JP2837408B2 - Acrylic fiber treatment method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for treating a fiber bundle in a gel-swelled state after washing with a draw when producing an acrylic synthetic fiber by wet spinning. . (Prior Art) A fiber bundle in a gel-swelled state after wet spinning, stretching and washing with water is dried and densified by a hot air dryer. Fiber bundles in a gel swelling state running in a hot-air dryer are inferior in fiber separation because single fibers are in contact with each other, causing sticking of the fibers. For this reason, a method is used in which an oil agent, for example, polyether or a spinning oil agent is supplied before heat treatment with a hot air dryer. (Problems to be Solved by the Invention) A large amount of polyether or spinning oil is applied to an oil agent applied to a fiber bundle in a gel swelling state in order to prevent sticking between single fibers. The polyether mixes and accumulates in the finishing oil to lower the spinning performance of the finishing oil. Since the spinning oil contains components unnecessary for preventing sticking between the single fibers, the cost increases. In the case of multi-product production, if the oil before heat treatment by hot-air drying has the same component as the finishing oil, the frequency of oil switching is increased, work efficiency is reduced, oil loss is increased, and there is no waste in terms of resource conservation. Not only that, the COD in the wastewater is significantly increased, which is also undesirable. (Means for Solving the Problems) In view of this situation, the present inventors have conducted intensive studies and found that after applying a specific oil agent to a fiber bundle in a gel-swelled state after wet spinning, stretching and washing with water, hot air By heat treatment with a dryer, it is possible to obtain a fiber bundle of acrylic fibers having excellent fibrillating properties, devitrification prevention properties and gloss, and furthermore, no sticking is developed even in the post-stretching and shrinking steps, and in the finishing step The inventor has found that the spinnability is not changed even if the spinning oil is supplied, and the present invention has been completed. An object of the present invention is to provide an oil agent that is suitable as an oil agent that is applied before heat-treating a fiber bundle in a gel-swelled state after wet spinning, drawing and washing with a hot air dryer. Another object of the present invention is to provide an acrylic fiber which does not change spinnability even when an oil agent is applied. Still another object is to provide such excellent properties as a fiber bundle of an acrylic fiber in a gel-swelled state. To provide an industrially advantageous method of imparting the That is, the present invention provides a fiber bundle of acrylic fibers in a gel swelling state after wet spinning and stretching after water washing, the average molecular weight is 2000 to 15,000, and the molecular weight distribution is 4000 to 7000 and 8000.
Propylene oxide / ethylene oxide (PO / EO-based) block copolymerized polyether [1] having a peak at ~ 20,000 and a carbon number of 12-18 and an ethylene oxide addition mole of 10-20 moles And then heat-treated with a roller drier having a surface temperature of 120 to 160 ° C. and / or a hot air drier having a dry heat of 120 to 180 ° C. to obtain a dry and dense product. And a method of treating the acrylic fiber by applying 0.02 to 0.2% by weight of the mixed oil agent with respect to the fiber weight. The acrylic polymer used in the present invention has at least 40
Any polymer can be used as long as it contains acrylonitrile by weight as a constituent unit and has a fiber-forming ability. That is, acrylonitrile is contained in an amount of 40% by weight or more and other vinyl monomers such as acrylic acid, methacrylic acid, or alkyl esters thereof, vinyl acetate, vinyl chloride, vinylidene chloride, sodium allyl sulfonate, sodium methallyl sulfonate, and vinyl sulfone. Examples thereof include those obtained by copolymerizing an acid soda, a sodium styrenesulfonate and the like as appropriate in a proportion of less than 60% by weight. In particular, acrylonitrile 80% or more and 20% by weight or less of a copolymer of a vinyl monomer and a sulfonic acid group-containing monomer, or 20 to 60% by weight of vinyl chloride and / or vinylidene chloride and a sulfonic acid-containing monomer.
Copolymers are preferred. The acrylic polymer may contain a resin incompatible with an acrylic polymer such as cellulose acetate, polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate copolymer, and polyvinyl butyral. Solvents for the acrylic polymer used in the wet spinning of the present invention include organic and inorganic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, an aqueous solution of zinc chloride, an aqueous solution of rodane salt, and concentrated nitric acid. The propylene oxide and ethylene oxide (PO / EO) block copolymer type polyether [1] used in the present invention has an average molecular weight of 2,000 to 15,000 and a molecular weight distribution of 4 to 4.
It has a two-peak distribution having peaks at 000 to 7000 and 8000 to 20000, respectively, and particularly preferably has a molecular weight distribution of 4500
It has two peaks with peaks at ~ 6500 and 9000 ~ 17,000, respectively. Heat treatment of a fiber bundle with an average molecular weight of less than 2000 or a peak with a molecular weight distribution of one peak to a gel bundle in a gel-swelled state to obtain a dry, dense and adhered acrylic fiber with inferior fibrillation properties. It cannot be done. The PO / EO-based block copolymer type polyether is obtained by, for example, copolymerizing at a composition ratio of PO / EO = 20 to 40/80 to 60 (hereinafter referred to as PO / EO ratio). PO / EO = 20-40 /
When copolymerized at a composition ratio of 80 to 60, the fiber bundle in a gel swelling state is lubricated, heat-treated, and dried and densified, which is excellent in fiber separation properties, and thus is preferable. The polyoxyethylene alkyl ether [2] used in the present invention has 12 to 18 carbon atoms in the alkyl group and 10 to 20 moles of ethylene oxide. Fibers in which the alkyl group has less than 12 carbon atoms, more than 18 carbon atoms, less than 10 moles of ethylene oxide added, and more than 20 moles are mixed with polyether [1] and gel swelled Even if it is applied to a bundle, heat-treated and dried and densified, only acrylic fibers having poor fiber separation and spinnability can be obtained. The oil agent used in the present invention is a mixture of polyether [1] and polyoxyethylene alkyl ether [2]. A mixture of polyether [1] / polyoxyethylene alkyl ether [2] at a weight ratio of 90 to 60/10 to 40 is lubricated to a fiber bundle in a gel swelling state, heat-treated, and dried and densified. Excellent in fiber separation and spinning properties. The oil agent used in the present invention is usually used as an aqueous solution at 50 to 70 ° C. to penetrate into the fiber bundle at a concentration of 0.2 to 1.0% by weight. In using this oil agent, other components other than those described above, as long as they do not affect the fiber separation, devitrification prevention, or spinning properties of the fiber bundle dried and densified by heat treatment with a hot air dryer. May be added. In order to apply the oil agent to the fiber bundle in the gel swelling state after drawing and washing with water, any method may be adopted.However, it is preferable that the oil agent be uniformly attached to the fiber bundle, The law is adopted. The amount of oil agent applied is 0.02 to 0.2
% By weight, more preferably 0.03 to 0.1% by weight
It is. If the amount of the oil agent is 0.02% by weight or less, uneven fiber separation occurs, while if it exceeds 0.2% by weight, the oil is mixed into the spinning oil agent in the finishing process to deteriorate the spinnability. In the present invention, after applying the oil agent, it is heat-treated with a hot air drier to perform dry densification. As a condition for the dry densification, the surface temperature of the roller dryer is 120 to 160 ° C, preferably 130 to 150 ° C. And / or a hot air dryer at 120 to 180 ° C, preferably 130 to 160 ° C. The drying time is preferably 1 to 7 minutes. When the temperature is lower than the above-mentioned temperature, the drying and densification becomes insufficient, and the fiber properties such as whitening of the fiber, poor dyeing color, and low elongation become large. If the temperature exceeds the above-mentioned temperature, loss due to scattering of the oil agent increases, so that it must be avoided. In the present invention, after the drying and densification, a heat treatment is usually further performed, and the heat treatment temperature at this time is usually a dry heat of 180 ° C. or less and / or a wet heat of 130 ° C. or less. (Examples) Hereinafter, the present invention will be specifically described with reference to examples. In addition,% in an Example means weight%. A Evaluation of fiber splitting property The obtained fiber bundle is cut into 5 mm, and 0.5 g of the cut fiber is cut into 5 mm.
Put into a 00ml aqueous solution, stirrer for 1 minute, 100r
Stirred at pm. After one minute, the state of the separated fibers was observed, and the number of adhered fibers (diameter of 0.5 mm or more) was counted. Evaluation: 0 ... excellent, 1-10, good, 11-50, acceptable
51 or more: Not possible B Evaluation of anti-devitrification property Anisole value indicating the transparency of the fiber was measured as follows. Approximately 1 g of a dried fiber sample is defibrated and aligned in a certain direction, and a piece having a diameter of about 1.5 cm is cut into 3 cm pieces. Next, take 0.04 g so as not to disturb the fiber alignment, put it in a 20 mm glass cell, immerse it in anisole for 30 minutes, and then add 100% anisole
Was used as a control and the transmittance was measured at 562 mm, and this was defined as the anisole value. C. Measurement of Attached Amount The amount of attached fiber of the oil agent was measured by using a fiber bundle of 20 g and a solvent of benzene / alcohol = 2/1 (volume ratio) of 120 ml with a Soxhlet extractor for 3 hours to measure the attached amount. D Evaluation of spinnability The dried and densified fiber bundle was continuously stretched, shrunk, applied with a spinning oil agent, and mechanically crimped.
A mm-cut cotton was prototyped, and the spinnability was evaluated based on the card spinning property. Example-1 Acrylonitrile (AN) / methyl acrylate (MA)
Dimethylformamide (DMF) solution with an acrylic polymer concentration of 22% by weight / 20% sodium methallylsulfonate (SMAS) = 91.4 / 8.0 / 0.6 is spun into a 55% DMF aqueous solution at 20 ° C., and subjected to a normal drawing and washing step. PO / EO-based block copolymerized polyether [1] and polyoxy resin having an average molecular weight of 11,000 and a molecular weight distribution of 12000 and 6500, respectively, in the fiber bundle in the gel swelling state (PO / EO ratio = 30/70) 0.03, 0.1, 0.3, 0.5, 0.7, 1.5 of an oil agent (hereinafter referred to as oil agent A) in which ethylene (20) stearyl ether [2] is combined with polyether [1] / polyoxyethylene (20) stearyl ether = 80/20. % Oil solution is applied and dried and densified at 140 ° C. using a roller drier, and the dried and densified fiber bundle (Sample No. 1 ~
6) The attached oil and fat content and the fibrillation property were evaluated, and subsequently stretch, shrinkage, spinning oil application, and mechanical crimp application were performed.
Table 1 shows the results of evaluating spinnability by cutting a single yarn into 2 deniers of 51 mm. Example 2 Instead of the oil agent A used in Example 1, peaks were found at 17000 and 6800 at an average molecular weight of 12500, respectively (PO / EO
Ratio = 20/80) PO / EO block copolymer type polyether / polyoxyethylene (20) stearyl ether = 90/10 combined oil agent (Sample No. 7).
(PO / EO ratio = 35/65) PO / EO block copolymer type polyether / polyoxyethylene (10) lauryl ether = 60/40 with peaks at 500/500 (sample N
o.8), having a peak (one peak) at 10500 with an average molecular weight of 7500 (PO / EO ratio = 30/70) PO / EO block copolymer type polyether / polyoxyethylene (20) stearyl ether = 80 / For the fiber bundle using 0.3% oil solution each of the oil solution (sample No. 9) and the spinning oil polyoxyethylene (15) cetyl ether phosphate potassium salt (sample No. 10), the splitting property was 2 Table 2 shows the results of examining the spinnability and devitrification prevention properties of the denier 51 mm cut cotton. (Effects of the Invention) According to the treatment method of the present invention, it is possible to produce a fiber bundle of acrylic fibers having excellent fiber separation properties and glossiness for preventing devitrification. Furthermore, the obtained fiber bundle has an effect that no agglutination occurs even in the drawing and shrinking steps, and the spinnability is not reduced even if a spinning oil agent is applied in the finishing step, which is a very significant method.

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Claims (1)

(57) [Claims] Wet spinning, drawing, and bimodal distribution of propylene having an average molecular weight of 2,000 to 15,000 and a peak of molecular weight distribution of 4,000 to 7000 and 8,000 to 20,000 in a fiber bundle of acrylic fibers in a gel-swelled state after washing with water. Oxide (PO / EO
System) block copolymer type polyether [1] and carbon number 12
After adding an oil agent obtained by mixing a polyoxyethylene alkyl ether [2] having an ethylene oxide addition mole number of 10 to 20 mol with a roller dryer of 120 to 160 ° C. and / or a dry heat of 120 to 160 ° C. Heat densification with hot air dryer at ~ 180 ° C to dry and densify, 0.02-0.2
A method for treating an acrylic fiber, wherein the oil agent is added in an amount of at least 1% by weight. 2. 2. The method according to claim 1, wherein the polyether [1] is copolymerized at a composition ratio of PO / EO = 20 to 40/80 to 60. Manufacturing method. 3. The mixing weight ratio of polyether [1] and polyoxyethylene alkyl ether [2] is polyether [1].
/ Polyoxyethylene alkyl ether [2] = 90-60
The method of claim 1 wherein the ratio is between / 10 and 40. 4. The method according to claim 1, wherein the surface temperature of the roller dryer is 130 to 150C. 5. The method according to claim 1, wherein the temperature of the hot air dryer is 130C to 160C.