WO2021187446A1 - 超臨界二酸化炭素を用いて染色するための染料 - Google Patents

超臨界二酸化炭素を用いて染色するための染料 Download PDF

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WO2021187446A1
WO2021187446A1 PCT/JP2021/010477 JP2021010477W WO2021187446A1 WO 2021187446 A1 WO2021187446 A1 WO 2021187446A1 JP 2021010477 W JP2021010477 W JP 2021010477W WO 2021187446 A1 WO2021187446 A1 WO 2021187446A1
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compound
formula
dye
carbon atoms
dyeing
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PCT/JP2021/010477
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English (en)
French (fr)
Japanese (ja)
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堀照夫
宮崎慶輔
松本敏昭
小林樹
杉村亮治
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国立大学法人福井大学
学校法人金沢工業大学
紀和化学工業株式会社
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Priority to KR1020227026954A priority Critical patent/KR20220123293A/ko
Priority to CN202180020401.1A priority patent/CN115244139A/zh
Priority to JP2021536695A priority patent/JP7205841B2/ja
Publication of WO2021187446A1 publication Critical patent/WO2021187446A1/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
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • 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
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • 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
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0081—Isothiazoles or condensed isothiazoles
    • 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
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • 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
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • C09B29/0822—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by NO2
    • 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
    • C09B29/3608—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a dye for dyeing a polyolefin fiber using supercritical carbon dioxide, a method for dyeing a polyolefin fiber using supercritical carbon dioxide, and a polyolefin fiber dyed by the dyeing method.
  • Polyolefin-based resins such as polypropylene resin and polyethylene resin are crystalline thermoplastic resins, and are inexpensive, easy to process, high strength, high chemical resistance, high scratch resistance, high bending resistance, light weight, and low moisture absorption. It has excellent properties such as low thermal conductivity and high antistatic property.
  • the polyolefin-based resin is a polymer compound composed of hydrocarbons in both the main chain and the side chain, has low affinity and compatibility with conventional dye compounds, and has a functional group effective for a chemical reaction. It has been considered that high-concentration and high-fast dyeing is extremely difficult due to reasons such as lack of dyeing.
  • polypropylene resin and polyethylene resin are four major general-purpose synthetic resins along with polyvinyl chloride resin and polystyrene resin, and are used in a wide range of fields.
  • Patent Documents 1 to 5 propose dyes for dyeing polyolefin-based resin fibers.
  • Patent Document 1 describes an example of producing a red dye and a purple dye in which an alkyl group having 3 to 12 carbon atoms or a phenoxy group having a cycloalkyl group as a substituent is introduced into an anthraquinone dye, and a polypropylene resin fiber using them. An example of dyeing is described.
  • Patent Document 2 describes an example of producing a blue dye in which an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or a phenoxy group having a halogeno group as a substituent is introduced into an anthraquinone dye, and a polyester fiber using them. Examples of dyeing of polyamide fibers and polyolefin resin fibers are described.
  • Patent Document 3 describes an example of producing a blue dye in which an alkyl group having 1 to 9 carbon atoms or a phenoxy group having a halogeno group as a substituent is introduced into an anthraquinone dye, and an example of dyeing a polyolefin resin fiber using them. Is described.
  • Patent Document 4 describes an example of dyeing a polyolefin-based resin fiber using a blue dye in which an alkylamino group and a cycloalkylamino group are introduced at the ⁇ -position of an anthraquinone-based dye.
  • Patent Document 5 uses an example of producing 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 the like.
  • An example of dyeing the polypropylene resin fiber is described.
  • Patent Document 6 describes an example of producing a monoazo dye having a long-chain alkyl group and an example of dyeing fine denier polyester fibers using them. However, no example of dyeing polyolefin fibers using them is described.
  • Various reforming techniques include blending dyeable resin components such as polyester, copolymerization with vinyl-based monomers having a dyeable group, blending of dyeing accelerators such as metal stearate, and the like. are known.
  • Patent Document 7 describes that supercritical carbon dioxide is used as a dyeing medium and a hydrophobic fiber material is dyed with various dyes as a dyeing method instead of water-based dyeing.
  • polypropylene is described as an example of the hydrophobic fiber material, only the dyeing example of polyester cloth is described in the examples, and the dyeing example of polypropylene fiber is not described.
  • the present invention dyes polyolefin fibers with supercritical carbon dioxide, which can dye polyolefin fibers in various hues at high concentration and has excellent dyeing fastness such as light resistance, sublimation, and washing of dyed products. It is an object of the present invention to provide a dyeing method for a polyolefin fiber using supercritical carbon dioxide, and a polyolefin fiber dyed by the dyeing method.
  • the present invention is a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which contains at least one of the compounds of the following general formulas (A) to (G).
  • X A is a nitro group
  • Y A represents a halogen atom
  • R A1, R A2 and R A3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms)
  • RA4 represents an alkyl group having 1 to 4 carbon atoms.
  • R B1 , R B2, and R B3 each independently represent an alkyl group having 1 to 14 carbon atoms (however , at least one of R B1 , R B2, and R B3 has 4 to 14 carbon atoms. It is an alkyl group).
  • X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
  • R C1, R C2 and R C3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms).
  • X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
  • R D1 represents an alkyl group having 1 to 14 carbon atoms.
  • R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms.
  • R F1 and R F2 each independently represent an alkyl group having 4 to 14 carbon atoms.
  • RG represents an alkyl group having 7 to 18 carbon atoms.
  • the present invention is a method for dyeing polyolefin fibers using supercritical carbon dioxide. Provided is a method including a step of dyeing a polyolefin fiber in the presence of supercritical carbon dioxide using the dye of the present invention.
  • the present invention also provides polyolefin fibers dyed by the dyeing method of the present invention.
  • the dye of the present invention can dye polyolefin fibers in various hues at high concentration in the presence of supercritical carbon dioxide, and the dyed product has excellent dyeing fastness such as light resistance, sublimation, and washing.
  • the supercritical carbon dioxide dyeing apparatus used for dyeing is shown.
  • the present inventors have improved affinity for lipophilic polyolefin fibers with dyes containing the following specific compounds, and dye the polyolefin fibers in various hues at high concentrations in the presence of supercritical carbon dioxide. We found that and completed the present invention.
  • X A is a nitro group
  • Y A represents a halogen atom
  • R A1, R A2 and R A3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms)
  • RA4 represents an alkyl group having 1 to 4 carbon atoms.
  • R B1 , R B2, and R B3 each independently represent an alkyl group having 1 to 14 carbon atoms (however , at least one of R B1 , R B2, and R B3 has 4 to 14 carbon atoms. It is an alkyl group).
  • X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
  • R C1, R C2 and R C3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms).
  • X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
  • R D1 represents an alkyl group having 1 to 14 carbon atoms.
  • R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However , at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms.
  • R F1 and R F2 each independently represent an alkyl group having 4 to 14 carbon atoms.
  • RG represents an alkyl group having 7 to 18 carbon atoms.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferred ones are a fluorine atom and a chlorine atom. Atoms and bromine atoms can be mentioned.
  • the alkyl group having 1 to 14 carbon atoms includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group.
  • alkyl group having 1 to 14 carbon atoms such as -ethyl-1-methylpropyl group.
  • alkyl group having 1 to 14 carbon atoms an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.
  • the alkyl group having 1 to 4 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or a sec-butyl group.
  • T-Butyl group and other linear or branched alkyl groups having 1 to 4 carbon atoms can be mentioned.
  • the alkyl group having 1 to 4 carbon atoms an alkyl group having 1 to 2 carbon atoms is preferable, and an alkyl group having 1 carbon atom is more preferable.
  • the alkyl group having 4 to 14 carbon atoms is, for example, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-.
  • Pentyl group i-pentyl group, sec-pentyl group, t-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group Straight chain such as group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 1-ethyl-1-methylpropyl group.
  • Alkyl groups having 4 to 14 carbon atoms in the form or branched form can be mentioned. As the alkyl group having 4 to 14 carbon atoms, an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl group having 4 to 8 carbon atoms is more preferable.
  • the alkyl group having 4 to 18 carbon atoms includes, for example, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, and the like.
  • alkyl group having 4 to 18 carbon atoms an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl group having 8 to 12 carbon atoms is more preferable.
  • the alkyl group having 7 to 18 carbon atoms includes, for example, an n-heptyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, and 1 -A linear or branched alkyl having 7 to 18 carbon atoms such as an ethylpentyl group, a 2-ethylpentyl group, a 1,1-dimethylpentyl group, a 2,2-dimethylpentyl group, and a 3,3-dimethylpentyl group.
  • the group can be mentioned.
  • As the alkyl group having 7 to 18 carbon atoms an alkyl group having 11 to 18 carbon atoms is preferable, and an alkyl group having 15 to 18 carbon atoms is more preferable.
  • X A is a nitro group
  • Y A represents a halogen atom
  • R A1, R A2 and R A3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms)
  • RA4 represents an alkyl group having 1 to 4 carbon atoms.
  • the compound of the formula (A) is a blue dye compound.
  • Y A is a bromine atom.
  • RA1 , RA2, and RA3 are each independently an alkyl group having 4 to 14 carbon atoms, or RA1 and RA2 are independently alkyl groups having 4 to 14 carbon atoms, and RA3 is an alkyl group having 1 to 4 carbon atoms, or RA3 is an alkyl group having 4 to 14 carbon atoms. It is preferable that RA1 and RA2 are independently alkyl groups having 1 to 4 carbon atoms.
  • Y A is a bromine atom
  • RA1 , RA2, and RA3 are each independently an alkyl group having 4 to 14 carbon atoms, or RA1 and RA2 are independently alkyl groups having 4 to 14 carbon atoms, and RA3 is an alkyl group having 1 to 4 carbon atoms, or RA3 is an alkyl group having 4 to 14 carbon atoms. It is preferable that RA1 and RA2 are independently alkyl groups having 1 to 4 carbon atoms.
  • R B1 , R B2 and R B3 each independently represent an alkyl group having 1 to 14 carbon atoms. However , at least one of R B1 , R B 2 and R B 3 is an alkyl group having 4 to 14 carbon atoms.
  • the compound of the formula (B) is a blue or purple dye compound.
  • R B1 , R B2 and R B3 are independently alkyl groups having 4 to 14 carbon atoms, or R B1 and R B2 are independently alkyl groups having 4 to 14 carbon atoms, respectively.
  • B3 is an alkyl group having 1 to 4 carbon atoms, or R B3 is an alkyl group having 4 to 14 carbon atoms, and R B1 and R B2 are independently alkyl groups having 1 to 4 carbon atoms. Is preferable.
  • X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
  • R C1, R C2 and R C3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms).
  • the compound of the formula (C) is a red or purple dye compound.
  • X C and Y C represent any combination of hydrogen atom and chlorine atom, bromine atom and nitro group, bromine atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom. Is preferable.
  • X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
  • RC1 , RC2 and RC3 are each independently an alkyl group having 4 to 14 carbon atoms, or RC1 and RC2 are independently alkyl groups having 4 to 14 carbon atoms, RC3 is an alkyl group having 1 to 4 carbon atoms, or RC3 is an alkyl group having 4 to 14 carbon atoms. It is preferable that RC1 and RC2 are independently alkyl groups having 1 to 4 carbon atoms.
  • X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group in the formula (D), respectively.
  • R D1 represents an alkyl group having 1 to 14 carbon atoms.
  • R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms.
  • the compound of the formula (D) is an orange or red dye compound.
  • X D represents a hydrogen atom, a chlorine atom or a bromine atom.
  • Y D preferably represents a hydrogen atom, a chlorine atom, a bromine atom, or a cyano group.
  • X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
  • R D1 represents an alkyl group having 4 to 14 carbon atoms.
  • R D2 preferably represents an alkyl group having 4 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN.
  • the compound of the formula (E) is an orange dye compound.
  • X E and Y E preferably represent a chlorine atom.
  • R E is preferably an alkyl group having 4 to 12 carbon atoms.
  • X E and Y E represent chlorine atoms
  • R E is preferably an alkyl group having 4 to 12 carbon atoms.
  • RF1 and RF2 each independently represent an alkyl group having 4 to 14 carbon atoms.
  • the compound of the formula (F) is a purple dye compound.
  • R F1 and R F2 each independently represent an alkyl group having 4 to 12 carbon atoms.
  • the compound of the formula (G) is a yellow dye compound.
  • the RG is preferably an alkyl group having 11 to 18 carbon atoms.
  • the compound represented by the formula (A) is a 4-nitroaniline derivative represented by the formula (a-D) (in the formula (a-D), X A represents a nitro group and Y A represents a halogen atom).
  • the compound represented by the formula (a-C) in the formula (a-C), RA1 , RA2 and RA3 each independently represent an alkyl group having 1 to 14 carbon atoms (however, however). at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms), R A4 can be obtained by coupling a representative) an alkyl group of 1 to 4 carbon atoms.
  • a compound of formula (a-D) is added to a mineral acid or organic carboxylic acid in the presence of optionally added water as a nitrosating agent or nitrosyl. Diazotization with sulfuric acid to give the diazo compound.
  • the organic carboxylic acid used include acetic acid and propionic acid.
  • the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
  • the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
  • the reaction temperature for diazotization is preferably ⁇ 10 to 40 ° C., more preferably 0 to 40 ° C.
  • the compound represented by the formula (a-D) is generally widely used as a raw material for an azo-based disperse dye.
  • the pH of the compound solution or suspension represented by the formula (a-C) is preferably weakly acidic, and it may be advantageous in the coupling reaction to add a buffer such as triethylamine or sodium acetate.
  • the compound of the general formula (A) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
  • the compound represented by the formula (a-C2) is nitrated with concentrated nitric acid and concentrated sulfuric acid to obtain the compound represented by the formula (a-C3).
  • the compound represented by the formula (a-C3) is reduced with tin in an acidic hydrochloric acid alcohol (for example, methanol) to obtain the compound represented by the formula (a-C4).
  • an acidic hydrochloric acid alcohol for example, methanol
  • an alkyl radical of formula (a-C4) R A1 in the compound represented by -X and R A2 -X (R A1 and R A2 are each independently a carbon number 1 to 14, X is The alkyl halide represented by (representing a halogen atom) is reacted to obtain the formula (a-C).
  • R A1 -X R A1 represents an alkyl group of 1 to 14 carbon atoms
  • X represents a halogen atom
  • RA2 RA2 represents an alkyl group having 1 to 14 carbon atoms
  • ( RA2 ) 2 SO 4 can be used to introduce RA2.
  • the compound represented by the formula (B) is a diazo compound of 3-amino-5-nitro-2,1-benzoisothiazole represented by the formula (bD) and a diazo compound represented by the formula (bc).
  • R B1 , R B 2 and R B 3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R B1 , R B 2 and R B 3 is carbon. It is obtained by coupling the alkyl groups of numbers 4 to 14).).
  • a compound of formula (b-D) is added to a mineral acid or organic carboxylic acid in the presence of optionally added water as a nitrosating agent or nitrosyl.
  • the organic carboxylic acid used include acetic acid and propionic acid.
  • the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
  • the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
  • the reaction temperature for diazotization is preferably ⁇ 10 to 15 ° C., more preferably ⁇ 5 to 10 ° C.
  • the compound represented by the formula (bD) is generally widely used as a raw material for an azo-based disperse dye.
  • the pH of the compound solution or suspension represented by the formula (bc) is preferably weakly acidic, and it may be advantageous in the coupling reaction to add a buffer such as triethylamine or sodium acetate.
  • the compound of the general formula (B) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
  • R B3 -COX in m- nitroaniline R B3 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom
  • R B3 represents an alkyl group of 1 to 14 carbon atoms
  • X represents a halogen atom
  • the compound represented by the formula (b-C1) is reduced with tin in an acidic hydrochloric acid alcohol (for example, methanol) to obtain a compound represented by the formula (b-C2).
  • an acidic hydrochloric acid alcohol for example, methanol
  • the compound represented by the formula (b-C2) contains RB1- X and RB2- X ( RB1 and RB2 each independently represent an alkyl group having 1 to 14 carbon atoms, and X represents an alkyl group having 1 to 14 carbon atoms.
  • the alkyl halide represented by (representing a halogen atom) is reacted to obtain the formula (bc).
  • R B1 -X compounds of the formula (b-C2) R B1 -X (R B1 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) reacting a halogenated hydrocarbon represented by
  • R B2 RB2 represents an alkyl group having 1 to 14 carbon atoms
  • ( RB2 ) 2 SO 4 can be used to introduce R B2.
  • X C and Y C is a hydrogen atom and a halogen atom
  • a halogen Represented by a diazo compound of (representing any combination of an atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom)
  • a diazo compound of Representing any combination of an atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom
  • R C1 , R C2 and R C3 are an alkyl group having 1 to 14 carbon atoms each independently (provided that R C1, at least one of R C2 and R C3 are carbon atoms It is obtained by coupling 4 or more alkyl groups))).
  • the compound represented by the formula (cd) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of optionally added water. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
  • the organic carboxylic acid used include acetic acid and propionic acid.
  • the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
  • the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
  • the diazotization temperature is preferably ⁇ 10 to 40 ° C., more preferably 0 to 35 ° C.
  • the compound represented by the formula (cd) is generally widely used as a raw material for an azo-based disperse dye.
  • the pH of the compound solution or suspension represented by the formula (cc) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
  • the compound of the general formula (C) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
  • R C3 -COX in m- nitroaniline R C3 represents an alkyl group of 1 to 14 carbon atoms, X is halogen atom
  • R C3 represents an alkyl group of 1 to 14 carbon atoms, X is halogen atom
  • a carboxylic acid halide represented by the formula (c -The compound represented by C1) is obtained.
  • the compound represented by the formula (c-C1) is reduced with tin in an acidic hydrochloric acid alcohol (for example, methanol) to obtain a compound represented by the formula (c-C2).
  • an acidic hydrochloric acid alcohol for example, methanol
  • an alkyl radical of formula (c-C2) a compound represented by R C1 -X and R C2 -X (R C1 and R C2 having 1 to carbon atoms each independently 14, X is The alkyl halide represented by) (which is a halogen atom) is reacted to obtain the formula (cc).
  • R C1 -X to a compound of formula (c-C2) (R C1 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) reacting a halogenated hydrocarbon represented by
  • RC2 ( RC2 represents an alkyl group having 1 to 14 carbon atoms)
  • ( RC2 ) 2 SO 4 can be used to introduce RC2.
  • the compound represented by the formula (D) is a 4-nitroaniline derivative represented by the formula (d-D) (in the formula (d-D), X D and Y D are independently hydrogen atoms and halogen atoms, respectively.
  • X D and Y D are independently hydrogen atoms and halogen atoms, respectively.
  • RD1 represents an alkyl group having 1 to 14 carbon atoms
  • RD2 represents an alkyl group.
  • at least one of RD1 and RD2 is an alkyl group having 4 to 14 carbon atoms. Obtained by ringing.
  • the compound represented by the formula (d-D) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of water optionally added. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
  • the organic carboxylic acid used include acetic acid and propionic acid.
  • the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
  • the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
  • the diazotization temperature is preferably ⁇ 10 to 40 ° C., more preferably 0 to 30 ° C.
  • the compound represented by the formula (DD) is generally widely used as a raw material for azo-based disperse dyes.
  • the pH of the compound solution or suspension represented by the formula (dc) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
  • the compound of the general formula (D) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less of water, and used for staining using supercritical carbon dioxide as a medium. use.
  • R D1 -X and R D2 -X (R D1 to aniline, an alkyl group of 1 to 14 carbon atoms, R D2 is substituted with an alkyl group or CN of 1 to 14 carbon atoms represents an alkyl group having 1 to 14 carbon atoms. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms .
  • X reaction an alkyl halide represented by a halogen atom.
  • aniline R D1 -X (R D1 is an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) after reacting the halogenated hydrocarbon represented by, according to a known reaction, R D2 ( RD2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced.
  • R D2 ( RD2 represents an alkyl group having 1 to 14 carbon atoms)
  • ( RD2 ) 2 SO 4 can be used to introduce R D2.
  • the compound represented by the formula (E) is a diazo compound of a 4-nitroaniline derivative represented by the formula (ED) (where X E and Y E represent halogen atoms in the formula (ED)).
  • ED 4-nitroaniline derivative
  • EC the compound represented by the formula (EC) (in the formula (EC), RE represents an alkyl group having 4 to 18 carbon atoms) is obtained by coupling.
  • the compound represented by the formula (ed) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of water optionally added. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
  • the organic carboxylic acid used include acetic acid and propionic acid.
  • the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
  • the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
  • the diazotization temperature is preferably ⁇ 10 to 40 ° C., more preferably 0 to 30 ° C.
  • the compound represented by the formula (ed) is generally widely used as a raw material for azo-based disperse dyes.
  • the pH of the compound solution or suspension represented by the formula (EC) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
  • the compound of the general formula (E) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for staining using supercritical carbon dioxide as a medium. use.
  • the compound represented by the formula (F) is a diazo compound of 3-amino-5-nitro-2,1-benzoisothiazole represented by the formula (fD) and a diazo compound represented by the formula (fc). It is obtained by coupling the compounds to be compounded (in the formula (FC), RF1 and RF2 each independently represent an alkyl group having 4 to 14 carbon atoms).
  • the compound represented by the formula (fD) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of water optionally added. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
  • the organic carboxylic acid used include acetic acid and propionic acid.
  • the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
  • the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
  • the diazotization temperature is preferably ⁇ 10 to 15 ° C., more preferably ⁇ 5 to 10 ° C.
  • the compound represented by the formula (fD) is generally widely used as a raw material for azo-based disperse dyes.
  • the diazo compound of the formula (fD) is added to a solution or suspension of an alcohol (for example, methanol) of the compound represented by the formula (fc). Is added in a temperature range of, for example, ⁇ 5 to 10 ° C. to obtain a compound represented by the above formula (F).
  • an alcohol for example, methanol
  • the pH of the compound solution or suspension represented by the formula (fc) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
  • the compound of the general formula (F) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
  • aniline R F1 -X (R F1 represents an alkyl group having 4 to 14 carbon atoms, X represents a halogen atom) after reacting the halogenated hydrocarbon represented by, according to a known reaction, R F2 ( RF2 represents an alkyl group having 4 to 14 carbon atoms) may be introduced.
  • R F2 RF2 represents an alkyl group having 4 to 14 carbon atoms
  • ( RF2 ) 2 SO 4 can be used to introduce R F2.
  • the compound represented by the formula (G) is 5-amino-anthra [9,1-cd] isothiazole-6-one represented by the formula (g) in an inert solvent such as toluene, xylene and chlorobenzene.
  • R G -COX R G represents an alkyl group having 7 to 18 carbon atoms, X is halogen atom
  • the reaction temperature is preferably 80 ° C to 140 ° C, more preferably 110 to 140 ° C.
  • the compound represented by the formula (g) is generally widely used as a raw material for a polycyclic disperse dye.
  • the compound of the general formula (G) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
  • the compounds of the general formulas (A) to (G) contained in the dye for dyeing the polyolefin fiber of the present invention have blue, purple, red, orange, or yellow.
  • the dye may contain the compounds of the general formulas (A) to (G) alone or in combination of two or more. When the dye contains two or more compounds of the general formulas (A) to (G), a dye for dyeing the polyolefin fiber in various hues or black can be obtained.
  • the dye for dyeing the polyolefin fiber in black is selected from the group consisting of the compound of the general formula (A), the compound of the general formula (B), the compound of the general formula (C), and the compound of the general formula (F).
  • At least one of a purple or blue dye compound comprising one or more selected from the group consisting of a compound of the general formula (A), a compound of the general formula (B) and a compound of the general formula (F), and the general formula ( It is more preferable to include a red dye compound of the compound of C) and an orange dye compound containing one or more selected from the group consisting of the compound of the general formula (D) and the compound of the general formula (E). It is more preferable to include a blue dye compound of the compound of the general formula (A), a red dye compound of the compound of the general formula (C), and an orange dye compound of the compound of the general formula (D).
  • the composition of the dye compound in the dye for dyeing the polyolefin fiber to black is such that the mixing ratio of the purple or blue dye compound is 30 to 70% by mass, and the mixing ratio of the red dye compound is 5 to 25% by mass.
  • the mixing ratio of the yellow or orange dye compound is preferably in the range of 15 to 55% by mass, the mixing ratio of the purple or blue dye compound is 40 to 60% by mass, and the mixing ratio of the red dye compound is. More preferably, the mixing ratio of the yellow or orange dye compound is in the range of 5 to 25% by mass and 25 to 45% by mass.
  • the dye of the present invention may further contain an additive.
  • the additive include a color-auxiliary agent, a dispersant, a filler, a stabilizer, a plasticizer, a crystal nucleating agent, a modifier, a foaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antibacterial agent, and an antibacterial agent.
  • examples thereof include mold agents, antistatic agents, flame retardants, inorganic fillers, and elastomers for improving impact resistance.
  • the polyolefin fiber of the object to be dyed which is dyed with the dye of the present invention, is, for example, ⁇ -such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene and the like. Fibers formed from polymers selected from homopolymers of olefins, copolymers of these ⁇ -olefins, or copolymers of these ⁇ -olefins with other unsaturated monomers copolymerizable. .. Further, examples of the type of copolymer include block copolymers, random copolymers, graft copolymers and the like.
  • polystyrene-based resins such as propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, and propylene-ethylene- (1-butene) copolymer, and low density.
  • Polyethylene resins such as polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, poly 1-butene, poly 4-methyl-1 -Examples include polymers.
  • the polymer may be used alone or in combination of two or more to form polyolefin fibers.
  • the polyolefin fiber of the object to be dyed to be dyed with the dye of the present invention is preferably formed of polypropylene resin and / or polyethylene resin, and more preferably formed of polypropylene-based resin.
  • the shape of the polyolefin fiber of the object to be dyed, which is dyed with the dye of the present invention, is, for example, lumpy (molded product, etc.), film-like, fibrous (cloth-like (woven fabric, knitted fabric, non-woven fabric, etc.), filamentous yarn (filament yarn, etc.). It may be any of spun yarn, slit yarn, split yarn, etc.)), and is preferably fibrous.
  • the polyolefin fiber of the object to be dyed which is dyed with the dye of the present invention, may be a fiber formed by blending a polypropylene resin and / or a polyethylene resin with another polymer component, bonding, or the like.
  • the polyolefin fiber may be a polypropylene fiber blended with other fibers such as polyester, or a blended fiber.
  • the present invention is a method for dyeing a polyolefin fiber using supercritical carbon dioxide, which comprises a step of dyeing the polyolefin fiber in the presence of supercritical carbon dioxide using the dye of the present invention.
  • supercritical carbon dioxide is used as the dyeing medium.
  • the dyeing method that uses supercritical carbon dioxide as the dyeing medium does not use water at the time of dyeing and does not require a washing step, so waste water is generated. It is attracting attention as an environment-friendly dyeing method because it does not generate, does not require a dyeing aid, has a short dyeing time, and can reuse carbon dioxide as a dyeing medium.
  • the dyeing step in the method 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 need to be equal to or higher than the critical point (31 ° C., 7.4 MPa) of carbon dioxide as a dyeing medium.
  • the dyeing temperature is mainly determined by the type of resin of the fiber to be dyed.
  • the dyeing temperature is usually in the range of 60 to 180 ° C, preferably in the range of 80 to 160 ° C.
  • the dyeing pressure is mainly determined by the type of resin of the fiber to be dyed.
  • the dyeing pressure is usually in the range of about 7.4 to 40.0 MPa, preferably 20 to 30 MPa.
  • the dyeing time in the dyeing step is determined by the type of resin of the fiber to be dyed, the dyeing temperature and the dyeing time.
  • the staining time is usually about 10 to 120 minutes, preferably 30 to 90 minutes.
  • the concentration of the dye with respect to the fiber depends on the type of fiber to be dyed and the processing state.
  • the concentration of the dye with respect 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. Is.
  • the bath ratio (mass ratio of the object to be dyed: carbon dioxide) depends on the type of the object 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 is relatively low in the dyeing method of the present invention, for example, 1: 2 to 1: 5.
  • the present invention provides polyolefin fibers dyed by the dyeing method of the present invention.
  • Applications of the polyolefin fiber include, for example, clothing such as clothing, underwear, hats, socks, gloves, sports clothing, vehicle interior materials such as seats, and interiors such as carpets, curtains, mats, sofa covers, and cushion covers. Supplies and the like can be mentioned.
  • Step 2 The N- (4-methoxyphenyl) octaneamide (12.5 g) obtained in the above step 1 was gradually added to concentrated sulfuric acid (30 g) cooled to 5 ° C. in the range of 5 to 10 ° C. Concentrated nitric acid (4.57 g) was added dropwise to this mixture over 1 hour in the range of 5 to 10 ° C., and then the mixture was stirred at the same temperature for 1 hour. The reaction mixture was purged into ice water (150 g) and ethyl acetate (100 g) was added to extract the organic phase.
  • Step 3 The mixture of N- (3-nitro-4-methoxyphenyl) octaneamide (16.9 g), tin (8.9 g) and methanol (7.5 g) obtained in the above step 2 was cooled to 5 ° C. Concentrated hydrochloric acid (31.4 g) was added dropwise to this mixture over 1 hour, the temperature was raised to 75 to 80 ° C., and the mixture was stirred for 40 minutes. After cooling the reaction mixture to 10 ° C., a 48% aqueous sodium hydroxide solution (55.2 ml) was gradually added in the range of 10 to 20 ° C. This mixture was filtered off, washed with water and dried to obtain N- (3-amino-4-methoxyphenyl) octaneamide (9.19 g, yield 69.5%) represented by the following formula (C1c).
  • Step 4 N- (3-amino-4-methoxyphenyl) octaneamide (13.2 g), triethylamine (15 g), DMF (15 g) and 1-bromooctane (purchased as commercial products) obtained in the above step 3 (38.
  • the mixture of 6 g) was heated to 120 ° C. and stirred at the same temperature for 3 hours to obtain N- [3- (N, N-dioctylamino) -4-methoxyphenyl] octane represented by the following formula (C1). Obtained an amide.
  • Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C1).
  • step 5 Preparation of diazo component solution (step 5) 2-Bromo-4,6-dinitroaniline (13.1 g) represented by the following formula (D1) is added to a mixture of concentrated sulfuric acid (16 g) and 43% nitrosylsulfuric acid (12.8 g) within the range of 25 to 30 ° C. And added slowly. The mixture was stirred at 30-40 ° C. for 2 hours to obtain a diazo component solution.
  • step 5 2-Bromo-4,6-dinitroaniline (13.1 g) represented by the following formula (D1) is added to a mixture of concentrated sulfuric acid (16 g) and 43% nitrosylsulfuric acid (12.8 g) within the range of 25 to 30 ° C. And added slowly. The mixture was stirred at 30-40 ° C. for 2 hours to obtain a diazo component solution.
  • step 1 Synthesis of coupler compound C5 and preparation of coupler component solution (step 1)
  • step 4 of Synthesis Example 1 N- (3-amino-4-methoxyphenyl) acetamide (purchased as a commercial product) (9.0 g) was used instead of N- (3-amino-4-methoxyphenyl) octaneamide.
  • N- [3- (N, N-dioctylamino) -4-methoxyphenyl] acetamide represented by the following formula (C5) was obtained in the same manner as in Step 4 of Synthesis Example 1 except that it was used.
  • Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C5).
  • Step 2 The following formula is used in the same manner as in Step 3 of Synthesis Example 1 except that N- (3-nitrophenyl) octaneamide (13.2 g) is used instead of N- (3-nitro-4-methoxyphenyl) octaneamide.
  • N- (3-aminophenyl) octaneamide represented by (C9b) (9.48 g, yield 80.9%) was obtained.
  • Step 3 The following formula is used in the same manner as in step 4 of Synthesis Example 1 except that N- (3-aminophenyl) octaneamide (11.7 g) is used instead of N- (3-amino-4-methoxyphenyl) octaneamide.
  • N- [3- (N, N-dioctylamino) phenyl] octaneamide represented by (C9) was obtained.
  • Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C9).
  • step 1 To a mixture of concentrated sulfuric acid (16 g) and 43% nitrosylsulfuric acid (15.6 g), 2-chloro-4-nitroaniline (8.65 g) represented by the following formula (D3) is added in the range of 30 to 35 ° C. A diazo component solution was obtained by stirring at the same temperature for 2 hours.
  • step 2 Synthesis of red dye compound (C-1) by coupling reaction (step 2)
  • the coupler component solution composed of the compound of the formula (C9) was prepared in the same manner as in steps 1 to 3 of Synthesis Example 9.
  • the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (28 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
  • the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
  • a red dye compound (24.3 g, yield 75.7%) represented by the following formula (C-1) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 642 (M +)).
  • the red dye represented by the following formula (C-2) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C10) is used instead of the compound of the formula (C9) as the coupler component solution.
  • a compound (10.4 g, yield 34.7%) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 600 (M +)).
  • the red dye represented by the following formula (C-3) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C11) is used instead of the compound of the formula (C9) as the coupler component solution.
  • a compound (12.9 g, yield 45.1%) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 572 (M +)).
  • the red dye represented by the following formula (C-4) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C12) is used instead of the compound of the formula (C9) as the coupler component solution. A compound (23.4 g, yield 83.9%) was obtained. The structure of the red dye compound was confirmed by LCMS analysis (m / z 558 (M +)).
  • the red dye represented by the following formula (C-5) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C13) is used instead of the compound of the formula (C9) as the coupler component solution.
  • a compound (25.3 g, yield 75.5%) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 670 (M +)).
  • red dye compound (C-6) by coupling reaction (step 2)
  • the red dye represented by the following formula (C-6) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C17) is used instead of the compound of the formula (C9) as the coupler component solution.
  • a compound (19.6 g, yield 87.9%) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 446 (M +)).
  • the red dye represented by the following formula (C-7) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C16) is used instead of the compound of the formula (C9) as the coupler component solution. A compound (16.6 g, yield 70.0%) was obtained. The structure of the red dye compound was confirmed by LCMS analysis (m / z 474 (M +)).
  • step 2 Preparation of diazo component solution (step 2) In a mixture of concentrated sulfuric acid (17 g) and 43% nitrosylsulfuric acid (14.7 g), 2,6-dichloro-4-nitroaniline (10.4 g) represented by the following formula (D4) was added in the range of 25 to 30 ° C. The diazo component solution was obtained by adding in 1 and stirring at the same temperature for 2 hours.
  • N-octanoyl chloride (19.5 g) is added dropwise to a mixture of 5-amino-anthra [9,1-cd] isothiazole-6-one (25.2 g), toluene (120 g) and pyridine (9.49 g). After that, the temperature was raised to 110 ° C., and the mixture was stirred for 1 hour. After cooling this mixture to room temperature, a precipitate was precipitated by adding methanol (150 g). This mixture was separated by filtration, washed with methanol, and dried to obtain a yellow dye compound (31.8 g, yield 83.9%) represented by the following formula (G-2). The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 379 (M +)).
  • the preparation of the coupler component solution composed of the compound of the formula (C18) is the same as in step 1 of Synthesis Example 24, and the preparation of the diazo component solution derived from the compound of the formula (D2) is the same as in step 4 of Synthesis Example 9. went.
  • the diazo component solution was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (35 g) in the range of 0 to 10 ° C. to carry out a coupling reaction. After stirring for 20 minutes in the range of 0-10 ° C., the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
  • a purple dye compound (13.0 g, yield 49.6%) represented by the following formula (F-1) was obtained.
  • the structure of the purple dye compound was confirmed by LCMS analysis (m / z 524 (M +)).
  • step 1 To a mixture of concentrated sulfuric acid (17 g) and 43% nitrosylsulfuric acid (14.7 g), 4-nitroaniline (6.91 g) represented by the following formula (D5) is added in the range of 30 to 35 ° C. at the same temperature. A diazo component solution was obtained by stirring with.
  • step 2 Synthesis of orange dye compound (D-4) by coupling reaction (step 2)
  • the coupler component solution composed of the compound of the formula (C18) was prepared in the same manner as in Step 1 of Synthesis Example 24.
  • the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 1 hour while appropriately adding triethylamine (20 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
  • the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
  • An orange dye compound (12.5 g, yield 53.5%) represented by the following formula (D-4) was obtained.
  • the structure of the orange dye compound was confirmed by LCMS analysis (m / z 467 (M +)).
  • step 1 Preparation of diazo component solution (step 1) In a mixture of concentrated sulfuric acid (17 g) and 43% nitrosylsulfuric acid (14.7 g), 2,6-dibromo-4-nitroaniline (14.8 g) represented by the following formula (D6) was added in the range of 25 to 30 ° C. The diazo component solution was obtained by adding in 1 and stirring at the same temperature for 2 hours.
  • step 2 Synthesis of orange dye compound (D-5) by coupling reaction (step 2)
  • the coupler component solution composed of the compound of the formula (C18) was prepared in the same manner as in Step 1 of Synthesis Example 24.
  • the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 1 hour while appropriately adding triethylamine (25 g) in the range of 0 to 10 ° C. to carry out a coupling reaction. After stirring for 20 minutes in the range of 0-10 ° C., the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
  • the orange dye represented by the following formula (D-6) is the same as in steps 1 and 2 of Synthesis Example 31 except that the compound of the formula (C20) is used instead of the compound of the formula (C18) as the coupler component solution. A compound (22.8 g, yield 89.2%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 511 (M +)).
  • diazo component solution 20 to 25 2-cyano-4-nitroaniline (8.15 g) represented by the following formula (D7) is added to a mixture of concentrated sulfuric acid (7.5 g), acetic acid (15 g) and 43% nitrosylsulfuric acid (14.9 g). The mixture was added in the range of ° C. and stirred at the same temperature for 2 hours to obtain a diazo component solution.
  • red dye compound (D-7) by coupling reaction (step 2)
  • the coupler component solution composed of the compound of the formula (C18) was prepared in the same manner as in Synthesis Example 24.
  • the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 1 hour while appropriately adding triethylamine (30 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
  • the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
  • a red dye compound (16.9 g, yield 68.9%) represented by the following formula (D-7) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 492 (M +)).
  • the preparation of the coupler component solution composed of the compound of the formula (C16) is the same as in step 1 of Synthesis Example 16, and the preparation of the diazo component solution derived from the compound of the formula (D1) is the same as in step 5 of Synthesis Example 1. went.
  • the diazo component solution was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (32 g) in the range of 0 to 10 ° C. to carry out a coupling reaction. After stirring for 20 minutes in the range of 0-10 ° C., the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
  • a purple dye compound (6.14 g, yield 21.8%) represented by the following formula (C-8) was obtained.
  • the structure of the purple dye compound was confirmed by the following formula (C-8) by the LCMS analytical molecular weight (m / z 563 (M +)).
  • the purple dye compound (12.1 g) represented by the following formula (C-9) is the same as in Synthesis Example 36 except that the compound of the formula (C9) is used instead of the compound of the formula (C16) as the coupler component solution.
  • Got The structure of the purple dye compound was confirmed by LCMS analysis (m / z 731 (M +)).
  • the product is filtered off from this reaction mixture, washed with water, dried at 60 ° C. until the water content is 1.0% by mass or less, and the purple dye compound (20.4 g) represented by the following formula (C-10). , Yield 64.2%).
  • the structure of the purple dye compound was confirmed by LCMS analysis (m / z 678 (M +)).
  • Step 1 2-Bromo-6-cyano-4-nitroaniline (11.1 g) represented by the following formula (D8) is added to a mixture of concentrated sulfuric acid (10.7 g) and acetic acid (28.8 g) within the range of 20 to 25 ° C. Added in. 43% Nitrosylsulfuric acid (15.6 g) was added to this mixture in the range of 20 to 25 ° C., and the mixture was stirred at the same temperature for 2 hours to obtain a diazo component solution.
  • step 2 2-Bromo-6-cyano-4-nitroaniline (11.1 g) represented by the following formula (D8) is added to a mixture of concentrated sulfuric acid (10.7 g) and acetic acid (28.8 g) within the range of 20 to 25 ° C. Added in. 43% Nitrosylsulfuric acid (15.6 g) was added to this mixture in the range of 20 to 25 ° C., and the mixture was stirred at the same temperature for 2 hours to obtain a diazo component solution.
  • step 2 Synthesis of purple dye compound (C-11) by coupling reaction (step 2)
  • the coupler component solution composed of the compound of the formula (C9) was prepared in the same manner as in steps 1 to 3 of Synthesis Example 9.
  • the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (20 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
  • the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
  • a purple dye compound (16.0 g, yield 45.0%) represented by the following formula (C-11) was obtained.
  • the structure of the purple dye compound was confirmed by LCMS analysis (m / z 711 (M +)).
  • the purple dye compound represented by the following formula (C-13) is obtained in the same manner as in Step 2 of Synthesis Example 39 except that the compound of the formula (C12) is used instead of the compound of the formula (C9) as the coupler component solution. 23.5 g, yield 75.0%) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 627 (M +)).
  • the purple dye compound represented by the following formula (C-14) is obtained in the same manner as in Step 2 of Synthesis Example 39 except that the compound of the formula (C16) is used instead of the compound of the formula (C9) as the coupler component solution. 10.8 g, yield 39.8%) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 543 (M +)).
  • the following formula (C-) is the same as in Synthesis Example 38 except that the purple dye compound (31.4 g) of the formula (C-13) is used instead of the purple dye compound of the formula (C-9) in Synthesis Example 38.
  • a purple dye compound (26.9 g, yield 93.7%) represented by 15) was obtained.
  • the structure of the purple dye compound was confirmed by LCMS analysis (m / z 574 (M +)).
  • the yellow dye compound represented by the following formula (G-3) is the same as in Synthesis Example 28 except that 2-ethylhexanoyl chloride (19.5 g) is used instead of n-octanoyl chloride. (33.1 g, yield 87.3%) was obtained. The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 379 (M +)).
  • the blue dye compound represented by the following formula (B-9) is used in the same manner as in Step 5 of Synthesis Example 9 except that the compound of the formula (C23) is used instead of the compound of the formula (C9) as the coupler component solution. 9.12 g, yield 33.0%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 553 (M +)).
  • the orange dye compound represented by the following formula (D-8) is the same as in Synthesis Example 24 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (15.2 g, yield 82.8%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 367 (M +)).
  • the orange dye compound represented by the following formula (D-9) is the same as in Synthesis Example 31 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (18.2 g, yield 80.0%) was obtained.
  • the structure of the orange dye compound was confirmed by LCMS analysis (m / z 455 (M +)).
  • the orange dye compound represented by the following formula (D-10) is the same as in Synthesis Example 30 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (9.35 g, yield 62.5%) was obtained.
  • the structure of the orange dye compound was confirmed by LCMS analysis (m / z 299 (M +)).
  • Step 2 The mixture of N-cyanoethylaniline (28.7 g), triethylamine (15 g), DMF (15 g) and 1-bromooctane (14.5 g) obtained in the above step was heated to 120 ° C. and 3 at the same temperature. By stirring for a time, N-cyanoethyl-N-octylaniline represented by the following formula (C25) was obtained. Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C25).
  • red dye compound (C-17) by coupling reaction (step 2)
  • the red dye compound (11.8 g, represented by the following formula (C-17)) is represented by the following formula (C-17) in the same manner as in Synthesis Example 17 except that the compound of the formula (C26) is used instead of the compound of the formula (C9) as the coupler compound. Yield 60.5%) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 390 (M +)).
  • the purple dye compound represented by the following formula (F-2) is the same as in Synthesis Example 29 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (10.6 g, yield 59.6%) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 356 (M +)).
  • the blue dye compound represented by the following formula (B-11) is the same as in steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C26) is used instead of the compound of the formula (C9) as the coupler compound. (11.9 g, yield 57.6%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 413 (M +)).
  • Step 2 The mixture of N- (3-cyanoethylamino-4-methoxyphenyl) octaneamide (15.9 g), DMF (15 g) and diethyl sulfate (11.6 g) obtained in the above step was heated to 90 ° C. and the same. The mixture was stirred under warm temperature for 2 hours to obtain N- (3-N-ethyl-N-cyanoethylamino-4-methoxyphenyl) octaneamide represented by the following formula (C27). Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C27).
  • Step 2 The blue dye represented by the following formula (A-11) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C29) is used instead of the compound of the formula (C1) as the coupler component solution. A compound (6.58 g, yield 20.2%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 653 (M +)).
  • red dye compound (C-18) by coupling reaction (step 2)
  • the red dye compound (20.1 g) represented by the following formula (C-18) is obtained in the same manner as in Synthesis Example 17 except that the compound of the formula (C34) is used instead of the compound of the formula (C9) as the coupler component solution. , Yield 80.1%) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 502 (M +)).
  • the orange dye compound (16.4 g) represented by the following formula (D-13) is used in the same manner as in Synthesis Example 30 except that the compound of the formula (C35) is used instead of the compound of the formula (C18) as the coupler component solution. , Yield 79.8%) was obtained.
  • the structure of the orange dye compound was confirmed by LCMS analysis (m / z 411 (M +)).
  • the red dye represented by the following formula (C-20) is the same as in steps 1 and 2 of Synthesis Example 30 except that the compound of the formula (C12) is used instead of the compound of the formula (C18) as the coupler component solution.
  • a compound (23.0 g, yield 87.7%) was obtained.
  • the structure of the red dye compound was confirmed by LCMS analysis (m / z 524 (M +)).
  • step 1 of Synthesis Example 1 valeryl chloride (25.3 g) is used instead of n-octanoyl chloride, and 1-bromohexane (33.0 g) is used instead of 1-bromooctane in step 4.
  • N- [3- (N, N-dihexylamino) -4-methoxyphenyl] pentanamide represented by the following formula (C38) was obtained in the same manner as in Steps 1 to 4 of Synthesis Example 1 except for the above. Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C38).
  • Tables 3 to 9 show the structural formulas of the dye compounds described in the synthetic examples and the conventional dye compounds.
  • the supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG.
  • the dyeing equipment includes a liquid CO 2 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), and magnetic. It is composed of a drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).
  • the polypropylene cloth was cut and weighed to about 50 to 70 g, wound in the order of cotton cloth, polypropylene cloth, and cotton cloth on a stainless cylinder (21) having punch holes, and then loosely fixed with cotton thread.
  • the inner cotton cloth is an undercloth and the outer cotton cloth is a cover cloth.
  • a stainless steel cylinder around which the above-mentioned cloth sample (cotton cloth, polypropylene cloth, cotton cloth) is wound is fixed to a pressure-resistant stainless steel tank (22), and obtained in Synthesis Example 5 corresponding to 0.3% by mass with respect to the mass of the polypropylene cloth.
  • the blue dye compound A-5 was wrapped in a paper wipe and placed in the fluid passage above the stainless steel cylinder.
  • the volume of the pressure-resistant stainless steel tank was 2230 cm 3 . All valves in the dyeing apparatus were closed and heated to 120 ° C. by a preheater.
  • the stop valves (14) and (16) were opened, and 1.13 kg of liquid carbon dioxide was flowed into the pressure-resistant stainless steel tank using a high-pressure pump via a cooling jacket. After that, the stop valves (14) and (16) were closed and circulated by the impeller and the magnetic drive unit at the lower part of the pressure-resistant stainless steel tank.
  • the rotation speed of the magnetic drive unit is 750 rpm, and the circulation direction is from the inside to the outside of the cylinder.
  • the polypropylene cloth was dyed by maintaining these temperature and pressure conditions for 60 minutes. After dyeing, the stop valve (18) was opened and the needle valve was gradually opened to release carbon dioxide in the pressure-resistant stainless steel tank, and the pressure in the pressure-resistant stainless steel tank was lowered from 25 MPa to atmospheric pressure. Circulation continued until the critical pressure of carbon dioxide (about 8 MPa) was reached. After that, the polypropylene dyed cloth in the pressure-resistant stainless steel tank was taken out.
  • Dyeing Example P1 and Dyeing Example P1 except that the blue dye compound A-5 described in Dyeing Example 1 was changed to the dye compounds shown in Tables 3 to 9 or the disperse dye compound conventionally used for dyeing polyester fibers and the like. A polypropylene dyed cloth was obtained by the same dyeing procedure.
  • the dye compounds used in Dyeing Examples P1 to P82 and Dyeing Examples P98 to P101 are shown in Tables 10 to 16.
  • the dyeability was visually evaluated for the Total K / S value obtained by measuring the color of the dyed cloth and the dye residue after dyeing.
  • the color of the dyed cloth was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), the dyed cloth was glued on white paper, and the observation light source D65 was used in a 2 degree field of view.
  • the light fastness test was carried out by an 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 discoloration was determined after exposure to the dyed cloth for 20 hours under the condition of a black panel temperature of 63 ⁇ 3 ° C.
  • Sublimation fastness test was carried out by a method according to JIS L0854: 2013. The outline of the test method is as follows. The dyed cloth was sandwiched between nylon cloths and held at 120 ⁇ 2 ° C. for 80 minutes under a load of 12.5 kPa, and then discoloration and fading and contamination of the nylon cloth were judged.
  • the washing fastness test was carried out by a method according to JIS L0844: 2011 (A-2).
  • the outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, and washed for 30 minutes under the condition of 50 ⁇ 2 ° C in the presence of soap to determine discoloration and contamination of the cotton and nylon parts of the multi-woven mixed woven cloth. rice field. In addition, the contamination of the residual liquid after washing was determined.
  • Sweat fastness test The sweat fastness test was carried out by a method according to JIS L0848: 2004. The outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, soaked in acidic artificial sweat solution or alkaline artificial sweat for 30 minutes, held at 37 ⁇ 2 ° C. for 4 hours under a load of 12.5 kPa, and dried at 60 ° C. or lower. Discoloration and fading and contamination of the cotton and nylon parts of the multi-woven mixed woven fabric were determined.
  • Friction fastness test was carried out by a method according to JIS L0849: 2013. The outline of the test method is as follows. Using the friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the dyed cloth is rubbed 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N. The coloration of the cotton cloth was judged.
  • the fastness test for hot pressing was performed by a method according to JIS L0850: 2015 (A-2 drying). The outline of the test method is as follows. A dyed cloth was placed on the cotton cloth, and after holding for 15 seconds under a load of 4 ⁇ 1 kPa with a heating plate at 150 ° C., discoloration and fading and contamination of the cotton cloth were judged.
  • Tables 17 and 18 show the evaluation results of the dyed examples of the compound of the formula (A).
  • the stainability was good.
  • X A is a nitro group
  • Y A is a bromine atom
  • Table 19 shows the evaluation results of the dyeing example of the compound of the formula (B).
  • Tables 20 and 21 show the evaluation results of the dyeing examples of the compound of the formula (C).
  • X C is a chlorine atom
  • Y C is a hydrogen atom
  • X C is a hydrogen atom
  • Y C is a hydrogen atom
  • C3 compounds of independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms) was good.
  • Table 22 shows the evaluation results of the dyeing examples of the compound of the formula (D).
  • Table 23 shows the evaluation results of the dyeing examples of the compound of the formula (E).
  • the staining of the compounds of formula (E), R E used in Dyeing Example P62 or P63 is was good dyeability of a compound of the alkyl group having 4 to 18 carbon atoms.
  • Table 24 shows the evaluation results of dyeing examples of the compound of the formula (F).
  • Table 25 shows the evaluation results of the dyeing examples of the compound of the formula (G).
  • the stainability of the compound of the formula (G) As for the stainability of the compound of the formula (G), the stainability of the compound having an alkyl group having RG of 7 to 18 carbon atoms used in Staining Examples P68 to P71 was good.
  • Polypropylene fibers are dyed by the supercritical carbon dioxide dyeing method using the dye compounds shown in Tables 3 to 9 or the dyes obtained by mixing two or more kinds of the disperse dye compounds conventionally used for dyeing polyester fibers and the like. rice field.
  • the dyeability evaluation, the light fastness test, the sublimation fastness test, the washing fastness test, the sweat fastness test, and the friction are the same as in the case of the polypropylene dyed cloth with one kind of dye compound described above.
  • a fastness test and a fastness test against hot pressing were performed.
  • the dyeability was visually evaluated for the Total K / S value, L * value, a * value, b * value and the dye residue after dyeing obtained by measuring the color of the dyed cloth.
  • the color of the dyed cloth was measured by using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), gluing the dyed cloth on white paper, and using an observation light source D65 and a 2 degree field of view.
  • the supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG.
  • the dyeing equipment includes a liquid CO 2 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), and magnetic. It is composed of a drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).
  • the polyethylene cloth was cut and weighed to about 50 to 70 g, wound in the order of cotton cloth, polyethylene cloth, and cotton cloth on a stainless cylinder (21) having punch holes, and then loosely fixed with cotton thread.
  • the inner cotton cloth is an undercloth and the outer cotton cloth is a cover cloth.
  • a stainless steel cylinder around which the above-mentioned cloth sample (cotton cloth, polyethylene cloth, cotton cloth) is wound is fixed to a pressure-resistant stainless steel tank (22), and obtained in Synthesis Example 5 corresponding to 0.3% by mass with respect to the mass of the polyethylene cloth.
  • the blue dye compound A-5 was wrapped in a paper wipe and placed in the fluid passage above the stainless steel cylinder.
  • the volume of the pressure-resistant stainless steel tank was 2230 cm 3 . All valves in the dyeing apparatus were closed and heated to 98 ° C. by a preheater.
  • the stop valves (14) and (16) were opened, and 1.13 kg of liquid carbon dioxide was flowed into the pressure-resistant stainless steel tank using a high-pressure pump via a cooling jacket. After that, the stop valves (14) and (16) were closed and circulated by the impeller and the magnetic drive unit at the lower part of the pressure-resistant stainless steel tank.
  • the rotation speed of the magnetic drive unit is 750 rpm, and the circulation direction is from the inside to the outside of the cylinder.
  • the polyethylene cloth was dyed by maintaining these temperature and pressure conditions for 60 minutes. After dyeing, the stop valve (18) was opened and the needle valve was gradually opened to release carbon dioxide in the pressure-resistant stainless steel tank, and the pressure in the pressure-resistant stainless steel tank was lowered from 25 MPa to atmospheric pressure. Circulation continued until the critical pressure of carbon dioxide (about 8 MPa) was reached. After that, the polyethylene dyed cloth in the pressure-resistant stainless steel tank was taken out.
  • the polyethylene dyed cloths obtained in Dyeing Examples E1 to E14 and Dyeing Examples E18 to E20 were subjected to a dyeability evaluation, a light fastness test, a washing fastness test, a sweat fastness test and a friction fastness test.
  • the dyeability was visually evaluated for the Total K / S value obtained by measuring the color of the dyed cloth and the dye residue after dyeing.
  • the color of the dyed cloth was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), the dyed cloth was glued on white paper, and the observation light source D65 was used in a 2 degree field of view.
  • the light fastness test was carried out by an 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 discoloration was determined after exposure to the dyed cloth for 20 hours under the condition of a black panel temperature of 63 ⁇ 3 ° C.
  • washing fastness test was carried out by a method according to JIS L0844: 2011 (A-2).
  • the outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, and washed for 30 minutes under the condition of 50 ⁇ 2 ° C in the presence of soap to determine discoloration and contamination of the cotton and nylon parts of the multi-woven mixed woven cloth. rice field. In addition, the contamination of the residual liquid after washing was determined.
  • the sweat fastness test was carried out by a method according to JIS L0848: 2004.
  • the outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, soaked in acidic artificial sweat solution or alkaline artificial sweat for 30 minutes, held at 37 ⁇ 2 ° C. for 4 hours under a load of 12.5 kPa, and dried at 60 ° C. or lower. Discoloration and fading and contamination of the cotton and nylon parts of the multi-woven mixed woven fabric were determined.
  • Friction fastness test was carried out by a method according to JIS L0849: 2013. The outline of the test method is as follows. Using the friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the dyed cloth is rubbed 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N. The coloration of the cotton cloth was judged.
  • Table 33 shows the evaluation results of dyeing examples of the compound of the formula (A).
  • the staining of the compounds of (A), Dyeing Example E1 to E4, and Dyeing Example R A1 used in E18, R A2 and R A3 are each independently the number alkyl group or a C 1 to 14 carbon atoms and 1 or represents the alkyl group having 1 to 14 carbon atoms substituted by 4 alkoxy or CN (at least one provided that R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms) dyeability compounds It was good.
  • X A is a nitro group
  • Y A is a bromine atom
  • R A1 R number of carbon atoms of A2 and R A3 is larger compound.
  • Table 34 shows the evaluation results of dyeing examples of the compound of the formula (B).
  • Table 35 shows the evaluation results of the dyeing examples of the compound of the formula (C).
  • Dyeing Example E5 to E7, and R C1, R C2 and R C3 used in Dyeing Example E20 each independently represents an alkyl group having 1 to 14 carbon atoms ( R C1, at least one of R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms), or, each independently X C and Y C denotes a hydrogen atom and a halogen atom, R C1, R C2 and R C3 is was good dyeability independent compound represents an alkyl group having 1 to 14 carbon atoms and.
  • X C is a chlorine atom
  • Y C is a hydrogen atom
  • R C1 was as good as R C1
  • R C2 the number of carbon atoms in R C3 is greater compound.
  • Table 36 shows the evaluation results of dyeing examples of the compound of the formula (D).
  • R D1 used in Dyeing Example E8 to E12 represent an alkyl group having 1 to 14 carbon atoms
  • R D2 is an alkyl group or CN of 1 to 14 carbon atoms
  • the stainability of the compound was good.
  • both X D and Y D are chlorine atoms, or both X D and Y D are bromine atoms, or both X D and Y D are hydrogen atoms.
  • R D1 and R D2 with larger carbon numbers were better.
  • Table 37 shows the evaluation results of dyeing examples of the compound of the formula (G).
  • R G used in Dyeing Example E14 was good dyeability of a compound of the alkyl group having 7 to 18 carbon atoms.
  • Polyethylene fibers are dyed by a supercritical carbon dioxide dyeing method using the dye compounds shown in Tables 3 to 9 or dyes using a mixture of two or more types of disperse dye compounds conventionally used for dyeing polyester fibers and the like. rice field.
  • the obtained dyed cloth is subjected to dyeing property evaluation, light fastness test, washing fastness test, sweat fastness test and friction fastness test in the same manner as in the case of the polyethylene dyeing cloth with one kind of dye compound described above. went.
  • Table 38 shows the evaluation results of dyeing using the dye.
  • the dyeability was visually evaluated for the Total K / S value, L * value, a * value, b * value and the dye residue after dyeing obtained by measuring the color of the dyed cloth.
  • the color of the dyed cloth was measured by using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), gluing the dyed cloth on white paper, and using an observation light source D65 and a 2 degree field of view.
  • the dyeing examples E15, E16, and E18 obtained by mixing the orange dye, the red dye, the purple dye, and the blue dye of the present invention have good dyeability and fastness. It was a good black dyed cloth.
  • the present invention is not limited to the above-described embodiment, and the present invention also includes those in which the configurations of the embodiments are appropriately combined or substituted.
  • the present invention is a polyolefin fiber used for clothing such as clothing, underwear, hats, socks, gloves, sports clothing, vehicle interior materials such as seats, and interior products such as carpets, curtains, mats, sofa covers, and cushion covers. Can be used to stain.

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