WO2022080024A1 - Method for dyeing acrylic fibers and method for producing dyed acrylic fibers - Google Patents

Method for dyeing acrylic fibers and method for producing dyed acrylic fibers Download PDF

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Publication number
WO2022080024A1
WO2022080024A1 PCT/JP2021/031804 JP2021031804W WO2022080024A1 WO 2022080024 A1 WO2022080024 A1 WO 2022080024A1 JP 2021031804 W JP2021031804 W JP 2021031804W WO 2022080024 A1 WO2022080024 A1 WO 2022080024A1
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Prior art keywords
dyeing
disperse dye
dye
acrylic fibers
acrylic
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PCT/JP2021/031804
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French (fr)
Japanese (ja)
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里子 奥林
良友 松本
渉 河内
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株式会社カネカ
国立大学法人京都工芸繊維大学
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Publication of WO2022080024A1 publication Critical patent/WO2022080024A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B9/00—Solvent-treatment of textile materials
    • D06B9/02—Solvent-treatment of textile materials solvent-dyeing
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/20—Anthraquinone dyes
    • 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
    • D06P3/72—Material containing nitrile groups using dispersed dyestuffs
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric

Definitions

  • the present invention relates to a method for dyeing acrylic fibers and a method for producing dyed acrylic fibers.
  • Acrylic fibers are generally dyed with an aqueous system in which a cationic dye is dissolved in water, and it is known that the dyed acrylic fibers are excellent in sharpness and dyeing fastness.
  • this dyeing method since the dyeing is performed in an aqueous system, a dye waste liquid is generated and an environmental load is increased. Therefore, a dyeing method that hardly produces a dye waste liquid is desired.
  • Patent Document 1 a method of dyeing in supercritical carbon dioxide has been proposed as a method of dyeing fibers that generate almost no waste water, and polyester fibers and cellulosic fibers are disclosed as applicable fibers (Patent Document 1). 2).
  • acrylic fibers cannot be dyed with a cationic dye in supercritical carbon dioxide.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a method for dyeing acrylic fibers in a supercritical fluid and a method for producing acrylic fibers dyed by the method.
  • the present inventors have excellent color development by adsorbing a disperse dye in a hydrophobic supercritical fluid in a dyeing method for acrylic fibers.
  • the present invention was completed by finding that a system fiber can be obtained.
  • the first aspect of the present invention relates to a dyeing method for adsorbing a disperse dye in a hydrophobic supercritical fluid in a dyeing method for acrylic fibers.
  • the disperse dye substance contained in the disperse dye is preferably one or more selected from the group consisting of anthraquinone type and condensation type.
  • the content of the dispersant contained in the disperse dye is preferably 20% by mass or less with respect to the total mass of the disperse dye substance contained in the disperse dye.
  • the disperse dye does not contain a dispersant.
  • the supercritical fluid is preferably carbon dioxide.
  • a second aspect of the present invention relates to a method for producing a dyed acrylic fiber, which comprises adsorbing a disperse dye on the acrylic fiber in a hydrophobic supercritical fluid.
  • the content of the dispersant contained in the disperse dye is preferably 20% by mass or less with respect to the total mass of the disperse dye substance contained in the disperse dye.
  • the disperse dye does not contain a dispersant.
  • the supercritical fluid is preferably carbon dioxide.
  • the present invention it is possible to provide a method for dyeing an acrylic fiber having excellent color-developing property of a disperse dye and a method for producing the acrylic fiber.
  • the disperse dye is adsorbed on the acrylic fibers in a hydrophobic supercritical fluid.
  • acrylic fibers having excellent color-developing properties can be obtained.
  • acrylic fibers are used as the dyeing target.
  • the acrylic fiber is a fiber made of a long-chain synthetic polymer containing 35% or more and less than 85% by mass of the repeating unit of the acrylonitrile group. Therefore, the acrylic fiber does not include the acrylic fiber made of a homopolymer of acrylonitrile.
  • the acrylic fiber used in the dyeing method of the present embodiment is not particularly limited as long as it is a fiber made of an acrylic copolymer in which the repeating unit of the acrylonitrile group satisfies the above range, but the content of the monomer is not particularly limited.
  • Acrylonitrile is preferably 30 to 85% by mass
  • halogen-containing vinyl and / or halogen-containing vinylidene is 70 to 15% by mass
  • a vinyl-based monomer copolymerizable with these is 0 to 10% by mass, more preferably acrylonitrile.
  • halogen-containing vinyl and / or halogen-containing vinylidene 70 to 30% by mass, and 0 to 10% by mass of a vinyl-based monomer copolymerizable with these can be used.
  • the total content of the above-mentioned acrylonitrile, halogen-containing vinyl and / or halogen-containing vinylidene, and the vinyl-based monomer copolymerizable with these is 100% by mass.
  • the vinyl-based monomer used in the copolymer is not particularly limited as long as it is a vinyl compound that can be copolymerized with the halogen-containing vinyl and / or the halogen-containing vinylidene, and is, for example, acrylic acid, methyl acrylate, and acrylic.
  • Acrylic acids such as butyl acid and their esters; Methacrylic acids such as methacrylic acid, methyl methacrylate and butyl methacrylate and their esters; Amids such as acrylamide and methacrylamide; Vinyl acetates such as vinyl acetate and vinyl acrylate; Vinyl sulfone Acids and salts thereof, methallyl sulfonic acid and salts thereof, styrene sulfonic acid and salts thereof, sulfonic acid group-containing monomers such as 2-acrylamide-2-methylpropane sulfonic acid and salts thereof; and the like.
  • One kind or two or more kinds can be used.
  • the content of acrylonitrile in the acrylic copolymer is in the range of 30 to 70% by mass, it is preferable because both heat resistance and flame retardancy can be achieved.
  • the obtained filament has flame retardancy, physical properties (strength, heat resistance, etc.), dyeability, etc. Is preferable.
  • Polymerization such as emulsion polymerization, suspension polymerization, and solution polymerization can be used as a method for obtaining an acrylic copolymer from these acrylonitriles, halogen-containing vinyl and / or halogen-containing vinylidene, and vinyl-based monomers copolymerizable with these.
  • the method can be used.
  • the obtained acrylic copolymer can be spun into acrylic fibers by, for example, a wet spinning method or a dry wet spinning method.
  • the acrylic fiber both short fiber and long fiber can be used, but the form of short fiber or tow is preferable.
  • the fineness of the acrylic fiber is not particularly limited, but is preferably 0.5 dtex or more, and more preferably 1.0 dtex or more and 100 dtex or less.
  • acrylic fiber a commercially available product can also be preferably used, and examples thereof include Kanekalon and Protex (all manufactured by Kaneka Corporation).
  • a hydrophobic supercritical fluid is used as a dyeing medium.
  • a supercritical fluid is a fluid whose temperature and pressure are equal to or higher than the critical temperature and the critical pressure.
  • the hydrophobic supercritical fluid used in the present invention means a supercritical fluid that is difficult to dissolve in water, and examples thereof include carbon dioxide, methane, ethane, propane, ethylene, and propylene. Among these, carbon dioxide is preferable from the viewpoints of high supercritical density and therefore high ability to dissolve solutes, and excellent safety and stability during use of supercritical fluids.
  • a disperse dye is used as the dye.
  • the disperse dye is a dye that is sparingly soluble in water and is used for dyeing hydrophobic fibers in a system dispersed in water.
  • the disperse dye includes a mode in which the disperse dye base material is used alone, and a mode in which a dispersant is added to the disperse dye base material.
  • the disperse dye base is not particularly limited, and for example, benzeneazo (monoazo, disazo, etc.), heterocyclic azo (thiazole azo, benzenethiazole azo, quinoline azo, pyrizone azo, imidazole azo, thiophene azo, etc.), anthraquinone, and condensation.
  • benzeneazo monoazo, disazo, etc.
  • heterocyclic azo thiazole azo, benzenethiazole azo, quinoline azo, pyrizone azo, imidazole azo, thiophene azo, etc.
  • anthraquinone and condensation.
  • Systems quinophthalone, styryl, coumarin, etc.
  • anthraquinone type and condensation type are preferable.
  • the bulk dye material one type may be used alone, or two or more types may be used in combination.
  • the disperse dye drug substance may be synthesized and the disperse dye drug substance may be used alone, or a commercially available disperse dye may be used.
  • a dispersant is added to the bulk of the disperse dye in a commercially available disperse dye, but from the viewpoint of improving the dyeability, it is preferable to use a dispersant from which the dispersant has been removed.
  • the content of the dispersant contained in the disperse dye is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total mass of the disperse dye substance contained in the disperse dye.
  • the acrylic fiber is dyed by adsorbing the disperse dye to the acrylic fiber in a hydrophobic supercritical fluid.
  • the dyeing conditions are not particularly limited, and may be appropriately set according to the types of acrylic fibers and disperse dyes, and are not particularly limited.
  • the dye concentration for the acrylic fiber may be appropriately set according to the hue of the target color.
  • the temperature at the time of dyeing is preferably 40 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 105 ° C. or lower.
  • the pressure at the time of dyeing is preferably 7.4 MPa or more and 40 MPa or less, and more preferably 10 MPa or more and 25 MPa or less.
  • the time for dyeing is preferably 5 minutes or more and 240 minutes or less, and more preferably 30 minutes or more and 180 minutes or less.
  • the acrylic fiber dyed by the dyeing method of the present embodiment has the disperse dye sufficiently dyed on the acrylic fiber and is excellent in color development.
  • the method for dyeing acrylic fibers according to the above-described embodiment can also be defined as a method for producing dyed acrylic fibers.
  • the method for producing a dyed acrylic fiber of the present embodiment includes adsorbing a disperse dye on the acrylic fiber in a hydrophobic supercritical fluid. By using the production method, an acrylic fiber having excellent color-developing property can be obtained.
  • the adsorption conditions for the acrylic fiber as the dyeing target, the hydrophobic supercritical fluid as the dyeing medium, the disperse dye, and the disperse dye are the acrylic fiber as the dyeing target described in the above-mentioned ⁇ Dyeing method for acrylic fiber>. , It has the same meaning and content as the adsorption conditions of the hydrophobic supercritical fluid as a dyeing medium, the disperse dye, and the disperse dye.
  • the dyeing property of the acrylic fiber after the dyeing treatment was visually evaluated according to the following evaluation criteria.
  • the dyeing property is one of the indexes for evaluating the dyeing property, and indicates how much the fiber has adsorbed the dye. ⁇ : Sufficiently colored ⁇ : Colored ⁇ : Not colored
  • the color development property of the acrylic fiber after the dyeing treatment was visually evaluated according to the following evaluation criteria.
  • the color development property is one of the indexes for evaluating the dyeability, and indicates how much the dye adsorbed on the fiber develops the original color.
  • ⁇ The dye is developing properly
  • ⁇ The dye is developing abnormally
  • Acrylic short fibers (“Kanecaron” manufactured by Kaneka Co., Ltd., 50% by mass of acrylonitrile, 49% by mass of vinyl chloride and styrene) are hereinafter abbreviated as “A1” as acrylic fibers in a SUS316 thick pressure container having an internal capacity of 50 cc. 1 g of acrylic copolymer composed of 1% by mass of sodium sulfonate, fineness 1.7 dtex), and a disperse dye (“Terasil Fiber 10GEF” manufactured by CLARIANT), which is abbreviated as “DD1” below, condensation system: coumarin, fluorescence.
  • Example 2 the acrylic fiber is composed of an acrylic short fiber (“Protex” manufactured by Kaneka Co., Ltd., 50% by mass of acrylonitrile, 49% by mass of vinylidene chloride, and 1% by mass of sodium styrene sulfonate”, which are hereinafter abbreviated as “A2”.
  • Acrylic copolymer, fineness 2.2 dtex is used, and as a dye, a disperse dye (“Sumikaron Yellow SE-RPD” manufactured by Sumika Chemtex Co., Ltd., which is abbreviated as “DD2” below, a condensation system: quinophthalone, dyed in yellow.
  • the dyeing treatment was carried out in the same manner as in Example 1 except that the dyeing temperature was set to 100 ° C. using (possible, including a dispersant). Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
  • Example 3 In Example 1, the dyeing treatment was carried out in the same manner as in Example 1 except that the dyeing temperature was set to 100 ° C. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
  • Example 4 In Example 2, the dyeing treatment was carried out in the same manner as in Example 2 except that a disperse dye (Disperse Yellow 54 dye substance, condensation system: quinophthalone, which can be dyed yellow), which is abbreviated as "DD3", was used as the dye. bottom.
  • the dispersion dye DD3 does not contain a dispersant. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
  • Example 5 the dyeing treatment was carried out in the same manner as in Example 2 except that a disperse dye (Disperse Red 60 dye substance, anthraquinone-based, capable of dyeing red), which is abbreviated as “DD4”, was used as the dye.
  • the dispersion dye DD4 does not contain a dispersant. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
  • Example 6 the dyeing treatment was carried out in the same manner as in Example 2 except that a disperse dye (Disperse Blue 56 dye substance, anthraquinone-based, capable of dyeing blue), which is abbreviated as “DD5”, was used as the dye.
  • the dispersion dye DD5 does not contain a dispersant. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
  • Example 3 (Comparative Example 1)
  • a cationic dye (“Kayacryl Yellow 3RL-ED” manufactured by Nippon Kayaku Co., Ltd.), which is hereinafter abbreviated as “CD1”, was used as the dye, water was used as the medium, and the dyeing pressure was set to normal pressure. Except for this, the dyeing treatment was carried out in the same manner as in Example 3.
  • Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
  • the composition of the dyeing bath was 0.01 g of CD1, 50 g of water, and 0.015 g of "Ultra MT # 110" manufactured by Mitejima Chemical.
  • Example 2 In Example 1, the dyeing treatment was carried out in the same manner as in Example 1 except that the dye concentration was 0.5% omf, the dyeing temperature was 98 ° C., water was used as a medium, and the dyeing pressure was normal pressure. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
  • the composition of the dyeing bath was 0.01 g of DD1, 50 g of water, 0.05 g of acetic acid, and 0.1 g of "TANAVOL DAP" manufactured by TANATEX.
  • Example 3 (Comparative Example 3)
  • the dyeing treatment was carried out in the same manner as in Example 2 except that CD1 was used as the dye.
  • Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.

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Abstract

The present invention provides: a method for dyeing acrylic fibers in a supercritical fluid; and a method for producing acrylic fibers that are dyed by the above-described method.　The first embodiment of the present invention relates to a method for dyeing acrylic fibers, said method having a disperse dye adsorbed in a hydrophobic supercritical fluid.　It is preferable that the disperse dye does not contain a dispersant.　It is preferable that the supercritical fluid is carbon dioxide.　The second embodiment of the present invention relates to a method for producing dyed acrylic fibers, said method comprising a step wherein a disperse dye is caused to adsorb onto acrylic fibers in a hydrophobic supercritical fluid.

Description

アクリル系繊維の染色方法及び染色されたアクリル系繊維の製造方法Acrylic fiber dyeing method and dyed acrylic fiber manufacturing method
　本発明は、アクリル系繊維の染色方法及び染色されたアクリル系繊維の製造方法に関する。 The present invention relates to a method for dyeing acrylic fibers and a method for producing dyed acrylic fibers.
　アクリル系繊維は、一般的にカチオン染料を水に溶解した水系で染色されており、染色後のアクリル系繊維は、鮮明さ及び染色堅牢度に優れていることが知られている。しかしながら、この染色方法では、水系で染色を行うので、染料廃液が発生し、環境負荷が大きくなるため、染料廃液をほとんど出さない染色法が要望されている。 Acrylic fibers are generally dyed with an aqueous system in which a cationic dye is dissolved in water, and it is known that the dyed acrylic fibers are excellent in sharpness and dyeing fastness. However, in this dyeing method, since the dyeing is performed in an aqueous system, a dye waste liquid is generated and an environmental load is increased. Therefore, a dyeing method that hardly produces a dye waste liquid is desired.
　近年、排水をほとんど出さない繊維の染色方法として、超臨界二酸化炭素中で染色を行う方法が提案されており、適用される繊維として、ポリエステル繊維やセルロース系繊維が開示されている（特許文献１、２を参照）。 In recent years, a method of dyeing in supercritical carbon dioxide has been proposed as a method of dyeing fibers that generate almost no waste water, and polyester fibers and cellulosic fibers are disclosed as applicable fibers (Patent Document 1). 2).
特開２００２－３３９２６６号公報Japanese Unexamined Patent Publication No. 2002-339266 特開２００１－２２６８８４号公報Japanese Unexamined Patent Publication No. 2001-226884
　しかしながら、本発明者らの検討によれば、超臨界二酸化炭素中では、アクリル系繊維はカチオン染料で染色できないことが確認された。 However, according to the study by the present inventors, it was confirmed that acrylic fibers cannot be dyed with a cationic dye in supercritical carbon dioxide.
　本発明は、上記課題に鑑みてなされたものであり、超臨界流体中でアクリル系繊維を染色させる方法、及び該方法により染色されたアクリル系繊維の製造方法を提供することを目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for dyeing acrylic fibers in a supercritical fluid and a method for producing acrylic fibers dyed by the method.
　本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、アクリル系繊維の染色方法において、疎水性の超臨界流体中で分散染料を吸着させることで、発色性に優れたアクリル系繊維が得られることを見出し、本発明を完成した。 As a result of diligent research to solve the above problems, the present inventors have excellent color development by adsorbing a disperse dye in a hydrophobic supercritical fluid in a dyeing method for acrylic fibers. The present invention was completed by finding that a system fiber can be obtained.
　すなわち、本発明の第１の態様は、アクリル系繊維の染色方法において、疎水性の超臨界流体中で分散染料を吸着させる染色方法に関する。 That is, the first aspect of the present invention relates to a dyeing method for adsorbing a disperse dye in a hydrophobic supercritical fluid in a dyeing method for acrylic fibers.
　第１の態様において、前記分散染料に含まれる分散染料原体は、アントラキノン系及び縮合系からなる群より選択される１種以上であることが好ましい。 In the first aspect, the disperse dye substance contained in the disperse dye is preferably one or more selected from the group consisting of anthraquinone type and condensation type.
　第１の態様において、前記分散染料に含まれる分散剤の含有量は、分散染料に含まれる分散染料原体の全質量に対して、２０質量％以下であることが好ましい。 In the first aspect, the content of the dispersant contained in the disperse dye is preferably 20% by mass or less with respect to the total mass of the disperse dye substance contained in the disperse dye.
　第１の態様において、前記分散染料に、分散剤が含まれていないことが好ましい。 In the first aspect, it is preferable that the disperse dye does not contain a dispersant.
　第１の態様において、前記超臨界流体は、二酸化炭素であることが好ましい。 In the first aspect, the supercritical fluid is preferably carbon dioxide.
　本発明の第２の態様は、疎水性の超臨界流体中で、アクリル系繊維に分散染料を吸着させることを含む、染色されたアクリル系繊維の製造方法に関する。 A second aspect of the present invention relates to a method for producing a dyed acrylic fiber, which comprises adsorbing a disperse dye on the acrylic fiber in a hydrophobic supercritical fluid.
　第２の態様において、前記分散染料に含まれる分散剤の含有量は、分散染料に含まれる分散染料原体の全質量に対して、２０質量％以下であることが好ましい。 In the second aspect, the content of the dispersant contained in the disperse dye is preferably 20% by mass or less with respect to the total mass of the disperse dye substance contained in the disperse dye.
　第２の態様において、前記分散染料に、分散剤が含まれていないことが好ましい。 In the second aspect, it is preferable that the disperse dye does not contain a dispersant.
　第２の態様において、前記超臨界流体は、二酸化炭素であることが好ましい。 In the second aspect, the supercritical fluid is preferably carbon dioxide.
　本発明によれば、分散染料の発色性に優れたアクリル系繊維の染色方法、及び該アクリル系繊維の製造方法を提供することができる。 According to the present invention, it is possible to provide a method for dyeing an acrylic fiber having excellent color-developing property of a disperse dye and a method for producing the acrylic fiber.
＜アクリル系繊維の染色方法＞
　本実施形態のアクリル系繊維の染色方法は、疎水性の超臨界流体中でアクリル系繊維に分散染料を吸着させる。該染色方法を用いることにより、発色性に優れたアクリル系繊維を得ることができる。 <Dyeing method for acrylic fibers>
In the method for dyeing acrylic fibers of the present embodiment, the disperse dye is adsorbed on the acrylic fibers in a hydrophobic supercritical fluid. By using the dyeing method, acrylic fibers having excellent color-developing properties can be obtained.
　本実施形態の染色方法では、染色対象としてアクリル系繊維が用いられる。アクリル系繊維とは、ＪＩＳ　Ｌ０２０４に規定されているように、アクリロニトリル基の繰り返し単位が質量比で３５％以上８５％未満含む長鎖状合成高分子からなる繊維をいう。したがって、アクリル系繊維には、アクリロニトリルの単独重合体からなるアクリル繊維は含まれない。 In the dyeing method of this embodiment, acrylic fibers are used as the dyeing target. As defined in JIS L0204, the acrylic fiber is a fiber made of a long-chain synthetic polymer containing 35% or more and less than 85% by mass of the repeating unit of the acrylonitrile group. Therefore, the acrylic fiber does not include the acrylic fiber made of a homopolymer of acrylonitrile.
　本実施形態の染色方法で用いられるアクリル系繊維としては、アクリロニトリル基の繰り返し単位が上記範囲を満たすアクリル系共重合体からなる繊維であれば、特に限定されないが、単量体の含有量としては、好ましくはアクリロニトリル３０～８５質量％、ハロゲン含有ビニル及び／又はハロゲン含有ビニリデン７０～１５質量％、及び、これらと共重合可能なビニル系単量体０～１０質量％であり、より好ましくはアクリロニトリル３０～７０質量％、ハロゲン含有ビニル及び／又はハロゲン含有ビニリデン７０～３０質量％、及び、これらと共重合可能なビニル系単量体０～１０質量％を用いることができる。なお、上記したアクリロニトリル、ハロゲン含有ビニル及び／又はハロゲン含有ビニリデン、及び、これらと共重合可能なビニル系単量体の合計の含有量は１００質量％である。 The acrylic fiber used in the dyeing method of the present embodiment is not particularly limited as long as it is a fiber made of an acrylic copolymer in which the repeating unit of the acrylonitrile group satisfies the above range, but the content of the monomer is not particularly limited. Acrylonitrile is preferably 30 to 85% by mass, halogen-containing vinyl and / or halogen-containing vinylidene is 70 to 15% by mass, and a vinyl-based monomer copolymerizable with these is 0 to 10% by mass, more preferably acrylonitrile. 30 to 70% by mass, halogen-containing vinyl and / or halogen-containing vinylidene 70 to 30% by mass, and 0 to 10% by mass of a vinyl-based monomer copolymerizable with these can be used. The total content of the above-mentioned acrylonitrile, halogen-containing vinyl and / or halogen-containing vinylidene, and the vinyl-based monomer copolymerizable with these is 100% by mass.
　上記共重合体に用いられるビニル系単量体としては、上記ハロゲン含有ビニル及び／又はハロゲン含有ビニリデンに共重合可能なビニル化合物であれば特に限定されないが、例えば、アクリル酸、アクリル酸メチル、アクリル酸ブチル等のアクリル酸類とそのエステル；メタクリル酸、メタクリル酸メチル、メタクリル酸ブチル等のメタクリル酸類とそのエステル；アクリルアミド、メタクリルアミド等のアミド類；酢酸ビニル、蟻酸ビニル等のビニルアセテート類；ビニルスルホン酸とその塩、メタリルスルホン酸とその塩、スチレンスルホン酸とその塩、２－アクリルアミド－２－メチルプロパンスルホン酸とその塩等のスルホン酸基含有単量体；等が挙げられ、これらの１種または２種以上を用いることができる。 The vinyl-based monomer used in the copolymer is not particularly limited as long as it is a vinyl compound that can be copolymerized with the halogen-containing vinyl and / or the halogen-containing vinylidene, and is, for example, acrylic acid, methyl acrylate, and acrylic. Acrylic acids such as butyl acid and their esters; Methacrylic acids such as methacrylic acid, methyl methacrylate and butyl methacrylate and their esters; Amids such as acrylamide and methacrylamide; Vinyl acetates such as vinyl acetate and vinyl acrylate; Vinyl sulfone Acids and salts thereof, methallyl sulfonic acid and salts thereof, styrene sulfonic acid and salts thereof, sulfonic acid group-containing monomers such as 2-acrylamide-2-methylpropane sulfonic acid and salts thereof; and the like. One kind or two or more kinds can be used.
　本実施形態の染色方法において、アクリル系共重合体中のアクリロニトリルの含有量が３０～７０質量％の範囲であれば、耐熱性、難燃性を両立できるために好ましい。 In the dyeing method of the present embodiment, when the content of acrylonitrile in the acrylic copolymer is in the range of 30 to 70% by mass, it is preferable because both heat resistance and flame retardancy can be achieved.
　一方、ハロゲン含有ビニル及び／又はハロゲン含有ビニリデンの含有量が３０質量％以上８５重量％以下の範囲であれば、得られたフィラメントの難燃性や物性（強度、耐熱性など）、染色性などが好ましい。 On the other hand, when the content of halogen-containing vinyl and / or halogen-containing vinylidene is in the range of 30% by mass or more and 85% by weight or less, the obtained filament has flame retardancy, physical properties (strength, heat resistance, etc.), dyeability, etc. Is preferable.
　これらアクリロニトリルとハロゲン含有ビニル及び／又はハロゲン含有ビニリデン、及び、これらと共重合可能なビニル系単量体からアクリル系共重合体を得る方法としては、乳化重合、懸濁重合、溶液重合等の重合方法を用いることができる。得られたアクリル系共重合体は、例えば、湿式紡糸法や乾湿式紡糸法により、紡糸することで、アクリル系繊維を得ることができる。 Polymerization such as emulsion polymerization, suspension polymerization, and solution polymerization can be used as a method for obtaining an acrylic copolymer from these acrylonitriles, halogen-containing vinyl and / or halogen-containing vinylidene, and vinyl-based monomers copolymerizable with these. The method can be used. The obtained acrylic copolymer can be spun into acrylic fibers by, for example, a wet spinning method or a dry wet spinning method.
　アクリル系繊維としては、短繊維と長繊維のいずれも使用できるが、短繊維若しくはトウの形態が好ましい。アクリル系繊維の繊度は特に限定されないが、０．５ｄｔｅｘ以上が好ましく、１．０ｄｔｅｘ以上１００ｄｔｅｘ以下がより好ましい。 As the acrylic fiber, both short fiber and long fiber can be used, but the form of short fiber or tow is preferable. The fineness of the acrylic fiber is not particularly limited, but is preferably 0.5 dtex or more, and more preferably 1.0 dtex or more and 100 dtex or less.
　アクリル系繊維としては市販品も好ましく使用でき、例えば、カネカロン、プロテックス（以上カネカ社製）等が挙げられる。 As the acrylic fiber, a commercially available product can also be preferably used, and examples thereof include Kanekalon and Protex (all manufactured by Kaneka Corporation).
　本実施形態の染色方法では、染色媒体として疎水性の超臨界流体が用いられる。疎水性の超臨界流体を用いることで、分散染料の発色性を向上させることができるとともに、染料廃液が出ないため、環境負荷を低減することができる。超臨界流体とは、その温度と圧力が、臨界温度及び臨界圧力以上である流体をいう。本発明で用いられる疎水性の超臨界流体とは、水に溶解しにくい超臨界流体を意味し、例えば、二酸化炭素、メタン、エタン、プロパン、エチレン、プロピレン等が挙げられる。これらの中では、超臨界密度が高くそのため溶質を溶解する能力が高い点、超臨界流体の安全性や使用時の安定性に優れる観点から、二酸化炭素が好ましい。 In the dyeing method of this embodiment, a hydrophobic supercritical fluid is used as a dyeing medium. By using a hydrophobic supercritical fluid, the color development property of the disperse dye can be improved, and since the dye waste liquid is not generated, the environmental load can be reduced. A supercritical fluid is a fluid whose temperature and pressure are equal to or higher than the critical temperature and the critical pressure. The hydrophobic supercritical fluid used in the present invention means a supercritical fluid that is difficult to dissolve in water, and examples thereof include carbon dioxide, methane, ethane, propane, ethylene, and propylene. Among these, carbon dioxide is preferable from the viewpoints of high supercritical density and therefore high ability to dissolve solutes, and excellent safety and stability during use of supercritical fluids.
　本実施形態の染色方法では染料として分散染料が用いられる。分散染料とは、水に難溶性で、水中に分散した系中で、疎水性繊維の染色に用いられる染料をいう。分散染料としては、分散染料原体単独での態様の他、分散染料原体に分散剤を添加した態様も含まれる。分散染料原体としては特に限定されず、例えば、ベンゼンアゾ系（モノアゾ、ジスアゾなど）、複素環アゾ系（チアゾールアゾ、ベンゼンチアゾールアゾ、キノリンアゾ、ピリゾンアゾ、イミダゾールアゾ、チオフェンアゾなど）、アントラキノン系、縮合系（キノフタロン、スチリル、クマリンなど）等が挙げられる。これらの中では、アントラキノン系、縮合系が好ましい。
　分散染料原体は、１種を単独で用いてもよく、２種以上を併用してもよい。 In the dyeing method of this embodiment, a disperse dye is used as the dye. The disperse dye is a dye that is sparingly soluble in water and is used for dyeing hydrophobic fibers in a system dispersed in water. The disperse dye includes a mode in which the disperse dye base material is used alone, and a mode in which a dispersant is added to the disperse dye base material. The disperse dye base is not particularly limited, and for example, benzeneazo (monoazo, disazo, etc.), heterocyclic azo (thiazole azo, benzenethiazole azo, quinoline azo, pyrizone azo, imidazole azo, thiophene azo, etc.), anthraquinone, and condensation. Systems (quinophthalone, styryl, coumarin, etc.) and the like can be mentioned. Among these, anthraquinone type and condensation type are preferable.
As the bulk dye material, one type may be used alone, or two or more types may be used in combination.
　分散染料としては、例えば、上記分散染料原体を合成して、該分散染料原体を単独で使用してもよいし、市販の分散染料を使用してもよい。市販の分散染料には、分散染料原体に分散剤が添加されている場合が多いが、染色性を向上させる観点から、分散剤を除去したものを使用することが好ましい。分散染料に含まれる分散剤の含有量としては、分散染料に含まれる分散染料原体の全質量に対して、２０質量％以下であることが好ましく、１０質量％以下であることがより好ましい。 As the disperse dye, for example, the disperse dye drug substance may be synthesized and the disperse dye drug substance may be used alone, or a commercially available disperse dye may be used. In many cases, a dispersant is added to the bulk of the disperse dye in a commercially available disperse dye, but from the viewpoint of improving the dyeability, it is preferable to use a dispersant from which the dispersant has been removed. The content of the dispersant contained in the disperse dye is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total mass of the disperse dye substance contained in the disperse dye.
　本実施形態の染色方法では、疎水性の超臨界流体中で分散染料をアクリル系繊維に吸着させることにより、アクリル系繊維の染色が行われる。染色条件は特に限定されず、アクリル系繊維及び分散染料の種類に応じて適宜設定すればよく特に限定されない。アクリル系繊維に対する染料濃度は目標色の色相に応じて適宜設定すればよい。染色時の温度は、４０℃以上１２０℃以下が好ましく、７０℃以上１０５℃以下がより好ましい。染色時の圧力は、７．４ＭＰａ以上４０ＭＰａ以下が好ましく、１０ＭＰａ以上２５ＭＰａ以下がより好ましい。染色時の時間は、５分以上２４０分以下が好ましく、３０分以上１８０分以下がより好ましい。 In the dyeing method of the present embodiment, the acrylic fiber is dyed by adsorbing the disperse dye to the acrylic fiber in a hydrophobic supercritical fluid. The dyeing conditions are not particularly limited, and may be appropriately set according to the types of acrylic fibers and disperse dyes, and are not particularly limited. The dye concentration for the acrylic fiber may be appropriately set according to the hue of the target color. The temperature at the time of dyeing is preferably 40 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 105 ° C. or lower. The pressure at the time of dyeing is preferably 7.4 MPa or more and 40 MPa or less, and more preferably 10 MPa or more and 25 MPa or less. The time for dyeing is preferably 5 minutes or more and 240 minutes or less, and more preferably 30 minutes or more and 180 minutes or less.
　本実施形態の染色方法により染色されたアクリル系繊維は、分散染料がアクリル系繊維に十分に染着しており、発色性に優れている。 The acrylic fiber dyed by the dyeing method of the present embodiment has the disperse dye sufficiently dyed on the acrylic fiber and is excellent in color development.
＜染色されたアクリル系繊維の製造方法＞
　前述した実施形態に係るアクリル系繊維の染色方法は、染色されたアクリル系繊維の製造方法として定義することもできる。 <Manufacturing method of dyed acrylic fiber>
The method for dyeing acrylic fibers according to the above-described embodiment can also be defined as a method for producing dyed acrylic fibers.
　本実施形態の染色されたアクリル系繊維の製造方法は、疎水性の超臨界流体中で、アクリル系繊維に分散染料を吸着させることを含む。該製造方法を用いることにより、発色性に優れたアクリル系繊維を得ることができる。 The method for producing a dyed acrylic fiber of the present embodiment includes adsorbing a disperse dye on the acrylic fiber in a hydrophobic supercritical fluid. By using the production method, an acrylic fiber having excellent color-developing property can be obtained.
　染色対象としてのアクリル系繊維、染色媒体としての疎水性の超臨界流体、分散染料、及び分散染料の吸着条件は、前述した＜アクリル系繊維の染色方法＞で説明した染色対象としてのアクリル系繊維、染色媒体としての疎水性の超臨界流体、分散染料、及び分散染料の吸着条件と同様の意味内容を有する。 The adsorption conditions for the acrylic fiber as the dyeing target, the hydrophobic supercritical fluid as the dyeing medium, the disperse dye, and the disperse dye are the acrylic fiber as the dyeing target described in the above-mentioned <Dyeing method for acrylic fiber>. , It has the same meaning and content as the adsorption conditions of the hydrophobic supercritical fluid as a dyeing medium, the disperse dye, and the disperse dye.
　以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。実施例及び比較例における染色処理後のアクリル系繊維の評価方法は以下のとおりである。なお、「％ｏｍｆ」とは、アクリル系繊維に対する染料濃度を質量基準で示すものである。また、「ｏｍｆ」とは、ｏｎ　ｔｈｅ　ｍａｓｓ　ｏｆ　ｆｉｂｅｒ」を意味する。 Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. The evaluation method of the acrylic fiber after the dyeing treatment in Examples and Comparative Examples is as follows. The "% omf" indicates the dye concentration with respect to the acrylic fiber on a mass basis. Further, "omf" means "on the mass of fiber".
（染着性）
　以下の評価基準により、染色処理後のアクリル系繊維の染着性を目視評価した。なお、染着性とは、染色性を評価するための指標の一つであり、繊維がどの程度の染料を吸着したかを示す。
◎：　十分に着色できている
〇：　着色できている
×：　着色できていない (Dyeing property)
The dyeing property of the acrylic fiber after the dyeing treatment was visually evaluated according to the following evaluation criteria. The dyeing property is one of the indexes for evaluating the dyeing property, and indicates how much the fiber has adsorbed the dye.
◎: Sufficiently colored 〇: Colored ×: Not colored
（発色性）
　以下の評価基準により、染色処理後のアクリル系繊維の発色性を目視評価した。なお、発色性とは、染色性を評価するための指標の一つであり、繊維に吸着した染料が、どの程度本来の色に発色したかを示す。
〇：　染料が適正に発色している
×：　染料が異常発色している (Color development)
The color development property of the acrylic fiber after the dyeing treatment was visually evaluated according to the following evaluation criteria. The color development property is one of the indexes for evaluating the dyeability, and indicates how much the dye adsorbed on the fiber develops the original color.
〇: The dye is developing properly ×: The dye is developing abnormally
（測色：Ｌ＊ａ＊ｂ＊値）
　染色後のアクリル系繊維０．２ｇを開繊後、ドーナッツ型のシリコンゴム（厚み１０ｍｍ×外径４５ｍｍ×内径１４ｍｍ）に詰めて測定サンプルとした。分光測色計（コニカミノルタ社製「ＣＭ-３６００ｄ」）を用いて、測定サンプルのＬ＊ａ＊ｂ＊色空間色度を求めた。Ｌ＊値が小さいほど、試料は濃染されており、ａ＊が大きいと赤味が強く、ｂ＊が大きいと黄味が強くなる。
　なお、染色前のアクリル系繊維を参照試料として、Ｌ＊ａ＊ｂ＊値を測定した。 (Color measurement: L * a * b * value)
After opening 0.2 g of the dyed acrylic fiber, it was packed in a donut-shaped silicone rubber (thickness 10 mm × outer diameter 45 mm × inner diameter 14 mm) to prepare a measurement sample. The L * a * b * color space chromaticity of the measurement sample was determined using a spectrocolorimeter (“CM-3600d” manufactured by Konica Minolta). The smaller the L * value, the deeper the sample is dyed. When a * is large, the redness is strong, and when b * is large, the yellowness is strong.
The L * a * b * value was measured using the acrylic fiber before dyeing as a reference sample.
（染料廃液の有無）
〇：染料廃液が発生しない
×：染料廃液が発生する (Presence or absence of dye waste liquid)
〇: No dye waste liquid is generated ×: Dye waste liquid is generated
（実施例１）
　内容量５０ｃｃのＳＵＳ３１６製肉厚圧力容器中に、アクリル系繊維として、以下、「Ａ１」と略記するアクリル系短繊維（カネカ社製「カネカロン」、アクリロニトリル５０質量％、塩化ビニル４９質量％及びスチレンスルホン酸ナトリウム１質量％からなるアクリル系共重合体、繊度１．７ｄｔｅｘ）を１ｇ、及び、以下、「ＤＤ１」と略記する分散染料（ＣＬＡＲＩＡＮＴ社製「Ｔｅｒａｓｉｌ　Ｆｌａｖｉｎｅ　１０ＧＥＦ」、縮合系：クマリン、蛍光黄色に染色可能、分散剤を含む）を０．０１ｇ、それぞれ投入し、密閉した（染料濃度１％ｏｍｆ）。
　次いで、二酸化炭素ボンベより、二酸化炭素を２０ＭＰａになるまで徐々に上記圧力容器に注入し、同時に該圧力容器を８０℃に加熱したオーブンに入れ、６０分間染色処理した。
　その後、放圧により上記圧力容器内を常圧に戻した後、染色処理した繊維を取り出した。この際、二酸化炭素及び圧力容器壁面に残留する染料を回収した。染色処理後のアクリル系繊維の評価結果を表１に示す。 (Example 1)
Acrylic short fibers (“Kanecaron” manufactured by Kaneka Co., Ltd., 50% by mass of acrylonitrile, 49% by mass of vinyl chloride and styrene) are hereinafter abbreviated as “A1” as acrylic fibers in a SUS316 thick pressure container having an internal capacity of 50 cc. 1 g of acrylic copolymer composed of 1% by mass of sodium sulfonate, fineness 1.7 dtex), and a disperse dye (“Terasil Fiber 10GEF” manufactured by CLARIANT), which is abbreviated as “DD1” below, condensation system: coumarin, fluorescence. 0.01 g (which can be dyed yellow and contains a dispersant) was added and sealed (dye concentration 1% omf).
Next, carbon dioxide was gradually injected into the pressure vessel from the carbon dioxide cylinder until the pressure reached 20 MPa, and at the same time, the pressure vessel was placed in an oven heated to 80 ° C. and dyed for 60 minutes.
Then, the pressure vessel was returned to normal pressure by releasing pressure, and then the dyed fibers were taken out. At this time, carbon dioxide and the dye remaining on the wall surface of the pressure vessel were recovered. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
（実施例２）
　実施例１において、アクリル系繊維として、以下、「Ａ２」と略記するアクリル系短繊維（カネカ社製「プロテックス」、アクリロニトリル５０質量％、塩化ビニリデン４９質量％及びスチレンスルホン酸ナトリウム１質量％からなるアクリル系共重合体、繊度２．２ｄｔｅｘ）を使用し、染料として、以下、「ＤＤ２」と略記する分散染料（住化ケムテックス社製「Ｓｕｍｉｋａｒｏｎ　Ｙｅｌｌｏｗ　ＳＥ－ＲＰＤ」、縮合系：キノフタロン、黄色に染色可能、分散剤を含む）を使用し、染色温度を１００℃としたこと以外は、実施例１と同様に染色処理した。染色処理後のアクリル系繊維の評価結果を表１に示す。 (Example 2)
In Example 1, the acrylic fiber is composed of an acrylic short fiber (“Protex” manufactured by Kaneka Co., Ltd., 50% by mass of acrylonitrile, 49% by mass of vinylidene chloride, and 1% by mass of sodium styrene sulfonate”, which are hereinafter abbreviated as “A2”. Acrylic copolymer, fineness 2.2 dtex) is used, and as a dye, a disperse dye (“Sumikaron Yellow SE-RPD” manufactured by Sumika Chemtex Co., Ltd., which is abbreviated as “DD2” below, a condensation system: quinophthalone, dyed in yellow. The dyeing treatment was carried out in the same manner as in Example 1 except that the dyeing temperature was set to 100 ° C. using (possible, including a dispersant). Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
（実施例３）
　実施例１において、染色温度を１００℃としたこと以外は、実施例１と同様に染色処理した。染色処理後のアクリル系繊維の評価結果を表１に示す。 (Example 3)
In Example 1, the dyeing treatment was carried out in the same manner as in Example 1 except that the dyeing temperature was set to 100 ° C. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
（実施例４）
　実施例２において、染料として、以下「ＤＤ３」と略記する分散染料（Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ　５４染料原体、縮合系：キノフタロン、黄色に染色可能）を使用したこと以外は、実施例２と同様に染色処理した。なお、分散染料ＤＤ３には、分散剤が含まれていない。染色処理後のアクリル系繊維の評価結果を表１に示す。 (Example 4)
In Example 2, the dyeing treatment was carried out in the same manner as in Example 2 except that a disperse dye (Disperse Yellow 54 dye substance, condensation system: quinophthalone, which can be dyed yellow), which is abbreviated as "DD3", was used as the dye. bottom. The dispersion dye DD3 does not contain a dispersant. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
（実施例５）
　実施例２において、染料として、以下「ＤＤ４」と略記する分散染料（Ｄｉｓｐｅｒｓｅ　Ｒｅｄ　６０染料原体、アントラキノン系、赤色に染色可能）を使用したこと以外は、実施例２と同様に染色処理した。なお、分散染料ＤＤ４には、分散剤が含まれていない。染色処理後のアクリル系繊維の評価結果を表１に示す。 (Example 5)
In Example 2, the dyeing treatment was carried out in the same manner as in Example 2 except that a disperse dye (Disperse Red 60 dye substance, anthraquinone-based, capable of dyeing red), which is abbreviated as “DD4”, was used as the dye. The dispersion dye DD4 does not contain a dispersant. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
（実施例６）
　実施例２において、染料として、以下「ＤＤ５」と略記する分散染料（Ｄｉｓｐｅｒｓｅ　Ｂｌｕｅ　５６染料原体、アントラキノン系、青色に染色可能）を使用したこと以外は、実施例２と同様に染色処理した。なお、分散染料ＤＤ５には、分散剤が含まれていない。染色処理後のアクリル系繊維の評価結果を表１に示す。 (Example 6)
In Example 2, the dyeing treatment was carried out in the same manner as in Example 2 except that a disperse dye (Disperse Blue 56 dye substance, anthraquinone-based, capable of dyeing blue), which is abbreviated as “DD5”, was used as the dye. The dispersion dye DD5 does not contain a dispersant. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
（比較例１）
　実施例３において、染料として、以下、「ＣＤ１」と略記するカチオン染料（日本化薬社製「Ｋａｙａｃｒｙｌ　Ｙｅｌｌｏｗ　３ＲＬ－ＥＤ」）を使用し、媒体として水を使用し、染色圧力を常圧としたこと以外は、実施例３と同様に染色処理した。染色処理後のアクリル系繊維の評価結果を表１に示す。なお、染浴の組成は、ＣＤ１　０．０１ｇ、水　５０ｇ、ミテジマ化学製「ウルトラＭＴ＃１１０」　０．０１５ｇであった。 (Comparative Example 1)
In Example 3, a cationic dye (“Kayacryl Yellow 3RL-ED” manufactured by Nippon Kayaku Co., Ltd.), which is hereinafter abbreviated as “CD1”, was used as the dye, water was used as the medium, and the dyeing pressure was set to normal pressure. Except for this, the dyeing treatment was carried out in the same manner as in Example 3. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment. The composition of the dyeing bath was 0.01 g of CD1, 50 g of water, and 0.015 g of "Ultra MT # 110" manufactured by Mitejima Chemical.
（比較例２）
　実施例１において、染料濃度を０．５％ｏｍｆとし、染色温度を９８℃とし、媒体として水を使用し、染色圧力を常圧としたこと以外は、実施例１と同様に染色処理した。染色処理後のアクリル系繊維の評価結果を表１に示す。なお、染浴の組成は、ＤＤ１　０．０１ｇ、水５０ｇ、酢酸０．０５ｇ、ＴＡＮＡＴＥＸ製「ＴＡＮＡＶＯＬ　ＤＡＰ」　０．１ｇであった。 (Comparative Example 2)
In Example 1, the dyeing treatment was carried out in the same manner as in Example 1 except that the dye concentration was 0.5% omf, the dyeing temperature was 98 ° C., water was used as a medium, and the dyeing pressure was normal pressure. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment. The composition of the dyeing bath was 0.01 g of DD1, 50 g of water, 0.05 g of acetic acid, and 0.1 g of "TANAVOL DAP" manufactured by TANATEX.
（比較例３）
　実施例２において、染料としてＣＤ１を使用したこと以外は、実施例２と同様に染色処理した。染色処理後のアクリル系繊維の評価結果を表１に示す。 (Comparative Example 3)
In Example 2, the dyeing treatment was carried out in the same manner as in Example 2 except that CD1 was used as the dye. Table 1 shows the evaluation results of the acrylic fiber after the dyeing treatment.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から、カチオン染料を含有する水系媒体でアクリル系繊維を染色すると、比較例１に示すように、染着性と発色性に優れるが、染料廃液が発生した。また、分散染料を含有する水系媒体で染色すると、比較例２に示すように、染着性に優れるものの、ａ＊値が大きくなり、Ｆｌａｖｉｎｅ染料が赤味に異常発色して、従来の蛍光黄色に対する発色性に劣る結果となり、また、染料廃液も発生した。さらに、カチオン染料を用いて超臨界二酸化炭素中で染色した比較例３では、染料廃液が発生しないものの、ｂ＊値が小さくなり、染着性と発色性に劣った。
　一方、分散染料を用いて超臨界二酸化炭素中で染色すると、実施例１～３に示すように、染着性と発色性に優れるとともに、染料廃液も発生しなかった。また、実施例４～６の結果から分かるように、分散染料として分散剤を含まない分散染料を用いると、分散剤を含む実施例１～３と比較して、染着性が向上した。
  From Table 1, when the acrylic fiber was dyed with an aqueous medium containing a cationic dye, as shown in Comparative Example 1, the dyeing property and the color developing property were excellent, but a dye waste liquid was generated. Further, when dyeing with an aqueous medium containing a disperse dye, as shown in Comparative Example 2, although the dyeing property is excellent, the a * value becomes large, and the Flavin dye abnormally develops a reddish color, resulting in conventional fluorescent yellow color. As a result, the color-developing property was inferior, and dye waste liquid was also generated. Further, in Comparative Example 3 dyed in supercritical carbon dioxide using a cationic dye, although no dye waste liquid was generated, the b * value was small and the dyeing property and the color developing property were inferior.
On the other hand, when dyeing in supercritical carbon dioxide using a disperse dye, as shown in Examples 1 to 3, the dyeing property and the color developing property were excellent, and no dye waste liquid was generated. Further, as can be seen from the results of Examples 4 to 6, when the disperse dye containing no dispersant was used as the disperse dye, the dyeability was improved as compared with Examples 1 to 3 containing the dispersant.

Claims (10)

  1. 　アクリル系繊維の染色方法において、疎水性の超臨界流体中で分散染料を吸着させる染色方法。 A dyeing method for adsorbing disperse dyes in a hydrophobic supercritical fluid in the dyeing method for acrylic fibers.
  2. 　前記分散染料に含まれる分散染料原体が、アントラキノン系及び縮合系からなる群より選択される１種以上である、請求項１に記載の染色方法。 The dyeing method according to claim 1, wherein the disperse dye drug substance contained in the disperse dye is at least one selected from the group consisting of anthraquinone type and condensation type.
  3. 　前記分散染料に含まれる分散剤の含有量が、前記分散染料に含まれる分散染料原体の全質量に対して、２０質量％以下である、請求項１又は２に記載の染色方法。 The dyeing method according to claim 1 or 2, wherein the content of the dispersant contained in the disperse dye is 20% by mass or less with respect to the total mass of the disperse dye substance contained in the disperse dye.
  4. 　前記分散染料に、分散剤が含まれていない、請求項１又は２に記載の染色方法。 The dyeing method according to claim 1 or 2, wherein the disperse dye does not contain a dispersant.
  5. 　前記超臨界流体は、二酸化炭素である、請求項１に記載の染色方法。 The dyeing method according to claim 1, wherein the supercritical fluid is carbon dioxide.
  6. 　疎水性の超臨界流体中で、アクリル系繊維に分散染料を吸着させることを含む、染色されたアクリル系繊維の製造方法。 A method for producing dyed acrylic fibers, which comprises adsorbing a disperse dye to acrylic fibers in a hydrophobic supercritical fluid.
  7. 　前記分散染料に含まれる分散染料原体が、アントラキノン系及び縮合系からなる群より選択される１種以上である、請求項６に記載の製造方法。 The production method according to claim 6, wherein the disperse dye drug substance contained in the disperse dye is at least one selected from the group consisting of anthraquinone type and condensation type.
  8. 　前記分散染料に含まれる分散剤の含有量が、前記分散染料に含まれる分散染料原体の全質量に対して、２０質量％以下である、請求項６又は７に記載の製造方法。 The production method according to claim 6 or 7, wherein the content of the dispersant contained in the disperse dye is 20% by mass or less with respect to the total mass of the disperse dye substance contained in the disperse dye.
  9. 　前記分散染料に、分散剤が含まれていない、請求項６又は７に記載の製造方法。 The production method according to claim 6 or 7, wherein the dispersant dye does not contain a dispersant.
  10. 　前記超臨界流体は、二酸化炭素である、請求項６に記載の製造方法。
          The production method according to claim 6, wherein the supercritical fluid is carbon dioxide.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106757918A (en) * 2016-11-21 2017-05-31 大连工业大学 One kind can the colour changing engineering anhydrous dyeing and finishing system and method for supercritical carbon dioxide fluid
CN108086022A (en) * 2017-12-26 2018-05-29 中原工学院 Supercritical CO used for textiles2Fluid dyestuff composition and coloring system and method
CN108884632A (en) * 2016-02-18 2018-11-23 戴库纺织系统有限公司 Dyeing includes the method for the matrix of elastomeric fibre and non-elastomeric fibers and the dyed substrates comprising these fibers
US20180355536A1 (en) * 2016-11-21 2018-12-13 Dalian Polytechnic University Multifunctional dyeing and finishing kettle and industrialized supercritical co2 fluid anhydrous dyeing and finishing apparatus with a scale over 1000 liters
WO2020077701A1 (en) * 2018-10-16 2020-04-23 苏州大学 Anhydrous fiber dyeing method for cotton
CN111574848A (en) * 2020-06-12 2020-08-25 大连工业大学 Mixed dye and supercritical CO using same2Anhydrous black split dyeing method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108884632A (en) * 2016-02-18 2018-11-23 戴库纺织系统有限公司 Dyeing includes the method for the matrix of elastomeric fibre and non-elastomeric fibers and the dyed substrates comprising these fibers
CN106757918A (en) * 2016-11-21 2017-05-31 大连工业大学 One kind can the colour changing engineering anhydrous dyeing and finishing system and method for supercritical carbon dioxide fluid
US20180355536A1 (en) * 2016-11-21 2018-12-13 Dalian Polytechnic University Multifunctional dyeing and finishing kettle and industrialized supercritical co2 fluid anhydrous dyeing and finishing apparatus with a scale over 1000 liters
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