JPH1112853A - Oil agent for carbon fiber precursor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oil agent for a carbon fiber precursor excellent in process passableness and heat resistance without causing fusion among single filaments and any fuzz present therein by emulsifying and dispersing a specific amino-modified silicone and a specified nonionic surfactant and an antioxidant in a specific proportion in water. SOLUTION: This oil agent is obtained by emulsifying and dispersing (A) an amino-modified silicone represented by the formula R is a 1-20C alkyl or a 6-20C aryl; X is Q-(NH-Q')p -NH2 [Q and Q' are each a 1-10C bivalent hydrocarbon; (p) is 0-2]; Y is X, R, a 1-5C alkoxy or hydroxyl group; (m) is 10-10,000; (n) is 0-100}, (B) 0.01-20 wt.% (based on the component A) of an antioxidant such as an aromatic amino group-containing organopolysiloxane and (C) 5-100 wt.% (based on the component A) of a nonionic surfactant having 6-16 HLB such as a polyoxyethylene alkyl ether or a polyoxyethylene alkylphenyl ether in water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an oil agent for a carbon fiber precursor having good heat resistance and suitable for producing carbon fiber having excellent quality and physical properties.

[0002]

2. Description of the Related Art Carbon fiber is produced by a flame-proofing process in which a precursor fiber is converted into a flame-resistant fiber by heating at 200 to 400 ° C. in an oxidizing atmosphere, and subsequently in an inert atmosphere at least at 1,000 ° C. This is a method including a so-called carbonization step for performing carbonization by a conventional method.
In the above-mentioned flame-proofing step, fusion between the single fibers occurs, and the firing becomes uneven, and troubles such as fluff and yarn breakage occur. It is known that in order to avoid this fusion, it is important to select an oil agent to be imparted to the carbon fiber precursor before flame resistance, and many oil agents have been introduced. For example, it has good heat resistance and effectively suppresses fusion between single fibers.
The silicone oil disclosed in 5-140821 gazette,
It is widely used as an oil agent for carbon fiber precursors.

[0003] However, the oil agent for the carbon fiber precursor not only needs to have no fusion between the single fibers in the flame-proofing step, but also has no fusion to the carbon fiber precursor fiber itself and has substantially fuzz. It is also necessary that they do not occur. For example, in the oil agent used in the carbon fiber precursor spinning step, the yarn discharged from the spinning nozzle is coagulated in a coagulation bath, and washed or stretched. In the drying step of heating and densifying, it is required to prevent fusion between the single fibers to form a uniform and dense fiber structure, and to provide fibers having good processability. When a silicone oil is used as an oil for a carbon fiber precursor, the oil is liable to gel when heated, and the gelled silicone oil may cause fluff and thread breakage in the drying step. Is required to have high heat resistance and to be hardly gelled. In general, silicon oxide, which is a decomposition product of a silicone oil agent, is generated in the oxidization process, and is deposited on the oxidization furnace wall and the exhaust gas treatment line, resulting in a decrease in operability. Oil agents are required to have a small amount of decomposition products in the flame-proofing step. However, no oil agent for a carbon fiber precursor satisfying all of the above performances has been reported so far.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a carbon fiber precursor in which there is no fusion between single yarns, there is substantially no fluff, and the fluff of the precursor fiber in the oxidization-resistant step. An oil agent for a carbon fiber precursor, in which yarn breakage and fusion between single yarns are effectively suppressed, and the processability in the oxidization process is significantly improved by suppressing the amount of silicone decomposition products generated in the oxidization process. Is to provide.

[0005]

Means for Solving the Problems The inventors of the present invention have found that the addition of a specific antioxidant and a surfactant to a specific amino-modified silicone significantly improves the gelation temperature of the amino-modified silicone mixture and reduces the carbonation of the mixture. There is no fusion between the single yarns at the stage of the fiber precursor, there is substantially no fluff, and the fluff, breakage of the precursor fibers and the fusion between the single yarns in the flameproofing process are effectively suppressed, and the flame resistance It has been found that by suppressing the amount of silicone decomposition products generated in the oxidizing step, the processability in the oxidizing step is significantly improved, and the present invention has been completed.

That is, the gist of the present invention is the following (A) to (C)
An oil agent for a carbon fiber precursor comprising a heat-resistant amino-modified silicone mixture obtained by emulsifying and dispersing components in water. (A) an amino-modified silicone represented by the following general formula (Formula 1),

Embedded image [Wherein, R represents the same or different alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms, and X represents a general formula -Q- (N
H—Q ′) _p —NH ₂ , where Q and Q ′ are the same or different and are divalent hydrocarbon groups having 1 to 10 carbon atoms, and Y is X, R, an alkoxy group having 1 to 5 carbon atoms. , A hydroxyl group, and p
Is 0, 1, or 2. Also, 10 ≦ m ≦ 10,000,
0 ≦ n ≦ 100. (B) 0.01-20% by weight of antioxidant (A), (C) 5-100% by weight of nonionic surfactant of HLB 6-16 (A). Examples of the component (C) include polyoxyethylene alkyl ether and / or polyoxyethylene alkyl phenyl ether. Examples of the component (B) include an aromatic amino group-containing organopolysiloxane, and particularly preferred is an aromatic amino group-containing organopolysiloxane represented by the following general formula (Formula 6).

Embedded image [Wherein, R ′ is the same or different alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, and Z is R ′
Or a monovalent aromatic amino group selected from -O-Ph-NH-Ph, -O-Ph-NH-Ph-NH-Ph, and groups represented by the following formulas (7) and (8): is there. Further, q and r are 1 ≦ q ≦ 50, 0
≦ r ≦ 10, but it is necessary to have at least one or more aromatic amino groups in the molecule. Therefore, when r = 0, at least one of Z in the formula is a monovalent aromatic amino group as described above. is there. ]

Embedded image

Embedded image

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the general formula (Chemical Formula 1) of the component (A) in the present invention, R in the formula is the same or different and is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. , Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, tetradecyl, octadecyl, phenyl, tolyl, naphthyl, etc. or a bond to these carbon atoms A monovalent hydrocarbon group in which part or all of the hydrogen atom has been substituted with a halogen atom, a hydroxyl group, or the like,
Preferably it is a methyl group. X is a general formula -Q- (NH-Q ') _p -N
An amino group represented by H ₂ , wherein Q and Q ′ are the same or different divalent hydrocarbon groups having 1 to 10 carbon atoms, and specifically include a methylene group, a dimethylene group, a trimethylene group, and a tetramethylene group. , Pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group,
Decamethylene group and those in which some of these carbon atoms are replaced with other atoms such as oxygen atoms and sulfur atoms, and those in which some or all of the hydrogen atoms of these carbon atoms are replaced with halogen atoms, hydroxyl groups, etc. And a hydrocarbon group. Preferably, it is a dimethylene group or a trimethylene group. Y is any of the aforementioned X, R or an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, and examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a butoxy group, and a propoxy group. Can be p is 0, 1, or 2. From the viewpoint of production, p is preferably 0 or 1. Also, 10 ≦ m ≦ 10,000 and 0 ≦ n ≦ 100, preferably 50 ≦ m ≦ 1,000 and 0 ≦ n ≦ 10.

Specific examples of the amino-modified silicone of the component (A) include the following general formulas (9) to (1).
The compound represented by 9) can be mentioned, but the present invention is not limited to these.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

The antioxidant (B) in the present invention is used to suppress the thermal oxidative deterioration of the amino group, and is represented by the following formulas (20) and (21). Hindered phenols, PhNHPhNHPh, PhNHPh, aromatic amines represented by the following formulas (Formula 22) and (Formula 23), hindered phenol group-containing organopolysiloxanes, aromatic amino group-containing organopolysiloxanes, and the like. Particularly preferred are those represented by the general formula (Chemical Formula 2)
And an aromatic amino group-containing organopolysiloxane represented by the formula:

Embedded image

Embedded image

Embedded image

Embedded image

In the present invention, the amount of the component (B) added is preferably 0.01 to 20% by weight of the amino-modified silicone of the component (A).
It is. If less than 0.01%, the effect of improving heat resistance is weak, and 20%
The effect of improving heat resistance does not change even if added in excess of 0.1, and instead, the stability of the silicone emulsion deteriorates.
It is preferably from 01 to 20%, more preferably from 0.1 to 5%.

Next, HLB6 of the component (C) in the present invention is used.
The nonionic surfactants Nos. To 16 are surfactants for emulsifying and dispersing both the components (A) and (B) in water. When the HLB exceeds 16, the heat resistance of the obtained silicone emulsion is increased. If the HLB is less than 6, the emulsion stabilizer of the silicone emulsion will be poor if the HLB is less than 6. Therefore, the HLB is preferably from 6 to 16, more preferably from 10 to 14.

Specific examples of the nonionic surfactant (C) in the present invention include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, and sorbitan fatty acid ester. Among them, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl ether are preferred. This addition amount is 5 to 100% by weight of the amino-modified silicone of the component (A). If the amount is less than 5% by weight, the emulsification stability of the amino-modified silicone is deteriorated. If the amount exceeds 100% by weight, the properties of the amino-modified silicone may be impaired.
00% by weight, more preferably 10 to 50% by weight.
% By weight. In addition, an antistatic agent, a penetrating agent, a thickener, a defoaming agent, a pigment, an inorganic powder, an antiseptic, and the like are appropriately blended into the silicone emulsion composition comprising these components as various additives in order to improve its properties. That is fine.

Examples of the carbon fiber precursor to be treated with the oil agent of the present invention include known rayon fibers, acrylic fibers, vinylon fibers, various pitch yarn fibers, and the like. And an acrylic fiber are more preferable. As the acrylic fiber, a known carbon fiber precursor acrylic fiber can be exemplified, and is not particularly limited. From 95% by weight or more of acrylonitrile monomer and 5% by weight or less of vinyl monomer copolymerizable with acrylonitrile. Acrylic fibers are preferred. Further, the vinyl monomer is selected from a group of monomers such as acrylic acid, methacrylic acid, itaconic acid, or alkali metal salts or ammonium salts of these acids and acrylamide, which have an action of promoting a flame-resistant reaction. It is preferable to use one or more monomers in order to promote the flame-resistant reaction. The method for producing such fibers is not particularly limited, either, and any of the known wet, dry, and dry-wet spinning methods may be employed.

[0014]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention. The degree of gelation, weight retention, number of fusions, passability of the oil agent before the oxidization process, amount of scattered silicone oil decomposition products, and strand strength of the oil agent were evaluated by the following methods.

[Method for Measurement and Evaluation of Heat Resistance (Degree of Gelation)]
2.0 g of the oil emulsion of the present invention was precisely weighed in an aluminum Petri dish (60 mm in diameter, 10 mm in depth), preliminarily dried at 105 ° C. for 1 hour, and heated at 150 ° C. for 24 hours. The content was calculated as the degree of gelation, and the heat resistance was evaluated. The smaller the degree of gelation, the better the heat resistance and the better the processability in the drying step after the oil emulsion is attached, that is, less fuzz and yarn breakage induced by the gelled silicone oil. .

[Measurement and evaluation method of decomposed and scattered matter (weight retention)] 2.0 g of the oil agent emulsion of the present invention was precisely weighed in an aluminum dish (diameter 60 mm, depth 10 mm), and preliminarily dried at 105 ° C. for 1 hour. The weight retention of the residue after heating at 250 ° C. for one hour was calculated, and the scattering behavior of the decomposition product was evaluated. The higher the weight retention ratio, the smaller the amount of decomposition products of the silicone oil agent generated in the flame-proofing step.

[Measurement and evaluation method of fusion between single fibers (number of fusion)] A carbon fiber tow was cut into a length of 3 mm, dispersed in acetone, and stirred with a magnetic stirrer for 10 minutes. And the number of fusions were counted, and the number of fusions per 100 fibers was calculated. The evaluation criteria are as follows. ○: Number of fusions (pieces / 100 pieces) ≦ 1 ×: 1 <Number of fusions (pieces / 100 pieces)

[Passability of Step Before Oxidizing Step] Using acrylic fiber of the carbon fiber precursor, winding it around a roll or the like at the stage of the carbon fiber precursor acrylic fiber before the oxidizing step at the time of continuous sampling for one week. By the number of times, the amount of fluff and thread breakage at the stage of the precursor acrylic fiber was evaluated. The evaluation criteria are as follows. ：: Number of windings (times / day) ≦ 1 Δ: 1 <Number of windings (times / day) ≦ 10 ×: 10 <Number of windings (times / day)

[Scattering of Silicone-based Oil Decomposed Product] The amount of silicone-based oil-based decomposed product in the flameproofing furnace was represented by the cleaning frequency of the flameproofing furnace when carbon fibers were continuously sampled for one week. The evaluation criteria are as follows. ○: Number of cleaning times (times / week) ≦ 1 ×: 1 <number of cleaning times (times / week)

[Measurement and Evaluation Method of Physical Properties of Carbon Fiber (Strand Strength)] This is a value measured according to the epoxy resin-impregnated strand method specified in JIS-R-7601.
(Note that the number of measurements was 10 times, and the physical properties were indicated by their average values.)

(Example 1) 150 g of an amino-modified silicone represented by the following (Formula 24)

Embedded image As an antioxidant, 0.5 g of an aromatic amino group-containing organopolysiloxane represented by the following (Formula 25)

Embedded image Polyoxyethylene lauryl ether [E
O: 5 mol, HLB: 10.8], a mixture of 30 g of water and 820 g of water were emulsified by a homomixer, and further emulsified by a high-pressure homogenizer.
Secondary emulsification was performed at 0 kg / cm ² to obtain an oil emulsion.
The heat resistance (gelling degree, the same applies hereinafter) of this oil agent was measured, and the results are shown in Table 1.

Example 2 The formula (Formula 2) used in Example 1 was used.
4) 150 g of an amino-modified silicone represented by the formula:
A mixture of 0.5 g of the aromatic amino group-containing organopolysiloxane represented by 5), 50 g of polyoxyethylene lauryl ether [EO: 10 mol, HLB: 14.0] as an emulsifier, and 800 g of water was homomixed in the same manner as in Example 1. And then subjected to secondary emulsification with a high-pressure homogenizer to obtain an oil emulsion. The heat resistance of this oil agent was measured, and the results are shown in Table 1.

Example 3 150 g of an amino-modified silicone represented by the following formula (Formula 26)

Embedded image 0.5 g of an aromatic amino group-containing organopolysiloxane represented by the formula (Formula 25), 50 g of polyoxyethylene lauryl ether [EO: 5 mol, HLB: 10.8] as an emulsifier,
A mixture of 820 g of water was emulsified with a homomixer in the same manner as in Example 1, and further subjected to secondary emulsification with a high-pressure homogenizer to obtain an oil emulsion. Measure the heat resistance of this oil,
The results are shown in Table 1.

Example 4 150 g of an amino-modified silicone represented by the following formula (Formula 27)

Embedded image 3 g of an aromatic amino group-containing organopolysiloxane represented by the formula (Formula 25) and 50 g of polyoxyethylene tridecyl ether [EO: 10 mol, HLB: 13.7] as an emulsifier
And 797 g of water were emulsified with a homomixer in the same manner as in Example 1 and further subjected to secondary emulsification with a high-pressure homogenizer to obtain an oil emulsion. The heat resistance of this composition was measured, and the results are shown in Table 1.

Example 5 150 g of an amino-modified silicone represented by the following formula (Formula 28)

Embedded image 3 g of an aromatic amino group-containing organopolysiloxane represented by the formula (Formula 25) and 50 g of polyoxyethylene tridecyl ether [EO: 10 mol, HLB: 13.7] as an emulsifier
And 797 g of water were emulsified with a homomixer in the same manner as in Example 1 and further subjected to secondary emulsification with a high-pressure homogenizer to obtain an oil emulsion. The oil agent heat resistance was measured, and the results are shown in Table 1.

Example 6 150 g of an amino-modified silicone represented by the following formula (Formula 29)

Embedded image 3 g of an aromatic amino group-containing organopolysiloxane represented by the formula (Formula 25) and 50 g of polyoxyethylene tridecyl ether [EO: 10 mol, HLB: 13.7] as an emulsifier
And 797 g of water were emulsified with a homomixer in the same manner as in Example 1 and further subjected to secondary emulsification with a high-pressure homogenizer to obtain an oil emulsion. The heat resistance of this oil agent was measured, and the results are shown in Table 1.

Comparative Example 1 The formula (Formula 2) used in Example 1 was used.
4) 150 g of an amino-modified silicone represented by the formula:
0.5 g of an organopolysiloxane containing an aromatic amino group represented by 5), 15 g of polyoxyethylene lauryl ether [EO: 4 mol, HLB: 9.6] as an emulsifier, 23 g of polyoxyethylene lauryl ether [EO: 23 mol, HLB:
16.9] A mixture of 15 g of water and 820 g of water was emulsified with a homomixer in the same manner as in Example 1 and further emulsified with a high-pressure homogenizer to obtain an oil emulsion. The heat resistance of this oil agent was measured, and the results are shown in Table 1.

Comparative Example 2 The formula (Formula 2) used in Example 1 was used.
A mixture of 150 g of the amino-modified silicone shown in 4), 15 g of polyoxyethylene lauryl ether [EO: 10 mol, HLB: 14.0] as an emulsifier, and 835 g of water was emulsified with a homomixer in the same manner as in Example 1, and further a high-pressure homogenizer. To carry out secondary emulsification to obtain an oil emulsion. The heat resistance of this oil agent was measured, and the results are shown in Table 1.

Comparative Example 3 The formula used in Example 1 (Chemical Formula 2)
4) 150 g of an amino-modified silicone represented by the formula:
A mixture of 0.1 g of the aromatic amino group-containing organopolysiloxane represented by 5), 5 g of polyoxyethylene lauryl ether [EO: 10 mol, HLB: 14.0] as an emulsifier, and 845 g of water was treated with a homomixer in the same manner as in Example 1. Emulsify,
Further, secondary emulsification was performed with a high-pressure homogenizer to obtain an oil emulsion. The heat resistance of this oil agent was measured, and the results are shown in Table 1.

Example 7 An acrylonitrile copolymer (weight ratio of acrylonitrile / methacrylic acid / acrylamide 97.1 / 0.9 / 2.0) was dissolved in dimethylacetamide, and the polymer concentration was 21% by weight and the viscosity at 60 ° C. was 500 poise. A spinning dope is prepared, discharged once into the air through a spinneret having a hole diameter of 0.15 mmφ and a number of holes of 1,500, passed through a space of about 5 mm, and then passed through a coagulation bath filled with a 69% by weight aqueous solution of dimethylacetamide at 35 ° C. Into a coagulated yarn. The coagulated yarn was desolvated in a water washing tank and stretched 3.5 times to obtain a water-swelled acrylic fiber. The acrylic fiber in the water-swelled state was led to an oil bath filled with the oil agent emulsion shown in Example 1, and after the emulsion was attached thereto, it was dried and densified with a heating roll having a surface temperature of 130 ° C. It was stretched 2.0 times between heating rolls to obtain a precursor acrylic fiber. This precursor acrylic fiber has a single yarn fineness of 1.1 denier, a tensile strength of 7 g / denier, and an elongation of 1 denier.
At 2.5%, the applied amount of the oil agent to the fiber was 1.0% by weight.
The precursor acrylic fiber is passed through a stabilization furnace having a temperature gradient of 230 to 270 ° C. for 60 minutes, and further in a nitrogen atmosphere.
It was fired in a carbonization furnace having a temperature gradient of 300 to 1,300 ° C to obtain carbon fibers. Table 2 shows the fusion number and strand strength of the carbon fibers obtained here, evaluation of the passability of the process before the oxidization process, and the amount of scattered silicone decomposed products in the oxidization process (evaluated by the number of times of furnace cleaning, the same applies hereinafter). Indicated.

COMPARATIVE EXAMPLE 4 3 kg of the amino-modified silicone represented by the same chemical formula as in Example 1 and polyoxyethylene lauryl ether [EO: 5 mol, HL as an emulsifier]
B: 10.8] A mixture containing 600 g of water and 16.4 kg of water without an antioxidant was emulsified in the same manner to obtain an oil emulsion. The same spinning dope as in Example 7 was prepared from this oil agent emulsion, and attached to the fiber obtained by the same operation to obtain a precursor acrylic fiber. This precursor acrylic fiber has a single yarn fineness of 1.1 denier, a tensile strength of 6.8 g / denier, and an elongation of 1 denier.
At 1.8%, the adhesion amount of the oil agent to the fiber was 1.0% by weight.
This precursor acrylic fiber was fired in the same manner as in Example 7 to obtain a carbon fiber. Table 2 shows the evaluation results of the number of fused carbon fibers, the strand strength, the passability of the process before the oxidization process, and the scattering amount of the silicone decomposition product in the oxidization process.

Comparative Example 5 The formula (Formula 2) used in Example 5 was used.
8% of the amino-modified silicone shown in 8), 600 g of polyoxyethylene lauryl ether [EO: 5 mol, HLB: 10.8] as an emulsifier, and 16.4 kg of water were emulsified in the same manner as described above to obtain an oil emulsion. Obtained. The same spinning dope as in Example 7 was prepared from this oil agent emulsion, and an emulsion precursor acrylic fiber applied to the fiber obtained by the same operation was obtained. This precursor acrylic fiber had a single yarn fineness of 1.1 denier, a tensile strength of 6.7 g / denier, an elongation of 11.5%, and the applied amount of the oil agent to the fiber was 1.0% by weight. This precursor acrylic fiber was fired in the same manner as in Example 7 to obtain a carbon fiber. Table 2 shows the evaluation results of the number of fused carbon fibers, the strand strength, the passability of the process before the oxidization process, and the scattering amount of the silicone decomposition product in the oxidization process.

Example 8 The same spinning dope as in Example 7 was prepared and discharged from a spinneret having a pore size of 0.075 mmφ and 12,000 holes into a coagulation bath filled with a 69% by weight aqueous solution of dimethylacetamide at 35 ° C. And The coagulated yarn was desolvated in a washing tank and stretched 5 times to obtain a water-swelled acrylic fiber. The acrylic fiber in the water-swelled state was prepared in Example 1
After introducing the emulsion into the oil bath filled with the emulsion shown in the above, the emulsion is adhered, and then dried and densified with a heating roll having a surface temperature of 130 ° C.
It was stretched 1.7 times to obtain a precursor acrylic fiber. This precursor acrylic fiber has a single yarn fineness of 1.1 denier, a tensile strength of 7 g / denier, an elongation of 10.5%, and the amount of oil agent adhering to the fiber.
1.0% by weight. This precursor acrylic fiber was fired in the same manner as in Example 7 to obtain a carbon fiber. Table 2 shows the evaluation results of the number of fused carbon fibers, the strand strength, the passability of the process before the oxidization process, and the scattering amount of the silicone decomposition product in the oxidization process.

[0034]

[Table 1]

[Table 2]

[0035]

The oil agent for a carbon fiber precursor of the present invention has good heat resistance, so there is no fusion between the single yarns at the stage of the carbon fiber precursor, there is substantially no fuzz, and in the flame-proofing step. Fuzz of the precursor fiber, yarn breakage and fusion between the single yarns are effectively suppressed, and the amount of the silicone decomposed matter scattered in the flame-proofing process is small, so that the processability in the process is significantly improved.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Satoshi Kuwata 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory Shin-Etsu Chemical Co., Ltd. (72) Inventor Masayoshi Tanaka Otemachi, Chiyoda-ku, Tokyo 2-6-1, Shin-Etsu Chemical Co., Ltd. (72) Inventor Tomoyuki Kotani 20-1, Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Central Research Laboratory (72) Inventor Yoshitaka Kageyama Otake City, Hiroshima Prefecture 20-1 Miyukicho Mitsubishi Rayon Co., Ltd. Central Research Laboratory

Claims (5)

[Claims] 1. An oil agent for a carbon fiber precursor obtained by emulsifying and dispersing the following components (A) to (C) in water: (A) an amino-modified silicone represented by the following general formula (1): [Wherein, R represents the same or different alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 20 carbon atoms, and X represents a general formula -Q- (N
H—Q ′) _p —NH ₂ , where Q and Q ′ are the same or different and are divalent hydrocarbon groups having 1 to 10 carbon atoms, and Y is X, R, an alkoxy group having 1 to 5 carbon atoms. , A hydroxyl group, and p
Is 0, 1, or 2. Also, 10 ≦ m ≦ 10,000,
0 ≦ n ≦ 100. (B) 0.01-20% by weight of antioxidant (A), (C) 5-100% by weight of nonionic surfactant of HLB 6-16 (A). 2. The oil agent for a carbon fiber precursor according to claim 1, wherein the carbon fiber precursor is a polyacrylonitrile fiber. 3. The composition according to claim 1, wherein the component (C) is a polyoxyethylene alkyl ether and / or a polyoxyethylene alkyl phenyl ether.
3. The oil agent for a carbon fiber precursor according to item 1. 4. The composition according to claim 1, wherein the component (B) is an organopolysiloxane containing an aromatic amino group.
The oil agent for a carbon fiber precursor according to any one of the above items. 5. The carbon fiber precursor according to claim 1, wherein the component (B) is an aromatic amino group-containing organopolysiloxane represented by the following general formula (Formula 2). Body oil. Embedded image [Wherein, R ′ is the same or different alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, and Z is R ′ or
-O-Ph-NH-Ph, -O-Ph-NH-Ph-NH-Ph, a monovalent aromatic amino group selected from the groups represented by the following formulas (3) and (4), q , R satisfies 1 ≦ q ≦ 50 and 0 ≦ r ≦ 10, and at least one of Z in the formula when r = 0 since it is necessary to have at least one aromatic amino group in the molecule. Is the above-mentioned monovalent aromatic amino group. Here, Ph represents a phenyl group. ] Embedded image