JP3481342B2 - Precursor oil composition for carbon fiber - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil composition for use in precursor fibers for carbon fibers (hereinafter referred to as precursors). 2. Description of the Related Art Carbon fibers, such as acrylic, rayon, polyvinyl alcohol or pitch fibers, which are precursors thereof, are converted into oxidized fibers in an oxidizing atmosphere at 250 to 300 ° C. (flame-resistant treatment). ), And then industrially manufactured by a method of carbonizing (carbonizing treatment) at a high temperature of 300 to 2,000 ° C in an inert atmosphere. Due to its excellent physical properties, it is widely used as a reinforcing fiber for composite materials. It's being used. However, in the above-mentioned industrial method for producing carbon fibers, in the flame-proofing treatment or the carbonizing treatment of the precursor, the single fibers are fixed or fused to each other, or the fluff or yarn accompanying the occurrence of mechanical defects on the fiber surface. The quality and physical properties of the obtained carbon fiber are low due to troubles such as cutting. [0003] These problems differ significantly depending on the type of oil agent attached to the yarn, and if the heat resistance of the oil agent is low, it is difficult to prevent such sticking or fusion between single fibers and occurrence of fiber defects. Can not. In order to prevent such single fibers from sticking or fusing to each other and to prevent troubles caused by mechanical defects on the surface of the fibers, Japanese Patent Publication No. 52-24136 and Japanese Patent Application Laid-Open No. 135
No. 510, Japanese Patent Application Laid-Open No. 63-203878 and many other methods have been proposed. It is well known that silicone oils have properties such as excellent heat resistance, good slippage between fibers / fibers, and good releasability. These properties make it possible to fix or fuse single fibers in a firing process. It has been proved by patents and the like that wear can be reduced to some extent. [0004] On the other hand, however, since the treated silicone oil has a strong water repellency, static electricity is liable to be generated, and fuzz is generated in a precursor manufacturing process and a flameproofing process.
Operational deterioration such as winding around rollers and guides and thread breakage is caused. In addition, a part of the silicon oxide is generated in an oxidizing atmosphere of a flame-proofing step, and silicon nitride is generated when nitrogen is used as an inert gas in an inert atmosphere of a carbonization step,
Deposits occur during the firing process, which lowers the physical properties of the carbon fibers and causes damage to the firing furnace. SUMMARY OF THE INVENTION An object of the present invention is to provide a high-quality, high-performance precursor oil for carbon fiber which satisfies the above-mentioned problems. [0006] That is, the present invention provides:
(A) a terminal amide compound obtained by reacting a fatty acid alkanolamide with a condensate obtained from a dibasic acid and a polyol having an oxyalkylene unit; and (B) an amide compound obtained by reacting a polyamine with a fatty acid. It can be achieved by a precursor oil composition for carbon fibers, which comprises an alkylene oxide adduct. The feature of the oil agent used in the present invention is that it contains a high-molecular amide compound and thus has excellent heat resistance and, in particular, has good adhesion to acrylic fibers, so that a uniform film is formed on the fiber surface. Excellent performance in fiber / fiber slippage and peelability. Therefore, it has a remarkable effect in preventing troubles caused by the above. In the terminal amide compound obtained by reacting a fatty acid alkanolamide with a condensate obtained from a dibasic acid as the component (A) of the present invention and a polyol having an oxyalkylene unit, the dibasic acid includes Fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid,
Sebacic acid, phthalic acid, thiodipropionic acid and the like. Of these, preferred are saturated dibasic acids such as adipic acid and sebacic acid. As a polyol having an oxyalkylene unit (hereinafter simply referred to as a polyol, and a polyhydric alcohol such as glycerin having no oxyalkylene unit as a polyhydric alcohol to distinguish between the two), two or more Examples include an alkylene oxide adduct of a compound having an active hydrogen group, and the polyol may be either a polyether polyol or a polyester polyol. In the present invention, a polyether polyol means a polyalkylene glycol such as cellosolve and polyethylene glycol in which an alkylene oxide such as ethylene oxide and propylene oxide has been added to a polyhydric alcohol, and polytetramethylene ether glycol. It means a polyol having two or more ester bonds. The average molecular weight is in the range of 500 to 10,000, preferably 1,000 to 5,000. Examples of the compound having two or more active hydrogen groups include aliphatic polyhydric alcohols and polyhydric phenols, and it is particularly preferable to use aliphatic polyhydric alcohols. Aliphatic polyhydric alcohols include dihydric alcohols such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and trihydric or higher alcohols such as glycerin, trimethylolpropane, pentaerythritol, and castor oil. Can be illustrated. The oxyalkylene unit is an oxyalkylene unit having 2 to 4 carbon atoms, such as an oxyethylene (EO) unit, an oxypropylene (PO) unit, and an oxybutylene (BO) unit. Two or more of these oxyalkylene units may be used in combination, and the oxyalkylene units may be random or block. Oxyethylene (EO) units are preferred. The fatty acid of the aliphatic alkanolamide is a fatty acid having 8 to 30 carbon atoms and may be saturated or unsaturated. Preferably it has 12 to 22 carbon atoms. When the carbon number is 8 or less, the heat resistance of the condensate decreases, and when it is 30 or more, the dispersibility in water is deteriorated, which is not preferable. Examples of the alkanolamine include monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, and monobutylethanolamine. The condensation method (esterification method) of the above condensate may be a conventional method, for example, 130 to 2 in the presence of a catalyst such as p-toluenesulfonic acid, hypophosphorous acid, and alkyl titanate.
What is necessary is just to make it react at 20 degreeC normal pressure. The ratio of the polyol to the dibasic acid is 0.15 to 0.95, preferably 0.3 to 0.8 in terms of the equivalent ratio of the hydroxyl group to the carboxyl group, and the acid value of the condensate is in the range of 20 to 60. Is good.
The reaction between the condensate and the fatty acid alkanolamide may be carried out in a conventional manner, but the acid value of the reactant is preferably adjusted to 5 or less. In the alkylene oxide adduct of the amide compound obtained by reacting the polyamine (B) with a fatty acid, the polyamine of the amide compound includes ethylenediamine, diethylenetriamine, triethylenetetramine, phenylenediamine and the like. The fatty acid is a fatty acid having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms, and more preferably a saturated fatty acid. If the number of carbon atoms is 8 or less, the heat resistance of the reaction product is lowered, and if it is 30 or more, dispersibility in water is deteriorated, which is not preferable. The alkylene oxide to be added to the amide compound is an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Two or more of these alkylene oxides can be used in combination, and the unit thereof may be either random or block. Preferably ethylene oxide (E
O) is good. The number of moles to be added is 5 to 100, preferably 10 to 30 mol. When the number of added moles is 5 moles or less, the dispersibility in water decreases, and 100
If the amount is more than mol, the thermal stability and the adhesion to the fiber become poor. In the oil agent composition of the present invention, the mixing ratio of the component (A) and the component (B) is not particularly limited.
(A): (B) = 90 to 10:10 to 90, preferably 80 to 50:20 to 50. Although the above oil composition is sufficient to satisfy the above-mentioned problems by blending the components (A) and (B), it is possible to add a silicone oil or an antioxidant as long as the performance is not impaired. Is also good. The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The percentages shown in the following examples are% by weight unless otherwise specified. Example 1 (A) A terminal obtained by reacting 0.8 mol of diethanolamide oleate with a condensate (acid value: 30) of 1.5 mol of adipic acid and 1 mol of an adduct of 20 mol of EO of hydrogenated castor oil ether. 70% of the amide compound was mixed with 30% of an adduct of 10 mol of EO of the amide compound obtained by reacting 1 mol of (B) diethylenetriamine and 2 mol of stearic acid, and dispersed in water to obtain a uniform emulsion. [0014] This is 12,000f (single yarn denier 1.3)
100% of the acrylic fiber of d) with a target adhesion amount of 1%
Drying was performed at ~ 140 ° C to obtain a precursor. This precursor is subjected to an oxidation treatment (treatment time of 30 minutes) in an oxidation furnace at 250 to 280 ° C.
It was baked in a carbonization furnace having a temperature gradient of 1,400 ° C. to be converted into carbon fibers. The physical properties of the precursor and the carbon fiber thus obtained are shown in Tables 1 and 2. Example 2 The ratio of the A component to the B component in Example 1 was A: B = 80: 20.
A precursor and a carbon fiber were obtained in the same manner as in Example 1 except that The properties are shown in Tables 1 and 2. Example 3 The ratio of the component A and the component B in Example 1 was A: B = 60: 40.
A precursor and a carbon fiber were obtained in the same manner as in Example 1 except that The properties are shown in Tables 1 and 2. Example 4 A component of Example 1 was reacted with 1.5 mol of adipic acid and 1 mol of an adduct of 30 mol EO of trimethylolpropane with 0.8 mol of diethanolamide stearate to a condensate (acid value 30). A precursor and a carbon fiber were obtained in the same manner as in Example 1 except that the terminal amide compound obtained as described above was used. The properties are shown in Tables 1 and 2. Example 5 To the component A of Example 1, 0.9 mol of diethanolamide oleate was added to a condensate (acid value 40) of 1.5 mol of sebacic acid and 30 mol of an adduct of 30 mol of EO of hydrogenated castor oil ether. A precursor and a carbon fiber were obtained in the same manner as in Example 1 except that the terminal amide compound obtained by the reaction was used. The properties are shown in Tables 1 and 2. Comparative Examples 1 and 2 Instead of the above oil agent of the present invention, an amino-modified silicone having a modification degree shown in the following (1) and (2) was emulsified and dispersed in water with a nonionic surfactant. Apply,
A precursor and a carbon fiber were obtained in the same manner as in Example 1. The properties are shown in Tables 1 and 2. (1) Amino equivalent = 1,800, viscosity (25 ° C.) = 1,2
00cst (2) amino equivalent = 3,000, viscosity (25 ° C.) = 3.5
[0091] [Table 1] [Table 2] Evaluation Method [Fuzzing / Yarn Breaking] When using a Toray fluff counter measuring device and passing a precursor through 1,000 m, 2 mm
The number of the above fluffs was counted. [Generation of scum] The oil was removed from the surface of the roller (surface chrome plating, mirror-finished roller) in the fiber processing step where continuous operation was performed. [Table 3] [Adhesion of Threads] The presence or absence of adhesion of the threads within the measurement range is observed by an electron microscope. According to the present invention, a condensate obtained from a dibasic acid and a polyol having an oxyalkylene unit is
By using an oil agent composition containing a terminal amide compound obtained by reacting a fatty acid alkanolamide and an alkylene oxide adduct of an amide compound obtained by reacting a polyamine and a fatty acid, the operation in the precursor production process is started. The performance can be improved. Further, since there is no generation of inorganic substances in the flame-proofing step, it is effective in stabilizing the step and preventing deterioration of physical properties. Therefore, it is possible to obtain high quality and high performance carbon fibers.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takao Masaki 2-3-1, Shibukawa-cho, Yao-shi, Osaka Matsumoto Yushi Pharmaceutical Co., Ltd. (56) References JP-A-1-221579 (JP, A) JP-A-1-221519 (JP, A) JP-A-9-78340 (JP, A) JP-A-9-78341 (JP, A) WO 97/09474 (WO, A1) (58) Fields investigated (Int) .Cl. ⁷ , DB name) D01F 9/22 D01F 6/18 D01F 11/06 D06M 13/402-13/438

Claims (1)

(57) Claims: (A) A terminal amide compound obtained by reacting a fatty acid alkanolamide with a condensate obtained from a dibasic acid and a polyol having an oxyalkylene unit; B) A precursor oil composition for carbon fibers, comprising an alkylene oxide adduct of an amide compound obtained by reacting a polyamine with a fatty acid.