WO2021187446A1

WO2021187446A1 - Dye for staining by using supercritical carbon dioxide

Info

Publication number: WO2021187446A1
Application number: PCT/JP2021/010477
Authority: WO
Inventors: 堀照夫; 宮崎慶輔; 松本敏昭; 小林樹; 杉村亮治
Original assignee: 国立大学法人福井大学; 学校法人金沢工業大学; 紀和化学工業株式会社
Priority date: 2020-03-17
Filing date: 2021-03-16
Publication date: 2021-09-23
Also published as: JP7205841B2; TW202338009A; CN115244139A; TW202142626A; KR20220123293A; TWI810535B; JPWO2021187446A1

Abstract

The present invention addresses the problem of providing: a dye for staining polyolefin fibers by using supercritical carbon dioxide, in which it is possible to stain the polyolefin fibers into a variety of hues at high concentration and the stained product has excellent color fastness to light, sublimation, laundering, and the like; a method for staining polyolefin fibers by using supercritical carbon dioxide; and polyolefin fibers stained by said staining method. Provided are: a dye for staining polyolefin fibers by using supercritical carbon dioxide, the dye containing at least one compound among general formulas (A) to (G); a method for staining polyolefin fibers by using said dye and supercritical carbon dioxide; and polyolefin fibers stained by said staining method.

Description

Dyes for dyeing with supercritical carbon dioxide

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.

On the other hand, 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.

For this reason, most of the colored polyolefin resins currently on the market are made by adding a colored pigment at the manufacturing stage of polymer pellets, etc., and then spinning, molding, etc. into a desired shape.

With this coloring method, it is necessary to determine the color at the initial stage of the resin product manufacturing process. In consideration of profitability, it is necessary to produce one color in a certain amount or more, and as a result, the freedom of choice of color is restricted.

Further, when changing the color of the resin product, it is necessary to replace the colored resin of the previous color remaining in the resin product manufacturing apparatus with the colored resin of the next color, and at that time, a large amount of waste is required. As the resin is generated, problems such as wasting time and energy occur.

As described in Non-Patent Document 1, 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.

However, the uses of polypropylene resin and polyethylene resin as synthetic fibers are very limited.

The reason for this is that, as described above, high-concentration and high-fast dyeing of polypropylene resin fibers and polyethylene resin fibers is extremely difficult, and the undiluted solution coloring method using a colored pigment, which is the only effective coloring method, has no choice but to increase the single yarn fineness. However, it is considered that the freedom of color selection is restricted.

So far, attempts have been made to change the molecular structure of dyes in order to dye polyolefin resin fibers in water. Specifically, 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.

However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone-based red dyes or anthraquinone-based purple dyes. Furthermore, regarding the form of the dye when used for dyeing, there is a description that these anthraquinone-based red dyes are used after being dissolved in alcohol or acetone which are organic solvents, and it is said that this dyeing method is environmentally friendly. It's hard to say.

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.

However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone blue dyes, and there is no specific description about the dyeing fastness of the obtained dyed product. Furthermore, regarding the form of the dye when it is used for dyeing, there is a description that these anthraquinone-based blue dyes are used after being dissolved in alcohol or acetone which are organic solvents, and it cannot be said that they are environmentally friendly.

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.

However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone blue dyes, and there is no specific description about the dyeing fastness of the obtained dyed product. Furthermore, regarding the form of the dye when it is used for dyeing, there is a description that it is used after being dissolved in alcohol or acetone which is an organic solvent, and it is said that the method using such a dye is environmentally friendly. hard.

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 α-position of an anthraquinone-based dye.

However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone blue dyes, and there is no specific description about the dyeing fastness of the obtained dyed product.

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.

However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone-based red dyes, and there is no specific description about the dyeing fastness of the obtained dyed product. Furthermore, regarding the form of the dye when it is used for dyeing, there is a description that it is used after being dissolved in dimethylformamide, which is an organic solvent, and it is hard to say that the method using such a dye is environmentally friendly. ..

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.

Further, in order to improve the dyeability of the polyolefin-based resin fiber, various modifications to the polyolefin-based resin fiber have been studied.

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.

Although the dyeability of these modified polyolefin resin fibers has been improved, there is a problem that the strength of the yarn is lowered by the dyeing treatment and the strength becomes insufficient when used for clothes or the like.

By the way, 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.

However, although 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.

Special Publication No. 38-10741 Tokukousho 40-1277 Gazette Special Publication No. 41-3515 UK Pat. No. 872,882 U.S. Pat. No. 3,536,735 Japanese Unexamined Patent Publication No. 55-152869 Japanese Patent No. 3253649

Therefore, 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).

[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. ]

[In 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 _B2, and R _B3 has 4 to 14 carbon atoms. It is an alkyl group). ]

[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). ]

[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. ]

Wherein _(E), X E and Y _E is a halogen atom independently, R _E represents an alkyl group having 4 to 18 carbon atoms. ]

[In formula (F), R _F1 and R _F2 each independently represent an alkyl group having 4 to 14 carbon atoms. ]

[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.

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.

<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.

[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. ]

[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.

In the formulas (A) to (D), 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. 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. Group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 1 Examples thereof include linear or branched alkyl groups having 1 to 14 carbon atoms such as -ethyl-1-methylpropyl group. As the 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.

In the formula (A), 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. As 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.

In the formulas (A) to (D) and (F), 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.

In the formula (E), 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. sec-pentyl group, t-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2 Linear or branched alkyl groups such as -ethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 1-ethyl-1-methylpropyl group. Can be mentioned. As the 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.

In the formula (G), 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.

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.

The compound of the formula (A) is a blue dye compound.

In the formula (A),
From the viewpoint of dyeing concentration, light fastness, sublimation fastness, etc.
Y _A is a bromine atom.

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.

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.

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 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.

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.

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).

The compound of the formula (C) is a red or purple dye compound.

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.

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.

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.

The compound of the formula (D) is an orange or red dye compound.

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.

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.

Compounds of general formula (E) are those wherein (E), X _E and Y _E is a halogen atom independently, R _E represents an alkyl group having 4 to 18 carbon atoms.

The compound of the formula (E) is an orange dye compound.

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.

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.

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.

In the compound of the general formula (F), in the formula (F), _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.

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.

Compounds of general formula (G) are those wherein (G), R _G is an alkyl group having 7 to 18 carbon atoms.

The compound of the formula (G) is a yellow dye compound.

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.

<Method for producing the compound of the general formula (A)>
A method for producing the compound represented by the formula (A) will be described.

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). And 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.

(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.

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.

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).

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.

(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.

N, N- dimethylformamide to (DMF) as a solvent, (wherein (a-C1), R _A4 represents an alkyl group of 1 to 4 carbon atoms) and a compound represented by formula (a-C1) to R _A3 -COX (R _A3 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) is reacted with a carboxylic acid halide represented by, obtaining a compound represented by the formula (a-C2).

Next, 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).

DMF as solvent, 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).

Alternatively, compounds of the formula _{(a-C4) R A1 -X} (R A1 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) reacting a halogenated hydrocarbon represented by _{After that, RA2} ( _RA2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced according to a known reaction. For example, ( _RA2 ) ₂ SO ₄ can be used to introduce _RA2.

<Method for producing the compound of general formula (B)>
A method for producing the compound represented by the formula (B) will be described.

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). In the compound (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).).

(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.

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.

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).

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.

(Iii) Method for Producing Compound of Formula (bC) The compound of formula (bC) which is a raw material can be produced as follows.

DMF as solvent, R _B3 -COX in m- nitroaniline (R _B3 represents an alkyl group of 1 to 14 carbon atoms, X represents a halogen atom) is reacted with a carboxylic acid halide represented by the formula (b -The compound represented by C1) is obtained.

Next, 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).

Using DMF as a solvent, 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).

Alternatively, 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 _{After that, R B2} ( _RB2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced according to a known reaction. For example, ( _RB2 ) ₂ SO ₄ can be used to introduce _{R B2.}

<Method for producing compound of general formula (C)>
A method for producing the compound represented by the formula (C) will be described.

The compound represented by formula (C) during 4-nitroaniline derivative represented by the formula (c-D) (Formula (c-D), 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), and the formula (CC). that in the compound (formula _{(c-C), 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))).

(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.

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.

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).

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.

(Iii) Method for Producing Compound of Formula (CC) The compound of formula (cc) which is a raw material can be produced as follows.

DMF as solvent, R _C3 -COX in m- nitroaniline (R _C3 represents an alkyl group of 1 to 14 carbon atoms, X is halogen atom) is reacted with a carboxylic acid halide represented by the formula (c -The compound represented by C1) is obtained.

Next, 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).

DMF as solvent, 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).

Or, 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 _{After that, RC2} ( _RC2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced according to a known reaction. For example, ( _RC2 ) ₂ SO ₄ can be used to introduce _RC2.

<Method for producing the compound of general formula (D)>
A method for producing the compound represented by the formula (D) will be described.

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. , Or a diazo compound represented by a cyano group) and a compound represented by the formula (dc) (in the formula (dc), _RD1 represents an alkyl group having 1 to 14 carbon atoms, and _{RD2 represents an alkyl group.} , Representing 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 RD1} and _RD2 is an alkyl group having 4 to 14 carbon atoms. Obtained by ringing.

(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.

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.

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).

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.

(Iii) Method for Producing Compound of Formula (dc) The compound of formula (dc) which is a raw material can be produced as follows.

DMF as solvent, 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.) And obtain the formula (dc).

Or, 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. For example, ( _RD2 ) ₂ SO ₄ can be used to introduce _{R D2.}

<Method for producing compound of general formula (E)>
A method for producing the compound represented by the formula (E) will be described.

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)).} And 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.

(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.

The compound represented by the formula (ed) is generally widely used as a raw material for azo-based disperse dyes.

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).

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.

(Iii) Method for Producing Compound of Formula (eC) The compound of formula (eC) which is a raw material can be produced as follows.

DMF as solvent, in the 2-phenyl -1H- indole of formula _{(e-C1) R E1 -X} (R E1 represents an alkyl group having 4 to 18 carbon atoms, X is halogen atom) The represented alkyl halide is reacted to give the formula (EC).

<Method for producing the compound of general formula (F)>
A method for producing the compound represented by the formula (F) will be described.

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).

(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.

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.

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).

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.

(Iii) Method for Producing Compound of Formula (fc) The compound of formula (fc) which is a raw material can be produced as follows.

Halogen DMF as solvent, aniline (alkyl group R _F1 and R _F2 having 4 to atoms each independently 14, X is the halogen atom) R _F1 -X and R _F2 -X represented by The alkyl compound is reacted to give the formula (fc).

Or, 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. For example, ( _RF2 ) ₂ SO ₄ can be used to introduce _{R F2.}

<Method for producing compound of general formula (G)>
A method for producing the compound represented by the formula (G) will be described.

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. When, R _{_G} -COX (R _G represents an alkyl group having 7 to 18 carbon atoms, X is halogen atom) is obtained by reacting a carboxylic acid halide represented by.

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.

<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.

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). A red dye compound containing at least one of a purple or blue dye compound containing one or more, and one or more selected from the group consisting of a compound of the general formula (C) and a compound of the general formula (D). It preferably contains at least one of a yellow or orange dye compound containing one or more selected from the group consisting of the compound of the general formula (D), the compound of the general formula (E) and the compound of the general formula (G). , 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. Examples of 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, α-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 α-olefins, or copolymers of these α-olefins with other unsaturated monomers copolymerizable. .. Further, examples of the type of copolymer include block copolymers, random copolymers, graft copolymers and the like. Specific examples of the polymer include polypropylene-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.

<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.

Compared with the general dyeing method that uses water 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.

Further, since supercritical carbon dioxide is lipophilic and both the dye and the polyolefin-based resin of the present invention are lipophilic, the dyeing medium, the dye, and the object to be dyed have high affinity with each other, resulting in a high-quality dyed product. can get.

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.

In the dyeing step, 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.

In the dyeing step, 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.

In the dyeing step, the concentration of the dye with respect to the fiber depends on the type of fiber to be dyed and the processing state. When the fiber to be dyed is fibrous, 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.

In the dyeing method of the present invention, 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. When the object to be dyed is a polypropylene cloth wrapped in a suitable cheese, 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.

Hereinafter, the present invention will be described in more detail with reference to examples, but the embodiments of the present invention are not limited thereto.

[Example]
(Synthesis Example 1)
[Synthesis of blue dye compound (A-1)]
The blue dye compound (A-1) was produced according to the following scheme.

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.

(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. After washing this extract with saturated brine, the solvent was distilled off under reduced pressure to obtain N- (3-nitro-4-methoxyphenyl) octaneamide (16.9 g, yield 114) represented by the following formula (C1b). 8.8%) was obtained as a crude product.

(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).

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.

1-C. Synthesis of blue dye compound (A-1) by coupling reaction (step 6)
The diazo component solution obtained in step 5 is added dropwise to the coupler component solution obtained in step 4 over 2 hours while appropriately adding triethylamine (84 g) in the range of 0 to 10 ° C., and coupling is performed. The reaction was carried out. The mixture is stirred in the range 0-10 ° C. for 30 minutes, then the product is filtered off from the reaction mixture, washed with methanol and then water at 60 ° C. until the water content is 1.0% by mass or less. The mixture was dried to obtain a blue dye compound (5.93 g, yield 15.5%) represented by the following formula (A-1). The structure of the blue-stained compound was confirmed by LCMS analysis (m / z 761 (M ^+)).

(Synthesis Example 2)
[Synthesis of blue dye compound (A-2)]
The blue dye compound (A-2) was produced according to the following scheme.

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 Steps 1 to 4 of Synthesis Example 1 except that Valeryl chloride (25.3 g) is used instead of n-octanoyl chloride in Step 1 of Synthesis Example 1. N- [3- (N, N-dioctylamino) -4-methoxyphenyl] pentanamide 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 (C2).

2-B. Synthesis of blue dye compound (A-2) by coupling reaction (step 2)
The following formula (A-2) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C2) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (8.03 g, yield 22.3%). The structure of this blue-stained compound was confirmed by LCMS analysis (m / z 719 (M ^+)).

(Synthesis Example 3)
[Synthesis of blue dye compound (A-3)]
The blue dye compound (A-3) was produced according to the following scheme.

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 Steps 1 to 4 of Synthesis Example 1 except that propionyl chloride (19.4 g) is used instead of n-octanoyl chloride in Step 1 of Synthesis Example 1. -[3- (N, N-dioctylamino) -4-methoxyphenyl] propanamide 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 (C3).

3-B. Synthesis of blue dye compound (A-3) by coupling reaction (step 2)
The following formula (A-3) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C3) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (5.85 g, yield 16.9%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 691 (M ^+)).

(Synthesis Example 4)
[Synthesis of blue dye compound (A-4)]
The blue dye compound (A-4) was produced according to the following scheme.

4-A. Synthesis of coupler compound C4 and preparation of coupler component solution (step 1)
The following formula (C4) is the same as in Steps 1 to 4 of Synthesis Example 1 except that 2-ethylhexanoyl chloride (34.2 g) is used instead of n-octanoyl chloride in Step 1 of Synthesis Example 1. N- [3- (N, N-dioctylamino) -4-methoxyphenyl] -2-ethylhexaneamide represented by (1) 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 (C4).

4-B. Synthesis of blue dye compound (A-4) by coupling reaction (step 2)
The following formula (A-4) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C4) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (9.63 g, yield 25.3%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 761 (M ^+)).

(Synthesis Example 5)
[Synthesis of blue dye compound (A-5)]
The blue dye compound (A-5) was produced according to the following scheme.

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).

5-B. Synthesis of blue dye compound (A-5) by coupling reaction (step 2)
The following formula (A-5) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C5) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (20.3 g, yield 60.0%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 677 (M ^+)).

(Synthesis Example 6)
[Synthesis of blue dye compound (A-6)]
The blue dye compound (A-6) was produced according to the following scheme.

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).

6-B. Synthesis of blue dye compound (A-6) by coupling reaction (step 2)
The following formula (A-6) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C6) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (19.3 g, yield 48.9%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 789 (M ^+)).

(Synthesis Example 7)
[Synthesis of blue dye compound (A-7)]
The blue dye compound (A-7) was produced according to the following scheme.

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).

7-B. Synthesis of blue dye compound (A-7) by coupling reaction (step 2)
The following formula (A-7) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C7) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (7.71 g, yield 26.0%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 593 (M ^+)).

(Synthesis Example 8)
[Synthesis of blue dye compound (A-8)]
The blue dye compound (A-8) was produced according to the following scheme.

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 Steps 1 to 4 of Synthesis Example 1 except that 4-ethoxyaniline (27.4 g) is used instead of p-anisidine in Step 1 of Synthesis Example 1. -[3- (N, N-dioctylamino) -4-ethoxyphenyl] 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 (C8).

8-B. Synthesis of blue dye compound (A-8) by coupling reaction (step 2)
The following formula (A-8) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C8) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (4.50 g, yield 11.6%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 775 (M ^+)).

(Synthesis Example 9)
[Synthesis of blue dye compound (B-1)]
The blue dye compound (B-1) was produced according to the following scheme.

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 Step 1 of Synthesis Example 1 except that 3-nitroaniline (27.6 g) is used instead of p-anisidine (27.6 g). 53.6 g, yield 101.4%) was obtained as a crude product.

(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. The 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. 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).

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.

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 ^+)).

(Synthesis Example 10)
[Synthesis of blue dye compound (B-2)]
The blue dye compound (B-2) was produced according to the following scheme.

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 Steps 1 to 3 of Synthesis Example 9 except that Valeryl chloride (25.3 g) is used instead of n-octanoyl chloride in Step 1 of Synthesis Example 9. N- [3- (N, N-dioctylamino) phenyl] pentanamide 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 (C10).

10-B. Synthesis of blue dye compound (B-2) by coupling reaction (step 2)
The following formula (B-2) is the same as in steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C10) obtained in step 1 is used instead of the compound of the formula (C9) as the coupler component solution. ) Was obtained (9.47 g, yield 30.4%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 623 (M ^+)).

(Synthesis Example 11)
[Synthesis of blue dye compound (B-3)]
The blue dye compound (B-3) was produced according to the following scheme.

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 steps 1 to 3 of Synthesis Example 9 except that propionyl chloride (19.4 g) is used instead of n-octanoyl chloride in Step 1 of Synthesis Example 9. -[3- (N, N-dioctylamino) phenyl] propanamide 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 (C11).

11-B. Synthesis of blue dye compound (B-3) by coupling reaction (step 2)
The following formula (B-3) is the same as in steps 4 and 5 of Synthesis Example 9 except that the compound of formula (C11) obtained in step 1 is used instead of the compound of formula (C9) as the coupler component solution. ) Was obtained (13.4 g, yield 45.0%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 595 (M ^+)).

(Synthesis Example 12)
[Synthesis of blue dye compound (B-4)]
The blue dye compound (B-4) was produced according to the following scheme.

12-A. Synthesis of coupler compound C12 and preparation of coupler component solution (step 1)
In the same manner as in Step 3 of Synthesis Example 9, the following formula ( The N- [3- (N, N-dioctylamino) phenyl] acetamide represented by C12) 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 (C12).

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 steps 4 and 5 of Synthesis Example 9 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 (20.3 g, yield 69.9%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 581 (M ^+)).

(Synthesis Example 13)
[Synthesis of blue dye compound (B-5)]
The blue dye compound (B-5) was produced according to the following scheme.

13-A. Synthesis of coupler compound C13 and preparation of coupler component solution (step 1)
In step 3 of Synthesis Example 9, 1-bromododecane (49.8 g) is used instead of 1-bromooctane, and 3'-aminoacetanilide (7.50 g) is used instead of N- (3-aminophenyl) octaneamide. ) Was used, and N- [3- (N, N-didodecylamino) phenyl] acetamide represented by the following formula (C13) was obtained in the same manner as in Step 3 of Synthesis Example 9. 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 (C13).

13-B. Synthesis of blue dye compound (B-5) by coupling reaction (step 2)
The following formula (B-5) is the same as in steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C13) obtained in step 1 is used instead of the compound of the formula (C9) as the coupler component solution. ) Was obtained (9.81 g, yield 28.3%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 693 (M ^+)).

(Synthesis Example 14)
[Synthesis of blue dye compound (B-6)]
The blue dye compound (B-6) was produced according to the following scheme.

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 step 1 of Synthesis Example 9, and 1-bromododecane (49.8 g) was used in place of 1-bromooctane in step 3 of Synthesis Example 9. In the same manner as in Steps 1 to 3 of Synthesis Example 9, N- [3- (N, N-didodecylamino) phenyl] propanamide represented by the following formula (C14) 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 (C14).

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 steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C14) is used instead of the compound of the formula (C9) as the coupler component solution. A compound (5.73 g, yield 16.2%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 707 (M ^+)).

(Synthesis Example 15)
[Synthesis of blue dye compound (B-7)]
The blue dye compound (B-7) was produced according to the following scheme.

15-A. Synthesis of coupler compound C15 and preparation of coupler component solution (step 1)
In step 3 of Synthesis Example 9, use 3'-aminoacetanilide (7.50 g) instead of N- (3-aminophenyl) octaneamide, 1-bromo-2-ethylhexane instead of 1-bromooctane. N- [3- [N, N-di (2-ethylhexyl) amino] phenyl] propane represented by the following formula (C15) in the same manner as in step 3 of Synthesis Example 9 except that (38.6 g) is used. 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 (C15).

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 steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C15) is used instead of the compound of the formula (C9) as the coupler component solution. A compound (4.72 g, yield 16.2%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 581 (M ^+)).

(Synthesis Example 16)
[Synthesis of blue dye compound (B-8)]
The blue dye compound (B-8) was produced according to the following scheme.

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 steps 1 to 3 of synthesis example 9 except that 1-bromoethane (27.3 g) is used instead of 1-bromooctane in step 3 of synthesis example 9. -[3- (N, N-diethylamino) phenyl] 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 (C16).

16-B. Synthesis of blue dye compound (B-8) by coupling reaction (step 2)
The following formula (B-8) is the same as in steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C16) obtained in step 1 is used instead of the compound of the formula (C9) as the coupler component solution. ) Was obtained (23.2 g, yield 93.4%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 497 (M ^+)).

(Synthesis Example 17)
[Synthesis of red dye compound (C-1)]
The red dye compound (C-1) was produced according to the following scheme.

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.

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 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. 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 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 ^+)).

(Synthesis Example 18)
[Synthesis of red dye compound (C-2)]
The red dye compound (C-2) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 19)
[Synthesis of red dye compound (C-3)]
The red dye compound (C-3) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 20)
[Synthesis of red dye compound (C-4)]
The red dye compound (C-4) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 21)
[Synthesis of red dye compound (C-5)]
The red dye compound (C-5 was produced according to the following scheme.

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 ^+)).

(Synthesis Example 22)
[Synthesis of red dye compound (C-6)]
The red dye compound (C-6) was produced according to the following scheme.

22-A. Synthesis of coupler compound C17 and preparation of coupler component solution (step 1)
In step 3 of Synthesis Example 9, use 3'-aminoacetanilide (7.50 g) instead of N- (3-aminophenyl) octaneamide, 1-bromobutane (27.4 g) instead of 1-bromooctane. In the same manner as in Step 3 of Synthesis Example 9, N- [3- (N, N-dibutylamino) phenyl] acetamide represented by the following formula (C17) 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 (C17).

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 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 ^+)).

(Synthesis Example 23)
[Synthesis of red dye compound (C-7)]
The red dye compound (C-7) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 24)
[Synthesis of orange dye compound (D-1)]
The orange dye compound (D-1) was produced according to the following scheme.

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).

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.

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 step 1 over 2 hours while appropriately adding triethylamine (20 g) in the range of 0 to 10 ° C. And dropped, and a coupling reaction was carried out. 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. An orange dye compound (23.1 g, yield 86.4%) represented by the following formula (D-1) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 535 (M ^+)).

(Synthesis Example 25)
[Synthesis of orange dye compound (D-2)]
The orange dye compound (D-2) was produced according to the following scheme.

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).

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 steps 2 and 3 of Synthesis Example 24 except that the compound of the formula (C19) is used instead of the compound of the formula (C18) as the coupler component solution. A compound (14.1 g, yield 43.6%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 647 (M ^+)).

(Synthesis Example 26)
[Synthesis of orange dye compound (D-3)]
The orange dye compound (D-3) was produced according to the following scheme.

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).

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 steps 2 and 3 of Synthesis Example 24 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 (10.2 g, yield 48.2%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 423 (M ^+)).

(Synthesis Example 27)
[Synthesis of yellow dye compound (G-1)]
The yellow dye compound (G-1) was produced according to the following scheme.

A mixture of thionyl chloride (14.3 g) and toluene (20 g) was added dropwise to a mixture of 2-hexyl decanoic acid (30.8 g) and toluene (30 g). A mixture of pyridine (9.49 g) and toluene (30 g) was slowly added dropwise to this mixture over 1 hour, then the temperature was raised to 110 ° C. and the mixture was stirred for 1 hour. After cooling to room temperature, a mixture of 5-amino-anthra [9,1-cd] isothiazole-6-one (25.2 g) and toluene (30 g) was added dropwise. The temperature was raised to 110 ° C. and the mixture was stirred for 2 hours, the solvent was distilled off under reduced pressure, and methanol (100 g) was added to precipitate a precipitate. The mixture was filtered off, washed with methanol and then with water, dried at 60 ° C. until the water content was 1.0% by mass or less, and the yellow dye compound represented by the following formula (G-1) (36.7 g, Yield 74.7%) was obtained. The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 491 (M ^+)).

(Synthesis Example 28)
[Synthesis of yellow dye compound (G-2)]
The yellow dye compound (G-2) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 29)
[Synthesis of purple dye compound (F-1)]
The purple dye compound (F-1) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 30)
[Synthesis of orange dye compound (D-4)]
The orange dye compound (D-4) was produced according to the following scheme.

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.

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 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. 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. 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 ^+)).

(Synthesis Example 31)
[Synthesis of orange dye compound (D-5)]
The orange dye compound (D-5) was produced according to the following scheme.

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.

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 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. An orange dye compound (27.6 g, yield 88.6%) represented by the following formula (D-5) was obtained. The structure of the orange dye compound was confirmed by the following formula (D-5) by LCMS analysis (m / z 623 (M ^+)).

(Synthesis Example 32)
[Synthesis of orange dye compound (D-6)]
The orange dye compound (D-6) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 33)
[Synthesis of orange dye compound (E-1)]
The orange dye compound (E-1) was produced according to the following scheme.

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).

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 step 1 over 1 hour while appropriately adding triethylamine (20 g) in the range of 0 to 10 ° C., and a coupling reaction was carried out. 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. An orange dye compound (11.3 g, yield 43.2%) represented by the following formula (E-1) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 523 (M ^+)).

(Synthesis Example 34)
[Synthesis of orange dye compound (E-2)]
The orange dye compound (E-2) was produced according to the following scheme.

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 Step 1 of Synthesis Example 33 except that 1-bromobutane (7.53 g) was used instead of 1-bromooctane. .. 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 (C22).

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 steps 1 and 2 of Synthesis Example 33 except that the compound of the formula (C22) is used instead of the compound of the formula (C21) as the coupler component solution. A compound (14.5 g, yield 62.1%) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m / z 467 (M ^+)).

(Synthesis Example 35)
[Synthesis of red dye compound (D-7)]
The red dye compound (D-7) was produced according to the following scheme.

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.

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 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. 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 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 ^+)).

(Synthesis Example 36)
[Synthesis of purple dye compound (C-8)]
The purple dye compound (C-8) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 37)
[Synthesis of purple dye compound (C-9)]
The purple dye compound (C-9) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 38)
[Synthesis of purple dye compound (C-10)]
The purple dye compound (C-10) was produced according to the following scheme.

A mixture of sodium bromide (5.92 g), triethylamine (0.50 g) and DMF (80 g) was stirred in the range of 35-40 ° C. for 15 minutes, cuprous cyanide (5.0 g) was added and the same. The mixture was stirred at warm temperature for 15 minutes. Purple dye compound (C-9) (34.3 g) was added to this mixture, the temperature was raised to 110 ° C., and the mixture was stirred for 1 hour. After cooling to 80 ° C., a mixture of water (190 g) and sodium hypochlorite (18 g) was added, and the mixture was stirred at 70 to 80 ° C. for 1 hour and then cooled to room temperature. 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 ^+)).

(Synthesis Example 39)
[Synthesis of purple dye compound (C-11)]
The purple dye compound (C-11) was produced according to the following scheme.

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.

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 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. 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 (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 ^+)).

(Synthesis Example 40)
[Synthesis of purple dye compound (C-12)]
The purple dye compound (C-12) was produced according to the following scheme.

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 Steps 1 to 3 of Synthesis Example 9 except that 1-Bromobutane (27.4 g) is used instead of 1-Bromooctane in Step 3 of Synthesis Example 9. -[3- (N, N-dibutylamino) phenyl] 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 (C23).

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 ^+)).

(Synthesis Example 41)
[Synthesis of purple dye compound (C-13)]
The purple dye compound (C-13) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 42)
[Synthesis of purple dye compound (C-14)]
The purple dye compound (C-14) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 43)
[Synthesis of purple dye compound (C-15)]
The purple dye compound (C-15) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 44)
[Synthesis of purple dye compound (C-16)]
The purple dye compound (C-16) was produced according to the following scheme.

In Synthesis Example 38, the following formula (C) is the same as in Synthesis Example 38 except that the purple dye compound (27.2 g) of formula (C-14) is used instead of the purple dye compound of formula (C-9). A purple dye compound (22.0 g, yield 89.8%) represented by -16) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 490 (M ^+)).

(Synthesis Example 45)
[Synthesis of yellow dye compound (G-3)]
The yellow dye compound (G-3) was produced according to the following scheme.

In Synthesis Example 28, 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 ^+)).

(Synthesis Example 46)
[Synthesis of yellow dye compound (G-4)]
The yellow dye compound (G-4) was produced according to the following scheme.

In Synthesis Example 28, the yellow dye compound represented by the following formula (G-4) (31. 0 g, yield 78.9%) was obtained. The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 393 (M ^+)).

(Synthesis Example 47)
[Synthesis of blue dye compound (B-9)]
The blue dye compound (B-9) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 48)
[Synthesis of blue dye compound (B-10)]
The blue dye compound (B-10) was produced according to the following scheme.

48-A. Synthesis of coupler compound C24 and preparation of coupler component solution (step 1)
The following formula (C24) is the same as in steps 1 to 3 of Synthesis Example 9 except that 2-ethylhexanoyl chloride (34.2 g) is used instead of n-octanoyl chloride in Step 1 of Synthesis Example 9. N- [3- (N, N-dioctylamino) phenyl] -2-ethylhexaneamide represented by. 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 (C24).

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 steps 4 and 5 of Synthesis Example 9 except that the compound of the formula (C24) is used instead of the compound of the formula (C9) as the coupler component solution. A compound (19.0 g, yield 57.1%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 665 (M ^+)).

(Synthesis Example 49)
[Synthesis of orange dye compound (D-8)]
The orange dye compound (D-8) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 50)
[Synthesis of orange dye compound (D-9)]
The orange dye compound (D-9) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 51)
[Synthesis of orange dye compound (D-10)]
The orange dye compound (D-10) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 52)
[Synthesis of orange dye compound (D-11)]
The orange dye compound (D-11) was produced according to the following scheme.

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.

(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).

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 ^+)).

(Synthesis Example 53)
[Synthesis of red dye compound (C-17)]
The red dye compound (C-17) was produced according to the following scheme.

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).

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 ^+)).

(Synthesis Example 54)
[Synthesis of purple dye compound (F-2)]
The purple dye compound (F-2) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 55)
[Synthesis of blue dye compound (B-11)]
The blue dye compound (B-11) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 56)
[Synthesis of blue dye compound (A-9)]
The blue dye compound (A-9) was produced according to the following scheme.

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 step 3 of Synthesis Example 1 ) Was heated to 110 ° C. and stirred for 3 hours. After cooling to room temperature, toluene (50 g) and a 10% aqueous sodium carbonate solution (75 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- (3-cyanoethylamino-4-methoxyphenyl) octaneamide (9.05 g, yield) represented by the following formula (C27a). 57.0%) was obtained as a crude product.

(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).

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 steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C27) is used instead of the compound of the formula (C1) as the coupler component solution. A compound (9.70 g, yield 31.4%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 618 (M ^+)).

(Synthesis Example 57)
[Synthesis of blue dye compound (A-10)]
The blue dye compound (A-10) was produced according to the following scheme.

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 step 1 of Synthesis Example 56. The mixture of 0 g) was heated to 120 ° C. and stirred for 8 hours to obtain N- (3-N-octyl-N-cyanoethylamino-4-methoxyphenyl) octaneamide represented by the following formula (C28). .. 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 (C28).

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 steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C28) is used instead of the compound of the formula (C1) as the coupler component solution. A compound (5.52 g, yield 15.7%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 702 (M ^+)).

(Synthesis Example 58)
[Synthesis of blue dye compound (A-11)]
The blue dye compound (A-11) was produced according to the following scheme.

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 step 3 of Synthesis Example 1 ) Is heated to 110 ° C. and stirred for 8 hours to obtain N- [3-N, N- (2-dimethoxyethyl) amino-4-methoxyphenyl] octaneamide represented by the following formula (C29). 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 (C29).

(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 ^+)).

(Synthesis Example 59)
[Synthesis of blue dye compound (A-12)]
The blue dye compound (A-12) was produced according to the following scheme.

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).

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 steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C30) is used instead of the compound of the formula (C1) as the coupler component solution. A compound (14.1 g, yield 49.9%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 565 (M ^+)).

(Synthesis Example 60)
[Synthesis of blue dye compound (A-13)]
The blue dye compound (A-13) was produced according to the following scheme.

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).

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 steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C31) is used instead of the compound of the formula (C1) as the coupler component solution. A compound (10.7 g, yield 34.5%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 621 (M ^+)).

(Synthesis Example 61)
[Synthesis of blue dye compound (A-14)]
The blue dye compound (A-14) was produced according to the following scheme.

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 step 1 of Synthesis Example 1 and using 1-bromoethane (27.3 g) instead of 1-bromooctane in step 4. Obtained N- [3- (N, N-diethylamino) -4-methoxyphenyl] pentanamide represented by the following formula (C32) in the same manner as in Steps 1 to 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 (C32).

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 steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C32) is used instead of the compound of the formula (C1) as the coupler component solution. A compound (24.1 g, yield 87.5%) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m / z 551 (M ^+)).

(Synthesis Example 62)
[Synthesis of blue dye compound (A-15)]
The blue dye compound (A-15) was produced according to the following scheme.

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 step 1 of Synthesis Example 1 and the use of 1-bromoethane (27.3 g) in place of 1-bromooctane in step 4. N- [3- (N, N-diethylamino) -4-methoxyphenyl] dodecaneamide represented by the following formula (C33) was obtained in the same manner as in Steps 1 to 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 (C33).

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 ^+)).

(Synthesis Example 63)
[Synthesis of red dye compound (C-18)]
The red dye compound (C-18) was produced according to the following scheme.

63-A. Synthesis of coupler compound C34 and preparation of coupler component solution (step 1)
In step 3 of Synthesis Example 9, 1-bromohexane (33.0 g) was used instead of 1-bromooctane, and 3'-aminoacetanilide (7.50 g) was used instead of N- (3-aminophenyl) octaneamide. ) Was used, and N- [3- (N, N-dihexylamino) phenyl] acetamide represented by the following formula (C34) was obtained in the same manner as in Step 3 of Synthesis Example 9. 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 (C34).

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 ^+)).

(Synthesis Example 64)
[Synthesis of orange dye compound (D-12)]
The orange dye compound (D-12) was produced according to the following scheme.

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).

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 ^+)).

(Synthesis Example 65)
[Synthesis of orange dye compound (D-13)]
The orange dye compound (D-13) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 66)
[Synthesis of blue dye compound (A-16)]
The blue dye compound (A-16) was produced according to the following scheme.

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 step 1 of Synthesis Example 1. In the same manner as in Steps 1 to 4, N- [3- (N, N-dioctylamino) -4-butoxyphenyl] propanamide represented by the following formula (C36) 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 (C36).

66-B. Synthesis of blue dye compound (A-16) by coupling reaction (step 2)
The following formula (A-16) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C36) obtained in step 1 is used instead of the compound of formula (C1) as the coupler component solution. ) Was obtained (6.45 g, yield 17.6%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 733 (M ^+)).

(Synthesis Example 67)
[Synthesis of red dye compound (C-19)]
The red dye compound (C-19) was produced according to the following scheme.

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 step 1 of Synthesis Example 9, and 1-bromohexane (33.0 g) was used in place of 1-bromooctane in step 3 of Synthesis Example 9. In the same manner as in Steps 1 to 3 of Synthesis Example 9, N- [3- (N, N-dihexylamino) phenyl] propanamide represented by the following formula (C37) 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 (C37).

67-B. Synthesis of red dye compound (C-19) by coupling reaction (step 2)
Similar to steps 1 and 2 of Synthesis Example 17, the following formula (C-19) is used as the coupler component solution, except that the compound of the formula (C37) obtained in step 1 is used instead of the compound of formula (C9). ) Was obtained (17.6 g, yield 68.2%). The structure of the red dye compound was confirmed by LCMS analysis (m / z 516 (M ^+)).

(Synthesis Example 68)
[Synthesis of red dye compound (C-20)]
The red dye compound (C-20) was produced according to the following scheme.

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 ^+)).

(Synthesis Example 69)
[Synthesis of blue dye compound (A-17)]
The blue dye compound (A-17) was produced according to the following scheme.

69-A. Synthesis of coupler compound C38 and preparation of coupler component solution (step 1)
In 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).

69-B. Synthesis of blue dye compound (A-17) by coupling reaction (step 2)
The following formula (A-17) is the same as in steps 5 and 6 of Synthesis Example 1 except that the compound of the formula (C38) obtained in the step 1 is used instead of the compound of the formula (C1) as the coupler component solution. ) Was obtained (15.3 g, yield 48.4%). The structure of the blue dye compound was confirmed by LCMS analysis (m / z 663 (M ^+)).

Tables 3 to 9 show the structural formulas of the dye compounds described in the synthetic examples and the conventional dye compounds.

<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.

<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).

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.

After reaching the dyeing temperature, 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.

After the inside of the pressure-resistant stainless steel tank reached a predetermined temperature and pressure (120 ° C., 25 MPa), 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.

[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.

Regarding the polypropylene dyed cloths obtained in Dyeing Examples P1 to P82 and Dyeing Examples P98 to P101, dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, friction fastness test and Robustness tests against hot pressing were performed.

(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.

(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.

(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.

(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.

(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.

(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.

(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.

Tables 17 and 18 show the evaluation results of the dyed examples of the compound of the formula (A).

The staining of the compounds of formula _{(A), R A1, R} A2, at least one is alkyl group having 4 or more carbon atoms the compound of R _A3 used in Dyeing Example P1 to P7 and P73 to P77, P98 and P99 The stainability was good.

However, a disperse dye or the like used in the dyeing of such polyester fibers conventionally used in Dyeing Example P8 to P14, R _A1, R _A2, all R _A3 is less than 4 carbon atoms alkyl or CN and OCH The dyeability of the compound which is an alkyl group substituted with ₃ or CH = CH _{2 was poor.}

Also, for each fastness of the compound of formula (A), X _A is a nitro group, Y _A is a bromine atom, and at R _A1, R _A2, at least one is alkyl group having 4 or more carbon atoms of R _A3 Some compounds were good.

Table 19 shows the evaluation results of the dyeing example of the compound of the formula (B).

Wherein the staining of the compounds of (B), R _B1 used in Dyeing Example P15 to P23 and and P78, R _B2, R _B3 represents an alkyl group (provided that R _B1 of 1 to 14 carbon atoms, R _B2 and R _B3 The stainability of the compound (at least one of which is an alkyl group having 4 to 14 carbon atoms) was good.

However, the dyeability of the alkyl group compound in which _{R B1} and R _B2 are _{substituted with OCH 3} , which is the disperse dye used for dyeing polyester fibers and the like used in Dyeing Example P24 or P25, is poor. there were.

Tables 20 and 21 show the evaluation results of the dyeing examples of the compound of the formula (C).

For staining of compound of formula (C), the alkyl group of Dyeing Example P26 to P39, P79, P80, P100 and R _C1 used in P101, R _C2 and R _C3 having 1 to carbon atoms each independently 14 It represents (wherein R _C1, at least one of R _C2 and R _C3 are an alkyl group having 4 to 14 carbon atoms) staining of the compounds was good.

However, the dyeability of the compound such as the disperse dye used for dyeing polyester fibers and the like used in the dyeing examples P40 to P46 was poor.

Regarding the fastness of each compound of the formula (C), X _C is a chlorine atom, Y _C is a hydrogen atom, or X _C is a hydrogen atom, Y _C is a hydrogen atom, and _RC1 , _RC2, and R. _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).

The staining of the compounds of formula (D), Dyeing Example P47 to P53, P60, P81, and R _D1 and R _D2 used in the P82 staining of independently Compound alkyl group having 1 to 14 carbon atoms Was good.

However, the dyeability of the disperse dyes and the like conventionally used for dyeing polyester fibers and the like used in dyeing examples P54 to P59 and P61 was poor.

Regarding the fastness of the compound of the formula (D), the compound in which _{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 is used. It was good.

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.

However, the dyeing property of the dye compound conventionally used for dyeing polyester fibers and the like used in dyeing example P64 was poor.

Also, for each fastness of the compound of formula (E), it was as good as the number of carbon atoms of the hydrocarbon group R _E is large.

Table 24 shows the evaluation results of dyeing examples of the compound of the formula (F).

The staining of the compounds of formula (F), staining of the compounds of the alkyl group R _F1 and R _F2 having 4 to atoms each independently 14 used in Dyeing Example P65 was good.

However, the dyeability of the disperse dyes and the like conventionally used for dyeing polyester fibers and the like used in dyeing example P66 or P67 was poor.

Also, for each fastness of the compound of formula (F), it was as good as compound larger number of carbon atoms of R _F1 and R _F2.

Table 25 shows the evaluation results of the dyeing examples 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.}

However, the dyeing property of the dye compound conventionally used for dyeing polyester fibers and the like used in dyeing example P72 was poor.

Further, the fastness of each compound of the formula (G) was better as the carbon number of _{RG was larger.}

<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.

Regarding the obtained dyed cloth, 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 evaluation results of the dye are shown in Tables 26 and 27.

As shown in Tables 26 and 27, when the orange dye, the red dye, the purple dye and the blue dye of the present invention obtained in the dyeing examples P83 to P95 and P102 to P107 are mixed and used, the dyeability is good. Moreover, a black dyed cloth having good fastness was obtained.

<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).

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.

After the inside of the pressure-resistant stainless steel tank reached a predetermined temperature and pressure (98 ° C., 25 MPa), 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.

[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.

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.

(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.

(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.

(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.

Table 33 shows the evaluation results of dyeing examples of the compound of the formula (A).

Wherein 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.

Also, for each fastness of the compound of formula (A), X _A is a nitro group, Y _A is a bromine atom, and was as good as 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).

Wherein the staining of the compounds of (B), at least one of carbon atoms of R _B1, R _B2, R _B3 represents an alkyl group (provided that R _B1 of 1 to 14 carbon atoms, R _B2 and R _B3 used in Dyeing Example E19 The stainability of the compound (which is an alkyl group of No. 4 to 14) was good.

Table 35 shows the evaluation results of the dyeing examples of the compound of the formula (C).

For staining of compound of 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.

Also, for each fastness of the compound of formula (C), X _C is a chlorine atom, Y _C is a hydrogen atom, and 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).

The staining of the compounds of 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 Represents a substituted alkyl group having 1 to 14 carbon atoms (where, when _RD2 is a CN-substituted alkyl group having 1 to 14 carbon atoms, _RD1 is an alkyl group having 4 to 14 carbon atoms. ) The stainability of the compound was good.

However, the dyeability of the compound having an alkyl group having 3 or less carbon atoms in both _{R D1} and R _D2 , which are the disperse dyes conventionally used for dyeing polyester fibers and the like used in Dyeing Example E13, was poor. ..

Regarding the fastness of each compound of the formula (D), _{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).

Stainability of the compound of formula (G) is, R _G used in Dyeing Example E14 was good dyeability of a compound of the alkyl group having 7 to 18 carbon atoms.

Regarding the fastness of each of the compounds of the formula (G), those having a hydrocarbon group _RG having 15 carbon atoms were good.

<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.

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.

As shown in Table 38, 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.

As described above, 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.

Further, it is also possible to appropriately rearrange the combinations and the order of processes in the embodiment based on the knowledge of those skilled in the art, and to add modifications such as various design changes to the embodiments, and such modifications are added. The embodiments described may also be included in the scope of the present invention.

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.

Claims

A dye for dyeing polyolefin fibers with supercritical carbon dioxide, which contains at least one of the compounds of the following general formulas (A) to (G).

[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. ]

[In 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 B2, and R B3 has 4 to 14 carbon atoms. It is an alkyl group). ]

[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). ]

[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. ]

Wherein (E), X E and Y E is a halogen atom independently, R E represents an alkyl group having 4 to 18 carbon atoms. ]

[In formula (F), R F1 and R F2 each independently represent an alkyl group having 4 to 14 carbon atoms. ]

[In formula (G), RG represents an alkyl group having 7 to 18 carbon atoms. ]
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).
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).
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.
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.
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.
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.
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.
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).
The dyeing method according to any one of claims 7 to 9, wherein the polyolefin fiber is a polypropylene resin fiber.
The dyeing method according to any one of claims 7 to 9, wherein the polyolefin fiber is a polyethylene resin fiber.
Polyolefin fiber dyed by the dyeing method according to any one of claims 7 to 11.