JPH11181675A - Synthetic fiber treatment agent for carbon fiber production and treatment of synthetic fiber for carbon fiber production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject treatment agent simultaneously satisfying fusing prevention during the incombustibilizing process in carbon fiber production and the prevention of in-baking oven contaminant emission during the carbonization process by formulating a specific cumylphenol derivative, a modified polysiloxane and a surfactant. SOLUTION: This treatment agent is obtained by formulating 15-75 wt.% of a cumylphenol derivative of the formula [X is a 2-18C bivalent (un)saturated aliphatic hydrocarbon or 6-10C bivalent aromatic hydrocarbon; A<1> and A<2> are each a 2-4C alkoxy, pref. epoxy and/or propoxy; (m) and (n) are each an integer of 0-10] as lubricating agent, 25-75 wt.% of an amino-modified polysiloxane with an average molecular weight of 4,000-50,000, and 5-50 wt.% of a nonionic surfactant. This treatment agent is applied at 0.2-1.5 wt.% to acrylic fiber for carbon fiber production.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber treating agent for producing carbon fibers (hereinafter simply referred to as a treating agent) and a synthetic fiber treating method for producing carbon fibers (hereinafter simply referred to as a treating method). When manufacturing carbon fibers from pitch fibers or acrylic fibers, it is required to prevent fusion of the oxidized fibers in the oxidization process in order to produce high quality carbon fibers at low cost. It is required to prevent the generation of pollutants in the firing furnace. The present invention relates to a treating agent and a treating method that meet such demands.

[0002]

2. Description of the Related Art Conventionally, a treatment agent containing silicone has been used as a lubricant. However, although such a treating agent can prevent fusion of the oxidized fibers, in the carbonization process after the oxidizing process, decomposition of the treating agent generates contaminants in the firing furnace such as silicon oxide and silicon nitride. Therefore, it is necessary to frequently clean the inside of the firing furnace because of the deposition, and there is a disadvantage that productivity is significantly reduced. Therefore, conventionally, a treatment agent containing no silicone has been proposed as a lubricant. Examples of this include 1) a mixture of a fatty acid ester of an alkylene oxide adduct of bisphenol A and an alkylene oxide adduct of an amide compound (JP-A-9-78340), 2) condensation of a dibasic acid and a polyol having an oxyalkylene unit. There is a mixture of a compound having an amide group at a terminal obtained by reacting a compound with an aliphatic alkanolamide and an alkylene oxide adduct of an amide compound (JP-A-9-78341). However,
These treatment agents have the disadvantage that the fusion of the oxidized fibers cannot be sufficiently prevented.

[0003]

The problem to be solved by the present invention is that the conventional treating agent has a problem in that, when carbon fibers are produced from pitch fibers or acrylic fibers, fusion of the oxidized fibers in the oxidizing process is difficult. The point is that it is not possible to simultaneously and sufficiently prevent the adhesion and the generation of pollutants in the firing furnace in the carbonization step.

[0004]

Means for Solving the Problems Thus, the present inventors have
As a result of research to solve the above-mentioned problems, it has been found that a treating agent containing a specific cumylphenol derivative is properly and suitably used as a lubricant.

That is, the present invention relates to a treating agent comprising a cumylphenol derivative represented by the following formula 1 as a lubricant and a treating method using the treating agent.

[0006]

(Equation 1)

In the formula 1, X is a divalent saturated aliphatic hydrocarbon group having 2 to 18 carbon atoms, a divalent unsaturated aliphatic hydrocarbon group having 2 to 18 carbon atoms, or a divalent having 6 to 10 carbon atoms. aromatic hydrocarbon group a ¹ of, a ^2: alkoxy group having 2 to 4 carbon atoms m, n: 1 to 10 integer

[0008] In the present invention, the formula 1 used as a lubricant
The cumylphenol derivative represented by the formula (1) is a cumylphenol to which a lower alkylene oxide is subjected to ring-opening addition or ring-opening addition polymerization, and 2 mol of cumylphenyloxy (poly) alkoxylate and 1 mol of dicarboxylic acid or ester forming property of dicarboxylic acid. This is a diester obtained by reacting 1 mol of a derivative.

The lower alkylene oxide used for the synthesis of the cumylphenol derivative represented by the formula 1 includes ethylene oxide, propylene oxide, 1,2-butylene oxide and the like. Cumyl phenyloxy (poly) alkoxylates obtained by ring-opening addition or ring-opening addition polymerization of cumylphenol with lower alkylene oxide include a single lower alkylene oxide adduct and 2
There may be mentioned from 3 to 3 kinds of lower alkylene oxide mixed adducts, but those obtained by reacting ethylene oxide at a ratio of 50 mol% or more are preferable, and those obtained by reacting ethylene oxide alone are more preferable. In such cumylphenyloxy (poly) alkoxylate, the number of moles of the lower alkylene oxide to be added is 1 to 10,
Preferably it is 1 or 2 mol.

The dicarboxylic acids and ester-forming derivatives of the dicarboxylic acids to be used for the synthesis of the cumylphenol derivative represented by the formula 1 include: 1) succinic acid, adipic acid, azelaic acid, sebacic acid, α, ω-dodecanedicarboxylic acid 2) dimethyl succinate, dimethyl adipate, dimethyl azelate, dimethyl sebacate, dichloride succinate, etc.
Adipic dichloride, azelaic dichloride,
The ester-forming derivative of the above 1) such as sebacic acid dichloride; 3) unsaturated aliphatic dicarboxylic acid having 4 to 20 carbon atoms such as maleic acid, dodecenyl succinic acid, octadecenyl dicarboxylic acid; 4) dimethyl maleate and dodecenyl succinic acid Ester-forming derivatives of the above 3) such as dimethyl dimethyl octadecenyldicarboxylate, maleic dichloride, dodecenyl succinic dichloride, octadecenyl dicarboxylic dichloride, etc. 5) terephthalic acid, isophthalic acid, 2,6-naphthalene Dicarboxylic acid,
8 to 12 carbon atoms such as 2,3-naphthalenedicarboxylic acid
Aromatic dicarboxylic acid, 6) dimethyl terephthalate, dimethyl isophthalate, dimethyl 2,6-naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate,
Dimethyl 1,4-naphthalenedicarboxylate, terephthalic dichloride, isophthalic dichloride, 2,6-
Examples of the ester-forming derivatives of the above 5) such as naphthalenedicarboxylic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride, and 1,4-naphthalenedicarboxylic acid dichloride. Among them, saturated aliphatic dicarboxylic acids having 4 to 6 carbon atoms such as succinic acid and adipic acid and ester-forming derivatives thereof can be advantageously used.

In the present invention, the cumylphenol derivative represented by the formula 1 is a diester obtained by an esterification reaction between the above-mentioned cumylphenyloxy (poly) alkoxylate and dicarboxylic acid or an ester-forming derivative of dicarboxylic acid. is there. The present invention does not particularly limit such an esterification reaction, and a known method can be applied thereto. For example, 1) cumylphenyloxy (poly) alkoxylate and dicarboxylic acid are subjected to an esterification reaction by distilling off the produced water under heating and reduced pressure in the presence of p-toluenesulfonic acid as an acid catalyst. Method 2) Esterification reaction of cumylphenyloxy (poly) alkoxylate and dimethyl dicarboxylate in the presence of paratoluenesulfonic acid, which is an acid catalyst, by distilling off the produced methanol under heating and reduced pressure. And the like.

In the present invention, the content of the cumylphenol derivative represented by the above-mentioned formula 1 is not particularly limited, but it is preferably 15 to 75% by weight, preferably 20 to 70% by weight in the treating agent. More preferably,

The treating agent of the present invention contains a cumylphenol derivative represented by the formula 1 as a lubricant.
Further, a modified polysiloxane may be contained. Such modified polysiloxanes include 1) amino-modified polysiloxane, 2) polyether-modified polysiloxane, 3)
Epoxy-modified polysiloxane and the like can be mentioned, and among them, amino-modified polysiloxane is preferable, and the average molecular weight is 4
000-50,000 amino-modified polysiloxanes are particularly preferred.

In the present invention, the content of the modified polysiloxane is not particularly limited.
It is preferably 75% by weight, more preferably 30 to 70% by weight.

The treating agent of the present invention contains a cumylphenol derivative represented by the formula 1 as a lubricant, or contains the above-mentioned modified polysiloxane, and further contains a surfactant. can do. The present invention does not particularly limit such surfactants, but nonionic surfactants are preferred. Nonionic surfactants include polyoxyalkylene polyhydric alcohol fatty acid esters, polyoxyalkylene glycol fatty acid esters, polyoxyalkylene glycol ethers of aliphatic alcohols, polyoxyalkylene glycol ethers of aliphatic amines, and polyoxyalkylene glycol ethers of alkyl-substituted phenols. Oxyalkylene glycol ethers and polyhydric alcohol partial fatty acid esters are exemplified. The number of repeating oxyalkylene units, the type of oxyalkylene units, and the form of repeating oxyalkylene units of the nonionic surfactant may be adjusted to a desired emulsifiability or dispersibility in the aqueous liquid when preparing an aqueous liquid of the treating agent. Can be appropriately selected so as to obtain the property.

In the present invention, the content of the above-mentioned surfactant is not particularly limited.
And more preferably 10 to 40% by weight.

Although the treatment agent of the present invention has been described above, a cumylphenol derivative using the treatment agent as a lubricant,
When it is composed of a modified polysiloxane and a surfactant, the cumylphenol derivative is 30 to 45% by weight, the modified polysiloxane is 30 to 45% by weight, and the surfactant is 10 to 4%.
Most preferably, the content is 0% by weight (total 100% by weight).

In the treatment method of the present invention, the treatment agent of the present invention is used in an amount of 0.2 to 1.5% by weight, preferably 0.3 to 1.2% by weight, based on the synthetic fiber for producing carbon fiber. To adhere.

The treatment method of the present invention does not particularly limit the method of adhering the treating agent of the present invention to the synthetic fiber for producing carbon fiber. Examples of the adhering method include a dipping lubrication method, a roller lubrication method, and a metering pump. Well-known methods such as a guide lubrication method, a spray lubrication method and the like, but an immersion lubrication method,
A roller lubrication method or a guide lubrication method using a metering pump is preferable.

In attaching the treating agent of the present invention to the synthetic fibers for producing carbon fiber, the treating agent may be an aqueous emulsion thereof, an organic solvent solution thereof, or a uniform liquid obtained by heating to 40 to 80 ° C. Can be used as it is, but is preferably used as an aqueous emulsion.
When attaching the treating agent to the synthetic fiber for carbon fiber production,
Other components, for example, antioxidants, preservatives, rust preventives and the like can be used together for the purpose, but it is preferable to use as little as possible.

The treatment agent and the treatment method of the present invention can be applied to pitch fibers or acrylic fibers for producing carbon fibers, but are more effective when applied to acrylic fibers.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the treating agent and the treating method according to the present invention include the following 1) to 8). 1) As a lubricant (M-1), X in the formula 1 is an ethylene group,
When A ¹ and A ² are ethoxy groups, and m and n are 1, 90% by weight of a cumylphenol derivative, a surfactant (N-
1) Polyoxyethylene (the number of repeating oxyethylene units is 10) lauryl ether {POE (v
= 10) A treating agent (T-1) containing｝ as lauryl ether at a ratio of 10% by weight. Then, the treating agent (T-1) is converted into an aqueous emulsion, and the aqueous emulsion is immersed in oil so as to be 1% by weight with respect to the acrylic filament for carbon fiber production.

2) As the lubricant (M-2), X in the formula 1 is a tetramethylene group, A ¹ and A ² are ethoxy groups, m and n
2 is 90% by weight of a cumylphenol derivative and 10% by weight of POE (v = 6) nonylphenyl ether as a surfactant (N-2) (T-2). ). Then, the treating agent (T-2) is converted into an aqueous emulsion, and the aqueous emulsion is immersed and supplied in an amount of 1.2% by weight with respect to the acrylic filament for producing carbon fiber.

3) As the lubricant (M-3), X in the formula 1 is a vinylene group, A ¹ and A ² are ethoxy groups / propoxy groups =
A mixture of 2/1 (molar ratio), 90% by weight of a cumylphenol derivative when m and n are 3, a surfactant (N-
3) A treating agent (T-3) containing 10% by weight of POE (v = 25) hydrogenated castor oil. Then, the treating agent (T-3) is converted into an aqueous emulsion, and the aqueous emulsion is immersed and supplied in an amount of 1.0% by weight to the acrylic filament for producing carbon fibers.

4) As the lubricant (M-4), X in the formula 1 is a phenylene group, A ¹ and A ² are ethoxy groups, and m and n are 5
A treating agent (T-4) containing 90% by weight of a cumylphenol derivative and 10% by weight of a surfactant (N-1). Then, the treatment agent (T-4) is converted into an aqueous emulsion, and the aqueous emulsion is immersed in oil so as to be 1.2% by weight of the acrylic filament for producing carbon fiber.

5) An amino-modified polysiloxane (S-1) having a lubricant (M-1) of 45% by weight and an average molecular weight of 8,000.
(T-5) containing 45% by weight of a surfactant and 10% by weight of a surfactant (N-1). Then, the treating agent (T-5) was made into an aqueous emulsion, and the aqueous emulsion was added to the acrylic filament for producing carbon fiber in an amount of 0.1%.
A treatment method in which oil is immersed so as to be 6% by weight.

6) Amino-modified polysiloxane having an average molecular weight of 20,000 containing 40% by weight of a lubricant (M-2) (S-
2) 30% by weight, surfactant (N-2) 30% by weight
(T-6). Then, the treating agent (T-6) is converted into an aqueous emulsion, and the aqueous emulsion is immersed in oil so as to be 0.6% by weight with respect to the acrylic filament for producing carbon fiber.

7) Amino-modified polysiloxane having an average molecular weight of 45,000 (S-
3) 26% by weight, surfactant (N-1) 50% by weight
(T-7). Then, the treating agent (T-7) is converted into an aqueous emulsion, and the aqueous emulsion is immersed in oil so as to be 0.6% by weight with respect to the acrylic filament for producing carbon fibers.

8) 45% by weight of a lubricant (M-4), 45% by weight of an amino-modified polysiloxane (S-1), and 10% by weight of a surfactant (N-1). Treatment agent (T-8). Then, the treating agent (T-8) is converted into an aqueous emulsion, and the aqueous emulsion is immersed in oil so as to be 0.6% by weight with respect to the acrylic filament for producing carbon fiber.

Hereinafter, examples and the like will be described in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following examples and the like, parts are parts by weight and% is% by weight unless otherwise specified.
It is.

[0031]

[Example] Test Category 1 (Synthesis of cumylphenol derivative)-Synthesis of cumylphenol derivative (M-1) 212 g (1 mol) of paracumylphenol and 2 g of triethylamine were charged into an autoclave, and purged with nitrogen gas. While maintaining the temperature at エ チ レ ン 140 ° C., 44 g (1 mol) of ethylene oxide were injected. After an aging reaction for 1 hour, the catalyst was removed to obtain a reaction product. The obtained reaction product was prepared by adding 1 mole of paracumylphenol to 1 mole of ethylene oxide.
It was a paracumylphenyloxyethylate having a hydroxyl value of 219 and an average molecular weight of 256 (GPC method, converted to polystyrene, the same applies hereinafter) to which moles were added (NMR analysis, the same applies hereinafter). Next, 512 g (2 mol) of paracumylphenyloxyethylate, 146 g (1 mol) of adipic acid and 2 g of paratoluenesulfonic acid monohydrate were charged into a flask, and stirred at 120 to 130 ° C. under a nitrogen gas stream.
Was heated. The reaction was continued for 2 hours while removing water generated at the same temperature under reduced pressure to obtain a product. When the obtained product was analyzed, it was a cumylphenol derivative (M-1) which is diparacumylphenyloxyethyl adipate having an average molecular weight of 622.

Cumylphenol derivative (M-2)
Synthesis of (M-4), (m-1) and (m-2) In the same manner as in the synthesis of cumylphenol derivative (M-1), cumylphenol derivatives (M-2) to (M-
4), (m-1) and (m-2) were synthesized. These contents are summarized in Table 1.

[0033]

[Table 1]

In Table 1, X, A ¹ , A ² , m, and n correspond to the symbols in Equation 1, respectively.

Test Category 2 (Preparation of treatment agent) Treatment agents (T-1) to (T-8) and (t-1), (t
-2), (t-5), (t-6), (t-8) to (t-
Preparation of 11) Cumylphenol derivative (M-1) 9 obtained in Test Category 1
0 parts and 10 parts of POE (v = 10) lauryl ether are mixed at 30 to 50 ° C. until uniform, and the treating agent (T-
1) was prepared. Similarly, treating agents (T-2) to (T
-8) and (t-1), (t-2), (t-5), (t
-6), (t-8) to (t-11) were prepared. The contents are summarized in Tables 2 and 3.

Processing agents (t-3), (t-4), (t-
Preparation of 7) Ethylene oxide of an amide compound of 1 mole of ester / diethylenetriamine and 2 mole of stearic acid obtained by further reacting adipic acid with a monoester of bisphenol A ethylene oxide 2 mole adduct and lauric acid
The treating agent (t-3) was prepared as a mixture of a molar adduct = 60/40 (weight ratio). Similarly, the treatment agent (t-
4) and (t-7) were prepared. These contents are summarized in Table 3.

Test Category 3 (Attachment and Evaluation of Treatment Agent to Acrylic Filament for Carbon Fiber Production)-Attachment of Treatment Agent to Acrylic Filament for Carbon Fiber Production 70 parts of water was added to 30 parts of treatment agent prepared in Test Category 2. In addition,
An aqueous emulsion was prepared using a homogenizer. This aqueous emulsion was adhered to an acrylic filament (16,000 denier / 12,000 filament) manufactured by a conventional method by an immersion oiling method, and then dried at 115 ° C. for 4 seconds using a dry heat roller to obtain a precursor tow. The precursor tow is oxidized for 60 minutes in a forced circulation oven at 240 ° C. to obtain oxidized fiber, and the oxidized fiber is baked in a firing furnace having a temperature gradient of 300 to 1800 ° C. in a nitrogen atmosphere for 50 minutes. Carbon fiber.

Measurement of Attached Amount of Treatment Agent According to JIS-L1073 (Synthetic fiber filament yarn test method), a normal hexane / ethanol (70/30 volume ratio) mixed solvent was used as an extraction solvent, Of the treating agent was measured. The results are summarized in Tables 2 and 3.

Evaluation of anti-fusing property Ten pieces of 2 cm long short fibers were cut out from the above-mentioned oxidized fiber at arbitrary 10 locations to obtain sample pieces. This sample piece was shaken lightly on white paper, the fusion state was visually observed, and the anti-fusion property was evaluated based on the following criteria. ◎: No fusion ○: Very little fusion △: Some fusion ×: Large fusion

Evaluation of Prevention of Contaminant Generation in Firing Furnace When 50 kg of the oxidized fiber was used as carbon fiber, the state of contamination in the firing furnace was visually observed and evaluated according to the following criteria. ◎: No contamination, no problem in process passability ：: Very slight contamination, no problem in process passability △: Contamination was apparent, and there was a problem in process passability ×: Severe contamination, process passability Problem with

[0041]

[Table 2]

In Table 2, the attached amount: the attached amount of the treating agent to the acrylic filament ratio: weight% Evaluation 1: Anti-fusing property Evaluation 2: Anti-generation of contaminants in firing furnace S-1: Amino having an average molecular weight of 8,000 Modified polysiloxane S-2: Amino-modified polysiloxane having an average molecular weight of 20,000 S-3: Amino-modified polysiloxane having an average molecular weight of 45,000 N-1: POE (v = 10) lauryl ether N-2: POE (v = 6) nonyl Phenyl ether N-3: POE (v = 25) hydrogenated castor oil These are the same below

[0043]

[Table 3]

In Table 3, C-1 is an ester obtained by further reacting adipic acid with a monoester of bisphenol A ethylene oxide 2 mol adduct and lauric acid / an amide compound of 1 mol of diethylenetriamine and 2 mol of stearic acid. Mixture of 10 mol of ethylene oxide adduct = 60/40 (weight ratio) C-2: Condensation product of 1.5 mol of adipic acid and 1 mol of 20 mol of ethylene oxide adduct of hydrogenated castor oil was added with 0.1 mol of oleic acid diethanolamide. Mixture of terminal amide compound reacted with 8 mol / ethylene oxide 10 mol adduct of amide compound reacted with 1 mol of diethylenetriamine and 2 mol of stearic acid = 70/30 (weight ratio) C-3: ethylene of bisphenol A Diester of oleic acid with 2 moles of oxide adduct C-4: C-5: Diester of ethylene oxide 10 mol adduct of benzyl acid with phthalic acid C-5: Diester of 49 mol ethylene oxide adduct of α-methylstyrylphenol and adipic acid C-6: 2 mol of ethylene oxide of bisphenol A C-7: Diester of 1 mol of paracumylphenyloxyethylate, 1 mol of ethyl alcohol, and 1 mol of adipic acid C-8: 5 mol of ethylene oxide adduct of oleyl alcohol and benzoic acid Ester with acid C-9: Ester of coconut oil reduced alcohol with benzoic acid

[0045]

As is apparent from the above description, the present invention described above has the following advantages in the production of carbon fibers: prevention of fusion of the oxidized fibers in the oxidization process and prevention of contaminants in the firing furnace during the carbonization process. There is an effect that the occurrence can be simultaneously and sufficiently prevented.

Claims (9)

[Claims] 1. A synthetic fiber treating agent for producing carbon fibers, comprising a cumylphenol derivative represented by the following formula 1 as a lubricant. (Equation 1) (In the formula 1, X: a divalent saturated aliphatic hydrocarbon group having 2 to 18 carbon atoms, a divalent unsaturated aliphatic hydrocarbon group having 2 to 18 carbon atoms, or a divalent aromatic having 6 to 10 carbon atoms. Group hydrocarbon group A ¹ , A ² : alkoxy group having 2 to 4 carbons m, n: integer of 1 to 10) 2. The cumylphenol derivative is represented by the formula
Is a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms, and A ¹
Is a ethoxy group and / or a propoxy group, and A ² is an ethoxy group and / or a propoxy group. 3. The cumylphenol derivative is represented by the formula m
Is 1 or 2, and n is 1 or 2. The synthetic fiber treating agent for carbon fiber production according to claim 1 or 2, wherein n is 1 or 2. 4. The synthetic fiber treating agent according to claim 1, which comprises a cumylphenol derivative in a proportion of 15 to 75% by weight. 5. The synthetic fiber treating agent according to claim 4, further comprising 25 to 75% by weight of the modified polysiloxane. 6. The modified polysiloxane has an average molecular weight of 40.
The synthetic fiber treating agent according to claim 5, which is an amino-modified polysiloxane having a molecular weight of from 00 to 50,000. 7. The synthetic fiber treating agent according to claim 4, further comprising a surfactant in a ratio of 5 to 50% by weight. 8. The synthetic fiber treating agent for producing carbon fiber according to claim 1, 2, 3, 4, 5, 6, or 7 in an amount of 0.2 to 1.5% by weight based on the synthetic fiber for producing carbon fiber. A method for treating a synthetic fiber for producing carbon fiber, the method comprising: 9. The method according to claim 8, wherein the synthetic fiber for producing carbon fiber is an acrylic fiber.