Carbon fiber precursor treatment agent and carbon fiber precursor

Abstract

To provide a carbon fiber precursor treatment agent high in fuzz suppression and emulsion stability, and a carbon fiber precursor to which the carbon fiber precursor treatment agent is stuck.SOLUTION: The carbon fiber precursor treatment agent contains: a saccharide (A); a nonionic surface active agent (B) having a polyoxyalkylene group; and a basis (C). The saccharide (A) is at least one compound selected from the group consisting of an alditol (A1), an alditol dehydration product (A2) which is at least one dehydration product selected from the group consisting of an alditol intramolecular dehydration product, an alditol intermolecular dehydration product, and an alditol intramolecular and intermolecular dehydration product and which has no epoxy group in a molecular structure, and a disaccharide (A3). The basis (C) is at least one compound selected from the group consisting of a silicon compound (C1), an ester compound (C2), and hydrocarbon oil (C3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a treating agent for a carbon fiber precursor and a carbon fiber precursor. [Background technology]

[0002] A commonly used method for producing carbon fibers is to spin a fibrous material and then calcinate the material, and this fibrous material is called a carbon fiber precursor. As the carbon fiber precursor, a fibrous material such as a polymer, to which a treating agent for carbon fiber precursors has adhered on the surface, may be used. Such a treating agent is used for the purpose of improving the handleability of the carbon fiber precursor in various steps when producing carbon fibers.

[0003] Japanese Patent Laid-Open Publication No. 11-152626 (Patent Document 1) discloses an invention relating to a method for producing carbon fiber, characterized in that a polyhydric alcohol is added when a precursor (carbon fiber precursor) containing a boron compound is calcined. According to the invention described in Patent Document 1, the addition of a polyhydric alcohol improves the heat resistance of the surface layer of the precursor, preventing surface layer defects in the carbon fiber, thereby producing a high-strength carbon fiber.

[0004] WO 2024 / 057740 (Patent Document 2) discloses an invention relating to a treatment agent for acrylic fibers that contains an amino-modified silicone and a compound having a five-membered ring structure containing sulfur and nitrogen atoms and / or a derivative thereof. The invention described in Patent Document 2 can improve the bundling ability of acrylic fibers used in carbon fiber production during the flame-resistant treatment process. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-152626 [Patent Document 2] International Publication No. 2024 / 057740 Summary of the Invention [Problem to be solved by the invention]

[0006] Patent Documents 1 and 2 to The described inventions have room for improvement in terms of suppressing fluffing that occurs during the production of carbon fiber precursors. If fluffing can be suppressed, it is expected that the operability during the production of carbon fiber precursors and the quality of the carbon fiber precursors will be improved. In addition, Patent Documents 1 and 2 to The described invention also leaves room for improvement in the emulsion stability of the treatment agent for carbon fiber precursors. If a treatment agent for carbon fiber precursors with high emulsion stability is used, it is expected that the operability when producing carbon fiber precursors will be improved.

[0007] Therefore, it is desired to realize a treatment agent for carbon fiber precursors that is excellent in fuzz suppression and emulsion stability, and a carbon fiber precursor to which such a treatment agent for carbon fiber precursors is attached. [Means for solving the problem]

[0008] The present invention First The treatment agent for carbon fiber precursors contains a saccharide (A), a nonionic surfactant (B) having a polyoxyalkylene group, and a base (C), wherein the saccharide (A) is at least one compound selected from the group consisting of an alditol (A1), an alditol dehydrate (A2) which is at least one dehydrate selected from the group consisting of an intramolecular dehydrate of alditol, an intermolecular dehydrate of alditol, and an intramolecular and intermolecular dehydrate of alditol, and which does not have an epoxy group in its molecular structure, and a disaccharide (A3), and the base (C) is Contains amino-modified silicone It is characterized by:

[0009] A second treatment agent for carbon fiber precursors according to the present invention contains a saccharide (A) containing four or more carbon atoms per molecule, a nonionic surfactant (B) having a polyoxyalkylene group, and a base (C), wherein the saccharide (A) is at least one compound selected from the group consisting of an alditol (A1), an alditol dehydrate (A2), which is at least one dehydration product selected from the group consisting of an intramolecular dehydration product of alditol, an intermolecular dehydration product of alditol, and an intramolecular and intermolecular dehydration product of alditol, and which does not have an epoxy group in its molecular structure, and a disaccharide (A3), and the base (C) is at least one compound selected from the group consisting of a silicone compound (C1), an ester compound (C2), and a hydrocarbon oil (C3).

[0010] A third treatment agent for carbon fiber precursors according to the present invention contains a saccharide (A), a nonionic surfactant (B) having a polyoxyalkylene group, and a base (C), wherein the saccharide (A) is at least one dehydration product selected from the group consisting of intramolecular dehydration products of alditol, intermolecular dehydration products of alditol, and intramolecular and intermolecular dehydration products of alditol, and is at least one compound selected from the group consisting of an alditol dehydration product (A2) that does not have an epoxy group in its molecular structure and a disaccharide (A3), and the base (C) is at least one compound selected from the group consisting of a silicone compound (C1), an ester compound (C2), and a hydrocarbon oil (C3).

[0011] The carbon fiber precursor according to the present invention is EitherThe carbon fiber precursor treatment agent is attached to the fiber material.

[0012] The treating agent for carbon fiber precursors according to the above configuration can suppress fluffing when used in the production of carbon fiber precursors, and has high stability as an emulsion. Therefore, the continuous operability of the production of carbon fiber precursors can be improved. In addition, the carbon fiber precursor according to the above configuration has little fluffing.

[0013] Preferred embodiments of the present invention will be described below, but the scope of the present invention is not limited to the preferred embodiments described below.

[0014] In one embodiment of the treating agent for carbon fiber precursors according to the present invention, the proportion of the saccharide (A) in the nonvolatile content is preferably 0.3% by mass or more and 30% by mass or less.

[0015] This configuration makes it possible to achieve both high levels of fuzz suppression and emulsion stability.

[0016] In one embodiment of the treating agent for carbon fiber precursors according to the present invention, the nonionic surfactant (B) preferably has a branched hydrocarbon group having 6 to 24 carbon atoms.

[0017] According to this configuration, the treatment agent for carbon fiber precursors tends to be particularly stable as an emulsion.

[0018] In one embodiment, the treating agent for carbon fiber precursors according to the present invention has a nonvolatile content in which the sugar (A) is 0.01% by mass or more and 50% by mass or less, the nonionic surfactant (B) is 5% by mass or more and 70% by mass or less, and the base (C) is 1% by mass or more and 90% by mass or less. below It is preferable that:

[0019] This configuration makes it possible to achieve both high levels of fuzz suppression and emulsion stability.

[0020] Further features and advantages of the present invention will become more apparent from the following description of illustrative and non-limiting embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, embodiments of the treating agent for carbon fiber precursors and the carbon fiber precursor according to the present invention will be described.

[0022] [Configuration of treatment agent for carbon fiber precursor] The treating agent for carbon fiber precursors according to this embodiment contains a saccharide (A), a nonionic surfactant (B) having a polyoxyalkylene group, and a base (C).

[0023] (Sugars) The sugar (A) contained in the treatment agent for carbon fiber precursors according to this embodiment is at least one compound selected from the group consisting of alditol (A1), alditol dehydrate (A2), and disaccharide (A3). When the sugar (A) contains at least one compound selected from the group consisting of alditol dehydrate (A2) and disaccharide (A3), fluffing of the carbon fiber precursor is particularly easily suppressed, which is preferable.

[0024] Alditol (A1) is a sugar having a molecular structure in which the aldehyde group of an aldose is reduced to a hydroxymethyl group. Examples of alditol (A1) include, but are not limited to, sorbitol, mannitol, erythritol, xylitol, and glycerin. Alditol (A1) may be a single compound or a mixture of multiple compounds.

[0025] The alditol dehydrate (A2) is at least one dehydrate selected from the group consisting of intramolecular dehydration products of alditol, intermolecular dehydration products of alditol, and intramolecular and intermolecular dehydration products of alditol. The definition of alditol is as described for alditol (A1). Examples of intramolecular dehydration products of alditol include sorbitan and isosorbide, which are intramolecular dehydration products of sorbitol. Examples of intermolecular dehydration products of alditol include polyglycerol and diglycerol, which are intermolecular dehydration products of glycerin. Examples of intramolecular and intermolecular dehydration products of alditol include the intermolecular dehydration product of sorbitan and sorbitol, and the intermolecular dehydration product of sorbitan with itself (intramolecular and intermolecular dehydration products of sorbitol). Note that none of these examples limits the alditol dehydrate (A2) according to the present embodiment. The alditol dehydrate (A2) may be a single compound or a mixture of multiple compounds.

[0026] The alditol dehydrate (A2) does not have an epoxy group in its molecular structure. The present inventors have found that when a treating agent for carbon fiber precursors containing an alditol dehydrate (A2) having no epoxy group in its molecular structure is used, fluffing of the carbon fiber precursor can be suppressed more effectively than when a treating agent for carbon fiber precursors containing an alditol dehydrate having an epoxy group in its molecular structure is used.

[0027] Disaccharides (A3) are sugars having a molecular structure formed by dehydration condensation of two monosaccharide molecules. Examples of disaccharides (A3) include, but are not limited to, sucrose, lactose, and maltose. Disaccharides (A3) may be a single compound or a mixture of multiple compounds.

[0028] It is preferable that the sugar (A) is a compound containing four or more carbon atoms per molecule, since this particularly helps to suppress fuzzing of the carbon fiber precursor. When the sugar (A) contains multiple compounds, it is preferable that at least one compound contains four or more carbon atoms per molecule. Sorbitol, mannitol, and erythritol are examples of alditols (A1) containing four or more carbon atoms per molecule. Sorbitan, polyglycerin, and diglycerin are examples of alditol dehydrates (A2) containing four or more carbon atoms per molecule. Note that all compounds corresponding to disaccharides (A3) contain four or more carbon atoms per molecule.

[0029] The saccharide (A) is preferably a compound having no polyoxyalkylene group in the molecule. When the saccharide (A) contains a plurality of compounds, it is preferable that at least one compound has no polyoxyalkylene group in the molecule, and it is more preferable that all compounds have no polyoxyalkylene group in the molecule.

[0030] The saccharide (A) is preferably a compound with a molecular weight of 1500 or less, and more preferably a compound with a molecular weight of 750 or less. When the saccharide (A) is an isolable compound or a mixture thereof, the molecular weight can be determined based on the molecular structure. When the saccharide (A) is a mixture of compounds with different molecular weights (such as when the saccharide (A) is an oligomer or polymer), the molecular weight of the saccharide (A) can be controlled by using saccharide (A) isolated according to molecular weight. For example, polyglycerin, an example of an alditol dehydrate (A2), is commercially available in products with different mass-average molecular weights.

[0031] (nonionic surfactant) The nonionic surfactant (B) contained in the treatment agent for carbon fiber precursors according to this embodiment may be any nonionic surfactant commonly used in the art and may be one having a polyoxyalkylene group. The nonionic surfactant (B) may be a single compound or a mixture of multiple compounds.

[0032] The nonionic surfactant (B) may be, for example, an alkylene oxide adduct of a compound having a hydroxy group, or a derivative thereof (such as an esterified product.) Examples of the compound having a hydroxy group include, but are not limited to, isotridecanol, isohexanol, isohexadecanol, 2-ethylhexanol, 2-dodecanol, 2-tridecanol, 1-hexanol, lauryl alcohol, oleyl alcohol, hydrogenated castor oil, coconut oil alkylamine, glycerin, polypropylene glycol, and polyethylene glycol.

[0033] The nonionic surfactant (B) is preferably a compound having a branched hydrocarbon group with 6 to 24 carbon atoms. When the nonionic surfactant (B) contains multiple compounds, it is preferable that at least one of the compounds is a branched hydrocarbon group with 6 to 24 carbon atoms. When the nonionic surfactant (B) satisfies the above conditions, the treatment agent for carbon fiber precursors tends to be particularly stable as an emulsion. The number of carbon atoms in the hydrocarbon group is more preferably 10 to 14.

[0034] Examples of alkylene oxides constituting the nonionic surfactant (B) include, but are not limited to, ethylene oxide and propylene oxide. The nonionic surfactant (B) may be a compound having one type of oxyalkylene group derived from a single alkylene oxide, or a compound having multiple types of oxyalkylene groups derived from multiple alkylene oxides. The multiple types of oxyalkylene groups may be present in a block form or randomly. The number of alkylene oxides added to the nonionic surfactant (B) is not particularly limited, but is preferably 2 to 40, and more preferably 3 to 15, per molecule.

[0035] (Base) The base (C) contained in the treatment agent for carbon fiber precursors according to this embodiment is at least one compound selected from the group consisting of silicone compounds (C1), ester compounds (C2), and hydrocarbon oils (C3).

[0036] The silicone compound (C1) may be a modified or unmodified silicone compound. Non-limiting examples of the silicone compound (C1) include, but are not limited to, amino-modified silicone, polyether-modified silicone, dimethyl silicone, etc. The kinematic viscosity of the silicone compound (C1) is not particularly limited, but may be, for example, 50 mm 2 / s or more 40000mm 2 / s or less (value at 25°C). When the silicone compound (C1) contains an amino-modified silicone, the amino equivalent of the amino-modified silicone is not limited, but can be, for example, 500 g / mol or more and 20,000 g / mol or less. When the silicone compound (C1) contains a polyether-modified silicone, the ratio of silicone residues to polyether residues in the polyether-modified silicone and the structure of the polyether residue are not limited. The silicone compound (C1) may be a single compound or a mixture of multiple compounds.

[0037] The ester compound (C2) may be an ester compound of any acid compound and any alcohol compound. Non-limiting examples of the acid compound include, but are not limited to, lauric acid, thiodipropionic acid, trimellitic acid, and oleic acid. Non-limiting examples of the alcohol compound include, but are not limited to, alkylene oxide adducts of bisphenol A, 2-hexyl-1-decanol, stearyl alcohol, sorbitan, glycerin, and pentaerythritol. The ester compound (C2) may be a single compound or a mixture of multiple compounds.

[0038] The hydrocarbon oil (C3) can be any hydrocarbon oil. The kinematic viscosity of the hydrocarbon oil (C3) is not limited, but is, for example, 3.0 mm 2 / s or more 40mm2 / s or less (values ​​at 40°C).

[0039] (Content of each ingredient) The proportion of sugars (A) in the non-volatile content of the treatment agent for carbon fiber precursors is preferably 0.3% by mass or more and 30% by mass or less. When the proportion of sugars (A) is 0.3% by mass or more, fluffing of the carbon fiber precursor is particularly easily suppressed. When the proportion of sugars (A) is 30% by mass or less, the treatment agent for carbon fiber precursors is particularly likely to be stable as an emulsion. The proportion of sugars (A) in the non-volatile content is more preferably 0.5% by mass or more and 10% by mass or less. The non-volatile content of the treatment agent for carbon fiber precursors refers to the components that remain without volatilization after heating the treatment agent for carbon fiber precursors in a hot air dryer at 105°C for 2 hours. When sugars (A) contain multiple compounds, the proportion of sugars (A) is the sum of the proportions of the multiple compounds in the non-volatile content.

[0040] The proportion of the sugar (A) in the nonvolatile content of the treatment agent for carbon fiber precursors is 0.01% by mass or more and 50% by mass or less, the proportion of the nonionic surfactant (B) is 5% by mass or more and 70% by mass or less, and the proportion of the base (C) is 1% by mass or more and 90% by mass or less. below It is preferable that the ratio of the sugar (A), the nonionic surfactant (B), and the base (C) satisfies the above conditions. When the ratio of the sugar (A), the nonionic surfactant (B), and the base (C) satisfies the above conditions, fluffing of the carbon fiber precursor is particularly likely to be suppressed, and the treatment agent for carbon fiber precursors is particularly likely to be stable as an emulsion. When one or more of the sugar (A), the nonionic surfactant (B), and the base (C) contain multiple compounds, the total ratio of the multiple compounds corresponding to each category to the nonvolatile content is defined as the ratio of the components in that category.

[0041] (Other ingredients) The treating agent for carbon fiber precursors according to this embodiment may contain components (other components) other than the saccharide (A), the nonionic surfactant (B), and the base (C). Examples of such other components include, but are not limited to, preservatives, surfactants (anionic surfactants, cationic surfactants, and nonionic surfactants other than the nonionic surfactant (B)), resins, antistatic agents, antioxidants, ultraviolet absorbers, and antifoaming agents.

[0042] A typical example of a carbon fiber precursor treatment agent used to treat a carbon fiber precursor is one in which the sugar (A), nonionic surfactant (B), and base (C), as well as any other optional components, are diluted with a diluent. Such a diluent is also an example of the other components. Examples of diluents include, but are not limited to, water (tap water, industrial water, ion-exchanged water, distilled water, etc.), acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, and hexane. The concentration of the nonvolatile components in a carbon fiber precursor treatment agent diluted with a diluent is not particularly limited, but can be, for example, 1% by mass or more and 60% by mass or less. As described above, the nonvolatile components of a carbon fiber precursor treatment agent refer to the components that remain unvolatilized after heating the treatment agent in a hot air dryer at 105°C for 2 hours. The concentration refers to the ratio of the mass of the nonvolatile components in the treatment agent to the mass of the carbon fiber precursor treatment agent.

[0043] (Effect of treatment agent for carbon fiber precursor) The treatment agent for carbon fiber precursors according to the present embodiment is advantageous in that when used in the production of carbon fiber precursors, it can suppress fuzzing and has high stability as an emulsion, thereby improving the continuous operability of the production of carbon fiber precursors.

[0044] Furthermore, as shown in the examples described later, a treatment agent for carbon fiber precursors containing all of the sugar (A), nonionic surfactant (B), and base (C) tended to be superior in both fuzz suppression and emulsion stability compared to a treatment agent for carbon fiber precursors lacking either the sugar (A) or the nonionic surfactant (B). This suggests that in addition to the contribution of the sugar (A) to fuzz suppression and the contribution of the nonionic surfactant (B) to emulsion stability, there is also a contribution of the synergistic effect of the sugar (A) and the nonionic surfactant (B) to both performances.

[0045] [Method for producing a treating agent for carbon fiber precursors] The treating agent for carbon fiber precursors according to this embodiment can be obtained by mixing the sugar (A), the nonionic surfactant (B), the base (C), and any other components that may be added by a known method. For example, it can be produced by adding water to the sugar (A), the nonionic surfactant (B), the base (C), and any other components that may be added by stirring at a temperature between 10°C and 90°C over 5 hours.

[0046] [Carbon fiber precursor] The carbon fiber precursor according to the present embodiment is a fiber material generally used as a carbon fiber precursor, to which the treatment agent for a carbon fiber precursor according to the present embodiment is attached. The fiber material here refers to a fibrous material that becomes carbon fiber after a calcination process, and may be polyacrylonitrile-based fiber, polyamide-based fiber, polyester-based fiber, polyolefin-based fiber, cellulose-based fiber, lignin-based fiber, phenolic resin, pitch, or a combination thereof.

[0047] As a method for adhering the treatment agent for carbon fiber precursors to a fiber material, a method commonly used in the art for adhering this type of treatment agent to a fiber material can be applied. That is, an immersion oiling method, a spray oiling method, a roller oiling method, a guide oiling method, etc. can be adopted. When applying each method, the treatment agent for carbon fiber precursors can be appropriately diluted with a solvent such as water.

[0048] In the carbon fiber precursor according to this embodiment, the amount of the treatment agent for carbon fiber precursors attached is not particularly limited. For example, it is preferable that the amount of the treatment agent for carbon fiber precursors attached is 0.3 mass % to 3 mass % of the entire carbon fiber precursor to which the treatment agent for carbon fiber precursors is attached.

[0049] Other Embodiments The present invention may provide a treatment agent for carbon fiber precursors, comprising a saccharide (A), a nonionic surfactant (B) having a polyoxyalkylene group, and a base (C), wherein the saccharide (A) is at least one dehydration product selected from the group consisting of alditol (A1), intramolecular dehydration products of alditol, intermolecular dehydration products of alditol, and intramolecular and intermolecular dehydration products of alditol, and wherein the alditol dehydration product (A2) does not have an epoxy group in its molecular structure, and at least one compound selected from the group consisting of a disaccharide (A3), and the base (C) is at least one compound selected from the group consisting of a silicone compound (C1), an ester compound (C2), and a hydrocarbon oil (C3). When used in the production of carbon fiber precursors, this treatment agent can suppress fuzzing and has high emulsion stability. This can improve the continuous operability of the carbon fiber precursor production. Moreover, the carbon fiber precursor according to the above configuration has little fluff.

[0050] In one embodiment of the treating agent for carbon fiber precursors, the saccharide (A) preferably contains four or more carbon atoms per molecule. This configuration makes it particularly easy to suppress fluffing of the carbon fiber precursor.

[0051] In one embodiment of the treating agent for carbon fiber precursors, the saccharide (A) is preferably at least one compound selected from the group consisting of the alditol dehydrate (A2) and the disaccharide (A3). This configuration makes it particularly easy to suppress fluffing of the carbon fiber precursor.

[0052] Regarding other configurations, it should be understood that the embodiments disclosed in this specification are illustrative in all respects and that the scope of the present invention is not limited thereby. Those skilled in the art will easily understand that appropriate modifications are possible without departing from the spirit of the present invention. Therefore, other embodiments modified without departing from the spirit of the present invention are naturally included in the scope of the present invention. [Example]

[0053] The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

[0054] [Preparation of treating agent for carbon fiber precursor] Treating agents for carbon fiber precursors of Examples 1 to 20 and Comparative Examples 1 to 7 shown in Tables 1 to 3 below were obtained by the following method.

[0055] (1) Reagents (1-1) Sugars (A) The following 11 compounds were used as sugars (A). Each compound was assigned a compound number consisting of a combination of the symbols A1 to A3, which indicate the classification of alditol (A1), alditol dehydrate (A2), and disaccharide (A3), and a serial number 1 to 11, which is assigned to each of the 11 compounds in order.

[0056] The following six sugars (A) are examples of alditol dehydrates (A2). A2-1: Sorbitan A2-2: Polyglycerin #750 (manufactured by Sakamoto Pharmaceutical Co., Ltd.) (a polyglycerin with a mass-average molecular weight of 750) A2-3: Polyglycerin #500 (manufactured by Sakamoto Pharmaceutical Co., Ltd.) (a polyglycerin with a mass average molecular weight of 500) A2-4: Polyglycerin #310 (manufactured by Sakamoto Pharmaceutical Co., Ltd.) (a polyglycerin with a mass-average molecular weight of 310) A2-5: R-PG (manufactured by Sakamoto Pharmaceutical Co., Ltd.) (a polyglycerin with a mass-average molecular weight of 240) A2-6: Diglycerin

[0057] The following sugar (A) is an example of a disaccharide (A3): A3-7: Sucrose

[0058] The following four sugars (A) are examples of alditols (A1): A1-8: Sorbitol A1-9: Mannitol A1-10: Erythritol A1-11: Glycerin

[0059] (1-2) Nonionic surfactant (B) The following 22 types of compounds were used as nonionic surfactants (B). Each compound is assigned a compound number consisting of a combination of the symbol B, which indicates nonionic surfactant (B), and a serial number from 1 to 22, which is assigned to the 22 types of compounds in order. Nonionic surfactants B-1 to B-9 are compounds having a branched hydrocarbon group with 6 to 24 carbon atoms, while nonionic surfactants B-10 to B-22 are compounds that do not satisfy this condition. Note that, when a method for producing nonionic surfactant (B) is shown, each production method is merely an example, and the results of the examples and comparative examples will not change even if the nonionic surfactant (B) is produced by a method other than the method exemplified below.

[0060] (Nonionic surfactant B-1) Isotridecanol and ethylene oxide were reacted in a molar ratio of 1:5 to obtain a nonionic surfactant B-1, which is an ethylene oxide adduct of isotridecanol.

[0061] (Nonionic surfactant B-2) Isotridecanol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain a nonionic surfactant B-2, which is an ethylene oxide adduct of isotridecanol.

[0062] (Nonionic surfactant B-3) Isotridecanol and ethylene oxide were reacted in a molar ratio of 1:15 to obtain a nonionic surfactant B-3, which is an ethylene oxide adduct of isotridecanol.

[0063] (Nonionic surfactant B-4) Isohexanol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain a nonionic surfactant B-4, which is an ethylene oxide adduct of isohexanol.

[0064] (Nonionic surfactant B-5) Isohexadecanol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain a nonionic surfactant B-5, which is an ethylene oxide adduct of isohexadecanol.

[0065] (Nonionic surfactant B-6) Isotridecanol was reacted with ethylene oxide and propylene oxide in a molar ratio of 1:5:6 in one step to obtain nonionic surfactant B-6, which is a random adduct of ethylene oxide and propylene oxide with isotridecanol.

[0066] (Nonionic surfactant B-7) Isotridecanol was reacted with ethylene oxide and propylene oxide in a molar ratio of 1:5:6 in the order of ethylene oxide and propylene oxide to obtain nonionic surfactant B-7, an ethylene oxide-propylene oxide block adduct of isotridecanol.

[0067] (Nonionic surfactant B-8) Isohexanol was reacted with ethylene oxide and propylene oxide in a stepwise manner in a molar ratio of 1:5:6, in the order of ethylene oxide and propylene oxide, to obtain nonionic surfactant B-8, an ethylene oxide-propylene oxide block adduct of isohexanol.

[0068] (Nonionic surfactant B-9) 2-Ethylhexanol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain nonionic surfactant B-9, which is an ethylene oxide adduct of 2-ethylhexanol.

[0069] (Nonionic surfactant B-10) 2-dodecanol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain nonionic surfactant B-10, which is an ethylene oxide adduct of 2-dodecanol.

[0070] (Nonionic surfactant B-11) 2-Tridecanol and ethylene oxide were reacted in a molar ratio of 1:5 to obtain nonionic surfactant B-11, which is an ethylene oxide adduct of 2-tridecanol.

[0071] (Nonionic surfactant B-12) 2-Tridecanol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain nonionic surfactant B-12, which is an ethylene oxide adduct of 2-tridecanol.

[0072] (Nonionic surfactant B-13) 2-Tridecanol and ethylene oxide were reacted in a molar ratio of 1:15 to obtain nonionic surfactant B-13, which is an ethylene oxide adduct of 2-tridecanol.

[0073] (Nonionic surfactant B-14) The nonionic surfactant B-14, a random adduct of ethylene oxide and propylene oxide with 2-dodecanol, was obtained by reacting 2-dodecanol with ethylene oxide and propylene oxide in a single step in a molar ratio of 1:5:6.

[0074] (Nonionic surfactant B-15) 2-dodecanol was reacted with ethylene oxide and propylene oxide in a molar ratio of 1:5:6 in the order of ethylene oxide and propylene oxide to obtain nonionic surfactant B-15, an ethylene oxide-propylene oxide block adduct of 2-dodecanol.

[0075] (Nonionic surfactant B-16) 1-Hexanol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain nonionic surfactant B-16, which is an ethylene oxide adduct of 1-hexanol.

[0076] (Nonionic surfactant B-17) Lauryl alcohol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain nonionic surfactant B-17, which is an ethylene oxide adduct of lauryl alcohol.

[0077] (Nonionic surfactant B-18) Oleyl alcohol and ethylene oxide were reacted in a molar ratio of 1:10 to obtain nonionic surfactant B-18, which is an ethylene oxide adduct of oleyl alcohol.

[0078] (Nonionic surfactant B-19) Hydrogenated castor oil and ethylene oxide were reacted in a molar ratio of 1:20 to obtain nonionic surfactant B-19, which is an ethylene oxide adduct of hydrogenated castor oil.

[0079] (Nonionic surfactant B-20) A coconut oil alkylamine and ethylene oxide were reacted in a molar ratio of 1:5 to obtain nonionic surfactant B-20, which is an ethylene oxide adduct of coconut oil alkylamine.

[0080] (Nonionic surfactant B-21) Glycerin, ethylene oxide, and propylene oxide were reacted in a 1:20:20 ratio in the order of propylene oxide and ethylene oxide to obtain nonionic surfactant B-21, a propylene oxide-ethylene oxide block adduct of glycerin.

[0081] (Nonionic surfactant B-22) A Pluronic (registered trademark) type surfactant in which polyethylene glycol blocks having a mass average molecular weight of 400 are bonded to both ends of a polypropylene glycol block having a mass average molecular weight of 1000 was designated as nonionic surfactant B-22.

[0082] (1-3) Base (C) The following 22 types of compounds were used as the base (C). Each compound was assigned a compound number consisting of a combination of the symbols C1 to C3, which indicate the classification of the compound as a silicone compound (C1), an ester compound (C2), or a hydrocarbon oil (C3), and a serial number from 1 to 22, which was assigned to each of the 22 compounds in order.

[0083] The following ten bases (C) are examples of amino-modified silicones, which are examples of silicone compounds (C1). Note that the kinematic viscosity of the silicone compounds (C1) is the value at 25°C. C1-1: WACKER (registered trademark) FINISH WR300 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (kinematic viscosity 600 mm 2 / s, amino equivalent 3300g / mol) C1-2: WACKER (registered trademark) FINISH WR1100 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (kinematic viscosity 5000 mm 2 / s, amino equivalent 7000g / mol) C1-3: WACKER (registered trademark) FINISH WR1200 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (kinematic viscosity 7000 mm 2 / s, amino equivalent 4000g / mol) C1-4: WACKER (registered trademark) FINISH WR1300 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (kinematic viscosity 1000 mm 2 / s, amino equivalent 3300g / mol) C1-5: WACKER (registered trademark) FINISH WR1600 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (kinematic viscosity 1000 mm 2 / s, amino equivalent 1700g / mol) C1-6: TSF4702 (manufactured by Momentive Performance Materials Japan, LLC) (kinematic viscosity 500mm 2 / s, amino equivalent 1600g / mol) C1-7: TSF4704 (manufactured by Momentive Performance Materials Japan, LLC) (kinematic viscosity 40,000 mm 2 / s, amino equivalent 20000g / mol) C1-8: TSF4706 (manufactured by Momentive Performance Materials Japan, LLC) (kinematic viscosity 50 mm 2 / s, amino equivalent 2100g / mol) C1-9: TSF4708 (manufactured by Momentive Performance Materials Japan, LLC) (kinematic viscosity 1000mm 2 / s, amino equivalent 2800g / mol) C1-10: TSF4709 (manufactured by Momentive Performance Materials Japan, LLC) (kinematic viscosity 2000mm 2 / s, amino equivalent 10000g / mol)

[0084] The following two types of bases (C) are examples of silicone compounds (C1) other than amino-modified silicones. The kinematic viscosity of the silicone compounds (C1) is measured at 25°C. C1-11: Polyether modified silicone (kinematic viscosity 500mm 2 / s, silicone chain / polyether = 50 / 50 (mass ratio), ethylene oxide / propylene oxide in the polyether portion = 50 / 50 (molar ratio) C1-12: KF-96-100CS (Shin-Etsu Chemical Co., Ltd.) (kinematic viscosity 100 mm 2 / s dimethyl silicone)

[0085] The following two bases (C) are examples of ester compounds (C2). Although the production methods for these compounds are shown, each production method is merely an example, and the results of the examples and comparative examples will not change even if the ester compounds (C2) are produced by a method other than the methods exemplified below.

[0086] (Ester compound C2-13) Bisphenol A and ethylene oxide were reacted in a molar ratio of 1:2 to obtain an ethylene oxide adduct of bisphenol A. Subsequently, the ethylene oxide adduct of bisphenol A was reacted with lauric acid in a molar ratio of 1:2 to obtain an ester compound C2-13.

[0087] (Ester compound C2-14) Thiodipropionic acid and 2-hexyl-1-decanol were reacted in a molar ratio of 1:2 to obtain the ester compound C2-14.

[0088] The following two bases (C) are examples of ester compounds (C2): C2-15: Trimellitic acid triisostearate C2-16: Sorbitan monooleate

[0089] The following six base materials (C) are examples of hydrocarbon oils (C3). The kinematic viscosity of the hydrocarbon oils (C3) is measured at 40°C. C3-17: Shell (registered trademark) GTL Solvent GS-310 (manufactured by Shell Lubricants Japan Co., Ltd.) (kinematic viscosity 5.9 mm 2 / s) C3-18: ISAN® BIOLIFE 1518 (manufactured by Total Energies Lubricants Japan Co., Ltd.) (kinematic viscosity 3.4 mm 2 / s) C3-19: ISAN® BIOLIFE 58 (manufactured by Total Energies Lubricants Japan Co., Ltd.) (kinematic viscosity 3 mm 2 / s) C3-20: ISAN® BIOLIFE 78 (manufactured by Total Energies Lubricants Japan Co., Ltd.) (kinematic viscosity 3.9 mm 2 / s) C3-21: Synfluid (registered trademark) PAO 4 cSt (manufactured by Chevron Phillips Chemical Co., Ltd.) (kinematic viscosity 16.8 mm 2 / s) C3-22: Synfluid (registered trademark) PAO 6 cSt (manufactured by Chevron Phillips Chemical Co., Ltd.) (kinematic viscosity 30.5 mm 2 / s)

[0090] (1-4) Other ingredients (D) The following 11 compounds were used as other components (D) that do not fall under any of the categories of sugars (A), nonionic surfactants (B), and bases (C). Each compound is assigned a compound number consisting of a combination of the letter D, which indicates the other component (D), and a serial number from 1 to 11, which is assigned to each of the 11 compounds in order. Compounds D-4 to D-10 are examples of preservatives. D-1: Sodium dodecylbenzenesulfonate D-2: Potassium 2-ethylhexyl phosphate D-3: Polyethylene glycol (mass average molecular weight 600) D-4: Permakem (registered trademark) OM-17 (manufactured by Permakem Asia Co., Ltd.) D-5: Permakem (registered trademark) OM-27 (manufactured by Permakem Asia Co., Ltd.) D-6: Permakem (registered trademark) OM-30 (manufactured by Permakem Asia Co., Ltd.) D-7: ACTICIDE® LA (manufactured by Thor Japan Co., Ltd.) D-8: ACTICIDE® LA2011 (manufactured by Thor Japan Co., Ltd.) D-9: ACTICIDE® MBS (manufactured by Thor Japan Co., Ltd.) D-10: PROXEL (registered trademark) GXL (manufactured by Lonza Japan Co., Ltd.) D-11: Polyglycerol polyglycidyl ether

[0091] (2) Preparation of a treatment agent for carbon fiber precursors (Preparation of Example 1) The components were weighed in the following mass ratios. Saccharide A2-1 1% by mass Nonionic surfactant B-1 10% by mass Nonionic surfactant B-3 10% by mass Nonionic surfactant B-12 9% by mass Base C1-1 35% by mass Base C1-3 30% by mass Base C1-7 5% by mass The weighed components were placed in a beaker and mixed thoroughly, and then ion-exchanged water was gradually added while stirring to adjust the non-volatile content to 3% by mass, thereby preparing the treatment agent for carbon fiber precursors of Example 1.

[0092] (Preparation of Other Examples and Comparative Examples) Except for changing the types and ratios of the reagents to be mixed, the treating agent for carbon fiber precursors of each example was prepared in the same manner as in Example 1. The preparation conditions for all examples, including Example 1, are shown in Tables 1 to 3 below.

[0093] [Evaluation of Treatment Agents for Carbon Fiber Precursors] (1) Evaluation of fluff A copolymer consisting of 95% by mass of acrylonitrile, 3.5% by mass of methyl acrylate, and 1.5% by mass of methacrylic acid with an intrinsic viscosity of 1.80 was dissolved in dimethylacetamide (DMAC) to prepare a spinning dope with a polymer concentration of 21.0% by mass and a viscosity of 500 poise at 60°C. The spinning dope was extruded at a draft ratio of 0.8 from a spinneret with a pore size (inner diameter) of 0.075 mm and 12,000 holes into a coagulation bath of a 70% by mass aqueous solution of DMAC maintained at a spinning bath temperature of 35°C. The coagulated yarn was stretched 5 times in a water washing tank while the solvent was removed, producing a water-swollen acrylic fiber strand.

[0094] A 3% ion-exchange aqueous solution of the treating agent for carbon fiber precursors of each of the Examples and Comparative Examples was applied to the prepared acrylic fiber strand by immersion so that the amount of the treating agent attached was 1 mass % (excluding the solvent). Thereafter, the acrylic fiber strand to which the treating agent for carbon fiber precursors was attached was subjected to a drying and densification treatment with heated rollers at 150°C, and further stretched 1.7 times between heated rollers at 170°C, and then wound around a bobbin to obtain a carbon fiber precursor.

[0095] The obtained carbon fiber precursor was rewound for 100 m, and the location of fuzzing was visually inspected and evaluated according to the following four levels, where A is the best level and D is the worst level. A: No noticeable fuzz (0 to 1 spot). B: Very little fuzz is observed (2-3 places). C: Slight fuzzing is observed (4 to 5 places). D: A large amount of fuzz is observed (6 or more places).

[0096] (2) Emulsion stability A 10% ion-exchange aqueous solution of the treatment agent for carbon fiber precursors of each of the Examples and Comparative Examples was circulated in an oil bath using a pump, and the state of the aqueous solution was visually observed. The observation results were classified into the following four levels. A is the best level, and D is the worst level. A: No gel formation was observed after 7 days, and smooth continuous operation was possible. B: After 7 days, a small amount of gel was observed, but no problems were observed with circulation by pump. C: After 7 days, gel formation was observed and circulation by pumping was possible. D: After 7 days, a lot of gel was generated and circulation by pump was unstable.

[0097] 〔result〕 Tables 1 to 3 show the raw material composition and the evaluation results of each example of the examples and comparative examples.

[0098] Table 1: Examples 1 to 10 [Table 1]

[0099] Table 2: Examples 11 to 20 [Table 2]

[0100] Table 3: Comparative Examples 1 to 7 [Table 3]

[0101] A comparison of the examples and comparative examples showed that when a treatment agent for carbon fiber precursors containing a sugar (A), a nonionic surfactant (B) having a polyoxyalkylene group, and a base (C) was used, the carbon fiber precursors had less fuzz and the emulsion of the treatment agent for carbon fiber precursors had high stability.

[0102] Examples 1 and 11, which contained a sugar (A) together with a nonionic surfactant (B), exhibited higher fuzz suppression properties than Comparative Example 2, which contained the same type of sugar (A) but no nonionic surfactant (B). Comparison of these Examples and Comparative Examples suggests that the fuzz suppression properties are enhanced by the synergistic effect of the sugar (A) and the nonionic surfactant (B).

[0103] Furthermore, when Example 1, Comparative Example 5, and Comparative Example 6, which contain the same type and proportion of nonionic surfactant (B), are compared, Example 1, which contains saccharide (A), exhibits higher emulsion stability than Comparative Examples 5 and 6, which do not contain saccharide (A). A comparison between these Examples and Comparative Examples suggests that emulsion stability is enhanced by the synergistic effect of saccharide (A) and nonionic surfactant (B). [Industrial Applicability]

[0104] The present invention can be used, for example, in the production of carbon fiber precursors.

Claims

1. The composition contains a saccharide (A), a nonionic surfactant (B) having a polyoxyalkylene group, and a base (C), The saccharide (A) is Alditol (A1), an alditol dehydrate (A2) which is at least one dehydrate selected from the group consisting of intramolecular dehydrations of alditol, intermolecular dehydrations of alditol, and intramolecular and intermolecular dehydrations of alditol, and which does not have an epoxy group in its molecular structure; a disaccharide (A3), and at least one compound selected from the group consisting of The base (C) is a silicone compound (C1); an ester compound (C2); a hydrocarbon oil (C3); A treating agent for carbon fiber precursors, comprising at least one compound selected from the group consisting of:

2. The treating agent for carbon fiber precursors according to claim 1, wherein the saccharide (A) contains four or more carbon atoms per molecule.

3. 2. The treatment agent for carbon fiber precursors according to claim 1, wherein the saccharide (A) is at least one compound selected from the group consisting of the alditol dehydrate (A2) and the disaccharide (A3).

4. The treating agent for carbon fiber precursors according to claim 1, wherein the proportion of the saccharide (A) in the nonvolatile content is 0.3 mass % or more and 30 mass % or less.

5. 2. The treatment agent for carbon fiber precursors according to claim 1, wherein the nonionic surfactant (B) has a branched hydrocarbon group having 6 to 24 carbon atoms.

6. of non-volatile matter, The proportion of the saccharide (A) is 0.01% by mass or more and 50% by mass or less, The proportion of the nonionic surfactant (B) is 5% by mass or more and 70% by mass or less, and The treatment agent for carbon fiber precursors according to claim 1, wherein the proportion of the base agent (C) is 1% by mass or more and 90% by mass or more.

7. A carbon fiber precursor comprising a fiber material to which the treating agent for carbon fiber precursors according to any one of claims 1 to 6 is adhered.

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