WO2021187446A1 - Dye for staining by using supercritical carbon dioxide - Google Patents
Dye for staining by using supercritical carbon dioxide Download PDFInfo
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- WO2021187446A1 WO2021187446A1 PCT/JP2021/010477 JP2021010477W WO2021187446A1 WO 2021187446 A1 WO2021187446 A1 WO 2021187446A1 JP 2021010477 W JP2021010477 W JP 2021010477W WO 2021187446 A1 WO2021187446 A1 WO 2021187446A1
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- 0 *c1cc(N(*)*)ccc1N=Nc1c(cc(cc2)[N+]([O-])=O)c2n[s]1 Chemical compound *c1cc(N(*)*)ccc1N=Nc1c(cc(cc2)[N+]([O-])=O)c2n[s]1 0.000 description 13
- YHDUVEMXCYXIOR-QNEJGDQOSA-N Bc(cc(cc1Br)[N+]([O-])=O)c1/N=N/c(cc1)ccc1N(CCCCCCCC)CCCCCCCC Chemical compound Bc(cc(cc1Br)[N+]([O-])=O)c1/N=N/c(cc1)ccc1N(CCCCCCCC)CCCCCCCC YHDUVEMXCYXIOR-QNEJGDQOSA-N 0.000 description 1
- PYWGXPUOLRAMKI-ULDVOPSXSA-N CCCCCCCCN(CCCCCCCC)c(cc1)cc(NC(C)=O)c1/N=N/c(c(C#N)cc([N+]([O-])=O)c1)c1Br Chemical compound CCCCCCCCN(CCCCCCCC)c(cc1)cc(NC(C)=O)c1/N=N/c(c(C#N)cc([N+]([O-])=O)c1)c1Br PYWGXPUOLRAMKI-ULDVOPSXSA-N 0.000 description 1
- HTIQBAVWYVBLJP-FLWNBWAVSA-N CCCCCCCCN(CCCCCCCC)c(cc1)ccc1/N=N\c(cc1)ccc1[N+]([O-])=O Chemical compound CCCCCCCCN(CCCCCCCC)c(cc1)ccc1/N=N\c(cc1)ccc1[N+]([O-])=O HTIQBAVWYVBLJP-FLWNBWAVSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
- C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
- C09B29/0081—Isothiazoles or condensed isothiazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3608—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
- D06P1/04—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/94—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in solvents which are in the supercritical state
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to a dye for dyeing a polyolefin fiber using supercritical carbon dioxide, a method for dyeing a polyolefin fiber using supercritical carbon dioxide, and a polyolefin fiber dyed by the dyeing method.
- Polyolefin-based resins such as polypropylene resin and polyethylene resin are crystalline thermoplastic resins, and are inexpensive, easy to process, high strength, high chemical resistance, high scratch resistance, high bending resistance, light weight, and low moisture absorption. It has excellent properties such as low thermal conductivity and high antistatic property.
- the polyolefin-based resin is a polymer compound composed of hydrocarbons in both the main chain and the side chain, has low affinity and compatibility with conventional dye compounds, and has a functional group effective for a chemical reaction. It has been considered that high-concentration and high-fast dyeing is extremely difficult due to reasons such as lack of dyeing.
- polypropylene resin and polyethylene resin are four major general-purpose synthetic resins along with polyvinyl chloride resin and polystyrene resin, and are used in a wide range of fields.
- Patent Documents 1 to 5 propose dyes for dyeing polyolefin-based resin fibers.
- Patent Document 1 describes an example of producing a red dye and a purple dye in which an alkyl group having 3 to 12 carbon atoms or a phenoxy group having a cycloalkyl group as a substituent is introduced into an anthraquinone dye, and a polypropylene resin fiber using them. An example of dyeing is described.
- Patent Document 2 describes an example of producing a blue dye in which an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or a phenoxy group having a halogeno group as a substituent is introduced into an anthraquinone dye, and a polyester fiber using them. Examples of dyeing of polyamide fibers and polyolefin resin fibers are described.
- Patent Document 3 describes an example of producing a blue dye in which an alkyl group having 1 to 9 carbon atoms or a phenoxy group having a halogeno group as a substituent is introduced into an anthraquinone dye, and an example of dyeing a polyolefin resin fiber using them. Is described.
- Patent Document 4 describes an example of dyeing a polyolefin-based resin fiber using a blue dye in which an alkylamino group and a cycloalkylamino group are introduced at the ⁇ -position of an anthraquinone-based dye.
- Patent Document 5 uses an example of producing a red dye in which a phenoxy group having two substituents selected from a sec-butyl group, a sec-pentyl group, and a tert-pentyl group is introduced into an anthraquinone dye, and the like.
- An example of dyeing the polypropylene resin fiber is described.
- Patent Document 6 describes an example of producing a monoazo dye having a long-chain alkyl group and an example of dyeing fine denier polyester fibers using them. However, no example of dyeing polyolefin fibers using them is described.
- Various reforming techniques include blending dyeable resin components such as polyester, copolymerization with vinyl-based monomers having a dyeable group, blending of dyeing accelerators such as metal stearate, and the like. are known.
- Patent Document 7 describes that supercritical carbon dioxide is used as a dyeing medium and a hydrophobic fiber material is dyed with various dyes as a dyeing method instead of water-based dyeing.
- polypropylene is described as an example of the hydrophobic fiber material, only the dyeing example of polyester cloth is described in the examples, and the dyeing example of polypropylene fiber is not described.
- the present invention dyes polyolefin fibers with supercritical carbon dioxide, which can dye polyolefin fibers in various hues at high concentration and has excellent dyeing fastness such as light resistance, sublimation, and washing of dyed products. It is an object of the present invention to provide a dyeing method for a polyolefin fiber using supercritical carbon dioxide, and a polyolefin fiber dyed by the dyeing method.
- the present invention is a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which contains at least one of the compounds of the following general formulas (A) to (G).
- X A is a nitro group
- Y A represents a halogen atom
- R A1, R A2 and R A3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms)
- RA4 represents an alkyl group having 1 to 4 carbon atoms.
- R B1 , R B2, and R B3 each independently represent an alkyl group having 1 to 14 carbon atoms (however , at least one of R B1 , R B2, and R B3 has 4 to 14 carbon atoms. It is an alkyl group).
- X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
- R C1, R C2 and R C3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms).
- X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
- R D1 represents an alkyl group having 1 to 14 carbon atoms.
- R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms.
- R F1 and R F2 each independently represent an alkyl group having 4 to 14 carbon atoms.
- RG represents an alkyl group having 7 to 18 carbon atoms.
- the present invention is a method for dyeing polyolefin fibers using supercritical carbon dioxide. Provided is a method including a step of dyeing a polyolefin fiber in the presence of supercritical carbon dioxide using the dye of the present invention.
- the present invention also provides polyolefin fibers dyed by the dyeing method of the present invention.
- the dye of the present invention can dye polyolefin fibers in various hues at high concentration in the presence of supercritical carbon dioxide, and the dyed product has excellent dyeing fastness such as light resistance, sublimation, and washing.
- the supercritical carbon dioxide dyeing apparatus used for dyeing is shown.
- the present inventors have improved affinity for lipophilic polyolefin fibers with dyes containing the following specific compounds, and dye the polyolefin fibers in various hues at high concentrations in the presence of supercritical carbon dioxide. We found that and completed the present invention.
- X A is a nitro group
- Y A represents a halogen atom
- R A1, R A2 and R A3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms)
- RA4 represents an alkyl group having 1 to 4 carbon atoms.
- R B1 , R B2, and R B3 each independently represent an alkyl group having 1 to 14 carbon atoms (however , at least one of R B1 , R B2, and R B3 has 4 to 14 carbon atoms. It is an alkyl group).
- X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
- R C1, R C2 and R C3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms).
- X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
- R D1 represents an alkyl group having 1 to 14 carbon atoms.
- R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However , at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms.
- R F1 and R F2 each independently represent an alkyl group having 4 to 14 carbon atoms.
- RG represents an alkyl group having 7 to 18 carbon atoms.
- the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferred ones are a fluorine atom and a chlorine atom. Atoms and bromine atoms can be mentioned.
- the alkyl group having 1 to 14 carbon atoms includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group.
- alkyl group having 1 to 14 carbon atoms such as -ethyl-1-methylpropyl group.
- alkyl group having 1 to 14 carbon atoms an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.
- the alkyl group having 1 to 4 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or a sec-butyl group.
- T-Butyl group and other linear or branched alkyl groups having 1 to 4 carbon atoms can be mentioned.
- the alkyl group having 1 to 4 carbon atoms an alkyl group having 1 to 2 carbon atoms is preferable, and an alkyl group having 1 carbon atom is more preferable.
- the alkyl group having 4 to 14 carbon atoms is, for example, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-.
- Pentyl group i-pentyl group, sec-pentyl group, t-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group Straight chain such as group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 1-ethyl-1-methylpropyl group.
- Alkyl groups having 4 to 14 carbon atoms in the form or branched form can be mentioned. As the alkyl group having 4 to 14 carbon atoms, an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl group having 4 to 8 carbon atoms is more preferable.
- the alkyl group having 4 to 18 carbon atoms includes, for example, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, and the like.
- alkyl group having 4 to 18 carbon atoms an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl group having 8 to 12 carbon atoms is more preferable.
- the alkyl group having 7 to 18 carbon atoms includes, for example, an n-heptyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, and 1 -A linear or branched alkyl having 7 to 18 carbon atoms such as an ethylpentyl group, a 2-ethylpentyl group, a 1,1-dimethylpentyl group, a 2,2-dimethylpentyl group, and a 3,3-dimethylpentyl group.
- the group can be mentioned.
- As the alkyl group having 7 to 18 carbon atoms an alkyl group having 11 to 18 carbon atoms is preferable, and an alkyl group having 15 to 18 carbon atoms is more preferable.
- X A is a nitro group
- Y A represents a halogen atom
- R A1, R A2 and R A3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms)
- RA4 represents an alkyl group having 1 to 4 carbon atoms.
- the compound of the formula (A) is a blue dye compound.
- Y A is a bromine atom.
- RA1 , RA2, and RA3 are each independently an alkyl group having 4 to 14 carbon atoms, or RA1 and RA2 are independently alkyl groups having 4 to 14 carbon atoms, and RA3 is an alkyl group having 1 to 4 carbon atoms, or RA3 is an alkyl group having 4 to 14 carbon atoms. It is preferable that RA1 and RA2 are independently alkyl groups having 1 to 4 carbon atoms.
- Y A is a bromine atom
- RA1 , RA2, and RA3 are each independently an alkyl group having 4 to 14 carbon atoms, or RA1 and RA2 are independently alkyl groups having 4 to 14 carbon atoms, and RA3 is an alkyl group having 1 to 4 carbon atoms, or RA3 is an alkyl group having 4 to 14 carbon atoms. It is preferable that RA1 and RA2 are independently alkyl groups having 1 to 4 carbon atoms.
- R B1 , R B2 and R B3 each independently represent an alkyl group having 1 to 14 carbon atoms. However , at least one of R B1 , R B 2 and R B 3 is an alkyl group having 4 to 14 carbon atoms.
- the compound of the formula (B) is a blue or purple dye compound.
- R B1 , R B2 and R B3 are independently alkyl groups having 4 to 14 carbon atoms, or R B1 and R B2 are independently alkyl groups having 4 to 14 carbon atoms, respectively.
- B3 is an alkyl group having 1 to 4 carbon atoms, or R B3 is an alkyl group having 4 to 14 carbon atoms, and R B1 and R B2 are independently alkyl groups having 1 to 4 carbon atoms. Is preferable.
- X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
- R C1, R C2 and R C3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms).
- the compound of the formula (C) is a red or purple dye compound.
- X C and Y C represent any combination of hydrogen atom and chlorine atom, bromine atom and nitro group, bromine atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom. Is preferable.
- X C and Y C represent any combination of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom.
- RC1 , RC2 and RC3 are each independently an alkyl group having 4 to 14 carbon atoms, or RC1 and RC2 are independently alkyl groups having 4 to 14 carbon atoms, RC3 is an alkyl group having 1 to 4 carbon atoms, or RC3 is an alkyl group having 4 to 14 carbon atoms. It is preferable that RC1 and RC2 are independently alkyl groups having 1 to 4 carbon atoms.
- X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group in the formula (D), respectively.
- R D1 represents an alkyl group having 1 to 14 carbon atoms.
- R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms.
- the compound of the formula (D) is an orange or red dye compound.
- X D represents a hydrogen atom, a chlorine atom or a bromine atom.
- Y D preferably represents a hydrogen atom, a chlorine atom, a bromine atom, or a cyano group.
- X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
- R D1 represents an alkyl group having 4 to 14 carbon atoms.
- R D2 preferably represents an alkyl group having 4 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN.
- the compound of the formula (E) is an orange dye compound.
- X E and Y E preferably represent a chlorine atom.
- R E is preferably an alkyl group having 4 to 12 carbon atoms.
- X E and Y E represent chlorine atoms
- R E is preferably an alkyl group having 4 to 12 carbon atoms.
- RF1 and RF2 each independently represent an alkyl group having 4 to 14 carbon atoms.
- the compound of the formula (F) is a purple dye compound.
- R F1 and R F2 each independently represent an alkyl group having 4 to 12 carbon atoms.
- the compound of the formula (G) is a yellow dye compound.
- the RG is preferably an alkyl group having 11 to 18 carbon atoms.
- the compound represented by the formula (A) is a 4-nitroaniline derivative represented by the formula (a-D) (in the formula (a-D), X A represents a nitro group and Y A represents a halogen atom).
- the compound represented by the formula (a-C) in the formula (a-C), RA1 , RA2 and RA3 each independently represent an alkyl group having 1 to 14 carbon atoms (however, however). at least one of R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms), R A4 can be obtained by coupling a representative) an alkyl group of 1 to 4 carbon atoms.
- a compound of formula (a-D) is added to a mineral acid or organic carboxylic acid in the presence of optionally added water as a nitrosating agent or nitrosyl. Diazotization with sulfuric acid to give the diazo compound.
- the organic carboxylic acid used include acetic acid and propionic acid.
- the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
- the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
- the reaction temperature for diazotization is preferably ⁇ 10 to 40 ° C., more preferably 0 to 40 ° C.
- the compound represented by the formula (a-D) is generally widely used as a raw material for an azo-based disperse dye.
- the pH of the compound solution or suspension represented by the formula (a-C) is preferably weakly acidic, and it may be advantageous in the coupling reaction to add a buffer such as triethylamine or sodium acetate.
- the compound of the general formula (A) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
- the compound represented by the formula (a-C2) is nitrated with concentrated nitric acid and concentrated sulfuric acid to obtain the compound represented by the formula (a-C3).
- the compound represented by the formula (a-C3) is reduced with tin in an acidic hydrochloric acid alcohol (for example, methanol) to obtain the compound represented by the formula (a-C4).
- an acidic hydrochloric acid alcohol for example, methanol
- an alkyl radical of formula (a-C4) R A1 in the compound represented by -X and R A2 -X (R A1 and R A2 are each independently a carbon number 1 to 14, X is The alkyl halide represented by (representing a halogen atom) is reacted to obtain the formula (a-C).
- R A1 -X R A1 represents an alkyl group of 1 to 14 carbon atoms
- X represents a halogen atom
- RA2 RA2 represents an alkyl group having 1 to 14 carbon atoms
- ( RA2 ) 2 SO 4 can be used to introduce RA2.
- the compound represented by the formula (B) is a diazo compound of 3-amino-5-nitro-2,1-benzoisothiazole represented by the formula (bD) and a diazo compound represented by the formula (bc).
- R B1 , R B 2 and R B 3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R B1 , R B 2 and R B 3 is carbon. It is obtained by coupling the alkyl groups of numbers 4 to 14).).
- a compound of formula (b-D) is added to a mineral acid or organic carboxylic acid in the presence of optionally added water as a nitrosating agent or nitrosyl.
- the organic carboxylic acid used include acetic acid and propionic acid.
- the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
- the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
- the reaction temperature for diazotization is preferably ⁇ 10 to 15 ° C., more preferably ⁇ 5 to 10 ° C.
- the compound represented by the formula (bD) is generally widely used as a raw material for an azo-based disperse dye.
- the pH of the compound solution or suspension represented by the formula (bc) is preferably weakly acidic, and it may be advantageous in the coupling reaction to add a buffer such as triethylamine or sodium acetate.
- the compound of the general formula (B) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
- R B3 -COX in m- nitroaniline R B3 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom
- R B3 represents an alkyl group of 1 to 14 carbon atoms
- X represents a halogen atom
- the compound represented by the formula (b-C1) is reduced with tin in an acidic hydrochloric acid alcohol (for example, methanol) to obtain a compound represented by the formula (b-C2).
- an acidic hydrochloric acid alcohol for example, methanol
- the compound represented by the formula (b-C2) contains RB1- X and RB2- X ( RB1 and RB2 each independently represent an alkyl group having 1 to 14 carbon atoms, and X represents an alkyl group having 1 to 14 carbon atoms.
- the alkyl halide represented by (representing a halogen atom) is reacted to obtain the formula (bc).
- R B1 -X compounds of the formula (b-C2) R B1 -X (R B1 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) reacting a halogenated hydrocarbon represented by
- R B2 RB2 represents an alkyl group having 1 to 14 carbon atoms
- ( RB2 ) 2 SO 4 can be used to introduce R B2.
- X C and Y C is a hydrogen atom and a halogen atom
- a halogen Represented by a diazo compound of (representing any combination of an atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom)
- a diazo compound of Representing any combination of an atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom
- R C1 , R C2 and R C3 are an alkyl group having 1 to 14 carbon atoms each independently (provided that R C1, at least one of R C2 and R C3 are carbon atoms It is obtained by coupling 4 or more alkyl groups))).
- the compound represented by the formula (cd) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of optionally added water. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
- the organic carboxylic acid used include acetic acid and propionic acid.
- the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
- the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
- the diazotization temperature is preferably ⁇ 10 to 40 ° C., more preferably 0 to 35 ° C.
- the compound represented by the formula (cd) is generally widely used as a raw material for an azo-based disperse dye.
- the pH of the compound solution or suspension represented by the formula (cc) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
- the compound of the general formula (C) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
- R C3 -COX in m- nitroaniline R C3 represents an alkyl group of 1 to 14 carbon atoms, X is halogen atom
- R C3 represents an alkyl group of 1 to 14 carbon atoms, X is halogen atom
- a carboxylic acid halide represented by the formula (c -The compound represented by C1) is obtained.
- the compound represented by the formula (c-C1) is reduced with tin in an acidic hydrochloric acid alcohol (for example, methanol) to obtain a compound represented by the formula (c-C2).
- an acidic hydrochloric acid alcohol for example, methanol
- an alkyl radical of formula (c-C2) a compound represented by R C1 -X and R C2 -X (R C1 and R C2 having 1 to carbon atoms each independently 14, X is The alkyl halide represented by) (which is a halogen atom) is reacted to obtain the formula (cc).
- R C1 -X to a compound of formula (c-C2) (R C1 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) reacting a halogenated hydrocarbon represented by
- RC2 ( RC2 represents an alkyl group having 1 to 14 carbon atoms)
- ( RC2 ) 2 SO 4 can be used to introduce RC2.
- the compound represented by the formula (D) is a 4-nitroaniline derivative represented by the formula (d-D) (in the formula (d-D), X D and Y D are independently hydrogen atoms and halogen atoms, respectively.
- X D and Y D are independently hydrogen atoms and halogen atoms, respectively.
- RD1 represents an alkyl group having 1 to 14 carbon atoms
- RD2 represents an alkyl group.
- at least one of RD1 and RD2 is an alkyl group having 4 to 14 carbon atoms. Obtained by ringing.
- the compound represented by the formula (d-D) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of water optionally added. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
- the organic carboxylic acid used include acetic acid and propionic acid.
- the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
- the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
- the diazotization temperature is preferably ⁇ 10 to 40 ° C., more preferably 0 to 30 ° C.
- the compound represented by the formula (DD) is generally widely used as a raw material for azo-based disperse dyes.
- the pH of the compound solution or suspension represented by the formula (dc) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
- the compound of the general formula (D) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less of water, and used for staining using supercritical carbon dioxide as a medium. use.
- R D1 -X and R D2 -X (R D1 to aniline, an alkyl group of 1 to 14 carbon atoms, R D2 is substituted with an alkyl group or CN of 1 to 14 carbon atoms represents an alkyl group having 1 to 14 carbon atoms. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms .
- X reaction an alkyl halide represented by a halogen atom.
- aniline R D1 -X (R D1 is an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) after reacting the halogenated hydrocarbon represented by, according to a known reaction, R D2 ( RD2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced.
- R D2 ( RD2 represents an alkyl group having 1 to 14 carbon atoms)
- ( RD2 ) 2 SO 4 can be used to introduce R D2.
- the compound represented by the formula (E) is a diazo compound of a 4-nitroaniline derivative represented by the formula (ED) (where X E and Y E represent halogen atoms in the formula (ED)).
- ED 4-nitroaniline derivative
- EC the compound represented by the formula (EC) (in the formula (EC), RE represents an alkyl group having 4 to 18 carbon atoms) is obtained by coupling.
- the compound represented by the formula (ed) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of water optionally added. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
- the organic carboxylic acid used include acetic acid and propionic acid.
- the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
- the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
- the diazotization temperature is preferably ⁇ 10 to 40 ° C., more preferably 0 to 30 ° C.
- the compound represented by the formula (ed) is generally widely used as a raw material for azo-based disperse dyes.
- the pH of the compound solution or suspension represented by the formula (EC) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
- the compound of the general formula (E) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for staining using supercritical carbon dioxide as a medium. use.
- the compound represented by the formula (F) is a diazo compound of 3-amino-5-nitro-2,1-benzoisothiazole represented by the formula (fD) and a diazo compound represented by the formula (fc). It is obtained by coupling the compounds to be compounded (in the formula (FC), RF1 and RF2 each independently represent an alkyl group having 4 to 14 carbon atoms).
- the compound represented by the formula (fD) is nitrosated in a mineral acid or an organic carboxylic acid in the presence of water optionally added. Diazotization with an agent or nitrosyl sulfate gives a diazo compound.
- the organic carboxylic acid used include acetic acid and propionic acid.
- the mineral acid include hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid.
- the nitrosating agent to be used is an alkali metal nitrite, for example, sodium nitrite in a solid state or an aqueous solution state.
- the diazotization temperature is preferably ⁇ 10 to 15 ° C., more preferably ⁇ 5 to 10 ° C.
- the compound represented by the formula (fD) is generally widely used as a raw material for azo-based disperse dyes.
- the diazo compound of the formula (fD) is added to a solution or suspension of an alcohol (for example, methanol) of the compound represented by the formula (fc). Is added in a temperature range of, for example, ⁇ 5 to 10 ° C. to obtain a compound represented by the above formula (F).
- an alcohol for example, methanol
- the pH of the compound solution or suspension represented by the formula (fc) is preferably weakly acidic, and it may be advantageous to add a buffer such as triethylamine or sodium acetate.
- the compound of the general formula (F) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
- aniline R F1 -X (R F1 represents an alkyl group having 4 to 14 carbon atoms, X represents a halogen atom) after reacting the halogenated hydrocarbon represented by, according to a known reaction, R F2 ( RF2 represents an alkyl group having 4 to 14 carbon atoms) may be introduced.
- R F2 RF2 represents an alkyl group having 4 to 14 carbon atoms
- ( RF2 ) 2 SO 4 can be used to introduce R F2.
- the compound represented by the formula (G) is 5-amino-anthra [9,1-cd] isothiazole-6-one represented by the formula (g) in an inert solvent such as toluene, xylene and chlorobenzene.
- R G -COX R G represents an alkyl group having 7 to 18 carbon atoms, X is halogen atom
- the reaction temperature is preferably 80 ° C to 140 ° C, more preferably 110 to 140 ° C.
- the compound represented by the formula (g) is generally widely used as a raw material for a polycyclic disperse dye.
- the compound of the general formula (G) is dried to, for example, 1.0% by mass or less of water, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and used for dyeing using supercritical carbon dioxide as a medium. use.
- the compounds of the general formulas (A) to (G) contained in the dye for dyeing the polyolefin fiber of the present invention have blue, purple, red, orange, or yellow.
- the dye may contain the compounds of the general formulas (A) to (G) alone or in combination of two or more. When the dye contains two or more compounds of the general formulas (A) to (G), a dye for dyeing the polyolefin fiber in various hues or black can be obtained.
- the dye for dyeing the polyolefin fiber in black is selected from the group consisting of the compound of the general formula (A), the compound of the general formula (B), the compound of the general formula (C), and the compound of the general formula (F).
- At least one of a purple or blue dye compound comprising one or more selected from the group consisting of a compound of the general formula (A), a compound of the general formula (B) and a compound of the general formula (F), and the general formula ( It is more preferable to include a red dye compound of the compound of C) and an orange dye compound containing one or more selected from the group consisting of the compound of the general formula (D) and the compound of the general formula (E). It is more preferable to include a blue dye compound of the compound of the general formula (A), a red dye compound of the compound of the general formula (C), and an orange dye compound of the compound of the general formula (D).
- the composition of the dye compound in the dye for dyeing the polyolefin fiber to black is such that the mixing ratio of the purple or blue dye compound is 30 to 70% by mass, and the mixing ratio of the red dye compound is 5 to 25% by mass.
- the mixing ratio of the yellow or orange dye compound is preferably in the range of 15 to 55% by mass, the mixing ratio of the purple or blue dye compound is 40 to 60% by mass, and the mixing ratio of the red dye compound is. More preferably, the mixing ratio of the yellow or orange dye compound is in the range of 5 to 25% by mass and 25 to 45% by mass.
- the dye of the present invention may further contain an additive.
- the additive include a color-auxiliary agent, a dispersant, a filler, a stabilizer, a plasticizer, a crystal nucleating agent, a modifier, a foaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antibacterial agent, and an antibacterial agent.
- examples thereof include mold agents, antistatic agents, flame retardants, inorganic fillers, and elastomers for improving impact resistance.
- the polyolefin fiber of the object to be dyed which is dyed with the dye of the present invention, is, for example, ⁇ -such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene and the like. Fibers formed from polymers selected from homopolymers of olefins, copolymers of these ⁇ -olefins, or copolymers of these ⁇ -olefins with other unsaturated monomers copolymerizable. .. Further, examples of the type of copolymer include block copolymers, random copolymers, graft copolymers and the like.
- polystyrene-based resins such as propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, and propylene-ethylene- (1-butene) copolymer, and low density.
- Polyethylene resins such as polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, poly 1-butene, poly 4-methyl-1 -Examples include polymers.
- the polymer may be used alone or in combination of two or more to form polyolefin fibers.
- the polyolefin fiber of the object to be dyed to be dyed with the dye of the present invention is preferably formed of polypropylene resin and / or polyethylene resin, and more preferably formed of polypropylene-based resin.
- the shape of the polyolefin fiber of the object to be dyed, which is dyed with the dye of the present invention, is, for example, lumpy (molded product, etc.), film-like, fibrous (cloth-like (woven fabric, knitted fabric, non-woven fabric, etc.), filamentous yarn (filament yarn, etc.). It may be any of spun yarn, slit yarn, split yarn, etc.)), and is preferably fibrous.
- the polyolefin fiber of the object to be dyed which is dyed with the dye of the present invention, may be a fiber formed by blending a polypropylene resin and / or a polyethylene resin with another polymer component, bonding, or the like.
- the polyolefin fiber may be a polypropylene fiber blended with other fibers such as polyester, or a blended fiber.
- the present invention is a method for dyeing a polyolefin fiber using supercritical carbon dioxide, which comprises a step of dyeing the polyolefin fiber in the presence of supercritical carbon dioxide using the dye of the present invention.
- supercritical carbon dioxide is used as the dyeing medium.
- the dyeing method that uses supercritical carbon dioxide as the dyeing medium does not use water at the time of dyeing and does not require a washing step, so waste water is generated. It is attracting attention as an environment-friendly dyeing method because it does not generate, does not require a dyeing aid, has a short dyeing time, and can reuse carbon dioxide as a dyeing medium.
- the dyeing step in the method of the present invention is preferably carried out at a temperature of 31 ° C. or higher and a pressure of 7.4 MPa or higher. This is because the dyeing temperature and dyeing pressure need to be equal to or higher than the critical point (31 ° C., 7.4 MPa) of carbon dioxide as a dyeing medium.
- the dyeing temperature is mainly determined by the type of resin of the fiber to be dyed.
- the dyeing temperature is usually in the range of 60 to 180 ° C, preferably in the range of 80 to 160 ° C.
- the dyeing pressure is mainly determined by the type of resin of the fiber to be dyed.
- the dyeing pressure is usually in the range of about 7.4 to 40.0 MPa, preferably 20 to 30 MPa.
- the dyeing time in the dyeing step is determined by the type of resin of the fiber to be dyed, the dyeing temperature and the dyeing time.
- the staining time is usually about 10 to 120 minutes, preferably 30 to 90 minutes.
- the concentration of the dye with respect to the fiber depends on the type of fiber to be dyed and the processing state.
- the concentration of the dye with respect to the fiber is 0.1 to 6.0 o. m. f. (On the mass of fiber), preferably 0.1 to 4.0 o. m. f. Is.
- the bath ratio (mass ratio of the object to be dyed: carbon dioxide) depends on the type of the object to be dyed and the processing state.
- the bath ratio is usually 1: 2 to 1: 100, preferably 1: 5 to 1:75.
- the bath ratio is relatively low in the dyeing method of the present invention, for example, 1: 2 to 1: 5.
- the present invention provides polyolefin fibers dyed by the dyeing method of the present invention.
- Applications of the polyolefin fiber include, for example, clothing such as clothing, underwear, hats, socks, gloves, sports clothing, vehicle interior materials such as seats, and interiors such as carpets, curtains, mats, sofa covers, and cushion covers. Supplies and the like can be mentioned.
- Step 2 The N- (4-methoxyphenyl) octaneamide (12.5 g) obtained in the above step 1 was gradually added to concentrated sulfuric acid (30 g) cooled to 5 ° C. in the range of 5 to 10 ° C. Concentrated nitric acid (4.57 g) was added dropwise to this mixture over 1 hour in the range of 5 to 10 ° C., and then the mixture was stirred at the same temperature for 1 hour. The reaction mixture was purged into ice water (150 g) and ethyl acetate (100 g) was added to extract the organic phase.
- Step 3 The mixture of N- (3-nitro-4-methoxyphenyl) octaneamide (16.9 g), tin (8.9 g) and methanol (7.5 g) obtained in the above step 2 was cooled to 5 ° C. Concentrated hydrochloric acid (31.4 g) was added dropwise to this mixture over 1 hour, the temperature was raised to 75 to 80 ° C., and the mixture was stirred for 40 minutes. After cooling the reaction mixture to 10 ° C., a 48% aqueous sodium hydroxide solution (55.2 ml) was gradually added in the range of 10 to 20 ° C. This mixture was filtered off, washed with water and dried to obtain N- (3-amino-4-methoxyphenyl) octaneamide (9.19 g, yield 69.5%) represented by the following formula (C1c).
- Step 4 N- (3-amino-4-methoxyphenyl) octaneamide (13.2 g), triethylamine (15 g), DMF (15 g) and 1-bromooctane (purchased as commercial products) obtained in the above step 3 (38.
- the mixture of 6 g) was heated to 120 ° C. and stirred at the same temperature for 3 hours to obtain N- [3- (N, N-dioctylamino) -4-methoxyphenyl] octane represented by the following formula (C1). Obtained an amide.
- Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C1).
- step 5 Preparation of diazo component solution (step 5) 2-Bromo-4,6-dinitroaniline (13.1 g) represented by the following formula (D1) is added to a mixture of concentrated sulfuric acid (16 g) and 43% nitrosylsulfuric acid (12.8 g) within the range of 25 to 30 ° C. And added slowly. The mixture was stirred at 30-40 ° C. for 2 hours to obtain a diazo component solution.
- step 5 2-Bromo-4,6-dinitroaniline (13.1 g) represented by the following formula (D1) is added to a mixture of concentrated sulfuric acid (16 g) and 43% nitrosylsulfuric acid (12.8 g) within the range of 25 to 30 ° C. And added slowly. The mixture was stirred at 30-40 ° C. for 2 hours to obtain a diazo component solution.
- step 1 Synthesis of coupler compound C5 and preparation of coupler component solution (step 1)
- step 4 of Synthesis Example 1 N- (3-amino-4-methoxyphenyl) acetamide (purchased as a commercial product) (9.0 g) was used instead of N- (3-amino-4-methoxyphenyl) octaneamide.
- N- [3- (N, N-dioctylamino) -4-methoxyphenyl] acetamide represented by the following formula (C5) was obtained in the same manner as in Step 4 of Synthesis Example 1 except that it was used.
- Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C5).
- Step 2 The following formula is used in the same manner as in Step 3 of Synthesis Example 1 except that N- (3-nitrophenyl) octaneamide (13.2 g) is used instead of N- (3-nitro-4-methoxyphenyl) octaneamide.
- N- (3-aminophenyl) octaneamide represented by (C9b) (9.48 g, yield 80.9%) was obtained.
- Step 3 The following formula is used in the same manner as in step 4 of Synthesis Example 1 except that N- (3-aminophenyl) octaneamide (11.7 g) is used instead of N- (3-amino-4-methoxyphenyl) octaneamide.
- N- [3- (N, N-dioctylamino) phenyl] octaneamide represented by (C9) was obtained.
- Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C9).
- step 1 To a mixture of concentrated sulfuric acid (16 g) and 43% nitrosylsulfuric acid (15.6 g), 2-chloro-4-nitroaniline (8.65 g) represented by the following formula (D3) is added in the range of 30 to 35 ° C. A diazo component solution was obtained by stirring at the same temperature for 2 hours.
- step 2 Synthesis of red dye compound (C-1) by coupling reaction (step 2)
- the coupler component solution composed of the compound of the formula (C9) was prepared in the same manner as in steps 1 to 3 of Synthesis Example 9.
- the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (28 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
- the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
- a red dye compound (24.3 g, yield 75.7%) represented by the following formula (C-1) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 642 (M +)).
- the red dye represented by the following formula (C-2) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C10) is used instead of the compound of the formula (C9) as the coupler component solution.
- a compound (10.4 g, yield 34.7%) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 600 (M +)).
- the red dye represented by the following formula (C-3) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C11) is used instead of the compound of the formula (C9) as the coupler component solution.
- a compound (12.9 g, yield 45.1%) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 572 (M +)).
- the red dye represented by the following formula (C-4) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C12) is used instead of the compound of the formula (C9) as the coupler component solution. A compound (23.4 g, yield 83.9%) was obtained. The structure of the red dye compound was confirmed by LCMS analysis (m / z 558 (M +)).
- the red dye represented by the following formula (C-5) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C13) is used instead of the compound of the formula (C9) as the coupler component solution.
- a compound (25.3 g, yield 75.5%) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 670 (M +)).
- red dye compound (C-6) by coupling reaction (step 2)
- the red dye represented by the following formula (C-6) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C17) is used instead of the compound of the formula (C9) as the coupler component solution.
- a compound (19.6 g, yield 87.9%) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 446 (M +)).
- the red dye represented by the following formula (C-7) is the same as in steps 1 and 2 of Synthesis Example 17 except that the compound of the formula (C16) is used instead of the compound of the formula (C9) as the coupler component solution. A compound (16.6 g, yield 70.0%) was obtained. The structure of the red dye compound was confirmed by LCMS analysis (m / z 474 (M +)).
- step 2 Preparation of diazo component solution (step 2) In a mixture of concentrated sulfuric acid (17 g) and 43% nitrosylsulfuric acid (14.7 g), 2,6-dichloro-4-nitroaniline (10.4 g) represented by the following formula (D4) was added in the range of 25 to 30 ° C. The diazo component solution was obtained by adding in 1 and stirring at the same temperature for 2 hours.
- N-octanoyl chloride (19.5 g) is added dropwise to a mixture of 5-amino-anthra [9,1-cd] isothiazole-6-one (25.2 g), toluene (120 g) and pyridine (9.49 g). After that, the temperature was raised to 110 ° C., and the mixture was stirred for 1 hour. After cooling this mixture to room temperature, a precipitate was precipitated by adding methanol (150 g). This mixture was separated by filtration, washed with methanol, and dried to obtain a yellow dye compound (31.8 g, yield 83.9%) represented by the following formula (G-2). The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 379 (M +)).
- the preparation of the coupler component solution composed of the compound of the formula (C18) is the same as in step 1 of Synthesis Example 24, and the preparation of the diazo component solution derived from the compound of the formula (D2) is the same as in step 4 of Synthesis Example 9. went.
- the diazo component solution was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (35 g) in the range of 0 to 10 ° C. to carry out a coupling reaction. After stirring for 20 minutes in the range of 0-10 ° C., the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
- a purple dye compound (13.0 g, yield 49.6%) represented by the following formula (F-1) was obtained.
- the structure of the purple dye compound was confirmed by LCMS analysis (m / z 524 (M +)).
- step 1 To a mixture of concentrated sulfuric acid (17 g) and 43% nitrosylsulfuric acid (14.7 g), 4-nitroaniline (6.91 g) represented by the following formula (D5) is added in the range of 30 to 35 ° C. at the same temperature. A diazo component solution was obtained by stirring with.
- step 2 Synthesis of orange dye compound (D-4) by coupling reaction (step 2)
- the coupler component solution composed of the compound of the formula (C18) was prepared in the same manner as in Step 1 of Synthesis Example 24.
- the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 1 hour while appropriately adding triethylamine (20 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
- the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
- An orange dye compound (12.5 g, yield 53.5%) represented by the following formula (D-4) was obtained.
- the structure of the orange dye compound was confirmed by LCMS analysis (m / z 467 (M +)).
- step 1 Preparation of diazo component solution (step 1) In a mixture of concentrated sulfuric acid (17 g) and 43% nitrosylsulfuric acid (14.7 g), 2,6-dibromo-4-nitroaniline (14.8 g) represented by the following formula (D6) was added in the range of 25 to 30 ° C. The diazo component solution was obtained by adding in 1 and stirring at the same temperature for 2 hours.
- step 2 Synthesis of orange dye compound (D-5) by coupling reaction (step 2)
- the coupler component solution composed of the compound of the formula (C18) was prepared in the same manner as in Step 1 of Synthesis Example 24.
- the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 1 hour while appropriately adding triethylamine (25 g) in the range of 0 to 10 ° C. to carry out a coupling reaction. After stirring for 20 minutes in the range of 0-10 ° C., the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
- the orange dye represented by the following formula (D-6) is the same as in steps 1 and 2 of Synthesis Example 31 except that the compound of the formula (C20) is used instead of the compound of the formula (C18) as the coupler component solution. A compound (22.8 g, yield 89.2%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 511 (M +)).
- diazo component solution 20 to 25 2-cyano-4-nitroaniline (8.15 g) represented by the following formula (D7) is added to a mixture of concentrated sulfuric acid (7.5 g), acetic acid (15 g) and 43% nitrosylsulfuric acid (14.9 g). The mixture was added in the range of ° C. and stirred at the same temperature for 2 hours to obtain a diazo component solution.
- red dye compound (D-7) by coupling reaction (step 2)
- the coupler component solution composed of the compound of the formula (C18) was prepared in the same manner as in Synthesis Example 24.
- the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 1 hour while appropriately adding triethylamine (30 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
- the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
- a red dye compound (16.9 g, yield 68.9%) represented by the following formula (D-7) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 492 (M +)).
- the preparation of the coupler component solution composed of the compound of the formula (C16) is the same as in step 1 of Synthesis Example 16, and the preparation of the diazo component solution derived from the compound of the formula (D1) is the same as in step 5 of Synthesis Example 1. went.
- the diazo component solution was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (32 g) in the range of 0 to 10 ° C. to carry out a coupling reaction. After stirring for 20 minutes in the range of 0-10 ° C., the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
- a purple dye compound (6.14 g, yield 21.8%) represented by the following formula (C-8) was obtained.
- the structure of the purple dye compound was confirmed by the following formula (C-8) by the LCMS analytical molecular weight (m / z 563 (M +)).
- the purple dye compound (12.1 g) represented by the following formula (C-9) is the same as in Synthesis Example 36 except that the compound of the formula (C9) is used instead of the compound of the formula (C16) as the coupler component solution.
- Got The structure of the purple dye compound was confirmed by LCMS analysis (m / z 731 (M +)).
- the product is filtered off from this reaction mixture, washed with water, dried at 60 ° C. until the water content is 1.0% by mass or less, and the purple dye compound (20.4 g) represented by the following formula (C-10). , Yield 64.2%).
- the structure of the purple dye compound was confirmed by LCMS analysis (m / z 678 (M +)).
- Step 1 2-Bromo-6-cyano-4-nitroaniline (11.1 g) represented by the following formula (D8) is added to a mixture of concentrated sulfuric acid (10.7 g) and acetic acid (28.8 g) within the range of 20 to 25 ° C. Added in. 43% Nitrosylsulfuric acid (15.6 g) was added to this mixture in the range of 20 to 25 ° C., and the mixture was stirred at the same temperature for 2 hours to obtain a diazo component solution.
- step 2 2-Bromo-6-cyano-4-nitroaniline (11.1 g) represented by the following formula (D8) is added to a mixture of concentrated sulfuric acid (10.7 g) and acetic acid (28.8 g) within the range of 20 to 25 ° C. Added in. 43% Nitrosylsulfuric acid (15.6 g) was added to this mixture in the range of 20 to 25 ° C., and the mixture was stirred at the same temperature for 2 hours to obtain a diazo component solution.
- step 2 Synthesis of purple dye compound (C-11) by coupling reaction (step 2)
- the coupler component solution composed of the compound of the formula (C9) was prepared in the same manner as in steps 1 to 3 of Synthesis Example 9.
- the diazo component solution obtained in step 1 was added dropwise to the coupler component solution over 2 hours while appropriately adding triethylamine (20 g) in the range of 0 to 10 ° C. to carry out a coupling reaction.
- the product is filtered off from this reaction mixture, washed with methanol and then water, and dried at 60 ° C. until the water content is 1.0% by mass or less.
- a purple dye compound (16.0 g, yield 45.0%) represented by the following formula (C-11) was obtained.
- the structure of the purple dye compound was confirmed by LCMS analysis (m / z 711 (M +)).
- the purple dye compound represented by the following formula (C-13) is obtained in the same manner as in Step 2 of Synthesis Example 39 except that the compound of the formula (C12) is used instead of the compound of the formula (C9) as the coupler component solution. 23.5 g, yield 75.0%) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 627 (M +)).
- the purple dye compound represented by the following formula (C-14) is obtained in the same manner as in Step 2 of Synthesis Example 39 except that the compound of the formula (C16) is used instead of the compound of the formula (C9) as the coupler component solution. 10.8 g, yield 39.8%) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 543 (M +)).
- the following formula (C-) is the same as in Synthesis Example 38 except that the purple dye compound (31.4 g) of the formula (C-13) is used instead of the purple dye compound of the formula (C-9) in Synthesis Example 38.
- a purple dye compound (26.9 g, yield 93.7%) represented by 15) was obtained.
- the structure of the purple dye compound was confirmed by LCMS analysis (m / z 574 (M +)).
- the yellow dye compound represented by the following formula (G-3) is the same as in Synthesis Example 28 except that 2-ethylhexanoyl chloride (19.5 g) is used instead of n-octanoyl chloride. (33.1 g, yield 87.3%) was obtained. The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 379 (M +)).
- the blue dye compound represented by the following formula (B-9) is used in the same manner as in Step 5 of Synthesis Example 9 except that the compound of the formula (C23) is used instead of the compound of the formula (C9) as the coupler component solution. 9.12 g, yield 33.0%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 553 (M +)).
- the orange dye compound represented by the following formula (D-8) is the same as in Synthesis Example 24 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (15.2 g, yield 82.8%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 367 (M +)).
- the orange dye compound represented by the following formula (D-9) is the same as in Synthesis Example 31 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (18.2 g, yield 80.0%) was obtained.
- the structure of the orange dye compound was confirmed by LCMS analysis (m / z 455 (M +)).
- the orange dye compound represented by the following formula (D-10) is the same as in Synthesis Example 30 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (9.35 g, yield 62.5%) was obtained.
- the structure of the orange dye compound was confirmed by LCMS analysis (m / z 299 (M +)).
- Step 2 The mixture of N-cyanoethylaniline (28.7 g), triethylamine (15 g), DMF (15 g) and 1-bromooctane (14.5 g) obtained in the above step was heated to 120 ° C. and 3 at the same temperature. By stirring for a time, N-cyanoethyl-N-octylaniline represented by the following formula (C25) was obtained. Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C25).
- red dye compound (C-17) by coupling reaction (step 2)
- the red dye compound (11.8 g, represented by the following formula (C-17)) is represented by the following formula (C-17) in the same manner as in Synthesis Example 17 except that the compound of the formula (C26) is used instead of the compound of the formula (C9) as the coupler compound. Yield 60.5%) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 390 (M +)).
- the purple dye compound represented by the following formula (F-2) is the same as in Synthesis Example 29 except that N, N-diethylaniline (7.45 g) is used instead of the compound of the formula (C18) as the coupler compound. (10.6 g, yield 59.6%) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 356 (M +)).
- the blue dye compound represented by the following formula (B-11) is the same as in steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C26) is used instead of the compound of the formula (C9) as the coupler compound. (11.9 g, yield 57.6%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 413 (M +)).
- Step 2 The mixture of N- (3-cyanoethylamino-4-methoxyphenyl) octaneamide (15.9 g), DMF (15 g) and diethyl sulfate (11.6 g) obtained in the above step was heated to 90 ° C. and the same. The mixture was stirred under warm temperature for 2 hours to obtain N- (3-N-ethyl-N-cyanoethylamino-4-methoxyphenyl) octaneamide represented by the following formula (C27). Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C27).
- Step 2 The blue dye represented by the following formula (A-11) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C29) is used instead of the compound of the formula (C1) as the coupler component solution. A compound (6.58 g, yield 20.2%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 653 (M +)).
- red dye compound (C-18) by coupling reaction (step 2)
- the red dye compound (20.1 g) represented by the following formula (C-18) is obtained in the same manner as in Synthesis Example 17 except that the compound of the formula (C34) is used instead of the compound of the formula (C9) as the coupler component solution. , Yield 80.1%) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 502 (M +)).
- the orange dye compound (16.4 g) represented by the following formula (D-13) is used in the same manner as in Synthesis Example 30 except that the compound of the formula (C35) is used instead of the compound of the formula (C18) as the coupler component solution. , Yield 79.8%) was obtained.
- the structure of the orange dye compound was confirmed by LCMS analysis (m / z 411 (M +)).
- the red dye represented by the following formula (C-20) is the same as in steps 1 and 2 of Synthesis Example 30 except that the compound of the formula (C12) is used instead of the compound of the formula (C18) as the coupler component solution.
- a compound (23.0 g, yield 87.7%) was obtained.
- the structure of the red dye compound was confirmed by LCMS analysis (m / z 524 (M +)).
- step 1 of Synthesis Example 1 valeryl chloride (25.3 g) is used instead of n-octanoyl chloride, and 1-bromohexane (33.0 g) is used instead of 1-bromooctane in step 4.
- N- [3- (N, N-dihexylamino) -4-methoxyphenyl] pentanamide represented by the following formula (C38) was obtained in the same manner as in Steps 1 to 4 of Synthesis Example 1 except for the above. Methanol (30 g) was added to this reaction mixture, and the mixture was cooled to 5 ° C. to obtain a coupler component solution composed of the compound of the formula (C38).
- Tables 3 to 9 show the structural formulas of the dye compounds described in the synthetic examples and the conventional dye compounds.
- the supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG.
- the dyeing equipment includes a liquid CO 2 cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high-pressure pump (5), a preheater (6), a pressure gauge (7 to 9), and magnetic. It is composed of a drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).
- the polypropylene cloth was cut and weighed to about 50 to 70 g, wound in the order of cotton cloth, polypropylene cloth, and cotton cloth on a stainless cylinder (21) having punch holes, and then loosely fixed with cotton thread.
- the inner cotton cloth is an undercloth and the outer cotton cloth is a cover cloth.
- a stainless steel cylinder around which the above-mentioned cloth sample (cotton cloth, polypropylene cloth, cotton cloth) is wound is fixed to a pressure-resistant stainless steel tank (22), and obtained in Synthesis Example 5 corresponding to 0.3% by mass with respect to the mass of the polypropylene cloth.
- the blue dye compound A-5 was wrapped in a paper wipe and placed in the fluid passage above the stainless steel cylinder.
- the volume of the pressure-resistant stainless steel tank was 2230 cm 3 . All valves in the dyeing apparatus were closed and heated to 120 ° C. by a preheater.
- the stop valves (14) and (16) were opened, and 1.13 kg of liquid carbon dioxide was flowed into the pressure-resistant stainless steel tank using a high-pressure pump via a cooling jacket. After that, the stop valves (14) and (16) were closed and circulated by the impeller and the magnetic drive unit at the lower part of the pressure-resistant stainless steel tank.
- the rotation speed of the magnetic drive unit is 750 rpm, and the circulation direction is from the inside to the outside of the cylinder.
- the polypropylene cloth was dyed by maintaining these temperature and pressure conditions for 60 minutes. After dyeing, the stop valve (18) was opened and the needle valve was gradually opened to release carbon dioxide in the pressure-resistant stainless steel tank, and the pressure in the pressure-resistant stainless steel tank was lowered from 25 MPa to atmospheric pressure. Circulation continued until the critical pressure of carbon dioxide (about 8 MPa) was reached. After that, the polypropylene dyed cloth in the pressure-resistant stainless steel tank was taken out.
- Dyeing Example P1 and Dyeing Example P1 except that the blue dye compound A-5 described in Dyeing Example 1 was changed to the dye compounds shown in Tables 3 to 9 or the disperse dye compound conventionally used for dyeing polyester fibers and the like. A polypropylene dyed cloth was obtained by the same dyeing procedure.
- the dye compounds used in Dyeing Examples P1 to P82 and Dyeing Examples P98 to P101 are shown in Tables 10 to 16.
- the dyeability was visually evaluated for the Total K / S value obtained by measuring the color of the dyed cloth and the dye residue after dyeing.
- the color of the dyed cloth was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), the dyed cloth was glued on white paper, and the observation light source D65 was used in a 2 degree field of view.
- the light fastness test was carried out by an ultraviolet carbon arc lamp method according to JIS L0842: 2004.
- the outline of the test method is as follows. Using an ultraviolet fade meter U48 (manufactured by Suga Test Instruments Co., Ltd.), the discoloration was determined after exposure to the dyed cloth for 20 hours under the condition of a black panel temperature of 63 ⁇ 3 ° C.
- Sublimation fastness test was carried out by a method according to JIS L0854: 2013. The outline of the test method is as follows. The dyed cloth was sandwiched between nylon cloths and held at 120 ⁇ 2 ° C. for 80 minutes under a load of 12.5 kPa, and then discoloration and fading and contamination of the nylon cloth were judged.
- the washing fastness test was carried out by a method according to JIS L0844: 2011 (A-2).
- the outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, and washed for 30 minutes under the condition of 50 ⁇ 2 ° C in the presence of soap to determine discoloration and contamination of the cotton and nylon parts of the multi-woven mixed woven cloth. rice field. In addition, the contamination of the residual liquid after washing was determined.
- Sweat fastness test The sweat fastness test was carried out by a method according to JIS L0848: 2004. The outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, soaked in acidic artificial sweat solution or alkaline artificial sweat for 30 minutes, held at 37 ⁇ 2 ° C. for 4 hours under a load of 12.5 kPa, and dried at 60 ° C. or lower. Discoloration and fading and contamination of the cotton and nylon parts of the multi-woven mixed woven fabric were determined.
- Friction fastness test was carried out by a method according to JIS L0849: 2013. The outline of the test method is as follows. Using the friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the dyed cloth is rubbed 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N. The coloration of the cotton cloth was judged.
- the fastness test for hot pressing was performed by a method according to JIS L0850: 2015 (A-2 drying). The outline of the test method is as follows. A dyed cloth was placed on the cotton cloth, and after holding for 15 seconds under a load of 4 ⁇ 1 kPa with a heating plate at 150 ° C., discoloration and fading and contamination of the cotton cloth were judged.
- Tables 17 and 18 show the evaluation results of the dyed examples of the compound of the formula (A).
- the stainability was good.
- X A is a nitro group
- Y A is a bromine atom
- Table 19 shows the evaluation results of the dyeing example of the compound of the formula (B).
- Tables 20 and 21 show the evaluation results of the dyeing examples of the compound of the formula (C).
- X C is a chlorine atom
- Y C is a hydrogen atom
- X C is a hydrogen atom
- Y C is a hydrogen atom
- C3 compounds of independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R C1, R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms) was good.
- Table 22 shows the evaluation results of the dyeing examples of the compound of the formula (D).
- Table 23 shows the evaluation results of the dyeing examples of the compound of the formula (E).
- the staining of the compounds of formula (E), R E used in Dyeing Example P62 or P63 is was good dyeability of a compound of the alkyl group having 4 to 18 carbon atoms.
- Table 24 shows the evaluation results of dyeing examples of the compound of the formula (F).
- Table 25 shows the evaluation results of the dyeing examples of the compound of the formula (G).
- the stainability of the compound of the formula (G) As for the stainability of the compound of the formula (G), the stainability of the compound having an alkyl group having RG of 7 to 18 carbon atoms used in Staining Examples P68 to P71 was good.
- Polypropylene fibers are dyed by the supercritical carbon dioxide dyeing method using the dye compounds shown in Tables 3 to 9 or the dyes obtained by mixing two or more kinds of the disperse dye compounds conventionally used for dyeing polyester fibers and the like. rice field.
- the dyeability evaluation, the light fastness test, the sublimation fastness test, the washing fastness test, the sweat fastness test, and the friction are the same as in the case of the polypropylene dyed cloth with one kind of dye compound described above.
- a fastness test and a fastness test against hot pressing were performed.
- the dyeability was visually evaluated for the Total K / S value, L * value, a * value, b * value and the dye residue after dyeing obtained by measuring the color of the dyed cloth.
- the color of the dyed cloth was measured by using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), gluing the dyed cloth on white paper, and using an observation light source D65 and a 2 degree field of view.
- the supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG.
- the dyeing equipment includes a liquid CO 2 cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high-pressure pump (5), a preheater (6), a pressure gauge (7 to 9), and magnetic. It is composed of a drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).
- the polyethylene cloth was cut and weighed to about 50 to 70 g, wound in the order of cotton cloth, polyethylene cloth, and cotton cloth on a stainless cylinder (21) having punch holes, and then loosely fixed with cotton thread.
- the inner cotton cloth is an undercloth and the outer cotton cloth is a cover cloth.
- a stainless steel cylinder around which the above-mentioned cloth sample (cotton cloth, polyethylene cloth, cotton cloth) is wound is fixed to a pressure-resistant stainless steel tank (22), and obtained in Synthesis Example 5 corresponding to 0.3% by mass with respect to the mass of the polyethylene cloth.
- the blue dye compound A-5 was wrapped in a paper wipe and placed in the fluid passage above the stainless steel cylinder.
- the volume of the pressure-resistant stainless steel tank was 2230 cm 3 . All valves in the dyeing apparatus were closed and heated to 98 ° C. by a preheater.
- the stop valves (14) and (16) were opened, and 1.13 kg of liquid carbon dioxide was flowed into the pressure-resistant stainless steel tank using a high-pressure pump via a cooling jacket. After that, the stop valves (14) and (16) were closed and circulated by the impeller and the magnetic drive unit at the lower part of the pressure-resistant stainless steel tank.
- the rotation speed of the magnetic drive unit is 750 rpm, and the circulation direction is from the inside to the outside of the cylinder.
- the polyethylene cloth was dyed by maintaining these temperature and pressure conditions for 60 minutes. After dyeing, the stop valve (18) was opened and the needle valve was gradually opened to release carbon dioxide in the pressure-resistant stainless steel tank, and the pressure in the pressure-resistant stainless steel tank was lowered from 25 MPa to atmospheric pressure. Circulation continued until the critical pressure of carbon dioxide (about 8 MPa) was reached. After that, the polyethylene dyed cloth in the pressure-resistant stainless steel tank was taken out.
- the polyethylene dyed cloths obtained in Dyeing Examples E1 to E14 and Dyeing Examples E18 to E20 were subjected to a dyeability evaluation, a light fastness test, a washing fastness test, a sweat fastness test and a friction fastness test.
- the dyeability was visually evaluated for the Total K / S value obtained by measuring the color of the dyed cloth and the dye residue after dyeing.
- the color of the dyed cloth was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), the dyed cloth was glued on white paper, and the observation light source D65 was used in a 2 degree field of view.
- the light fastness test was carried out by an ultraviolet carbon arc lamp method according to JIS L0842: 2004.
- the outline of the test method is as follows. Using an ultraviolet fade meter U48 (manufactured by Suga Test Instruments Co., Ltd.), the discoloration was determined after exposure to the dyed cloth for 20 hours under the condition of a black panel temperature of 63 ⁇ 3 ° C.
- washing fastness test was carried out by a method according to JIS L0844: 2011 (A-2).
- the outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, and washed for 30 minutes under the condition of 50 ⁇ 2 ° C in the presence of soap to determine discoloration and contamination of the cotton and nylon parts of the multi-woven mixed woven cloth. rice field. In addition, the contamination of the residual liquid after washing was determined.
- the sweat fastness test was carried out by a method according to JIS L0848: 2004.
- the outline of the test method is as follows. A multi-woven mixed woven cloth is attached to the dyed cloth, soaked in acidic artificial sweat solution or alkaline artificial sweat for 30 minutes, held at 37 ⁇ 2 ° C. for 4 hours under a load of 12.5 kPa, and dried at 60 ° C. or lower. Discoloration and fading and contamination of the cotton and nylon parts of the multi-woven mixed woven fabric were determined.
- Friction fastness test was carried out by a method according to JIS L0849: 2013. The outline of the test method is as follows. Using the friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the dyed cloth is rubbed 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N. The coloration of the cotton cloth was judged.
- Table 33 shows the evaluation results of dyeing examples of the compound of the formula (A).
- the staining of the compounds of (A), Dyeing Example E1 to E4, and Dyeing Example R A1 used in E18, R A2 and R A3 are each independently the number alkyl group or a C 1 to 14 carbon atoms and 1 or represents the alkyl group having 1 to 14 carbon atoms substituted by 4 alkoxy or CN (at least one provided that R A1, R A2 and R A3 is an alkyl group having 4 to 14 carbon atoms) dyeability compounds It was good.
- X A is a nitro group
- Y A is a bromine atom
- R A1 R number of carbon atoms of A2 and R A3 is larger compound.
- Table 34 shows the evaluation results of dyeing examples of the compound of the formula (B).
- Table 35 shows the evaluation results of the dyeing examples of the compound of the formula (C).
- Dyeing Example E5 to E7, and R C1, R C2 and R C3 used in Dyeing Example E20 each independently represents an alkyl group having 1 to 14 carbon atoms ( R C1, at least one of R C2 and R C3 are an alkyl group having 4 to 14 carbon atoms), or, each independently X C and Y C denotes a hydrogen atom and a halogen atom, R C1, R C2 and R C3 is was good dyeability independent compound represents an alkyl group having 1 to 14 carbon atoms and.
- X C is a chlorine atom
- Y C is a hydrogen atom
- R C1 was as good as R C1
- R C2 the number of carbon atoms in R C3 is greater compound.
- Table 36 shows the evaluation results of dyeing examples of the compound of the formula (D).
- R D1 used in Dyeing Example E8 to E12 represent an alkyl group having 1 to 14 carbon atoms
- R D2 is an alkyl group or CN of 1 to 14 carbon atoms
- the stainability of the compound was good.
- both X D and Y D are chlorine atoms, or both X D and Y D are bromine atoms, or both X D and Y D are hydrogen atoms.
- R D1 and R D2 with larger carbon numbers were better.
- Table 37 shows the evaluation results of dyeing examples of the compound of the formula (G).
- R G used in Dyeing Example E14 was good dyeability of a compound of the alkyl group having 7 to 18 carbon atoms.
- Polyethylene fibers are dyed by a supercritical carbon dioxide dyeing method using the dye compounds shown in Tables 3 to 9 or dyes using a mixture of two or more types of disperse dye compounds conventionally used for dyeing polyester fibers and the like. rice field.
- the obtained dyed cloth is subjected to dyeing property evaluation, light fastness test, washing fastness test, sweat fastness test and friction fastness test in the same manner as in the case of the polyethylene dyeing cloth with one kind of dye compound described above. went.
- Table 38 shows the evaluation results of dyeing using the dye.
- the dyeability was visually evaluated for the Total K / S value, L * value, a * value, b * value and the dye residue after dyeing obtained by measuring the color of the dyed cloth.
- the color of the dyed cloth was measured by using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), gluing the dyed cloth on white paper, and using an observation light source D65 and a 2 degree field of view.
- the dyeing examples E15, E16, and E18 obtained by mixing the orange dye, the red dye, the purple dye, and the blue dye of the present invention have good dyeability and fastness. It was a good black dyed cloth.
- the present invention is not limited to the above-described embodiment, and the present invention also includes those in which the configurations of the embodiments are appropriately combined or substituted.
- the present invention is a polyolefin fiber used for clothing such as clothing, underwear, hats, socks, gloves, sports clothing, vehicle interior materials such as seats, and interior products such as carpets, curtains, mats, sofa covers, and cushion covers. Can be used to stain.
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Abstract
Description
XAはニトロ基、
YAはハロゲン原子を表し、
RA1、RA2及びRA3はそれぞれ独立して炭素数1乃至14のアルキル基を表し(ただしRA1、RA2及びRA3の少なくともひとつは炭素数4乃至14のアルキル基である)、
RA4は炭素数1乃至4のアルキル基を表す。] [In formula (A),
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. ]
XC及びYCは、水素原子およびハロゲン原子、ハロゲン原子およびニトロ基、ハロゲン原子およびシアノ基、シアノ基およびシアノ基、ニトロ基およびシアノ基、水素原子および水素原子のいずれかの組合せを表し、
RC1、RC2及びRC3はそれぞれ独立して炭素数1乃至14のアルキル基を表す(ただしRC1、RC2及びRC3の少なくともひとつは炭素数4乃至14のアルキル基である)。] [In formula (C),
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). ]
RD1は、炭素数1乃至14のアルキル基を表し、
RD2は、炭素数1乃至14のアルキル基またはCNで置換された炭素数1乃至14のアルキル基を表す。ただし、RD1及びRD2の少なくともひとつは炭素数4乃至14のアルキル基である。] [In formula (D), X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
R D1 represents an alkyl group having 1 to 14 carbon atoms.
R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms. ]
また、本発明は、超臨界二酸化炭素を用いたポリオレフィン繊維の染色方法であって、
本発明の前記染料を用いて超臨界二酸化炭素存在下にポリオレフィン繊維を染色する工程を含む方法を提供する。 [In formula (G), RG represents an alkyl group having 7 to 18 carbon atoms. ]
Further, the present invention is a method for dyeing polyolefin fibers using supercritical carbon dioxide.
Provided is a method including a step of dyeing a polyolefin fiber in the presence of supercritical carbon dioxide using the dye of the present invention.
本発明の染料に含まれる一般式(A)~(G)の化合物は以下のとおりである。 <Compounds of general formulas (A) to (G)>
The compounds of the general formulas (A) to (G) contained in the dye of the present invention are as follows.
XAはニトロ基、
YAはハロゲン原子を表し、
RA1、RA2及びRA3はそれぞれ独立して炭素数1乃至14のアルキル基を表し(ただしRA1、RA2及びRA3の少なくともひとつは炭素数4乃至14のアルキル基である)、
RA4は炭素数1乃至4のアルキル基を表す。] [In formula (A),
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. ]
XC及びYCは、水素原子およびハロゲン原子、ハロゲン原子およびニトロ基、ハロゲン原子およびシアノ基、シアノ基およびシアノ基、ニトロ基およびシアノ基、水素原子および水素原子のいずれかの組合せを表し、
RC1、RC2及びRC3はそれぞれ独立して炭素数1乃至14のアルキル基を表す(ただしRC1、RC2及びRC3の少なくともひとつは炭素数4乃至14のアルキル基である)。] [In formula (C),
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). ]
RD1は、炭素数1乃至14のアルキル基を表し、
RD2は、炭素数1乃至14のアルキル基またはCNで置換された炭素数1乃至14のアルキル基を表す。
ただしRD1及びRD2の少なくともひとつは炭素数4乃至14のアルキル基である。] [In formula (D), X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group, respectively.
R D1 represents an alkyl group having 1 to 14 carbon atoms.
R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN.
However , at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms. ]
前記式(A)、式(C)、式(D)、式(E)中、ハロゲン原子とはフッ素原子、塩素原子、臭素原子、およびヨウ素原子であり、好適なものとしてはフッ素原子、塩素原子、臭素原子が挙げられる。 [In formula (G), RG represents an alkyl group having 7 to 18 carbon atoms. ]
In the formulas (A), (C), (D), and (E), 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.
XAはニトロ基、
YAはハロゲン原子を表し、
RA1、RA2及びRA3はそれぞれ独立して炭素数1乃至14のアルキル基を表し(ただしRA1、RA2及びRA3の少なくともひとつは炭素数4乃至14のアルキル基である)、
RA4は炭素数1乃至4のアルキル基を表す。 The compound of the general formula (A) is described in the formula (A).
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.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
YAは臭素原子が好ましい。 In the formula (A),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
Y A is a bromine atom.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
RA1、RA2及びRA3は、それぞれ独立して、炭素数4乃至14のアルキル基であるか、または、
RA1およびRA2が、それぞれ独立して炭素数4乃至14のアルキル基であり、RA3が炭素数1乃至4のアルキル基であるか、または
RA3が炭素数4乃至14のアルキル基であり、RA1およびRA2が、それぞれ独立して炭素数1乃至4のアルキル基であるのが好ましい。 In addition, in the above formula (A),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
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.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
YAは臭素原子であり、
RA1、RA2及びRA3は、それぞれ独立して、炭素数4乃至14のアルキル基であるか、または、
RA1およびRA2が、それぞれ独立して炭素数4乃至14のアルキル基であり、RA3が炭素数1乃至4のアルキル基であるか、または
RA3が炭素数4乃至14のアルキル基であり、RA1およびRA2が、それぞれ独立して炭素数1乃至4のアルキル基であるのが好ましい。 In addition, in the above formula (A),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
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.
RB1、RB2及びRB3はそれぞれ独立して炭素数1乃至14のアルキル基を表す。ただしRB1、RB2及びRB3の少なくともひとつは炭素数4乃至14のアルキル基である。 The compound of the general formula (B) is described in the formula (B).
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
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
RB1、RB2及びRB3は、それぞれ独立して、炭素数4乃至14のアルキル基であるか、RB1およびRB2が、それぞれ独立して炭素数4乃至14のアルキル基であり、RB3が炭素数1乃至4のアルキル基であるか、または
RB3が炭素数4乃至14のアルキル基であり、RB1およびRB2が、それぞれ独立して炭素数1乃至4のアルキル基であるのが好ましい。 In the formula (B),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
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.
XC及びYCは、水素原子およびハロゲン原子、ハロゲン原子およびニトロ基、ハロゲン原子およびシアノ基、シアノ基およびシアノ基、ニトロ基およびシアノ基、水素原子および水素原子のいずれかの組合せを表し、
RC1、RC2及びRC3はそれぞれ独立して炭素数1乃至14のアルキル基を表す(ただしRC1、RC2及びRC3の少なくともひとつは炭素数4乃至14のアルキル基である)。 The compound of the general formula (C) is described in the formula (C).
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).
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
XC及びYCは、水素原子および塩素原子、臭素原子およびニトロ基、臭素原子およびシアノ基、シアノ基およびシアノ基、ニトロ基およびシアノ基、水素原子および水素原子のいずれかの組合せを表すのが好ましい。 In the formula (C),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
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.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
XC及びYCは、水素原子およびハロゲン原子、ハロゲン原子およびニトロ基、ハロゲン原子およびシアノ基、シアノ基およびシアノ基、ニトロ基およびシアノ基、水素原子および水素原子のいずれかの組合せを表し、
RC1、RC2及びRC3は、それぞれ独立して、炭素数4乃至14のアルキル基であるか、または、
RC1およびRC2が、それぞれ独立して炭素数4乃至14のアルキル基であり、RC3が炭素数1乃至4のアルキル基であるか、または
RC3が炭素数4乃至14のアルキル基であり、RC1およびRC2が、それぞれ独立して炭素数1乃至4のアルキル基であるのが好ましい。 In the formula (C),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
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.
RD1は、炭素数1乃至14のアルキル基を表し、
RD2は、炭素数1乃至14のアルキル基またはCNで置換された炭素数1乃至14のアルキル基を表す。ただし、RD1及びRD2の少なくともひとつは炭素数4乃至14のアルキル基である。 In the compound of the general formula (D), X D and Y D independently represent a hydrogen atom, a halogen atom, or a cyano group in the formula (D), respectively.
R D1 represents an alkyl group having 1 to 14 carbon atoms.
R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
XDは、水素原子、塩素原子または臭素原子を表し、
YDは、水素原子、塩素原子、臭素原子、またはシアノ基を表すのが好ましい。 In the formula (D),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
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.
RD1は、炭素数4乃至14のアルキル基を表し、
RD2は、炭素数4乃至14のアルキル基またはCNで置換された炭素数1乃至14のアルキル基を表すのが好ましい。 Further, in the above formula (D), 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.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
XE及びYEは、塩素原子を表すのが好ましい。 In the formula (E),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
X E and Y E preferably represent a chlorine atom.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
REは炭素数4乃至12のアルキル基が好ましい。 In the formula (E),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
R E is preferably an alkyl group having 4 to 12 carbon atoms.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
XE及びYEは、塩素原子を表し、
REは炭素数4乃至12のアルキル基が好ましい。 In the formula (E),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
X E and Y E represent chlorine atoms
R E is preferably an alkyl group having 4 to 12 carbon atoms.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
RF1及びRF2はそれぞれ独立して炭素数4乃至12のアルキル基を表すのが好ましい。 In the formula (F),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
It is preferable that R F1 and R F2 each independently represent an alkyl group having 4 to 12 carbon atoms.
染色濃度、耐光堅牢度、昇華堅牢度等の観点から、
RGは炭素数11~18のアルキル基が好ましい。 In the formula (G),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
The RG is preferably an alkyl group having 11 to 18 carbon atoms.
前記式(A)で表される化合物の製造方法について説明する。 <Method for producing the compound of the general formula (A)>
A method for producing the compound represented by the formula (A) will be described.
まず、式(a-D)の化合物を、鉱酸又は有機カルボン酸中において、場合により追加させた水の存在下でニトロソ化剤又はニトロシル硫酸を使用してジアゾ化してジアゾ化合物を得る。使用する有機カルボン酸としては、例えば酢酸及びプロピオン酸が挙げられる。また鉱酸としては例えば塩酸、リン酸及び硫酸、好ましくは硫酸が挙げられる。使用するニトロソ化剤としては、アルカリ金属の亜硝酸塩、例えば、固体状態若しくは水溶液状態の亜硝酸ナトリウムである。 (I) Diazotization of compound of formula (a-D) First, 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. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Examples of 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.
式(a-C)で表される化合物のアルコール(例えば、メタノール)の溶液又は懸濁液に、前記式(a-D)のジアゾ化合物の溶液を、例えば、-5乃至10℃の温度範囲で添加して、前記式(A)で表される化合物を得る。 Coupling with the compound of the formula (a-C) (ii) The diazo of the formula (a-D) is added to a solution or suspension of an alcohol (for example, methanol) of the compound represented by the formula (a-C). A solution of the compound is added, for example, in the temperature range of −5 to 10 ° C. to obtain the compound represented by the above formula (A).
原料である式(a-C)の化合物は、以下のようにして製造することができる。 (Iii) Method for Producing Compound of Formula (a-C) The compound of formula (a-C) which is a raw material can be produced as follows.
前記式(B)で表される化合物の製造方法について説明する。 <Method for producing the compound of general formula (B)>
A method for producing the compound represented by the formula (B) will be described.
まず、式(b-D)の化合物を、鉱酸又は有機カルボン酸中において、場合により追加させた水の存在下でニトロソ化剤又はニトロシル硫酸を使用してジアゾ化してジアゾ化合物を得る。使用する有機カルボン酸としては、例えば酢酸及びプロピオン酸が挙げられる。また鉱酸としては例えば塩酸、リン酸及び硫酸、好ましくは硫酸が挙げられる。使用するニトロソ化剤としては、アルカリ金属の亜硝酸塩、例えば、固体状態若しくは水溶液状態の亜硝酸ナトリウムである。 (I) Diazotization of compound of formula (b-D) First, 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. Diazotization with sulfuric acid to give the diazo compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Examples of 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.
式(b-C)で表される化合物のアルコール(例えばメタノール)の溶液又は懸濁液に、前記式(b-D)のジアゾ化合物の溶液を、例えば-5乃至10℃の温度範囲で添加して、前記式(B)で表される化合物を得る。 Coupling with the compound of the formula (bC) (ii) The diazo compound of the formula (bD) is added to a solution or suspension of an alcohol (for example, methanol) of the compound represented by the formula (bC). Is added in a temperature range of, for example, −5 to 10 ° C. to obtain a compound represented by the above formula (B).
原料である式(b-C)の化合物は、以下のようにして製造することができる。 (Iii) Method for Producing Compound of Formula (bC) The compound of formula (bC) which is a raw material can be produced as follows.
前記式(C)で表される化合物の製造方法について説明する。 <Method for producing compound of general formula (C)>
A method for producing the compound represented by the formula (C) will be described.
まず、式(c-D)で表される化合物を、鉱酸又は有機カルボン酸中において、場合により追加させた水の存在下でニトロソ化剤又はニトロシル硫酸を使用してジアゾ化してジアゾ化合物を得る。使用する有機カルボン酸としては、例えば酢酸及びプロピオン酸が挙げられる。また鉱酸としては例えば塩酸、リン酸及び硫酸、好ましくは硫酸が挙げられる。使用するニトロソ化剤としては、アルカリ金属の亜硝酸塩、例えば、固体状態若しくは水溶液状態の亜硝酸ナトリウムである。 (I) Diazotization of the compound of the formula (cd) First, 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. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Examples of 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.
式(c-C)で表される化合物のアルコール(例えばメタノール)の溶液又は懸濁液に、前記式(c-D)のジアゾ化合物の溶液を、例えば-5乃至10℃の温度範囲で添加して、前記式(C)で表される化合物を得る。 Coupling with the compound of the formula (cc) (ii) The diazo compound of the formula (cc) is added to a solution or suspension of an alcohol (for example, methanol) of the compound represented by the formula (cc). Is added in a temperature range of, for example, −5 to 10 ° C. to obtain a compound represented by the above formula (C).
原料である式(c-C)の化合物は、以下のようにして製造することができる。 (Iii) Method for Producing Compound of Formula (CC) The compound of formula (cc) which is a raw material can be produced as follows.
前記式(D)で表される化合物の製造方法について説明する。 <Method for producing the compound of general formula (D)>
A method for producing the compound represented by the formula (D) will be described.
まず、式(d-D)で表される化合物を、鉱酸又は有機カルボン酸中において、場合により追加させた水の存在下でニトロソ化剤又はニトロシル硫酸を使用してジアゾ化してジアゾ化合物を得る。使用する有機カルボン酸としては、例えば酢酸及びプロピオン酸が挙げられる。また鉱酸としては例えば塩酸、リン酸及び硫酸、好ましくは硫酸が挙げられる。使用するニトロソ化剤としては、アルカリ金属の亜硝酸塩、例えば、固体状態若しくは水溶液状態の亜硝酸ナトリウムである。 (I) Diazotization of the compound of the formula (d-D) First, 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. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Examples of 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.
式(d-C)で表される化合物のアルコール(例えばメタノール)の溶液又は懸濁液に、前記式(d-D)のジアゾ化合物の溶液を、例えば-5乃至10℃の温度範囲で添加して、前記式(D)で表される化合物を得る。 Coupling with the compound of the formula (dD) (ii) The diazo compound of the formula (dD) is added to a solution or suspension of an alcohol (for example, methanol) of the compound represented by the formula (dc). Is added in a temperature range of, for example, −5 to 10 ° C. to obtain a compound represented by the above formula (D).
原料である式(d-C)の化合物は、以下のようにして製造することができる。 (Iii) Method for Producing Compound of Formula (dc) The compound of formula (dc) which is a raw material can be produced as follows.
前記式(E)で表される化合物の製造方法について説明する。 <Method for producing compound of general formula (E)>
A method for producing the compound represented by the formula (E) will be described.
まず、式(e-D)で表される化合物を、鉱酸又は有機カルボン酸中において、場合により追加させた水の存在下でニトロソ化剤又はニトロシル硫酸を使用してジアゾ化してジアゾ化合物を得る。使用する有機カルボン酸としては、例えば酢酸及びプロピオン酸が挙げられる。また鉱酸としては例えば塩酸、リン酸及び硫酸、好ましくは硫酸が挙げられる。使用するニトロソ化剤としては、アルカリ金属の亜硝酸塩、例えば、固体状態若しくは水溶液状態の亜硝酸ナトリウムである。 (I) Diazotization of the compound of the formula (ed) First, 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. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Examples of 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.
式(e-C)で表される化合物のアルコール(例えばメタノール)の溶液又は懸濁液に、前記式(e-D)のジアゾ化合物の溶液を、例えば-5乃至10℃の温度範囲で添加して、前記式(E)で表される化合物を得る。 Coupling with the compound of the formula (eC) (ii) The diazo compound of the formula (ed) is added to a solution or suspension of an alcohol (for example, methanol) of the compound represented by the formula (eC). Is added in a temperature range of, for example, −5 to 10 ° C. to obtain a compound represented by the above formula (E).
原料である式(e-C)の化合物は、以下のようにして製造することができる。 (Iii) Method for Producing Compound of Formula (eC) The compound of formula (eC) which is a raw material can be produced as follows.
前記式(F)で表される化合物の製造方法について説明する。 <Method for producing the compound of general formula (F)>
A method for producing the compound represented by the formula (F) will be described.
まず、式(f-D)で表される化合物を、鉱酸又は有機カルボン酸中において、場合により追加させた水の存在下でニトロソ化剤又はニトロシル硫酸を使用してジアゾ化してジアゾ化合物を得る。使用する有機カルボン酸としては、例えば酢酸及びプロピオン酸が挙げられる。また鉱酸としては例えば塩酸、リン酸及び硫酸、好ましくは硫酸が挙げられる。使用するニトロソ化剤としては、アルカリ金属の亜硝酸塩、例えば、固体状態若しくは水溶液状態の亜硝酸ナトリウムである。 (I) Diazotization of the compound of the formula (fD) First, 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. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Examples of 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.
式(f-C)で表される化合物のアルコール(例えばメタノール)の溶液又は懸濁液に、前記式(f-D)のジアゾ化合物の溶液を、例えば-5乃至10℃の温度範囲で添加して、前記式(F)で表される化合物を得る。 Coupling with the compound of the formula (fc) (iii) 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).
原料である式(f-C)の化合物は、以下のようにして製造することがでいる。 (Iii) Method for Producing Compound of Formula (fc) The compound of formula (fc) which is a raw material can be produced as follows.
前記式(G)で表される化合物の製造方法について説明する。 <Method for producing compound of general formula (G)>
A method for producing the compound represented by the formula (G) will be described.
本発明のポリオレフィン繊維を染色するための染料に含まれる、一般式(A)~(G)の化合物は、青色、紫色、赤色、橙色、または黄色を有する。前記染料は、一般式(A)~(G)の化合物を単独または2つ以上を含んでもよい。前記染料が一般式(A)~(G)の化合物を2つ以上含む場合、様々な色相または黒色にポリオレフィン繊維を染色するための染料を得ることができる。 <Dye for dyeing polyolefin fibers using supercritical carbon dioxide>
The compounds of the general formulas (A) to (G) contained in the dye for dyeing the polyolefin fiber of the present invention have blue, purple, red, orange, or yellow. The dye may contain the compounds of the general formulas (A) to (G) alone or in combination of two or more. When the dye contains two or more compounds of the general formulas (A) to (G), a dye for dyeing the polyolefin fiber in various hues or black can be obtained.
本発明は、超臨界二酸化炭素を用いたポリオレフィン繊維の染色方法であって、前記本発明の染料を用いて超臨界二酸化炭素存在下にポリオレフィン繊維を染色する工程を含む方法である。前記方法において、染色媒体として超臨界二酸化炭素を用いる。 <Dyeing method for polyolefin fibers using supercritical carbon dioxide>
The present invention is a method for dyeing a polyolefin fiber using supercritical carbon dioxide, which comprises a step of dyeing the polyolefin fiber in the presence of supercritical carbon dioxide using the dye of the present invention. In the above method, supercritical carbon dioxide is used as the dyeing medium.
(合成例1)
[青色染料化合物(A-1)の合成]
青色染料化合物(A-1)は、下記スキームに従って製造した。 [Example]
(Synthesis Example 1)
[Synthesis of blue dye compound (A-1)]
The blue dye compound (A-1) was produced according to the following scheme.
(工程1)
p-アニシジン(市販品として購入)(24.6g)をDMF(35g)に溶解させ、ピリジン(19g)を滴下した。n-オクタノイルクロリド(市販品として購入)(34.2g)を滴下後、110℃に加熱して、1時間撹拌した。室温に冷却後、2M塩酸(150ml)を加えて沈殿を析出させた。この混合物を濾別し、水洗、乾燥して下記式(C1a)で示されるN-(4-メトキシフェニル)オクタンアミド(53.1g、収率106.5%)を粗生成物として得た。 1-A. Synthesis of coupler compound (C1) and preparation of coupler component solution (step 1)
P-anisidine (purchased as a commercial product) (24.6 g) was dissolved in DMF (35 g), and pyridine (19 g) was added dropwise. After dropping n-octanoyl chloride (purchased as a commercial product) (34.2 g), the mixture was heated to 110 ° C. and stirred for 1 hour. After cooling to room temperature, 2M hydrochloric acid (150 ml) was added to precipitate a precipitate. This mixture was filtered off, washed with water and dried to obtain N- (4-methoxyphenyl) octaneamide (53.1 g, yield 106.5%) represented by the following formula (C1a) as a crude product.
5℃に冷却した濃硫酸(30g)に、前記工程1で得られたN-(4-メトキシフェニル)オクタンアミド(12.5g)を5乃至10℃の範囲で徐々に加えた。この混合物に濃硝酸(4.57g)を5乃至10℃の範囲で1時間かけて滴下した後、同温下で1時間撹拌した。この反応混合物を氷水(150g)中にパージし、酢酸エチル(100g)を加えて有機相を抽出した。この抽出物を飽和食塩水で洗浄した後、溶媒を減圧留去することにより下記式(C1b)で示されるN-(3-ニトロ-4-メトキシフェニル)オクタンアミド(16.9g、収率114.8%)を粗生成物として得た。 (Step 2)
The N- (4-methoxyphenyl) octaneamide (12.5 g) obtained in the
前記工程2で得られたN-(3-ニトロ-4-メトキシフェニル)オクタンアミド(16.9g)とスズ(8.9g)とメタノール(7.5g)の混合物を5℃に冷却した。この混合物に濃塩酸(31.4g)を1時間かけて滴下した後、75乃至80℃に昇温し、40分間撹拌した。反応混合物を10℃まで冷却した後、48%水酸化ナトリウム水溶液(55.2ml)を10乃至20℃の範囲で徐々に加えた。この混合物を濾別し、水洗、乾燥して下記式(C1c)で示されるN-(3-アミノ-4-メトキシフェニル)オクタンアミド(9.19g、収率69.5%)を得た。 (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).
前記工程3で得られたN-(3-アミノ-4-メトキシフェニル)オクタンアミド(13.2g)とトリエチルアミン(15g)とDMF(15g)と1-ブロモオクタン(市販品として購入)(38.6g)の混合物を120℃に昇温し、同温下で3時間撹拌することにより下記式(C1)で示されるN-[3-(N,N-ジオクチルアミノ)-4-メトキシフェニル]オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C1)の化合物からなるカップラー成分溶液を得た。 (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).
(工程5)
濃硫酸(16g)と43%ニトロシル硫酸(12.8g)の混合物に、下記式(D1)で示される2-ブロモ-4,6-ジニトロアニリン(13.1g)を25乃至30℃の範囲内でゆっくりと加えた。この混合物を30乃至40℃で2時間撹拌することでジアゾ成分溶液を得た。 1-B. 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.
(工程6)
前記工程5で得られたジアゾ成分溶液を、前記工程4で得られた前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(84g)を適宜加えながら2時間かけて滴下し、カップリング反応を行った。この混合物を0乃至10℃の範囲内で30分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(A-1)で示される青色染料化合物(5.93g、収率15.5%)を得た。前記青色染色化合物は、LCMS分析(m/z 761(M+))により、その構造を確認した。 1-C. Synthesis of blue dye compound (A-1) by coupling reaction (step 6)
The diazo component solution obtained in
[青色染料化合物(A-2)の合成]
青色染料化合物(A-2)は、下記スキームに従って、製造した。 (Synthesis Example 2)
[Synthesis of blue dye compound (A-2)]
The blue dye compound (A-2) was produced according to the following scheme.
(工程1)
合成例1の工程1において、n-オクタノイルクロリドの代わりにバレリルクロリド(25.3g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C2)で示されるN-[3-(N,N-ジオクチルアミノ)-4-メトキシフェニル]ペンタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C2)の化合物からなるカップラー成分溶液を得た。 2-A. Synthesis of coupler compound (C2) and preparation of coupler component solution (step 1)
It is represented by the following formula (C2) in the same manner as in
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C2)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-2)で示される青色染料化合物(8.03g、収率22.3%)を得た。この青色染色化合物は、LCMS分析(m/z 719(M+))により、その構造を確認した。 2-B. Synthesis of blue dye compound (A-2) by coupling reaction (step 2)
The following formula (A-2) is the same as in
[青色染料化合物(A-3)の合成]
青色染料化合物(A-3)は、下記スキームに従って、製造した。 (Synthesis Example 3)
[Synthesis of blue dye compound (A-3)]
The blue dye compound (A-3) was produced according to the following scheme.
(工程1)
合成例1の工程1において、n-オクタノイルクロリドの代わりにプロピオニルクロリド(19.4g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C3)で示されるN-[3-(N,N-ジオクチルアミノ)-4-メトキシフェニル]プロパンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C3)の化合物からなるカップラー成分溶液を得た。 3-A. Synthesis of coupler compound (C3) and preparation of coupler component solution (step 1)
N represented by the following formula (C3) in the same manner as in
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C3)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-3)で示される青色染料化合物(5.85g、収率16.9%)を得た。前記青色染料化合物は、LCMS分析(m/z 691(M+))により、その構造を確認した。 3-B. Synthesis of blue dye compound (A-3) by coupling reaction (step 2)
The following formula (A-3) is the same as in
[青色染料化合物(A-4)の合成]
青色染料化合物(A-4)は、下記スキームに従って、製造した。 (Synthesis Example 4)
[Synthesis of blue dye compound (A-4)]
The blue dye compound (A-4) was produced according to the following scheme.
(工程1)
合成例1の工程1において、n-オクタノイルクロリドの代わりに2-エチルヘキサノイルクロリド(34.2g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C4)で示されるN-[3-(N,N-ジオクチルアミノ)-4-メトキシフェニル]-2-エチルヘキサンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C4)の化合物からなるカップラー成分溶液を得た。 4-A. Synthesis of coupler compound C4 and preparation of coupler component solution (step 1)
The following formula (C4) is the same as in
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C4)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-4)で示される青色染料化合物(9.63g、収率25.3%)を得た。前記青色染料化合物は、LCMS分析(m/z 761(M+))により、その構造を確認した。 4-B. Synthesis of blue dye compound (A-4) by coupling reaction (step 2)
The following formula (A-4) is the same as in
[青色染料化合物(A-5)の合成]
青色染料化合物(A-5)は、下記スキームに従って、製造した。 (Synthesis Example 5)
[Synthesis of blue dye compound (A-5)]
The blue dye compound (A-5) was produced according to the following scheme.
(工程1)
合成例1の工程4において、N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにN-(3-アミノ-4-メトキシフェニル)アセトアミド(市販品として購入)(9.0g)を用いること以外は合成例1の工程4と同様にして、下記式(C5)で示されるN-[3-(N,N-ジオクチルアミノ)-4-メトキシフェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C5)の化合物からなるカップラー成分溶液を得た。 5-A. Synthesis of coupler compound C5 and preparation of coupler component solution (step 1)
In 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).
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C5)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-5)で示される青色染料化合物(20.3g、収率60.0%)を得た。前記青色染料化合物は、LCMS分析(m/z 677(M+))により、その構造を確認した。 5-B. Synthesis of blue dye compound (A-5) by coupling reaction (step 2)
The following formula (A-5) is the same as in
[青色染料化合物(A-6)の合成]
青色染料化合物(A-6)は、下記スキームに従って、製造した。 (Synthesis Example 6)
[Synthesis of blue dye compound (A-6)]
The blue dye compound (A-6) was produced according to the following scheme.
(工程1)
合成例1の工程4において、1-ブロモオクタンの代わりに1-ブロモドデカン(49.8g)を用いること、N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにN-(3-アミノ-4-メトキシフェニル)アセトアミド(9.0g)を用いること以外は合成例1の工程4と同様にして、下記式(C6)で示されるN-[3-(N,N-ジドデシルアミノ)-4-メトキシフェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C6)の化合物からなるカップラー成分溶液を得た。 6-A. Synthesis of coupler compound (C6) and preparation of coupler component solution (step 1)
In step 4 of Synthesis Example 1, 1-bromododecane (49.8 g) is used instead of 1-bromooctane, and N- (3- (3-amino-4-methoxyphenyl) octaneamide is used instead of N- (3-amino-4-methoxyphenyl) octaneamide. N- [3- (N, N-didodecylamino) represented by the following formula (C6) in the same manner as in step 4 of Synthesis Example 1 except that amino-4-methoxyphenyl) acetamide (9.0 g) is used. ) -4-Methoxyphenyl] acetamide 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 (C6).
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C6)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-6)で示される青色染料化合物(19.3g、収率48.9%)を得た。前記青色染料化合物は、LCMS分析(m/z 789(M+))により、その構造を確認した。 6-B. Synthesis of blue dye compound (A-6) by coupling reaction (step 2)
The following formula (A-6) is the same as in
[青色染料化合物(A-7)の合成]
青色染料化合物(A-7)は、下記スキームに従って、製造した。 (Synthesis Example 7)
[Synthesis of blue dye compound (A-7)]
The blue dye compound (A-7) was produced according to the following scheme.
(工程1)
合成例1の工程4において、1-ブロモオクタンの代わりに1-ブロモエタン(27.3g)を用いること以外は合成例1の工程4と同様にして、下記式(C7)で示されるN-[3-(N,N-ジエチルアミノ)-4-メトキシフェニル]オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C7)の化合物からなるカップラー成分溶液を得た。 7-A. Synthesis of coupler compound C7 and preparation of coupler component solution (step 1)
N— [ 3- (N, N-diethylamino) -4-methoxyphenyl] octaneamide 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 (C7).
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C7)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-7)で示される青色染料化合物(7.71g、収率26.0%)を得た。前記青色染料化合物は、LCMS分析(m/z 593(M+))により、その構造を確認した。 7-B. Synthesis of blue dye compound (A-7) by coupling reaction (step 2)
The following formula (A-7) is the same as in
[青色染料化合物(A-8)の合成]
青色染料化合物(A-8)は、下記スキームに従って、製造した。 (Synthesis Example 8)
[Synthesis of blue dye compound (A-8)]
The blue dye compound (A-8) was produced according to the following scheme.
(工程1)
合成例1の工程1において、p-アニシジンの代わりに4-エトキシアニリン(27.4g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C8)で示されるN-[3-(N,N-ジオクチルアミノ)-4-エトキシフェニル]オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C8)の化合物からなるカップラー成分溶液を得た。 8-A. Synthesis of coupler compound C8 and preparation of coupler component solution (step 1)
N represented by the following formula (C8) in the same manner as in
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C8)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-8)で示される青色染料化合物(4.50g、収率11.6%)を得た。前記青色染料化合物は、LCMS分析(m/z 775(M+))により、その構造を確認した。 8-B. Synthesis of blue dye compound (A-8) by coupling reaction (step 2)
The following formula (A-8) is the same as in
[青色染料化合物(B-1)の合成]
青色染料化合物(B-1)は、下記スキームに従って、製造した。 (Synthesis Example 9)
[Synthesis of blue dye compound (B-1)]
The blue dye compound (B-1) was produced according to the following scheme.
(工程1)
p-アニシジンの代わりに3-ニトロアニリン(27.6g)を用いること以外は合成例1の工程1と同様にして、下記式(C9a)で示されるN-(3-ニトロフェニル)オクタンアミド(53.6g、収率101.4%)を粗生成物として得た。 9-A. Synthesis of coupler compound C9 and preparation of coupler component solution (step 1)
N- (3-nitrophenyl) octaneamide represented by the following formula (C9a) in the same manner as in
N-(3-ニトロ-4-メトキシフェニル)オクタンアミドの代わりにN-(3-ニトロフェニル)オクタンアミド(13.2g)を用いること以外は合成例1の工程3と同様にして、下記式(C9b)で示されるN-(3-アミノフェニル)オクタンアミド(9.48g、収率80.9%)を得た。 (Step 2)
The following formula is used in the same manner as in
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにN-(3-アミノフェニル)オクタンアミド(11.7g)を用いること以外は合成例1の工程4と同様にして、下記式(C9)で示されるN-[3-(N,N-ジオクチルアミノ)フェニル]オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C9)の化合物からなるカップラー成分溶液を得た。 (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. The 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).
(工程4)
濃硫酸(29g)と43%ニトロシル硫酸(12.7g)の混合物に、下記式(D2)で示される3-アミノ-5-ニトロ-2,1-ベンゾイソチアゾール(8.15g)を0乃至5℃の範囲内でゆっくりと加えた。この混合物に80%酢酸(10g)を0乃至5℃の範囲内でゆっくりと滴下した後、同温下で2時間撹拌することでジアゾ成分溶液を得た。 9-B. Preparation of diazo component solution (step 4)
0 to 0 to 3-amino-5-nitro-2,1-benzoisothiazole (8.15 g) represented by the following formula (D2) is added to a mixture of concentrated sulfuric acid (29 g) and 43% nitrosylsulfuric acid (12.7 g). It was added slowly within the range of 5 ° C. 80% acetic acid (10 g) was slowly added dropwise to this mixture in the range of 0 to 5 ° C., and then the mixture was stirred at the same temperature for 2 hours to obtain a diazo component solution.
(工程5)
前記ジアゾ成分溶液(D2)を前記カップラー成分溶液(C9)に、0乃至10℃の範囲内でトリエチルアミン(43g)を適宜加えながら2時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(B-1)で示される青色染料化合物(20.9g、収率62.9%)を得た。前記青色染料化合物は、LCMS分析(m/z 665(M+))により、その構造を確認した。 9-C. Synthesis of blue dye compound (B-1) by coupling reaction (step 5)
The diazo component solution (D2) was added dropwise to the coupler component solution (C9) over 2 hours while appropriately adding triethylamine (43 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 blue dye compound (20.9 g, yield 62.9%) represented by the following formula (B-1) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 665 (M +)).
[青色染料化合物(B-2)の合成]
青色染料化合物(B-2)は、下記スキームに従って、製造した。 (Synthesis Example 10)
[Synthesis of blue dye compound (B-2)]
The blue dye compound (B-2) was produced according to the following scheme.
(工程1)
合成例9の工程1において、n-オクタノイルクロリドの代わりにバレリルクロリド(25.3g)を用いること以外は合成例9の工程1乃至3と同様にして、下記式(C10)で示されるN-[3-(N,N-ジオクチルアミノ)フェニル]ペンタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C10)の化合物からなるカップラー成分溶液を得た。 10-A. Synthesis of coupler compound C10 and preparation of coupler component solution (step 1)
It is represented by the following formula (C10) in the same manner as in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに工程1で得られた式(C10)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-2)で示される青色染料化合物(9.47g、収率30.4%)を得た。前記青色染料化合物は、LCMS分析(m/z 623(M+))により、その構造を確認した。 10-B. Synthesis of blue dye compound (B-2) by coupling reaction (step 2)
The following formula (B-2) is the same as in
[青色染料化合物(B-3)の合成]
青色染料化合物(B-3)は、下記スキームに従って、製造した。 (Synthesis Example 11)
[Synthesis of blue dye compound (B-3)]
The blue dye compound (B-3) was produced according to the following scheme.
(工程1)
合成例9の工程1において、n-オクタノイルクロリドの代わりにプロピオニルクロリド(19.4g)を用いること以外は合成例9の工程1乃至3と同様にして、下記式(C11)で示されるN-[3-(N,N-ジオクチルアミノ)フェニル]プロパンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C11)の化合物からなるカップラー成分溶液を得た。 11-A. Synthesis of coupler compound C11 and preparation of coupler component solution (step 1)
N represented by the following formula (C11) in the same manner as in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに工程1で得られた式(C11)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-3)で示される青色染料化合物(13.4g、収率45.0%)を得た。前記青色染料化合物は、LCMS分析(m/z 595(M+))により、その構造を確認した。 11-B. Synthesis of blue dye compound (B-3) by coupling reaction (step 2)
The following formula (B-3) is the same as in
[青色染料化合物(B-4)の合成]
青色染料化合物(B-4)は、下記スキームに従って、製造した。 (Synthesis Example 12)
[Synthesis of blue dye compound (B-4)]
The blue dye compound (B-4) was produced according to the following scheme.
(工程1)
合成例9の工程3において、N-(3-アミノフェニル)オクタンアミドの代わりに3’-アミノアセトアニリド(7.50g)を用いること以外は合成例9の工程3と同様にして、下記式(C12)で示されるN-[3-(N,N-ジオクチルアミノ)フェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C12)の化合物からなるカップラー成分溶液を得た。 12-A. Synthesis of coupler compound C12 and preparation of coupler component solution (step 1)
In the same manner as in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに式(C12)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-4)で示される青色染料化合物(20.3g、収率69.9%)を得た。前記青色染料化合物は、LCMS分析(m/z 581(M+))により、その構造を確認した。 12-B. Synthesis of blue dye compound (B-4) by coupling reaction (step 2)
The blue dye represented by the following formula (B-4) is the same as in
[青色染料化合物(B-5)の合成]
青色染料化合物(B-5)は、下記スキームに従って、製造した。 (Synthesis Example 13)
[Synthesis of blue dye compound (B-5)]
The blue dye compound (B-5) was produced according to the following scheme.
(工程1)
合成例9の工程3において、1-ブロモオクタンの代わりに1-ブロモドデカン(49.8g)を用いること、N-(3-アミノフェニル)オクタンアミドの代わりに3’-アミノアセトアニリド(7.50g)を用いること以外は合成例9の工程3と同様にして、下記式(C13)で示されるN-[3-(N,N-ジドデシルアミノ)フェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C13)の化合物からなるカップラー成分溶液を得た。 13-A. Synthesis of coupler compound C13 and preparation of coupler component solution (step 1)
In
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに工程1で得られた式(C13)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-5)で示される青色染料化合物(9.81g、収率28.3%)を得た。前記青色染料化合物は、LCMS分析(m/z 693(M+))により、その構造を確認した。 13-B. Synthesis of blue dye compound (B-5) by coupling reaction (step 2)
The following formula (B-5) is the same as in
[青色染料化合物(B-6)の合成]
青色染料化合物(B-6)は、下記スキームに従って、製造した。 (Synthesis Example 14)
[Synthesis of blue dye compound (B-6)]
The blue dye compound (B-6) was produced according to the following scheme.
(工程1)
合成例9の工程1において、n-オクタノイルクロリドの代わりにプロピオニルクロリド(19.4g)を用いること、合成例9の工程3において1-ブロモオクタンの代わりに1-ブロモドデカン(49.8g)を用いること以外は合成例9の工程1乃至3と同様にして、下記式(C14)で示されるN-[3-(N,N-ジドデシルアミノ)フェニル]プロパンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C14)の化合物からなるカップラー成分溶液を得た。 14-A. Synthesis of coupler compound C14 and preparation of coupler component solution (step 1)
Propionyl chloride (19.4 g) was used in place of n-octanoyl chloride in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに式(C14)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-6)で示される青色染料化合物(5.73g、収率16.2%)を得た。前記青色染料化合物は、LCMS分析(m/z 707(M+))により、その構造を確認した。 14-B. Synthesis of blue dye compound (B-6) by coupling reaction (step 2)
The blue dye represented by the following formula (B-6) is the same as in
[青色染料化合物(B-7)の合成]
青色染料化合物(B-7)は、下記スキームに従って、製造した。 (Synthesis Example 15)
[Synthesis of blue dye compound (B-7)]
The blue dye compound (B-7) was produced according to the following scheme.
(工程1)
合成例9の工程3において、N-(3-アミノフェニル)オクタンアミドの代わりに3’-アミノアセトアニリド(7.50g)を用いること、1-ブロモオクタンの代わりに1-ブロモ-2-エチルヘキサン(38.6g)を用いること以外は合成例9の工程3と同様にして、下記式(C15)で示されるN-[3-[N,N-ジ(2-エチルヘキシル)アミノ]フェニル]プロパンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C15)の化合物からなるカップラー成分溶液を得た。 15-A. Synthesis of coupler compound C15 and preparation of coupler component solution (step 1)
In
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに式(C15)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-7)で示される青色染料化合物(4.72g、収率16.2%)を得た。前記青色染料化合物は、LCMS分析(m/z 581(M+))により、その構造を確認した。 15-B. Synthesis of blue dye compound (B-7) by coupling reaction (step 2)
The blue dye represented by the following formula (B-7) is the same as in
[青色染料化合物(B-8)の合成]
青色染料化合物(B-8)は、下記スキームに従って、製造した。 (Synthesis Example 16)
[Synthesis of blue dye compound (B-8)]
The blue dye compound (B-8) was produced according to the following scheme.
(工程1)
合成例9の工程3において、1-ブロモオクタンの代わりに1-ブロモエタン(27.3g)を用いること以外は合成例9の工程1乃至3と同様にして、下記式(C16)で示されるN-[3-(N,N-ジエチルアミノ)フェニル]オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C16)の化合物からなるカップラー成分溶液を得た。 16-A. Synthesis of coupler compound C16 and preparation of coupler component solution (step 1)
N represented by the following formula (C16) in the same manner as in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに工程1で得られた式(C16)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-8)で示される青色染料化合物(23.2g、収率93.4%)を得た。前記青色染料化合物は、LCMS分析(m/z 497(M+))により、その構造を確認した。 16-B. Synthesis of blue dye compound (B-8) by coupling reaction (step 2)
The following formula (B-8) is the same as in
[赤色染料化合物(C-1)の合成]
赤色染料化合物(C-1)は、下記スキームに従って、製造した。 (Synthesis Example 17)
[Synthesis of red dye compound (C-1)]
The red dye compound (C-1) was produced according to the following scheme.
(工程1)
濃硫酸(16g)と43%ニトロシル硫酸(15.6g)の混合物に、下記式(D3)で示される2-クロロ-4-ニトロアニリン(8.65g)を30乃至35℃の範囲内で加え、同温下で2時間撹拌することでジアゾ成分溶液を得た。 17-A. Preparation of diazo component solution (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.
(工程2)
式(C9)の化合物からなるカップラー成分溶液の調製は合成例9の工程1乃至3と同様にして行った。工程1で得られた前記ジアゾ成分溶液を前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(28g)を適宜加えながら2時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(C-1)で示される赤色染料化合物(24.3g、収率75.7%)を得た。前記赤色染料化合物は、LCMS分析(m/z 642(M+))により、その構造を確認した。 17-B. 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
[赤色染料化合物(C-2)の合成]
赤色染料化合物(C-2)は、下記スキームに従って、製造した。 (Synthesis Example 18)
[Synthesis of red dye compound (C-2)]
The red dye compound (C-2) was produced according to the following scheme.
[赤色染料化合物(C-3)の合成]
赤色染料化合物(C-3)は、下記スキームに従って製造した。 (Synthesis Example 19)
[Synthesis of red dye compound (C-3)]
The red dye compound (C-3) was produced according to the following scheme.
[赤色染料化合物(C-4)の合成]
赤色染料化合物(C-4)は、下記スキームに従って、製造した。 (Synthesis Example 20)
[Synthesis of red dye compound (C-4)]
The red dye compound (C-4) was produced according to the following scheme.
[赤色染料化合物(C-5)の合成]
赤色染料化合物(C-5は、下記スキームに従って、製造した。 (Synthesis Example 21)
[Synthesis of red dye compound (C-5)]
The red dye compound (C-5 was produced according to the following scheme.
[赤色染料化合物(C-6)の合成]
赤色染料化合物(C-6)は、下記スキームに従って、製造した。 (Synthesis Example 22)
[Synthesis of red dye compound (C-6)]
The red dye compound (C-6) was produced according to the following scheme.
(工程1)
合成例9の工程3において、N-(3-アミノフェニル)オクタンアミドの代わりに3’-アミノアセトアニリド(7.50g)を用いること、1-ブロモオクタンの代わりに1-ブロモブタン(27.4g)を用いること以外は合成例9の工程3と同様にして、下記式(C17)で示されるN-[3-(N,N-ジブチルアミノ)フェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C17)の化合物からなるカップラー成分溶液を得た。 22-A. Synthesis of coupler compound C17 and preparation of coupler component solution (step 1)
In
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに式(C17)の化合物を用いること以外は合成例17の工程1および2と同様にして、下記式(C-6)で示される赤色染料化合物(19.6g、収率87.9%)を得た。前記赤色染料化合物は、LCMS分析(m/z 446(M+))により、その構造を確認した。 22-B. Synthesis of 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
[赤色染料化合物(C-7)の合成]
赤色染料化合物(C-7)は、下記スキームに従って、製造した。 (Synthesis Example 23)
[Synthesis of red dye compound (C-7)]
The red dye compound (C-7) was produced according to the following scheme.
[橙色染料化合物(D-1)の合成]
橙色染料化合物(D-1)は、下記スキームに従って、製造した。 (Synthesis Example 24)
[Synthesis of orange dye compound (D-1)]
The orange dye compound (D-1) was produced according to the following scheme.
(工程1)
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにアニリン(4.66g)を用いること以外は合成例1の工程4と同様にして、下記式(C18)で示されるN,N-ジオクチルアニリンを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C18)の化合物からなるカップラー成分溶液を得た。 24-A. Synthesis of coupler compound C18 and preparation of coupler component solution (step 1)
N, N represented by the following formula (C18) in the same manner as in Step 4 of Synthesis Example 1 except that aniline (4.66 g) is used instead of N- (3-amino-4-methoxyphenyl) octaneamide. -Obtained dioctylaniline. 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 (C18).
(工程2)
濃硫酸(17g)と43%ニトロシル硫酸(14.7g)の混合物に、下記式(D4)で示される2,6-ジクロロ-4-ニトロアニリン(10.4g)を25乃至30℃の範囲内で加え、同温下で2時間撹拌することでジアゾ成分溶液を得た。 24-B. 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.
(工程3)
工程2で得られた前記ジアゾ成分溶液を工程1で得られた式(C18)の化合物からなる前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(20g)を適宜加えながら2時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(D-1)で示される橙色染料化合物(23.1g、収率86.4%)を得た。前記橙色染料化合物は、LCMS分析(m/z 535(M+))により、その構造を確認した。 24-C. Synthesis of orange dye compound (D-1) by coupling reaction (step 3)
The diazo component solution obtained in step 2 was added to the coupler component solution composed of the compound of the formula (C18) obtained in
[橙色染料化合物(D-2)の合成]
橙色染料化合物(D-2)は、下記スキームに従って、製造した。 (Synthesis Example 25)
[Synthesis of orange dye compound (D-2)]
The orange dye compound (D-2) was produced according to the following scheme.
(工程1)
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにアニリン(4.66g)を用いること、1-ブロモオクタンの代わりに1-ブロモドデカン(49.8g)を用いること以外は合成例1の工程4と同様にして、下記式(C19)で示されるN,N-ジドデシルアニリンを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C19)の化合物からなるカップラー成分溶液を得た。 25-A. Synthesis of coupler compound C19 and preparation of coupler component solution (step 1)
Synthesis example except that aniline (4.66 g) is used instead of N- (3-amino-4-methoxyphenyl) octaneamide and 1-bromododecane (49.8 g) is used instead of 1-bromooctane. N, N-zidodecylaniline represented by the following formula (C19) was obtained in the same manner as in step 4 of 1. 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 (C19).
(工程2)
カップラー成分溶液として、式(C18)の化合物の代わりに式(C19)の化合物を用いること以外は合成例24の工程2および3と同様にして、下記式(D-2)で示される橙色染料化合物(14.1g、収率43.6%)を得た。前記橙色染料化合物は、LCMS分析(m/z 647(M+))により、その構造を確認した。 25-B. Synthesis of orange dye compound (D-2) by coupling reaction (step 2)
The orange dye represented by the following formula (D-2) is the same as in
[橙色染料化合物(D-3)の合成]
橙色染料化合物(D-3)は、下記スキームに従って、製造した。 (Synthesis Example 26)
[Synthesis of orange dye compound (D-3)]
The orange dye compound (D-3) was produced according to the following scheme.
(工程1)
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにアニリン(4.66g)を用いること、1-ブロモオクタンの代わりに1-ブロモブタン(27.4g)を用いること以外は合成例1の工程4と同様にして、下記式(C20)で示されるN,N-ジブチルアニリンを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C20)の化合物からなるカップラー成分溶液を得た。 26-A. Synthesis of coupler compound C20 and preparation of coupler component solution (step 1)
Synthesis Example 1 except that aniline (4.66 g) is used instead of N- (3-amino-4-methoxyphenyl) octaneamide and 1-bromobutane (27.4 g) is used instead of 1-bromooctane. In the same manner as in Step 4, N, N-dibutylaniline represented by the following formula (C20) 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 (C20).
(工程2)
カップラー成分溶液として、式(C18)の化合物の代わりに式(C20)の化合物を用いること以外は合成例24の工程2および3と同様にして、下記式(D-3)で示される橙色染料化合物(10.2g、収率48.2%)を得た。前記橙色染料化合物は、LCMS分析(m/z 423(M+))により、その構造を確認した。 26-B. Synthesis of orange dye compound (D-3) by coupling reaction (step 2)
The orange dye represented by the following formula (D-3) is the same as in
[黄色染料化合物(G-1)の合成]
黄色染料化合物(G-1)は、下記スキームに従って、製造した。 (Synthesis Example 27)
[Synthesis of yellow dye compound (G-1)]
The yellow dye compound (G-1) was produced according to the following scheme.
[黄色染料化合物(G-2)の合成]
黄色染料化合物(G-2)は、下記スキームに従って、製造した。 (Synthesis Example 28)
[Synthesis of yellow dye compound (G-2)]
The yellow dye compound (G-2) was produced according to the following scheme.
[紫色染料化合物(F-1)の合成]
紫色染料化合物(F-1)は、下記スキームに従って、製造した。 (Synthesis Example 29)
[Synthesis of purple dye compound (F-1)]
The purple dye compound (F-1) was produced according to the following scheme.
[橙色染料化合物(D-4)の合成]
橙色染料化合物(D-4)は、下記スキームに従って、製造した。 (Synthesis Example 30)
[Synthesis of orange dye compound (D-4)]
The orange dye compound (D-4) was produced according to the following scheme.
(工程1)
濃硫酸(17g)と43%ニトロシル硫酸(14.7g)の混合物に、下記式(D5)で示される4-ニトロアニリン(6.91g)を30乃至35℃の範囲内で加え、同温下で2時間撹拌することでジアゾ成分溶液を得た。 30-A. Preparation of diazo component solution (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.
(工程2)
式(C18)の化合物からなるカップラー成分溶液の調製は合成例24の工程1と同様にして行った。工程1で得られた前記ジアゾ成分溶液を前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(20g)を適宜加えながら1時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(D-4)で示される橙色染料化合物(12.5g、収率53.5%)を得た。前記橙色染料化合物は、LCMS分析(m/z 467(M+))により、その構造を確認した。 30-B. 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
[橙色染料化合物(D-5)の合成]
橙色染料化合物(D-5)は、下記スキームに従って、製造した。 (Synthesis Example 31)
[Synthesis of orange dye compound (D-5)]
The orange dye compound (D-5) was produced according to the following scheme.
(工程1)
濃硫酸(17g)と43%ニトロシル硫酸(14.7g)の混合物に、下記式(D6)で示される2,6-ジブロモ-4-ニトロアニリン(14.8g)を25乃至30℃の範囲内で加え、同温下で2時間撹拌することでジアゾ成分溶液を得た。 31-A. 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.
(工程2)
式(C18)の化合物からなるカップラー成分溶液の調製は合成例24の工程1と同様にして行った。工程1で得た前記ジアゾ成分溶液を前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(25g)を適宜加えながら1時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(D-5)で示される橙色染料化合物(27.6g、収率88.6%)を得た。前記橙色染料化合物は、LCMS分析(m/z 623(M+))により、その構造は下記式(D-5)であると確認した。 31-B. 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
[橙色染料化合物(D-6)の合成]
橙色染料化合物(D-6)は、下記スキームに従って、製造した。 (Synthesis Example 32)
[Synthesis of orange dye compound (D-6)]
The orange dye compound (D-6) was produced according to the following scheme.
[橙色染料化合物(E-1)の合成]
橙色染料化合物(E-1)は、下記スキームに従って、製造した。 (Synthesis Example 33)
[Synthesis of orange dye compound (E-1)]
The orange dye compound (E-1) was produced according to the following scheme.
(工程1)
2-フェニル-1H-インドール(9.67g)とトリエチルアミン(7.5g)とDMF(15g)と1-ブロモオクタン(11.6g)の混合物を120℃に昇温し、同温下で3時間撹拌することにより下記式(C21)で示されるN-オクチル-2-フェニルインドールを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C21)の化合物からなるカップラー成分溶液を得た。 33-A. Synthesis of coupler compound C21 and preparation of coupler component solution (step 1)
A mixture of 2-phenyl-1H-indole (9.67 g), triethylamine (7.5 g), DMF (15 g) and 1-bromooctane (11.6 g) was heated to 120 ° C. and kept at the same temperature for 3 hours. By stirring, N-octyl-2-phenylindole represented by the following formula (C21) 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 (C21).
(工程2)
式(D4)の化合物から誘導されたジアゾ成分溶液の調製は合成例24と同様にして行った。前記ジアゾ成分溶液を工程1で得た前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(20g)を適宜加えながら1時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(E-1)で示される橙色染料化合物(11.3g、収率43.2%)を得た。前記橙色染料化合物は、LCMS分析(m/z 523(M+))により、その構造を確認した。 33-B. Synthesis of orange dye compound (E-1) by coupling reaction (step 2)
The preparation of the diazo component solution derived from the compound of the formula (D4) was carried out in the same manner as in Synthesis Example 24. The diazo component solution was added dropwise to the coupler component solution obtained in
[橙色染料化合物(E-2)の合成]
橙色染料化合物(E-2)は、下記スキームに従って、製造した。 (Synthesis Example 34)
[Synthesis of orange dye compound (E-2)]
The orange dye compound (E-2) was produced according to the following scheme.
(工程1)
1-ブロモオクタンの代わりに1-ブロモブタン(7.53g)を用いること以外は合成例33の工程1と同様にして、下記式(C22)で示されるN-ブチル-2-フェニルインドールを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C22)の化合物からなるカップラー成分溶液を得た。 34-A. Synthesis of coupler compound C22 and preparation of coupler component solution (step 1)
N-Butyl-2-phenylindole represented by the following formula (C22) was obtained in the same manner as in
(工程2)
カップラー成分溶液として、式(C21)の化合物の代わりに式(C22)の化合物を用いること以外は合成例33の工程1および2と同様にして、下記式(E-2)で示される橙色染料化合物(14.5g、収率62.1%)を得た。前記橙色染料化合物は、LCMS分析(m/z 467(M+))により、その構造を確認した。 34-B. Synthesis of orange dye compound (E-2) by coupling reaction (step 2)
The orange dye represented by the following formula (E-2) is the same as in
[赤色染料化合物(D-7)の合成]
赤色染料化合物(D-7)は、下記スキームに従って、製造した。 (Synthesis Example 35)
[Synthesis of red dye compound (D-7)]
The red dye compound (D-7) was produced according to the following scheme.
(工程1)
濃硫酸(7.5g)と酢酸(15g)と43%ニトロシル硫酸(14.9g)の混合物に下記式(D7)で示される2-シアノ-4-ニトロアニリン(8.15g)を20乃至25℃の範囲内で加え、同温下で2時間撹拌することでジアゾ成分溶液を得た。 35-A. Preparation of diazo component solution (step 1)
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.
(工程2)
式(C18)の化合物からなるカップラー成分溶液の調製は合成例24と同様にして行った。工程1で得られた前記ジアゾ成分溶液を前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(30g)を適宜加えながら1時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(D-7)で示される赤色染料化合物(16.9g、収率68.9%)を得た。前記赤色染料化合物は、LCMS分析(m/z 492(M+))により、その構造を確認した。 35-B. Synthesis of 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
[紫色染料化合物(C-8)の合成]
紫色染料化合物(C-8)は、下記スキームに従って、製造した。 (Synthesis Example 36)
[Synthesis of purple dye compound (C-8)]
The purple dye compound (C-8) was produced according to the following scheme.
[紫色染料化合物(C-9)の合成]
紫色染料化合物(C-9)は、下記スキームに従って、製造した。 (Synthesis Example 37)
[Synthesis of purple dye compound (C-9)]
The purple dye compound (C-9) was produced according to the following scheme.
[紫色染料化合物(C-10)の合成]
紫色染料化合物(C-10)は、下記スキームに従って、製造した。 (Synthesis Example 38)
[Synthesis of purple dye compound (C-10)]
The purple dye compound (C-10) was produced according to the following scheme.
[紫色染料化合物(C-11)の合成]
紫色染料化合物(C-11)は、下記スキームに従って、製造した。 (Synthesis Example 39)
[Synthesis of purple dye compound (C-11)]
The purple dye compound (C-11) was produced according to the following scheme.
(工程1)
濃硫酸(10.7g)と酢酸(28.8g)の混合物に下記式(D8)で示される2-ブロモ-6-シアノ-4-ニトロアニリン(11.1g)を20乃至25℃の範囲内で加えた。この混合物に43%ニトロシル硫酸(15.6g)を20乃至25℃の範囲内で加え、同温下で2時間撹拌することでジアゾ成分溶液を得た。 39-A. Preparation of diazo component solution (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.
(工程2)
式(C9)の化合物からなるカップラー成分溶液の調製は合成例9の工程1乃至3と同様にして行った。工程1で得られた前記ジアゾ成分溶液を前記カップラー成分溶液に、0乃至10℃の範囲内でトリエチルアミン(20g)を適宜加えながら2時間かけて滴下し、カップリング反応を行った。0乃至10℃の範囲内で20分間撹拌した後、この反応混合物から生成物を濾別し、メタノール、次いで水で洗浄し、水分が1.0質量%以下になるまで60℃で乾燥して下記式(C-11)で示される紫色染料化合物(16.0g、収率45.0%)を得た。前記紫色染料化合物は、LCMS分析(m/z 711(M+))により、その構造を確認した。 39-B. 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
[紫色染料化合物(C-12)の合成]
紫色染料化合物(C-12)は、下記スキームに従って、製造した。 (Synthesis Example 40)
[Synthesis of purple dye compound (C-12)]
The purple dye compound (C-12) was produced according to the following scheme.
(工程1)
合成例9の工程3において、1-ブロモオクタンの代わりに1-ブロモブタン(27.4g)を用いること以外は合成例9の工程1乃至3と同様にして、下記式(C23)で示されるN-[3-(N,N-ジブチルアミノ)フェニル]オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C23)の化合物からなるカップラー成分溶液を得た。 40-A. Synthesis of coupler compound C23 and preparation of coupler component solution (step 1)
N represented by the following formula (C23) in the same manner as in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに式(C23)の化合物を用いること以外は合成例39の工程2と同様にして、下記式(C-12)で示される紫色染料化合物(5.99g、収率20.0%)を得た。前記紫色染料化合物は、LCMS分析(m/z 599(M+))により、その構造を確認した。 40-B. Synthesis of purple dye compound (C-12) by coupling reaction (step 2)
The purple dye compound represented by the following formula (C-12) is obtained in the same manner as in Step 2 of Synthesis Example 39 except that the compound of the formula (C23) is used instead of the compound of the formula (C9) as the coupler component solution. 5.99 g, yield 20.0%) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 599 (M +)).
[紫色染料化合物(C-13)の合成]
紫色染料化合物(C-13)は、下記スキームに従って、製造した。 (Synthesis Example 41)
[Synthesis of purple dye compound (C-13)]
The purple dye compound (C-13) was produced according to the following scheme.
[紫色染料化合物(C-14)の合成]
紫色染料化合物(C-14)は、下記スキームに従って、製造した。 (Synthesis Example 42)
[Synthesis of purple dye compound (C-14)]
The purple dye compound (C-14) was produced according to the following scheme.
[紫色染料化合物(C-15)の合成]
紫色染料化合物(C-15)は、下記スキームに従って、製造した。 (Synthesis Example 43)
[Synthesis of purple dye compound (C-15)]
The purple dye compound (C-15) was produced according to the following scheme.
[紫色染料化合物(C-16)の合成]
紫色染料化合物(C-16)は、下記スキームに従って、製造した。 (Synthesis Example 44)
[Synthesis of purple dye compound (C-16)]
The purple dye compound (C-16) was produced according to the following scheme.
[黄色染料化合物(G-3)の合成]
黄色染料化合物(G-3)は、下記スキームに従って、製造した。 (Synthesis Example 45)
[Synthesis of yellow dye compound (G-3)]
The yellow dye compound (G-3) was produced according to the following scheme.
[黄色染料化合物(G-4)の合成]
黄色染料化合物(G-4)は、下記スキームに従って、製造した。 (Synthesis Example 46)
[Synthesis of yellow dye compound (G-4)]
The yellow dye compound (G-4) was produced according to the following scheme.
[青色染料化合物(B-9)の合成]
青色染料化合物(B-9)は、下記スキームに従って、製造した。 (Synthesis Example 47)
[Synthesis of blue dye compound (B-9)]
The blue dye compound (B-9) was produced according to the following scheme.
[青色染料化合物(B-10)の合成]
青色染料化合物(B-10)は、下記スキームに従って、製造した。 (Synthesis Example 48)
[Synthesis of blue dye compound (B-10)]
The blue dye compound (B-10) was produced according to the following scheme.
(工程1)
合成例9の工程1において、n-オクタノイルクロリドの代わりに2-エチルヘキサノイルクロリド(34.2g)を用いること以外は合成例9の工程1乃至3と同様にして、下記式(C24)で示されるN-[3-(N,N-ジオクチルアミノ)フェニル]-2-エチルヘキサンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C24)の化合物からなるカップラー成分溶液を得た。 48-A. Synthesis of coupler compound C24 and preparation of coupler component solution (step 1)
The following formula (C24) is the same as in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに式(C24)の化合物を用いること以外は合成例9の工程4および5と同様にして、下記式(B-10)で示される青色染料化合物(19.0g、収率57.1%)を得た。前記青色染料化合物は、LCMS分析(m/z 665(M+))により、その構造を確認した。 48-B. Synthesis of blue dye compound (B-10) by coupling reaction (step 2)
The blue dye represented by the following formula (B-10) is the same as in
[橙色染料化合物(D-8)の合成]
橙色染料化合物(D-8)は、下記スキームに従って、製造した。 (Synthesis Example 49)
[Synthesis of orange dye compound (D-8)]
The orange dye compound (D-8) was produced according to the following scheme.
[橙色染料化合物(D-9)の合成]
橙色染料化合物(D-9)は、下記スキームに従って、製造した。 (Synthesis Example 50)
[Synthesis of orange dye compound (D-9)]
The orange dye compound (D-9) was produced according to the following scheme.
[橙色染料化合物(D-10)の合成]
橙色染料化合物(D-10)は、下記スキームに従って、製造した。 (Synthesis Example 51)
[Synthesis of orange dye compound (D-10)]
The orange dye compound (D-10) was produced according to the following scheme.
[橙色染料化合物(D-11)の合成]
橙色染料化合物(D-11)は、下記スキームに従って、製造した。 (Synthesis Example 52)
[Synthesis of orange dye compound (D-11)]
The orange dye compound (D-11) was produced according to the following scheme.
(工程1)
アニリン(18.6g)、酢酸(50g)、塩化第一銅(1.3g)、アクリロニトリル(20g)の混合物を110℃に加熱して3時間撹拌した。室温に冷却後、トルエン(100g)と10%炭酸ナトリウム水溶液(150g)を加えて有機層を抽出した。この抽出物を飽和食塩水で洗浄した後、溶媒を減圧留去することにより下記式(C25a)で示されるN-シアノエチルアニリン(28.7g、収率98.2%)を粗生成物として得た。 52-A. Synthesis of coupler compound C25 and preparation of coupler component solution (step 1)
A mixture of aniline (18.6 g), acetic acid (50 g), cuprous chloride (1.3 g) and acrylonitrile (20 g) was heated to 110 ° C. and stirred for 3 hours. After cooling to room temperature, toluene (100 g) and a 10% aqueous sodium carbonate solution (150 g) were added to extract the organic layer. After washing this extract with saturated brine, the solvent was distilled off under reduced pressure to obtain N-cyanoethylaniline (28.7 g, yield 98.2%) represented by the following formula (C25a) as a crude product. rice field.
前記工程で得られたN-シアノエチルアニリン(28.7g)とトリエチルアミン(15g)とDMF(15g)と1-ブロモオクタン(14.5g)の混合物を120℃に昇温し、同温下で3時間撹拌することにより下記式(C25)で示されるN-シアノエチル-N-オクチルアニリンを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C25)の化合物からなるカップラー成分溶液を得た。 (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).
(工程3)
カップラー成分溶液として、式(C18)の化合物の代わりに式(C25)の化合物を用いること以外は合成例30と同様にして、下記式(D-11)で示される橙色染料化合物(10.6g、収率52.0%)を得た。前記橙色染料化合物は、LCMS分析(m/z 408(M+))により、その構造を確認した。 52-B. Synthesis of orange dye compound (D-11) by coupling reaction (step 3)
The orange dye compound (10.6 g) represented by the following formula (D-11) is obtained in the same manner as in Synthesis Example 30 except that the compound of the formula (C25) is used instead of the compound of the formula (C18) as the coupler component solution. , Yield 52.0%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 408 (M +)).
[赤色染料化合物(C-17)の合成]
赤色染料化合物(C-17)は、下記スキームに従って、製造した。 (Synthesis Example 53)
[Synthesis of red dye compound (C-17)]
The red dye compound (C-17) was produced according to the following scheme.
(工程1)
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりに3’-アミノアセトアニリド(7.50g)を用いること、1-ブロモオクタンの代わりに1-ブロモエタン(27.3g)を用いること以外は合成例1の工程4と同様にして、下記式(C26)で示されるN-[3-(N,N-ジエチルアミノ)フェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C26)の化合物からなるカップラー成分溶液を得た。 53-A. Synthesis of coupler compound C26 and preparation of coupler component solution (step 1)
Other than using 3'-aminoacetanilide (7.50 g) instead of N- (3-amino-4-methoxyphenyl) octaneamide and 1-bromoethane (27.3 g) instead of 1-bromooctane Obtained N- [3- (N, N-diethylamino) phenyl] acetamide represented by the following formula (C26) in the same manner as in Step 4 of Synthesis Example 1. 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 (C26).
(工程2)
カップラー化合物として、式(C9)の化合物の代わりに式(C26)の化合物を用いること以外は合成例17と同様にして、下記式(C-17)で示される赤色染料化合物(11.8g、収率60.5%)を得た。前記赤色染料化合物は、LCMS分析(m/z 390(M+))により、その構造を確認した。 53-B. Synthesis of 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 +)).
[紫色染料化合物(F-2)の合成]
紫色染料化合物(F-2)は、下記スキームに従って、製造した。 (Synthesis Example 54)
[Synthesis of purple dye compound (F-2)]
The purple dye compound (F-2) was produced according to the following scheme.
[青色染料化合物(B-11)の合成]
青色染料化合物(B-11)は、下記スキームに従って、製造した。 (Synthesis Example 55)
[Synthesis of blue dye compound (B-11)]
The blue dye compound (B-11) was produced according to the following scheme.
[青色染料化合物(A-9)の合成]
青色染料化合物(A-9)は、下記スキームに従って、製造した。 (Synthesis Example 56)
[Synthesis of blue dye compound (A-9)]
The blue dye compound (A-9) was produced according to the following scheme.
(工程1)
合成例1の工程3で得られたN-(3-アミノ-4-メトキシフェニル)オクタンアミド(13.2g)、酢酸(15g)、塩化第一銅(0.32g)、アクリロニトリル(5.0g)の混合物を110℃に加熱して3時間撹拌した。室温に冷却後、トルエン(50g)と10%炭酸ナトリウム水溶液(75g)を加えて有機層を抽出した。この抽出物を飽和食塩水で洗浄した後、溶媒を減圧留去することにより下記式(C27a)で示されるN-(3-シアノエチルアミノ-4-メトキシフェニル)オクタンアミド(9.05g、収率57.0%)を粗生成物として得た。 56-A. Synthesis of coupler compound C27 and preparation of coupler component solution (step 1)
N- (3-amino-4-methoxyphenyl) octaneamide (13.2 g), acetic acid (15 g), cuprous chloride (0.32 g), acrylonitrile (5.0 g) obtained in
前記工程で得られたN-(3-シアノエチルアミノ-4-メトキシフェニル)オクタンアミド(15.9g)とDMF(15g)と硫酸ジエチル(11.6g)の混合物を90℃に昇温し、同温下で2時間撹拌することにより下記式(C27)で示されるN-(3-N-エチル-N-シアノエチルアミノ-4-メトキシフェニル)オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C27)の化合物からなるカップラー成分溶液を得た。 (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).
(工程3)
カップラー成分溶液として、式(C1)の化合物の代わりに式(C27)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-9)で示される青色染料化合物(9.70g、収率31.4%)を得た。前記青色染料化合物は、LCMS分析(m/z 618(M+))により、その構造を確認した。 56-B. Synthesis of blue dye compound (A-9) by coupling reaction (step 3)
The blue dye represented by the following formula (A-9) is the same as in
[青色染料化合物(A-10)の合成]
青色染料化合物(A-10)は、下記スキームに従って、製造した。 (Synthesis Example 57)
[Synthesis of blue dye compound (A-10)]
The blue dye compound (A-10) was produced according to the following scheme.
(工程1)
合成例56の工程1で得られたN-(3-シアノエチルアミノ-4-メトキシフェニル)オクタンアミド(15.9g)とDMF(20g)とトリエチルアミン(12.6g)と1-ブロモオクタン(29.0g)の混合物を120℃に昇温し、8時間撹拌することにより下記式(C28)で示されるN-(3-N-オクチル-N-シアノエチルアミノ-4-メトキシフェニル)オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C28)からなるカップラー成分溶液を得た。 57-A. Synthesis of coupler compound C28 and preparation of coupler component solution (step 1)
N- (3-cyanoethylamino-4-methoxyphenyl) octaneamide (15.9 g), DMF (20 g), triethylamine (12.6 g) and 1-bromooctane (29.) obtained in
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに式(C28)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-10)で示される青色染料化合物(5.52g、収率15.7%)を得た。前記青色染料化合物は、LCMS分析(m/z 702(M+))により、その構造を確認した。 57-B. Synthesis of blue dye compound (A-10) by coupling reaction (step 2)
The blue dye represented by the following formula (A-10) is the same as in
[青色染料化合物(A-11)の合成]
青色染料化合物(A-11)は、下記スキームに従って、製造した。 (Synthesis Example 58)
[Synthesis of blue dye compound (A-11)]
The blue dye compound (A-11) was produced according to the following scheme.
(工程1)
合成例1の工程3で得られたN-(3-アミノ-4-メトキシフェニル)オクタンアミド(13.2g)とDMF(15g)とトリエチルアミン(15g)と2-ブロモエチルメチルエーテル(27.8g)の混合物を110℃に昇温し、8時間撹拌することにより下記式(C29)で示されるN-[3-N,N-(2-ジメトキシエチル)アミノ-4-メトキシフェニル]オクタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C29)からなるカップラー成分溶液を得た。 58-A. Synthesis of coupler compound C29 and preparation of coupler component solution (step 1)
N- (3-amino-4-methoxyphenyl) octaneamide (13.2 g), DMF (15 g), triethylamine (15 g) and 2-bromoethylmethyl ether (27.8 g) obtained in
カップラー成分溶液として、式(C1)の化合物の代わりに式(C29)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-11)で示される青色染料化合物(6.58g、収率20.2%)を得た。前記青色染料化合物は、LCMS分析(m/z 653(M+))により、その構造を確認した。 (Step 2)
The blue dye represented by the following formula (A-11) is the same as in
[青色染料化合物(A-12)の合成]
青色染料化合物(A-12)は、下記スキームに従って、製造した。 (Synthesis Example 59)
[Synthesis of blue dye compound (A-12)]
The blue dye compound (A-12) was produced according to the following scheme.
(工程1)
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにN-(3-アミノ-4-メトキシフェニル)アセトアミド(市販品として購入)(9.0g)を用いること、1-ブロモオクタンの代わりに1-ブロモブタン(27.4g)を用いること以外は合成例1の工程4と同様にして、下記式(C30)で示されるN-[3-(N,N-ジヘキシルアミノ)-4-メトキシフェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C30)からなるカップラー成分溶液を得た。 59-A. Synthesis of coupler compound C30 and preparation of coupler component solution (step 1)
Using N- (3-amino-4-methoxyphenyl) acetamide (purchased as a commercial product) (9.0 g) instead of N- (3-amino-4-methoxyphenyl) octaneamide, 1-bromooctane N- [3- (N, N-dihexylamino) -4- represented by the following formula (C30) in the same manner as in step 4 of Synthesis Example 1 except that 1-bromobutane (27.4 g) is used instead. Methoxyphenyl] acetamide 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 having the formula (C30).
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに式(C30)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-12)で示される青色染料化合物(14.1g、収率49.9%)を得た。前記青色染料化合物は、LCMS分析(m/z 565(M+))により、その構造を確認した。 59-B. Synthesis of blue dye compound (A-12) by coupling reaction (step 2)
The blue dye represented by the following formula (A-12) is the same as in
[青色染料化合物(A-13)の合成]
青色染料化合物(A-13)は、下記スキームに従って、製造した。 (Synthesis Example 60)
[Synthesis of blue dye compound (A-13)]
The blue dye compound (A-13) was produced according to the following scheme.
(工程1)
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにN-(3-アミノ-4-メトキシフェニル)アセトアミド(市販品として購入)(9.0g)を用いること、1-ブロモオクタンの代わりに1-ブロモヘキサン(33.0g)を用いること以外は合成例1の工程4と同様にして、下記式(C31)で示されるN-[3-(N,N-ジヘキシルアミノ)-4-メトキシフェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C31)の化合物からなるカップラー成分溶液を得た。 60-A. Synthesis of coupler compound C31 and preparation of coupler component solution (step 1)
Using N- (3-amino-4-methoxyphenyl) acetamide (purchased as a commercial product) (9.0 g) instead of N- (3-amino-4-methoxyphenyl) octaneamide, 1-bromooctane N- [3- (N, N-dihexylamino) -4 represented by the following formula (C31) in the same manner as in step 4 of Synthesis Example 1 except that 1-bromohexane (33.0 g) is used instead. -Methoxyphenyl] acetamide 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 (C31).
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに式(C31)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-13)で示される青色染料化合物(10.7g、収率34.5%)を得た。前記青色染料化合物は、LCMS分析(m/z 621(M+))により、その構造を確認した。 60-B. Synthesis of blue dye compound (A-13) by coupling reaction (step 2)
The blue dye represented by the following formula (A-13) is the same as in
[青色染料化合物(A-14)の合成]
青色染料化合物(A-14)は、下記スキームに従って、製造した。 (Synthesis Example 61)
[Synthesis of blue dye compound (A-14)]
The blue dye compound (A-14) was produced according to the following scheme.
(工程1)
合成例1の工程1において、n-オクタノイルクロリドの代わりにバレリルクロリド(25.3g)を用いること、工程4において1-ブロモオクタンの代わりに1-ブロモエタン(27.3g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C32)で示されるN-[3-(N,N-ジエチルアミノ)-4-メトキシフェニル]ペンタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C32)の化合物からなるカップラー成分溶液を得た。 61-A. Synthesis of coupler compound C32 and preparation of coupler component solution (step 1)
Except for using valeryl chloride (25.3 g) instead of n-octanoyl chloride in
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに式(C32)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-14)で示される青色染料化合物(24.1g、収率87.5%)を得た。前記青色染料化合物は、LCMS分析(m/z 551(M+))により、その構造を確認した。 61-B. Synthesis of blue dye compound (A-14) by coupling reaction (step 2)
The blue dye represented by the following formula (A-14) is the same as in
[青色染料化合物(A-15)の合成]
青色染料化合物(A-15)は、下記スキームに従って、製造した。 (Synthesis Example 62)
[Synthesis of blue dye compound (A-15)]
The blue dye compound (A-15) was produced according to the following scheme.
(工程1)
合成例1の工程1において、n-オクタノイルクロリドの代わりにラウロイルクロリド(45.9g)を用いること、工程4において1-ブロモオクタンの代わりに1-ブロモエタン(27.3g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C33)で示されるN-[3-(N,N-ジエチルアミノ)-4-メトキシフェニル]ドデカンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C33)の化合物からなるカップラー成分溶液を得た。 62-A. Synthesis of coupler compound C33 and preparation of coupler component solution (step 1)
Except for the use of lauroyl chloride (45.9 g) in place of n-octanoyl chloride in
(工程2)
カップラー成分溶液として、式(C1)の代わりに式(C33)を用いること以外は合成例1の工程5および6と同様にして、下記式(A-15)で示される青色染料化合物(26.8g、収率82.6%)を得た。前記青色染料化合物は、LCMS分析(m/z 649(M+))により、その構造を確認した。 62-B. Synthesis of blue dye compound (A-15) by coupling reaction (step 2)
The blue dye compound (26. 8 g, yield 82.6%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 649 (M +)).
[赤色染料化合物(C-18)の合成]
赤色染料化合物(C-18)は、下記スキームに従って、製造した。 (Synthesis Example 63)
[Synthesis of red dye compound (C-18)]
The red dye compound (C-18) was produced according to the following scheme.
(工程1)
合成例9の工程3において、1-ブロモオクタンの代わりに1-ブロモヘキサン(33.0g)を用いること、N-(3-アミノフェニル)オクタンアミドの代わりに3’-アミノアセトアニリド(7.50g)を用いること以外は合成例9の工程3と同様にして、下記式(C34)で示されるN-[3-(N,N-ジヘキシルアミノ)フェニル]アセトアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C34)の化合物からなるカップラー成分溶液を得た。 63-A. Synthesis of coupler compound C34 and preparation of coupler component solution (step 1)
In
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに式(C34)の化合物を用いること以外は合成例17と同様にして、下記式(C-18)で示される赤色染料化合物(20.1g、収率80.1%)を得た。前記赤色染料化合物は、LCMS分析(m/z 502(M+))により、その構造を確認した。 63-B. Synthesis of 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 +)).
[橙色染料化合物(D-12)の合成]
橙色染料化合物(D-12)は、下記スキームに従って、製造した。 (Synthesis Example 64)
[Synthesis of orange dye compound (D-12)]
The orange dye compound (D-12) was produced according to the following scheme.
(工程1)
N-(3-アミノ-4-メトキシフェニル)オクタンアミドの代わりにアニリン(4.66g)を用いること、1-ブロモオクタンの代わりに1-ブロモヘキサン(33.0g)を用いること以外は合成例1の工程4と同様にして、下記式(C35)で示されるN,N-ジヘキシルアニリンを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C35)の化合物からなるカップラー成分溶液を得た。 64-A. Synthesis of coupler compound C35 and preparation of coupler component solution (step 1)
Synthesis example except that aniline (4.66 g) is used instead of N- (3-amino-4-methoxyphenyl) octaneamide and 1-bromohexane (33.0 g) is used instead of 1-bromooctane. N, N-dihexylaniline represented by the following formula (C35) was obtained in the same manner as in step 4 of 1. 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 (C35).
(工程2)
カップラー成分溶液として、式(C18)の化合物の代わりに式(C35)の化合物を用いること以外は合成例24と同様にして、下記式(D-12)で示される橙色染料化合物(13.5g、収率56.4%)を得た。前記橙色染料化合物は、LCMS分析(m/z 479(M+))により、その構造を確認した。 64-B. Synthesis of orange dye compound (D-12) by coupling reaction (step 2)
The orange dye compound (13.5 g) represented by the following formula (D-12) is used in the same manner as in Synthesis Example 24 except that the compound of the formula (C35) is used instead of the compound of the formula (C18) as the coupler component solution. , Yield 56.4%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 479 (M +)).
[橙色染料化合物(D-13)の合成]
橙色染料化合物(D-13)は、下記スキームに従って、製造した。 (Synthesis Example 65)
[Synthesis of orange dye compound (D-13)]
The orange dye compound (D-13) was produced according to the following scheme.
[青色染料化合物(A-16)の合成]
青色染料化合物(A-16)は、下記スキームに従って、製造した。 (Synthesis Example 66)
[Synthesis of blue dye compound (A-16)]
The blue dye compound (A-16) was produced according to the following scheme.
(工程1)
合成例1の工程1において、p-アニシジンの代わりに4-ブトキシアニリン(33.0g)を用いること、n-オクタノイルクロリドの代わりにプロピオニルクロリド(19.4g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C36)で示されるN-[3-(N,N-ジオクチルアミノ)-4-ブトキシフェニル]プロパンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C36)の化合物からなるカップラー成分溶液を得た。 66-A. Synthesis of coupler compound C8 and preparation of coupler component solution (step 1)
Synthesis Example 1 except that 4-butoxyaniline (33.0 g) is used instead of p-anisidine and propionyl chloride (19.4 g) is used instead of n-octanoyl chloride in
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C36)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-16)で示される青色染料化合物(6.45g、収率17.6%)を得た。前記青色染料化合物は、LCMS分析(m/z 733(M+))により、その構造を確認した。 66-B. Synthesis of blue dye compound (A-16) by coupling reaction (step 2)
The following formula (A-16) is the same as in
[赤色染料化合物(C-19)の合成]
赤色染料化合物(C-19)は、下記スキームに従って、製造した。 (Synthesis Example 67)
[Synthesis of red dye compound (C-19)]
The red dye compound (C-19) was produced according to the following scheme.
(工程1)
合成例9の工程1において、n-オクタノイルクロリドの代わりにプロピオニルクロリド(19.4g)を用いること、合成例9の工程3において1-ブロモオクタンの代わりに1-ブロモヘキサン(33.0g)を用いること以外は合成例9の工程1乃至3と同様にして、下記式(C37)で示されるN-[3-(N,N-ジヘキシルアミノ)フェニル]プロパンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C37)の化合物からなるカップラー成分溶液を得た。 67-A. Synthesis of coupler compound C37 and preparation of coupler component solution (step 1)
Propionyl chloride (19.4 g) was used in place of n-octanoyl chloride in
(工程2)
カップラー成分溶液として、式(C9)の化合物の代わりに工程1で得られた式(C37)の化合物を用いること以外は合成例17の工程1および2と同様にして、下記式(C-19)で示される赤色染料化合物(17.6g、収率68.2%)を得た。前記赤色染料化合物は、LCMS分析(m/z 516(M+))により、その構造を確認した。 67-B. Synthesis of red dye compound (C-19) by coupling reaction (step 2)
Similar to
[赤色染料化合物(C-20)の合成]
赤色染料化合物(C-20)は、下記スキームに従って、製造した。 (Synthesis Example 68)
[Synthesis of red dye compound (C-20)]
The red dye compound (C-20) was produced according to the following scheme.
[青色染料化合物(A-17)の合成]
青色染料化合物(A-17)は、下記スキームに従って、製造した。 (Synthesis Example 69)
[Synthesis of blue dye compound (A-17)]
The blue dye compound (A-17) was produced according to the following scheme.
(工程1)
合成例1の工程1において、n-オクタノイルクロリドの代わりにバレリルクロリド(25.3g)を用いること、工程4において1-ブロモオクタンの代わりに1-ブロモヘキサン(33.0g)を用いること以外は合成例1の工程1乃至4と同様にして、下記式(C38)で示されるN-[3-(N,N-ジヘキシルアミノ)-4-メトキシフェニル]ペンタンアミドを得た。この反応混合物にメタノール(30g)を加え、5℃に冷却することで式(C38)の化合物からなるカップラー成分溶液を得た。 69-A. Synthesis of coupler compound C38 and preparation of coupler component solution (step 1)
In
(工程2)
カップラー成分溶液として、式(C1)の化合物の代わりに工程1で得られた式(C38)の化合物を用いること以外は合成例1の工程5および6と同様にして、下記式(A-17)で示される青色染料化合物(15.3g、収率48.4%)を得た。前記青色染料化合物は、LCMS分析(m/z 663(M+))により、その構造を確認した。 69-B. Synthesis of blue dye compound (A-17) by coupling reaction (step 2)
The following formula (A-17) is the same as in
表3~9に記載した染料化合物または従来からポリエステル繊維等の染色に使用されている分散染料化合物等の1種類のみを使用して超臨界二酸化炭素染色法によりポリプロピレン布、またはポリエチレン布の染色を行った。 <Dyeing example>
Dyeing polypropylene cloth or polyethylene cloth by supercritical carbon dioxide dyeing method using only one kind of dye compounds shown in Tables 3 to 9 or disperse dye compounds conventionally used for dyeing polyester fibers and the like. went.
[染色例P1]
染色に使用した超臨界二酸化炭素染色装置を図1に示す。
染色装置は、液体CO2ボンベ(1)、フィルター(2)、冷却ジャケット(3)、冷却器(4)、高圧ポンプ(5)、予熱器(6)、圧力ゲージ(7乃至9)、磁気駆動部(10)、DCモーター(11)、安全弁(12、13)、停止弁(14乃至18)、ニードル弁(19)、加熱器(20)から構成される。 <Polypropylene dyeing example>
[Staining example P1]
The supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG.
The dyeing equipment includes a liquid CO 2 cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high-pressure pump (5), a preheater (6), a pressure gauge (7 to 9), and magnetic. It is composed of a drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).
染色例1に記載する青色染料化合物A-5を表3~9に記載した染料化合物または従来からポリエステル繊維等の染色に使用されている分散染料化合物等に変更したこと以外は、染色例P1と同様の染色手順によりポリプロピレン染色布を得た。染色例P1乃至P82、および染色例P98乃至P101で使用した染料化合物を表10~表16に示す。 [Staining Examples P2 to P82 and Staining Examples P98 to P101]
Dyeing Example P1 and Dyeing Example P1 except that the blue dye compound A-5 described in Dyeing Example 1 was changed to the dye compounds shown in Tables 3 to 9 or the disperse dye compound conventionally used for dyeing polyester fibers and the like. A polypropylene dyed cloth was obtained by the same dyeing procedure. The dye compounds used in Dyeing Examples P1 to P82 and Dyeing Examples P98 to P101 are shown in Tables 10 to 16.
染色性は、染色布の測色により得られたTotalK/S値、及び染色後の染料残渣を目視により評価した。染色布の測色は積分球分光光度計 Color-Eye 5(グレタグマクベス社製)を用い、白色紙上に染色布を糊付し、観察光源D65、2度視野にて行った。 (1) Evaluation of dyeability The dyeability was visually evaluated for the Total K / S value obtained by measuring the color of the dyed cloth and the dye residue after dyeing. The color of the dyed cloth was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), the dyed cloth was glued on white paper, and the observation light source D65 was used in a 2 degree field of view.
耐光堅牢度試験は、JIS L0842:2004に準じた紫外線カーボンアーク灯法で行った。試験方法の概略は次のとおりである。紫外線フェードメータ U48(スガ試験機(株)製)を用いて、ブラックパネル温度63±3℃の条件下で、染色布に20時間露光後、変褪色の判定を行った。 (2) Light fastness test 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.
昇華堅牢度試験は、JIS L0854:2013に準じた方法で行った。試験方法の概略は次の通りである。染色布をナイロン布に挟み、12.5kPaの荷重下で、120±2℃で80分間保持後、変退色およびナイロン布への汚染の判定を行った。 (3) Sublimation fastness test The 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.
洗濯堅牢度試験は、JIS L0844:2011(A-2号)に準じた方法で行った。試験方法の概略は次の通りである。染色布に多織交織布を添付し、石けんの存在下、50±2℃の条件下で30分間洗濯を行い、変退色および多織交織布の綿部分とナイロン部分への汚染の判定を行った。また洗濯後の残液の汚染の判定を行った。 (4) Washing fastness test 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.
汗堅牢度試験は、JIS L0848:2004に準じた方法で行った。試験方法の概略は次の通りである。染色布に多織交織布を添付し、酸性人工汗液またはアルカリ性人工汗に30分間浸漬した後、12.5kPaの荷重下で、37±2℃で4時間保持後、60℃以下で乾燥し、変退色および多織交織布の綿部分とナイロン部分への汚染の判定を行った。 (5) 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.
摩擦堅牢度試験は、JIS L0849:2013に準じた方法で行った。試験方法の概略は次の通りである。摩擦堅牢度試験機RT-300((株)大栄科学精器製作所製)を用いて、染色布を、乾燥状態の綿布または湿潤状態の綿布で2Nの荷重をかけて100回往復摩擦を行い、綿布への着色の判定を行った。 (6) Friction fastness test The friction fastness test was carried out by a method according to JIS L0849: 2013. The outline of the test method is as follows. Using the friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the dyed cloth is rubbed 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N. The coloration of the cotton cloth was judged.
ホットプレッシングに対する堅牢度試験は、JIS L0850:2015(A-2号 乾燥)に準じた方法で行った。試験方法概略は次のとおりである。綿布の上に染色布を重ね、150℃の加熱板により4±1kPaの荷重下で、15秒間保持後、変退色および綿布への汚染の判定を行った。 (7) Fastness test for hot pressing 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.
表3~9に記載した染料化合物または従来からポリエステル繊維等の染色に使用されている分散染料化合物等を2種類以上混合使用した染料を用いて超臨界二酸化炭素染色法によりポリプロピレン繊維の染色を行った。 <Another example of polypropylene dyeing>
Polypropylene fibers are dyed by the supercritical carbon dioxide dyeing method using the dye compounds shown in Tables 3 to 9 or the dyes obtained by mixing two or more kinds of the disperse dye compounds conventionally used for dyeing polyester fibers and the like. rice field.
[染色例E1]
染色に使用した超臨界二酸化炭素染色装置を図1に示す。染色装置は、液体CO2ボンベ(1)、フィルター(2)、冷却ジャケット(3)、冷却器(4)、高圧ポンプ(5)、予熱器(6)、圧力ゲージ(7乃至9)、磁気駆動部(10)、DCモーター(11)、安全弁(12、13)、停止弁(14乃至18)、ニードル弁(19)、加熱器(20)から構成される。 <Example of polyethylene dyeing>
[Staining example E1]
The supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG. The dyeing equipment includes a liquid CO 2 cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high-pressure pump (5), a preheater (6), a pressure gauge (7 to 9), and magnetic. It is composed of a drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).
染色例E1に記載する青色染料化合物A-5を表3~9に記載した染料化合物または従来からポリエステル繊維等の染色に使用されている分散染料化合物等に変更したこと以外は、染色例E1と同様の染色手順によりポリエチレン染色布を得た。染色例E1乃至E14、および染色例E18乃至E20で使用した染料化合物を表28~32に示す。 [Staining Examples E2 to E14 and Staining Examples E18 to E20]
Dyeing Example E1 and Dyeing Example E1 except that the blue dye compound A-5 described in Dyeing Example E1 was changed to the dye compounds shown in Tables 3 to 9 or the disperse dye compound conventionally used for dyeing polyester fibers and the like. A polyethylene dyed cloth was obtained by the same dyeing procedure. The dye compounds used in Dyeing Examples E1 to E14 and Dyeing Examples E18 to E20 are shown in Tables 28 to 32.
染色性は、染色布の測色により得られたTotalK/S値、及び染色後の染料残渣を目視により評価した。染色布の測色は積分球分光光度計 Color-Eye 5(グレタグマクベス社製)を用い、白色紙上に染色布を糊付し、観察光源D65、2度視野にて行った。 (1) Evaluation of dyeability The dyeability was visually evaluated for the Total K / S value obtained by measuring the color of the dyed cloth and the dye residue after dyeing. The color of the dyed cloth was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), the dyed cloth was glued on white paper, and the observation light source D65 was used in a 2 degree field of view.
耐光堅牢度試験は、JIS L0842:2004に準じた紫外線カーボンアーク灯法で行った。試験方法の概略は次のとおりである。紫外線フェードメータ U48(スガ試験機(株)製)を用いて、ブラックパネル温度63±3℃の条件下で、染色布に20時間露光後、変褪色の判定を行った。 (2) Light fastness test 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.
洗濯堅牢度試験は、JIS L0844:2011(A-2号)に準じた方法で行った。試験方法の概略は次の通りである。染色布に多織交織布を添付し、石けんの存在下、50±2℃の条件下で30分間洗濯を行い、変退色および多織交織布の綿部分とナイロン部分への汚染の判定を行った。また洗濯後の残液の汚染の判定を行った。 (3) Washing fastness test 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.
汗堅牢度試験は、JIS L0848:2004に準じた方法で行った。試験方法の概略は次の通りである。染色布に多織交織布を添付し、酸性人工汗液またはアルカリ性人工汗に30分間浸漬した後、12.5kPaの荷重下で、37±2℃で4時間保持後、60℃以下で乾燥し、変退色および多織交織布の綿部分とナイロン部分への汚染の判定を行った。 (4) 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.
摩擦堅牢度試験は、JIS L0849:2013に準じた方法で行った。試験方法の概略は次の通りである。摩擦堅牢度試験機RT-300((株)大栄科学精器製作所製)を用いて、染色布を、乾燥状態の綿布または湿潤状態の綿布で2Nの荷重をかけて100回往復摩擦を行い、綿布への着色の判定を行った。 (5) Friction fastness test The friction fastness test was carried out by a method according to JIS L0849: 2013. The outline of the test method is as follows. Using the friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the dyed cloth is rubbed 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N. The coloration of the cotton cloth was judged.
表3~9に記載した染料化合物または従来からポリエステル繊維等の染色に使用されている分散染料化合物等を2種類以上混合使用した染料を用い、超臨界二酸化炭素染色法によりポリエチレン繊維の染色を行った。 <Another example of polyethylene dyeing>
Polyethylene fibers are dyed by a supercritical carbon dioxide dyeing method using the dye compounds shown in Tables 3 to 9 or dyes using a mixture of two or more types of disperse dye compounds conventionally used for dyeing polyester fibers and the like. rice field.
Claims (12)
- 下記一般式(A)~(G)の化合物の少なくとも一つを含む、超臨界二酸化炭素を用いてポリオレフィン繊維を染色するための染料。
XAはニトロ基、
YAはハロゲン原子を表し、
RA1、RA2及びRA3はそれぞれ独立して炭素数1乃至14のアルキル基を表し(ただしRA1、RA2及びRA3の少なくともひとつは炭素数4乃至14のアルキル基である)、
RA4は炭素数1乃至4のアルキル基を表す。]
XC及びYCは、水素原子およびハロゲン原子、ハロゲン原子およびニトロ基、ハロゲン原子およびシアノ基、シアノ基およびシアノ基、ニトロ基およびシアノ基、水素原子および水素原子のいずれかの組合せを表し、
RC1、RC2及びRC3はそれぞれ独立して炭素数1乃至14のアルキル基を表す(ただしRC1、RC2及びRC3の少なくともひとつは炭素数4乃至14のアルキル基である)。]
RD1は、炭素数1乃至14のアルキル基を表し、
RD2は、炭素数1乃至14のアルキル基またはCNで置換された炭素数1乃至14のアルキル基を表す。ただし、RD1及びRD2の少なくともひとつは炭素数4乃至14のアルキル基である。]
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. ]
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). ]
R D1 represents an alkyl group having 1 to 14 carbon atoms.
R D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. However, at least one of R D1 and R D2 is an alkyl group having 4 to 14 carbon atoms. ]
- 請求項1に記載の染料であって
黒色であり、
一般式(A)の化合物、一般式(B)の化合物、一般式(C)の化合物、及び一般式(F)の化合物からなる群から選択される一つ以上を含む紫色または青色の染料化合物の少なくとも一つと、
一般式(C)の化合物及び一般式(D)の化合物からなる群から選択される一つ以上を含む赤色の染料化合物と、
一般式(D)の化合物、一般式(E)の化合物及び一般式(G)の化合物からなる群から選択される一つ以上を含む黄色または橙色の染料化合物の少なくとも一つとを含む、染料。 The dye according to claim 1, which is black and has
A purple or blue dye compound containing one or more selected from the group consisting of a compound of the general formula (A), a compound of the general formula (B), a compound of the general formula (C), and a compound of the general formula (F). At least one of
A red dye compound containing one or more selected from the group consisting of the compound of the general formula (C) and the compound of the general formula (D), and
A dye comprising at least one of a yellow or orange dye compound comprising one or more selected from the group consisting of a compound of the general formula (D), a compound of the general formula (E) and a compound of the general formula (G). - 請求項2に記載の染料であって、
黒色であり、
一般式(A)の化合物、一般式(B)の化合物及び一般式(F)の化合物からなる群から選択される一つ以上を含む紫色または青色の染料化合物の少なくとも一つと、
一般式(C)の化合物の赤色の染料化合物と、
一般式(D)の化合物及び一般式(E)の化合物からなる群から選択される一つ以上を含む橙色の染料化合物とを含む、染料。 The dye according to claim 2.
It is black and
At least one of a purple or blue dye compound containing one or more selected from the group consisting of a compound of the general formula (A), a compound of the general formula (B) and a compound of the general formula (F).
The red dye compound of the compound of the general formula (C) and
A dye comprising an orange dye compound comprising one or more selected from the group consisting of a compound of the general formula (D) and a compound of the general formula (E). - 請求項2または3に記載の染料が、
一般式(A)の化合物の青色の染料化合物と、
一般式(C)の化合物の赤色の染料化合物と、
一般式(D)の化合物の橙色の染料化合物とを含む、
染料。 The dye according to claim 2 or 3 is
The blue dye compound of the compound of the general formula (A) and
The red dye compound of the compound of the general formula (C) and
Including the orange dye compound of the compound of the general formula (D),
dye. - 前記紫色または青色の染料化合物を30乃至70質量%、
前記赤色の染料化合物を5乃至25質量%、
前記黄色または橙色の染料化合物を15乃至55質量%の範囲含む
請求項2~4のいずれか一項にの染料。 30 to 70% by mass of the purple or blue dye compound,
5 to 25% by mass of the red dye compound,
The dye according to any one of claims 2 to 4, which contains the yellow or orange dye compound in the range of 15 to 55% by mass. - 前記紫色または青色の染料化合物を40乃至60質量%、
前記赤色の染料化合物を5乃至25質量%、
前記黄色または橙色の染料化合物を25乃至45質量%含む
請求項5に記載の染料。 40-60% by mass of the purple or blue dye compound,
5 to 25% by mass of the red dye compound,
The dye according to claim 5, which contains 25 to 45% by mass of the yellow or orange dye compound. - 超臨界二酸化炭素を用いたポリオレフィン繊維の染色方法であって、
請求項1~6のいずれか一項に記載の染料を用いて超臨界二酸化炭素存在下にポリオレフィン繊維を染色する工程を含む方法。 A method for dyeing polyolefin fibers using supercritical carbon dioxide.
A method comprising a step of dyeing a polyolefin fiber in the presence of supercritical carbon dioxide using the dye according to any one of claims 1 to 6. - 前記染色工程は、31℃以上かつ7.4MPa以上の圧力で行われる請求項7に記載の染色方法。 The dyeing method according to claim 7, wherein the dyeing step is performed at a pressure of 31 ° C. or higher and 7.4 MPa or higher.
- 前記繊維に対する前記染料の濃度は、0.1乃至6.0o.m.f.(on the mass of fiber)の範囲である請求項7または8に記載の染色方法。 The concentration of the dye with respect to the fiber is 0.1 to 6.0 o. m. f. The dyeing method according to claim 7 or 8, which is within the scope of (on the mass of fiber).
- 前記ポリオレフィン繊維が、ポリプロピレン樹脂繊維である請求項7~9のいずれか一項に記載の染色方法。 The dyeing method according to any one of claims 7 to 9, wherein the polyolefin fiber is a polypropylene resin fiber.
- 前記ポリオレフィン繊維が、ポリエチレン樹脂繊維である請求項7~9のいずれか一項に記載の染色方法。 The dyeing method according to any one of claims 7 to 9, wherein the polyolefin fiber is a polyethylene resin fiber.
- 請求項7~11のいずれか一項に記載の染色方法により染色されたポリオレフィン繊維。 Polyolefin fiber dyed by the dyeing method according to any one of claims 7 to 11.
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