WO2024122628A1 - 超臨界二酸化炭素を用いてポリオレフィン繊維を染色するための染料 - Google Patents

超臨界二酸化炭素を用いてポリオレフィン繊維を染色するための染料 Download PDF

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WO2024122628A1
WO2024122628A1 PCT/JP2023/043952 JP2023043952W WO2024122628A1 WO 2024122628 A1 WO2024122628 A1 WO 2024122628A1 JP 2023043952 W JP2023043952 W JP 2023043952W WO 2024122628 A1 WO2024122628 A1 WO 2024122628A1
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carbon atoms
alkyl group
formula
group
hydrogen atom
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French (fr)
Japanese (ja)
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松本敏昭
小林樹
杉村亮治
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Kiwa Chemical Industry Co Ltd
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Kiwa Chemical Industry Co Ltd
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Priority to JP2024532575A priority Critical patent/JP7681368B2/ja
Priority to CN202380043572.5A priority patent/CN119301203A/zh
Priority to KR1020257015098A priority patent/KR20250081932A/ko
Publication of WO2024122628A1 publication Critical patent/WO2024122628A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3
    • 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
    • D06P1/02—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 azo dyes
    • D06P1/04—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 azo dyes not containing metal
    • 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
    • D06P1/94—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 dyes dissolved in solvents which are in the supercritical state
    • 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
    • D06P3/79—Polyolefins

Definitions

  • the present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, a method for dyeing polyolefin fibers using supercritical carbon dioxide, polyolefin fibers dyed by the dyeing method, and a compound.
  • Polyolefin resins such as polypropylene resin and polyethylene resin are crystalline thermoplastic resins that have excellent properties such as low cost, easy processability, high strength, high chemical resistance, high abrasion resistance, high bending resistance, light weight, low moisture absorption, low thermal conductivity, high antistatic properties, and recyclability.
  • polyolefin resins are polymeric compounds in which both the main chain and side chain are made of hydrocarbons, and because they have low affinity and compatibility with conventional dye compounds and do not have functional groups that are effective in chemical reactions, it has been considered extremely difficult to achieve high-concentration, high-fastness dyeing.
  • polypropylene resin and polyethylene resin are among the four major general-purpose synthetic resins, along with polyvinyl chloride resin and polystyrene resin, and are used in a wide range of fields.
  • JP 38-10741 B describes examples of producing red and purple dyes in which a phenoxy group having an alkyl or cycloalkyl group with 3 to 12 carbon atoms as a substituent has been introduced into an anthraquinone dye, as well as examples of dyeing polypropylene resin fibers using these dyes.
  • JP 40-1277 B describes examples of producing blue dyes in which an anthraquinone dye is modified with a phenoxy group having an alkyl group, a cycloalkyl group, or a halogeno group having 1 to 9 carbon atoms as a substituent, and examples of using them to dye polyester fibers, polyamide fibers, and polyolefin resin fibers.
  • JP 41-3515 B describes an example of the production of a blue dye in which a phenoxy group having an alkyl group with 1 to 9 carbon atoms or a halogeno group as a substituent is introduced into an anthraquinone dye, and an example of the dyeing of polyolefin resin fibers using the dye.
  • British Patent No. 872,882 describes an example of dyeing polyolefin resin fibers using a blue dye in which an alkylamino group or a cycloalkylamino group has been introduced at the alpha position of an anthraquinone dye.
  • U.S. Patent No. 3,536,735 describes an example of the production of a red dye in which a phenoxy group having two substituents selected from a sec-butyl group, a sec-pentyl group, and a tert-pentyl group is introduced into an anthraquinone dye, and also describes an example of the dyeing of polypropylene resin fibers using the dye.
  • JP 2019-203223 A describes an example of dyeing polypropylene fibers in water using a disperse dye composition containing an anthraquinone yellow dye, an anthraquinone red dye, or an anthraquinone blue dye having a long-chain alkyl group.
  • JP Patent Publication 55-152869 describes examples of producing monoazo dyes with long-chain alkyl groups, and examples of dyeing fine denier polyester fibers using them. However, it does not describe examples of dyeing polyolefin fibers using them. In addition, there is no mention of yellow dyes.
  • Japanese Patent Publication No. 3253649 describes a dyeing method that uses supercritical carbon dioxide as a dyeing medium to dye hydrophobic fiber materials with various dyes as an alternative to aqueous dyeing.
  • polypropylene is listed as an example of a hydrophobic fiber material, the examples only include dyeing examples of polyester fabric, and do not include examples of dyeing polypropylene fibers.
  • Patent Publication No. 6721172 describes the use of supercritical carbon dioxide as a dyeing medium to dye polypropylene fibers, which are polyolefin fibers, with anthraquinone blue dye, anthraquinone yellow dye, anthraquinone red dye, or a mixture of these dyes.
  • the present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which contains a compound represented by the following general formula (I):
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • the supercritical carbon dioxide dyeing equipment used for dyeing is shown.
  • the present invention aims to provide a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which can dye polyolefin fibers a high-concentration yellow and provide dyed products with excellent color fastness to light, sublimation, washing, etc.; a method for dyeing polyolefin fibers using supercritical carbon dioxide; and polyolefin fibers and compounds dyed by the dyeing method.
  • the present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which contains a compound represented by the following general formula (I).
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • the present invention also provides a method for dyeing polyolefin fibers using supercritical carbon dioxide, comprising the steps of: A process is provided which comprises the step of dyeing polyolefin fibres in the presence of supercritical carbon dioxide with the dye of the present invention.
  • the present invention also provides polyolefin fibers dyed by a dyeing method including a step of dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the dye of the present invention.
  • the present invention also provides a compound represented by the following general formula (I):
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • the dye of the present invention can dye polyolefin fibers in a high-concentration yellow color in the presence of supercritical carbon dioxide, and the dyed product has excellent color fastness to light, sublimation, washing, etc.
  • dyes containing the following specific compounds have improved affinity for lipophilic polyolefin fibers and dye polyolefin fibers a high concentration of yellow in the presence of supercritical carbon dioxide, thus completing the present invention.
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • examples of the alkyl group having 8 to 14 carbon atoms include linear alkyl groups such as n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, and n-tetradecyl groups, and branched alkyl groups such as 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, 2-tridecyl, and 2-butyloctyl groups.
  • the alkyl group having 8 to 14 carbon atoms is preferably a linear or branched alkyl group having 9 to 14 carbon atoms, more preferably a linear or branched alkyl group having 10 to 14 carbon atoms, more preferably a linear or branched alkyl group having 12 to 14 carbon atoms, more preferably a linear or branched alkyl group having 8 to 12 carbon atoms, more preferably a linear or branched alkyl group having 9 to 12 carbon atoms, more preferably a linear or branched alkyl group having 10 to 12 carbon atoms, more preferably a linear or branched alkyl group having 8 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 9 to 10 carbon atoms.
  • examples of the alkyl group having 1 to 8 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl, and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 1-ethyl-1-methylpropyl.
  • examples of the alkoxy group having 1 to 4 carbon atoms include linear or branched alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these, alkoxy groups having 4 carbon atoms are preferred.
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is preferably an alkyl group having 9 to 14 carbon atoms, preferably an alkyl group having 10 to 14 carbon atoms, preferably an alkyl group having 12 to 14 carbon atoms, preferably an alkyl group having 8 to 12 carbon atoms, preferably an alkyl group having 9 to 12 carbon atoms, preferably an alkyl group having 10 to 12 carbon atoms, preferably an alkyl group having 8 to 10 carbon atoms, and preferably an alkyl group having 9 to 10 carbon atoms.
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms; More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms. It is more preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R2 , R3 , R4 , R5 , and R6 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and it is more preferable that at least one of R2 , R3 , R4 , R5 , and R6 is a linear or branched alkyl group having 4 carbon atoms.
  • R2 and R6 are preferably hydrogen atoms.
  • R3 and R5 each independently preferably represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, More preferably, it is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms. A hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms is more preferred.
  • R 1 represents an alkyl group having 8 carbon atoms and R 2 , R 3 , R 4 , R 5 and R 6 all represent hydrogen atoms.
  • R 1 represents an alkyl group having 9 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 10 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 9 to 12 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 10 to 12 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 8 to 12 carbon atoms; It is preferred that R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 10 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • At least one of R 2 , R 3 , R 4 , R 5 and R 6 is preferably an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 12 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • At least one of R 2 , R 3 , R 4 , R 5 and R 6 is preferably an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 10 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • At least one of R 2 , R 3 , R 4 , R 5 and R 6 is preferably an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; It is preferred that at least one of R 2 , R 3 , R 4 , R 5 and R 6 is an alkyl group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 14 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • the compounds of formula (I) are preferably the following compounds, and more preferably the compounds of formulas (1), (3), (4), (5), (7), (8), (13), (14), (15), (16), and (17).
  • the compound of formula (I) is a yellow dye compound.
  • R 1 is preferably an alkyl group having 9 to 14 carbon atoms, preferably an alkyl group having 10 to 14 carbon atoms, preferably an alkyl group having 12 to 14 carbon atoms, preferably an alkyl group having 8 to 12 carbon atoms, preferably an alkyl group having 9 to 12 carbon atoms, preferably an alkyl group having 10 to 12 carbon atoms, preferably an alkyl group having 8 to 10 carbon atoms, and preferably an alkyl group having 9 to 10 carbon atoms.
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms; More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms. It is more preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R2 , R3 , R4 , R5 , and R6 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and it is more preferable that at least one of R2 , R3 , R4 , R5 , and R6 is a linear or branched alkyl group having 4 carbon atoms.
  • R2 and R6 are preferably hydrogen atoms.
  • R3 and R5 each independently preferably represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, More preferably, it is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms. More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms. A hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms is more preferred.
  • R 1 represents an alkyl group having 8 carbon atoms
  • R 2 , R 3 , R 4 , R 5 and R 6 all represent hydrogen atoms.
  • R 1 represents an alkyl group having 9 to 14 carbon atoms; It is preferred that R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 10 to 14 carbon atoms; It is preferred that R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 9 to 12 carbon atoms; It is preferred that R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 10 to 12 carbon atoms; It is preferred that R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.
  • R 1 represents an alkyl group having 8 to 12 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 10 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • At least one of R 2 , R 3 , R 4 , R 5 and R 6 is preferably an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 12 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • At least one of R 2 , R 3 , R 4 , R 5 and R 6 is preferably an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 10 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • At least one of R 2 , R 3 , R 4 , R 5 and R 6 is preferably an alkoxy group having 1 to 4 carbon atoms.
  • R 1 represents an alkyl group having 8 to 14 carbon atoms
  • R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms
  • R 1 is an alkyl group having 8 to 14 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R1 is an alkyl group having 8 to 12 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • R 1 is an alkyl group having 8 to 10 carbon atoms
  • R2 and R6 are hydrogen atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.
  • the compound of formula (I) of the dye is From the viewpoint of dyeing density, light fastness, sublimation fastness, etc.
  • the following compounds are preferred, and the compounds of formulae (1), (3), (4), (5), (7), (8), (13), (14), (15), (16) and (17) are more preferred.
  • the compound represented by formula (I) can be obtained by coupling a diazo compound of an aniline derivative represented by formula (i-D) (in formula (i-D), R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms) with a compound represented by formula (i-C) (in formula (i-C), R 1 represents an alkyl group having 8 to 14 carbon atoms).
  • a compound of formula (i-D) is diazotized in a mineral acid or an organic carboxylic acid using a nitrosating agent or nitrosylsulfuric acid in the presence of water, which is optionally added, to obtain a diazo compound.
  • a nitrosating agent or nitrosylsulfuric acid in the presence of water, which is optionally added, to obtain a diazo compound.
  • the organic carboxylic acid used include acetic acid and propionic acid.
  • the mineral acid used include hydrochloric acid, phosphoric acid, and sulfuric acid, preferably sulfuric acid.
  • the nitrosating agent used is an alkali metal nitrite, for example, sodium nitrite in a solid state or in an aqueous solution state.
  • the compound of formula (i-D) may be commercially available or may be produced by a known method.
  • the diazotization reaction temperature is preferably -10 to 40°C, more preferably 0 to 40°C.
  • a cyanoacetate e.g., methyl cyanoacetate
  • R 1 NH 2 R 1 represents an alkyl group having 8 to 14 carbon atoms
  • an acetoacetate e.g., methyl acetoacetate
  • the dyes of the present invention have the compound of formula (I).
  • the dye of the present invention may further contain additives.
  • additives include auxiliary colorants, dispersants, fillers, stabilizers, plasticizers, crystal nucleating agents, modifiers, foaming agents, UV absorbers, light stabilizers, antioxidants, antibacterial agents, antifungal agents, antistatic agents, flame retardants, inorganic fillers, and elastomers for improving impact resistance.
  • the polyolefin fibers of the dyed object dyed with the dye of the present invention are, for example, fibers formed from a polymer selected from homopolymers of ⁇ -olefins such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, etc., copolymers of these ⁇ -olefins, or copolymers of these ⁇ -olefins with other unsaturated monomers copolymerizable therewith.
  • the types of copolymers include, for example, block copolymers, random copolymers, graft copolymers, etc.
  • polymers include polypropylene-based resins such as propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, and propylene-ethylene-(1-butene) copolymers, polyethylene-based resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymers, and ethylene-ethyl acrylate copolymers, poly-1-butene, poly-4-methyl-1-pentene, etc.
  • polypropylene-based resins such as propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, and propylene-ethylene-(1-butene) copolymers
  • polyethylene-based resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene
  • the above polymers may be used alone or in combination to form polyolefin fibers.
  • the polyolefin fibers are preferably made of polypropylene-based resin and/or polyethylene-based resin, and more preferably made of polypropylene-based resin.
  • the polyolefin fiber may be in any shape, such as a block (molded product, etc.), a film, or a fiber (fabric (woven fabric, knitted fabric, nonwoven fabric, etc.), thread (filament yarn, spun yarn, slit yarn, split yarn, etc.), etc.), and is preferably in a fiber shape.
  • the polyolefin fiber may be a fiber formed by blending other polymer components with polypropylene resin and/or polyethylene resin, bonding, etc.
  • the polyolefin fiber may be a fiber obtained by blending or blending polypropylene fiber with other fibers such as polyester.
  • the present invention relates to a method for dyeing polyolefin fibers using supercritical carbon dioxide, which comprises a step of dyeing polyolefin fibers with the dye of the present invention in the presence of supercritical carbon dioxide.
  • supercritical carbon dioxide is used as a dyeing medium.
  • the dyeing method that uses supercritical carbon dioxide as the dyeing medium does not use water during dyeing, does not require a washing process, and therefore does not generate wastewater, does not require dyeing auxiliaries, has a short dyeing time, and allows the carbon dioxide dyeing medium to be reused. As a result, it has attracted attention as an environmentally friendly dyeing method.
  • supercritical carbon dioxide is lipophilic
  • both the dye and polyolefin resin of the present invention are lipophilic, so there is a high affinity between the dyeing medium, dye, and dyed object, resulting in high-quality dyed objects.
  • the dyeing process in the method of dyeing polyolefin fibers using supercritical carbon dioxide of the present invention is preferably carried out at a temperature of 31°C or higher and a pressure of 7.4 MPa or higher. This is because the dyeing temperature and dyeing pressure must be equal to or higher than the critical point of carbon dioxide, which is the dyeing medium (7.4 MPa at 31°C).
  • the dyeing temperature is mainly determined by the type of resin in the fiber to be dyed.
  • the dyeing temperature is usually in the range of 60 to 180°C, and preferably in the range of 80 to 160°C.
  • the dyeing pressure is mainly determined by the type of resin in the dyed fiber.
  • the dyeing pressure is usually in the range of about 7.4 to 40.0 MPa, and preferably 20 to 30 MPa.
  • the dyeing time in the dyeing process is determined by the type of resin in the dyed fiber and the dyeing temperature.
  • the dyeing time is usually about 10 to 120 minutes, preferably 30 to 90 minutes.
  • the concentration of the dye relative to the fiber depends on the type and processing state of the fiber to be dyed.
  • the concentration of the dye relative to the fiber is 0.1 to 6.0% o.m.f. (on the mass of fiber), preferably 0.1 to 4.0% o.m.f.
  • the bath ratio (mass ratio of material to be dyed: carbon dioxide) depends on the type of material to be dyed and the processing state.
  • the bath ratio is usually 1:2 to 1:100, preferably 1:5 to 1:75.
  • the bath ratio in the dyeing method of the present invention is relatively low, for example, 1:2 to 1:5.
  • the present invention provides a polyolefin fiber dyed by the dyeing method of the present invention.
  • the dyed polyolefin fiber is dyed to a high concentration, particularly to a high concentration yellow, and has excellent color fastness to light, sublimation, washing, etc.
  • Applications of the polyolefin fiber include, for example, clothing, underwear, hats, socks, gloves, sportswear, and other clothing items, vehicle interior materials such as seat covers, and interior goods such as carpets, curtains, mats, sofa covers, and cushion covers.
  • Step 2 A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 4-butylaniline (14.9 g) represented by the following formula (D1) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D1).
  • D1 4-butylaniline
  • D1 10% hydrochloric acid
  • step 3 Synthesis of yellow dye compound (1) by coupling reaction (step 3)
  • the diazo component solution (D1) obtained in the step 2 was added dropwise to the coupler component solution (C1) obtained in the step 1 over 1 hour at a temperature in the range of 0 to 10° C., to carry out a coupling reaction.
  • the mixture was stirred at a temperature in the range of 0 to 10° C. for 30 minutes, and then 500 g of water was added.
  • the product was filtered from the reaction mixture, washed with water, and dried at 60° C. until the moisture content was 1.0 mass% or less, to obtain a yellow dye compound represented by the following formula (1) (29.0 g, yield 60.6%).
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 479 (M + )).
  • Step 1 A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of aniline (9.31 g) represented by the following formula (D2) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D2).
  • aniline 9.31 g
  • D2 10% hydrochloric acid
  • Step 1 To a mixture of p-toluidine (10.7 g) represented by the following formula (D3) and 10% hydrochloric acid (140 g), 36% aqueous sodium nitrite solution (21.1 g) was added dropwise at 5 to 10° C., and the mixture was stirred for 1 hour at 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at 5 to 10° C., to obtain a diazo component solution (D3).
  • D3 diazo component solution
  • Step 1 Preparation of diazo component solution (Step 1) To a mixture of m-toluidine (10.7 g) represented by the following formula (D4) and 10% hydrochloric acid (140 g), 36% aqueous sodium nitrite solution (21.1 g) was added dropwise at 5 to 10° C., and the mixture was stirred for 1 hour at 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at 5 to 10° C., to obtain a diazo component solution (D4).
  • D4 diazo component solution
  • step 2 Synthesis of yellow dye compound (4) by coupling reaction (step 2)
  • a yellow dye compound represented by the following formula (4) (30.1 g, yield 69.0%) was obtained in the same manner as in Step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 437 (M + )).
  • a yellow dye compound represented by the following formula (6) (22.5 g, yield 61.3%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D2) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C2) was used instead of coupler component solution (C1) as the coupler component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 367 (M + )).
  • a yellow dye compound represented by the following formula (7) (24.4 g, yield 64.2%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D3) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C2) was used instead of coupler component solution (C1) as the coupler component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 381 (M + )).
  • a yellow dye compound represented by the following formula (8) (22.8 g, yield 60.0%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C2) was used instead of coupler component solution (C1) as the coupler component solution.
  • diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution
  • coupler component solution (C2) was used instead of coupler component solution (C1) as the coupler component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 381 (M + )).
  • a yellow dye compound represented by the following formula (10) (11.5 g, yield 31.4%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D2) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C3) was used instead of coupler component solution (C1) as the coupler component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 367 (M + )).
  • a yellow dye compound represented by the following formula (11) (14.5 g, yield 38.2%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D3) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C3) was used instead of coupler component solution (C1) as the coupler component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 381 (M + )).
  • a yellow dye compound represented by the following formula (12) (12.2 g, yield 32.1%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C3) was used instead of coupler component solution (C1) as the coupler component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 381 (M + )).
  • a yellow dye compound represented by the following formula (14) (29.0 g, yield 71.0%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C4) was used instead of coupler component solution (C1) as the coupler component solution.
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 409 (M + )).
  • Step 1 To a mixture of 4-ethylaniline (12.1 g) represented by the following formula (D5) and 10% hydrochloric acid (140 g), 36% aqueous sodium nitrite solution (21.1 g) was added dropwise at 5 to 10° C., and the mixture was stirred for 1 hour at 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at 5 to 10° C., to obtain a diazo component solution (D5).
  • 4-ethylaniline represented by the following formula (D5)
  • hydrochloric acid 140 g
  • Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at 5 to 10° C., to obtain a diazo component solution (D5).
  • Step 1 A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 3,5-dimethylaniline (12.1 g) represented by the following formula (D6) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D6).
  • D6 diazo component solution
  • Step 1 To a mixture of 3,4-dimethylaniline (12.1 g) represented by the following formula (D7) and 10% hydrochloric acid (140 g), 36% aqueous sodium nitrite solution (21.1 g) was added dropwise at 5 to 10° C., and the mixture was stirred for 1 hour at 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at 5 to 10° C., to obtain a diazo component solution (D7).
  • D7 1,3-dimethylaniline (12.1 g) represented by the following formula (D7) and 10% hydrochloric acid (140 g)
  • Step 1 A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 4-butoxyaniline (16.5 g) represented by the following formula (D8) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D8).
  • 4-butoxyaniline (16.5 g) represented by the following formula (D8)
  • 10% hydrochloric acid 140 g
  • Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D8).
  • step 2 Synthesis of yellow dye compound (18) by coupling reaction (step 2)
  • the diazo component solution (D8) obtained in step 1 was added dropwise to the coupler component solution (C2) over 1 hour at a temperature in the range of 0 to 10° C., to carry out a coupling reaction.
  • the mixture was stirred at a temperature in the range of 0 to 10° C. for 30 minutes, and then 500 g of water was added.
  • the product was filtered from the reaction mixture, washed with water, and dried at 60° C. until the moisture content was 1.0 wt % or less, to obtain a yellow dye compound represented by the following formula (18) (14.6 g, yield 33.3%).
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 439 (M+)).
  • the reaction mixture was cooled to room temperature, and a mixture of 5-amino-anthra[9,1-cd]isothiazol-6-one (25.2 g) and toluene (30 g) was added dropwise to the reaction mixture.
  • the reaction mixture was heated to 110° C. and stirred for 2 hours, after which the solvent was removed from the mixture by vacuum distillation, and methanol (100 g) was added to the residue to cause precipitation.
  • the mixture was filtered, and the filtered product was washed with methanol and then with water, and dried at 60° C. until the moisture content was 1.0 wt % or less, to obtain a yellow dye compound represented by the following formula (22) (36.7 g, yield 74.7%).
  • the structure of the yellow dye compound was confirmed by LCMS analysis (m/z 491 (M + )).
  • the reaction mixture was heated to 110°C and stirred for 2 hours, and then cooled to room temperature, and 20 g of a 24% aqueous sodium hydroxide solution was added, and 300 g of water was added to extract the organic layer. This extract was washed with saturated saline, and then the solvent was distilled off under reduced pressure, and methanol (300 g) was added to the residue to cause precipitation. The mixture was filtered, and the filtered product was washed with methanol and then with water, and dried at 60° C. until the moisture content was 1.0 wt % or less to obtain a yellow dye compound represented by the following formula (28) (22.6 g, yield 31.6%). The structure of the yellow dye compound was confirmed by LCMS analysis (m/z 715 (M + )).
  • Step 2 A mixture of 2-ethylhexylaminobenzoic acid (28.9 g), acetic anhydride (50 g), and acetic acid (50 g) obtained in the above step 1 was heated to 110° C. and stirred for 7 hours. After the reaction mixture was cooled to room temperature, 200 g of water and 200 g of ethyl acetate were added to extract the organic layer, which was washed with saturated saline, and the solvent was distilled off under reduced pressure to obtain 4-hydroxy-1-(2-ethylhexyl)quinolin-2-one (36.7 g, yield 134%) represented by the following formula (C5) as a crude product. 100 g of methanol was added to this crude product, and the mixture was cooled to 5° C. to obtain a coupler component solution (C5) consisting of the compound of formula (C5).
  • C5 4-hydroxy-1-(2-ethylhexyl)quinolin-2-one
  • the supercritical carbon dioxide dyeing apparatus used for dyeing is shown in Figure 1.
  • the dyeing apparatus is composed of a liquid CO2 cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high-pressure pump (5), a preheater (6), a pressure gauge (7 to 9), a magnetic drive unit (10), a DC motor (11), safety valves (12, 13), stop valves (14 to 18), a needle valve (19), and a heater (20).
  • the polypropylene cloth was cut into pieces of approximately 50 to 70 g, weighed, and wrapped around a stainless steel cylinder (21) with punched holes in the order of cotton cloth, polypropylene cloth, and cotton cloth from the inside, and then loosely secured with cotton thread.
  • the inner cotton cloth was the undercloth, and the outer cotton cloth was the cover cloth.
  • a stainless steel cylinder wrapped with the above-mentioned fabric samples (cotton fabric, polypropylene fabric, cotton fabric) was fixed to a pressure-resistant stainless steel tank (22), and the yellow dye compound 1 obtained in Synthesis Example 1, which corresponds to 0.3% by mass relative to the mass of the polypropylene fabric, was wrapped in a paper wipe and placed in the fluid passage at the top of the stainless steel cylinder.
  • the volume of the pressure-resistant stainless steel tank was 2230 cm3 . All valves in the dyeing apparatus were closed, and the tank was heated to 120°C by a preheater.
  • the stop valves (14) and (16) were opened, and 1.13 kg of liquid carbon dioxide was introduced into the pressure-resistant stainless steel tank using a high-pressure pump connected via a cooling jacket. After that, the stop valves (14) and (16) were closed, and the liquid was circulated by the impeller and magnetic drive unit at the bottom of the pressure-resistant stainless steel tank.
  • the rotation speed of the magnetic drive unit was 750 rpm, and the circulation direction was from the inside to the outside of the cylinder.
  • Dyeing examples P2 to P26 A yellow dyed polypropylene fabric was obtained by the same dyeing procedure as in Dyeing Example P1, except that the yellow dye compound 1 described in Dyeing Example P1 was changed to a dye compound described in Tables 1 and 2.
  • the dye compounds used in Dyeing Examples P1 to P26 are shown in Tables 3 and 4.
  • the polypropylene dyed fabrics obtained in dyeing examples P1 to P26 were subjected to dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, friction fastness test, and hot pressing fastness test.
  • Dyeability Evaluation was evaluated based on the total K/S value and K/S value (measured at the maximum wavelength) obtained by color measurement of the dyed fabric, and by visual inspection of the dye residue after dyeing.
  • the color of the dyed fabric was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by GretagMacbeth) with the dyed fabric glued onto white paper, under an observation light source of D65 and a 2-degree visual field.
  • the light fastness test was performed by the ultraviolet carbon arc lamp method according to JIS L0842: 2004.
  • the outline of the test method is as follows: Using an ultraviolet fade meter U48 (manufactured by Suga Test Instruments Co., Ltd.), the dyed fabric was exposed to light for 20 hours under the condition of a black panel temperature of 63 ⁇ 3° C., and then discoloration was judged.
  • Sublimation Fastness Test was performed according to JIS L0854: 2013. The outline of the test method is as follows: The dyed fabric was sandwiched between nylon fabrics and held at 120 ⁇ 2° C. for 80 minutes under a load of 12.5 kPa, and then the discoloration and staining of the nylon fabric were evaluated.
  • the washing fastness test was performed according to JIS L0844:2011 (A-2).
  • the outline of the test method is as follows. A multi-woven fabric was attached to the dyed fabric, and washed for 30 minutes at 50 ⁇ 2°C in the presence of soap, and discoloration and staining of the cotton and nylon parts of the multi-woven fabric were evaluated. In addition, staining of the residual liquid after washing was evaluated.
  • Sweat fastness test was performed according to JIS L0848: 2004.
  • the outline of the test method is as follows: A multi-woven fabric was attached to the dyed fabric, and the fabric was immersed in acidic artificial sweat or alkaline artificial sweat for 30 minutes, and then kept at 37 ⁇ 2°C for 4 hours under a load of 12.5 kPa, and then dried at 60°C or less, and the discoloration and staining of the cotton and nylon parts of the multi-woven fabric were evaluated.
  • Friction Fastness Test was performed according to JIS L0849:2013. The outline of the test method is as follows. Using a friction fastness tester RT-300 (manufactured by Daiei Scientific Instruments Co., Ltd.), the dyed fabric was rubbed back and forth 100 times with a dry cotton fabric or a wet cotton fabric under a load of 2N, and the coloring of the cotton fabric was judged.
  • Table 5 shows the evaluation results for dyeing examples using the compound of formula (I)
  • Table 6 shows the evaluation results for dyeing examples using dye compounds other than the compound of formula (I).
  • the compounds used in Dyeing Examples P1 to P15 in which R 1 is an alkyl group having 8 to 12 carbon atoms, and R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, had good fastnesses.
  • the present invention is not limited to the above-mentioned embodiments, and suitable combinations or substitutions of the configurations of the embodiments are also included in the present invention.
  • the present invention can be utilized for dyeing polyolefin fibers used in clothing such as clothes, underwear, hats, socks, gloves, and sportswear, vehicle interior materials such as seat covers, and interior goods such as carpets, curtains, mats, sofa covers, and cushion covers.

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PCT/JP2023/043952 2022-12-08 2023-12-08 超臨界二酸化炭素を用いてポリオレフィン繊維を染色するための染料 Ceased WO2024122628A1 (ja)

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