WO2021187447A1

WO2021187447A1 - Dye composition

Info

Publication number: WO2021187447A1
Application number: PCT/JP2021/010481
Authority: WO
Inventors: 松本敏昭; 小林樹; 杉村亮治
Original assignee: 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: CN115279839A; JPWO2021187447A1; JP7222565B2; TW202140681A; KR20220123299A

Abstract

The present invention addresses the issue of providing: a dye composition that is capable of high-concentration dying of fibers into a variety of hues and has excellent dyeing durability, e.g., light-resistance, sublimation, and washing of the dyed object; a fiber dyeing method; fiber that has been dyed using said dyeing method; and a compound. Provided are: a dye composition that includes at least one compound indicated in general formulas (A)–(G) and a nonionic dispersant; a fiber dyeing method; fiber dyed using said dyeing method; and a compound.

Description

Dye composition

The present invention relates to a dye composition, a method for dyeing fibers, fibers dyed by the dyeing method, and a compound.

Polyolefin resins such as polypropylene resin and polyethylene resin are crystalline thermoplastic resins, which are inexpensive, easy to process, high strength, high chemical resistance, high scratch resistance, high bending resistance, light weight, and low moisture absorption. It has excellent properties such as low thermal conductivity and high antistatic property.

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 the dye in order to dye the polyolefin-based resin fiber in an aqueous manner, and Patent Documents 1 to 5 propose a dye for dyeing the polyolefin-based resin fiber.

Patent Document 1 describes an example of producing a red dye and a purple dye in which an alkyl group having 3 to 12 carbon atoms or a phenoxy group having a cycloalkyl group as a substituent is introduced into an anthraquinone dye, and a polypropylene resin fiber using them. An example of dyeing is described.

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 cannot be said that they are environmentally friendly.

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 used for dyeing, there is a description that these anthraquinone-based blue dyes are pulverized and used together with an appropriate dispersant such as sodium dinaphthylmethanesulfonic acid. Not listed. In addition, there is a description that it is used after being dissolved in alcohol or acetone, which is an organic solvent, as another form, and it cannot be said that this is environmentally friendly.

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. Further, regarding the form of the dye when used for dyeing, there is a description that these anthraquinone-based red dyes are used in a paste state, but a specific method for producing a dye paste is not described. As another form, there is a description that it is used after being dissolved in dimethylformamide, which is an organic solvent, and it cannot be said that this 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. Furthermore, regarding the form of dyes when used for dyeing, there is a description that these monoazo dyes are used in a paste state using an appropriate dispersant, but a specific method for producing a dye paste is not described. ..

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 modification techniques include blending dyeable resin components such as polyester, copolymerization with vinyl-based monomers having a dyeable group, blending of dyeing accelerators such as metal stearate, and the like. It has been known.

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.

When a method for dyeing polypropylene resin fibers and polyethylene resin fibers with high concentration and high fastness is put into practical use, it has become possible to color regular yarns of uncolored small single yarns with low fineness without any number of colors. It is expected to develop new applications in fields where high designability is required, such as clothing and vehicle interior materials to which resin fibers and polyethylene resin fibers have not been applied.

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

Therefore, the present invention uses a dye composition, a method for dyeing fibers, and a method for dyeing the fibers, which can dye fibers in various hues at high concentrations and have excellent dyeing fastness such as light resistance, sublimation, and washing of dyed products. It is an object of the present invention to provide dyed fibers and compounds.

The present invention is a dye composition containing at least one of the compounds of the following general formulas (A) to (G) and a nonionic dispersant.

[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.
_RD2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN (provided that _{at least one of RD1} and _RD2 is an alkyl group having 4 to 14 carbon atoms. ). ]

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 or 10 to 18 carbon atoms. ]

The present invention also provides a method for dyeing fibers, which includes a step of water-based dyeing of fibers using the dye composition of the present invention.

The present invention also provides fibers dyed by the dyeing method of the present invention.

The present invention also provides a compound of any of the following general formulas (A) to (G).

The dye composition of the present invention can dye fibers in various hues at high concentration, and the dyed product has excellent dyeing fastness such as light resistance, sublimation, and washing.

The present inventors have found that dyes containing the following specific compounds have improved affinity for fibers and dye fibers in various hues at high concentrations, and have completed the present invention.

<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 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.
_RD2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN (provided that _{at least one of RD1} and _RD2 is an alkyl group having 4 to 14 carbon atoms. ).

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

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.

In the compound of the general formula (G), in the formula (G), _RG represents an alkyl group having 7 or 10 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 compound 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). Is added in a temperature range of, for example, −5 to 10 ° C. to obtain a 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 water content of the compound of the general formula (A) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.

(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 water content of the compound of the general formula (B) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.

(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 water content of the compound of the general formula (C) may be within a range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.

(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.} 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 RD1} and _RD2 is an alkyl group having 4 to 14 carbon atoms. Obtained by coupling.

(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 (d-D) is generally widely used as a raw material for an azo-based disperse dye.

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 water content of the compound of the general formula (D) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.

(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 diazotization temperature is preferably −10 to 40 ° C., more preferably 0 to 30 ° C.
The compound represented by the formula (ed) is generally widely used as a raw material for an azo-based disperse dye.

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 water content of the compound of the general formula (E) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.

(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 an azo-based disperse dye.

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 water content of the compound of the general formula (F) may be within a range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.

(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 of 1 to 14 carbon atoms, X represents a halogen atom) after reacting the halogenated hydrocarbon represented by, according to a known reaction, R _F2 ( _RF2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced. 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 water content of the compound of the general formula (G) may be within the range in which an aqueous dispersion can be produced, and is adjusted to, for example, 60% by mass or less, preferably 40% by mass or less, and used for dyeing.

<Dye composition>
As described above, the dye composition of the present invention contains at least one of the compounds of the general formulas (A) to (G) and a nonionic dispersant.

Examples of the nonionic dispersant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene aryl phenyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene aryl aryl ether, polyoxyethylene sorbitan fatty acid ester, and poly. Examples thereof include oxyethylene acetylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and oxyethylene-oxypropylene copolymer. Among these, at least one selected from polyoxyethylene alkylphenyl ether, polyoxyethylene arylphenyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene arylaryl ether, and oxyethylene-oxypropylene copolymer should be used. Is preferable, at least one selected from polyoxyethylene arylphenyl ether, polyoxyethylene arylaryl ether, and oxyethylene-oxypropylene copolymer is more preferable, and polyoxyethylene arylphenyl ether and oxyethylene-oxy are more preferable. It is more preferable to use at least one selected from propylene copolymers.

The polymerization form of the oxyethylene-oxypropylene copolymer is not limited, and may be any of a random polymer, a block polymer, and the like.
In order to use the dye composition as a powder by spray-drying or the like instead of using a liquid aqueous dispersion by using a nonionic dispersant, the nonionic dispersants include polyoxyethylenearylphenyl ether and oxyethylene-oxy. It is preferable that both propylene copolymers are contained.

The amount of the nonionic dispersant used is adjusted to the mass of the compounds represented by the formulas (A) to (G) for the purpose of maintaining good dispersion stability of the compounds represented by the formulas (A) to (G). On the other hand, it is preferably 20 to 200% by mass, more preferably 20 to 100% by mass.

The dye composition of the present invention contains a viscosity regulator, a surface tension regulator, a pH regulator, a moisturizer, a hydrotrope, a sequestrant, a preservative, and an antibacterial agent as long as the object of the present invention is not hindered. A mold agent, an antifoaming agent and the like may be added as needed.

The dye composition of the present invention may further contain an additive. 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 the like. Examples thereof include antifungal agents, antistatic agents, flame retardants, inorganic fillers, and elastomers for improving impact resistance.

The dye composition of the present invention is preferably an aqueous dispersion from the viewpoint of ease of handling, safety and the like. Since the compounds represented by the formulas (A) to (G) have high lipophilicity, in order to obtain a dye composition in the form of an aqueous dispersion, the dispersant is used in combination and fine particles are used in a disperser such as a bead mill. It is necessary to perform decentralization processing.

The dye composition of the present invention is a liquid aqueous dispersion in which the compounds represented by the formulas (A) to (G) are atomized and dispersed in an aqueous dispersion medium using a nonionic dispersant, or the above. It may be in the form of a powder obtained by removing the dispersion medium of the liquid aqueous dispersion by spray drying or the like, but it is preferably in the form of a powder from the viewpoint of product life.

The content of the compounds represented by the formulas (A) to (G) in the dye composition of the present invention may be as long as it can be easily handled during dyeing, and is preferably 5 to 40% by mass, more preferably. Is 10 to 30% by mass.

The method for producing the dye composition of the present invention preferably includes the following methods.
(1) Add various additives such as nonionic dispersant and, if necessary, viscosity modifier to water and stir to prepare a dispersant solution.
(2) The compounds represented by the formulas (A) to (G) are added to the dispersant solution of (1) and stirred to prepare an aqueous slurry.
(3) Using a wet disperser such as a bead mill, the aqueous slurry fine particle dispersion treatment of (2) is carried out so that the volume median particle diameter of the compounds represented by the formulas (A) to (G) is 1.0 μm or less, preferably 1.0 μm or less. Continue until the volume is 0.5 μm or less.
(4) Water is added to the fine particle-dispersed product of (3) to adjust the concentration to obtain a liquid aqueous dispersion.
(5) Various additives such as dispersants are added to the liquid aqueous dispersion of (4) as needed, stirred, and the dispersion medium is removed by spray drying or the like to obtain a powdery dye composition.
Using the obtained (4) liquid aqueous dispersion or (5) powdery dye composition, the fibers can be subjected to aqueous dyeing by a dyeing method, a printing method or the like.

The compounds of the general formulas (A) to (G) contained in the dye composition for dyeing the fibers of the present invention have blue, purple, red, orange, or yellow. The dye composition may contain the compounds of the general formulas (A) to (G) alone or in combination of two or more. When the dye composition contains two or more compounds of the general formulas (A) to (G), dyes for dyeing fibers in various hues or blacks can be obtained.

The dye composition for dyeing the fiber black is selected from the group consisting of the compound of the general formula (A), the compound of the general formula (B), the compound of the general formula (C), and the compound of the general formula (F). At least one of a purple or blue compound containing at least one compound and at least one of a red compound containing one or more selected from the group consisting of a compound of the general formula (C) and a compound of the general formula (D). It is preferable to contain at least one of a compound of the general formula (D), a compound of the general formula (E) and a yellow or orange compound selected from the compound of the general formula (G), and the compound of the general formula (A). At least one of a purple or blue compound containing one or more selected from the group consisting of a compound, a compound of the general formula (B) and a compound of the general formula (F), and a red compound of the compound of the general formula (C). It is more preferable to include at least one of an orange compound containing at least one selected from the group consisting of the compound of the general formula (D) and the compound of the general formula (E), and the compound of the general formula (A). It is more preferable to include the blue compound of the general formula (C), the red compound of the compound of the general formula (C), and the orange compound of the compound of the general formula (D).

The composition of the compound in the dye composition for dyeing fibers in black is such that the mixing ratio of the purple or blue compound is 30 to 70% by mass, the mixing ratio of the red compound is 5 to 25% by mass, and the yellow Alternatively, the mixing ratio of the orange compound is preferably in the range of 15 to 55% by mass, the mixing ratio of the purple or blue compound is 40 to 60% by mass, and the mixing ratio of the red compound is 5 to 25% by mass. The mixing ratio of the yellow or orange compound is more preferably in the range of 25 to 45% by mass.

Examples of the fiber to be dyed in the present invention include polyester fiber, polyolefin fiber, acrylic fiber and the like, and polyolefin fiber is preferable.

The polyolefin fiber is a copolymer of an α-olefin such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, or a copolymer of these α-olefins. Examples include fibers formed from heavy compounds or polymers selected from copolymers with other unsaturated monomers copolymerizable with these α-olefins. 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 is preferably formed from a polypropylene-based resin and / or a polyethylene-based resin, and more preferably formed from a polypropylene-based resin.

The shape of the polyolefin fiber is, for example, lump-like (molded product, etc.), film-like, fibrous (cloth-like (woven fabric, knitted fabric, non-woven fabric, etc.), thread-like (filament yarn, spun yarn, slit yarn, split yarn, etc.)). Etc., and is preferably fibrous.

The polyolefin fiber may be a fiber formed by blending a polypropylene resin and / or a polyethylene resin with another polymer component, bonding, or the like. The polyolefin fiber may be a polypropylene fiber blended with other fibers such as polyester, or a blended fiber.

<Fiber dyeing method>
As described above, the present invention provides a method for dyeing fibers, which comprises a step of water-based dyeing of fibers using the dye composition of the present invention.

Further, the dyeing step is preferably at least one selected from the group consisting of dyeing, printing, inkjet dyeing, transfer dyeing, and continuous dyeing, and at least one selected from dyeing and printing. More preferably, printing is even more preferable. When the dyeing step is dyeing, the dyeing step is performed, for example, by subjecting the object to be dyed into the dye composition of the present invention under pressure, preferably 80 ° C. to 130 ° C., more preferably 90 ° C. to 120 ° C., preferably. It is carried out by immersing for 30 to 60 minutes.

When the fiber is polyolefin, the dyeing step is preferably performed at 80 ° C to 130 ° C. The dyeing step is preferably carried out for 30 to 60 minutes.

When the fiber is polypropylene, the dyeing step is preferably performed at 110 ° C to 130 ° C. The dyeing step is preferably carried out for 30 to 60 minutes.

When the fiber is polyethylene, the dyeing step is preferably performed at 90 ° C to 110 ° C. The dyeing step is preferably carried out for 30 to 60 minutes.

When the dyeing step is printing, in the dyeing step, for example, the dye composition of the present invention is mixed with a glue such as a natural glue (for example, guar gum) or a processed glue (for example, carboxymethyl cellulose). After the prepared printing paste is printed on the object to be dyed, it is subjected to, for example, steaming treatment at 90 ° C. to 200 ° C. for 1 minute to 20 minutes, or dry heat treatment for 20 seconds to 5 minutes.

When the fiber is polyolefin, the dyeing step is preferably carried out at 80 ° C. to 130 ° C., and the steaming treatment is preferably carried out for 1 minute to 10 minutes.

When the fiber is polypropylene, the dyeing step is preferably carried out at 110 ° C. to 130 ° C., and the steaming treatment is preferably carried out for 1 minute to 10 minutes.

When the fiber is polyethylene, the dyeing step is preferably performed at 90 ° C. to 110 ° C., and the steaming treatment is preferably performed for 1 minute to 10 minutes.

When the dyeing step is inkjet dyeing, for example, in the dyeing step, an ink for inkjet printing is prepared by adding a low volatile water-soluble organic solvent such as glycerin or diethylene glycol to the liquid dye composition of the present invention. After printing on a cloth or fiber to which a glue or the like has been previously applied by padding or the like using an inkjet printer, steaming treatment at 90 ° C. to 200 ° C. for 1 minute to 20 minutes, for example, Alternatively, it is subjected to dry heat treatment for 20 seconds to 5 minutes.

In the case of dyeing, the concentration of the dye of the present invention with respect to the fiber is, for example, 0.001% o. m. f. To 10% o. m. f. It is preferably 0.001% o. m. f. ~ 5% o. m. f. Is. Note that o. m. f. Means on the mass of fiber (against fiber mass).

In the case of printing, the concentration of the dye of the present invention with respect to the printing paste is, for example, 0.001% o. m. p. ~ 5% o. m. p. It is preferably 0.001% o. m. p. ~ 2% o. m. p. Is. Note that o. m. p. Means on the mass of paste (mass against paste).

The present invention provides fibers dyed by the dyeing method of the present invention. Applications of the fiber include, for example, clothing such as clothing, underwear, hats, socks, gloves, sports clothing, vehicle interior materials such as seats, and interior products such as carpets, curtains, mats, sofa covers, and cushion covers. And so on.

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 formula (C10) obtained in step 1 is used instead of the compound of formula (C9) as the coupler component solution. A blue dye compound (9.47 g, yield 30.4%) represented by (1) was obtained. 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 compound 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. (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 obtained in the same manner as in Synthesis Example 36 except that the compound of the formula (C9) is used instead of the compound of the formula (C16) as the coupler component solution. ) Was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m / z 731 (M ^+)).

(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.

In Synthesis Example 38, the following formula (C) is the same as in Synthesis Example 38 except that the purple dye compound (31.4 g) of formula (C-13) is used instead of the purple dye compound of formula (C-9). 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.

<Production example of dye composition>
Dye compositions of the compounds listed in Tables 3-9 were produced for water-based dyeing. A production example is shown below. In this production example, the dye composition is in the form of a liquid aqueous dispersion or powder. Specifically, Dye Composition Production Examples 1 to 105 are production examples of a liquid dye composition, and Dye Composition Production Examples 106 to 141 are production examples of a powdery dye composition. The volume median particle size of the compound in the dye composition was measured by a dynamic light scattering type particle size distribution measuring device LB-500 manufactured by HORIBA, Ltd.

(Dye Composition Production Example 1)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry is subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.17 μm and a concentration of 20% by mass A -5 dye composition was obtained.

(Dye Composition Production Example 2)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 76 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry is subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.20 μm and a concentration of 20% by mass A -5 dye composition was obtained.

(Dye Composition Production Example 3)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.16 μm and a concentration of 20% by mass A -5 dye composition was obtained.

(Dye Composition Production Example 4)
30 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 50 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.19 μm and a concentration of 20% by mass was obtained. A -5 dye composition was obtained.

(Dye Composition Production Example 5)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 50 g of water, and then 10 g of propylene glycol is dissolved. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.19 μm and a concentration of 20% by mass was obtained. A -5 dye composition was obtained.

(Dye Composition Production Example 6)
20 g of a 50 mol adduct of tristyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.19 μm and a concentration of 20% by mass was obtained. A -5 dye composition was obtained.

(Dye Composition Production Example 7)
20 g of a 23 mol adduct of tribenzylphenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.15 μm and a concentration of 20% by mass was obtained. A -5 dye composition was obtained.

(Dye Composition Production Example 8)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound A-3 obtained in Synthesis Example 3 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.12 μm and a concentration of 20% by mass was obtained. -3 Dye composition was obtained.

(Dye Composition Production Example 9)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of a 50 mol adduct of tristyrene phenol-ethylene oxide as a dispersant are dissolved in 60 g of water. 20 g of the compound A-3 obtained in Synthesis Example 3 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.14 μm and a concentration of 20% by mass was obtained. -3 Dye composition was obtained.

(Dye Composition Production Example 10)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of a 23 mol adduct of tribenzylphenol-ethylene oxide as dispersants are dissolved in 60 g of water. 20 g of the compound A-3 obtained in Synthesis Example 3 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.12 μm and a concentration of 20% by mass was obtained. -3 Dye composition was obtained.

(Dye Composition Production Example 11)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of sodium lignin sulfonate as a dispersant are dissolved in 60 g of water. 20 g of the compound A-3 obtained in Synthesis Example 3 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.16 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 12)
10 g of a 24 mol adduct of distyreneed phenol-ethylene oxide and 10 g of a sodium sulfate of a 29 mol adduct of tristyrene phenol-ethylene oxide as a dispersant are dissolved in 60 g of water. 20 g of the compound A-3 obtained in Synthesis Example 3 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.15 μm and a concentration of 20% by mass was obtained. -3 Dye composition was obtained.

(Dye Composition Production Example 13)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound A-1 obtained in Synthesis Example 1 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.27 μm and a concentration of 20% by mass -1 Dye composition was obtained.

(Dye Composition Production Example 14)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound B-4 obtained in Synthesis Example 12 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.22 μm and a concentration of 20% by mass -4 Dye composition was obtained.

(Dye Composition Production Example 15)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water, and then 10 g of propylene glycol is dissolved. 20 g of the compound B-4 obtained in Synthesis Example 12 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.20 μm and a concentration of 20% by mass -4 Dye composition was obtained.

(Dye Composition Production Example 16)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.17 μm and a concentration of 20% by mass was obtained. -3 Dye composition was obtained.

(Dye Composition Production Example 17)
20 g of a 50 mol adduct of tristyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.15 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 18)
20 g of a 23 mol adduct of tribenzylphenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and the volume medium particle size was 0.16 μm and the concentration was 20% by mass. The dye composition of 3 was obtained.

(Dye Composition Production Example 19)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 50 g of water, and then 10 g of propylene glycol is dissolved. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.16 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 20)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound B-1 obtained in Synthesis Example 9 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.22 μm and a concentration of 20% by mass -1 Dye composition was obtained.

(Dye Composition Production Example 21)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound B-10 obtained in Synthesis Example 49 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. 10 Dye compositions were obtained.

(Dye Composition Production Example 22)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 76 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 23)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 24)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. 4 Dye composition was obtained.

(Dye Composition Production Example 25)
30 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 50 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. 4 Dye composition was obtained.

(Dye Composition Production Example 26)
10 g of a 24 mol adduct of distyreneated phenol-ethylene oxide as a dispersant is dissolved in 60 g of water, and then 10 g of diethylene glycol is dissolved. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. 4 Dye composition was obtained.

(Dye Composition Production Example 27)
20 g of a 50 mol adduct of tristyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound C having a volume medium particle size of 0.25 μm and a concentration of 20% by mass -4 Dye composition was obtained.

(Dye Composition Production Example 28)
20 g of a 23 mol adduct of tobenzylphenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 29)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound C having a volume medium particle size of 0.25 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 30)
20 g of a 50 mol adduct of tristyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -3 Dye composition was obtained.

(Dye Composition Production Example 31)
20 g of a 23 mol adduct of tobenzylphenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound C having a volume medium particle size of 0.25 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 32)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 50 g of water, and then 10 g of ethylene glycol is dissolved. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -3 Dye composition was obtained.

(Dye Composition Production Example 33)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound C-1 obtained in Synthesis Example 17 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 34)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-3 obtained in Synthesis Example 26 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -3 Dye composition was obtained.

(Dye Composition Production Example 35)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water, and then 10 g of dipropylene glycol is dissolved. 20 g of the compound D-3 obtained in Synthesis Example 26 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -3 Dye composition was obtained.

(Dye Composition Production Example 36)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-1 obtained in Synthesis Example 24 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound D- having a volume median particle diameter of 0.27 μm and a concentration of 20% by mass was obtained. 1 Dye composition was obtained.

(Dye Composition Production Example 37)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-6 obtained in Synthesis Example 32 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -6 dye composition was obtained.

(Dye Composition Production Example 38)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water, and then 10 g of ethylene glycol is dissolved. 20 g of the compound D-6 obtained in Synthesis Example 32 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -6 dye composition was obtained.

(Dye Composition Production Example 39)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-5 obtained in Synthesis Example 31 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -5 dye composition was obtained.

(Dye Composition Production Example 40)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 41)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 76 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 42)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 43)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water, and then 10 g of propylene glycol is dissolved. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 44)
10 g of the 58 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 45)
10 g of a 50 mol adduct of tristyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 46)
10 g of a 23 mol adduct of tribenzylphenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 47)
10 g of a 40 mol adduct of tribenzylphenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 48)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 70 g of water. 20 g of the compound G-1 obtained in Synthesis Example 27 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 49)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant is dissolved in 60 g of water, and then 10 g of polyethylene glycol (average molecular weight 400) is dissolved. 20 g of the compound G-1 obtained in Synthesis Example 27 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 50)
20 g of a formalin condensate of sodium naphthalene sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 51)
20 g of sodium lignin sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 52)
20 g of sodium sulfate of a tristyrene phenol-ethylene oxide 29 mol adduct as a dispersant is dissolved in 60 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 53)
20 g of a formalin condensate of sodium naphthalene sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 54)
20 g of sodium lignin sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 55)
20 g of sodium sulfate of a tristyrene phenol-ethylene oxide 29 mol adduct as a dispersant is dissolved in 60 g of water. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 56)
20 g of a formalin condensate of sodium naphthalene sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, it was not possible to disperse the fine particles.

(Dye Composition Production Example 57)
20 g of a formalin condensate of sodium creosote oil sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, it was not possible to disperse the fine particles.

(Dye Composition Production Example 58)
20 g of sodium lignin sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 59)
20 g of a formalin condensate of sodium naphthalene sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, it was not possible to disperse the fine particles.

(Dye Composition Production Example 60)
20 g of a formalin condensate of sodium creosote oil sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, it was not possible to disperse the fine particles.

(Dye Composition Production Example 61)
20 g of sodium lignin sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 62)
20 g of sodium sulfate of a tristyrene phenol-ethylene oxide 29 mol adduct as a dispersant is dissolved in 60 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 63)
10 g of a formalin condensate of sodium creosote oil sulfonate and 10 g of sodium lignin sulfonate as a dispersant are dissolved in 60 g of water. 20 g of the compound D-1 obtained in Synthesis Example 24 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 64)
20 g of a formalin condensate of sodium naphthalene sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, it was not possible to disperse the fine particles.

(Dye Composition Production Example 65)
20 g of a formalin condensate of sodium methylnaphthalene sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, it was not possible to disperse the fine particles.

(Dye Composition Production Example 66)
20 g of sodium lignin sulfonate as a dispersant is dissolved in 60 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, it was not possible to disperse the fine particles.

(Dye Composition Production Example 67)
10 g of a formalin condensate of sodium naphthalene sulfonate and 10 g of sodium lignin sulfonate as a dispersant are dissolved in 60 g of water. 20 g of the compound G-1 obtained in Synthesis Example 24 was added thereto and stirred to prepare an aqueous slurry. With respect to this aqueous slurry, 200 g of glass beads having a diameter of 0.3 mm were used, and a fine particle dispersion treatment was attempted with a vertical bead mill. However, the fine particles could not be dispersed and the dye composition could not be obtained.

(Dye Composition Production Example 68)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound A-13 obtained in Synthesis Example 60 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.15 μm and a concentration of 20% by mass was obtained. A -13 dye composition was obtained.

(Dye Composition Production Example 69)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound A-17 obtained in Synthesis Example 69 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry is subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.17 μm and a concentration of 20% by mass A -17 dye composition was obtained.

(Dye Composition Production Example 70)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound A-2 obtained in Synthesis Example 2 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.19 μm and a concentration of 20% by mass was obtained. -A dye composition was obtained.

(Dye Composition Production Example 71)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound A-16 obtained in Synthesis Example 66 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.18 μm and a concentration of 20% by mass was obtained. A -16 dye composition was obtained.

(Dye Composition Production Example 72)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound B-2 obtained in Synthesis Example 10 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume median particle diameter of 0.19 μm and a concentration of 20% by mass was obtained. -A dye composition was obtained.

(Dye Composition Production Example 73)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound C-19 obtained in Synthesis Example 67 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -19 dye composition was obtained.

(Dye Composition Production Example 74)
20 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 60 g of water. 20 g of the compound C-20 obtained in Synthesis Example 68 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -20 dye composition was obtained.

(Dye Composition Production Example 75)
10 g of a 24 mol adduct of distyrene phenol-ethylene oxide as a dispersant was dissolved in 70 g of water. 20 g of the compound D-13 obtained in Synthesis Example 65 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 20 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -13 dye composition was obtained.

(Dye Composition Production Example 76)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound A-13 obtained in Synthesis Example 60 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.16 μm and a concentration of 20% by mass was obtained. A -13 dye composition was obtained.

(Dye Composition Production Example 77)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.17 μm and a concentration of 20% by mass was obtained. A -5 dye composition was obtained.

(Dye Composition Production Example 78)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound A-5 obtained in Synthesis Example 5 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry is subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.15 μm and a concentration of 20% by mass A -5 dye composition was obtained.

(Dye Composition Production Example 79)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound A-3 obtained in Synthesis Example 3 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry is subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.15 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 80)
4 g of an adduct of 58 mol of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound A-3 obtained in Synthesis Example 3 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry is subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volumetric dye particle size of 0.15 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 81)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound A-2 obtained in Synthesis Example 2 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.18 μm and a concentration of 20% by mass was obtained. -A dye composition was obtained.

(Dye Composition Production Example 82)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (360 mol) -oxypropylene (70 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound A-4 obtained in Synthesis Example 4 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.18 μm and a concentration of 20% by mass was obtained. -4 Dye composition was obtained.

(Dye Composition Production Example 83)
8 g of an adduct of 58 mol of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (360 mol) -oxypropylene (70 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound A-1 obtained in Synthesis Example 1 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound A having a volume medium particle size of 0.20 μm and a concentration of 20% by mass -1 Dye composition was obtained.

(Dye Composition Production Example 84)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound B-4 obtained in Synthesis Example 12 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.22 μm and a concentration of 20% by mass -4 Dye composition was obtained.

(Dye Composition Production Example 85)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound B-3 obtained in Synthesis Example 11 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.19 μm and a concentration of 20% by mass -3 Dye composition was obtained.

(Dye Composition Production Example 86)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound B-2 obtained in Synthesis Example 10 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -A dye composition was obtained.

(Dye Composition Production Example 87)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound B-2 obtained in Synthesis Example 10 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.22 μm and a concentration of 20% by mass -A dye composition was obtained.

(Dye Composition Production Example 88)
8 g of an adduct of 58 mol of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (360 mol) -oxypropylene (70 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound B-1 obtained in Synthesis Example 9 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.20 μm and a concentration of 20% by mass was obtained. -1 Dye composition was obtained.

(Dye Composition Production Example 89)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound B-10 obtained in Synthesis Example 48 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound B having a volume medium particle size of 0.24 μm and a concentration of 20% by mass was obtained. A -10 dye composition was obtained.

(Dye Composition Production Example 90)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 91)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound C-4 obtained in Synthesis Example 20 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -4 Dye composition was obtained.

(Dye Composition Production Example 92)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -3 Dye composition was obtained.

(Dye Composition Production Example 93)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound C-3 obtained in Synthesis Example 19 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -3 Dye composition was obtained.

(Dye Composition Production Example 94)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound C-2 obtained in Synthesis Example 18 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -A dye composition was obtained.

(Dye Composition Production Example 95)
8 g of a 50 mol adduct of tristyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound C-1 obtained in Synthesis Example 17 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 96)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound C-20 obtained in Synthesis Example 68 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -20 dye composition was obtained.

(Dye Composition Production Example 97)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (160 mol) -oxypropylene (60 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound D-3 obtained in Synthesis Example 26 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -3 Dye composition was obtained.

(Dye Composition Production Example 98)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound D-1 obtained in Synthesis Example 24 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 99)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (160 mol) -oxypropylene (60 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound D-6 obtained in Synthesis Example 32 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -6 dye composition was obtained.

(Dye Composition Production Example 100)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound D-5 obtained in Synthesis Example 31 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -5 dye composition was obtained.

(Dye Composition Production Example 101)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound D-13 obtained in Synthesis Example 65 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. A -13 dye composition was obtained.

(Dye Composition Production Example 102)
4 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 10 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 66 g of water. 20 g of the compound D-4 obtained in Synthesis Example 30 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm, and compound D having a volume median particle diameter of 0.20 μm and a concentration of 20% by mass -4 Dye composition was obtained.

(Dye Composition Production Example 103)
8 g of a 40 mol adduct of tribenzylphenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound E-1 obtained in Synthesis Example 33 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 104)
8 g of a 23 mol adduct of tribenzylphenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound F-1 obtained in Synthesis Example 29 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 105)
8 g of a 24 mol adduct of distyrene phenol-ethylene oxide and 8 g of an oxyethylene (300 mol) -oxypropylene (55 mol) copolymer as a dispersant were dissolved in 64 g of water. 20 g of the compound G-1 obtained in Synthesis Example 27 was added thereto and stirred to prepare an aqueous slurry. This aqueous slurry was subjected to fine particle dispersion treatment for 24 hours with a vertical bead mill using 200 g of glass beads having a diameter of 0.3 mm. -1 Dye composition was obtained.

(Dye Composition Production Example 106)
To 50 g of the compound A-13 dye composition having a concentration of 20% by mass described in Production Example 76 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound A-13 having a concentration of 20% by mass.

(Dye Composition Production Example 107)
To 50 g of the compound A-5 dye composition having a concentration of 20% by mass described in Production Example 77 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound A-5 having a concentration of 20% by mass.

(Dye Composition Production Example 108)
To 50 g of the compound A-5 dye composition having a concentration of 20% by mass described in Production Example 77 of the dye composition, 33 g of a formalin condensate of sodium methylnaphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound A-5 having a concentration of 20% by mass.

(Dye Composition Production Example 109)
To 50 g of the compound A-5 dye composition having a concentration of 20% by mass described in Production Example 77 of the dye composition, 33 g of a formalin condensate of sodium creosote oil sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound A-5 having a concentration of 20% by mass.

(Dye Composition Production Example 110)
To 50 g of the compound A-5 dye composition having a concentration of 20% by mass described in Production Example 77 of the dye composition, 33 g of sodium lignin sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound A-5 having a concentration of 20% by mass.

(Dye Composition Production Example 111)
To 50 g of the compound A-3 dye composition having a concentration of 20% by mass described in Production Example 79 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound A-3 having a concentration of 20% by mass.

(Dye Composition Production Example 112)
To 50 g of the compound A-3 dye composition having a concentration of 20% by mass described in Production Example 79 of the dye composition, 33 g of a formalin condensate of sodium methylnaphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound A-3 having a concentration of 20% by mass.

(Dye Composition Production Example 113)
To 50 g of the compound A-2 dye composition having a concentration of 20% by mass described in Production Example 81 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound A-2 having a concentration of 20% by mass.

(Dye Composition Production Example 114)
To 50 g of the compound B-3 dye composition having a concentration of 20% by mass described in Production Example 85 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound B-3 having a concentration of 20% by mass.

(Dye Composition Production Example 115)
To 50 g of the compound B-2 dye composition having a concentration of 20% by mass described in Production Example 87 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound B-2 having a concentration of 20% by mass.

(Dye Composition Production Example 116)
To 50 g of the compound B-2 dye composition having a concentration of 20% by mass described in Production Example 87 of the dye composition, 32 g of a formalin condensate of sodium methylnaphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound B-2 having a concentration of 20% by mass.

(Dye Composition Production Example 117)
To 50 g of the compound B-2 dye composition having a concentration of 20% by mass described in Production Example 87 of the dye composition, 32 g of sodium lignin sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound B-2 having a concentration of 20% by mass.

(Dye Composition Production Example 118)
To 50 g of the compound B-1 dye composition having a concentration of 20% by mass described in Production Example 88 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound B-1 having a concentration of 20% by mass.

(Dye Composition Production Example 119)
To 50 g of the compound B-10 dye composition having a concentration of 20% by mass described in Production Example 89 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound B-10 having a concentration of 20% by mass.

(Dye Composition Production Example 120)
To 50 g of the compound C-4 dye composition having a concentration of 20% by mass described in Production Example 90 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-4 having a concentration of 20% by mass.

(Dye Composition Production Example 121)
To 50 g of the compound C-4 dye composition having a concentration of 20% by mass described in Production Example 90 of the dye composition, 33 g of a formalin condensate of sodium methylnaphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-4 having a concentration of 20% by mass.

(Dye Composition Production Example 122)
To 50 g of the compound C-4 dye composition having a concentration of 20% by mass described in Production Example 90 of the dye composition, 33 g of a formalin condensate of sodium creosote oil sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-4 having a concentration of 20% by mass.

(Dye Composition Production Example 123)
To 50 g of the compound C-4 dye composition having a concentration of 20% by mass described in Production Example 90 of the dye composition, 33 g of sodium lignin sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-4 having a concentration of 20% by mass.

(Dye Composition Production Example 124)
To 50 g of the compound C-3 dye composition having a concentration of 20% by mass described in Production Example 92 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-3 having a concentration of 20% by mass.

(Dye Composition Production Example 125)
To 50 g of the compound C-3 dye composition having a concentration of 20% by mass described in Production Example 92 of the dye composition, 33 g of a formalin condensate of sodium methylnaphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-3 having a concentration of 20% by mass.

(Dye Composition Production Example 126)
To 50 g of the compound C-20 dye composition having a concentration of 20% by mass described in Production Example 96 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-20 having a concentration of 20% by mass.

(Dye Composition Production Example 127)
To 50 g of the compound C-20 dye composition having a concentration of 20% by mass described in Production Example 96 of the dye composition, 33 g of a formalin condensate of sodium creosote oil sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound C-20 having a concentration of 20% by mass.

(Dye Composition Production Example 128)
To 50 g of the compound D-1 dye composition having a concentration of 20% by mass described in Production Example 98 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound D-1 having a concentration of 20% by mass.

(Dye Composition Production Example 129)
To 50 g of the compound D-1 dye composition having a concentration of 20% by mass described in Production Example 98 of the dye composition, 32 g of a formalin condensate of sodium methylnaphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound D-1 having a concentration of 20% by mass.

(Dye Composition Production Example 130)
To 50 g of the compound D-1 dye composition having a concentration of 20% by mass described in Production Example 98 of the dye composition, 32 g of sodium lignin sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound D-1 having a concentration of 20% by mass.

(Dye Composition Production Example 131)
To 50 g of the compound D-5 dye composition having a concentration of 20% by mass described in Production Example 100 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound D-5 having a concentration of 20% by mass.

(Dye Composition Production Example 132)
To 50 g of the compound D-5 dye composition having a concentration of 20% by mass described in Production Example 100 of the dye composition, 32 g of a formalin condensate of sodium methylnaphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound D-5 having a concentration of 20% by mass.

(Dye Composition Production Example 133)
To 50 g of the compound D-5 dye composition having a concentration of 20% by mass described in Production Example 100 of the dye composition, 32 g of sodium lignin sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of Compound D-5 having a concentration of 20% by mass.

(Dye Composition Production Example 134)
To 50 g of the compound D-13 dye composition having a concentration of 20% by mass described in Production Example 101 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound D-13 having a concentration of 20% by mass.

(Dye Composition Production Example 135)
To 50 g of the compound D-4 dye composition having a concentration of 20% by mass described in Production Example 102 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound D-4 having a concentration of 20% by mass.

(Dye Composition Production Example 136)
To 50 g of the compound D-4 dye composition having a concentration of 20% by mass described in Production Example 102 of the dye composition, 33 g of a formalin condensate of sodium naphthalene sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound D-4 having a concentration of 20% by mass.

(Dye Composition Production Example 137)
To 50 g of the compound D-4 dye composition having a concentration of 20% by mass described in Production Example 102 of the dye composition, 33 g of sodium lignin sulfonate and 17 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound D-4 having a concentration of 20% by mass.

(Dye Composition Production Example 138)
To 50 g of the compound E-1 dye composition having a concentration of 20% by mass described in Production Example 103 of the dye composition, 32 g of sodium lignin sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound E-1 having a concentration of 20% by mass.

(Dye Composition Production Example 139)
To 50 g of the compound F-1 dye composition having a concentration of 20% by mass described in Production Example 104 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound F-1 having a concentration of 20% by mass.

(Dye Composition Production Example 140)
To 50 g of the compound G-1 dye composition having a concentration of 20% by mass described in Production Example 105 of the dye composition, 32 g of a formalin condensate of sodium naphthalene sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound G-1 having a concentration of 20% by mass.

(Dye Composition Production Example 141)
To 50 g of the compound G-1 dye composition having a concentration of 20% by mass described in Production Example 105 of the dye composition, 32 g of a formalin condensate of sodium creosote oil sulfonate and 18 g of water were added and stirred for 20 minutes. This dye dispersion was spray-dried to obtain a powdery dye composition of compound G-1 having a concentration of 20% by mass.

Dispersants for making the compound of the present invention into a dye composition are the distyrenated phenol-ethylene oxide adduct and the tristyrene phenol-ethylene oxide adduct described in Dye Composition Production Examples 1 to 49 and 68 to 105. , Tribenzylphenol-ethylene oxide adduct, oxyethylene-oxypropylene copolymer and other nonionic dispersants were effective.

On the other hand, the compound of the present invention alone is an anionic dispersant such as the formalin condensate of sodium naphthalenesulfonate, the formalin condensate of sodium cleosort oil sulfonate, and sodium ligninsulfonate described in Production Examples 50 to 67 of the dye composition. Could not be obtained as a dye composition having a desired particle size (volume median particle size is 1.0 μm or less).

<Dyeing example>
(Polypropylene fiber dyeing 1)
Dyeing method using only one type of dye composition of the compound shown in Tables 3 to 9 or a dye composition such as a disperse dye compound conventionally used for dyeing polyester fibers and the like shown in Tables 3 to 9. The polypropylene fiber was dyed with.

(Staining example P1)
Dye composition Water and acetic acid were added to 1.5 g of the dye composition (dye concentration 20% by mass) of the blue compound A-5 obtained in Production Example 1 to prepare a dye bath having a total amount of 2000 g and a pH of 4.5. .. 100 g of polypropylene fiber was immersed in the dyeing bath, dyed at 120 ° C. for 40 minutes (0.3% omf), and then thoroughly washed with water and dried to obtain a blue polypropylene fiber dyed product.

(Staining Examples P2 to P22)
A dyed polypropylene fiber dyed product was obtained by the same dyeing procedure as in dyeing example P1 except that the dye composition of the blue compound A-5 described in dyeing example P1 was changed to the dye composition of the compounds shown in Tables 10-14. ..

(Staining example P26)
To 5.0 g of the powdery dye composition (dye concentration 20% by mass) of the blue compound A-13 obtained in Production Example 106 of the dye composition was added with 95 g of water and stirred to obtain a dye dispersion. Water and acetic acid were added to this dye dispersion to prepare a dyeing bath having a total volume of 2000 g and a pH of 4.5. 100 g of polypropylene fiber was immersed in the dyeing bath and dyed at 130 ° C. for 60 minutes (1.0% omf), and then reduced washing, washing with water and drying to obtain a blue polypropylene fiber dyed product.

(Staining Examples P27 to P37)
By the same dyeing procedure as in Dyeing Example P26, except that the powdery dye composition of the blue compound A-13 described in Dyeing Example P26 was changed to the powdery dye composition of the compounds in Tables 10 to 14. A dyed polypropylene fiber dyed product was obtained.

Tables 10 to 14 show the compounds used in Staining Examples P1 to P22 and Staining Examples P26 to P37.

The polypropylene fiber dyed product obtained in the dyeing example was subjected to a dyeability evaluation, a light fastness test, a sublimation fastness test, a washing fastness test, a sweat fastness test, a friction fastness test and a fastness test against hot pressing. ..

(1) Evaluation of dyeability The dyeability was evaluated by the Total K / S value obtained by measuring the color of the dyed cloth. The color of the dyed cloth was measured using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), the dyed cloth was glued on white paper, and the observation light source D65 was used in a 2 degree field of view.

(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. Friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.)
The dyed cloth was rubbed back and forth 100 times with a dry cotton cloth or a wet cotton cloth under a load of 2N to determine the coloring of the cotton cloth.

(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.

Table 15 shows the evaluation results of dyeing examples of the compound of the formula (A).

For staining of compound of formula (A), Dyeing P1, P2 and R _A1 used in P26 to P28, R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that R _A1, At _{least one of RA2} and _RA3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good. A disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example P3, dyeability R _A1, all R _A2 and R _A3 is an alkyl group having 3 or less carbon compound poor there were.

With respect to the respective fastness of compound of formula (A), Dyeing P1, R used in the P2 and P26 to P28 _A1, R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that the R _A1, at least one is a is) an alkyl group having 4 to 14 carbon atoms compound of R _A2 and R _A3 are, sublimation fastness, washing fastness, perspiration fastness, good fastness to rubbing fastness and hot pressing Met.

Table 16 shows the evaluation results of the dyeing example of the compound of the formula (B).

The staining of the compounds of formula (B), Dyeing Example P4 to P7, and R _B1 used in P29 to P31, R _B2 represents an alkyl group having 1 to 14 carbon atoms each independently (provided that R _B1, The stainability of the compound (at least one of R _B2 and R _B3 is an alkyl group having 4 to 14 carbon atoms) was good. A disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example P8, dyeability R _B1 or R _B2 is not alkyl group of 1 to 14 carbon atoms compound was poor.
Regarding the fastness of the compound of the formula (B), R _B1 and R _B2 used in Staining Examples P4 to P7 and P29 to P31 each independently represent an alkyl group having 1 to 14 carbon atoms (however, R). _{Compounds (at least one of B1} , _RB2 and _RB3 is an alkyl group having 4 to 14 carbon atoms) have good light fastness, sublimation fastness, wash fastness, sweat fastness, and fastness to hot pressing. there were.

Table 17 shows the evaluation results of the dyeing example of the compound of the formula (C).

For staining of compound of formula (C), it represents a R _C1, R _C2 and R _C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example P9 to P11, and P32 to P34 (except staining of R _C1, at least one of R _C2 and R _C3 are an alkyl group having 4 to 14 carbon atoms) compounds was good. A disperse dye used for dyeing polyester fibers conventionally used in Dyeing Example P12, dyeability R _C1, at least one of R _C2 and R _C3 are an alkyl group having 3 or less carbon compound poor Met.

With respect to the respective fastness of compound of formula (C), at least one of R _C1, R _C2 and R _C3 are representing an alkyl group having 1 to 14 carbon atoms each independently (provided that R _C1, R _C2 and R _C3 Is an alkyl group having 4 to 14 carbon atoms) was generally good.

The respective fastness of compound of formula (C), represents a R _C1, R _C2 and R _C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example P9 to P12, and P32 to P34 ( provided that at least one of R _C1, R _C2 and R _C3 are an alkyl group having 4 to 14 carbon atoms) compounds, each fastness was good.

Table 18 shows the evaluation results of the dyeing examples of the compound of the formula (D).

Wherein the staining of the compounds of (D), Dyeing Example P13 to P17, and P35, representing the R _D1 and R _D2 are each independently an alkyl group having 1 to 14 carbon atoms used in the P36 (provided that R _D1乃And _{at least one of R D2} is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good. However, used in Dyeing Example P18 to P20, when a conventional disperse dye used in the dyeing of such polyester fibers, with each alkyl group having 1 to 3 carbon atoms in the alkyl group of R _D1乃beauty R _D2 Yes, the stainability was poor.

The fastness of each of the compounds of the formula (D) was better as the number of carbon atoms in _{R D1} and R _{D2 was larger.}

Table 19 shows the evaluation results of the dyeing example 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 7 or 10 to 18 carbon atoms in _{RG used in Staining Examples P21 and P37 was good.} Staining of the compound R _G is an alkyl group having 3 carbon atoms is a disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example P22 was poor.

Regarding each fastness of the compound of the formula (G), the compound having an alkyl group having 7 or 10 to 18 _{RG carbons used in Staining Examples P21 and P37 was good.}

(Polypropylene fiber dyeing 2)
Polypropylene fibers were dyed in the same manner as in Dyeing Example P1 using a dye composition in which two or more of the compounds shown in Tables 3 to 9 were mixed and used, and the obtained polypropylene fiber dyed product was evaluated for dyeability. Light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, friction fastness test and fastness test for hot pressing were performed. The dyeability was evaluated by the Total K / S value, the L ^* value, the a ^* value, and the b ^* value obtained by measuring the color of the dyed cloth. The color of the dyed cloth was measured by using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretag Macbeth), gluing the dyed cloth on white paper, and using an observation light source D65 and a 2 degree field of view.

Table 20 shows the evaluation results of dyeing examples using a dye composition in which two or more kinds of the compounds shown in Tables 3 to 9 are mixed and used.

As shown in Table 20, when the orange dye, the red dye, and the blue dye obtained in the present invention were mixed and used, a black dyed cloth having good dyeability and generally good fastness was obtained.

(Polyethylene fiber dyeing 1)
Dyeing method using only one type of dye composition of the compound shown in Tables 3 to 9 or a dye composition such as a disperse dye compound conventionally used for dyeing polyester fibers and the like shown in Tables 3 to 9. The polyethylene fibers were dyed with.

(Staining example E1)
Dye composition Water and acetic acid were added to 1.5 g of the dye composition (dye concentration 20% by mass) of the blue compound A-5 obtained in Production Example 1 to prepare a dye bath having a total amount of 2000 g and a pH of 4.5. .. 100 g of polyethylene fiber was immersed in the dyeing bath, dyed at 100 ° C. for 40 minutes (0.3% omf), and then thoroughly washed with water and dried to obtain a blue polyethylene fiber dyed product.

(Staining Examples E2 to E22)
A polyethylene fiber dyed product was obtained by the same dyeing procedure as in Dyeing Example E1 except that the dye composition of the blue compound A-5 described in Dyeing Example E1 was changed to the dye composition of the compounds shown in Tables 21 to 25.

(Staining example E26)
To 5.0 g of the powdery dye composition (dye concentration 20% by mass) of the blue compound A-13 obtained in Production Example 106 of the dye composition was added with 95 g of water and stirred to obtain a dye dispersion. Water and acetic acid were added to this dye dispersion to prepare a dyeing bath having a total volume of 2000 g and a pH of 4.5. 100 g of polyethylene fiber was immersed in the above dyeing bath, dyed at 110 ° C. for 60 minutes (1.0% omf), and then thoroughly washed with water and dried to obtain a blue polypropylene fiber dyed product.

(Staining Examples E27 to E37)
By the same dyeing procedure as in Dyeing Example E26, except that the powdery dye composition of the blue compound A-13 described in Dyeing Example E26 was changed to the powdery dye composition of the compounds in Tables 21 to 25. A dyed polyethylene fiber dyed product was obtained.

Tables 10 to 14 show the compounds used in Staining Examples E1 to E22 and Staining Examples E26 to E37.

The polyethylene fiber dyed product obtained in the dyeing example has the same dyeability evaluation, light fastness test, washing fastness test, and sweat fastness as the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 1). A test and a friction fastness test were performed.

Table 26 shows the evaluation results of dyeing examples of the compound of the formula (A).

For staining of compound of formula (A), Dyeing E1, R _A1 used in the E2 and E26 to E28, R _A2 and R _A3 each independently represents an alkyl group having 1 to 14 carbon atoms (provided that R _At least one of A1, _RA2 and _RA3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good. Dyeing Example is a disperse dye used for dyeing polyester fibers conventionally used in E3, staining of R _A1, all R _A2 and R _A3 is an alkyl group having 3 or less carbon compound poor there were.

With respect to the respective fastness of compound of formula (A), Dyeing E1, E2 and E26 to R _A1 used in E28, R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that the R _The compound (at least one of A1, _RA2 and _RA3 is an alkyl group having 4 to 14 carbon atoms) had good wash fastness, sweat fastness, and friction fastness.

Table 27 shows the evaluation results of the dyeing examples of the compound of the formula (B).

The staining of the compounds of formula (B), represents R _B1, R _B2 are each independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example E4 to E7, and E29 to E31 (provided that R _B1, At _{least one of R B2} and R _B3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good. A disperse dye used for dyeing such as polyester fibers from a conventional used in Dyeing Example E8, dyeability R _B1 or R _B2 is not alkyl group of 1 to 14 carbon atoms compound was poor.

With respect to the respective fastness of the compound of formula (B), Dyeing Example E4 to E7, and E29 to R _B1 used in E31, R _B2 are each independently (provided that an alkyl group of 1 to 14 carbon atoms and R _The compounds (at least one of B1, _RB2 and _RB3 is an alkyl group having 4 to 14 carbon atoms) had generally good light fastness, wash fastness, sweat fastness, and friction fastness.

Table 28 shows the evaluation results of dyeing examples of the compound of the formula (C).

For staining of compound of formula (C), Dyeing Example E9 to E11, and E32 to R _C1 used in E34, R _C2 and R _C3 each independently represents an alkyl group having 1 to 14 carbon atoms ( staining of R _C1, at least one of R _C2 and R _C3 are an alkyl group having 4 to 14 carbon atoms) compounds was good. A disperse dye used for dyeing polyester fibers conventionally used in Dyeing Example E12, staining of R _C1, at least one of R _C2 and R _C3 are an alkyl group having 3 or less carbon compound poor Met.

With respect to the respective fastness of compound of formula (C), at least one of R _C1, R _C2 and R _C3 are representing an alkyl group having 1 to 14 carbon atoms each independently (provided that R _C1, R _C2 and R _C3 The light fastness, sweat fastness, and friction fastness of the compound (which is an alkyl group having 4 to 14 carbon atoms) were generally good.

The respective fastness of compound of formula (C), Dyeing Example E9 to E11, and E32 to R _C1 used in E34, R _C2 and R _C3 each independently represents an alkyl group having 1 to 14 carbon atoms ( provided that at least one of R _C1, R _C2 and R _C3 are an alkyl group having 4 to 14 carbon atoms) compounds, each fastness was good.

Table 29 shows the evaluation results of dyeing examples of the compound of the formula (D).

The staining of the compounds of formula (D), Dyeing Example E13 to E17, and E35, R _D1 and R _D2 used in E36 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R _D1乃And _{at least one of R D2} is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good. However, in the case of the disperse dye used in dyeing examples E18 to E20, which has been conventionally used for dyeing polyester fibers and the like _{, each of the alkyl groups of R D1 and} R _{D2 has} an alkyl group having 1 to 3 carbon atoms. Yes, the stainability was poor.

Table 30 shows the evaluation results of the dyeing examples of the compound of the formula (G).

As for the stainability of the compound of the formula (G), the stainability of the compound having an alkyl group having 7 or 10 to 18 carbon atoms in _{RG used in Staining Examples E21 and E37 was good.} Staining of conventionally a disperse dye used for dyeing such as polyester fiber R _G is an alkyl group having 3 carbon atoms the compounds used in Dyeing Example E22 was poor.

Regarding each fastness of the compound of the formula (G), the compound having an alkyl group having 7 or 10 to 18 _{RG carbons used in Staining Examples E21 and E37 was good.}

(Polyethylene fiber dyeing 2)
Using a dye composition in which two or more of the compounds shown in Tables 3 to 9 were mixed and used, the polyethylene fibers were dyed in the same manner according to Dyeing Example E1, and the obtained polyethylene fiber dyed product was obtained from the above-mentioned (polypropylene). Similar to the polypropylene fiber dyed product obtained in the fiber dyeing 2), a dyeability evaluation, a light fastness test, a washing fastness test, a sweat fastness test, and a friction fastness test were performed.

Table 31 shows the evaluation results of dyeing examples using a dye composition in which two or more kinds of the compounds shown in Tables 3 to 9 are mixed and used.

As shown in Table 31, when the orange dye, the red dye, and the blue dye obtained in the present invention were mixed and used, a black dyed cloth having good dyeability and generally good fastness was obtained.

(Printing of polypropylene fiber 1)
Printing method using only one type of dye composition of the compound shown in Tables 3 to 9 or a dye composition such as a disperse dye compound conventionally used for dyeing polyester fibers and the like shown in Tables 3 to 9. The polypropylene fiber was dyed with.

(Staining example PP1)
5.8 g of carboxymethyl cellulose, 0.3 g of sodium chlorate, and 0.3 g of tartaric acid were added to 73.6 g of water, and the mixture was stirred until uniform to obtain paste A. To the paste A, a dye dispersion liquid obtained by adding 18.5 g of water to 1.5 g of the dye composition (dye concentration 20% by mass) of the blue compound A-13 obtained in Dye Composition Production Example 76 and stirring is added. Then, the dyeing paste was prepared by stirring until it became uniform (0.3% omp). The printing paste is printed on polypropylene fibers, dried by dry heat at 110 ° C. for 3 minutes, and then H.I. T. The color was developed at 130 ° C. for 6 minutes by a steamer, and then reduced washing, washing with water and drying to obtain a blue polypropylene fiber dyed product.

(Staining Examples PP2 to PP12)
A dyed polypropylene fiber dyed product was obtained by the same dyeing procedure as in the dyeing example PP1 except that the dye composition of the blue compound A-13 described in the dyeing example PP1 was changed to the dye composition of the compounds shown in Tables 32 to 36. ..

(Staining example PP13)
5.8 g of carboxymethyl cellulose, 0.3 g of sodium chlorate, and 0.3 g of tartaric acid were added to 73.6 g of water, and the mixture was stirred until uniform to obtain paste A. To the paste A, 1.5 g of a powdery dye composition (dye concentration 20% by mass) of the blue compound A-5 obtained in Dye Composition Production Example 107 was added with 18.5 g of water, and the mixture was stirred. The dispersion was added and stirred until uniform to prepare a printing paste (0.3% omp). The printing paste is printed on polypropylene fibers, dried by dry heat at 110 ° C. for 3 minutes, and then H.I. T. The color was developed at 130 ° C. for 6 minutes by a steamer, and then reduced washing, washing with water and drying to obtain a blue polypropylene fiber dyed product.

(Staining Examples PP14 to PP19)
By the same dyeing procedure as in Dyeing Example PP13, except that the powdery dye composition of the blue compound A-5 described in Dyeing Example PP13 was changed to the powdery dye composition of the compounds in Tables 32 to 36. A dyed polypropylene fiber dyed product was obtained.

The polypropylene fiber dyed product obtained in the dyeing example has the same dyeability evaluation, light fastness test, sublimation fastness test, and washing fastness as the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 1). Tests, sweat fastness test, friction fastness test and fastness test against hot pressing were performed.

Table 37 shows the evaluation results of dyeing examples of the compound of the formula (A).

Wherein the staining of the compounds of (A), Dyeing Example PP1 to PP3, and R _A1 used in PP 13, R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that R _A1, R _At least one of A2 and _RA3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.

Also, for each fastness of compounds of formula (A), Dyeing Example PP1 to PP3, and R _A1 used in PP 13, R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that the R _A1, at least one is a is) an alkyl group having 4 to 14 carbon atoms compound of R _A2 and R _A3 are, sublimation fastness, washing fastness, perspiration fastness, good fastness to rubbing fastness and hot pressing Met.

Table 38 shows the evaluation results of the dyeing examples of the compound of the formula (B).

The staining of the compounds of formula (B), Dyeing Example PP4 to PP6, and R _B1 used in the PP14, R _B2 represents an alkyl group having 1 to 14 carbon atoms each independently (provided that R _B1, R _B2 And _{at least one of RB3} is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.

Also, for each fastness of the compound of formula (B), R _B1 used in Dyeing Example PP4 to PP6, R _B2 each independently represents an alkyl group having 1 to 14 carbon atoms with (but R _B1, R _B2 And _{at least one of RB3} is an alkyl group having 4 to 14 carbon atoms), each of which has good fastness.

Table 39 shows the evaluation results of dyeing examples of the compound of the formula (C).

For staining of compound of formula (C), Dyeing Example PP7 to PP9, PP15 and R _C1 used in PP16, R _C2 and R _C3 are an alkyl group having 1 to 14 carbon atoms each independently (provided that R _{The stainability of the compound (at least one of C1} , _RC2 and _RC3 is an alkyl group having 4 to 14 carbon atoms) was good.

Also, for each fastness of compound of formula (C), represents a R _C1, R _C2 and R _C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example PP7 to PP9, PP15 and PP16 (provided that at least one of R _C1, R _C2 and R _C3 are an alkyl group having 4 to 14 carbon atoms) compounds, each fastness was good.

Table 40 shows the evaluation results of dyeing examples of the compound of the formula (D).

The staining of the compounds of formula (D), Dyeing PP10, PP11, PP17 and R _D1 and R _D2 used in the PP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R _D1 and R _{The stainability of the compound (at least one of D2} is an alkyl group having 4 to 14 carbon atoms) was good.

Also, for each fastness of the compound of formula (D), Dyeing PP10, PP11, PP17 and R _D1 and R _D2 used in the PP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R _The compounds (at least one of D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms) had good fastness.

Table 41 shows the evaluation results of the dyeing example of the compound of the formula (G).

Stainability of the compound of formula (G) is, R _G used in Dyeing Example PP12 and PP19 have had good dyeability of a compound of the alkyl group having 7 or 10 to 18 carbon atoms.

Regarding each fastness of the compound of the formula (G), the compound having an alkyl group having 7 or 10 to 18 _{RG carbons used in Staining Examples PP12 and PP19 was good.}

(Printing of polypropylene fiber 2)
Using a dye composition in which two or more of the compounds shown in Tables 3 to 9 were mixed and used, 1.2% o. m. p. Polypropylene fibers were dyed using the printing paste of.

Further, using a dye composition in which two or more kinds of the compounds shown in Tables 3 to 9 were mixed and used, 1.8% o. m. p. Polypropylene fibers were dyed using the printing paste of.

The obtained polypropylene fiber dyed product has the same dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, and sweat as the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 2). Fastness test, friction fastness test and fastness test against hot pressing were performed.

The results are shown in Table 42.

As shown in Table 42, when the orange dye, the red dye, and the blue dye obtained in the present invention were mixed and used, a black dyed cloth having good dyeability and good fastness was obtained.

(Polyethylene fiber printing 1)
Printing method using only one type of dye composition of the compound shown in Tables 3 to 9 or a dye composition such as a disperse dye compound conventionally used for dyeing polyester fibers and the like shown in Tables 3 to 9. The polyethylene fibers were dyed with.

(Staining example EP1)
5.8 g of carboxymethyl cellulose, 0.3 g of sodium chlorate, and 0.3 g of tartaric acid were added to 73.6 g of water, and the mixture was stirred until uniform to obtain paste A. To the paste A, a dye dispersion liquid obtained by adding 18.5 g of water to 1.5 g of the dye composition (dye concentration 20% by mass) of the blue compound A-13 obtained in Dye Composition Production Example 76 and stirring is added. Then, the dyeing paste was prepared by stirring until it became uniform (0.3% omp). The printing paste is printed on polyethylene fibers, dried by dry heat at 110 ° C. for 3 minutes, and then H.I. T. The color was developed at 110 ° C. for 6 minutes by a steamer, and then reduced washing, washing with water and drying to obtain a blue polyethylene fiber dyed product.

(Staining Examples EP2 to EP12)
A dyed polyethylene fiber dyed product was obtained by the same dyeing procedure as in the dyeing example EP1 except that the dye composition of the blue compound A-13 described in the dyeing example EP1 was changed to the dye composition of the compounds shown in Tables 43 to 47. ..

(Staining example EP13)
5.8 g of carboxymethyl cellulose, 0.3 g of sodium chlorate, and 0.3 g of tartaric acid were added to 73.6 g of water, and the mixture was stirred until uniform to obtain paste A. To the paste A, 1.5 g of a powdery dye composition (dye concentration 20% by mass) of the blue compound A-5 obtained in Dye Composition Production Example 105 was added with 18.5 g of water, and the mixture was stirred. The dispersion was added and stirred until uniform to prepare a printing paste (0.3% omp). The printing paste is printed on polyethylene fibers, dried by dry heat at 110 ° C. for 3 minutes, and then H.I. T. The color was developed at 110 ° C. for 6 minutes by a steamer, and then reduced washing, washing with water and drying to obtain a blue polyethylene fiber dyed product.

(Staining Examples EP14 to EP19)
By the same dyeing procedure as in Dyeing Example EP13, except that the powdery dye composition of the blue compound A-5 described in Dyeing Example EP13 was changed to the powdery dye composition of the compounds in Tables 44 to 47. A dyed polyethylene fiber dyed product was obtained.

Table 48 shows the evaluation results of dyeing examples of the compound of the formula (A).

Wherein the staining of the compounds of (A), Dyeing Example EP1 through EP3, and R _A1 used in EP13, R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that R _A1, R _At least one of A2 and _RA3 is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.

Also, for each fastness of compounds of formula (A), Dyeing Example EP1 through EP3, and R _A1 used in EP13, R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that the R _The compound (at least one of A1, _RA2 and _RA3 is an alkyl group having 4 to 14 carbon atoms) had good wash fastness, sweat fastness, and friction fastness.

Table 49 shows the evaluation results of the dyed examples of the compound of the formula (B).

The staining of the compounds of formula (B), Dyeing Example EP4 to EP6, and R _B1 used in EP14, R _B2 represents an alkyl group having 1 to 14 carbon atoms each independently (provided that R _B1, R _B2 And _{at least one of RB3} is an alkyl group having 4 to 14 carbon atoms), and the stainability of the compound was good.

Also, for each fastness of the compound of formula (B), Dyeing Example EP4 to EP6, and represents the R _B1, R _B2 are each independently an alkyl group having 1 to 14 carbon atoms used in EP14 (provided that R _B1 , At _{least one of RB2} and _RB3 is an alkyl group having 4 to 14 carbon atoms), each of which has good fastness.

Table 50 shows the evaluation results of the dyeing examples of the compound of the formula (C).

For staining of compound of formula (C), Dyeing Example EP7 to EP9, EP15 and R _C1 used in EP16, R _C2 and R _C3 are an alkyl group having 1 to 14 carbon atoms each independently (provided that R _{The stainability of the compound (at least one of C1} , _RC2 and _RC3 is an alkyl group having 4 to 14 carbon atoms) was good.

Also, for each fastness of compound of formula (C), represents a R _C1, R _C2 and R _C3 are independently an alkyl group having 1 to 14 carbon atoms used in Dyeing Example EP7 to EP9, EP15 and EP16 (wherein R _C1, at least one of R _C2 and R _C3 are an alkyl group having 4 to 14 carbon atoms) compounds, each fastness was good.

Table 51 shows the evaluation results of the dyeing examples of the compound of the formula (D).

The staining of the compounds of formula (D), Dyeing EP10, EP11, EP17 and R _D1, R _D2 used in EP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R _D1 and R _{The stainability of the compound (at least one of D2} is an alkyl group having 4 to 14 carbon atoms) was good.

Also, for each fastness of the compound of formula (D), Dyeing EP10, EP11, EP17 and R _D1 and R _D2 used in EP18 represent each independently an alkyl group having 1 to 14 carbon atoms (provided that R _The compounds (at least one of D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms) had good fastness.

Table 52 shows the evaluation results of the dyeing examples of the compound of the formula (G).

Stainability of the compound of formula (G) is, R _G used in Dyeing Example EP12 and EP19 have had good dyeability of a compound of the alkyl group having 7 or 10 to 18 carbon atoms.

Regarding each fastness of the compound of the formula (G), the compound having an alkyl group having 7 or 10 to 18 _{RG carbons used in Staining Examples EP12 and EP19 was good.}

(Polyethylene fiber printing 2)
Using a dye composition in which two or more of the compounds shown in Tables 3 to 9 were mixed and used, 1.2% o. m. p. Polyethylene fibers were dyed using the printing paste of.

Further, using a dye composition in which two or more kinds of the compounds shown in Tables 3 to 9 were mixed and used, 1.8% o. m. p. Polyethylene fibers were dyed using the printing paste of.

The obtained polyethylene fiber dyed product has a dyeability evaluation, a light fastness test, a washing fastness test, a sweat fastness test and friction, similarly to the polypropylene fiber dyed product obtained in the above-mentioned (polypropylene fiber dyeing 2). A fastness test was performed.

The results are shown in Table 53.

As shown in Table 53, when the orange dye, the red dye, and the blue dye obtained in the present invention were mixed and used, a black dyed cloth having good dyeability and good fastness was obtained.

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 composition containing at least one of the compounds of the following general formulas (A) to (G) and a nonionic dispersant.

[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.
RD2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN (provided that at least one of RD1 and RD2 is an alkyl group having 4 to 14 carbon atoms. ). ]

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 or 10 to 18 carbon atoms. ]
The nonionic dispersant is selected from the group consisting of polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl phenyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene aryl aryl ethers, and oxyethylene-oxypropylene copolymers. The dye composition according to claim 1, which is at least one of the following.
The nonionic dispersant according to claim 1 or 2, wherein the nonionic dispersant is at least one selected from the group consisting of polyoxyethylene aryl phenyl ethers, polyoxyethylene aryl aryl ethers, and oxyethylene-oxypropylene copolymers. Dye composition.
The dye composition according to any one of claims 1 to 3, wherein the nonionic dispersant is at least one selected from polyoxyethylene arylphenyl ether or oxyethylene-oxypropylene copolymer.
The dye composition according to any one of claims 1 to 4, wherein the nonionic dispersant is a polyoxyethylene arylphenyl ether and an oxyethylene-oxypropylene copolymer.
The dye composition according to any one of claims 1 to 5, wherein the dye composition is in the form of powder.
The dye composition according to claim 6, wherein the powdery dye composition is produced by a spray-drying treatment.
It is a method of dyeing fibers.
A method comprising a step of water-based dyeing of fibers using the dye composition according to any one of claims 1 to 7.
The dyeing method according to claim 8, wherein the dyeing step is at least one selected from the group consisting of dyeing, printing, inkjet dyeing, transfer dyeing, and continuous dyeing.
The dyeing method according to claim 8 or 9, wherein the dyeing step is at least one selected from dyeing and printing.
The dyeing method according to any one of claims 8 to 10, wherein the dyeing step is printing.
When the fiber is polyolefin
The dyeing method according to any one of claims 8 to 11, wherein the dyeing step is performed at 80 ° C. to 130 ° C.
When the fiber is polypropylene
The dyeing method according to any one of claims 8 to 11, wherein the dyeing step is performed at 110 ° C. to 130 ° C.
When the fiber is polyethylene
The dyeing method according to any one of claims 8 to 11, wherein the dyeing step is performed at 90 ° C to 110 ° C.
When the dyeing method is printing, the concentration of the dye with respect to the printing paste is 0.001% o. m. p. ~ 5% o. m. p. The dyeing method according to any one of claims 8 to 14, which is in the range of (on the mass of paste).
When the dyeing method is dyeing,
The concentration of the dye with respect to the fiber is 0.001% o. m. f. To 10% o. m. f. The dyeing method according to any one of claims 8 to 10 and 12 to 14, which is in the range of (on the mass of fiber).
Fiber dyed by the dyeing method according to any one of claims 9 to 16.
A compound according to any 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 or 10 to 18 carbon atoms. ]
The dye composition for dyeing polyolefin fibers black is
At least one of a purple or blue compound 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 the red compounds selected from the group consisting of the compound of the general formula (C) and the compound of the general formula (D), and
The dye composition according to claim 18, which comprises at least one of a yellow or orange compound 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). thing.
The dye composition for dyeing polyolefin fibers black is
At least one of a purple or blue compound 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 compound of the compound of the general formula (C) and
The dye composition according to claim 18 or 19, which comprises at least one of an orange compound selected from the group consisting of a compound of the general formula (D) and a compound of the general formula (E).
The dye composition for dyeing polyolefin fibers black is
Any one of claims 18 to 20, comprising a blue compound of the compound of the general formula (A), a red compound of the compound of the general formula (C), and an orange compound of the compound of the general formula (D). The dye composition according to the section.
The compounds in the dye composition for dyeing polyolefin fibers black
The ratio of the purple or blue compound is 30 to 70% by mass with respect to the total dye.
The ratio of the red compound is 5 to 25% by mass with respect to the total dye.
The ratio of the yellow or orange compound is in the range of 15 to 55% by mass with respect to the total dye.
The dye composition according to any one of claims 18 to 21.
The compounds in the dye composition for dyeing polyolefin fibers black
The ratio of the purple or blue compound is 40 to 60% by mass with respect to the total dye.
The ratio of the red compound is 5 to 25% by mass with respect to the total dye.
The ratio of the yellow or orange compound is in the range of 25 to 45% by mass with respect to the total dye.
The dye compound according to any one of claims 18 to 22.