Classifications

• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0079—Azoic dyestuff preparations
• • 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
• • 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
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/008—Preparations of disperse dyes or solvent dyes
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0084—Dispersions of dyes
  • C09B67/0085—Non common dispersing agents
  • C09B67/0089—Non common dispersing agents non ionic dispersing agent, e.g. EO or PO addition products
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
  • D06P1/18—Azo dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/79—Polyolefins

Definitions

• the present invention relates to a dye composition, a method for dyeing fibers, fibers dyed by the dyeing method, and a compound.
• Polyolefin resins such as polypropylene resin and polyethylene resin are crystalline thermoplastic resins, which 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 a dye for dyeing the polyolefin-based resin fiber.
• 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. Furthermore, regarding the form of dyes when used for dyeing, there is a description that these monoazo dyes are used in a paste state using an appropriate dispersant, but a specific method for producing a dye paste is not described. ..
• Various modification 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. It has been known.
• the present invention uses a dye composition, a method for dyeing fibers, and a method for dyeing the fibers, which can dye fibers in various hues at high concentrations and have excellent dyeing fastness such as light resistance, sublimation, and washing of dyed products. It is an object of the present invention to provide dyed fibers and compounds.
• the present invention is a dye composition containing at least one of the compounds of the following general formulas (A) to (G) and a nonionic dispersant.
• 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.
• RD2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN (provided that at least one of RD1 and RD2 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 or 10 to 18 carbon atoms.
• the present invention also provides a method for dyeing fibers, which includes a step of water-based dyeing of fibers using the dye composition of the present invention.
• the present invention also provides fibers dyed by the dyeing method of the present invention.
• the present invention also provides a compound of any 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.
• RD2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN (provided that at least one of RD1 and RD2 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 or 10 to 18 carbon atoms.
• the dye composition of the present invention can dye fibers in various hues at high concentration, and the dyed product has excellent dyeing fastness such as light resistance, sublimation, and washing.
• the present inventors have found that dyes containing the following specific compounds have improved affinity for fibers and dye fibers in various hues at high concentrations, and have 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.
• RD2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN (provided that at least one of RD1 and RD2 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 or 10 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.
• RD2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN (provided that at least one of RD1 and RD2 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.
• RG represents an alkyl group having 7 or 10 to 18 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 water content of the compound of the general formula (A) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.
• 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).
• compounds of the formula (a-C4) R A1 -X R A1 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) reacting a halogenated hydrocarbon represented by
• RA2 ( RA2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced according to a known reaction. For example, ( 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 water content of the compound of the general formula (B) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.
• 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 water content of the compound of the general formula (C) may be within a range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.
• 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 coupling.
• 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 (d-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 (dc) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
• the water content of the compound of the general formula (D) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.
• 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 an azo-based disperse dye.
• 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 water content of the compound of the general formula (E) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.
• 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 an azo-based disperse dye.
• 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 water content of the compound of the general formula (F) may be within a range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.
• aniline R F1 -X (R F1 represents 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 F2 ( RF2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced.
• R F2 RF2 represents an alkyl group having 1 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 water content of the compound of the general formula (G) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.
• the dye composition of the present invention contains at least one of the compounds of the general formulas (A) to (G) and a nonionic dispersant.
• nonionic dispersant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene aryl phenyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene aryl aryl ether, polyoxyethylene sorbitan fatty acid ester, and poly.
• examples thereof include oxyethylene acetylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and oxyethylene-oxypropylene copolymer.
• At least one selected from polyoxyethylene alkylphenyl ether, polyoxyethylene arylphenyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene arylaryl ether, and oxyethylene-oxypropylene copolymer should be used. Is preferable, at least one selected from polyoxyethylene arylphenyl ether, polyoxyethylene arylaryl ether, and oxyethylene-oxypropylene copolymer is more preferable, and polyoxyethylene arylphenyl ether and oxyethylene-oxy are more preferable. It is more preferable to use at least one selected from propylene copolymers.
• the polymerization form of the oxyethylene-oxypropylene copolymer is not limited, and may be any of a random polymer, a block polymer, and the like.
• the nonionic dispersants include polyoxyethylenearylphenyl ether and oxyethylene-oxy. It is preferable that both propylene copolymers are contained.
• the amount of the nonionic dispersant used is adjusted to the mass of the compounds represented by the formulas (A) to (G) for the purpose of maintaining good dispersion stability of the compounds represented by the formulas (A) to (G). On the other hand, it is preferably 20 to 200% by mass, more preferably 20 to 100% by mass.
• the dye composition of the present invention contains a viscosity regulator, a surface tension regulator, a pH regulator, a moisturizer, a hydrotrope, a sequestrant, a preservative, and an antibacterial agent as long as the object of the present invention is not hindered.
• a mold agent, an antifoaming agent and the like may be added as needed.
• the dye composition 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 the like.
• examples thereof include antifungal agents, antistatic agents, flame retardants, inorganic fillers, and elastomers for improving impact resistance.
• the dye composition of the present invention is preferably an aqueous dispersion from the viewpoint of ease of handling, safety and the like. Since the compounds represented by the formulas (A) to (G) have high lipophilicity, in order to obtain a dye composition in the form of an aqueous dispersion, the dispersant is used in combination and fine particles are used in a disperser such as a bead mill. It is necessary to perform decentralization processing.
• the dye composition of the present invention is a liquid aqueous dispersion in which the compounds represented by the formulas (A) to (G) are atomized and dispersed in an aqueous dispersion medium using a nonionic dispersant, or the above. It may be in the form of a powder obtained by removing the dispersion medium of the liquid aqueous dispersion by spray drying or the like, but it is preferably in the form of a powder from the viewpoint of product life.
• the content of the compounds represented by the formulas (A) to (G) in the dye composition of the present invention may be as long as it can be easily handled during dyeing, and is preferably 5 to 40% by mass, more preferably. Is 10 to 30% by mass.
• the method for producing the dye composition of the present invention preferably includes the following methods. (1) Add various additives such as nonionic dispersant and, if necessary, viscosity modifier to water and stir to prepare a dispersant solution. (2) The compounds represented by the formulas (A) to (G) are added to the dispersant solution of (1) and stirred to prepare an aqueous slurry. (3) Using a wet disperser such as a bead mill, the aqueous slurry fine particle dispersion treatment of (2) is carried out so that the volume median particle diameter of the compounds represented by the formulas (A) to (G) is 1.0 ⁇ m or less, preferably 1.0 ⁇ m or less. Continue until the volume is 0.5 ⁇ m or less.
• a wet disperser such as a bead mill
• the compounds of the general formulas (A) to (G) contained in the dye composition for dyeing the fibers of the present invention have blue, purple, red, orange, or yellow.
• the dye composition may contain the compounds of the general formulas (A) to (G) alone or in combination of two or more. When the dye composition contains two or more compounds of the general formulas (A) to (G), dyes for dyeing fibers in various hues or blacks can be obtained.
• the dye composition for dyeing the fiber 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 compound containing at least one compound and at least one of a red compound containing one or more selected from the group consisting of a compound of the general formula (C) and a compound of the general formula (D). It is preferable to contain at least one of a compound of the general formula (D), a compound of the general formula (E) and a yellow or orange compound selected from the compound of the general formula (G), and the compound of the general formula (A).
• the composition of the compound in the dye composition for dyeing fibers in black is such that the mixing ratio of the purple or blue compound is 30 to 70% by mass, the mixing ratio of the red compound is 5 to 25% by mass, and the yellow
• the mixing ratio of the orange compound is preferably in the range of 15 to 55% by mass
• the mixing ratio of the purple or blue compound is 40 to 60% by mass
• the mixing ratio of the red compound is 5 to 25% by mass.
• the mixing ratio of the yellow or orange compound is more preferably in the range of 25 to 45% by mass.
• Examples of the fiber to be dyed in the present invention include polyester fiber, polyolefin fiber, acrylic fiber and the like, and polyolefin fiber is preferable.
• the polyolefin fiber is a copolymer of an ⁇ -olefin such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, or a copolymer of these ⁇ -olefins.
• ⁇ -olefin such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, or a copolymer of these ⁇ -olefins.
• examples include fibers formed from heavy compounds or polymers selected from copolymers with other unsaturated monomers copolymerizable with these ⁇ -olefins.
• 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 is preferably formed from a polypropylene-based resin and / or a polyethylene-based resin, and more preferably formed from a polypropylene-based resin.
• the shape of the polyolefin fiber is, for example, lump-like (molded product, etc.), film-like, fibrous (cloth-like (woven fabric, knitted fabric, non-woven fabric, etc.), thread-like (filament yarn, spun yarn, slit yarn, split yarn, etc.)). Etc., and is preferably fibrous.
• the polyolefin fiber 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 provides a method for dyeing fibers, which comprises a step of water-based dyeing of fibers using the dye composition of the present invention.
• the dyeing step is preferably at least one selected from the group consisting of dyeing, printing, inkjet dyeing, transfer dyeing, and continuous dyeing, and at least one selected from dyeing and printing. More preferably, printing is even more preferable.
• the dyeing step is dyeing, the dyeing step is performed, for example, by subjecting the object to be dyed into the dye composition of the present invention under pressure, preferably 80 ° C. to 130 ° C., more preferably 90 ° C. to 120 ° C., preferably. It is carried out by immersing for 30 to 60 minutes.
• the dyeing step is preferably performed at 80 ° C to 130 ° C.
• the dyeing step is preferably carried out for 30 to 60 minutes.
• the dyeing step is preferably performed at 110 ° C to 130 ° C.
• the dyeing step is preferably carried out for 30 to 60 minutes.
• the dyeing step is preferably performed at 90 ° C to 110 ° C.
• the dyeing step is preferably carried out for 30 to 60 minutes.
• the dye composition of the present invention is mixed with a glue such as a natural glue (for example, guar gum) or a processed glue (for example, carboxymethyl cellulose).
• a glue such as a natural glue (for example, guar gum) or a processed glue (for example, carboxymethyl cellulose).
• the dyeing step is preferably carried out at 80 ° C. to 130 ° C., and the steaming treatment is preferably carried out for 1 minute to 10 minutes.
• the dyeing step is preferably carried out at 110 ° C. to 130 ° C., and the steaming treatment is preferably carried out for 1 minute to 10 minutes.
• the dyeing step is preferably performed at 90 ° C. to 110 ° C., and the steaming treatment is preferably performed for 1 minute to 10 minutes.
• an ink for inkjet printing is prepared by adding a low volatile water-soluble organic solvent such as glycerin or diethylene glycol to the liquid dye composition of the present invention.
• a low volatile water-soluble organic solvent such as glycerin or diethylene glycol
• steaming treatment at 90 ° C. to 200 ° C. for 1 minute to 20 minutes, for example, Alternatively, it is subjected to dry heat treatment for 20 seconds to 5 minutes.
• the concentration of the dye of the present invention with respect to the fiber is, for example, 0.001% o. m. f. To 10% o. m. f. It is preferably 0.001% o. m. f. ⁇ 5% o. m. f. Is. Note that o. m. f. Means on the mass of fiber (against fiber mass).
• the concentration of the dye of the present invention with respect to the printing paste is, for example, 0.001% o. m. p. ⁇ 5% o. m. p. It is preferably 0.001% o. m. p. ⁇ 2% o. m. p. Is. Note that o. m. p. Means on the mass of paste (mass against paste).
• the present invention provides fibers dyed by the dyeing method of the present invention.
• Applications of the fiber include, for example, 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. And so on.
• 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 obtained in the same manner 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. ) was obtained.
• 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 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.
• Dye compositions of the compounds listed in Tables 3-9 were produced for water-based dyeing.
• a production example is shown below.
• the dye composition is in the form of a liquid aqueous dispersion or powder.
• Dye Composition Production Examples 1 to 105 are production examples of a liquid dye composition
• Dye Composition Production Examples 106 to 141 are production examples of a powdery dye composition.
• the volume median particle size of the compound in the dye composition was measured by a dynamic light scattering type particle size distribution measuring device LB-500 manufactured by HORIBA, Ltd.
• This aqueous slurry is subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.15 ⁇ m and a concentration of 20% by mass A -5 dye composition was obtained.
• This aqueous slurry is subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.15 ⁇ m and a concentration of 20% by mass -3 Dye composition was obtained.
• This aqueous slurry is subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.15 ⁇ m and a concentration of 20% by mass -3 Dye composition was obtained.
• Dispersants for making the compound of the present invention into a dye composition are the distyrenated phenol-ethylene oxide adduct and the tristyrene phenol-ethylene oxide adduct described in Dye Composition Production Examples 1 to 49 and 68 to 105. , Tribenzylphenol-ethylene oxide adduct, oxyethylene-oxypropylene copolymer and other nonionic dispersants were effective.
• the compound of the present invention alone is an anionic dispersant such as the formalin condensate of sodium naphthalenesulfonate, the formalin condensate of sodium cleosort oil sulfonate, and sodium ligninsulfonate described in Production Examples 50 to 67 of the dye composition.
• an anionic dispersant such as the formalin condensate of sodium naphthalenesulfonate, the formalin condensate of sodium cleosort oil sulfonate, and sodium ligninsulfonate described in Production Examples 50 to 67 of the dye composition.
• a desired particle size volume median particle size is 1.0 ⁇ m or less.
• ⁇ Dyeing example> Polypropylene fiber dyeing 1
• the polypropylene fiber was dyed with.
• a dyed polypropylene fiber dyed product was obtained by the same dyeing procedure as in dyeing example P1 except that the dye composition of the blue compound A-5 described in dyeing example P1 was changed to the dye composition of the compounds shown in Tables 10-14. ..
• Tables 10 to 14 show the compounds used in Staining Examples P1 to P22 and Staining Examples P26 to P37.
• the polypropylene fiber dyed product obtained in the dyeing example was subjected to a dyeability evaluation, a light fastness test, a sublimation fastness test, a washing fastness test, a sweat fastness test, a friction fastness test and a fastness test against hot pressing. ..
• the dyeability was evaluated by the Total K / S value obtained by measuring the color of the dyed cloth.
• 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. Friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) The dyed cloth was rubbed back and forth 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N to determine the coloring of the cotton cloth.
• 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.
• Table 15 shows the evaluation results of dyeing examples of the compound of the formula (A).
• Dyeing P1, P2 and R A1 used in P26 to P28, R A2 and R A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that R A1, At least one of RA2 and RA3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• a disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example P3, dyeability R A1, all R A2 and R A3 is an alkyl group having 3 or less carbon compound poor there were.
• Dyeing P1, R used in the P2 and P26 to P28 A1, R A2 and R A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that the R A1, at least one is a is) an alkyl group having 4 to 14 carbon atoms compound of R A2 and R A3 are, sublimation fastness, washing fastness, perspiration fastness, good fastness to rubbing fastness and hot pressing Met.
• Table 16 shows the evaluation results of the dyeing example of the compound of the formula (B).
• R B2 represents an alkyl group having 1 to 14 carbon atoms each independently (provided that R B1, The stainability of the compound (at least one of R B2 and R B3 is an alkyl group having 4 to 14 carbon atoms) was good.
• a disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example P8, dyeability R B1 or R B2 is not alkyl group of 1 to 14 carbon atoms compound was poor.
• R B1 and R B2 used in Staining Examples P4 to P7 and P29 to P31 each independently represent an alkyl group having 1 to 14 carbon atoms (however, R).
• Compounds (at least one of B1 , RB2 and RB3 is an alkyl group having 4 to 14 carbon atoms) have good light fastness, sublimation fastness, wash fastness, sweat fastness, and fastness to hot pressing. there were.
• Table 17 shows the evaluation results of the dyeing example of the compound of the formula (C).
• R C1 For staining of compound of formula (C), it represents a R C1, R C2 and R C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example P9 to P11, and P32 to P34 (except staining of R C1, at least one of R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms) compounds was good.
• a disperse dye used for dyeing polyester fibers conventionally used in Dyeing Example P12, dyeability R C1, at least one of R C2 and R C3 are an alkyl group having 3 or less carbon compound poor Met.
• R C1, R C2 and R C3 are representing an alkyl group having 1 to 14 carbon atoms each independently (provided that R C1, R C2 and R C3 Is an alkyl group having 4 to 14 carbon atoms) was generally good.
• the respective fastness of compound of formula (C), represents a R C1, R C2 and R C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example P9 to P12, and P32 to P34 ( provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms) compounds, each fastness was good.
• Table 18 shows the evaluation results of the dyeing examples of the compound of the formula (D).
• the staining of the compounds of (D), Dyeing Example P13 to P17, and P35, representing the R D1 and R D2 are each independently an alkyl group having 1 to 14 carbon atoms used in the P36 (provided that R D1 ⁇ And at least one of R D2 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• Dyeing Example P18 to P20 when a conventional disperse dye used in the dyeing of such polyester fibers, with each alkyl group having 1 to 3 carbon atoms in the alkyl group of R D1 ⁇ beauty R D2 Yes, the stainability was poor.
• Table 19 shows the evaluation results of the dyeing example of the compound of the formula (G).
• the stainability of the compound of the formula (G) the stainability of the compound having an alkyl group having 7 or 10 to 18 carbon atoms in RG used in Staining Examples P21 and P37 was good.
• Staining of the compound R G is an alkyl group having 3 carbon atoms is a disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example P22 was poor.
• the compound having an alkyl group having 7 or 10 to 18 RG carbons used in Staining Examples P21 and P37 was good.
• Polypropylene fiber dyeing 2 Polypropylene fibers were dyed in the same manner as in Dyeing Example P1 using a dye composition in which two or more of the compounds shown in Tables 3 to 9 were mixed and used, and the obtained polypropylene fiber dyed product was evaluated for dyeability. Light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, friction fastness test and fastness test for hot pressing were performed. The dyeability was evaluated by the Total K / S value, the L * value, the a * value, and the b * value 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.
• Table 20 shows the evaluation results of dyeing examples using a dye composition in which two or more kinds of the compounds shown in Tables 3 to 9 are mixed and used.
• Polyethylene fiber dyeing 1 Dyeing method using only one type of dye composition of the compound shown in Tables 3 to 9 or a dye composition such as a disperse dye compound conventionally used for dyeing polyester fibers and the like shown in Tables 3 to 9. The polyethylene fibers were dyed with.
• Tables 10 to 14 show the compounds used in Staining Examples E1 to E22 and Staining Examples E26 to E37.
• the polyethylene fiber dyed product obtained in the dyeing example has the same dyeability evaluation, light fastness test, washing fastness test, and sweat fastness as the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 1). A test and a friction fastness test were performed.
• Table 26 shows the evaluation results of dyeing examples of the compound of the formula (A).
• Dyeing Example is a disperse dye used for dyeing polyester fibers conventionally used in E3, staining of R A1, all R A2 and R A3 is an alkyl group having 3 or less carbon compound poor there were.
• Dyeing E1, E2 and E26 to R A1 used in E28, R A2 and R A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that the R The compound (at least one of A1, RA2 and RA3 is an alkyl group having 4 to 14 carbon atoms) had good wash fastness, sweat fastness, and friction fastness.
• Table 27 shows the evaluation results of the dyeing examples of the compound of the formula (B).
• the staining of the compounds of formula (B), represents R B1, R B2 are each independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example E4 to E7, and E29 to E31 (provided that R B1, At least one of R B2 and R B3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• a disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example E8, dyeability R B1 or R B2 is not alkyl group of 1 to 14 carbon atoms compound was poor.
• R B2 are each independently (provided that an alkyl group of 1 to 14 carbon atoms and R
• the compounds at least one of B1, RB2 and RB3 is an alkyl group having 4 to 14 carbon atoms) had generally good light fastness, wash fastness, sweat fastness, and friction fastness.
• Table 28 shows the evaluation results of dyeing examples of the compound of the formula (C).
• R C2 and R C3 each independently represents an alkyl group having 1 to 14 carbon atoms ( staining of R C1, at least one of R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms) compounds was good.
• R C1, R C2 and R C3 are representing an alkyl group having 1 to 14 carbon atoms each independently (provided that R C1, R C2 and R C3
• the light fastness, sweat fastness, and friction fastness of the compound were generally good.
• 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) compounds, each fastness was good.
• Table 29 shows the evaluation results of dyeing examples of the compound of the formula (D).
• R D1 and R D2 used in E36 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R D1 ⁇ And at least one of R D2 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• each of the alkyl groups of R D1 and R D2 has an alkyl group having 1 to 3 carbon atoms. Yes, the stainability was poor.
• Table 30 shows the evaluation results of the dyeing examples of the compound of the formula (G).
• the stainability of the compound of the formula (G) the stainability of the compound having an alkyl group having 7 or 10 to 18 carbon atoms in RG used in Staining Examples E21 and E37 was good.
• Staining of conventionally a disperse dye used for dyeing such as polyester fiber R G is an alkyl group having 3 carbon atoms the compounds used in Dyeing Example E22 was poor.
• Polyethylene fiber dyeing 2 Using a dye composition in which two or more of the compounds shown in Tables 3 to 9 were mixed and used, the polyethylene fibers were dyed in the same manner according to Dyeing Example E1, and the obtained polyethylene fiber dyed product was obtained from the above-mentioned (polypropylene). Similar to the polypropylene fiber dyed product obtained in the fiber dyeing 2), a dyeability evaluation, a light fastness test, a washing fastness test, a sweat fastness test, and a friction fastness test were performed.
• Table 31 shows the evaluation results of dyeing examples using a dye composition in which two or more kinds of the compounds shown in Tables 3 to 9 are mixed and used.
• Printing of polypropylene fiber 1 Printing method using only one type of dye composition of the compound shown in Tables 3 to 9 or a dye composition such as a disperse dye compound conventionally used for dyeing polyester fibers and the like shown in Tables 3 to 9. The polypropylene fiber was dyed with.
• a dyed polypropylene fiber dyed product was obtained by the same dyeing procedure as in the dyeing example PP1 except that the dye composition of the blue compound A-13 described in the dyeing example PP1 was changed to the dye composition of the compounds shown in Tables 32 to 36. ..
• the polypropylene fiber dyed product obtained in the dyeing example has the same dyeability evaluation, light fastness test, sublimation fastness test, and washing fastness as the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 1). Tests, sweat fastness test, friction fastness test and fastness test against hot pressing were performed.
• Table 37 shows the evaluation results of dyeing examples of the compound of the formula (A).
• R A2 and R A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that R A1, R At least one of A2 and RA3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• Table 38 shows the evaluation results of the dyeing examples of the compound of the formula (B).
• R B2 represents an alkyl group having 1 to 14 carbon atoms each independently (provided that R B1, R B2 And at least one of RB3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• R B1 used in Dyeing Example PP4 to PP6 each independently represents an alkyl group having 1 to 14 carbon atoms with (but R B1, R B2 And at least one of RB3 is an alkyl group having 4 to 14 carbon atoms), each of which has good fastness.
• Table 39 shows the evaluation results of dyeing examples of the compound of the formula (C).
• Dyeing Example PP7 to PP9, PP15 and R C1 used in PP16, R C2 and R C3 are an alkyl group having 1 to 14 carbon atoms each independently (provided that R The stainability of the compound (at least one of C1 , RC2 and RC3 is an alkyl group having 4 to 14 carbon atoms) was good.
• each fastness of compound of formula (C) represents a R C1, R C2 and R C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example PP7 to PP9, PP15 and PP16 (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms) compounds, each fastness was good.
• Table 40 shows the evaluation results of dyeing examples of the compound of the formula (D).
• the staining of the compounds of formula (D), Dyeing PP10, PP11, PP17 and R D1 and R D2 used in the PP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R D1 and R The stainability of the compound (at least one of D2 is an alkyl group having 4 to 14 carbon atoms) was good.
• Dyeing PP10, PP11, PP17 and R D1 and R D2 used in the PP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R The compounds (at least one of D1 and R D2 is an alkyl group having 4 to 14 carbon atoms) had good fastness.
• Table 41 shows the evaluation results of the dyeing example of the compound of the formula (G).
• R G used in Dyeing Example PP12 and PP19 have had good dyeability of a compound of the alkyl group having 7 or 10 to 18 carbon atoms.
• the compound having an alkyl group having 7 or 10 to 18 RG carbons used in Staining Examples PP12 and PP19 was good.
• the obtained polypropylene fiber dyed product has the same dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, and sweat as the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 2). Fastness test, friction fastness test and fastness test against hot pressing were performed.
• Polyethylene fiber printing 1 Printing method using only one type of dye composition of the compound shown in Tables 3 to 9 or a dye composition such as a disperse dye compound conventionally used for dyeing polyester fibers and the like shown in Tables 3 to 9. The polyethylene fibers were dyed with.
• a dyed polyethylene fiber dyed product was obtained by the same dyeing procedure as in the dyeing example EP1 except that the dye composition of the blue compound A-13 described in the dyeing example EP1 was changed to the dye composition of the compounds shown in Tables 43 to 47. ..
• the polyethylene fiber dyed product obtained in the dyeing example has the same dyeability evaluation, light fastness test, washing fastness test, and sweat fastness as the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 1). A test and a friction fastness test were performed.
• Table 48 shows the evaluation results of dyeing examples of the compound of the formula (A).
• R A2 and R A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that R A1, R At least one of A2 and RA3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• R A2 and R A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that the R The compound (at least one of A1, RA2 and RA3 is an alkyl group having 4 to 14 carbon atoms) had good wash fastness, sweat fastness, and friction fastness.
• Table 49 shows the evaluation results of the dyed examples of the compound of the formula (B).
• R B2 represents an alkyl group having 1 to 14 carbon atoms each independently (provided that R B1, R B2 And at least one of RB3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.
• Dyeing Example EP4 to EP6 and represents the R B1, R B2 are each independently an alkyl group having 1 to 14 carbon atoms used in EP14 (provided that R B1 , At least one of RB2 and RB3 is an alkyl group having 4 to 14 carbon atoms), each of which has good fastness.
• Table 50 shows the evaluation results of the dyeing examples of the compound of the formula (C).
• Dyeing Example EP7 to EP9, EP15 and R C1 used in EP16, R C2 and R C3 are an alkyl group having 1 to 14 carbon atoms each independently (provided that R The stainability of the compound (at least one of C1 , RC2 and RC3 is an alkyl group having 4 to 14 carbon atoms) was good.
• each fastness of compound of formula (C) represents a R C1, R C2 and R C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example EP7 to EP9, EP15 and EP16 (wherein R C1, at least one of R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms) compounds, each fastness was good.
• Table 51 shows the evaluation results of the dyeing examples of the compound of the formula (D).
• the staining of the compounds of formula (D), Dyeing EP10, EP11, EP17 and R D1, R D2 used in EP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R D1 and R The stainability of the compound (at least one of D2 is an alkyl group having 4 to 14 carbon atoms) was good.
• Dyeing EP10, EP11, EP17 and R D1 and R D2 used in EP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R The compounds (at least one of D1 and R D2 is an alkyl group having 4 to 14 carbon atoms) had good fastness.
• Table 52 shows the evaluation results of the dyeing examples of the compound of the formula (G).
• R G used in Dyeing Example EP12 and EP19 have had good dyeability of a compound of the alkyl group having 7 or 10 to 18 carbon atoms.
• the compound having an alkyl group having 7 or 10 to 18 RG carbons used in Staining Examples EP12 and EP19 was good.
• Polyethylene fiber printing 2 Using a dye composition in which two or more of the compounds shown in Tables 3 to 9 were mixed and used, 1.2% o. m. p. Polyethylene fibers were dyed using the printing paste of.
• the obtained polyethylene fiber dyed product has a dyeability evaluation, a light fastness test, a washing fastness test, a sweat fastness test and friction, similarly to the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 2). A fastness test was performed.
• 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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