applied.
Thereafter, the precursor fiber bundle to which the oil agent was applied was dried and densified with a roller having a surface temperature of 150 ° C., and then stretched 5 times in water vapor at a pressure of 0.3 MPa to obtain a carbon fiber precursor acrylic fiber bundle. . The obtained carbon fiber precursor acrylic fiber bundle had 50,000 filaments and a single fiber fineness of 1.3 dTex.
The bundling property and operability in the production process were evaluated, and the oil agent adhesion amount of the obtained carbon fiber precursor acrylic fiber bundle was measured. The results are shown in Table 1.

<Manufacture of carbon fiber bundles>
The obtained carbon fiber precursor acrylic fiber bundle was passed through a flameproofing furnace having a temperature gradient of 220 to 260 ° C. over 40 minutes to make it flameproofed to obtain a flameproofed fiber bundle.
Subsequently, the flame-resistant fiber bundle was baked by passing it through a carbonization furnace having a temperature gradient of 400 to 1400 ° C. in a nitrogen atmosphere over 3 minutes to obtain a carbon fiber bundle.
The amount of Si scattering in the flameproofing process was measured. Further, the number of fusions between single fibers and the strand strength of the obtained carbon fiber bundle were measured. These results are shown in Table 1.

[Examples 2 to 7]
Except having changed the kind and compounding quantity of each component which comprise an oil agent composition as shown in Table 1, an oil agent composition and an oil agent process liquid were prepared like Example 1, and a carbon fiber precursor acrylic fiber bundle And carbon fiber bundles were manufactured, and each measurement and evaluation was performed. The results are shown in Table 1.
In addition, when adding an antistatic agent, it added, after emulsifying and refine | miniaturizing to a predetermined particle diameter.

  As is clear from Table 1, in the case of each example, the amount of oil agent adhered was an appropriate amount. In addition, the bundling property of the carbon fiber precursor acrylic fiber bundle and the operability of the production process are good, and in all of the examples, there are no problems in the process of continuously producing the carbon fiber bundle. There was no situation.

  In addition, the carbon fiber bundles obtained in each example had substantially no number of fusions between single fibers, showed a high strand strength, and were excellent in mechanical properties. Moreover, since no silicone was contained, there was substantially no amount of Si scattering in the firing step, and the process load in the firing step was small and good.

  In addition, the strand strength of the carbon fiber bundle showed a difference depending on the type and amount of components of the oil composition. Specifically, Example 3 containing 30% by mass of each of the ester compound (A-1) and the ester compound (C-1), 25% of each of the ester compound (A-1) and the ester compound (B-1). Example 6 containing 5%, and Example 7 containing 25% by mass of the ester compound (A-1) and the ester compound (C-1) each had particularly high strand strength of the carbon fiber bundle.

[Example 8]
<Preparation of oil agent composition and oil treatment liquid>
The ester compound (A-1) and the ester compound (D-1) were mixed and stirred to prepare an oil agent. Nonionic surfactants (H-1, H-3) were added thereto, and mixed and stirred to prepare an oil agent composition.
After sufficiently stirring, ion-exchanged water was further added so that the concentration of the oil composition was 30% by mass and emulsified with a homomixer. The average particle size of the micelles in this state was measured using a laser diffraction / scattering particle size distribution analyzer (trade name: LA-910, manufactured by Horiba, Ltd.), and was about 3.0 μm.
Then, it further disperse | distributed until the average particle diameter of the micelle became 0.3 micrometer or less with the high voltage | pressure homogenizer, and obtained the aqueous emulsion (emulsion) of the oil agent composition. The obtained aqueous emulsion was further diluted with ion-exchanged water to prepare an oil agent treatment liquid having an oil agent composition concentration of 1.3% by mass.
Table 2 shows the types and amounts (% by mass) of the components in the oil composition.
A carbon fiber precursor acrylic fiber bundle and a carbon fiber bundle were produced in the same manner as in Example 1 except that the obtained oil agent treatment liquid was used, and each measurement and evaluation were performed. The results are shown in Table 2.

[Examples 9 to 15]
Except having changed the kind and compounding quantity of each component which comprise an oil agent composition as shown in Table 2, an oil agent composition and an oil agent process liquid were prepared like Example 8, and a carbon fiber precursor acrylic fiber bundle And carbon fiber bundles were manufactured, and each measurement and evaluation was performed. The results are shown in Table 2.
In addition, when adding an antistatic agent, it added, after emulsifying and refine | miniaturizing to a predetermined particle diameter.

  As is apparent from Table 2, in the case of each example, the amount of oil agent adhered was an appropriate amount. In addition, the bundling property of the carbon fiber precursor acrylic fiber bundle and the operability of the production process are good, and in all of the examples, there are no problems in the process of continuously producing the carbon fiber bundle. There was no situation.

  In addition, the carbon fiber bundles obtained in each example had substantially no number of fusions between single fibers, showed a high strand strength, and were excellent in mechanical properties. Moreover, since no silicone was contained, there was substantially no amount of Si scattering in the firing step, and the process load in the firing step was small and good.

  In addition, the strand strength of the carbon fiber bundle showed a difference depending on the type and amount of components of the oil composition. Specifically, Example 10 containing 30% by mass of each of the ester compound (A-1) and the ester compound (E-1), 25% of each of the ester compound (A-1) and the ester compound (D-1). Example 13 containing 5% by weight, Example 14 containing 25% by weight of each of the ester compound (A-1) and the ester compound (E-1), and each of the ester compound (A-1) and the ester compound (D-2) In Example 15 containing 25% by mass, the strand strength of the carbon fiber bundle was particularly high.

[Example 16]
<Preparation of oil agent composition and oil treatment liquid>
The ester compound (A-1), ester compound (B-1), and isophorone diisocyanate-aliphatic alcohol adduct (F-1) were mixed and stirred to prepare an oil agent. Nonionic surfactants (H-1, H-3) were added thereto, and mixed and stirred to prepare an oil agent composition.
After sufficiently stirring, ion-exchanged water was further added so that the concentration of the oil composition was 30% by mass and emulsified with a homomixer. The average particle size of the micelles in this state was measured using a laser diffraction / scattering particle size distribution analyzer (trade name: LA-910, manufactured by Horiba, Ltd.), and was about 3.0 μm.
Then, it further disperse | distributed until the average particle diameter of the micelle became 0.3 micrometer or less with the high voltage | pressure homogenizer, and obtained the aqueous emulsion (emulsion) of the oil agent composition. The obtained aqueous emulsion was further diluted with ion-exchanged water to prepare an oil agent treatment liquid having an oil agent composition concentration of 1.3% by mass.
Table 3 shows the types and amounts (% by mass) of the components in the oil composition.
A carbon fiber precursor acrylic fiber bundle and a carbon fiber bundle were produced in the same manner as in Example 1 except that the obtained oil agent treatment liquid was used, and each measurement and evaluation were performed. The results are shown in Table 3.

[Examples 17 to 22]
Except having changed the kind and compounding quantity of each component which comprise an oil agent composition as shown in Table 3, an oil agent composition and an oil agent process liquid were prepared like Example 16, and a carbon fiber precursor acrylic fiber bundle And carbon fiber bundles were manufactured, and each measurement and evaluation was performed. The results are shown in Table 3.
In addition, when adding an antistatic agent, it added, after emulsifying and refine | miniaturizing to a predetermined particle diameter.

  As is apparent from Table 3, in the case of each example, the oil agent adhesion amount was an appropriate amount. In addition, the bundling property of the carbon fiber precursor acrylic fiber bundle and the operability of the production process are good, and in all of the examples, there are no problems in the process of continuously producing the carbon fiber bundle. There was no situation.

  In addition, the carbon fiber bundles obtained in each example had substantially no number of fusions between single fibers, showed a high strand strength, and were excellent in mechanical properties. Moreover, since no silicone was contained, there was substantially no amount of Si scattering in the firing step, and the process load in the firing step was small and good.

  In addition, the strand strength of the carbon fiber bundle showed a difference depending on the type and amount of components of the oil composition. Specifically, in Examples 19 to 22 in which the ester compound (A-1) and the isophorone diisocyanate-aliphatic alcohol adduct (F-1) have the same amount, the strand strength of the carbon fiber bundle was high. . Among them, the strand strength of the carbon fiber bundle of Example 20 containing 5% by mass of the antistatic agent (J-3) was particularly high.

[Example 23]
<Preparation of oil agent composition and oil treatment liquid>
The ester compound (A-1), the ester compound (D-1), and the isophorone diisocyanate-alcohol adduct (F-1) were mixed and stirred to prepare an oil agent. Nonionic surfactants (H-1, H-3) were added thereto, and mixed and stirred to prepare an oil agent composition.
After sufficiently stirring, ion-exchanged water was further added so that the concentration of the oil composition was 30% by mass and emulsified with a homomixer. The average particle size of the micelles in this state was measured using a laser diffraction / scattering particle size distribution measuring apparatus (trade name: LA-910, manufactured by Horiba, Ltd.), and was about 5.0 μm.
Then, it further disperse | distributed until the average particle diameter of the micelle became 0.3 micrometer or less with the high voltage | pressure homogenizer, and obtained the aqueous emulsion (emulsion) of the oil agent composition. The obtained aqueous emulsion was further diluted with ion-exchanged water to prepare an oil agent treatment liquid having an oil agent composition concentration of 1.3% by mass.
Table 4 shows the types and amounts (% by mass) of the components in the oil composition.
A carbon fiber precursor acrylic fiber bundle and a carbon fiber bundle were produced in the same manner as in Example 1 except that the obtained oil agent treatment liquid was used, and each measurement and evaluation were performed. The results are shown in Table 4.

[Examples 24-29]
An oil agent composition and an oil agent treatment liquid were prepared in the same manner as in Example 23 except that the types and blending amounts of the components constituting the oil agent composition were changed as shown in Table 4, and the carbon fiber precursor acrylic fiber bundle was prepared. And carbon fiber bundles were manufactured, and each measurement and evaluation was performed. The results are shown in Table 4.
In addition, when adding an antistatic agent, it added, after emulsifying and refine | miniaturizing to a predetermined particle diameter.

  As is apparent from Table 4, in the case of each example, the oil agent adhesion amount was an appropriate amount. In addition, the bundling property of the carbon fiber precursor acrylic fiber bundle and the operability of the production process are good, and in all of the examples, there are no problems in the process of continuously producing the carbon fiber bundle. There was no situation.

  In addition, the carbon fiber bundles obtained in each example had substantially no number of fusions between single fibers, showed a high strand strength, and were excellent in mechanical properties. Moreover, since no silicone was contained, there was substantially no amount of Si scattering in the firing step, and the process load in the firing step was small and good.

  In addition, the strand strength of the carbon fiber bundle showed a difference depending on the type and amount of components of the oil composition. Specifically, the ester compound (A-1) and the isophorone diisocyanate-alcohol adduct (F-1) have the same amount, and the ester compound (D-1), ester compound (E-1), ester Examples 25-29 in which any one of the compounds (D-2) has a blending amount equal to or greater than that of the ester compound (A-1) and the isophorone diisocyanate-alcohol adduct (F-1) are carbon fiber bundle strands The strength was high. Among them, the strand strength of the carbon fiber bundle of Example 27 containing a large amount of the nonionic surfactant and containing 5% by mass of the antistatic agent (J-3) was particularly high.

[Example 30]
<Preparation of oil agent composition and oil treatment liquid>
The oil agent was prepared by mixing and stirring the isophorone diisocyanate-alcohol adduct (F-1) and the ester compound (B-1). Nonionic surfactants (H-1, H-3) were added thereto, and mixed and stirred to prepare an oil agent composition.
After sufficiently stirring, ion-exchanged water was further added so that the concentration of the oil composition was 30% by mass and emulsified with a homomixer. The average particle size of the micelles in this state was measured using a laser diffraction / scattering particle size distribution measuring apparatus (trade name: LA-910, manufactured by Horiba, Ltd.), and was about 5.0 μm.
Then, it further disperse | distributed until the average particle diameter of the micelle became 0.3 micrometer or less with the high voltage | pressure homogenizer, and obtained the aqueous emulsion (emulsion) of the oil agent composition. The obtained aqueous emulsion was further diluted with ion-exchanged water to prepare an oil agent treatment liquid having an oil agent composition concentration of 1.3% by mass.
Table 5 shows the types and amounts (% by mass) of the components in the oil composition.
A carbon fiber precursor acrylic fiber bundle and a carbon fiber bundle were produced in the same manner as in Example 1 except that the obtained oil agent treatment liquid was used, and each measurement and evaluation were performed. The results are shown in Table 5.

[Examples 31 to 36]
An oil agent composition and an oil agent treatment liquid were prepared in the same manner as in Example 30 except that the types and blending amounts of the components constituting the oil agent composition were changed as shown in Table 5, and a carbon fiber precursor acrylic fiber bundle was prepared. And carbon fiber bundles were manufactured, and each measurement and evaluation was performed. The results are shown in Table 5.
In addition, when adding an antistatic agent, it added, after emulsifying and refine | miniaturizing to a predetermined particle diameter.

  As is apparent from Table 5, in the case of each example, the amount of oil agent adhered was an appropriate amount. In addition, the bundling property of the carbon fiber precursor acrylic fiber bundle and the operability of the production process are good, and in all of the examples, there are no problems in the process of continuously producing the carbon fiber bundle. There was no situation.

  In addition, the carbon fiber bundles obtained in each example had substantially no number of fusions between single fibers, showed a high strand strength, and were excellent in mechanical properties. Moreover, since no silicone was contained, there was substantially no amount of Si scattering in the firing step, and the process load in the firing step was small and good.

  In addition, the strand strength of the carbon fiber bundle showed a difference depending on the type and amount of components of the oil composition. Specifically, Example 32 containing 30% by mass of isophorone diisocyanate-alcohol adduct (F-1) and ester compound (C-1), isophorone diisocyanate-alcohol adduct (F-1) and ester compound ( Example 35 containing 25% by mass of B-1) and Example 36 containing 25% by mass of isophorone diisocyanate-alcohol adduct (F-1) and ester compound (C-1) were The strand strength was particularly high.

[Example 37]
<Preparation of oil agent composition and oil treatment liquid>
The oil agent was prepared by mixing and stirring the isophorone diisocyanate-alcohol adduct (F-1) and the ester compound (D-1). Nonionic surfactants (H-1, H-3) were added thereto, and mixed and stirred to prepare an oil agent composition.
After sufficiently stirring, ion-exchanged water was further added so that the concentration of the oil composition was 30% by mass and emulsified with a homomixer. The average particle size of the micelles in this state was measured using a laser diffraction / scattering particle size distribution measuring apparatus (trade name: LA-910, manufactured by Horiba, Ltd.), and was about 5.0 μm.
Then, it further disperse | distributed until the average particle diameter of the micelle became 0.3 micrometer or less with the high voltage | pressure homogenizer, and obtained the aqueous emulsion (emulsion) of the oil agent composition. The obtained aqueous emulsion was further diluted with ion-exchanged water to prepare an oil agent treatment liquid having an oil agent composition concentration of 1.3% by mass.
Table 6 shows the types and amounts (% by mass) of the components in the oil composition.
A carbon fiber precursor acrylic fiber bundle and a carbon fiber bundle were produced in the same manner as in Example 1 except that the obtained oil agent treatment liquid was used, and each measurement and evaluation were performed. The results are shown in Table 6.

[Examples 38 to 44]
Except having changed the kind and compounding quantity of each component which comprise an oil agent composition as shown in Table 6, an oil agent composition and an oil agent process liquid were prepared like Example 37, and a carbon fiber precursor acrylic fiber bundle And carbon fiber bundles were manufactured, and each measurement and evaluation was performed. The results are shown in Table 6.
In addition, when adding an antistatic agent, it added, after emulsifying and refine | miniaturizing to a predetermined particle diameter.

  As apparent from Table 6, in the case of each example, the amount of oil agent adhered was an appropriate amount. In addition, the bundling property of the carbon fiber precursor acrylic fiber bundle and the operability of the production process are good, and in all of the examples, there are no problems in the process of continuously producing the carbon fiber bundle. There was no situation.

  In addition, the carbon fiber bundles obtained in each example had substantially no number of fusions between single fibers, showed a high strand strength, and were excellent in mechanical properties. Moreover, since no silicone was contained, there was substantially no amount of Si scattering in the firing step, and the process load in the firing step was small and good.

  In addition, the strand strength of the carbon fiber bundle showed a difference depending on the type and amount of components of the oil composition. Specifically, Example 39 containing 30% by mass of isophorone diisocyanate-alcohol adduct (F-1) and ester compound (E-1), isophorone diisocyanate-alcohol adduct (F-1) and ester compound ( Example 43 containing 25% by mass of E-1) and Example 44 containing 25% by mass of isophorone diisocyanate-alcohol adduct (F-1) and ester compound (D-2) were The strand strength was particularly high.

[Comparative Examples 1-8]
<Preparation of oil agent composition and oil treatment liquid>
An oil agent composition and an oil agent treatment liquid were prepared in the same manner as in Example 1 except that the types and blending amounts of the components constituting the oil agent composition were changed as shown in Table 7.
In addition, when adding an antistatic agent, it added, after emulsifying and refine | miniaturizing to a predetermined particle diameter.
When amino-modified silicone is used, a nonionic surfactant is added to the ester compound after stirring. In the case of Comparative Examples 7 and 8 in which amino-modified silicone was used and no ester compound was used, ion-exchanged water was added after mixing and stirring the non-ionic surfactant in amino-modified silicone.
A carbon fiber precursor acrylic fiber bundle and a carbon fiber bundle were produced in the same manner as in Example 1 except that the oil agent treatment liquid thus prepared was used, and each measurement and evaluation were performed. The results are shown in Table 7.

As is apparent from Table 7, an ester compound (K-1) having one aromatic ring, an ester compound (K-2) having two aromatic rings, and a chain aliphatic ester compound (G-1) In the case of Comparative Examples 1 and 2 that were used and no amino-modified silicone was used, the strand strength of the carbon fiber bundle was lower than in each Example.
In the case of Comparative Examples 3 to 6 containing 15 to 20% by mass of amino-modified silicone and 40 to 60% by mass in total of the ester compounds (K-1), (K-2) and (G-1), Although the number of fusions was small and good, there was a problem in operational stability.

  Further, when the amino-modified silicone was contained (Comparative Examples 3 to 8), the produced carbon fiber bundle was not fused, and the strand strength was good. However, the amount of silicon scattering in the flameproofing process generated by using silicone is large, and there is a problem that the burden on the baking process is large in order to produce industrially continuously.

The carbon fiber precursor acrylic fiber oil agent of the present invention, the oil agent composition containing the oil agent, and the oil agent treatment liquid in which the oil agent composition is dispersed in water effectively melts the single fibers in the firing step. Can be suppressed. Furthermore, it is possible to obtain a carbon fiber precursor acrylic fiber bundle that can suppress a decrease in operability that occurs when using an oil composition containing silicone as a main component and that has good convergence. From the carbon fiber precursor acrylic fiber bundle, a carbon fiber bundle excellent in mechanical properties can be produced with high productivity.
The carbon fiber bundle obtained from the carbon fiber precursor acrylic fiber bundle to which the oil agent of the present invention is attached can be formed into a composite material after prepreg. In addition, the composite material using the carbon fiber bundle can be suitably used for sports applications such as golf shafts and fishing rods, and as a structural material for automobiles, aerospace applications, and various gas storage tank applications. .

Claims (11)

An oil agent for a carbon fiber precursor acrylic fiber containing two or more compounds selected from the group consisting of the following A, B, C, D, E, and F ,
An oil agent for a carbon fiber precursor acrylic fiber , comprising at least the following compound A and / or compound F.
A: Compound A obtained by reaction of hydroxybenzoic acid with a monovalent aliphatic alcohol having 8 to 20 carbon atoms.
B: Compound B obtained by reacting cyclohexanedicarboxylic acid with a monovalent aliphatic alcohol having 8 to 22 carbon atoms.
C: a cyclohexanedicarboxylic acid, a monovalent aliphatic alcohol having 8 to 22 carbon atoms, a polyhydric alcohol having 2 to 10 carbon atoms and / or a polyoxyalkylene glycol having 2 to 4 carbon atoms in an oxyalkylene group Compound C obtained by reaction.
D: Compound D obtained by reaction of cyclohexanedimethanol and / or cyclohexanediol with a fatty acid having 8 to 22 carbon atoms.
E: Compound E obtained by reaction of cyclohexanedimethanol and / or cyclohexanediol, a fatty acid having 8 to 22 carbon atoms and dimer acid.
F: One or more compounds selected from the group consisting of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = isocyanate, monovalent aliphatic alcohols having 8 to 22 carbon atoms and polyoxyalkylene ether compounds thereof Compound F obtained by reaction with The oil for carbon fiber precursor acrylic fibers according to claim 1, wherein the compound A is represented by the following formula (1a).

(In formula (1a), R ^1a is a hydrocarbon group having 8 to 20 carbon atoms.) The oil agent for carbon fiber precursor acrylic fibers according to claim 1, wherein the compound B is represented by the following formula (1b).

(In formula (1b), R ^1b and R ^2b are each independently a hydrocarbon group having 8 to 22 carbon atoms.) The oil agent for carbon fiber precursor acrylic fibers according to claim 1, wherein the compound C is represented by the following formula (2b).

(In the formula (2b), R ^3b and R ^5b are each independently a hydrocarbon group having 8 to 22 carbon atoms, and R ^4b is a hydrocarbon group having 2 to 10 carbon atoms or a carbon number of an oxyalkylene group. (This is a residue obtained by removing two hydroxyl groups from polyoxyalkylene glycol 2-4.) The oil agent for carbon fiber precursor acrylic fibers according to claim 1, wherein the compound D is represented by the following formula (1c).

(In formula (1c), R ^1c and R ^2c are each independently a hydrocarbon group having 7 to 21 carbon atoms, and nc are each independently 0 or 1.) The oil agent for carbon fiber precursor acrylic fibers according to claim 1, wherein the compound E is represented by the following formula (2c).

(In Formula (2c), R ^3c and R ^5c are each independently a hydrocarbon group having 7 to 21 carbon atoms, R ^4c is a hydrocarbon group having 30 to 38 carbon atoms, and mc is independently 0 or 1) The oil agent for carbon fiber precursor acrylic fibers according to claim 1, wherein the compound F is represented by the following formula (1d).

(In Formula (1d), R ^1d and R ^4d are each independently a hydrocarbon group having 8 to 22 carbon atoms, and R ^2d and R ^3d are each independently a hydrocarbon group having 2 to 4 carbon atoms. , Nd and md mean the average number of moles added and each independently represents a number of 0 to 5.) And the carbon fiber precursor acrylic fibers for oil according to any one of claims 1 to 7 containing a non-ionic surfactant, carbon fiber precursor acrylic fibers for oil composition. The oil composition for carbon fiber precursor acrylic fibers according to claim 8 , comprising 20 to 150 parts by mass of the nonionic surfactant with respect to 100 parts by mass of the oil agent for carbon fiber precursor acrylic fibers. The oil agent composition for carbon fiber precursor acrylic fibers according to claim 8 or 9 , comprising 1 to 5 parts by mass of an antioxidant with respect to 100 parts by mass of the oil agent for carbon fiber precursor acrylic fibers. The oil agent treatment liquid for carbon fiber precursor acrylic fibers in which the oil agent composition for carbon fiber precursor acrylic fibers according to any one of claims 8 to 10 is dispersed in water.