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WO2010101182A1 - Fibre absorbant l'humidité, pouvant être teinte par un colorant cationique, et son procédé de fabrication - Google Patents

Fibre absorbant l'humidité, pouvant être teinte par un colorant cationique, et son procédé de fabrication Download PDF

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Publication number
WO2010101182A1
WO2010101182A1 PCT/JP2010/053435 JP2010053435W WO2010101182A1 WO 2010101182 A1 WO2010101182 A1 WO 2010101182A1 JP 2010053435 W JP2010053435 W JP 2010053435W WO 2010101182 A1 WO2010101182 A1 WO 2010101182A1
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Prior art keywords
fiber
acrylonitrile
weight
hygroscopic
polymer
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Japanese (ja)
Inventor
藤本克也
安藝泰雄
家野正雄
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Japan Exlan Co Ltd
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Japan Exlan Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/70—Material containing nitrile groups
    • D06P3/76—Material containing nitrile groups using basic dyes

Definitions

  • the present invention relates to a dye-dyeable hygroscopic fiber composed of a crosslinked acrylic acid polymer and an acrylonitrile polymer, and a production method.
  • cross-linked acrylic acid fibers and the like are known, among which cross-linked acrylic acid fibers are compared with other natural fibers having moisture absorption / release properties, It is known to have a characteristic of having a high moisture absorption rate.
  • Such cross-linked acrylic fiber has a carboxyl group that functions as a dyeing seat, and it is possible to color the fiber with a cationic dye, but the ion bond between the carboxyl group and the dye is weak, so that the ion exchange is easy. Since the dyeing fastness is poor, a practical level of dyeing cannot be performed.
  • Patent Documents 1 and 2 propose a dyeing method using a reactive dye of a crosslinked acrylic fiber.
  • the fastness to dyeing is improved by using reactive dyes
  • the problem of dyeing with cationic dyes has not been solved, and when a fiber structure mixed with cellulosic fibers is dyed.
  • the hue with the cellulosic fiber is different, and there is a difficulty in practical color matching.
  • the pH during dyeing needs to be a strongly acidic condition, and that it is necessary to deal with facilities such as restrictions on mixed fibers and countermeasures against corrosion.
  • Patent Document 3 proposes a fiber in which a sulfonic acid group is introduced by impregnating and polymerizing a monomer having a sulfonic acid group into a raw material fiber having a carboxyl group.
  • this fiber can introduce a large amount of sulfonic acid groups and is colored with a cationic dye, it has been difficult to obtain sufficient color developability, dyeing fastness and hue stability.
  • a method of introducing a sulfonic acid group by impregnating and polymerizing a monomer having a sulfonic acid group into a raw fiber is employed, there is a problem that a complicated operation is required and the cost is increased.
  • conventional cross-linked acrylic fiber has harmonious functions such as pH buffering, antistatic properties, water retention, high moisture absorption rate, high moisture absorption rate, high moisture absorption difference or temperature control and humidity control functions derived therefrom.
  • the present invention is capable of practical dyeing with sufficient coloring property and fastness by a cationic dye while retaining the characteristics of the conventional crosslinked acrylic fiber, and is a low-cost hygroscopic fiber. The purpose is to provide.
  • Cationic dye dyeable characterized by comprising a cross-linked acrylic acid polymer region and a sulfonic acid group-containing acrylonitrile polymer region, and the acrylonitrile polymer region is 20 to 80%.
  • the hue of the fiber after dyeing with a cationic dye as defined below is such that L * in the L * a * b * color system (JIS-Z8729) is +45 or less, a * is ⁇ 5 or more and +5 or less, b * The cationic dye-dyeable hygroscopic fiber according to (1), wherein is from ⁇ 5 to +5.
  • Color of fiber after dyeing with cationic dye 1 g of hygroscopic fiber, 3.3 dtex, and 2 g of acrylonitrile fiber with a saturated dyeing amount of 1.8 g of Malacite Green, with respect to the total fiber weight (3 g) (2.5% by weight) and an acetic acid (2% by weight) aqueous solution for 30 minutes, then immersed in an aqueous solution of hydrosulfite 2 g / L for 15 minutes at 60 ° C., then washed with running water for 5 minutes and then air-dried And dyed hygroscopic fibers are obtained by removing the acrylonitrile fibers.
  • the acrylonitrile fiber is composed of at least two acrylonitrile polymers having different acrylonitrile contents, and the difference in the contents is 2% by weight or more (1) to (3)
  • the cationic dye-dyeable hygroscopic fiber of the present invention has high hygroscopic performance and is excellent in color developability by the cationic dye, so that practical dyeing is possible. Therefore, it can be developed in applications where the use of conventional cross-linked acrylic acid fibers is restricted because practical dyeing has been difficult.
  • the cationic dye-dyeable hygroscopic fiber of the present invention is a hygroscopic fiber obtained by crosslinking and hydrolyzing an acrylonitrile-based fiber having a sulfonic acid group of 0.03 mmol / g or more based on the fiber weight, It is a fiber having a structure comprising a region of a crosslinked acrylic acid polymer having a carboxyl group and a crosslinked structure and a region of an acrylonitrile polymer having a sulfonic acid group.
  • the sulfonic acid group in the region of the acrylonitrile polymer may be contained in the acrylonitrile polymer itself or may be contained in another polymer contained in the region of the acrylonitrile polymer.
  • the cationic dye-dyeable hygroscopic fiber of the present invention may be composed only of a cross-linked acrylic acid polymer region and an acrylonitrile polymer region, or an acrylic acid polymer region and an acrylonitrile polymer weight. There may be a region where these are mixed between the combined regions. Moreover, the area
  • the region of the cross-linked acrylic acid polymer having such a carboxyl group and a cross-linked structure is a part mainly responsible for moisture absorption performance.
  • the carboxyl group present in such a region functions as a dyeing seat, the ion bond with the dye is weak and the ion exchange is easy, so the dyeing fastness is poor and a practical level dyeing cannot be performed.
  • the region other than the cross-linked acrylic acid polymer is a portion mainly responsible for the dyeing performance. Therefore, the existence of such a region and its dyeing ability are important.
  • the cationic dyeable and hygroscopic fiber of the present invention by incorporating a sulfonic acid group functioning as a dyeing seat in such a region, it becomes possible to dye with the same formulation as in the case of acrylonitrile fiber. is there.
  • the ratio of the cross-linked acrylic acid polymer region to the acrylonitrile polymer region the higher the proportion of the cross-linked acrylic polymer region, the higher the moisture absorption rate.
  • the ratio of the area of the polymer is reduced and sufficient color developability is to be obtained, it is necessary to increase the concentration of the sulfonic acid group in the area of the acrylonitrile polymer. Therefore, it is necessary that the acrylonitrile-based polymer occupies an area of 20 to 80% of the fiber cross-sectional area in the dry state, and preferably 30 to 70%. Within such a range, a fiber in which both hygroscopicity and color development are balanced can be obtained.
  • the cross-linked acrylic acid polymer region and the acrylonitrile polymer region are dyed with a cationic dye, then the fiber cross section is observed with an optical microscope, and the dyed region is an acrylonitrile polymer region.
  • the region that is not dyed or in which the dyeing cannot be confirmed is the region of the crosslinked acrylic acid polymer. Therefore, the above-mentioned area ratio is calculated by cutting the dried fiber and observing the fiber cross section after the dyeing treatment.
  • the acrylonitrile fiber as the raw fiber has a sulfonic acid group of 0.03 mmol / g or more with respect to the fiber weight, preferably 0.05 mmol / g or more, more preferably 0. It is desirable to have a sulfonic acid group of 0.055 mmol / g or more, more preferably 0.065 mmol / g or more.
  • the dyeability of the cationic dyeable hygroscopic fiber of the present invention includes the hue of the hygroscopic fiber after dyeing in the same bath dyeing with the acrylonitrile fiber by the cationic dye, L * is +45 or less, and a * is ⁇ 5. It is preferably +5 or less and b * is ⁇ 5 or more and +5 or less, more preferably L * is +40 or less, and further preferably L * is +35 or less. If the upper limit of L * in this range is exceeded, sufficient color developability may not be obtained, and if it falls outside the range of a * and b *, it will be difficult to adjust the hue, and practical dyeing will be difficult. There is a case.
  • the acrylic sulfonic acid group-containing resin 1 to 90 contains 90 to 99% by weight of an acrylonitrile-based polymer containing 80% by weight or more of acrylonitrile and the remaining 10 to 70% by weight of acrylonitrile. It is preferably composed of 10% by weight of a polymer. Thereby, a sufficient amount of sulfonic acid groups can be easily introduced into the acrylonitrile fiber.
  • the acrylonitrile fiber is composed of at least two acrylonitrile polymers having different acrylonitrile contents, and the difference in the contents is 2% by weight or more.
  • the difference in the contents is 2% by weight or more.
  • Such an acrylonitrile fiber may be one in which two kinds of acrylonitrile polymers are joined side by side or may be randomly mixed, but one having a three-layer structure composed of ABA layers, Alternatively, a core-sheath structure is more preferable, and the B layer or the core part preferably has a high acrylonitrile content and has many sulfonic acid groups.
  • the acrylonitrile content in the B layer or the core portion is preferably 82% by weight or more, more preferably 85% by weight or more, and still more preferably 90% by weight or more. Is preferably 0.05 mmol / g or more, more preferably 0.07 mmol / g or more, and still more preferably 0.1 mmol / g or more.
  • an acrylonitrile fiber is introduced with a nitrogen-containing compound having two or more nitrogen atoms in one molecule, and an alkaline metal salt aqueous solution is introduced.
  • the method of partially forming a cross-linked acrylic acid polymer region by hydrolyzing by the above-mentioned method or carrying out these treatments at the same time and leaving the region of the acrylonitrile polymer containing the amount of sulfonic acid group is the manufacturing equipment and cost. It is desirable from the aspect of. This method will be described in detail below.
  • the starting acrylonitrile fiber (hereinafter sometimes referred to as acrylic fiber) contains acrylonitrile (hereinafter also referred to as AN) in an amount of 40% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more.
  • the fibers are formed from AN polymer, and may be in any form such as short fibers, tows, yarns, knitted fabrics, and non-woven fabrics.
  • the AN polymer may be either an AN homopolymer or a copolymer of AN and another monomer.
  • Examples of the other monomer include methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic acid ester compounds such as butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, sulfonic acid group-containing compounds such as methallylsulfonic acid and p-styrenesulfonic acid A monomer and a salt thereof; the monomer is not particularly limited as long as it is a monomer copolymerizable with AN, such as a monomer such as styrene and vinyl acetate, but 5 to 20% by weight of a vinyl ester compound represented by vinyl acetate. It is desirable to copolymerize.
  • Such vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
  • the starting acrylonitrile fiber employed in the present invention it is necessary to have a sulfonic acid group of 0.03 mmol / g or more with respect to the fiber weight, so that the acrylonitrile polymer itself has a sulfonic acid group. If it is, a method of introducing a sulfonic acid group at the terminal by a redox catalyst or a method of copolymerizing a sulfonic acid group-containing monomer can be adopted, and the sulfonic acid group is introduced by another polymer. In this case, a method of mixing a sulfonic acid group-containing resin or the like with an acrylonitrile-based polymer can be employed.
  • Examples of the monomer containing a sulfonic acid group include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, 4-sulfobutyl (meth) acrylate, methallyloxybenzene sulfonic acid, allyloxybenzene sulfonic acid, 2 -Acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate and metal salts of these monomers.
  • the sulfonic acid group-containing resin is not particularly limited as long as it contains a sulfonic acid group, but the above-described monomer containing a sulfonic acid group and a nitrile group such as acrylonitrile or methacrylonitrile are used. It is preferably an acrylic sulfonic acid group-containing resin obtained by copolymerizing a monomer having the above-mentioned monomers, and other monomers may be copolymerized in addition to such monomers.
  • acrylic sulfonic acid group-containing resins examples include acrylic sulfonic acid group-containing resins composed of acrylonitrile / acrylic acid methyl ester / styrene parasulfonic acid soda monomer, which are mixed uniformly with an acrylonitrile polymer. Alternatively, it may be mixed locally such as side-by-side.
  • the difference in the content of acrylonitrile is 2% by weight or more.
  • the method described in Japanese Patent Application Laid-Open No. 2000-45126 can be employed as a method for obtaining an acrylic fiber having a three-layer structure composed of an ABA layer. It is preferable to reduce the exposure of the B component to the fiber surface by lowering the viscosity of the stock solution.
  • the acrylic fiber is subjected to a crosslinking introduction treatment with an aqueous solution containing a nitrogen-containing compound having two or more nitrogen atoms in one molecule and a hydrolysis treatment with an aqueous solution containing an alkaline metal salt compound.
  • a crosslinking introduction treatment with an aqueous solution containing a nitrogen-containing compound having two or more nitrogen atoms in one molecule
  • a hydrolysis treatment with an aqueous solution containing an alkaline metal salt compound.
  • a cross-linked structure is formed by the reaction of the nitrogen-containing compound having two or more nitrogen atoms in one molecule and the nitrile group of the acrylonitrile polymer of acrylic fiber, and an aqueous alkali metal salt compound solution A nitrile group reacts to form a carboxyl group, which is converted into a crosslinked acrylic acid polymer.
  • the crosslinking introduction treatment and the hydrolysis treatment include a method in which a fiber is immersed in an aqueous solution used for the treatment, a method in which the aqueous solution is sprayed, and a method in which the aqueous solution is adhered to the fiber. Can be adopted.
  • the concentration of the nitrogen-containing compound having two or more nitrogen atoms in one molecule is preferably 0.1 to 5% by weight, more preferably 0.1%. ⁇ 2% by weight. If this concentration is too low, the effect of suppressing the dissolution of the acrylic acid polymer may not be obtained.
  • the concentration of the alkaline metal salt compound is preferably 0.5 to 5% by weight, more preferably 0.5 to 4% by weight. If the concentration of the alkaline metal salt compound is too low, the amount of carboxyl groups produced may be insufficient, and if it is too high, the acrylonitrile polymer to be left behind may be hydrolyzed.
  • the suitable range changes according to the density
  • concentration of the nitrogen-containing compound having two or more nitrogen atoms in one molecule is about 0.5 to 2% by weight and the concentration of the alkaline metal salt compound is about 1 to 2% by weight, Conditions of 90 to 100 ° C for about 2 hours are recommended.
  • the nitrogen-containing compound having two or more nitrogen atoms in one molecule is preferably an amino compound or a hydrazine-based compound having two or more primary amino groups.
  • amino compounds having two or more primary amino groups include diamine compounds such as ethylenediamine and hexamethylenediamine, diethylene and reamine, 3,3′-iminobis (propylamine), N-methyl-3, 3′- Triamine compounds such as iminobis (propylamine), triethylenetetramine, N, N′-bis (3-aminopropyl) -1,3-propylenediamine, N, N′-bis (3-aminopropyl) -1, Examples include tetraamine compounds such as 4-butylenediamine, polyamine compounds having two or more primary amino groups such as polyvinylamine and polyallylamine.
  • hydrazine-based compound examples include hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine bromate, and hydrazine carbonate.
  • the upper limit of the number of nitrogen atoms in one molecule is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and particularly preferably 4 or less. When the number of nitrogen atoms in one molecule exceeds the above upper limit, the cross-linking agent molecule becomes large and it may be difficult to introduce cross-linking into the fiber.
  • an alkaline metal salt compound An alkali metal hydroxide, an alkaline-earth metal hydroxide, an alkali metal carbonate, etc. can be used.
  • the fiber that has undergone the cross-linking introduction treatment may be subjected to an acid treatment before the hydrolysis treatment.
  • the coloring of the fiber can be lightened.
  • the acid used here include aqueous solutions of mineral acids such as nitric acid, sulfuric acid, and hydrochloric acid, and organic acids, but are not particularly limited.
  • the treatment conditions include immersing the fiber to be treated in an aqueous solution having an acid concentration of 5 to 20% by weight, preferably 7 to 15% by weight, at a temperature of 50 to 120 ° C. for 0.5 to 10 hours.
  • treatments such as washing with an acidic aqueous solution adopted by conventional crosslinked acrylic fibers, pH adjustment treatment with a buffer solution, etc. may be performed.
  • the cationic dye-dyeable hygroscopic fiber of the present invention can be obtained by the above method, it is preferable to further perform heat treatment.
  • the step of performing the heat treatment may be performed during any of the above steps, and may be before the cross-linking hydrolysis or after all the steps of the above steps are completed, but after the cross-linking hydrolysis or with an acidic aqueous solution. It is desirable to carry out after washing. By this heat treatment, the color developability can be further improved.
  • the heat treatment may be wet heat or dry heat, but it is desirable that the heat treatment be performed with hot water at 100 to 130 ° C. for 10 seconds or longer, preferably for 10 minutes or longer.
  • the sulfonic acid group of the acrylonitrile fiber is 0.05 mmol / g or more, or when the sulfonic acid group of the acrylonitrile group-containing resin is contained in an amount of the sulfonic acid group or more, two or more kinds of AN-based fibers are used.
  • a polymer it is not always necessary, but it is preferable to perform a heat treatment in order to obtain more excellent color developability.
  • the amount of carboxyl groups in the portion made of the crosslinked acrylic acid polymer is preferably 1.0 to 10 mmol / g, more preferably 2.0 to 5.0 mmol / g, based on the fiber weight. If the lower limit of the range is not reached, sufficient moisture absorption performance may not be obtained, and if the upper limit is exceeded, the color developability when cationic dyeing may not be obtained.
  • the carboxyl group may be a carboxylic acid or a carboxylate salt, or they may be mixed, but in the stage after fiber production, a carboxylic acid is used to facilitate processing such as spinning, After dyeing or at the final product stage, it is desirable that 50% or more is a carboxylate in order to obtain a high moisture absorption rate.
  • Examples of cations constituting the carboxylate include alkali metals such as Li, Na, and K, alkaline earth metals such as Be, Ca, and Ba, Cu, Zn, Al, Mn, Ag, Fe, and Co. And a metal such as Ni, a cation such as ammonium and amine, and a plurality of types of cations may be mixed.
  • the evaluation device uses a multi-light source spectrocolorimeter MSC-5 (C light source, 2-degree field of view) manufactured by Suga Test Instruments Co., Ltd., and is a screw-in cylindrical type having a bottom surface made of quartz glass and having a diameter of 40 mm.
  • the bottom surface fixed to the cell was measured with a measurement hole having a diameter of 30 mm, and L *, a *, and b * values of the L * a * b * color system were calculated according to a conventional method.
  • Example 1 A spinning stock solution in which 10 parts of acrylonitrile polymer A is dissolved in 90 parts of a 48% sodium rhodanoate aqueous solution is spun and stretched in accordance with a conventional method, then dried and wet heat treated, and an AN system having a single fiber fineness of 1.0 dtex. Fiber was obtained.
  • the AN fiber was subjected to crosslinking / hydrolysis treatment at 95 ° C. for 2 hours in an aqueous solution containing 0.5% hydrazine hydrate and 1.5% sodium hydroxide, and washed with water. Subsequently, it was heat treated in water at 120 ° C. for 1 hour, and then washed with a 3% nitric acid aqueous solution.
  • the treated fiber was washed with water, applied with a spinning oil, dehydrated and dried to obtain a hygroscopic fiber of Example 1.
  • Table 2 shows the evaluation results of the obtained fibers.
  • the adhesion amount of the oil agent was adjusted to 0.5% by weight with respect to the fiber.
  • Comparative Example 1 A spinning stock solution in which 10 parts of acrylonitrile polymer B is dissolved in 90 parts of a 48% sodium rhodanate aqueous solution is spun and stretched according to a conventional method, and then dried and wet heat treated, and then an AN system having a single fiber fineness of 1.0 dtex. Fiber was obtained.
  • the AN fiber was subjected to crosslinking / hydrolysis treatment at 95 ° C. for 2 hours in an aqueous solution containing 0.5% hydrazine hydrate and 2.0% sodium hydroxide, and washed with water. Subsequently, it was heat treated in water at 120 ° C. for 1 hour, and then washed with a 3% nitric acid aqueous solution.
  • the treated fiber was washed with water, applied with a spinning oil, dehydrated and dried to obtain a hygroscopic fiber of Comparative Example 1.
  • Table 2 shows the evaluation results of the obtained fibers.
  • Example 2 The AN fiber obtained in Comparative Example 1 was subjected to crosslinking and hydrolysis treatment at 95 ° C. for 2 hours in an aqueous solution containing 0.5% hydrazine hydrate and 1.5% sodium hydroxide, and washed with water. Subsequently, it was heat treated in water at 120 ° C. for 1 hour, and then washed with a 3% nitric acid aqueous solution. The treated fiber was washed with water, applied with a spinning oil, dehydrated and dried to obtain a hygroscopic fiber of Example 2. Table 2 shows the evaluation results of the obtained fibers.
  • Comparative Example 2 The AN fiber obtained in Comparative Example 1 was subjected to crosslinking and hydrolysis treatment at 95 ° C. for 2 hours in an aqueous solution containing 0.5% hydrazine hydrate and 1.5% sodium hydroxide, and washed with water. Washed with an aqueous solution of 3% nitric acid. The treated fiber was washed with water, applied with a spinning oil, dehydrated and dried to obtain a hygroscopic fiber of Comparative Example 2. Table 2 shows the evaluation results of the obtained fibers.
  • Comparative Example 3 The AN fiber obtained in Comparative Example 1 was subjected to crosslinking introduction treatment at 98 ° C. for 3 hours in a 20% aqueous solution of hydrazine hydrate and washed with water. Next, it was acid-treated at 90 ° C. for 2 hours in a 3% nitric acid aqueous solution and washed with water. Subsequently, hydrolysis was performed at 90 ° C. for 2 hours in a 3% aqueous solution of sodium hydroxide and washed with water. Subsequently, it was washed with an aqueous nitric acid solution having a pH of 2. The treated fiber was washed with water, applied with a spinning oil, dehydrated and dried to obtain a hygroscopic fiber of Comparative Example 3. Table 2 shows the evaluation results of the obtained fibers.
  • Example 3 10 parts of acrylonitrile polymer B was dissolved in 90 parts of a 48% aqueous sodium rhodate solution to prepare a spinning dope.
  • a sulfonic acid group-containing resin D was added to the spinning stock solution so as to have the ratio shown in Table 3, mixed and dissolved to continuously prepare a mixed stock solution, which was led to a spinning device.
  • the mixed stock solution led to the spinning device was spun and drawn according to a conventional method, and then dried and wet-heat treated to obtain AN fibers having a single fiber fineness of 1.0 dtex.
  • a hygroscopic fiber of Example 3 was obtained according to the production method of Example 1. Table 3 shows the evaluation results of the obtained fibers.
  • Example 4 A spinning dope was prepared in the same manner as in Example 3 except that the ratio of the acrylonitrile polymer B and the sulfonic acid group-containing resin D was changed to obtain AN fibers having a single fiber fineness of 1.0 dtex. Using the AN fiber, a hygroscopic fiber of Example 4 was obtained according to the production method of Example 1. Table 3 shows the evaluation results of the obtained fibers.
  • Example 5 A spinning stock solution Qb was prepared by dissolving 12 parts of acrylonitrile polymer B in 88 parts of a 48% aqueous sodium rhodate solution so that the polymer concentration was 12% by weight.
  • the spinning solution Qb had a viscosity of 3900 mPa ⁇ s at 30 ° C.
  • 12 parts of the acrylonitrile polymer C12 shown below was dissolved in 88 parts of a 48% sodium rhodanate aqueous solution so that the polymer concentration was 12% by weight to prepare a spinning dope Qc.
  • the spinning stock solution Qc had a viscosity at 30 ° C. of 4000 mPa ⁇ s.
  • the two spinning stock solutions are mixed at a ratio of 1: 1 through a spinning stock solution distribution layer and a spinneret to form a Qb layer- It was led to become Qc layer-Qb layer, then spun in accordance with a conventional method, drawn, dried, and wet heat treated to obtain an AN fiber having a single fiber fineness of 1.0 dtex.
  • a hygroscopic fiber of Example 5 was obtained according to the production method of Example 1. Table 3 shows the evaluation results of the obtained fibers.
  • the cationic dye-dyeable hygroscopic fiber of the present invention has high hygroscopic performance and is excellent in color developability by the cationic dye, so that practical dyeing is possible. Therefore, it can be developed in applications where the use of conventional cross-linked acrylic acid fibers is restricted because practical dyeing has been difficult.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention porte sur une fibre absorbant l'humidité, de faible coût, qui peut être teinte de façon pratique par un colorant cationique et qui peut développer suffisamment une couleur avec le colorant cationique, tout en conservant les caractéristiques d'une fibre réticulée à base d'acide acrylique. De façon spécifique, l'invention porte sur une fibre absorbant l'humidité, pouvant être teinte par un colorant cationique, qui est obtenue par réticulation et hydrolyse d'une fibre d'acrylonitrile qui contient pas moins de 0,03 mmole/g de groupes acide sulfonique par rapport au poids de la fibre. La fibre absorbant l'humidité, pouvant être teinte par un colorant cationique, est caractérisée en ce que la fibre est composée d'une région d'un polymère réticulé d'acide acrylique comportant un groupe carboxyle et une structure réticulée, et une région d'un polymère d'acrylonitrile comportant un groupe acide sulfonique. La fibre absorbant l'humidité, pouvant être teinte par un colorant cationique, est également caractérisée en ce que la région du polymère d'acrylonitrile se situe dans la plage de 20 à 80 %.
PCT/JP2010/053435 2009-03-06 2010-03-03 Fibre absorbant l'humidité, pouvant être teinte par un colorant cationique, et son procédé de fabrication Ceased WO2010101182A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077431A (ja) * 2010-09-08 2012-04-19 Japan Exlan Co Ltd 保温性繊維
CN106420799A (zh) * 2015-08-06 2017-02-22 日本爱克兰工业株式会社 抗病毒用原材料以及含有该原材料的具有抗病毒性的制品

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07150471A (ja) * 1993-11-30 1995-06-13 Japan Exlan Co Ltd 多孔質アクリロニトリル系繊維
JPH08325833A (ja) * 1995-06-05 1996-12-10 Mitsubishi Rayon Co Ltd アクリル系極細繊維およびその製造方法
JPH10156179A (ja) * 1996-11-29 1998-06-16 Japan Exlan Co Ltd 酸・アルデヒド吸収性重合体及びその製造方法ならびに該重合体を含有したシート状物
JP3248401B2 (ja) * 1995-06-05 2002-01-21 日本エクスラン工業株式会社 吸湿性架橋アクリル系繊維及び該繊維を用いた繊維構造体
WO2005064057A1 (fr) * 2003-12-26 2005-07-14 Kaneka Corporation Tissu duveté de moquette et procédé de production associé
JP3674202B2 (ja) * 1996-12-04 2005-07-20 日本エクスラン工業株式会社 抗菌性アクリロニトリル系繊維およびその製造方法
JP2006097159A (ja) * 2004-09-28 2006-04-13 Kaneka Corp アクリル系吸湿性繊維及びその製造法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07150471A (ja) * 1993-11-30 1995-06-13 Japan Exlan Co Ltd 多孔質アクリロニトリル系繊維
JPH08325833A (ja) * 1995-06-05 1996-12-10 Mitsubishi Rayon Co Ltd アクリル系極細繊維およびその製造方法
JP3248401B2 (ja) * 1995-06-05 2002-01-21 日本エクスラン工業株式会社 吸湿性架橋アクリル系繊維及び該繊維を用いた繊維構造体
JPH10156179A (ja) * 1996-11-29 1998-06-16 Japan Exlan Co Ltd 酸・アルデヒド吸収性重合体及びその製造方法ならびに該重合体を含有したシート状物
JP3674202B2 (ja) * 1996-12-04 2005-07-20 日本エクスラン工業株式会社 抗菌性アクリロニトリル系繊維およびその製造方法
WO2005064057A1 (fr) * 2003-12-26 2005-07-14 Kaneka Corporation Tissu duveté de moquette et procédé de production associé
JP2006097159A (ja) * 2004-09-28 2006-04-13 Kaneka Corp アクリル系吸湿性繊維及びその製造法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077431A (ja) * 2010-09-08 2012-04-19 Japan Exlan Co Ltd 保温性繊維
CN106420799A (zh) * 2015-08-06 2017-02-22 日本爱克兰工业株式会社 抗病毒用原材料以及含有该原材料的具有抗病毒性的制品

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