KR20220123293A - Dyes for dyeing using supercritical carbon dioxide - Google Patents

Abstract

A dye for dyeing polyolefin fibers using supercritical carbon dioxide, which can dye polyolefin fibers in various colors at high concentrations, and has excellent light resistance, sublimation, and washing fastness of dyed materials, polyolefin fibers using supercritical carbon dioxide An object of the present invention is to provide a dyeing method and a polyolefin fiber dyed by the dyeing method. A dye for dyeing polyolefin fibers using supercritical carbon dioxide, comprising at least one of the compounds of formulas (A) to (G), a method for dyeing polyolefin fibers using the dye and supercritical carbon dioxide, and A polyolefin fiber dyed by a dyeing method is provided.

Description

Dyes for dyeing using supercritical carbon dioxide

The present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, a method for dyeing polyolefin fibers using supercritical carbon dioxide, and polyolefin fibers dyed by the dyeing method.

Polyolefin resins such as polypropylene resins and polyethylene resins are crystalline thermoplastic resins, and are inexpensive, easy to process, high strength, high chemical resistance, high abrasion resistance, high flexural resistance, light weight, low moisture absorption, low thermal conductivity, high shear It has excellent properties such as intelligence.

On the other hand, polyolefin-based resins are high molecular compounds made of hydrocarbons in both the main chain and side chains, have low affinity and compatibility with conventional dye compounds, and do not have functional groups effective for chemical reactions. Therefore, high-concentration and high-fastness dyeing was considered to be extremely difficult.

For this reason, most of the colored polyolefin-based resins currently on the market are those in which a colored pigment is added at a production stage such as polymer pellets, and thereafter, spinning and molding into a desired shape are performed.

In this coloring method, it is necessary to determine the color at an early stage in the resin product manufacturing process. In addition, considering profitability, it is necessary to produce more than a certain amount of one color, and as a result, freedom of color selection is limited.

In addition, in the case of changing the color of the resin product, a process of replacing the colored resin of the previous color remaining in the resin product manufacturing apparatus with the colored resin of the next color is required, in which case a large amount of waste resin is generated and time and wasting energy.

As described in Non-Patent Document 1, polypropylene resin and polyethylene resin are four major general-purpose synthetic resins comparable to polyvinyl chloride resin and polystyrene resin, and are used in a wide range of fields.

However, the use of polypropylene resins and polyethylene resins as synthetic fibers is very limited.

The reason is that, as described above, high-concentration and high-fastness dyeing of polypropylene resin fibers and polyethylene resin fibers is extremely difficult. Inevitably, it is also believed that this is because freedom of color choice is limited.

Until now, in order to water-dye polyolefin-based resin fibers, attempts have been made to change the molecular structure of the dye. Specifically, in Patent Documents 1 to 5, dyes for dyeing polyolefin resin fibers are proposed.

Patent Document 1 describes production examples of red dyes and purple dyes in which a phenoxy group having an alkyl group having 3 to 12 carbon atoms or a cycloalkyl group as a substituent is introduced into anthraquinone dyes, and examples of dyeing polypropylene resin fibers using them. has been

However, with these anthraquinone-based red dyes or anthraquinone-based purple dyes, high-concentration dyeing of polyolefin-based resin fibers is difficult. Also, regarding the form of the dye when used for dyeing, there are descriptions such as dissolving these anthraquinone-based red dyes in alcohol or acetone as an organic solvent and then using them, so it is difficult to say that this dyeing method is environmentally friendly.

Patent Document 2 discloses a production example of a blue dye in which a phenoxy group having an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group or a halogeno group as a substituent is introduced into an anthraquinone-based dye, and polyester fibers, polyamide fibers using these, An example of dyeing of polyolefin-based resin fibers is described.

However, with these anthraquinone-based blue dyes, high-concentration dyeing of polyolefin-based resin fibers is difficult, and there is no specific description regarding the dyeing fastness of the obtained dyed product. In addition, regarding the form of the dye when used for dyeing, there are descriptions such as dissolving these anthraquinone-based blue dyes in an organic solvent such as alcohol or acetone and then using it, so it is difficult to say that it is environmentally friendly.

Patent Document 3 describes an example of production of a blue dye in which a phenoxy group having an alkyl group having 1 to 9 carbon atoms or a halogeno group as a substituent is introduced into an anthraquinone dye, and an example of dyeing polyolefin resin fibers using these.

However, with these anthraquinone-based blue dyes, high-concentration dyeing of polyolefin-based resin fibers is difficult, and there is no specific description regarding the dyeing fastness of the obtained dyed product. In addition, regarding the form of the dye when used for dyeing, there is a description such as dissolving it in alcohol or acetone, which is an organic solvent, and then using it.

Patent Document 4 describes a dyeing example of 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, with these anthraquinone-based blue dyes, high-concentration dyeing of polyolefin-based resin fibers is difficult, and there is no specific description regarding the dyeing fastness of the obtained dyed product.

Patent Document 5 discloses a production example of 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-based dye, and a polypropylene resin using the same Examples of dyeing fibers are described.

However, with these anthraquinone-based red dyes, high-concentration dyeing of polyolefin-based resin fibers is difficult, and there is no specific description regarding the dyeing fastness of the obtained dyed product. In addition, regarding the form of the dye when used for dyeing, there is a description such as dissolving it in dimethylformamide, an organic solvent, and then using it, so it is difficult to say that a method using such a dye is environmentally friendly.

Patent Document 6 describes a production example of a monoazo dye having a long-chain alkyl group, and an example of dyeing fine indenyl polyester fibers using these dyes. However, examples of dyeing polyolefin fibers using these are not described.

In addition, in order to improve the dyeability of the polyolefin-based resin fiber, various studies have been made on the modification of the polyolefin-based resin fiber.

As a modification technique, various things are known, such as mixing|blending of a flammable resin component, such as polyester, copolymerization with a vinylic monomer etc. which have a flammable group, and mixing|blending of dyeing accelerators, such as a metal stearate.

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

By the way, Patent Document 7 describes, as a dyeing method instead of water-based dyeing, using supercritical carbon dioxide as a dyeing medium and dyeing a hydrophobic fiber material with various dyes.

However, although polypropylene is described as an example of the hydrophobic fiber material, only examples of dyeing polyester fabrics are described in Examples, and examples of dyeing polypropylene fibers are not described.

Japanese Special Attack No. 38-10741 Gazette Japanese Special Attack No. 40-1277 Gazette Japanese Special Attack No. 41-3515 Gazette Japanese Patent No. 872,882 Specification Specification of U.S. Patent No. 3,536,735 Japanese Patent Laid-Open No. 55-152869 Japanese Patent No. 3253649 Publication

Hiroshi Yamamoto, Journal of the Korean Textile Society, 61 (2005), 319-321.

Therefore, in the present invention, polyolefin fibers are dyed using supercritical carbon dioxide, which can dye polyolefin fibers at high concentrations in various colors, and has excellent light resistance, sublimation, and color fastness such as washing. An object of the present invention is to provide a dye, a method for dyeing polyolefin fibers using supercritical carbon dioxide, and polyolefin fibers dyed by the dyeing method.

The present invention is a dye for dyeing polyolefin fibers using supercritical carbon dioxide containing at least one of the compounds of the following general formulas (A) to (G).

[In formula (A),

X _A is a nitro group,

Y _A represents a halogen atom,

R _A1 , R _A2 and R _A3 each independently represent 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);

R _A4 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 (provided that at least one of R _B1 , R _B2 and R _B3 is an alkyl group having 4 to 14 carbon atoms). ]

[In formula (C),

X _C and Y _C represent a combination of any one of a hydrogen atom and a halogen atom, a halogen atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom,

R _C1 , R _C2 and R _C3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _C1 , R _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms).

[In formula (D), X _D and Y _D each independently represents a hydrogen atom, a halogen atom, or a cyano group,

R _D1 represents an alkyl group having 1 to 14 carbon atoms,

R _D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN.

However, at least one of R _D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms.]

[In formula (E), X _E and Y _E each independently represent a halogen atom, and 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), R _G represents an alkyl group having 7 to 18 carbon atoms.]

In addition, the present invention is a method for dyeing polyolefin fibers using supercritical carbon dioxide,

It provides a method comprising the step of dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the dye of the present invention.

Further, the present invention provides a polyolefin fiber dyed by the dyeing method of the present invention.

The dye of the present invention can dye polyolefin fibers at a high concentration in various colors in the presence of supercritical carbon dioxide, and the dyed product is excellent in dyeing fastness such as light resistance, sublimation, and washing.

1 shows a supercritical carbon dioxide dyeing apparatus used for dyeing.

The present inventors have discovered that dyes containing the following specific compounds have improved affinity for lipophilic polyolefin fibers, and dye polyolefin fibers in various colors at high concentrations in the presence of supercritical carbon dioxide, and completed the present invention did.

<Compound of general formula (A) to general formula (G)>

The compounds of general formula (A) - general formula (G) contained in the dye of this invention are as follows.

[In formula (A),

X _A is a nitro group,

Y _A represents a halogen atom,

R _A1 , R _A2 and R _A3 each independently represent 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);

R _A4 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 (provided that at least one of R _B1 , R _B2 and R _B3 is an alkyl group having 4 to 14 carbon atoms). ]

[In formula (C),

X _C and Y _C represent a combination of any one of a hydrogen atom and a halogen atom, a halogen atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom,

R _C1 , R _C2 and R _C3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _C1 , R _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms).

[In formula (D), X _D and Y _D each independently represents a hydrogen atom, a halogen atom, or a cyano group,

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.

provided that at least one of R _D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms.]

[In formula (E), X _E and Y _E each independently represent a halogen atom, and 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), R _G represents an alkyl group having 7 to 18 carbon atoms.]

In the formulas (A), (C), (D), and (E), the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom, a chlorine atom and a bromine atom. can be exemplified.

In the formulas (A) to (D), the alkyl group having 1 to 14 carbon atoms is, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec- Butyl group, tert-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, tert-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl 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 A straight-chain or branched alkyl group having 1 to 14 carbon atoms, such as 1-ethyl-1-methylpropyl group, can be exemplified. As said C1-C14 alkyl group, a C1-C12 alkyl group is preferable, and a C1-C8 alkyl group is more preferable.

In the formula (A), an alkyl group having 1 to 4 carbon atoms is, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert- There is a linear or branched alkyl group having 1 to 4 carbon atoms, such as a butyl group. As said C1-C4 alkyl group, a C1-C2 alkyl group is preferable, and a C1-C4 alkyl group 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, tert-butyl group, n -pentyl group, i-pentyl group, sec-pentyl group, tert-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl 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-ethyl-1-methylpropyl group and a linear or branched alkyl group having 4 to 14 carbon atoms. As said C4-C14 alkyl group, a C4-C12 alkyl group is preferable, and a C4-C8 alkyl group is more preferable.

In the formula (E), the alkyl group having 4 to 18 carbon atoms is, for example, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, i-pentyl group, sec -pentyl group, tert-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, A straight-chain or branched alkyl group such as 2-ethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 1-ethyl-1-methylpropyl group have. As said C4-C18 alkyl group, a C4-C12 alkyl group is preferable, and a C8-C12 alkyl group is more preferable.

In the formula (G), the alkyl group having 7 to 18 carbon atoms is, for example, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 1- straight-chain or branched alkyl groups having 7 to 18 carbon atoms, such as ethylpentyl group, 2-ethylpentyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, and 3,3-dimethylpentyl group. As said C7-C18 alkyl group, a C11-C18 alkyl group is preferable, and a C15-C18 alkyl group is more preferable.

<Compound of general formula (A)>

The compound of general formula (A), in formula (A),

X _A is a nitro group,

Y _A represents a halogen atom,

R _A1 , R _A2 and R _A3 each independently represent 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);

R _A4 represents an alkyl group having 1 to 4 carbon atoms.

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

In the formula (A),

In terms of dyeing density, light fastness, sublimation fastness, etc.

Y _A is preferably a bromine atom.

In addition, in the formula (A),

In terms of dyeing density, light fastness, sublimation fastness, etc.

R _A1 , R _A2 and R _A3 are each independently an alkyl group having 4 to 14 carbon atoms, or

R _A1 and R _A2 are each independently an alkyl group having 4 to 14 carbon atoms, and R _A3 is an alkyl group having 1 to 4 carbon atoms, or

It is preferable that R _A3 is a C4-C14 alkyl group, and R _A1 and R _A2 are each independently a C1-C4 alkyl group.

In addition, in the formula (A),

In terms of dyeing density, light fastness, sublimation fastness, etc.

Y _A is a bromine atom,

R _A1 , R _A2 and R _A3 are each independently an alkyl group having 4 to 14 carbon atoms, or

R _A1 and R _A2 are each independently an alkyl group having 4 to 14 carbon atoms, and R _A3 is an alkyl group having 1 to 4 carbon atoms, or

It is preferable that R _A3 is a C4-C14 alkyl group, and R _A1 and R _A2 are each independently a C1-C4 alkyl group.

<Compound of general formula (B)>

The compound of general formula (B), in formula (B),

R _B1 , R _B2 and R _B3 each independently represent an alkyl group having 1 to 14 carbon atoms.

provided that at least one of R _B1 , R _B2 and R _B3 is an alkyl group having 4 to 14 carbon atoms.

The compound of the said Formula (B) is a blue or purple dye compound.

In the formula (B),

In terms of dyeing density, light fastness, sublimation fastness, etc.

R _B1 , R _B2 and R _B3 are each independently an alkyl group having 4 to 14 carbon atoms, R _B1 and R _B2 are each independently an alkyl group having 4 to 14 carbon atoms, and R _B3 is an alkyl group having 1 to 4 carbon atoms; , or

It is preferable that R _B3 is an alkyl group having 4 to 14 carbon atoms, and R _B1 and R _B2 are each independently an alkyl group having 1 to 4 carbon atoms.

<Compound of general formula (C)>

The compound of general formula (C), in formula (C),

X _C and Y _C represent a combination of any one of a hydrogen atom and a halogen atom, a halogen atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom,

R _C1 , R _C2 and R _C3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _C1 , R _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms).

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

In the formula (C),

In terms of dyeing density, light fastness, sublimation fastness, etc.

X _C and Y _C represent a combination of any one of a hydrogen atom and a chlorine atom, a bromine atom and a nitro group, a bromine 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 desirable.

In the formula (C),

In terms of dyeing density, light fastness, sublimation fastness, etc.

X _C and Y _C represent a combination of any one of a hydrogen atom and a halogen atom, a halogen atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom,

R _C1 , R _C2 and R _C3 are each independently an alkyl group having 4 to 14 carbon atoms, or

R _C1 and R _C2 are each independently an alkyl group having 4 to 14 carbon atoms, and R _C3 is an alkyl group having 1 to 4 carbon atoms, or

It is preferable that R _C3 is an alkyl group having 4 to 14 carbon atoms, and R _C1 and R _C2 are each independently an alkyl group having 1 to 4 carbon atoms.

<Compound of general formula (D)>

In the compound of the general formula (D), in the formula (D), X _D and Y _D each independently represents a hydrogen atom, a halogen atom, or a cyano group,

R _D1 represents an alkyl group having 1 to 14 carbon atoms,

R _D2 represents an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN.

However, at least one of R _D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms.

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

In the formula (D),

In terms of dyeing density, 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.

In addition, in the formula (D), X _D and Y _D each independently represents a hydrogen atom, a halogen atom, or a cyano group,

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.

<Compound of general formula (E)>

In the compound of the general formula (E), in the formula (E), X _E and Y _E each independently represent a halogen atom, and R _E represents an alkyl group having 4 to 18 carbon atoms.

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

In the above formula (E),

In terms of dyeing density, light fastness, sublimation fastness, etc.

It is preferable that X _E and Y _E represent a chlorine atom.

In the above formula (E),

In terms of dyeing density, light fastness, sublimation fastness, etc.

R _E is preferably an alkyl group having 4 to 12 carbon atoms.

In the above formula (E),

In terms of dyeing density, light fastness, sublimation fastness, etc.

X _E and Y _E represent a chlorine atom,

R _E is preferably an alkyl group having 4 to 12 carbon atoms.

<Compound of general formula (F)>

In the compound of the general formula (F), in the formula (F), R _F1 and R _F2 each independently represent an alkyl group having 4 to 14 carbon atoms.

The compound of the said Formula (F) is a purple dye compound.

In the above formula (F),

In terms of dyeing density, 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.

<Compound of general formula (G)>

In the compound of the general formula (G), in the formula (G), R _G represents an alkyl group having 7 to 18 carbon atoms.

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

In the above formula (G),

In terms of dyeing density, light fastness, sublimation fastness, etc.

R _G is preferably an alkyl group having 11 to 18 carbon atoms.

<Method for producing compound of general formula (A)>

The manufacturing method of the compound represented by the said Formula (A) is demonstrated.

The compound represented by the formula (A) is a diazo compound of the 4-nitroaniline derivative represented by the formula (aD) (in formula (aD), X _A represents a nitro group and Y _A represents a halogen atom); A compound represented by formula (aC) (in formula (aC), R _A1 , R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _A1 , R _A2 and R _A3 has a carbon number) is an alkyl group of 4 to 14) and R _A4 represents an alkyl group having 1 to 4 carbon atoms).

(i) diazotization of a compound of formula (a-D)

First, the compound of formula (a-D) is diazotized in a mineral acid or organic carboxylic acid in the presence of optionally added water using a nitrosating agent or nitrosylsulfuric acid to obtain a diazo compound. Examples of the organic carboxylic acid to be used include acetic acid and propionic acid. Moreover, as a mineral acid, they are hydrochloric acid, phosphoric acid, and sulfuric acid, Preferably they are sulfuric acid, for example. As a nitrosating agent to be used, it is an alkali metal nitrite, for example, sodium nitrite in a solid state or aqueous solution state.

The reaction temperature for diazotization is preferably -10 to 40°C, more preferably 0 to 40°C.

And the compound represented by a formula (a-D) is generally used widely as a raw material of an azo disperse dye.

(ii) coupling with a compound of formula (a-C)

To a solution or suspension of an alcohol (for example, methanol) of a compound represented by the formula (a-C), a solution of the diazo compound of the formula (a-D) is added at a temperature range of, for example, -5 to 10°C Thus, the compound represented by the formula (A) is obtained.

The pH of the compound solution or suspension represented by the formula (a-C) is preferably weakly acidic, and it is sometimes advantageous in the coupling reaction to add a buffer such as triethylamine or sodium acetate.

The compound of the general formula (A) is dried, for example, to a moisture content of 1.0 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and is used for dyeing using supercritical carbon dioxide as a medium.

(iii) a process for the preparation of a compound of formula (a-C)

The compound of formula (a-C) which is a raw material can be manufactured as follows.

Using N,N-dimethylformamide (DMF) as a solvent, to the compound represented by formula (a-C1) (in formula (a-C1), R _A4 represents an alkyl group having 1 to 4 carbon _atoms ) A carboxylic acid halide represented by COX (R _A3 represents an alkyl group having 1 to 14 carbon atoms and X represents a halogen atom) is reacted to obtain 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 hydrochloric acid alcohol (eg, methanol) to obtain the compound represented by the formula (a-C4).

In the compound represented by formula (a-C4) using DMF as a solvent, R _A1 -X and R _A2 -X (R _A1 and R _A2 each independently represent an alkyl group having 1 to 14 carbon atoms, and X represents a halogen atom shown) is reacted to obtain a formula (aC).

Alternatively, a compound represented by the formula (a-C4) is reacted with a halogenated hydrocarbon represented by R _A1 -X (R _A1 represents an alkyl group having 1 to 14 carbon atoms, X represents a halogen atom), followed by a known reaction. , R _A2 (R _A2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced. For example, (R _A2 ) ₂ SO ₄ can be used to introduce R _A2 .

<Method for producing compound of general formula (B)>

The manufacturing method of the compound represented by the said Formula (B) is demonstrated.

The compound represented by the formula (B) is a diazo compound of 3-amino-5-nitro-2,1-benzisothiazole represented by the formula (bD), and the compound represented by the formula (bC) (formula (bC) In (bC), R _B1 , R _B2 and R _B3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _B1 , R _B2 and R _B3 is an alkyl group having 4 to 14 carbon atoms). obtained by coupling.

(i) diazotization of a compound of formula (b-D)

First, the compound of formula (b-D) is diazotized in a mineral acid or organic carboxylic acid in the presence of optionally added water using a nitrosating agent or nitrosylsulfuric acid to obtain a diazo compound. Examples of the organic carboxylic acid to be used include acetic acid and propionic acid. Further, as the mineral acid, there are, for example, hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid. As a nitrosating agent to be used, it is an alkali metal nitrite, for example, sodium nitrite in a solid state or aqueous solution state.

The reaction temperature for diazotization is preferably -10 to 15°C, more preferably -5 to 10°C.

And the compound represented by a formula (b-D) is generally used widely as a raw material of an azo disperse dye.

(ii) coupling with a compound of formula (b-C)

To a solution or suspension of an alcohol (e.g., methanol) of the compound represented by the formula (b-C), a solution of the diazo compound of the formula (b-D) is added at a temperature range of, for example, -5 to 10 ° C. , to obtain a compound represented by the formula (B).

The pH of the compound solution or suspension represented by the formula (b-C) is preferably weakly acidic, and it is sometimes advantageous in the coupling reaction to add a buffer such as triethylamine or sodium acetate.

The compound of general formula (B) is dried to, for example, a moisture content of 1.0 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and is used for dyeing using supercritical carbon dioxide as a medium.

(iii) a process for preparing a compound of formula (b-C)

The compound of formula (b-C) which is a raw material can be manufactured as follows.

Using DMF as a solvent, m-nitroaniline is reacted with a carboxylic acid halide represented by R _B3 -COX (R _B3 represents an alkyl group having 1 to 14 carbon atoms, X represents a halogen atom), and formula (b-C1) to obtain a compound represented by

Next, the compound represented by the formula (b-C1) is reduced with tin in hydrochloric acid alcohol (eg, methanol) to obtain the compound represented by the formula (b-C2).

Using DMF as a solvent, in the compound represented by the formula (b-C2), R _B1 -X and R _B2 -X (R _B1 and R _B2 each independently represent an alkyl group having 1 to 14 carbon atoms, and X represents a halogen atom is reacted with an alkyl halide represented by ) to obtain a formula (bC).

Alternatively, a compound represented by the formula (b-C2) is reacted with a halogenated hydrocarbon represented by R _B1 -X (R _B1 represents an alkyl group having 1 to 14 carbon atoms, and X represents a halogen atom), followed by a known reaction. , R _B2 (R _B2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced. For example, (R _B2 ) ₂ SO ₄ can be used to introduce R _B2 .

<Method for producing compound of general formula (C)>

The manufacturing method of the compound represented by the said Formula (C) is demonstrated.

The compound represented by the formula (C) is a 4-nitroaniline derivative represented by the formula (cD) (in formula (cD), X _C and Y _C are a hydrogen atom and a halogen atom, a halogen atom and a nitro group, a halogen A diazo compound of an atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, or a combination of any one of a hydrogen atom and a hydrogen atom) and a compound represented by the formula (cC) (in the formula (cC) , R _C1 , R _C2 and R _C3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _C1 , R _C2 and R _C3 is an alkyl group having 4 or more carbon atoms).

(i) diazotization of a compound of formula (c-D)

First, the compound represented by the formula (c-D) is diazotized using a nitrosating agent or nitrosylsulfuric acid in the presence of optionally added water in a mineral acid or an organic carboxylic acid to obtain a diazo compound. Examples of the organic carboxylic acid to be used include acetic acid and propionic acid. Further, as the mineral acid, there are, for example, hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid. As a nitrosating agent to be used, it is an alkali metal nitrite, for example, sodium nitrite in a solid state or aqueous solution state.

The diazotization temperature is preferably -10 to 40°C, more preferably 0 to 35°C.

And the compound represented by a formula (c-D) is generally used widely as a raw material of an azo disperse dye.

(ii) coupling with a compound of formula (c-C)

To a solution or suspension of an alcohol (e.g., methanol) of the compound represented by the formula (c-C), a solution of the diazo compound of the formula (c-D) is added at a temperature range of, for example, -5 to 10 ° C. , to obtain a compound represented by the formula (C).

The pH of the compound solution or suspension represented by the formula (c-C) is preferably weakly acidic, and in some cases it is advantageous to add a buffer such as triethylamine or sodium acetate.

The compound of the general formula (C) is dried, for example, to a moisture content of 1.0 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and is used for dyeing using supercritical carbon dioxide as a medium.

(iii) a process for the preparation of a compound of formula (c-C)

The compound of formula (c-C) as a raw material can be manufactured as follows.

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

Next, the compound represented by the formula (c-C1) is reduced with tin in hydrochloric acid alcohol (eg, methanol) to obtain the compound represented by the formula (c-C2).

In the compound represented by formula (c-C2) using DMF as a solvent, R _C1 -X and R _C2 -X (R _C1 and R _C2 each independently represent an alkyl group having 1 to 14 carbon atoms, and X is a halogen atom ) is reacted with an alkyl halide to obtain formula (cC).

Alternatively, a compound represented by the formula (c-C2) is reacted with a halogenated hydrocarbon represented by R _C1 -X (R _C1 represents an alkyl group having 1 to 14 carbon atoms, X represents a halogen atom), followed by a known reaction , R _C2 (R _C2 represents an alkyl group having 1 to 14 carbon atoms) may be introduced. For example, (R _C2 ) ₂ SO ₄ can be used to introduce R _C2 .

<Method for producing compound of general formula (D)>

The manufacturing method of the compound represented by the said Formula (D) is demonstrated.

The compound represented by the formula (D) is a 4-nitroaniline derivative represented by the formula (dD) (in formula (dD), X _D and Y _D each independently represent a hydrogen atom, a halogen atom, or a cyano group) of the diazo compound and the compound represented by the formula (dC) (in formula (dC), R _D1 represents an alkyl group having 1 to 14 carbon atoms, and R _D2 is an alkyl group having 1 to 14 carbon atoms or the number of carbon atoms substituted with CN. An alkyl group of 1 to 14 is shown, provided that at least one of R _D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms).

(i) diazotization of a compound of formula (d-D)

First, the compound represented by the formula (d-D) is diazotized using a nitrosating agent or nitrosylsulfuric acid in the presence of optionally added water in a mineral acid or organic carboxylic acid to obtain a diazo compound. Examples of the organic carboxylic acid to be used include acetic acid and propionic acid. Further, as the mineral acid, there are, for example, hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid. As a nitrosating agent to be used, it is an alkali metal nitrite, for example, sodium nitrite in a solid state or 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.

(ii) coupling with a compound of formula (d-D)

To a solution or suspension of an alcohol (e.g., methanol) of the compound represented by the formula (d-C), a solution of the diazo compound of the formula (d-D) is added at a temperature range of, for example, -5 to 10 ° C. , to obtain a compound represented by the formula (D).

The pH of the compound solution or suspension represented by the formula (d-C) is preferably weakly acidic, and in some cases it is advantageous to add a buffer such as triethylamine or sodium acetate.

The compound of the general formula (D) is dried, for example, to a moisture content of 1.0 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and is used for dyeing using supercritical carbon dioxide as a medium.

(iii) a process for the preparation of a compound of formula (d-C)

The compound of formula (d-C) as a raw material can be manufactured as follows.

Using DMF as a solvent, R _D1 -X and R _D2 -X (R _D1 represents an alkyl group having 1 to 14 carbon atoms, R _D2 is an alkyl group having 1 to 14 carbon atoms or CN substituted C 1 to 14 carbon atoms to aniline , wherein at least one of R _D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms. X is a halogen atom.) is reacted with an alkyl halide represented by the formula (dC).

Alternatively, after reacting aniline with a halogenated hydrocarbon represented by R _D1 -X (R _D1 represents an alkyl group having 1 to 14 carbon atoms, X represents a halogen atom), R _D2 (R _D2 is represents an alkyl group having 1 to 14 carbon atoms) may be introduced. For example, (R _D2 ) ₂ SO ₄ can be used to introduce R _D2 .

<Method for producing compound of general formula (E)>

The manufacturing method of the compound represented by the said Formula (E) is demonstrated.

The compound represented by the formula (E) includes a diazo compound of the 4-nitroaniline derivative represented by the formula (eD) (wherein X _E and Y _E represents a halogen atom), and the formula (eC) ) (in formula (eC), R _E represents an alkyl group having 4 to 18 carbon atoms).

(i) diazotization of a compound of formula (e-D)

First, the compound represented by the formula (e-D) is diazotized using a nitrosating agent or nitrosylsulfuric acid in the presence of optionally added water in a mineral acid or organic carboxylic acid to obtain a diazo compound. Examples of the organic carboxylic acid to be used include acetic acid and propionic acid. Further, as the mineral acid, there are, for example, hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid. As a nitrosating agent to be used, it is an alkali metal nitrite, for example, sodium nitrite in a solid state or aqueous solution state.

The diazotization temperature is preferably -10 to 40°C, more preferably 0 to 30°C.

And the compound represented by a formula (e-D) is generally used widely as a raw material of an azo disperse dye.

(ii) coupling with a compound of formula (e-C)

To a solution or suspension of an alcohol (e.g., methanol) of the compound represented by the formula (e-C), a solution of the diazo compound of the formula (e-D) is added at a temperature range of, for example, -5 to 10 ° C. , to obtain a compound represented by the formula (E).

The pH of the compound solution or suspension represented by the formula (e-C) is preferably weakly acidic, and in some cases it is advantageous to add a buffer such as triethylamine or sodium acetate.

The compound of the general formula (E) is dried to, for example, a moisture content of 1.0 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and is used for dyeing using supercritical carbon dioxide as a medium.

(iii) a process for the preparation of a compound of formula (e-C)

The compound of formula (e-C) as a raw material can be manufactured as follows.

Halogenation represented by R _E1 -X (R _E1 represents an alkyl group having 4 to 18 carbon atoms, and X is a halogen atom) to 2-phenyl-1H-indole represented by the formula (e-C1) using DMF as a solvent The alkyl is reacted to give the formula (eC).

<Method for producing compound of general formula (F)>

The manufacturing method of the compound represented by the said Formula (F) is demonstrated.

The compound represented by the formula (F) is a diazo compound of 3-amino-5-nitro-2,1-benzisothiazole represented by the formula (fD), and the compound represented by the formula (fC) (formula In (fC), R _F1 and R _F2 each independently represent an alkyl group having 4 to 14 carbon atoms).

(i) diazotization of a compound of formula (f-D)

First, the compound represented by the formula (f-D) is diazotized using a nitrosating agent or nitrosylsulfuric acid in the presence of optionally added water in a mineral acid or organic carboxylic acid to obtain a diazo compound. Examples of the organic carboxylic acid to be used include acetic acid and propionic acid. Further, as the mineral acid, there are, for example, hydrochloric acid, phosphoric acid and sulfuric acid, preferably sulfuric acid. As a nitrosating agent to be used, it is an alkali metal nitrite, for example, sodium nitrite in a solid state or aqueous solution state.

The diazotization temperature is preferably -10 to 15°C, more preferably -5 to 10°C.

The compound represented by the formula (f-D) is generally widely used as a raw material for an azo disperse dye.

(ii) coupling with a compound of formula (f-C)

To a solution or suspension of an alcohol (e.g., methanol) of the compound represented by the formula (f-C), a solution of the diazo compound of the formula (f-D) is added at a temperature range of, for example, -5 to 10 ° C. , to obtain a compound represented by the formula (F).

The pH of the compound solution or suspension represented by the formula (f-C) is preferably weakly acidic, and in some cases it is advantageous to add a buffer such as triethylamine or sodium acetate.

The compound of the general formula (F) is dried, for example, to a moisture content of 1.0 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and is used for dyeing using supercritical carbon dioxide as a medium.

(iii) a process for preparing a compound of formula (f-C)

The compound of formula (f-C) as a raw material can be manufactured as follows.

Using DMF as a solvent, aniline is reacted with an alkyl halide represented by R _F1 -X and R _F2 -X (R _F1 and R _F2 each independently represent an alkyl group having 4 to 14 carbon atoms, and X is a halogen atom) , we get the formula (fC).

Alternatively, after reacting aniline with a halogenated hydrocarbon represented by R _F1 -X (R _F1 represents an alkyl group having 4 to 14 carbon atoms, and X represents a halogen atom), according to a known reaction, R _F2 (R _F2 is represents an alkyl group having 4 to 14 carbon atoms) may be introduced. For example, (R _F2 ) ₂ SO ₄ can be used to introduce R _F2 .

<Method for producing compound of general formula (G)>

The manufacturing method of the compound represented by the said Formula (G) is demonstrated.

The compound represented by the formula (G) is 5-amino-anthra[9,1-cd]isothiazol-6-one represented by the formula (g) in an inert solvent such as toluene, xylene or chlorobenzene; It is obtained by reacting a carboxylic acid halide represented by R _G -COX (R _G represents an alkyl group having 7 to 18 carbon atoms, and X is a halogen atom).

80 degreeC - 140 degreeC are preferable and, as for reaction temperature, 110-140 degreeC is more preferable.

The compound represented by the formula (g) is generally widely used as a raw material for a polycyclic disperse dye.

The compound of the general formula (G) is dried, for example, to a moisture content of 1.0 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and is used for dyeing using supercritical carbon dioxide as a medium.

<Dye for dyeing polyolefin fibers using supercritical carbon dioxide>

The compound of general formula (A) - general formula (G) contained in the dye for dyeing the polyolefin fiber of this invention has blue, purple, red, orange, or yellow. The said dye may contain the compound of general formula (A) - general formula (G) individually or 2 or more. When the dye contains two or more compounds of formulas (A) to (G), dyes for dyeing polyolefin fibers in various colors or black can be obtained.

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

[Table 1]

The composition of the dye compound in the dye for dyeing the polyolefin fiber in black, the mixing ratio of the purple or blue dye compound is 30 to 70 mass%, the mixing ratio of the red dye compound is 5 to 25 mass%, The mixing ratio of the yellow or orange dye compound is preferably in the range of 15 to 55 mass %, the mixing ratio of the purple or blue dye compound is 40 to 60 mass %, and the mixing ratio of the red dye compound is 5 -25 mass %, it is more preferable that the mixing ratio of the said yellow or orange dye compound is the range of 25-45 mass %.

[Table 2]

The dye of this invention may further contain an additive. The additive includes, for example, a colorant, a dispersant, a filler, a stabilizer, a plasticizer, a nucleating agent, a modifier, a foaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antibacterial agent, an antifungal agent, an antistatic agent, a flame retardant, an inorganic filler, and There are elastomers for improving impact properties.

The polyolefin fiber of the object to be dyed, which is dyed with the dye of the present invention, is, for example, α such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, and 1-octene. There are fibers formed of a polymer selected from homopolymers of -olefins, copolymers of these α-olefins, or copolymers of other unsaturated monomers copolymerizable with these α-olefins. In addition, the type of copolymer includes, for example, a block copolymer, a random copolymer, and a graft copolymer. Specific examples of the polymer include polypropylene resins such as propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, propylene-ethylene-(1-butene) copolymer, low density polyethylene, medium density polyethylene, high density polyethylene-based resins such as polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, poly 1-butene, poly 4-methyl-1-pentene, and the like.

The said polymer may be used individually or in combination of 2 or more types, and may form a polyolefin fiber.

The polyolefin fibers of the object to be dyed to be dyed with the dye of the present invention are preferably formed of a polypropylene resin and/or a polyethylene resin, and more preferably formed of a polypropylene-based resin.

The shape of the polyolefin fiber of the object to be dyed, which is dyed with the dye of the present invention, is, for example, a lump-like (molded article, etc.), a film-like, a fibrous (heaven-like (woven, knitted, non-woven, etc.), thread-like ( filament yarn, weaving yarn, slit yarn, split yarn, etc.), etc.), etc. may be sufficient, Preferably it is fibrous.

The polyolefin fiber of the object to be dyed to be dyed with the dye of the present invention may be a fiber formed by blending, bonding, etc. other polymer components to polypropylene resin and/or polyethylene resin. The polyolefin fibers may be obtained by mixing polypropylene fibers with other fibers such as polyester, blending fibers, or the like.

<Dyeing method of polyolefin fiber using supercritical carbon dioxide>

The present invention is a method for dyeing polyolefin fibers using supercritical carbon dioxide, comprising the step of dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the dye of the present invention. In the method, supercritical carbon dioxide is used as the dyeing medium.

As a dyeing medium, the dyeing method using supercritical carbon dioxide does not use water at the time of dyeing, and since a washing process is unnecessary, compared to a general dyeing method using water as a dyeing medium, no wastewater is generated, and dyeing aids It is attracting attention as an eco-friendly dyeing method because it is unnecessary, the dyeing time is short, and carbon dioxide, which is a dyeing medium, can be reused.

In addition, supercritical carbon dioxide is lipophilic, and since both the dye and polyolefin resin of the present invention are lipophilic, the affinity of each of the dyeing medium, the dye, and the object to be dyed is high, and as a result, a dyed product of high quality is obtained.

It is preferable that the dyeing|staining process in the method of this invention is performed at the temperature of 31 degreeC or more, and the pressure of 7.4 MPa or more. It is because the said dyeing temperature and dyeing pressure need to be more than the critical point (31 degreeC · 7.4 MPa) of carbon dioxide which is a dyeing medium.

In the above dyeing process, the dyeing temperature is mainly determined according to the kind of resin of the fiber to be dyed. The said dyeing temperature is the range of 60-180 degreeC normally, Preferably it is the range of 80-160 degreeC.

In the above dyeing process, the dyeing pressure is mainly determined according to the kind of resin of the fiber to be dyed. The said dyeing pressure is the range of about 7.4-40.0 MPa normally, Preferably it is 20-30 MPa.

The dyeing time in the said dyeing process is determined by the kind of resin of the to-be-dyed fiber, dyeing temperature, and dyeing time. The said dyeing time is about 10 to 120 minutes normally, Preferably it is 30 to 90 minutes.

The said dyeing process WHEREIN: The density|concentration of the said dye with respect to the said fiber depends on the kind of to-be-dyed fiber and a processing state. When the dyed fiber is fibrous, the concentration of the dye to the fiber is 0.1 to 6.0 o.m.f. (on the mass of fiber), preferably 0.1 to 4.0 o.m.f.

In the dyeing method of this invention, the mixing ratio (mass ratio of to-be-dyed material: carbon dioxide) depends on the kind of to-be-dyed material and a processing state. The mixing ratio is usually 1:2 to 1:100, preferably 1:5 to 1:75. In the case of a polypropylene cloth wound on cheese with a suitable dyeing object, in the dyeing method of the present invention, the mixing ratio is relatively low, for example, 1:2 to 1:5.

The present invention provides a polyolefin fiber dyed by the dyeing method of the present invention. Examples of the use of the polyolefin fiber include clothing, underwear, hats, socks, gloves, medical products such as sportswear, vehicle interior materials such as seat seats, interior products such as carpets, curtains, mats, sofa covers, cushion covers, etc. etc.

Hereinafter, although an Example is given and this invention is demonstrated more concretely, the aspect of this invention is not limited to these.

[Example]

(Synthesis Example 1)

[Synthesis of blue dye compound (A-1)]

The blue dye compound (A-1) was manufactured according to the following scheme.

1-A. Synthesis of coupler compound (C1) and preparation of coupler component solution

(Process 1)

p-anisidine (purchased as a commercial item) (24.6 g) was dissolved in DMF (35 g), and pyridine (19 g) was added dropwise. After dripping n-octanoyl chloride (purchased as a commercial item) (34.2 g), it heated at 110 degreeC, and stirred for 1 hour. After cooling to room temperature, 2M hydrochloric acid (150 ml) was added to precipitate a precipitate. The mixture was filtered, washed with water and dried to obtain N-(4-methoxyphenyl)octanamide (53.1 g, yield 106.5%) represented by the following formula (C1a) as a crude product.

(Process 2)

To concentrated sulfuric acid (30 g) cooled to 5°C, N-(4-methoxyphenyl)octanamide (12.5 g) obtained in step 1 above was slowly added in the range of 5 to 10°C. Concentrated nitric acid (4.57 g) was added dropwise to this mixture over 1 hour at a temperature of 5 to 10°C, followed by stirring at the same temperature for 1 hour. The reaction mixture was purged in 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)octanamide (16.9 g, yield 114.8%) represented by the following formula (C1b) as a crude product. obtained as

(Process 3)

A mixture of N-(3-nitro-4-methoxyphenyl)octanamide (16.9 g), tin (8.9 g), and methanol (7.5 g) obtained in step 2 was cooled to 5°C. Concentrated hydrochloric acid (31.4 g) was added dropwise to this mixture over 1 hour, and then the temperature was raised to 75 to 80°C, followed by stirring for 40 minutes. After the reaction mixture was cooled to 10 °C, a 48% aqueous sodium hydroxide solution (55.2 ml) was slowly added in the range of 10 to 20 °C. The mixture was filtered, washed with water and dried to obtain N-(3-amino-4-methoxyphenyl)octanamide (9.19 g, yield 69.5%) represented by the following formula (C1c).

(Process 4)

N-(3-amino-4-methoxyphenyl)octanamide (13.2 g), triethylamine (15 g), DMF (15 g), and 1-bromooctane (commercially available) obtained in step 3 above (38.6 g) ) was heated to 120 ° C., and stirred for 3 hours at the same temperature, whereby N-[3-(N,N-dioctylamino)-4-methoxyphenyl]octanamide represented by the following formula (C1) got Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C1).

1-B. Preparation of diazo component solution

(Process 5)

To a mixture of concentrated sulfuric acid (16 g) and 43% nitrosyl sulfuric acid (12.8 g), 2-bromo-4,6-dinitroaniline (13.1 g) represented by the following formula (D1) was added at 25 to 30 °C. was added slowly. The diazo component solution was obtained by stirring this mixture at 30-40 degreeC for 2 hours.

1-C. Synthesis of blue dye compound (A-1) by coupling reaction

(Process 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) within the range of 0 to 10°C, and coupling is performed. reaction was carried out. After stirring the mixture for 30 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, and dried at 60°C until the moisture content is 1.0% by mass or less, followed by the formula A blue dye compound (5.93 g, yield 15.5%) represented by (A-1) was obtained. The structure of the blue dyed 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 manufactured according to the following scheme.

2-A. Synthesis of coupler compound (C2) and preparation of coupler component solution

(Process 1)

In Step 1 of Synthesis Example 1, in the same manner as in Steps 1 to 4 of Synthesis Example 1, except that valeryl chloride (25.3 g) was used instead of n-octanoyl chloride, N- represented by the following formula (C2) [3-(N,N-dioctylamino)-4-methoxyphenyl]pentanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C2).

2-B. Synthesis of blue dye compound (A-2) by coupling reaction

(Process 2)

As a coupler component solution, in the same manner 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), and represented by Formula (A-2) A blue dye compound (8.03 g, yield 22.3%) was obtained. The structure of this blue dyeing 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 manufactured according to the following scheme.

3-A. Synthesis of coupler compound (C3) and preparation of coupler component solution

(Process 1)

In Step 1 of Synthesis Example 1, in the same manner as in Steps 1 to 4 of Synthesis Example 1 except that propionyl chloride (19.4 g) was used instead of n-octanoyl chloride, N- represented by the following formula (C3) [3-(N,N-dioctylamino)-4-methoxyphenyl]propanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C3).

3-B. Synthesis of blue dye compound (A-3) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner 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), and represented by the following Formula (A-3) A blue dye compound (5.85 g, yield 16.9%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 691(M ⁺ )).

(Synthesis Example 4)

[Synthesis of blue dye compound (A-4)]

The blue dye compound (A-4) was manufactured according to the following scheme.

4-A. Synthesis of coupler compound C4 and preparation of coupler component solution

(Process 1)

In Step 1 of Synthesis Example 1, except that 2-ethylhexanoyl chloride (34.2 g) was used instead of n-octanoyl chloride, in the same manner as in Steps 1 to 4 of Synthesis Example 1, and represented by the following formula (C4) N-[3-(N,N-dioctylamino)-4-methoxyphenyl]-2-ethylhexanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C4).

4-B. Synthesis of blue dye compound (A-4) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner 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), and represented by Formula (A-4) A blue dye compound (9.63 g, yield 25.3%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 761(M ⁺ )).

(Synthesis Example 5)

[Synthesis of blue dye compound (A-5)]

The blue dye compound (A-5) was manufactured according to the following scheme.

5-A. Synthesis of coupler compound C5 and preparation of coupler component solution

(Process 1)

In step 4 of Synthesis Example 1, N-(3-amino-4-methoxyphenyl)acetamide (purchased as a commercially available product) (9.0 g) was used instead of N-(3-amino-4-methoxyphenyl)octanamide. Except for using, it carried out similarly to Step 4 of Synthesis Example 1, to obtain N-[3-(N,N-dioctylamino)-4-methoxyphenyl]acetamide represented by the following formula (C5). Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C5).

5-B. Synthesis of blue dye compound (A-5) by coupling reaction

(Process 2)

As a coupler component solution, in the same manner 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), and represented by Formula (A-5) A blue dye compound (20.3 g, yield 60.0%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 677(M ⁺ )).

(Synthesis Example 6)

[Synthesis of blue dye compound (A-6)]

The blue dye compound (A-6) was manufactured according to the following scheme.

6-A. Synthesis of coupler compound (C6) and preparation of coupler component solution

(Process 1)

In step 4 of Synthesis Example 1, 1-bromododecane (49.8 g) is used instead of 1-bromooctane, N- (3-amino-4-methoxyphenyl) octanamide instead of N- (3- N-[3-(N,N-didodecyl) 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) was used. Amino)-4-methoxyphenyl]acetamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C6).

6-B. Synthesis of blue dye compound (A-6) by coupling reaction

(Process 2)

As a coupler component solution, in the same manner 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), and represented by Formula (A-6) A blue dye compound (19.3 g, yield 48.9%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 789(M ⁺ )).

(Synthesis Example 7)

[Synthesis of blue dye compound (A-7)]

The blue dye compound (A-7) was manufactured according to the following scheme.

7-A. Synthesis of coupler compound C7 and preparation of coupler component solution

(Process 1)

In Step 4 of Synthesis Example 1, in the same manner as in Step 4 of Synthesis Example 1, except that 1-bromoethane (27.3 g) was used instead of 1-bromooctane, N- represented by the following formula (C7) [3-(N,N-diethylamino)-4-methoxyphenyl]octanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C7).

7-B. Synthesis of blue dye compound (A-7) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner 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), and represented by Formula (A-7) A blue dye compound (7.71 g, yield 26.0%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 593(M ⁺ )).

(Synthesis Example 8)

[Synthesis of blue dye compound (A-8)]

The blue dye compound (A-8) was manufactured according to the following scheme.

8-A. Synthesis of coupler compound C8 and preparation of coupler component solution

(Process 1)

In Step 1 of Synthesis Example 1, in the same manner as in Steps 1 to 4 of Synthesis Example 1, except that 4-ethoxyaniline (27.4 g) was used instead of p-anisidine, N represented by the following formula (C8) -[3-(N,N-dioctylamino)-4-ethoxyphenyl]octanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C8).

8-B. Synthesis of blue dye compound (A-8) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner 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), and represented by Formula (A-8) A blue dye compound (4.50 g, yield 11.6%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 775(M ⁺ )).

(Synthesis Example 9)

[Synthesis of blue dye compound (B-1)]

The blue dye compound (B-1) was manufactured according to the following scheme.

9-A. Synthesis of coupler compound C9 and preparation of coupler component solution

(Process 1)

In the same manner as in Step 1 of Synthesis Example 1 except that 3-nitroaniline (27.6 g) was used instead of p-anisidine, N-(3-nitrophenyl)octanamide represented by the following formula (C9a) (53.6 g) , yield 101.4%) was obtained as a crude product.

(Process 2)

In the same manner as in Step 3 of Synthesis Example 1, except that N-(3-nitrophenyl)octanamide (13.2 g) was used instead of N-(3-nitro-4-methoxyphenyl)octanamide, the following formula (C9b ) to obtain N-(3-aminophenyl)octanamide (9.48 g, yield 80.9%).

(Process 3)

In the same manner as in Step 4 of Synthesis Example 1, except that N-(3-aminophenyl)octanamide (11.7 g) was used instead of N-(3-amino-4-methoxyphenyl)octanamide, the following formula (C9 ) to obtain N-[3-(N,N-dioctylamino)phenyl]octanamide. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C9).

9-B. Preparation of diazo component solution

(Process 4)

To a mixture of concentrated sulfuric acid (29 g) and 43% nitrosyl sulfuric acid (12.7 g), 3-amino-5-nitro-2,1-benzisothiazole (8.15 g) represented by the following formula (D2) was added from 0 to It was added slowly within the range of 5 °C. To this mixture, 80% acetic acid (10 g) was slowly added dropwise within the range of 0 to 5°C, followed by stirring 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

(Process 5)

The diazo component solution (D2) was added dropwise to the coupler component solution (C9) over 2 hours while appropriately adding triethylamine (43 g) within the range of 0 to 10°C, followed by a coupling reaction. . After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (B- A blue dye compound (20.9 g, yield 62.9%) represented by 1) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 665(M ⁺ )).

(Synthesis Example 10)

[Synthesis of blue dye compound (B-2)]

The blue dye compound (B-2) was manufactured according to the following scheme.

10-A. Synthesis of coupler compound C10 and preparation of coupler component solution

(Process 1)

In Step 1 of Synthesis Example 9, in the same manner as in Steps 1 to 3 of Synthesis Example 9, except that valeryl chloride (25.3 g) was used instead of n-octanoyl chloride, N- represented by the following formula (C10) [3-(N,N-dioctylamino)phenyl]pentanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C10).

10-B. Synthesis of blue dye compound (B-2) by coupling reaction

(Process 2)

In the same manner 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, the blue color represented by the following Formula (B-2) A dye compound (9.47 g, yield 30.4%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 623(M ⁺ )).

(Synthesis Example 11)

[Synthesis of blue dye compound (B-3)]

The blue dye compound (B-3) was manufactured according to the following scheme.

11-A. Synthesis of coupler compound C11 and preparation of coupler component solution

(Process 1)

In Step 1 of Synthesis Example 9, in the same manner as in Steps 1 to 3 of Synthesis Example 9, except that propionyl chloride (19.4 g) was used instead of n-octanoyl chloride, N- represented by the following formula (C11) [3-(N,N-dioctylamino)phenyl]propanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C11).

11-B. Synthesis of blue dye compound (B-3) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner 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), and represented by the following Formula (B-3) A blue dye compound (13.4 g, yield 45.0%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 595(M ⁺ )).

(Synthesis Example 12)

[Synthesis of blue dye compound (B-4)]

The blue dye compound (B-4) was manufactured according to the following scheme.

12-A. Synthesis of coupler compound C12 and preparation of coupler component solution

(Process 1)

In Step 3 of Synthesis Example 9, in the same manner as in Step 3 of Synthesis Example 9, except that 3'-aminoacetanilide (7.50 g) was used instead of N-(3-aminophenyl)octanamide, the formula ) to obtain N-[3-(N,N-dioctylamino)phenyl]acetamide. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C12).

12-B. Synthesis of blue dye compound (B-4) by coupling reaction

(Process 2)

A blue dye compound (20.3) represented by the following formula (B-4) in the same manner as in steps 4 and 5 of Synthesis Example 9 except that the compound of formula (C12) was used instead of the compound of formula (C9) as the coupler component solution g, yield 69.9%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 581(M ⁺ )).

(Synthesis Example 13)

[Synthesis of blue dye compound (B-5)]

The blue dye compound (B-5) was manufactured according to the following scheme.

13-A. Synthesis of coupler compound C13 and preparation of coupler component solution

(Process 1)

In step 3 of Synthesis Example 9, 1-bromododecane (49.8 g) is used instead of 1-bromooctane, 3'-aminoacetanilide (7.50 g) instead of N- (3-aminophenyl) octanamide In the same manner as in Step 3 of Synthesis Example 9 except that , N-[3-(N,N-didodecylamino)phenyl]acetamide represented by the following formula (C13) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C13).

13-B. Synthesis of blue dye compound (B-5) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner as in Steps 4 and 5 of Synthesis Example 9, except that the compound of Formula (C13) obtained in Step 1 is used instead of the compound of Formula (C9), and represented by Formula (B-5) A blue dye compound (9.81 g, yield 28.3%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 693(M ⁺ )).

(Synthesis Example 14)

[Synthesis of blue dye compound (B-6)]

The blue dye compound (B-6) was manufactured according to the following scheme.

14-A. Synthesis of coupler compound C14 and preparation of coupler component solution

(Process 1)

In step 1 of Synthesis Example 9, propionyl chloride (19.4 g) was used instead of n-octanoyl chloride, and 1-bromododecane (49.8 g) instead of 1-bromooctane in step 3 of Synthesis Example 9 In the same manner as in Steps 1 to 3 of Synthesis Example 9 except that , 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 cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C14).

14-B. Synthesis of blue dye compound (B-6) by coupling reaction

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (B-6) in the same manner as in steps 4 and 5 of Synthesis Example 9 except that the compound of formula (C14) is used instead of the compound of formula (C9) ( 5.73 g, yield 16.2%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 707(M ⁺ )).

(Synthesis Example 15)

[Synthesis of blue dye compound (B-7)]

The blue dye compound (B-7) was manufactured according to the following scheme.

15-A. Synthesis of coupler compound C15 and preparation of coupler component solution

(Process 1)

In step 3 of Synthesis Example 9, 3'-aminoacetanilide (7.50 g) was used instead of N-(3-aminophenyl)octanamide, 1-bromo-2-ethylhexane instead of 1-bromooctane (38.6 g) was used in the same manner as in Step 3 of Synthesis Example 9, except that N-[3-[N,N-di(2-ethylhexyl)amino]phenyl]propane represented by the following formula (C15) amide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C15).

15-B. Synthesis of blue dye compound (B-7) by coupling reaction

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (B-7) in the same manner as in steps 4 and 5 of Synthesis Example 9 except that the compound of formula (C15) is used instead of the compound of formula (C9) ( 4.72 g, yield 16.2%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 581(M ⁺ )).

(Synthesis Example 16)

[Synthesis of blue dye compound (B-8)]

The blue dye compound (B-8) was manufactured according to the following scheme.

16-A. Synthesis of coupler compound C16 and preparation of coupler component solution

(Process 1)

In Step 3 of Synthesis Example 9, except that 1-bromoethane (27.3 g) was used instead of 1-bromooctane, in the same manner as in Steps 1 to 3 of Synthesis Example 9, and represented by the following formula (C16) N-[3-(N,N-diethylamino)phenyl]octanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C16).

16-B. Synthesis of blue dye compound (B-8) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner as in Steps 4 and 5 of Synthesis Example 9, except that the compound of Formula (C16) obtained in Step 1 is used instead of the compound of Formula (C9), and represented by Formula (B-8) A blue dye compound (23.2 g, yield 93.4%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z497(M ⁺ )).

(Synthesis Example 17)

[Synthesis of red dye compound (C-1)]

The red dye compound (C-1) was manufactured according to the following scheme.

17-A. Preparation of diazo component solution

(Process 1)

To a mixture of concentrated sulfuric acid (16 g) and 43% nitrosyl sulfuric acid (15.6 g), 2-chloro-4-nitroaniline (8.65 g) represented by the following formula (D3) was added within 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

(Process 2)

Preparation of the coupler component solution which consists of a compound of Formula (C9) was performed similarly to Steps 1 to 3 of Synthesis Example 9. The diazo component solution obtained in step 1 was added dropwise to the coupler component solution while appropriately adding triethylamine (28 g) within the range of 0 to 10°C over 2 hours to conduct a coupling reaction. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (C- A red dye compound represented by 1) (24.3 g, yield 75.7%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 642(M ⁺ )).

(Synthesis Example 18)

[Synthesis of red dye compound (C-2)]

The red dye compound (C-2) was manufactured according to the following scheme.

As a coupler component solution, a red dye compound represented by the following formula (C-2) in the same manner as in Steps 1 and 2 of Synthesis Example 17 except that the compound of formula (C10) is used instead of the compound of formula (C9) ( 10.4 g, yield 34.7%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z600(M ⁺ )).

(Synthesis Example 19)

[Synthesis of red dye compound (C-3)]

The red dye compound (C-3) was manufactured according to the following scheme.

As the coupler component solution, the red dye compound represented by the following formula (C-3) in the same manner as in Steps 1 and 2 of Synthesis Example 17 except that the compound of formula (C11) is used instead of the compound of formula (C9) ( 12.9 g, yield 45.1%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 572(M ⁺ )).

(Synthesis Example 20)

[Synthesis of red dye compound (C-4)]

The red dye compound (C-4) was manufactured according to the following scheme.

As the coupler component solution, the red dye compound represented by the following formula (C-4) in the same manner as in steps 1 and 2 of Synthesis Example 17 except that the compound of formula (C12) is used instead of the compound of formula (C9) ( 23.4 g, yield 83.9%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 558(M ⁺ )).

(Synthesis Example 21)

[Synthesis of red dye compound (C-5)]

The red dye compound (C-5) was manufactured according to the following scheme.

As the coupler component solution, the red dye compound represented by the following formula (C-5) in the same manner as in Steps 1 and 2 of Synthesis Example 17 except that the compound of formula (C13) is used instead of the compound of formula (C9) ( 25.3 g, yield 75.5%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 670(M ⁺ )).

(Synthesis Example 22)

[Synthesis of red dye compound (C-6)]

The red dye compound (C-6) was manufactured according to the following scheme.

22-A. Synthesis of coupler compound C17 and preparation of coupler component solution

(Process 1)

In step 3 of Synthesis Example 9, 3'-aminoacetanilide (7.50 g) is used instead of N- (3-aminophenyl) octanamide, 1-bromobutane (27.4 g) instead of 1-bromooctane In the same manner as in Step 3 of Synthesis Example 9 except that , 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 cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C17).

22-B. Synthesis of red dye compound (C-6) by coupling reaction

(Process 2)

As the coupler component solution, a red dye compound represented by the following formula (C-6) in the same manner as in steps 1 and 2 of Synthesis Example 17 except that the compound of formula (C17) is used instead of the compound of formula (C9) ( 19.6 g, yield 87.9%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 446(M ⁺ )).

(Synthesis Example 23)

[Synthesis of red dye compound (C-7)]

The red dye compound (C-7) was manufactured according to the following scheme.

As the coupler component solution, the red dye compound represented by the following formula (C-7) in the same manner as in steps 1 and 2 of Synthesis Example 17 except that the compound of formula (C16) is used instead of the compound of formula (C9) ( 16.6 g, yield 70.0%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 474 (M ⁺ )).

(Synthesis Example 24)

[Synthesis of orange dye compound (D-1)]

The orange dye compound (D-1) was manufactured according to the following scheme.

24-A. Synthesis of coupler compound C18 and preparation of coupler component solution

(Process 1)

In the same manner as in Step 4 of Synthesis Example 1, except that aniline (4.66 g) was used instead of N-(3-amino-4-methoxyphenyl)octanamide, N,N-dioxide represented by the following formula (C18) Octylaniline was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C18).

24-B. Preparation of diazo component solution

(Process 2)

To a mixture of concentrated sulfuric acid (17 g) and 43% nitrosyl sulfuric acid (14.7 g), 2,6-dichloro-4-nitroaniline (10.4 g) represented by the following formula (D4) was added within the range of 25 to 30 ° C. was added and stirred at the same temperature for 2 hours to obtain a diazo component solution.

24-C. Synthesis of orange dye compound (D-1) by coupling reaction

(Process 3)

The diazo component solution obtained in step 2 was mixed with the coupler component solution comprising the compound of formula (C18) obtained in step 1 for 2 hours while appropriately adding triethylamine (20 g) within the range of 0 to 10 ° C. It was dripped over the span and a coupling reaction was performed. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (D- An orange dye compound represented by 1) (23.1 g, yield 86.4%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 535(M ⁺ )).

(Synthesis Example 25)

[Synthesis of orange dye compound (D-2)]

The orange dye compound (D-2) was manufactured according to the following scheme.

25-A. Synthesis of coupler compound C19 and preparation of coupler component solution

(Process 1)

Except for using aniline (4.66 g) instead of N- (3-amino-4-methoxyphenyl) octanamide, and using 1-bromododecane (49.8 g) instead of 1-bromooctane, in Synthesis Example 1 In the same manner as in step 4, N,N-didodecylaniline represented by the following formula (C19) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C19).

25-B. Synthesis of orange dye compound (D-2) by coupling reaction

(Process 2)

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

(Synthesis Example 26)

[Synthesis of orange dye compound (D-3)]

The orange dye compound (D-3) was manufactured according to the following scheme.

26-A. Synthesis of coupler compound C20 and preparation of coupler component solution

(Process 1)

Except for using aniline (4.66 g) instead of N- (3-amino-4-methoxyphenyl) octanamide, and using 1-bromobutane (27.4 g) instead of 1-bromooctane, in Synthesis Example 1 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 cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C20).

26-B. Synthesis of orange dye compound (D-3) by coupling reaction

(Process 2)

As the coupler component solution, the orange dye compound represented by the following formula (D-3) in the same manner as in steps 2 and 3 of Synthesis Example 24 except that the compound of formula (C20) is used instead of the compound of formula (C18) ( 10.2 g, yield 48.2%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 423(M ⁺ )).

(Synthesis Example 27)

[Synthesis of yellow dye compound (G-1)]

The yellow dye compound (G-1) was manufactured 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-hexyldecanoic acid (30.8 g) and toluene (30 g). To this mixture, a mixture of pyridine (9.49 g) and toluene (30 g) was slowly added dropwise over 1 hour, then heated up to 110°C and stirred for 1 hour. After cooling to room temperature, a mixture of 5-amino-anthra[9,1-cd]isothiazol-6-one (25.2 g) and toluene (30 g) was added dropwise. After heating up to 110 degreeC and stirring for 2 hours, the solvent was distilled off under reduced pressure, and methanol (100 g) was added to precipitate precipitation. The mixture was filtered, washed with methanol and then water, and dried at 60° C. until the moisture content became 1.0 mass% or less to obtain a yellow dye compound (36.7 g, yield 74.7%) represented by the following formula (G-1). got it The said yellow dye compound confirmed the structure by LCMS analysis (m/z 491(M ⁺ )).

(Synthesis Example 28)

[Synthesis of yellow dye compound (G-2)]

The yellow dye compound (G-2) was manufactured according to the following scheme.

After adding dropwise n-octanoyl chloride (19.5 g) to a mixture of 5-amino-anthra [9,1-cd] isothiazol-6-one (25.2 g), toluene (120 g) and pyridine (9.49 g) , the temperature was raised to 110°C, and the mixture was stirred for 1 hour. After cooling the mixture to room temperature, methanol (150 g) was added to precipitate a precipitate. The mixture was filtered, 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 said yellow dye compound confirmed the structure by LCMS analysis (m/z 379 (M ⁺ )).

(Synthesis Example 29)

[Synthesis of purple dye compound (F-1)]

The purple dye compound (F-1) was manufactured according to the following scheme.

The preparation of the coupler component solution composed of the compound of formula (C18) was performed in the same manner as in Step 1 of Synthesis Example 24, and the preparation of the diazo component solution derived from the compound of Formula (D2) was performed in the same manner as in Step 4 of Synthesis Example 9. did. The said diazo component solution was dripped over 2 hours while adding triethylamine (35g) suitably within the range of 0-10 degreeC to the said coupler component solution, and the coupling reaction was performed. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (F- A purple dye compound represented by 1) (13.0 g, yield 49.6%) 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 manufactured according to the following scheme.

30-A. Preparation of diazo component solution

(Process 1)

To a mixture of concentrated sulfuric acid (17 g) and 43% nitrosyl sulfuric acid (14.7 g), 4-nitroaniline (6.91 g) represented by the following formula (D5) was added within the range of 30 to 35 ° C., and 2 at the same temperature. A diazo component solution was obtained by stirring for a period of time.

30-B. Synthesis of orange dye compound (D-4) by coupling reaction

(Process 2)

Preparation of the coupler component solution which consists of a compound of Formula (C18) was performed similarly to Step 1 of Synthesis Example 24. The diazo component solution obtained in step 1 was added dropwise to the coupler component solution while appropriately adding triethylamine (20 g) within the range of 0 to 10°C over 1 hour to conduct a coupling reaction. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (D- An orange dye compound (12.5 g, yield 53.5%) represented by 4) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 467 (M ⁺ )).

(Synthesis Example 31)

[Synthesis of orange dye compound (D-5)]

The orange dye compound (D-5) was manufactured according to the following scheme.

31-A. Preparation of diazo component solution

(Process 1)

To a mixture of concentrated sulfuric acid (17 g) and 43% nitrosyl sulfuric acid (14.7 g), 2,6-dibromo-4-nitroaniline (14.8 g) represented by the following formula (D6) was added at 25 to 30 °C. A diazo component solution was obtained by adding it inside and stirring at the same temperature for 2 hours.

31-B. Synthesis of orange dye compound (D-5) by coupling reaction

(Process 2)

Preparation of the coupler component solution which consists of a compound of Formula (C18) was performed similarly to Step 1 of Synthesis Example 24. The diazo component solution obtained in step 1 was added dropwise to the coupler component solution while appropriately adding triethylamine (25 g) within the range of 0 to 10° C. over 1 hour to conduct a coupling reaction. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (D- An orange dye compound represented by 5) (27.6 g, yield 88.6%) was obtained. The said orange dye compound confirmed that the structure was a 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 manufactured according to the following scheme.

As the coupler component solution, the orange dye compound represented by the following formula (D-6) in the same manner as in steps 1 and 2 of Synthesis Example 31 except that the compound of formula (C20) is used instead of the compound of formula (C18) ( 22.8 g, yield 89.2%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 511(M ⁺ )).

(Synthesis Example 33)

[Synthesis of orange dye compound (E-1)]

The orange dye compound (E-1) was manufactured according to the following scheme.

33-A. Synthesis of coupler compound C21 and preparation of coupler component solution

(Process 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 stirred for 3 hours at the same temperature. Thus, N-octyl-2-phenylindole represented by the following formula (C21) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C21).

33-B. Synthesis of orange dye compound (E-1) by coupling reaction

(Process 2)

A diazo component solution derived from the compound of formula (D4) was prepared in the same manner as in Synthesis Example 24. The diazo component solution was added dropwise over 1 hour while appropriately adding triethylamine (20 g) to the coupler component solution obtained in step 1 within the range of 0 to 10°C, followed by coupling reaction. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the following formula (E- An orange dye compound represented by 1) (11.3 g, yield 43.2%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 523(M ⁺ )).

(Synthesis Example 34)

[Synthesis of orange dye compound (E-2)]

The orange dye compound (E-2) was manufactured according to the following scheme.

34-A. Synthesis of coupler compound C22 and preparation of coupler component solution

(Process 1)

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, N-butyl-2-phenylindole represented by the following formula (C22) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C22).

34-B. Synthesis of orange dye compound (E-2) by coupling reaction

(Process 2)

As the coupler component solution, the orange dye compound represented by the following formula (E-2) in the same manner as in Steps 1 and 2 of Synthesis Example 33 except that the compound of formula (C22) is used instead of the compound of formula (C21) ( 14.5 g, yield 62.1%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 467 (M ⁺ )).

(Synthesis Example 35)

[Synthesis of red dye compound (D-7)]

The red dye compound (D-7) was manufactured according to the following scheme.

35-A. Preparation of diazo component solution

(Process 1)

2-cyano-4-nitroaniline (8.15 g) represented by the following formula (D7) was added to a mixture of concentrated sulfuric acid (7.5 g), acetic acid (15 g), and 43% nitrosyl sulfuric acid (14.9 g) at 20-25 ° C. A diazo component solution was obtained by adding within the range of and stirring at the same temperature for 2 hours.

35-B. Synthesis of red dye compound (D-7) by coupling reaction

(Process 2)

Preparation of the coupler component solution which consists of a compound of Formula (C18) was performed similarly to Synthesis Example 24. The diazo component solution obtained in step 1 was added dropwise to the coupler component solution while appropriately adding triethylamine (30 g) within the range of 0 to 10°C over 1 hour to conduct a coupling reaction. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (D- 7) was obtained as a red dye compound (16.9 g, yield 68.9%). The said red dye compound confirmed the structure by LCMS analysis (m/z 492(M ⁺ )).

(Synthesis Example 36)

[Synthesis of purple dye compound (C-8)]

The purple dye compound (C-8) was manufactured according to the following scheme.

Preparation of the coupler component solution composed of the compound of 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 Formula (D1) is performed in the same manner as in Step 5 of Synthesis Example 1 did. The said diazo component solution was dripped over 2 hours while adding triethylamine (32g) suitably within the range of 0-10 degreeC to the said coupler component solution, and the coupling reaction was performed. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (C- 8), a purple dye compound (6.14 g, yield 21.8%) was obtained. The said purple dye compound confirmed that the structure was a following formula (C-8) by LCMS analysis molecular weight (m/z 563(M ⁺ )).

(Synthesis Example 37)

[Synthesis of purple dye compound (C-9)]

The purple dye compound (C-9) was manufactured according to the following scheme.

As a coupler component solution, a purple dye compound (12.1 g) represented by the following formula (C-9) was obtained in the same manner as in Synthesis Example 36 except that the compound of the formula (C9) was used instead of the compound of the formula (C16). . The structure of the said 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 manufactured 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 to 40 ° C. for 15 minutes, cuprous cyanide (5.0 g) was added, and 15 under the same temperature. stirred for minutes. The purple dye compound (C-9) (34.3 g) was added to this mixture, and it heated up to 110 degreeC, and stirred for 1 hour. After cooling to 80°C, a mixture of water (190 g) and sodium hypochlorite (18 g) was added, followed by stirring at 70 to 80°C for 1 hour, followed by cooling to room temperature. The product from this reaction mixture was filtered, washed with water, and dried at 60° C. until the moisture content became 1.0 mass% or less to obtain a purple dye compound (20.4 g, yield 64.2%) represented by the following formula (C-10). got it 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 manufactured according to the following scheme.

39-A. Preparation of diazo component solution

(Process 1)

2-bromo-6-cyano-4-nitroaniline (11.1 g) represented by the following formula (D8) was 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. To this mixture, 43% nitrosylsulfuric acid (15.6 g) was added within a range of 20 to 25°C, and 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

(Process 2)

Preparation of the coupler component solution which consists of a compound of Formula (C9) was performed similarly to Steps 1 to 3 of Synthesis Example 9. The diazo component solution obtained in step 1 was added dropwise to the coupler component solution while appropriately adding triethylamine (20 g) within the range of 0 to 10°C over 2 hours to conduct a coupling reaction. After stirring for 20 minutes within the range of 0 to 10°C, the product is filtered from the reaction mixture, washed with methanol and then water, dried at 60°C until the moisture content is 1.0% by mass or less, and the formula (C- A purple dye compound represented by 11) (16.0 g, yield 45.0%) 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 manufactured according to the following scheme.

40-A. Synthesis of coupler compound C23 and preparation of coupler component solution

(Process 1)

In step 3 of Synthesis Example 9, except that 1-bromobutane (27.4 g) was used instead of 1-bromooctane, in the same manner as in Steps 1 to 3 of Synthesis Example 9, and represented by the following formula (C23) N-[3-(N,N-dibutylamino)phenyl]octanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C23).

40-B. Synthesis of purple dye compound (C-12) by coupling reaction

(Process 2)

As the coupler component solution, a purple dye compound represented by the following formula (C-12) (5.99 g) in the same manner as in Step 2 of Synthesis Example 39 except that the compound of the formula (C23) was used instead of the compound of the formula (C9). , 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 manufactured according to the following scheme.

As the coupler component solution, a purple dye compound represented by the following formula (C-13) (23.5 g) in the same manner as in Step 2 of Synthesis Example 39 except that the compound of formula (C12) was used instead of the compound of formula (C9). , 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 manufactured according to the following scheme.

As the coupler component solution, a purple dye compound represented by the following formula (C-14) (10.8 g) in the same manner as in Step 2 of Synthesis Example 39 except that the compound of formula (C16) was used instead of the compound of formula (C9) , 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 manufactured according to the following scheme.

In Synthesis Example 38, in the same manner as in Synthesis Example 38, except that the purple dye compound (31.4 g) of the formula (C-13) was used instead of the purple dye compound of the formula (C-9), the following formula (C-15) ) was obtained as a purple dye compound (26.9 g, yield 93.7%). The structure of the said 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 manufactured according to the following scheme.

In Synthesis Example 38, in the same manner as in Synthesis Example 38, except that the purple dye compound (27.2 g) of the formula (C-14) was used instead of the purple dye compound of the formula (C-9), the following formula (C-16) ) was obtained as a purple dye compound (22.0 g, yield 89.8%). 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 manufactured according to the following scheme.

In Synthesis Example 28, in the same manner as in Synthesis Example 28 except that 2-ethylhexanoyl chloride (19.5 g) was used instead of n-octanoyl chloride, a yellow dye compound (33.1) represented by the following formula (G-3) g, yield 87.3%) was obtained. The said yellow dye compound confirmed the structure by LCMS analysis (m/z 379 (M ⁺ )).

(Synthesis Example 46)

[Synthesis of yellow dye compound (G-4)]

The yellow dye compound (G-4) was manufactured according to the following scheme.

In Synthesis Example 28, in the same manner as in Synthesis Example 28 except that nonanoyl chloride (21.2 g) was used instead of n-octanoyl chloride, a yellow dye compound represented by the following formula (G-4) (31.0 g, Yield 78.9%) was obtained. The said yellow dye compound confirmed the structure by LCMS analysis (m/z 393(M ⁺ )).

(Synthesis Example 47)

[Synthesis of blue dye compound (B-9)]

The blue dye compound (B-9) was manufactured according to the following scheme.

A blue dye compound (9.12 g) represented by the following formula (B-9) in the same manner as in Step 5 of Synthesis Example 9 except that the compound of Formula (C23) was used instead of the compound of Formula (C9) as the coupler component solution , yield 33.0%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 553(M ⁺ )).

(Synthesis Example 48)

[Synthesis of blue dye compound (B-10)]

The blue dye compound (B-10) was manufactured according to the following scheme.

48-A. Synthesis of coupler compound C24 and preparation of coupler component solution

(Process 1)

In Step 1 of Synthesis Example 9, except that 2-ethylhexanoyl chloride (34.2 g) was used instead of n-octanoyl chloride, in the same manner as in Steps 1 to 3 of Synthesis Example 9, represented by the following formula (C24) N-[3-(N,N-dioctylamino)phenyl]-2-ethylhexanamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C24).

48-B. Synthesis of blue dye compound (B-10) by coupling reaction

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (B-10) in the same manner as in steps 4 and 5 of Synthesis Example 9 except that the compound of formula (C24) is used instead of the compound of formula (C9) ( 19.0 g, yield 57.1%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 665(M ⁺ )).

(Synthesis Example 49)

[Synthesis of orange dye compound (D-8)]

The orange dye compound (D-8) was manufactured according to the following scheme.

As the coupler compound, an orange dye compound (15.2) represented by the following formula (D-8) in the same manner as in Synthesis Example 24 except that N,N-diethylaniline (7.45 g) was used instead of the compound of formula (C18) (15.2) g, yield 82.8%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 367(M< ⁺ >)).

(Synthesis Example 50)

[Synthesis of orange dye compound (D-9)]

The orange dye compound (D-9) was manufactured according to the following scheme.

An orange dye compound (18.2) represented by the following formula (D-9) in the same manner as in Synthesis Example 31 except that N,N-diethylaniline (7.45 g) was used instead of the compound of formula (C18) as the coupler compound (18.2) g, yield 80.0%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 455 (M ⁺ )).

(Synthesis Example 51)

[Synthesis of orange dye compound (D-10)]

The orange dye compound (D-10) was manufactured according to the following scheme.

As the coupler compound, in the same manner as in Synthesis Example 30 except that N,N-diethylaniline (7.45 g) was used instead of the compound of formula (C18), an orange dye compound represented by the following formula (D-10) (9.35) g, yield 62.5%) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 299(M ⁺ )).

(Synthesis Example 52)

[Synthesis of orange dye compound (D-11)]

The orange dye compound (D-11) was manufactured according to the following scheme.

52-A. Synthesis of coupler compound C25 and preparation of coupler component solution

(Process 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 10% aqueous sodium carbonate solution (150 g) were added, and the organic layer was extracted. After washing this extract with saturated brine, the solvent was distilled off under reduced pressure to obtain N-cyanoethylaniline represented by the following formula (C25a) (28.7 g, yield 98.2%) as a crude product.

(Process 2)

A 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 the temperature was increased to 3 hours at the same temperature. By stirring, N-cyanoethyl-N-octylaniline represented by the following formula (C25) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C25).

52-B. Synthesis of orange dye compound (D-11) by coupling reaction

(Process 3)

As the coupler component solution, the orange dye compound represented by the following formula (D-11) (10.6 g, yield 52.0) was performed in the same manner as in Synthesis Example 30 except that the compound of formula (C25) was used instead of the compound of formula (C18). %) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 408 (M ⁺ )).

(Synthesis Example 53)

[Synthesis of red dye compound (C-17)]

The red dye compound (C-17) was manufactured according to the following scheme.

53-A. Synthesis of coupler compound C26 and preparation of coupler component solution

(Process 1)

The use of 3'-aminoacetanilide (7.50 g) instead of N-(3-amino-4-methoxyphenyl)octanamide and the use of 1-bromoethane (27.3 g) instead of 1-bromooctane Except for that, in the same manner as in Step 4 of Synthesis Example 1, N-[3-(N,N-diethylamino)phenyl]acetamide represented by the following formula (C26) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C26).

53-B. Synthesis of red dye compound (C-17) by coupling reaction

(Process 2)

As the coupler compound, a red dye compound represented by the following formula (C-17) (11.8 g, yield 60.5%) was performed in the same manner as in Synthesis Example 17 except that the compound of formula (C26) was used instead of the compound of formula (C9). ) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 390 (M ⁺ )).

(Synthesis Example 54)

[Synthesis of purple dye compound (F-2)]

The purple dye compound (F-2) was manufactured according to the following scheme.

As the coupler compound, a purple dye compound (10.6) represented by the following formula (F-2) in the same manner as in Synthesis Example 29 except that N,N-diethylaniline (7.45 g) was used instead of the compound of the formula (C18) (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 manufactured according to the following scheme.

As the coupler compound, the blue dye compound (11.9) represented by the following formula (B-11) in the same manner as in steps 4 and 5 of Synthesis Example 9 except that the compound of formula (C26) was used instead of the compound of formula (C9). g, yield 57.6%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 413(M ⁺ )).

(Synthesis Example 56)

[Synthesis of blue dye compound (A-9)]

The blue dye compound (A-9) was manufactured according to the following scheme.

56-A. Synthesis of coupler compound C27 and preparation of coupler component solution

(Process 1)

N- (3-amino-4-methoxyphenyl) octanamide (13.2 g), acetic acid (15 g), cuprous chloride (0.32 g), acrylonitrile (5.0 g) obtained in Step 3 of Synthesis Example 1 The mixture was heated to 110° C. and stirred for 3 hours. After cooling to room temperature, toluene (50 g) and 10% aqueous sodium carbonate solution (75 g) were added, and the organic layer was extracted. After washing this extract with saturated brine, the solvent was distilled off under reduced pressure to obtain N-(3-cyanoethylamino-4-methoxyphenyl)octanamide represented by the following formula (C27a) (9.05 g, yield 57.0%) was obtained as a crude product.

(Process 2)

A mixture of N-(3-cyanoethylamino-4-methoxyphenyl)octanamide (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 temperature Under stirring for 2 hours, N-(3-N-ethyl-N-cyanoethylamino-4-methoxyphenyl)octanamide represented by the following formula (C27) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C27).

56-B. Synthesis of blue dye compound (A-9) by coupling reaction

(Process 3)

As a coupler component solution, the blue dye compound represented by the following formula (A-9) in the same manner as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C27) is used instead of the compound of formula (C1) ( 9.70 g, yield 31.4%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 618(M ⁺ )).

(Synthesis Example 57)

[Synthesis of blue dye compound (A-10)]

The blue dye compound (A-10) was manufactured according to the following scheme.

57-A. Synthesis of coupler compound C28 and preparation of coupler component solution

(Process 1)

N- (3-cyanoethylamino-4-methoxyphenyl) octanamide (15.9 g), DMF (20 g), triethylamine (12.6 g) and 1-bromooctane (12.6 g) obtained in step 1 of Synthesis Example 56 ( 29.0 g) of N-(3-N-octyl-N-cyanoethylamino-4-methoxyphenyl)octanamide represented by the following formula (C28) by heating the mixture to 120°C and stirring for 8 hours. got Methanol (30 g) was added to this reaction mixture, and the coupler component solution which consists of Formula (C28) was obtained by cooling to 5 degreeC.

57-B. Synthesis of blue dye compound (A-10) by coupling reaction

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (A-10) in the same manner as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C28) is used instead of the compound of formula (C1) ( 5.52 g, yield 15.7%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 702(M ⁺ )).

(Synthesis Example 58)

[Synthesis of blue dye compound (A-11)]

The blue dye compound (A-11) was manufactured according to the following scheme.

58-A. Synthesis of coupler compound C29 and preparation of coupler component solution

(Process 1)

N- (3-amino-4-methoxyphenyl) octanamide (13.2 g), DMF (15 g), triethylamine (15 g), and 2-bromoethyl methyl ether (27.8 g) obtained in step 3 of Synthesis Example 1 (27.8 g) ) of the mixture of N-[3-N,N-(2-dimethoxyethyl)amino-4-methoxyphenyl]octanamide represented by the following formula (C29) by heating the mixture to 110°C and stirring for 8 hours. got Methanol (30 g) was added to this reaction mixture, and the coupler component solution which consists of Formula (C29) was obtained by cooling to 5 degreeC.

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (A-11) in the same manner as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C29) is used instead of the compound of formula (C1) ( 6.58 g, yield 20.2%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 653(M ⁺ )).

(Synthesis Example 59)

[Synthesis of blue dye compound (A-12)]

The blue dye compound (A-12) was manufactured according to the following scheme.

59-A. Synthesis of coupler compound C30 and preparation of coupler component solution

(Process 1)

Using N-(3-amino-4-methoxyphenyl)acetamide (commercially available) (9.0 g) instead of N-(3-amino-4-methoxyphenyl)octanamide, 1-bromooctane In the same manner as in Step 4 of Synthesis Example 1 except that 1-bromobutane (27.4 g) was used instead, N-[3-(N,N-dihexylamino)-4 represented by the following formula (C30) -Methoxyphenyl]acetamide was obtained. Methanol (30 g) was added to this reaction mixture, and the coupler component solution which consists of Formula (C30) was obtained by cooling to 5 degreeC.

59-B. Synthesis of blue dye compound (A-12) by coupling reaction

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (A-12) in the same manner as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C30) is used instead of the compound of formula (C1) ( 14.1 g, yield 49.9%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 565(M ⁺ )).

(Synthesis Example 60)

[Synthesis of blue dye compound (A-13)]

The blue dye compound (A-13) was manufactured according to the following scheme.

60-A. Synthesis of coupler compound C31 and preparation of coupler component solution

(Process 1)

Using N-(3-amino-4-methoxyphenyl)acetamide (commercially available) (9.0 g) instead of N-(3-amino-4-methoxyphenyl)octanamide, 1-bromooctane In the same manner as in Step 4 of Synthesis Example 1 except that 1-bromohexane (33.0 g) was used instead, N-[3-(N,N-dihexylamino)-4 represented by the following formula (C31) -Methoxyphenyl]acetamide was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C31).

60-B. Synthesis of blue dye compound (A-13) by coupling reaction

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (A-13) in the same manner as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C31) is used instead of the compound of formula (C1) ( 10.7 g, yield 34.5%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 621(M ⁺ )).

(Synthesis Example 61)

[Synthesis of blue dye compound (A-14)]

The blue dye compound (A-14) was manufactured according to the following scheme.

61-A. Synthesis of coupler compound C32 and preparation of coupler component solution

(Process 1)

In step 1 of Synthesis Example 1, valeryl chloride (25.3 g) is used instead of n-octanoyl chloride, and 1-bromoethane (27.3 g) is used instead of 1-bromooctane in step 4 Except for the steps 1 to 4 of Synthesis Example 1, N-[3-(N,N-diethylamino)-4-methoxyphenyl]pentanamide represented by the following formula (C32) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C32).

61-B. Synthesis of blue dye compound (A-14) by coupling reaction

(Process 2)

As the coupler component solution, the blue dye compound represented by the following formula (A-14) in the same manner as in steps 5 and 6 of Synthesis Example 1 except that the compound of formula (C32) is used instead of the compound of formula (C1) ( 24.1 g, yield 87.5%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 551(M ⁺ )).

(Synthesis Example 62)

[Synthesis of blue dye compound (A-15)]

The blue dye compound (A-15) was manufactured according to the following scheme.

62-A. Synthesis of coupler compound C33 and preparation of coupler component solution

(Process 1)

In step 1 of Synthesis Example 1, lauroyl chloride (45.9 g) is used instead of n-octanoyl chloride, and 1-bromoethane (27.3 g) is used instead of 1-bromooctane in step 4 Except for the point, it carried out similarly to Steps 1 to 4 of Synthesis Example 1 to obtain N-[3-(N,N-diethylamino)-4-methoxyphenyl]dodecanamide represented by the following formula (C33). Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C33).

62-B. Synthesis of blue dye compound (A-15) by coupling reaction

(Process 2)

As a coupler component solution, in the same manner as in steps 5 and 6 of Synthesis Example 1 except that formula (C33) is used instead of formula (C1), a blue dye compound represented by the following formula (A-15) (26.8 g, Yield 82.6%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 649(M ⁺ )).

(Synthesis Example 63)

[Synthesis of red dye compound (C-18)]

The red dye compound (C-18) was manufactured according to the following scheme.

63-A. Synthesis of coupler compound C34 and preparation of coupler component solution

(Process 1)

In step 3 of Synthesis Example 9, using 1-bromohexane (33.0 g) instead of 1-bromooctane, 3'-aminoacetanilide (7.50 g) instead of N- (3-aminophenyl) octanamide In the same manner as in Step 3 of Synthesis Example 9 except that , N-[3-(N,N-dihexylamino)phenyl]acetamide represented by the following formula (C34) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5° C. to obtain a coupler component solution comprising the compound of formula (C34).

63-B. Synthesis of red dye compound (C-18) by coupling reaction

(Process 2)

As a coupler component solution, a red dye compound represented by the following formula (C-18) (20.1 g, yield 80.1) was performed in the same manner as in Synthesis Example 17 except that the compound of formula (C34) was used instead of the compound of formula (C9). %) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z502(M ⁺ )).

(Synthesis Example 64)

[Synthesis of orange dye compound (D-12)]

The orange dye compound (D-12) was manufactured according to the following scheme.

64-A. Synthesis of coupler compound C35 and preparation of coupler component solution

(Process 1)

Except for using aniline (4.66 g) instead of N- (3-amino-4-methoxyphenyl) octanamide, and using 1-bromohexane (33.0 g) instead of 1-bromooctane, in Synthesis Example 1 In the same manner as in step 4, N,N-dihexylaniline represented by the following formula (C35) was obtained. Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C35).

64-B. Synthesis of orange dye compound (D-12) by coupling reaction

(Process 2)

As a coupler component solution, the orange dye compound represented by the following formula (D-12) (13.5 g, yield 56.4) was performed in the same manner as in Synthesis Example 24 except that the compound of formula (C35) was used instead of the compound of formula (C18). %) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 479 (M ⁺ )).

(Synthesis Example 65)

[Synthesis of orange dye compound (D-13)]

The orange dye compound (D-13) was manufactured according to the following scheme.

As a coupler component solution, the orange dye compound represented by the following formula (D-13) (16.4 g, yield 79.8) was carried out in the same manner as in Synthesis Example 30 except that the compound of formula (C35) was used instead of the compound of formula (C18). %) was obtained. The said orange dye compound confirmed the structure by LCMS analysis (m/z 411(M ⁺ )).

(Synthesis Example 66)

[Synthesis of blue dye compound (A-16)]

The blue dye compound (A-16) was manufactured according to the following scheme.

66-A. Synthesis of coupler compound C8 and preparation of coupler component solution

(Process 1)

In step 1 of 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 (19.4 g) 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 cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C36).

66-B. Synthesis of blue dye compound (A-16) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner 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), represented by the following Formula (A-16) A blue dye compound (6.45 g, yield 17.6%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 733(M ⁺ )).

(Synthesis Example 67)

[Synthesis of red dye compound (C-19)]

The red dye compound (C-19) was manufactured according to the following scheme.

67-A. Synthesis of coupler compound C37 and preparation of coupler component solution

(Process 1)

In step 1 of Synthesis Example 9, propionyl chloride (19.4 g) is used instead of n-octanoyl chloride, and 1-bromohexane (33.0 g) instead of 1-bromooctane in step 3 of Synthesis Example 9 In the same manner as in Steps 1 to 3 of Synthesis Example 9 except that , 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 cooled to 5°C to obtain a coupler component solution composed of the compound of formula (C37).

67-B. Synthesis of red dye compound (C-19) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner as in Steps 1 and 2 of Synthesis Example 17, except that the compound of Formula (C37) obtained in Step 1 is used instead of the compound of Formula (C9), and represented by the following Formula (C-19) A red dye compound (17.6 g, yield 68.2%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 516(M ⁺ )).

(Synthesis Example 68)

[Synthesis of red dye compound (C-20)]

The red dye compound (C-20) was manufactured according to the following scheme.

A red dye compound represented by the following formula (C-20) in the same manner as in steps 1 and 2 of Synthesis Example 30 except that the compound of formula (C12) is used instead of the compound of formula (C18) as the coupler component solution ( 23.0 g, yield 87.7%) was obtained. The said red dye compound confirmed the structure by LCMS analysis (m/z 524(M ⁺ )).

(Synthesis Example 69)

[Synthesis of blue dye compound (A-17)]

The blue dye compound (A-17) was manufactured according to the following scheme.

69-A. Synthesis of coupler compound C38 and preparation of coupler component solution

(Process 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 Other than that, it carried out similarly to Steps 1 to 4 of Synthesis Example 1 to obtain N-[3-(N,N-dihexylamino)-4-methoxyphenyl]pentanamide represented by the following formula (C38). Methanol (30 g) was added to this reaction mixture and cooled to 5°C to obtain a coupler component solution composed of a compound of formula (C38).

69-B. Synthesis of blue dye compound (A-17) by coupling reaction

(Process 2)

As the coupler component solution, in the same manner as in Steps 5 and 6 of Synthesis Example 1, except that the compound of Formula (C38) obtained in Step 1 is used instead of the compound of Formula (C1), and represented by Formula (A-17) A blue dye compound (15.3 g, yield 48.4%) was obtained. The said blue dye compound confirmed the structure by LCMS analysis (m/z 663(M ⁺ )).

Structural formulas of the dye compounds and conventional dye compounds described in Synthesis Examples are shown in Tables 3 to 9.

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

<Dyeing example>

Polypropylene fabric or polyethylene fabric was dyed by a supercritical carbon dioxide dyeing method using only one of the dye compounds shown in Tables 3 to 9 or a disperse dye compound conventionally used for dyeing polyester fibers or the like.

<Polypropylene dyeing example>

[Dyeing Example P1]

A supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG. 1 .

The dyeing apparatus consists of a liquid CO ₂ cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high pressure pump (5), a preheater (6), a pressure gauge (7-9), a magnetic drive unit ( 10 ), a DC motor 11 , safety valves 12 and 13 , stop valves 14 to 18 , a needle valve 19 , and a heater 20 .

A polypropylene cloth was cut and weighed to about 50 to 70 g, and wound up from the inside into a stainless cylinder 21 having a punch hole in the order of cotton cloth, polypropylene cloth, and cotton cloth, and then loosely fixed with cotton yarn. The inner comedon is an undercloth, and the outer comedon is a cover cloth.

Synthesis Example 5, in which a stainless cylinder wound with the above-mentioned cloth sample (cotton cloth, polypropylene cloth, cotton cloth) is fixed to a pressure-resistant stainless steel tank 22, and corresponds to 0.3 mass % with respect to the mass of the polypropylene cloth The blue dye compound A-5 obtained at The volume of the pressure-resistant stainless steel tank was 2230 cm ³ . All the valves in the dyeing apparatus were closed, and it heated to 120 degreeC with the preheater.

After reaching the dyeing temperature, the stop valves 14 and 16 were opened, and 1.13 kg of liquid carbon dioxide was introduced into the pressure-resistant stainless steel bath using a high-pressure pump through a cooling jacket. Thereafter, the stop valves 14 and 16 were closed, and the pressure was circulated to the impeller and the magnetic drive unit at the bottom of the stainless steel tank. The rotational speed of the magnetic drive is 750 rpm, and the circulation direction is from the inside to the outside of the cylinder.

After the inside of the pressure-resistant stainless steel tank reached a predetermined temperature and pressure (120° C., 25 MPa), the polypropylene cloth was dyed by maintaining the temperature and pressure conditions for 60 minutes. After dyeing, the stop valve 18 was opened and the needle valve was gradually opened to release carbon dioxide in the pressure-resistant stainless steel tank, and the pressure in the pressure-resistant stainless steel tank was lowered from 25 MPa to atmospheric pressure. The cycle continued until the critical pressure of carbon dioxide (about 8 MPa) was reached. After that, the polypropylene dyed cloth in the pressure-resistant stainless steel tank was taken out.

[Staining examples P2 to P82, and staining examples P98 to P101]

The same dyeing as in Dyeing Example P1, except that the blue dye compound A-5 described in Dyeing Example 1 was changed to the dye compounds shown in Tables 3 to 9 or the disperse dye compound conventionally used for dyeing polyester fibers, etc. A polypropylene dyed cloth was obtained according to the procedure. The dye compounds used in the dyeing examples P1 to P82 and the dyeing examples P98 to P101 are shown in Tables 10 to 16.

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

For the polypropylene dyed fabrics obtained in Dyeing Examples P1 to P82 and Dyeing Examples P98 to P101, dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, rub fastness test and fastness test to hot pressing was done.

(1) Dyeability evaluation

The dyeing property visually evaluated the Total K/S value obtained by colorimetry of the dyed fabric, and the dye residue after dyeing|dyeing. Colorimetry of the dyed fabric was performed using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretak Macbeth), the dyed fabric was pasted on white paper with glue, and observation light source D65, 2 degree field of view.

(2) Light fastness test

The light fastness test was performed by the 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.), color change and discoloration were judged after exposure to dyed fabric for 20 hours under conditions of a black panel temperature of 63±3°C.

(3) Sublimation fastness test

The sublimation fastness test was performed by the method according to JIS L0854:2013. The outline of the test method is as follows. The dyed cloth was pinched by a nylon cloth, and under a load of 12.5 kPa, after holding|maintaining at 120±2 degreeC for 80 minutes, discoloration and contamination with respect to a nylon cloth were judged.

(4) Washing fastness test

The washing fastness test was performed by the method according to JIS L0844:2011 (A-2). The outline of the test method is as follows. A multi-woven multi-woven fabric was attached to the dyed fabric, and washed for 30 minutes under conditions of 50 ± 2 ° C. in the presence of soap, and the discoloration and contamination of the cotton and nylon parts of the multi-woven cross fabric were judged. Moreover, the contamination of the residual liquid after washing was judged.

(5) Sweat fastness test

The sweat fastness test was performed by the method according to JIS L0848:2004. The outline of the test method is as follows. After attaching a multi-woven woven fabric to the dyed fabric, immersing it in acidic artificial sweat solution or alkaline artificial sweat for 30 minutes, maintaining it at 37±2℃ for 4 hours under a load of 12.5kPa, drying it at 60℃ or less, discoloration and discoloration and Contamination to the cotton portion and the nylon portion of the multiwoven cross woven fabric was determined.

(6) Friction fastness test

The friction fastness test was performed by the method according to JIS L0849:2013. The outline of the test method is as follows. Using a friction fastness tester RT-300 (manufactured by Daiei Scientific Seonggi Manufacturing Co., Ltd.), the dyed cloth was subjected to 100 rounds of reciprocating friction by applying a load of 2N with a dry or wet cotton cloth, The coloration of the comedones was determined.

(7) Fastness test to hot pressing

The fastness test to hot pressing was performed by the method according to JIS L0850:2015 (A-2 drying). The outline of the test method is as follows. The dyed cloth was superimposed on the cotton cloth, and after holding for 15 seconds under a load of 4±1 kPa by a heating plate at 150° C., discoloration and contamination with the cotton cloth were judged.

Table 17 and Table 18 show the evaluation results of the staining examples of the compound of formula (A).

[Table 17]

[Table 18]

Regarding the dyeability of the compound of formula (A), the dyeability of the compound in which at least one of R _A1 , R _A2 , and R _A3 used in the dyeing examples P1 to P7 and P73 to P77, P98 and P99 is an alkyl group having 4 or more carbon atoms was good.

However, all of R _A1 , R _A2 , R _A3 , which are disperse dyes conventionally used for dyeing polyester fibers, etc. used in dyeing examples P8 to P14, are substituted with an alkyl group having less than 4 carbon atoms, or CN or OCH ₃ or CH=CH ₂ The dyeability of the compound which is an alkyl group was poor.

In addition, with respect to each fastness of the compound of formula (A), the compound in which X _A is a nitro group, Y _A is a bromine atom, and at least one of R _A1 , R _A2 , and R _A3 is an alkyl group having 4 or more carbon atoms, was good. .

Table 19 shows the evaluation results of the staining examples of the compound of formula (B).

[Table 19]

Regarding the dyeability of the compound of formula (B), R _B1 , R _B2 , and R _B3 used in the dyeing examples P15 to P23 and P78 are an alkyl group having 1 to 14 carbon atoms (provided that at least one of _{RB1 , R B2 and} R _B3 has a carbon number The dyeability of the compound of 4 to 14 is an alkyl group) was good.

However, the dyeability of the compound having an alkyl group in which _RB1 and _RB2 is substituted with OCH ₃ , such as a disperse dye conventionally used for dyeing polyester fibers or the like, used in the dyeing examples P24 or P25 was poor.

Table 20 and Table 21 show the evaluation results of the staining examples of the compound of formula (C).

[Table 20]

[Table 21]

Regarding the dyeability of the compound of formula (C), each of R _C1 , R _C2 and R _C3 used in staining examples P26 to P39, P79, P80, P100 and P101 independently represents an alkyl group having 1 to 14 carbon atoms (provided that R _C1 , at least one of R _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms) The dyeability of the compound was good.

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

In addition, with respect to each fastness of the compound of formula (C), X _C is a chlorine atom, Y _C is a hydrogen atom, or X _C is a hydrogen atom, Y _C is a hydrogen atom, and R _C1 , R _C2 and R _C3 are Compounds each independently representing an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _C1 , R _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms) were good.

Table 22 shows the evaluation results of the staining examples of the compound of formula (D).

[Table 22]

Regarding the dyeability of the compound of the formula (D), the dyeability of the compound of an alkyl group having 1 to 14 carbon atoms, each independently of which R _D1 and R _D2 used in the dyeing examples P47 to P53, P60, P81, and P82, was good.

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

In addition, with respect to each fastness of the compound of the formula (D), a compound in which both X _D and Y _D are chlorine atoms, or both X _D and Y _D are bromine atoms, or X _D and Y _D are both hydrogen atoms, is good did.

Table 23 shows the evaluation results of the staining examples of the compound of formula (E).

[Table 23]

About the dyeability of the compound of Formula ( _E ), the dyeability of the compound of the C4-C18 alkyl group used in dyeing example P62 or P63 was favorable.

However, the dyeability of the dye compound conventionally used for dyeing|dyeing of polyester fibers etc. used in dyeing example P64 was poor.

Moreover, about each fastness of the compound of Formula ( _E ), it was so favorable that carbon number of hydrocarbon group RE was large.

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

[Table 24]

Regarding the dyeability of the compound of the formula (F), R _F1 and R _F2 used in Dyeing Example P65 each independently showed good dyeability of the compound having an alkyl group having 4 to 14 carbon atoms.

However, the dyeability of the disperse dyes used for dyeing|dyeing of polyester fibers etc. conventionally used by dyeing example P66 or P67, etc. was poor.

Moreover, about each fastness of the compound of Formula (F), the compound with a large carbon number of R _F1 and R _F2 was favorable.

Table 25 shows the evaluation results of the staining examples of the compound of formula (G).

[Table 25]

The dyeability of the compound of formula (G) was favorable for the compound of the alkyl group in which R _G used in the dyeing examples P68 to P71 had 7 to 18 carbon atoms.

However, the dyeability of the dye compound conventionally used for dyeing|dyeing of polyester fibers etc. used in dyeing example P72 was poor.

Moreover, about each fastness of the compound of Formula (G), it was so favorable that carbon number of R _G was large.

<Example of separate polypropylene dyeing>

Polypropylene fibers were dyed by a supercritical carbon dioxide dyeing method using dye compounds described in Tables 3 to 9 or dyes using a mixture of two or more kinds of disperse dye compounds conventionally used for dyeing polyester fibers or the like.

For the obtained dyed fabric, similarly to the case of polypropylene dyed fabric with one type of dye compound described above, it was subjected to dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, rubbing fastness test and hot pressing. A fastness test was performed for The dyeability was visually evaluated for the TotalK/S value, L ^* value, a ^* value, b ^* value, and the dye residue after dyeing obtained by colorimetry of the dyed fabric. And colorimetry of the dyed fabric was performed using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretak Macbeth), and the dyed fabric was pasted on white paper with an observation light source D65 and a 2 degree field of view.

Table 26 and Table 27 show the evaluation results of the dyes.

[Table 26]

[Table 27]

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

<Polyethylene dyeing example>

[Dyeing Example E1]

A supercritical carbon dioxide dyeing apparatus used for dyeing is shown in FIG. 1 . The dyeing apparatus consists of a liquid CO ₂ cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high pressure pump (5), a preheater (6), a pressure gauge (7-9), a magnetic drive unit ( 10 ), a DC motor 11 , safety valves 12 and 13 , stop valves 14 to 18 , a needle valve 19 , and a heater 20 .

A polyethylene cloth was cut and weighed to about 50 to 70 g, and was wound around a stainless cylinder 21 having a punch hole in the order of a cotton cloth, a polyethylene cloth, and a cotton cloth from the inside, and then loosely fixed with a cotton thread. The inner comedon is an undercloth, and the outer comedon is a cover cloth.

The blue dye compound A obtained in Synthesis Example 5 equivalent to 0.3% by mass relative to the mass of the polyethylene cloth by fixing a stainless cylinder wound with the above-mentioned cloth sample (cotton cloth, polyethylene cloth, cotton cloth) to the pressure-resistant stainless steel tank 22. The -5 was wrapped in a paper wipe and placed in the fluid passageway above the stainless cylinder. The volume of the pressure-resistant stainless steel tank was 2230 cm ³ . All the valves in the dyeing apparatus were closed, and it heated to 98 degreeC with the preheater.

After reaching the dyeing temperature, the stop valves 14 and 16 were opened, and 1.13 kg of liquid carbon dioxide was introduced into the pressure-resistant stainless steel bath using a high-pressure pump through a cooling jacket. Thereafter, the stop valves 14 and 16 were closed, and the pressure was circulated to the impeller and the magnetic drive unit at the bottom of the stainless steel tank. The rotational speed of the magnetic drive is 750 rpm, and the circulation direction is from the inside to the outside of the cylinder.

After the inside of the pressure-resistant stainless steel tank reached a predetermined temperature and pressure (98°C, 25 MPa), the polyethylene cloth was dyed by maintaining the temperature and pressure conditions for 60 minutes. After dyeing, the stop valve 18 was opened and the needle valve was gradually opened to release carbon dioxide in the pressure-resistant stainless steel tank, and the pressure in the pressure-resistant stainless steel tank was lowered from 25 MPa to atmospheric pressure. The cycle continued until the critical pressure of carbon dioxide (about 8 MPa) was reached. After that, the polyethylene dyed cloth in the pressure-resistant stainless steel tank was taken out.

[Staining Examples E2 to E14, and Staining Examples E18 to E20]

The same dyeing as in Dyeing Example E1, except that the blue dye compound A-5 described in Dyeing Example E1 was changed to the dye compounds shown in Tables 3 to 9 or a disperse dye compound conventionally used for dyeing polyester fibers, etc. A polyethylene dyed cloth was obtained by the procedure. The dye compounds used in dyeing examples E1-E14 and dyeing examples E18-E20 are shown in Tables 28-32.

[Table 28]

[Table 29]

[Table 30]

[Table 31]

[Table 32]

Dyeability evaluation, light fastness test, washing fastness test, sweat fastness test and rub fastness test were performed on the polyethylene dyed fabrics obtained in Dyeing Examples E1 to E14 and Dyeing Examples E18 to E20.

(1) Dyeability evaluation

The dyeing property visually evaluated the TotalK/S value obtained by colorimetry of the dyed fabric, and the dye residue after dyeing|dyeing. The colorimetry of the dyed fabric was performed using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretak Macbeth), and the dyed fabric was pasted on white paper with an observation light source D65 and a 2 degree field of view.

(2) Light fastness test

The light fastness test was performed by the 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.), color change and discoloration were judged after exposure to dyed fabric for 20 hours under conditions of a black panel temperature of 63±3°C.

(3) Washing fastness test

The washing fastness test was performed by the method according to JIS L0844:2011 (A-2). The outline of the test method is as follows. A multi-woven multi-woven fabric was attached to the dyed fabric, and washed for 30 minutes under conditions of 50 ± 2 ° C. in the presence of soap, and the discoloration and contamination of the cotton and nylon parts of the multi-woven cross fabric were judged. Moreover, the contamination of the residual liquid after washing was judged.

(4) Sweat fastness test

The sweat fastness test was performed by the method according to JIS L0848:2004. The outline of the test method is as follows. After attaching a multi-woven woven fabric to the dyed fabric, immersing it in acidic artificial sweat solution or alkaline artificial sweat for 30 minutes, maintaining it at 37±2℃ for 4 hours under a load of 12.5kPa, drying it at 60℃ or less, discoloration and discoloration and Contamination to the cotton portion and the nylon portion of the multiwoven cross woven fabric was determined.

(5) Friction fastness test

The friction fastness test was performed by the method according to JIS L0849:2013. The outline of the test method is as follows. Using a friction fastness tester RT-300 (manufactured by Daiei Science Seonggi Co., Ltd.), apply a load of 2N to the dyed cloth with a dry cotton or wet cotton cloth, and perform reciprocating friction 100 times, and color the cotton cloth. was judged.

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

[Table 33]

Regarding the dyeability of the compound of formula (A), R _A1 , R _A2 and R _A3 used in Dyeing Examples E1 to E4 and E18 are each independently an alkyl group having 1 to 14 carbon atoms or alkoxy or CN having 1 to 4 carbon atoms. The dyeability of the compound exhibiting an alkyl group having 1 to 14 carbon atoms substituted with (provided that at least one of R _A1 , R _A2 and R _A3 is an alkyl group having 4 to 14 carbon atoms) was good.

In addition, about each fastness of the compound of Formula (A), the compound in which X _A is a nitro group, Y _A is a bromine atom, and R _A1 , R _A2 and R _A3 has a large carbon number was favorable.

Table 34 shows the evaluation results of the staining examples of the compound of formula (B).

[Table 34]

Regarding the dyeability of the compound of formula (B), R _B1 , R _B2 , and R _B3 used in Dyeing Example E19 are alkyl groups having 1 to 14 carbon atoms (provided that at least one of R _B1 , R _B2 and R _B3 has 4 to 14 carbon atoms) The dyeability of the compound of the alkyl group) was good.

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

[Table 35]

Regarding the dyeability of the compound of formula (C), R _C1 , R _C2 and R _C3 used in Dyeing Examples E5 to E7 and E20 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that R _C1 , R At least one of _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms), or X _C and Y _C each independently represents a hydrogen atom and a halogen atom, and R _C1 , R _C2 and R _C3 are each independently a C 1 The dyeability of the compound showing an alkyl group of -14 was good.

In addition, about each fastness of the compound of formula (C), the compound where X _C is a chlorine atom, Y _C is a hydrogen atom, and R _C1 , R _C2 , and R _C3 has a large carbon number was better.

Table 36 shows the evaluation results of the staining examples of the compound of formula (D).

[Table 36]

Regarding the dyeability of the compound of formula (D), R _D1 used in the dyeing examples E8 to E12 represents an alkyl group having 1 to 14 carbon atoms, and R _D2 is an alkyl group having 1 to 14 carbon atoms or an alkyl group having 1 to 14 carbon atoms substituted with CN. The dyeability of the compound representing an alkyl group of (however, when R _D2 is an alkyl group having 1 to 14 carbon atoms substituted with CN, R _D1 is an alkyl group having 4 to 14 carbon atoms) was good.

However, the dyeability of the compound having an alkyl group having 3 or less carbon atoms in both R _D1 and R _D2 , which are disperse dyes conventionally used for dyeing polyester fibers and the like used in the dyeing example E13, was poor.

In addition, with respect to each fastness of the compound of formula (D), X _D and Y _D are both chlorine atoms, or X _D and Y _D are both bromine atoms, or X _D and Y _D are both hydrogen atoms, and R The compound with a large carbon number of _D1 and R _D2 was more favorable.

Table 37 shows the evaluation results of the staining examples of the compound of formula (G).

[Table 37]

As for the dyeability of the compound of the formula (G), R _G used in the dyeing example E14 had good dyeability of the compound having an alkyl group having 7 to 18 carbon atoms.

Moreover, about each fastness of the compound of Formula ( _G ), it was favorable that carbon number of hydrocarbon group RG was 15.

<Example of separate polyethylene dyeing>

Polyethylene fibers were dyed by a supercritical carbon dioxide dyeing method using dyes using a mixture of two or more of the dye compounds shown in Tables 3 to 9 or disperse dye compounds conventionally used for dyeing polyester fibers and the like.

The obtained dyed fabric was subjected to dyeability evaluation, light fastness test, wash fastness test, sweat fastness test and rub fastness test as in the case of polyethylene dyed fabric with one type of dye compound described above. Table 38 shows the evaluation results of dyeing using the dye. The dyeability was visually evaluated for the TotalK/S value, L ^* value, a ^* value, b ^* value, and the dye residue after dyeing obtained by colorimetry of the dyed fabric. And colorimetry of the dyed fabric was performed using an integrating sphere spectrophotometer Color-Eye 5 (manufactured by Gretak Macbeth), and the dyed fabric was pasted on white paper with an observation light source D65 and a 2 degree field of view.

[Table 38]

As shown in Table 38, the ones obtained by mixing the orange dye, red dye, purple dye and blue dye of the present invention obtained in dyeing examples E15, E16, and E18 were black dyed fabrics with good dyeability and good color fastness. .

As mentioned above, this invention is not limited to embodiment mentioned above, The thing which combined or substituted the structure of embodiment suitably is also included in this invention.

In addition, based on the knowledge of those skilled in the art, it is also possible to add modifications such as combinations and steps in the embodiments appropriately recombined and various design changes to the embodiments based on the knowledge of those skilled in the art. can be included in

The present invention dyes polyolefin fibers used in clothing, underwear, hats, socks, gloves, medical products such as sportswear, vehicle interior materials such as seat seats, interior products such as carpets, curtains, mats, sofa covers, cushion covers, etc. can be used to

Claims (12)

A dye for dyeing polyolefin fibers using supercritical carbon dioxide, comprising at least one of the compounds of the following general formulas (A) to (G):

[In the above formula (A),
X _A is a nitro group,
Y _A represents a halogen atom,
R _A1 , R _A2 and R _A3 each independently represent 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);
R _A4 represents an alkyl group having 1 to 4 carbon atoms]

[In the formula (B), R _B1 , R _B2 and R _B3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _B1 , R _B2 and R _B3 is an alkyl group having 4 to 14 carbon atoms) ]

[In the formula (C),
X _C and Y _C represent a combination of any one of a hydrogen atom and a halogen atom, a halogen atom and a nitro group, a halogen atom and a cyano group, a cyano group and a cyano group, a nitro group and a cyano group, a hydrogen atom and a hydrogen atom,
R _C1 , R _C2 and R _C3 each independently represent an alkyl group having 1 to 14 carbon atoms (provided that at least one of R _C1 , R _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms)]

[In the formula (D), X _D and Y _D each independently represents a hydrogen atom, a halogen atom, or a cyano group,
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, provided that at least one of R _D1 and R _D2 is an alkyl group having 4 to 14 carbon atoms]

[In the formula (E), X _E and Y _E each independently represent a halogen atom, and R _E represents an alkyl group having 4 to 18 carbon atoms]

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

[In the formula (G), R _G represents an alkyl group having 7 to 18 carbon atoms]. As the dye according to claim 1,
is black,
At least one of a purple or blue dye compound comprising at least one 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) one and
A red dye compound comprising at least one selected from the group consisting of a compound of the general formula (C) and a compound of the general formula (D);
A dye comprising at least one of a yellow or orange dye compound comprising at least one selected from the group consisting of a compound of the general formula (D), a compound of the general formula (E), and a compound of the general formula (G). The dye according to claim 2,
is black,
At least one of a purple or blue dye compound comprising at least one 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);
A red dye compound of the compound of the general formula (C),
A dye comprising an orange dye compound comprising at least one selected from the group consisting of a compound of the general formula (D) and a compound of the general formula (E). The dye according to claim 2 or 3,
A blue dye compound of the compound of the general formula (A);
A red dye compound of the compound of the general formula (C),
A dye comprising an orange dye compound of the compound of formula (D). 5. The method according to any one of claims 2 to 4,
30 to 70 mass % of the purple or blue dye compound;
5-25 mass % of the said red dye compound,
A dye comprising 15 to 55 mass % of the yellow or orange dye compound. 6. The method of claim 5,
40-60 mass % of the purple or blue dye compound,
5-25 mass % of the said red dye compound,
A dye comprising 25 to 45 mass % of the yellow or orange dye compound. A method for dyeing polyolefin fibers using supercritical carbon dioxide, the method comprising:
A method comprising the step of dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the dye according to any one of claims 1 to 6. 8. The method of claim 7,
The said dyeing process is a dyeing method which is performed at 31 degreeC or more and a pressure of 7.4 MPa or more. 9. The method according to claim 7 or 8,
The concentration of the dye to the fiber is in the range of 0.1 to 6.0 omf (on the mass of fiber). 10. The method according to any one of claims 7 to 9,
The dyeing method, wherein the polyolefin fiber is a polypropylene resin fiber. 10. The method according to any one of claims 7 to 9,
The dyeing method, wherein the polyolefin fiber is a polyethylene resin fiber. A polyolefin fiber dyed by the dyeing method according to any one of claims 7 to 11.

Images