TW202142626A - Dye for staining by using supercritical carbon dioxide - Google Patents

Abstract

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

Description

Dyes for dyeing with supercritical carbon dioxide

The present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, a dyeing method for polyolefin fibers using supercritical carbon dioxide, and a polyolefin fiber obtained by dyeing the above-mentioned dyeing method.

Polyolefin resins such as polypropylene resins and polyethylene resins are crystalline thermoplastic resins that are inexpensive, easy to process, high strength, high chemical resistance, high friction resistance, high flexibility resistance, light weight, Excellent properties such as low moisture absorption, low thermal conductivity, and high antistatic properties.

On the other hand, polyolefin-based resins are polymer compounds whose main chain and side chains are composed of hydrocarbons. Because of their low affinity and compatibility with conventional dye compounds, they do not have functional groups that are effective for chemical reactions. Because of this, it is considered that high-density and high-fastness dyeing is extremely difficult.

Therefore, most of the colored polyolefin resins currently on the market are those that add colored pigments at the manufacturing stage of polymer particles and the like, and then perform spinning, molding, etc. to obtain the desired shape.

The coloring method needs to determine the color in the initial stage of the resin product manufacturing step. Moreover, considering the cost-effectiveness, it is necessary to produce more than a certain amount of one color, and as a result, the freedom of color selection is restricted.

Furthermore, in the case of changing the color of the resin product, it is necessary to replace the coloring resin of the previous color remaining in the resin product manufacturing device with the coloring resin of the next color. At this time, a large amount of waste resin will be generated and waste will be generated. Time and energy issues.

As described in Non-Patent Document 1, polypropylene resins and polyethylene resins are juxtaposed with polyvinyl chloride resins and polystyrene resins as four general-purpose synthetic resins, which are used in a wide range of fields.

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

It is believed that the reason is: as mentioned above, the high concentration and high fastness of polypropylene resin fiber and polyethylene resin fiber are extremely difficult to dye, and in the only effective coloring method, that is, the dope coloring method using colored pigments, it is necessary to make single yarn Denier becomes larger, and freedom of color choice is restricted, etc.

Prior to this, in order to dye polyolefin resin fibers with water, attempts were also made to change the molecular structure of the dye. Specifically, Patent Documents 1 to 5 propose dyes for dyeing polyolefin resin fibers.

Patent Document 1 describes the production examples of red dyes and violet dyes by introducing a phenoxy group having an alkyl group or cycloalkyl group having 3 to 12 carbons as a substituent into an anthraquinone dye, and a poly Dyeing example of acrylic resin fiber.

However, it is difficult for these anthraquinone-based red dyes or anthraquinone-based purple dyes to dye polyolefin resin fibers at a high concentration. Furthermore, regarding the form of dyes used for dyeing, it is described that the anthraquinone-based red dyes are dissolved in alcohol or acetone as an organic solvent and used. However, it is hard to say that the dyeing method is environmentally friendly.

Patent Document 2 describes a production example of a blue dye obtained by introducing a phenoxy group having an alkyl group, a cycloalkyl group or a halogen group with a carbon number of 1 to 9 as a substituent into an anthraquinone dye, and the use thereof. Examples of dyeing of polyester fibers, polyamide fibers, and polyolefin resin fibers.

However, these anthraquinone-based blue dyes are difficult to dye polyolefin-based resin fibers at a high concentration, and there is no specific description of the dye fastness of the obtained dyed product. Furthermore, regarding the form of dyes used for dyeing, it is described that the anthraquinone-based blue dyes are used after being dissolved in alcohol or acetone as an organic solvent, which is hardly environmentally friendly.

Patent Document 3 describes a production example of a blue dye obtained by introducing a phenoxy group having a C 1-9 alkyl group or a halogen group as a substituent into an anthraquinone dye, and a polyolefin resin using the same Examples of dyeing of fibers.

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

Patent Document 4 describes an example of dyeing a polyolefin resin fiber using a blue dye obtained by introducing an alkylamine group or a cycloalkylamine group into the α-position of an anthraquinone dye.

However, these anthraquinone-based blue dyes are difficult to dye polyolefin-based resin fibers at a high concentration, and there is no specific description of the dye fastness of the obtained dyed product.

Patent Document 5 describes the production example and use of a red dye obtained by introducing a phenoxy group having two substituents selected from the group consisting of second butyl, second pentyl, and third pentyl into anthraquinone dyes Examples of dyeing of polypropylene resin fibers.

However, it is difficult for these anthraquinone-based red dyes to perform high-density dyeing of polyolefin-based resin fibers, and the dye fastness of the obtained dyed product is not specifically described. Furthermore, regarding the form of the dye used for dyeing, it is described that it is used after being dissolved in dimethylformamide as an organic solvent, and it is difficult to say that the method of using this dye is environmentally friendly.

Patent Document 6 describes a production example of a monoazo dye having a long-chain alkyl group, and a dyeing example of fine Deny polyester fiber using the same. However, there is no description of an example of dyeing polyolefin-based fibers using them.

In addition, in order to improve the dyeability of polyolefin resin fibers, various studies have been conducted on the modification of polyolefin resin fibers.

As the modification technology, the following various technologies are known, such as blending dyeable resin components such as polyester, copolymerizing with vinyl monomers having dyeable groups, blending dyeing accelerators such as metal stearate, etc. .

Although the dyeability of these modified polyolefin resin fibers has been improved, there is a problem that the yarn strength is reduced due to the dyeing process, and the strength becomes insufficient when used in clothes or the like.

In addition, Patent Document 7 describes the use of supercritical carbon dioxide as a dyeing medium and the dyeing of hydrophobic fiber materials with various dyes as a dyeing method instead of water-based dyeing.

However, polypropylene is described as an example of the hydrophobic fiber material, but only the dyeing example of polyester cloth is described in the examples, and the dyeing example of polypropylene fiber is not described. Prior art literature Patent literature

Patent Document 1: Japanese Patent Publication No. 38-10741 Patent Document 2: Japanese Patent Publication No. 40-1277 Patent Document 3: Japanese Patent Publication No. 41-3515 Patent Document 4: Specification of British Patent No. 872,882 Patent Document 5: Specification of US Patent No. 3,536,735 Patent Document 6: Japanese Patent Laid-Open No. 55-152869 Patent Document 7: Japanese Patent No. 3253649 Non-patent literature

Non-Patent Document 1: Yamamoto Hiroshi, Journal of the Fiber Society, 61 (2005), 319-321.

[The problem to be solved by the invention]

Therefore, the object of the present invention is to provide a dye for dyeing polyolefin fibers with supercritical carbon dioxide, which can dye polyolefin fibers into various hues at a high concentration, and has excellent dye fastness to light, sublimation, washing, etc. , The dyeing method of polyolefin fiber using supercritical carbon dioxide, and the polyolefin fiber obtained by dyeing by the above-mentioned dyeing method. [Technical means to solve the problem]

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

式（A）

Formula (A)

[In formula (A), X _A represents a nitro group, Y _A represents a halogen atom, and R _A1 , R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein, R _A1 , R _A2 and R _A3 At least one of them is an alkyl group with 4 to 14 carbons), R _A4 represents an alkyl group with 1 to 4 carbons]

式（B）

Formula (B)

[In formula (B), R _B1 , R _B2 and R _B3 each independently represent an alkyl group having 1 to 14 carbons (wherein, _{at least one of R B1} , R _B2 and R _B3 is an alkane having 4 to 14 carbons base)]

式（C）

Formula (C)

[In formula (C), X _C and Y _C represent any of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom A combination, R _C1 , R _C2 and R _C3 each independently represent an alkyl group with 1 to 14 carbons (wherein, _{at least one of R C1} , R _C2 and R _C3 is an alkyl with 4 to 14 carbons)]

式（D）

Formula (D)

[In formula (D), X _D and Y _D each independently represent a hydrogen atom, a halogen atom, or a cyano group, R _D1 represents an alkyl group with 1 to 14 carbons, and R _D2 represents an alkyl group with 1 to 14 carbons or An alkyl group of 1 to 14 carbons substituted by CN; wherein _{at least one of R D1} and R _D2 is an alkyl group of 4 to 14 carbons]

式（E）

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]

式（F）

Formula (F)

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

式（G）

Formula (G)

[In formula (G), R _G represents an alkyl group having 7 to 18 carbon atoms]. In addition, the present invention provides a method for dyeing polyolefin fibers using supercritical carbon dioxide, which includes the step of dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the above-mentioned dye of the present invention.

Furthermore, the present invention provides a polyolefin fiber obtained by dyeing by the dyeing method of the present invention. [Effects of the invention]

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

The inventors found that dyes containing the following specific compounds have improved affinity for lipophilic polyolefin fibers, and that polyolefin fibers are dyed into various hues at high concentration in the presence of supercritical carbon dioxide, thereby completing the present invention .

＜Compounds of general formula (A)～(G)＞ The compounds of the general formulas (A) to (G) contained in the dye of the present invention are as follows.

式（A）

Formula (A)

[In formula (A), X _A represents a nitro group, Y _A represents a halogen atom, and R _A1 , R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein, R _A1 , R _A2 and R _A3 At least one of them is an alkyl group with 4 to 14 carbons), R _A4 represents an alkyl group with 1 to 4 carbons]

式（B）

Formula (B)

[In formula (B), R _B1 , R _B2 and R _B3 each independently represent an alkyl group having 1 to 14 carbons (wherein, _{at least one of R B1} , R _B2 and R _B3 is an alkane having 4 to 14 carbons base)]

式（C）

Formula (C)

[In formula (C), X _C and Y _C represent any of hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom A combination, R _C1 , R _C2 and R _C3 each independently represent an alkyl group with 1 to 14 carbons (wherein, _{at least one of R C1} , R _C2 and R _C3 is an alkyl with 4 to 14 carbons)]

式（D）

Formula (D)

[In formula (D), X _D and Y _D each independently represent a hydrogen atom, a halogen atom, or a cyano group, R _D1 represents an alkyl group with 1 to 14 carbons, and R _D2 represents an alkyl group with 1 to 14 carbons or An alkyl group of 1 to 14 carbons substituted by CN; wherein _{at least one of R D1} and R _D2 is an alkyl group of 4 to 14 carbons]

式（E）

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]

式（F）

Formula (F)

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

式（G）

Formula (G)

[In formula (G), R _G represents an alkyl group having 7 to 18 carbon atoms]. In the above formula (A), formula (C), formula (D), and formula (E), the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred ones include: fluorine atom, chlorine Atom, bromine atom.

In the above formulas (A) to (D), the alkyl groups having 1 to 14 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, Tertiary butyl, n-pentyl, isopentyl, second pentyl, tertiary pentyl, 2-methylbutyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Benzylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-di Linear or branched alkyl groups with 1 to 14 carbon atoms such as methylbutyl and 1-ethyl-1-methylpropyl. The alkyl group having 1 to 14 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

In the above formula (A), the alkyl group having 1 to 4 carbon atoms includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and tertiary butyl. Etc. straight-chain or branched-chain alkyl with 1 to 4 carbons. The alkyl group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 2 carbon atoms, and more preferably an alkyl group having 1 carbon atoms.

In the above formulas (A) to (D) and (F), the alkyl groups having 4 to 14 carbon atoms include, for example, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, iso Pentyl, second pentyl, third pentyl, 2-methylbutyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl , 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 1-ethyl Linear or branched alkyl groups with 4 to 14 carbon atoms such as -1-methylpropyl group. The alkyl group having 4 to 14 carbon atoms is preferably an alkyl group having 4 to 12 carbon atoms, and more preferably an alkyl group having 4 to 8 carbon atoms.

In the above formula (E), the alkyl group having 4 to 18 carbon atoms includes, for example, n-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, isopentyl, second pentyl, Tertiary pentyl, 2-methylbutyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-1-methylpropyl, etc. Linear or branched alkyl. The alkyl group having 4 to 18 carbon atoms is preferably an alkyl group having 4 to 12 carbon atoms, and more preferably an alkyl group having 8 to 12 carbon atoms.

In the above formula (G), the alkyl group having 7 to 18 carbon atoms includes, for example, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 1-ethyl Benzylpentyl, 2-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl and other linear or branched carbons The number is 7 to 18 alkyl group. The alkyl group having 7 to 18 carbon atoms is preferably an alkyl group having 11 to 18 carbon atoms, and more preferably an alkyl group having 15 to 18 carbon atoms.

＜The compound of general formula (A)＞

式（A）

Formula (A)

The compound of general formula (A) in formula (A), X _A represents a nitro group, Y _A represents a halogen atom, and R _A1 , R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein R _{At least one of A1} , R _A2, and R _A3 is an alkyl group with 4 to 14 carbons), and R _A4 represents an alkyl group with 1 to 4 carbons.

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

_{In the above formula (A), Y A is} preferably a bromine atom from the viewpoints of dyeing concentration, light fastness, and sublimation fastness.

In addition, in the above formula (A), from the viewpoints of dye concentration, light fastness, sublimation fastness, etc., it is preferable that 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 with 4 to 14 carbons, and R _A3 is an alkyl group with 1 to 4 carbons, or R _A3 is an alkyl group with 4 to 14 carbons, and R _A1 and R _A2 are each independently It is an alkyl group having 1 to 4 carbon atoms.

In addition, in the above formula (A), from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., it is preferable that Y _A is a bromine atom, and R _A1 , R _A2 and R _A3 each independently have a carbon number of 4 to 14 R _A1 and R _A2 are each independently an alkyl group having 4 to 14 carbons, and R _A3 is an alkyl group having 1 to 4 carbons, or R _A3 is an alkyl group having 4 to 14 carbons, and R _A1 and R _A2 are each independently an alkyl group having 1 to 4 carbons.

＜The compound of general formula (B)＞

式（B）

Formula (B)

Compounds 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. Wherein, _{at least one of R B1} , R _B2 and R _B3 is an alkyl group having 4 to 14 carbons.

The compound of the above formula (B) is a blue or purple dye compound.

In the above formula (B), from the viewpoints of dye concentration, light fastness, sublimation fastness, etc., it is preferable that R _B1 , R _B2 and R _B3 are each independently an alkyl group having 4 to 14 carbons, or R _B1 and R _{B2 is} each independently an alkyl group with 4 to 14 carbons, and R _B3 is an alkyl group with 1 to 4 carbons, or R _B3 is an alkyl group with 4 to 14 carbons, and R _B1 and R _B2 are each independently a carbon Number of alkyl groups from 1 to 4.

＜The compound of general formula (C)＞

式（C）

Formula (C)

The compound of general formula (C) in formula (C), X _C and Y _C represent hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, Any combination of hydrogen atoms and hydrogen atoms, R _C1 , R _C2 and R _C3 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein, _{at least one of R C1} , R _C2 and R _C3 is a carbon number of 4 to 14 alkyl).

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

In the above formula (C), from the viewpoints of dye concentration, light fastness, sublimation fastness, etc., it is preferable that X _C and Y _C represent a hydrogen atom and a chlorine atom, a bromine atom and a nitro group, a bromine atom and a cyano group, Any combination of cyano and cyano, nitro and cyano, hydrogen atom and hydrogen atom.

In the above formula (C), from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferably X _C and Y _C represent a hydrogen atom and a halogen atom, a halogen atom and a nitro group, a halogen atom and a cyano group, Any combination of cyano and cyano, nitro and cyano, hydrogen atom and hydrogen atom, R _C1 , R _C2 and R _C3 are each independently an alkyl group having 4 to 14 carbons, or R _C1 and R _C2 are each independently Is an alkyl group having 4 to 14 carbons, and R _C3 is an alkyl group having 1 to 4 carbons, or R _C3 is an alkyl group having 4 to 14 carbons, and R _C1 and R _C2 are each independently a carbon number of 1 to 4的alkyl.

＜The compound of general formula (D)＞

式（D）

Formula (D)

Compounds of general formula (D) in formula (D), X _D and Y _D each independently represent a hydrogen atom, a halogen atom, or a cyano group, R _D1 represents an alkyl group with 1 to 14 carbon atoms, and R _D2 represents a carbon number An alkyl group of 1 to 14 or an alkyl group of 1 to 14 carbons substituted by CN. Wherein, _{at least one of R D1} and R _D2 is an alkyl group having 4 to 14 carbon atoms.

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

In the above formula (D), from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., it is preferable that X _D represents a hydrogen atom, a chlorine atom, or a bromine atom, and Y _D represents a hydrogen atom, a chlorine atom, a bromine atom, Or cyano.

Furthermore, in the above formula (D), it is preferable that X _D and Y _D each independently represent a hydrogen atom, a halogen atom, or a cyano group, R _D1 represents an alkyl group having 4 to 14 carbons, and R _D2 represents a carbon number of 4 to The alkyl group of 14 or the alkyl group of 1 to 14 carbons substituted by CN.

＜The compound of general formula (E)＞

式（E）

Formula (E)

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

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

In the above formula (E), from the viewpoints of dyeing concentration, light fastness, and sublimation fastness, it is preferable that X _E and Y _E represent a chlorine atom.

In the above formula (E), on the concentration of dye, light fastness, sublimation fastness and the like viewpoint, preferably R _E is alkyl of 4 to 12.

In the above formula (E), from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., X _E and Y _E preferably represent a chlorine atom, and _RE is an alkyl group having 4 to 12 carbons.

＜The compound of general formula (F)＞

式（F）

Formula (F)

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

The compound of the above formula (F) is a purple dye compound.

In the above formula (F), from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., it is preferable that R _F1 and R _F2 each independently represent an alkyl group having 4 to 12 carbon atoms.

＜The compound of general formula (G)＞

式（G）

Formula (G)

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

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

In the above formula (G), from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., it is preferable that R _G is an alkyl group having 11 to 18 carbon atoms.

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

The compound represented by the above formula (A) is a diazo compound of the 4-nitroaniline derivative represented by the formula (aD) (in the formula (aD), X _A represents a nitro group and Y _A represents a halogen atom) With the 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 (wherein, at least one of _{R A1} , R _A2 and R _A3 Which is an alkyl group with 4 to 14 carbons), and R _A4 represents an alkyl group with 1 to 4 carbons) to be obtained by coupling.

(I) Diazotization of compound of formula (a-D) First, in an inorganic acid or an organic carboxylic acid, the compound of formula (a-D) is diazotized by using a nitrosating agent or nitrososulfuric acid in the presence of additional water as appropriate to obtain a diazonium compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Moreover, as an inorganic acid, hydrochloric acid, phosphoric acid, and sulfuric acid are mentioned, for example, Preferably, sulfuric acid is mentioned. The nitrosating agent used is alkali metal nitrite, such as sodium nitrite in a solid state or an aqueous solution state.

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

Furthermore, the compound represented by formula (a-D) is generally used as a raw material for azo disperse dyes and is widely used.

(Ii) Coupling with the compound of formula (a-C) For example, at a temperature range of -5 to 10°C, a solution or suspension of the compound represented by the formula (aC) is added to the solution or suspension of the diazonium compound of the formula (aD) to obtain the formula (A) ) Represented by the compound.

The pH value of the compound solution or suspension represented by the formula (a-C) is preferably weakly acidic, and the addition of buffers such as triethylamine, sodium acetate, etc. is advantageous in the coupling reaction.

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

(Iii) Manufacturing method of compound of formula (a-C) The compound of formula (a-C) as a raw material can be produced in the following manner.

Using N,N-dimethylformamide (DMF) as a solvent, the compound represented by formula (a-C1) (in formula (a-C1), R _A4 represents an alkyl group with 1 to 4 carbon atoms) and The carboxylic halide represented by R _A3 -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 formula (a-C2).

Then, the compound represented by the formula (a-C2) is nitrated with concentrated nitric acid and concentrated sulfuric acid to obtain the compound represented by the formula (a-C3).

The compound represented by the formula (a-C3) is reduced with tin in an acidic alcohol with hydrochloric acid (for example, methanol) to obtain the compound represented by the formula (a-C4).

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

Alternatively, the compound represented by formula (a-C4) can be reacted with a _{halogenated hydrocarbon represented by R A1} -X (R _A1 represents an alkyl group with 1 to 14 carbon atoms, and X represents a halogen atom), and then according to a known reaction, Introduce R _A2 (R _A2 represents an alkyl group with 1 to 14 carbon atoms). For example, (R _A2 ) ₂ SO ₄ can be used to import R _A2 .

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

The compound represented by the above formula (B) is represented by the diazonium compound of the 3-amino-5-nitro-2,1-benzisothiazole represented by the formula (bD) and the formula (bC) In the compound (formula (bC), R _B1 , R _B2 and R _B3 each independently represent an alkyl group having 1 to 14 carbons (wherein, _{at least one of R B1} , R _B2 and R _B3 is a carbon number of 4 to 14 Alkyl)) is obtained by coupling.

(I) Diazotization of compound of formula (b-D) First, in an inorganic acid or an organic carboxylic acid, the compound of formula (b-D) is diazotized by using a nitrosating agent or nitrososulfuric acid in the presence of additional water as appropriate to obtain a diazonium compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Moreover, as an inorganic acid, hydrochloric acid, phosphoric acid, and sulfuric acid are mentioned, for example, Preferably, sulfuric acid is mentioned. The nitrosating agent used is alkali metal nitrite, such as sodium nitrite in a solid state or an aqueous solution state.

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

Furthermore, the compound represented by the formula (b-D) is generally used as a raw material for azo disperse dyes and is widely used.

(Ii) Coupling with the compound of formula (b-C) For example, at a temperature range of -5 to 10°C, a solution or suspension of the compound represented by formula (bC) is added to the solution or suspension of the diazonium compound of the formula (bD) to obtain the formula (B) ) Represented by the compound.

The pH value of the compound solution or suspension represented by the formula (b-C) is preferably weakly acidic, and the addition of buffers such as triethylamine, sodium acetate, etc. is advantageous in the coupling reaction.

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

(Iii) Manufacturing method of compound of formula (b-C) The compound of formula (b-C) as a raw material can be produced in the following manner.

Using DMF as a solvent, meta-nitroaniline is reacted with a _{carboxyhalide represented by R B3-} COX ( _RB3 represents an alkyl group with 1 to 14 carbon atoms, and X represents a halogen atom) to obtain the formula (b-C1) The compound represented.

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

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

Alternatively, the compound represented by the formula (b-C2) can be reacted with a _{halogenated hydrocarbon represented by R B1} -X ( _RB1 represents an alkyl group with 1 to 14 carbon atoms, and X represents a halogen atom), and then according to a known reaction, Introduce R _B2 ( _RB2 represents an alkyl group with 1 to 14 carbon atoms). For example, (R _B2 ) ₂ SO ₄ can be used to import R _B2 .

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

The compound represented by the above formula (C) can be obtained by making the 4-nitroaniline derivative represented by the formula (cD) (in the formula (cD), X _C and Y _C represent a hydrogen atom and a halogen atom, a halogen atom and a nitro Group, halogen atom and cyano group, any combination of cyano group and cyano group, nitro group and cyano group, hydrogen atom and hydrogen atom) and the compound represented by formula (cC) (in formula (cC), R _C1 , R _C2 and R _C3 each independently represent an alkyl group having 1 to 14 carbons (wherein, _{at least one of R C1} , R _C2 and R _C3 is an alkyl group having 4 or more carbons), and obtained by coupling.

(I) Diazotization of compound of formula (c-D) First, in an inorganic acid or an organic carboxylic acid, the compound represented by the formula (c-D) is diazotized using a nitrosating agent or nitrososulfuric acid in the presence of additional water as appropriate to obtain a diazonium compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Moreover, as an inorganic acid, hydrochloric acid, phosphoric acid, and sulfuric acid are mentioned, for example, Preferably, sulfuric acid is mentioned. The nitrosating agent used is alkali metal nitrite, such as sodium nitrite in a solid state or an aqueous solution state.

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

Furthermore, the compound represented by the formula (c-D) is generally used as a raw material for azo disperse dyes and is widely used.

(Ii) Coupling with the compound of formula (c-C) For example, at a temperature range of -5 to 10°C, the solution or suspension of the compound represented by formula (cC) is added to the solution or suspension of the diazonium compound of the formula (cD) to obtain the formula (C) ) Represented by the compound.

The pH value of the compound solution or suspension represented by the formula (c-C) is preferably weakly acidic, and the addition of buffering agents such as triethylamine and sodium acetate may be advantageous.

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

(Iii) Manufacturing method of compound of formula (c-C) The compound of formula (c-C) as a raw material can be produced in the following manner.

Using DMF as a solvent, the meta-nitroaniline is reacted with _{the carboxylic halide represented by R C3-} COX (R _C3 represents an alkyl group with 1 to 14 carbon atoms, and X is a halogen atom) to obtain the formula (c-C1) The compound represented.

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

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

Alternatively, the compound represented by the formula (c-C2) can be reacted with a _{halogenated hydrocarbon represented by R C1} -X (R _C1 represents an alkyl group with 1 to 14 carbon atoms, and X represents a halogen atom), and then according to a known reaction, Introduce R _C2 (R _C2 represents an alkyl group with 1 to 14 carbon atoms). For example, (R _C2 ) ₂ SO ₄ can be used to introduce R _C2 .

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

The compound represented by the formula (D) is obtained by making the 4-nitroaniline derivative represented by the formula (dD) (in the formula (dD), X _D and Y _D each independently represent a hydrogen atom, a halogen atom, or a cyanide Group) and the compound represented by formula (dC) (in formula (dC), R _D1 represents an alkyl group with 1 to 14 carbons, and R _D2 represents an alkyl group with 1 to 14 carbons or substituted by CN An alkyl group having 1 to 14 carbon atoms; wherein _{at least one of R D1} and R _D2 is an alkyl group having 4 to 14 carbon atoms) is obtained by coupling.

(I) Diazotization of compound of formula (d-D) First, in an inorganic acid or an organic carboxylic acid, the compound represented by formula (d-D) is diazotized using a nitrosating agent or nitrososulfuric acid in the presence of additional water as appropriate to obtain a diazonium compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Moreover, as an inorganic acid, hydrochloric acid, phosphoric acid, and sulfuric acid are mentioned, for example, Preferably, sulfuric acid is mentioned. The nitrosating agent used is alkali metal nitrite, such as sodium nitrite in a solid state or an aqueous solution state.

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

The compound represented by the formula (d-D) is usually widely used as the raw material of azo disperse dyes.

(Ii) Coupling with the compound of formula (d-D) For example, at a temperature range of -5 to 10°C, a solution or suspension of a compound represented by formula (dC) in an alcohol (for example, methanol) is added to a solution of a diazonium compound of formula (dD) to obtain the formula (D) ) Represented by the compound.

The pH value of the compound solution or suspension represented by the formula (d-C) is preferably weakly acidic, and the addition of buffers such as triethylamine and sodium acetate may be advantageous.

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

(Iii) Manufacturing method of compound of formula (d-C) The compound of formula (d-C) as a raw material can be produced in the following manner.

Using DMF as a solvent, make aniline and R _D1 -X and R _D2 -X (R _D1 represents an alkyl group with 1 to 14 carbons, and R _D2 represents an alkyl group with 1 to 14 carbons or a CN-substituted carbon number 1 to 14 is an alkyl group; 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) represented by the halogenated alkyl group is reacted to obtain the formula (dC).

Alternatively, aniline can _{be reacted with halogenated hydrocarbon represented by R D1} -X (R _D1 represents an alkyl group with 1 to 14 carbon atoms, X represents a halogen atom), and then according to a known reaction, R _D2 (R _D2 represents carbon number 1 to 14 alkyl). For example, (R _D2 ) ₂ SO ₄ can be used to import R _D2 .

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

The compound represented by the above formula (E) is obtained by combining the 4-nitroaniline derivative represented by the formula (eD) (in the formula (eD), X _E and Y _E represent halogen atoms) with the diazonium compound of the formula ( The compound represented by eC) (in formula (eC), R _E represents an alkyl group having 4 to 18 carbon atoms) is obtained by coupling.

(I) Diazotization of compound of formula (e-D) First, in an inorganic acid or an organic carboxylic acid, the compound represented by the formula (e-D) is diazotized using a nitrosating agent or nitrososulfuric acid in the presence of additional water as appropriate to obtain a diazonium compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Moreover, as an inorganic acid, hydrochloric acid, phosphoric acid, and sulfuric acid are mentioned, for example, Preferably, sulfuric acid is mentioned. The nitrosating agent used is alkali metal nitrite, such as sodium nitrite in a solid state or an aqueous solution state.

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

Furthermore, the compound represented by the formula (e-D) is generally widely used as a raw material for azo disperse dyes.

(Ii) Coupling with the compound of formula (e-C) For example, at a temperature range of -5 to 10°C, a solution or suspension of the compound represented by the formula (eC) is added to the solution or suspension of the diazonium compound of the formula (eD) to obtain the formula (E) ) Represented by the compound.

The pH value of the compound solution or suspension represented by formula (e-C) is preferably weakly acidic, and the addition of buffers such as triethylamine and sodium acetate may be advantageous.

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

(Iii) Manufacturing method of compound of formula (e-C) The compound of formula (e-C) as a raw material can be produced in the following manner.

Using DMF as a solvent, the 2-phenyl-1H-indole represented by the formula (e-C1) and R _E1 -X (R _E1 represents an alkyl group with 4 to 18 carbon atoms, and X is a halogen atom) The alkyl halide reacts to obtain the formula (eC).

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

The compound represented by the above formula (F) is represented by the diazonium compound of the 3-amino-5-nitro-2,1-benzisothiazole represented by the formula (fD) and the formula (fC) Compounds (in formula (fC), R _F1 and R _F2 each independently represent an alkyl group having 4 to 14 carbon atoms) are obtained by coupling.

(I) Diazotization of compound of formula (f-D) First, in an inorganic acid or an organic carboxylic acid, the compound represented by the formula (f-D) is diazotized using a nitrosating agent or nitrosyl sulfuric acid in the presence of additional water as appropriate to obtain a diazonium compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Moreover, as an inorganic acid, hydrochloric acid, phosphoric acid, and sulfuric acid are mentioned, for example, Preferably, sulfuric acid is mentioned. The nitrosating agent used is alkali metal nitrite, such as sodium nitrite in a solid state or an aqueous solution state.

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

The compound represented by the formula (f-D) is usually widely used as the raw material of azo disperse dyes.

(Ii) Coupling with the compound of formula (f-C) For example, at a temperature range of -5 to 10°C, a solution or suspension of the compound represented by the formula (fC) in an alcohol (such as methanol) is added to the solution of the diazonium compound of the formula (fD) to obtain the formula (F) ) Represented by the compound.

The pH value of the compound solution or suspension represented by the formula (f-C) is preferably weakly acidic, and the addition of buffering agents such as triethylamine and sodium acetate may be advantageous.

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

(Iii) Manufacturing method of compound of formula (f-C) The compound of formula (f-C) as a raw material can be produced in the following manner.

Using DMF as a solvent to react aniline with a _{halogenated alkyl group represented by R F1} -X and R _F2 -X (R _F1 and R _F2 each independently represent an alkyl group with 4 to 14 carbon atoms, and X is a halogen atom), And get the formula (fC).

Or it is also possible to react aniline with _{halogenated hydrocarbon represented by R F1} -X (R _F1 represents an alkyl group with 4 to 14 carbon atoms, X represents a halogen atom), and then introduce R _F2 (R _F2 represents carbon number) according to a known reaction 4 to 14 alkyl). For example, (R _F2 ) ₂ SO ₄ can be used to introduce R _F2 .

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

The compound represented by formula (G) is prepared by making 5-aminoanthracene [9,1-cd]isothiazol-6-one represented by formula (g) in an inert solvent such as toluene, xylene, chlorobenzene, etc. It _{is obtained by reacting with a carboxyhalide represented by R G} -COX (R _G represents an alkyl group with 7 to 18 carbon atoms, and X is a halogen atom).

The reaction temperature is preferably 80°C to 140°C, more preferably 110 to 140°C.

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

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

＜Dyes for dyeing polyolefin fibers with supercritical carbon dioxide＞ The compounds of general formulas (A) to (G) contained in the dye for dyeing polyolefin fibers of the present invention have blue, purple, red, orange, or yellow. The above-mentioned dyes may contain compounds of the general formulae (A) to (G) alone or two or more kinds. When the above-mentioned dyes contain two or more compounds of general formula (A) to (G), dyes for dyeing polyolefin fibers into various hues or blacks can be obtained.

The dye used to dye polyolefin fibers black preferably includes: a compound selected from the group consisting of a compound of general formula (A), a compound of general formula (B), a compound of general formula (C), and a compound of general formula (F) At least one of purple or blue dye compounds in the group consisting of more than one compound, and one or more selected from the group consisting of compounds of general formula (C) and compounds of general formula (D) The red dye compound, and the yellow or orange dye compound containing more than one selected from the group consisting of the compound of general formula (D), the compound of general formula (E) and the compound of general formula (G) At least one of them, more preferably, includes: purple or blue that contains more than one selected from the group consisting of compounds of general formula (A), compounds of general formula (B), and compounds of general formula (F) At least one of the dye compound, the red dye compound of the compound of the general formula (C), and the orange color containing at least one selected from the group consisting of the compound of the general formula (D) and the compound of the general formula (E) The dye compound further preferably includes: a blue dye compound of the compound of general formula (A), a red dye compound of the compound of general formula (C), and an orange dye compound of the compound of general formula (D) .

[Table 1] Dyes for dyeing polyolefin fibers into black Purple or blue dye compound Red dye compound Yellow or orange dye compound Better The compound of general formula (A) The compound of general formula (B) The compound of general formula (C) The compound of general formula (F) Compound of general formula (C) Compound of general formula (D) The compound of general formula (D) The compound of general formula (E) The compound of general formula (G) Better The compound of general formula (A) The compound of general formula (B) The compound of general formula (F) Compound of general formula (C) Compound of general formula (D) Compound of general formula (E) Even better Compound of general formula (A) Compound of general formula (C) Compound of general formula (D)

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

[Table 2] About the mixing ratio Purple or blue dye compound Red dye compound Yellow or orange dye compound The compound of general formula (A) The compound of general formula (B) The compound of general formula (C) The compound of general formula (F) Compound of general formula (C) Compound of general formula (D) Compound of general formula (D), compound of general formula (E) compound of general formula (G) Better 30 to 70% by mass 5 to 25% by mass 15 to 55 mass% Better 40 to 60% by mass 5 to 25% by mass 25 to 45% by mass

The dye of the present invention may further contain additives. Examples of the above additives include: color aids, dispersants, fillers, stabilizers, plasticizers, crystal nucleating agents, modifiers, foaming agents, ultraviolet absorbers, light stabilizers, antioxidants, and antibacterial agents. Agents, antifungal agents, antistatic agents, flame retardants, inorganic fillers, and elastomers for improving impact resistance.

The polyolefin fiber of the dyed material dyed by the dye of the present invention may be, for example, a fiber formed from a polymer selected from the group consisting of propylene, ethylene, 1-butene, 3-methyl-1-butene, 4- Homopolymers of α-olefins such as methyl-1-pentene and 1-octene; copolymers of these α-olefins; or copolymers with other unsaturated monomers capable of copolymerizing with these α-olefins . Moreover, the type of copolymer includes, for example, block copolymers, random copolymers, graft copolymers, and the like. Specific examples of the aforementioned polymers include polypropylene resins such as propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, and propylene-ethylene-(1-butene) copolymers; Low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and other polyethylene resins; poly-1-butene, Poly 4-methyl-1-pentene and so on.

The above-mentioned polymers can be used alone or in combination of two or more to form polyolefin fibers.

As the polyolefin fiber of the dyed article dyed with the dye of the present invention, it is preferably formed of polypropylene resin and/or polyethylene resin, and more preferably formed of polypropylene resin.

The shape of the polyolefin fiber of the dyed article dyed with the dye of the present invention can be, for example, block (molded product, etc.), film, fiber (cloth (woven fabric, knitted fabric, non-woven fabric, etc.), silk (long) Any one of silk, machine-spun yarn, slit yarn, tear yarn, etc.) etc.) is preferably fibrous.

The polyolefin fiber of the dyed object dyed with the dye of the present invention may be a fiber formed by mixing polypropylene resin and/or polyethylene resin with other polymer components and performing bonding. The above-mentioned polyolefin fiber may be blended with polypropylene fiber, blended with other fibers such as polyester.

＜Dyeing method of polyolefin fiber using supercritical carbon dioxide＞ The present invention is a method for dyeing polyolefin fibers using supercritical carbon dioxide, which includes the step of dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the above-mentioned dye of the present invention. In the above method, supercritical carbon dioxide is used as the dyeing medium.

The dyeing method that uses supercritical carbon dioxide as the dyeing medium is compared with the usual dyeing method that uses water as the dyeing medium. Since water is not used during dyeing and no washing step is required, no waste water is produced and no dyeing auxiliaries are required. , The dyeing time is short, it can reuse carbon dioxide as a dyeing medium, etc., so it has attracted attention as an environmentally friendly dyeing method.

In addition, supercritical carbon dioxide is lipophilic, and the dyes and polyolefin resins of the present invention are lipophilic. Therefore, the dyeing medium, the dye, and the dyed material have a high affinity for each, and as a result, high-quality dyed products can be obtained.

The dyeing step in the method of the present invention is preferably performed at a temperature above 31°C and a pressure above 7.4 MPa. The reason is that the above-mentioned dyeing temperature and dyeing pressure must be above the critical point (31°C, 7.4 MPa) of carbon dioxide as the dyeing medium.

In the above-mentioned dyeing step, the dyeing temperature is mainly determined by the type of resin of the dyed fiber. The above-mentioned dyeing temperature is usually in the range of 60 to 180°C, preferably in the range of 80 to 160°C.

In the above-mentioned dyeing step, the dyeing pressure is mainly determined by the type of resin of the dyed fiber. The above-mentioned dyeing pressure is usually in the range of about 7.4 to 40.0 MPa, preferably 20 to 30 MPa.

The dyeing time in the above-mentioned dyeing step is determined by the type of resin, dyeing temperature and dyeing time of the dyed fiber. The aforementioned dyeing time is usually about 10 to 120 minutes, preferably 30 to 90 minutes.

In the dyeing step, the concentration of the dye relative to the fiber depends on the type and processing state of the dyed fiber. When the dyed fiber is fibrous, the concentration of the dye relative to the fiber is 0.1 to 6.0 o.m.f. (on the mass of fiber, based on the fiber quality), preferably 0.1 to 4.0 o.m.f.

In the dyeing method of the present invention, the bath ratio (the mass ratio of the dyed material: carbon dioxide) depends on the type and processing state of the dyed material. The above bath ratio is usually 1:2 to 1:100, preferably 1:5 to 1:75. When the dyed material is a polypropylene cloth wound on a suitable flat cone, in the dyeing method of the present invention, the bath 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 uses of the above polyolefin fibers include clothing, underwear, hats, socks, gloves, sports clothing and other clothing, vehicle interior materials such as seat cushions, carpets, curtains, cushions, sofa covers, cushion covers, etc. Supplies etc.

Hereinafter, the present invention will be explained in more detail with examples, but the aspects of the present invention are not limited to them.

[Example] (Synthesis example 1) [Synthesis of blue dye compound (A-1)] The blue dye compound (A-1) is manufactured according to the following process.

1-A. Synthesis of coupling agent compound (C1) and preparation of coupling agent component solution (step 1) P-anisidine (purchased as a commercially available product) (24.6 g) was dissolved in DMF (35 g), and pyridine (19 g) was added dropwise. After adding n-octyl chloride (purchased as a commercially available product) (34.2 g) dropwise, it was heated to 110°C and stirred for 1 hour. After cooling to room temperature, 2 M hydrochloric acid (150 ml) was added to precipitate a precipitate. The mixture was separated by filtration, washed with water, and dried to obtain N-(4-methoxyphenyl)octamide represented by the following formula (C1a) as a crude product (53.1 g, yield 106.5%) .

式（C1a）

Formula (C1a)

(Step 2) Slowly add the N-(4-methoxyphenyl)octamide (12.5 g) obtained in step 1 above to concentrated sulfuric acid (30 g) cooled to 5°C in the range of 5 to 10°C. Concentrated nitric acid (4.57 g) was added dropwise to the mixture in the range of 5 to 10°C for 1 hour, and then stirred at the same temperature for 1 hour. The reaction mixture was blown into ice water (150 g), ethyl acetate (100 g) was added, and the organic phase was extracted. After washing the extract with saturated brine, the solvent was distilled off under reduced pressure to obtain N-(3-nitro-4-methoxy group represented by the following formula (C1b) as a crude product Phenyl) octamide (16.9 g, yield 114.8%).

式（C1b）

Formula (C1b)

(Step 3) The mixture of N-(3-nitro-4-methoxyphenyl)octamide (16.9 g), tin (8.9 g) and methanol (7.5 g) obtained in step 2 above was cooled to 5°C. After 1 hour of adding concentrated hydrochloric acid (31.4 g) to the mixture, the temperature was raised to 75 to 80°C and stirred for 40 minutes. After cooling the reaction mixture to 10°C, 48% aqueous sodium hydroxide solution (55.2 ml) was slowly added in the range of 10 to 20°C. The mixture was separated by filtration, washed with water, and dried to obtain N-(3-amino-4-methoxyphenyl)octamide represented by the following formula (C1c) (9.19 g, yield 69.5%) .

式（C1c）

Formula (C1c)

(Step 4) Combine the N-(3-amino-4-methoxyphenyl)octamide (13.2 g), triethylamine (15 g), DMF (15 g) and 1-bromooctane obtained in step 3 above A mixture of alkane (purchased as a commercially available product) (38.6 g) was heated to 120°C, and stirred at the same temperature for 3 hours to obtain N-[3-(N,N) represented by the following formula (C1) -Dioctylamino)-4-methoxyphenyl]octamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C1).

式（C1）

Formula (C1)

1-B. Preparation of diazonium component solution (Step 5) Slowly add 2-bromo-4,6-dinitrogen represented by the following formula (D1) to a mixture of concentrated sulfuric acid (16 g) and 43% nitrososulfuric acid (12.8 g) in the range of 25 to 30°C Benzylaniline (13.1 g). The mixture was stirred at 30 to 40°C for 2 hours, thereby obtaining a diazo component solution.

式（D1）

Formula (D1)

1-C. Synthesis of Blue Dye Compound (A-1) by Coupling Reaction (Step 6) Triethylamine is appropriately added to the above-mentioned coupling agent component solution obtained in the above-mentioned Step 4 in the range of 0 to 10°C (84 g), and the diazonium component solution obtained in step 5 above was added dropwise over 2 hours at the same time to carry out the coupling reaction. After stirring the mixture in the range of 0 to 10°C for 30 minutes, the product was separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture reached 1.0 mass % Or less, and the blue dye compound (5.93 g, yield 15.5%) represented by the following formula (A-1) was obtained. The structure of the blue staining compound was confirmed by LCMS analysis (m/z 761 (M ⁺ )).

式（A-1）

Formula (A-1)

(Synthesis example 2) [Synthesis of blue dye compound (A-2)] The blue dye compound (A-2) is manufactured according to the following process.

2-A. Synthesis of coupling agent compound (C2) and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 1, pentanyl chloride (25.3 g) was used instead of n-octyl chloride, and except for that, the same procedure as Steps 1 to 4 of Synthesis Example 1 was performed to obtain the following formula (C2) The N-[3-(N,N-dioctylamino)-4-methoxyphenyl]pentanamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C2).

式（C2）

Formula (C2)

2-B. Synthesis of blue dye compound (A-2) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C2) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of Synthesis Example 1, and obtained the blue dye compound (8.03 g, yield 22.3%) represented by following formula (A-2). The structure of the blue staining compound was confirmed by LCMS analysis (m/z 719 (M ⁺ )).

式（A-2）

Formula (A-2)

(Synthesis example 3) [Synthesis of blue dye compound (A-3)] The blue dye compound (A-3) is manufactured according to the following process.

3-A. Synthesis of coupling agent compound (C3) and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 1, propyl chloride (19.4 g) was used instead of n-octyl chloride. The procedure was performed in the same manner as Steps 1 to 4 of Synthesis Example 1, except that propylene chloride (19.4 g) was used to obtain the following formula (C3) The N-[3-(N,N-dioctylamino)-4-methoxyphenyl]propanamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C3).

式（C3）

Formula (C3)

3-B. Synthesis of blue dye compound (A-3) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C3) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of the synthesis example 1, and obtained the blue dye compound (5.85 g, yield 16.9%) represented by following formula (A-3). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 691 (M ⁺ )).

式（A-3）

Formula (A-3)

(Synthesis example 4) [Synthesis of blue dye compound (A-4)] The blue dye compound (A-4) is manufactured according to the following process.

4-A. Synthesis of coupling agent compound C4 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 1, except that 2-ethylhexyl chloride (34.2 g) was used instead of n-octyl chloride, the operation was performed in the same manner as Steps 1 to 4 of Synthesis Example 1 to obtain the following formula ( C4) N-[3-(N,N-dioctylamino)-4-methoxyphenyl]-2-ethylhexanamide represented by. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C4).

式（C4）

Formula (C4)

4-B. Synthesis of blue dye compound (A-4) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C4) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of the synthesis example 1, and obtained the blue dye compound (9.63 g, yield 25.3%) represented by following formula (A-4). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 761 (M ⁺ )).

式（A-4）

Formula (A-4)

(Synthesis example 5) [Synthesis of blue dye compound (A-5)] The blue dye compound (A-5) is manufactured according to the following process.

5-A. Synthesis of coupling agent compound C5 and preparation of coupling agent component solution (step 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)octamide, except for this, the same operation as in Step 4 of Synthesis Example 1 was carried out to obtain N-[3-(N,N-Di) represented by the following formula (C5) Octylamino)-4-methoxyphenyl]acetamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C5).

式（C5）

Formula (C5)

5-B. Synthesis of blue dye compound (A-5) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C5) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of the synthesis example 1, and obtained the blue dye compound (20.3 g, yield 60.0%) represented by following formula (A-5). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 677 (M ⁺ )).

式（A-5）

Formula (A-5)

(Synthesis example 6) [Synthesis of blue dye compound (A-6)] The blue dye compound (A-6) is manufactured according to the following process.

6-A. Synthesis of coupling agent compound (C6) and preparation of coupling agent component solution (step 1) In Step 4 of Synthesis Example 1, 1-bromododecane (49.8 g) was used instead of 1-bromooctane, and N-(3-amino-4-methoxyphenyl)acetamide (9.0 g) ) In place of N-(3-amino-4-methoxyphenyl)octamide, the operation was performed in the same manner as Step 4 of Synthesis Example 1 except that N- represented by the following formula (C6) was obtained. [3-(N,N-Di(dodecyl)amino)-4-methoxyphenyl]acetamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C6).

式（C6）

Formula (C6)

6-B. Synthesis of blue dye compound (A-6) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C6) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of the synthesis example 1, and obtained the blue dye compound (19.3 g, yield 48.9%) represented by following formula (A-6). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 789 (M ⁺ )).

式（A-6）

Formula (A-6)

(Synthesis example 7) [Synthesis of Blue Dye Compound (A-7)] The blue dye compound (A-7) is manufactured according to the following process.

7-A. Synthesis of coupling agent compound C7 and preparation of coupling agent component solution (step 1) In Step 4 of Synthesis Example 1, except that 1-bromoethane (27.3 g) was used instead of 1-bromooctane, the operation was performed in the same manner as Step 4 of Synthesis Example 1 to obtain the following formula (C7) Represented by N-[3-(N,N-diethylamino)-4-methoxyphenyl]octamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C7).

式（C7）

Formula (C7)

7-B. Synthesis of blue dye compound (A-7) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C7) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of Synthesis Example 1, and obtained the blue dye compound (7.71 g, yield 26.0%) represented by following formula (A-7). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 593 (M ⁺ )).

式（A-7）

Formula (A-7)

(Synthesis example 8) [Synthesis of blue dye compound (A-8)] The blue dye compound (A-8) is manufactured according to the following process.

8-A. Synthesis of coupling agent compound C8 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 1, except that 4-ethoxyaniline (27.4 g) was used instead of p-anisidine, the operation was performed in the same manner as Steps 1 to 4 of Synthesis Example 1 to obtain the following formula (C8 ) Represented by N-[3-(N,N-dioctylamino)-4-ethoxyphenyl]octamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C8).

式（C8）

Formula (C8)

8-B. Synthesis of blue dye compound (A-8) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C8) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of Synthesis Example 1, and obtained the blue dye compound (4.50 g, yield 11.6%) represented by following formula (A-8). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 775 (M ⁺ )).

式（A-8）

Formula (A-8)

(Synthesis Example 9) [Synthesis of blue dye compound (B-1)] The blue dye compound (B-1) is manufactured according to the following process.

9-A. Synthesis of coupling agent compound C9 and preparation of coupling agent component solution (step 1) Except that 3-nitroaniline (27.6 g) was used instead of p-anisidine, the same procedure as in Step 1 of Synthesis Example 1 was carried out to obtain N-( represented by the following formula (C9a) as a crude product 3-nitrophenyl)octamide (53.6 g, yield 101.4%).

式（C9a）

Formula (C9a)

(Step 2) Use N-(3-nitrophenyl) octamide (13.2 g) instead of N-(3-nitro-4-methoxyphenyl) octamide. Otherwise, follow Step 3 of Synthesis Example 1 The same operation was performed to obtain N-(3-aminophenyl)octamide (9.48 g, yield 80.9%) represented by the following formula (C9b).

式（C9b）

Formula (C9b)

(Step 3) Use N-(3-aminophenyl) octamide (11.7 g) instead of N-(3-amino-4-methoxyphenyl) octamide. Otherwise, follow step 4 of Synthesis Example 1 In the same manner, N-[3-(N,N-dioctylamino)phenyl]octamide represented by the following formula (C9) was obtained. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C9).

式（C9）

Formula (C9)

9-B. Preparation of diazonium component solution (Step 4) Slowly add the 3-amino-5-nitro group represented by the following formula (D2) to the mixture of concentrated sulfuric acid (29 g) and 43% nitrososulfuric acid (12.7 g) in the range of 0 to 5°C 2,1-Benzisothiazole (8.15 g). After slowly adding 80% acetic acid (10 g) dropwise to the mixture in the range of 0 to 5°C, the mixture was stirred at the same temperature for 2 hours, thereby obtaining a diazo component solution.

式（D2）

Formula (D2)

9-C. Synthesis of blue dye compound (B-1) by coupling reaction (Step 5) Add triethylamine (43 g) to the above-mentioned coupling agent component solution (C9) within the range of 0 to 10°C At the same time, the diazonium component solution (D2) was added dropwise over 2 hours to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. The blue dye compound (20.9 g, yield 62.9%) represented by the following formula (B-1) was obtained. The structure of the blue dye compound was confirmed by LCMS analysis (m/z 665 (M ⁺ )).

式（B-1）

Formula (B-1)

(Synthesis example 10) [Synthesis of blue dye compound (B-2)] The blue dye compound (B-2) is manufactured according to the following process.

10-A. Synthesis of coupling agent compound C10 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 9, pentyl chloride (25.3 g) was used instead of n-octyl chloride, and except that the operation was performed in the same manner as Steps 1 to 3 of Synthesis Example 9 to obtain the following formula (C10) The N-[3-(N,N-dioctylamino)phenyl]pentanamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C10).

式（C10）

Formula (C10)

10-B. Synthesis of blue dye compound (B-2) using coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C10) obtained in step 1 instead of the compound of formula (C9), Except for this, it carried out similarly to the steps 4 and 5 of the synthesis example 9, and obtained the blue dye compound (9.47 g, yield 30.4%) represented by following formula (B-2). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 623 (M ⁺ )).

式（B-2）

Formula (B-2)

(Synthesis example 11) [Synthesis of blue dye compound (B-3)] The blue dye compound (B-3) is manufactured according to the following process.

11-A. Synthesis of coupling agent compound C11 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 9, propylene chloride (19.4 g) was used instead of n-octyl chloride. The procedure was performed in the same manner as Steps 1 to 3 of Synthesis Example 9 except that propyl chloride (19.4 g) was used to obtain the following formula (C11) The N-[3-(N,N-dioctylamino)phenyl]propanamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C11).

式（C11）

Formula (C11)

11-B. Synthesis of blue dye compound (B-3) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C11) obtained in step 1 instead of the compound of formula (C9), Except for this, it carried out similarly to the steps 4 and 5 of the synthesis example 9, and obtained the blue dye compound (13.4 g, yield 45.0%) represented by following formula (B-3). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 595 (M ⁺ )).

式（B-3）

Formula (B-3)

(Synthesis example 12) [Synthesis of blue dye compound (B-4)] The blue dye compound (B-4) is manufactured according to the following process.

12-A. Synthesis of coupling agent compound C12 and preparation of coupling agent component solution (step 1) In Step 3 of Synthesis Example 9, 3'-aminoacetaniline (7.50 g) was used instead of N-(3-aminophenyl)octamide, except that it was the same as Step 3 of Synthesis Example 9 The operation was performed to obtain N-[3-(N,N-dioctylamino)phenyl]acetamide represented by the following formula (C12). Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C12).

式（C12）

Formula (C12)

12-B. Synthesis of Blue Dye Compound (B-4) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C12) instead of the compound of formula (C9), and in addition, synthesize Steps 4 and 5 of Example 9 were similarly operated to obtain a blue dye compound (20.3 g, yield 69.9%) represented by the following formula (B-4). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 581 (M ⁺ )).

式（B-4）

Formula (B-4)

(Synthesis example 13) [Synthesis of blue dye compound (B-5)] The blue dye compound (B-5) is manufactured according to the following process.

13-A. Synthesis of coupling agent compound C13 and preparation of coupling agent component solution (step 1) In Step 3 of Synthesis Example 9, 1-bromododecane (49.8 g) was used instead of 1-bromooctane, and 3'-aminoacetaniline (7.50 g) was used instead of N-(3-aminophenyl) ) Octanamide, except for this, proceed in the same manner as Step 3 of Synthesis Example 9 to obtain N-[3-(N,N-di(dodecyl)amino) represented by the following formula (C13) Phenyl]acetamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C13).

式（C13）

Formula (C13)

13-B. Synthesis of blue dye compound (B-5) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C13) obtained in step 1 instead of the compound of formula (C9), Except for this, it carried out similarly to Steps 4 and 5 of Synthesis Example 9 to obtain a blue dye compound (9.81 g, yield 28.3%) represented by the following formula (B-5). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 693 (M ⁺ )).

式（B-5）

Formula (B-5)

(Synthesis example 14) [Synthesis of Blue Dye Compound (B-6)] The blue dye compound (B-6) is manufactured according to the following process.

14-A. Synthesis of coupling agent compound C14 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 9, propylene chloride (19.4 g) was used instead of n-octyl chloride, and in Step 3 of Synthesis Example 9, 1-bromododecane (49.8 g) was used instead of 1-bromooctane, Except for this, the operation was performed in the same manner as Steps 1 to 3 of Synthesis Example 9 to obtain N-[3-(N,N-di(dodecyl)amino)phenyl] represented by the following formula (C14) Acetamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C14).

式（C14）

Formula (C14)

14-B. Synthesis of Blue Dye Compound (B-6) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C14) instead of the compound of formula (C9). Otherwise, synthesize Steps 4 and 5 of Example 9 were similarly operated to obtain a blue dye compound (5.73 g, yield 16.2%) represented by the following formula (B-6). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 707 (M ⁺ )).

式（B-6）

Formula (B-6)

(Synthesis example 15) [Synthesis of blue dye compound (B-7)] The blue dye compound (B-7) is manufactured according to the following process.

15-A. Synthesis of coupling agent compound C15 and preparation of coupling agent component solution (step 1) In Step 3 of Synthesis Example 9, 3'-aminoacetaniline (7.50 g) was used instead of N-(3-aminophenyl)octamide, and 1-bromo-2-ethylhexane (38.6 g) In place of 1-bromooctane, except for this, the same operation as in Step 3 of Synthesis Example 9 was carried out to obtain N-[3-[N,N-bis(2-ethane) represented by the following formula (C15) Hexyl)amino]phenyl]propanamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C15).

式（C15）

Formula (C15)

15-B. Synthesis of blue dye compound (B-7) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C15) instead of the compound of formula (C9), and in addition, synthesize Steps 4 and 5 of Example 9 were similarly operated to obtain a blue dye compound (4.72 g, yield 16.2%) represented by the following formula (B-7). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 581 (M ⁺ )).

式（B-7）

Formula (B-7)

(Synthesis example 16) [Synthesis of blue dye compound (B-8)] The blue dye compound (B-8) is manufactured according to the following process.

16-A. Synthesis of coupling agent compound C16 and preparation of coupling agent component solution (step 1) In Step 3 of Synthesis Example 9, except that 1-bromoethane (27.3 g) was used instead of 1-bromooctane, the operation was performed in the same manner as Steps 1 to 3 of Synthesis Example 9 to obtain the following formula (C16 ) Represented by N-[3-(N,N-diethylamino)phenyl]octamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C16).

式（C16）

Formula (C16)

16-B. Synthesis of blue dye compound (B-8) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C16) obtained in step 1 instead of the compound of formula (C9), Except for this, it carried out similarly to the steps 4 and 5 of the synthesis example 9, and obtained the blue dye compound (23.2 g, 93.4% yield) represented by following formula (B-8). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 497 (M ⁺ )).

式（B-8）

Formula (B-8)

(Synthesis example 17) [Synthesis of Red Dye Compound (C-1)] The red dye compound (C-1) is manufactured according to the following process.

17-A. Preparation of diazonium component solution (step 1) Add 2-chloro-4-nitroaniline represented by the following formula (D3) (8.65 g) Stir at the same temperature for 2 hours, thereby obtaining a diazo component solution.

式（D3）

Formula (D3)

17-B. Synthesis of Red Dye Compound (C-1) Using Coupling Reaction (Step 2) The preparation of the coupling agent component solution composed of the compound of formula (C9) is the same as Steps 1 to 3 of Synthesis Example 9 Way to proceed. Triethylamine (28 g) is appropriately added to the above-mentioned coupling agent component solution in the range of 0 to 10°C, and the above-mentioned diazo component solution obtained in step 1 is added dropwise over 2 hours to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. The red dye compound (24.3 g, yield 75.7%) represented by the following formula (C-1) was obtained. The structure of the red dye compound was confirmed by LCMS analysis (m/z 642 (M ⁺ )).

式（C-1）

Formula (C-1)

(Synthesis Example 18) [Synthesis of Red Dye Compound (C-2)] The red dye compound (C-2) is manufactured according to the following process.

As the coupling agent component solution, except that the compound of formula (C10) was used instead of the compound of formula (C9), the operation was performed in the same manner as steps 1 and 2 of Synthesis Example 17 to obtain the following formula (C-2) The red dye compound (10.4 g, yield 34.7%). The structure of the red dye compound was confirmed by LCMS analysis (m/z 600 (M ⁺ )).

式（C-2）

Formula (C-2)

(Synthesis Example 19) [Synthesis of Red Dye Compound (C-3)] The red dye compound (C-3) is manufactured according to the following process.

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

式（C-3）

Formula (C-3)

(Synthesis example 20) [Synthesis of Red Dye Compound (C-4)] The red dye compound (C-4) is manufactured according to the following process.

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

式（C-4）

Formula (C-4)

(Synthesis example 21) [Synthesis of Red Dye Compound (C-5)] The red dye compound (C-5 is manufactured according to the following procedure.

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

式（C-5）

Formula (C-5)

(Synthesis example 22) [Synthesis of Red Dye Compound (C-6)] The red dye compound (C-6) is manufactured according to the following process.

22-A. Synthesis of coupling agent compound C17 and preparation of coupling agent component solution (step 1) In Step 3 of Synthesis Example 9, 3'-aminoacetaniline (7.50 g) was used instead of N-(3-aminophenyl)octamide, and 1-bromobutane (27.4 g) was used instead of 1- Except for this, the operation was performed in the same manner as in Step 3 of Synthesis Example 9 to obtain N-[3-(N,N-dibutylamino)phenyl]acetyl represented by the following formula (C17) amine. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C17).

式（C17）

Formula (C17)

22-B. Synthesis of Red Dye Compound (C-6) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C17) instead of the compound of formula (C9). In addition, follow the synthesis example Steps 1 and 2 of 17 were performed in the same manner to obtain a red dye compound (19.6 g, yield 87.9%) represented by the following formula (C-6). The structure of the above red dye compound was confirmed by LCMS analysis (m/z 446 (M ⁺ )).

式（C-6）

Formula (C-6)

(Synthesis example 23) [Synthesis of Red Dye Compound (C-7)] The red dye compound (C-7) is manufactured according to the following process.

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

式（C-7）

Formula (C-7)

(Synthesis example 24) [Synthesis of orange dye compound (D-1)] The orange dye compound (D-1) is manufactured according to the following process.

24-A. Synthesis of coupling agent compound C18 and preparation of coupling agent component solution (step 1) Except that aniline (4.66 g) was used instead of N-(3-amino-4-methoxyphenyl)octamide, the operation was carried out in the same manner as step 4 of Synthesis Example 1 to obtain the following formula (C18) Said N,N-dioctylaniline. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C18).

式（C18）

Formula (C18)

24-B. Preparation of diazonium component solution (Step 2) Add the 2,6-dichloro-4-nitro group represented by the following formula (D4) to a mixture of concentrated sulfuric acid (17 g) and 43% nitrososulfuric acid (14.7 g) in the range of 25 to 30°C Aniline (10.4 g) was stirred at the same temperature for 2 hours to obtain a diazo component solution.

式（D4）

Formula (D4)

24-C. Synthesis of Orange Dye Compound (D-1) Using Coupling Reaction (Step 3) The above-mentioned coupling agent component composed of the compound of formula (C18) obtained in Step 1 in the range of 0 to 10°C Triethylamine (20 g) was appropriately added to the solution, and the diazonium component solution obtained in step 2 was added dropwise over 2 hours at the same time to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. An orange dye compound (23.1 g, yield 86.4%) represented by the following formula (D-1) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m/z 535 (M ⁺ )).

式（D-1）

Formula (D-1)

(Synthesis Example 25) [Synthesis of orange dye compound (D-2)] The orange dye compound (D-2) is manufactured according to the following process.

25-A. Synthesis of coupling agent compound C19 and preparation of coupling agent component solution (step 1) Use aniline (4.66 g) instead of N-(3-amino-4-methoxyphenyl)octamide and 1-bromododecane (49.8 g) instead of 1-bromooctane. In addition, with Step 4 of Synthesis Example 1 was similarly operated to obtain N,N-bis(dodecyl)aniline represented by the following formula (C19). Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C19).

式（C19）

Formula (C19)

25-B. Synthesis of Orange Dye Compound (D-2) Using Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C19) instead of the compound of formula (C18). Otherwise, follow the synthesis example Steps 2 and 3 of 24 were similarly operated to obtain an orange dye compound (14.1 g, yield 43.6%) represented by the following formula (D-2). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 647 (M ⁺ )).

式（D-2）

Formula (D-2)

(Synthesis Example 26) [Synthesis of orange dye compound (D-3)] The orange dye compound (D-3) is manufactured according to the following process.

26-A. Synthesis of coupling agent compound C20 and preparation of coupling agent component solution (step 1) Use aniline (4.66 g) instead of N-(3-amino-4-methoxyphenyl)octamide, and use 1-bromobutane (27.4 g) instead of 1-bromooctane. In addition, the synthesis Step 4 of Example 1 was operated in the same manner to obtain N,N-dibutylaniline represented by the following formula (C20). Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C20).

式（C20）

Formula (C20)

26-B. Synthesis of Orange Dye Compound (D-3) Using Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C20) instead of the compound of formula (C18). In addition, follow the synthesis example Steps 2 and 3 of 24 were similarly operated to obtain an orange dye compound (10.2 g, yield 48.2%) represented by the following formula (D-3). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 423 (M ⁺ )).

式（D-3）

Formula (D-3)

(Synthesis Example 27) [Synthesis of yellow dye compound (G-1)] The yellow dye compound (G-1) is manufactured according to the following process.

To the mixture of 2-hexyldecanoic acid (30.8 g) and toluene (30 g) was added dropwise a mixture of sulfite chloride (14.3 g) and toluene (20 g). After a mixture of pyridine (9.49 g) and toluene (30 g) was slowly added dropwise to the mixture over 1 hour, the temperature was raised to 110°C and stirred for 1 hour. After cooling to room temperature, a mixture of 5-aminoanthracene [9,1-cd]isothiazol-6-one (25.2 g) and toluene (30 g) was added dropwise. After heating to 110° C. and stirring for 2 hours, the solvent was distilled off under reduced pressure, and methanol (100 g) was added to precipitate a precipitate. The mixture was separated by filtration, washed with methanol, then washed with water, and dried at 60°C until the water content became 1.0% by mass or less, to obtain a yellow dye compound represented by the following formula (G-1) (36.7 g, yield 74.7%). The structure of the yellow dye compound was confirmed by LCMS analysis (m/z 491 (M ⁺ )).

式（G-1）

Formula (G-1)

(Synthesis example 28) [Synthesis of yellow dye compound (G-2)] The yellow dye compound (G-2) is manufactured according to the following process.

After adding dropwise n-octyl chloride (19.5 g) to a mixture of 5-aminoanthracene [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 stirred for 1 hour. After the mixture was cooled to room temperature, methanol (150 g) was added to precipitate a precipitate. This mixture was separated by filtration, washed with methanol, and dried to obtain a yellow dye compound (31.8 g, yield 83.9%) represented by the following formula (G-2). The structure of the yellow dye compound was confirmed by LCMS analysis (m/z 379 (M ⁺ )).

式（G-2）

Formula (G-2)

(Synthesis Example 29) [Synthesis of Purple Dye Compound (F-1)] The purple dye compound (F-1) is manufactured according to the following process.

The preparation of the coupling agent component solution consisting of the compound of formula (C18) was carried out 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 the same as in Synthesis Example 9. Step 4 is performed in the same way. Triethylamine (35 g) is appropriately added to the above-mentioned coupling agent component solution in the range of 0 to 10°C, and the above-mentioned diazo component solution is added dropwise over 2 hours to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. The purple dye compound (13.0 g, yield 49.6%) represented by the following formula (F-1) was obtained. The structure of the purple dye compound was confirmed by LCMS analysis (m/z 524 (M ⁺ )).

式（F-1）

Formula (F-1)

(Synthesis example 30) [Synthesis of orange dye compound (D-4)] The orange dye compound (D-4) is manufactured according to the following process.

30-A. Preparation of diazonium component solution (step 1) Add 4-nitroaniline (6.91 g) represented by the following formula (D5) to a mixture of concentrated sulfuric acid (17 g) and 43% nitrososulfuric acid (14.7 g) in the range of 30 to 35°C. Stir at the same temperature for 2 hours, thereby obtaining a diazonium component solution.

式（D5）

Formula (D5)

30-B. Synthesis of Orange Dye Compound (D-4) Using Coupling Reaction (Step 2) The preparation of the coupling agent component solution composed of the compound of formula (C18) was carried out in the same manner as Step 1 of Synthesis Example 24 . Triethylamine (20 g) is appropriately added to the above-mentioned coupling agent component solution in the range of 0 to 10°C, and the above-mentioned diazo component solution obtained in step 1 is added dropwise over 1 hour to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. An orange dye compound (12.5 g, yield 53.5%) represented by the following formula (D-4) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m/z 467 (M ⁺ )).

式（D-4）

Formula (D-4)

(Synthesis example 31) [Synthesis of orange dye compound (D-5)] The orange dye compound (D-5) is manufactured according to the following process.

31-A. Preparation of diazo component solution (step 1) Add the 2,6-dibromo-4-nitro group represented by the following formula (D6) to the mixture of concentrated sulfuric acid (17 g) and 43% nitrososulfuric acid (14.7 g) in the range of 25 to 30°C Aniline (14.8 g) was stirred at the same temperature for 2 hours to obtain a diazo component solution.

式（D6）

Formula (D6)

31-B. Synthesis of Orange Dye Compound (D-5) Using Coupling Reaction (Step 2) The preparation of the coupling agent component solution composed of the compound of formula (C18) was carried out in the same manner as Step 1 of Synthesis Example 24 . Triethylamine (25 g) is appropriately added to the above-mentioned coupling agent component solution in the range of 0 to 10°C, and the above-mentioned diazo component solution obtained in step 1 is added dropwise over 1 hour to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. An orange dye compound (27.6 g, yield 88.6%) represented by the following formula (D-5) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m/z 623 (M ⁺ )) to be the following formula (D-5).

式（D-5）

Formula (D-5)

(Synthesis example 32) [Synthesis of orange dye compound (D-6)] The orange dye compound (D-6) is manufactured according to the following process.

As the coupling agent component solution, the compound of formula (C20) was used instead of the compound of formula (C18), except that the operation was performed in the same manner as Steps 1 and 2 of Synthesis Example 31 to obtain the following formula (D-6) The orange dye compound (22.8 g, yield 89.2%). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 511 (M ⁺ )).

式（D-6）

Formula (D-6)

(Synthesis Example 33) [Synthesis of orange dye compound (E-1)] The orange dye compound (E-1) is manufactured according to the following process.

33-A. Synthesis of coupling agent compound C21 and preparation of coupling agent component solution (step 1) The 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 at the same temperature In 3 hours, N-octyl-2-phenylindole represented by the following formula (C21) was thereby obtained. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C21).

式（C21）

Formula (C21)

33-B. Synthesis of Orange Dye Compound (E-1) Using Coupling Reaction (Step 2) The preparation of the diazonium component solution derived from the compound of formula (D4) was carried out in the same manner as in Synthesis Example 24. Triethylamine (20 g) is appropriately added to the above-mentioned coupling agent component solution obtained in step 1 in the range of 0 to 10°C, and the above-mentioned diazo component solution is added dropwise over 1 hour to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. An orange dye compound (11.3 g, yield 43.2%) represented by the following formula (E-1) was obtained. The structure of the orange dye compound was confirmed by LCMS analysis (m/z 523 (M ⁺ )).

式（E-1）

Formula (E-1)

(Synthesis example 34) [Synthesis of orange dye compound (E-2)] The orange dye compound (E-2) is manufactured according to the following process.

34-A. Synthesis of coupling agent compound C22 and preparation of coupling agent component solution (step 1) Except that 1-bromobutane (7.53 g) was used instead of 1-bromooctane, the operation was carried out in the same manner as in Step 1 of Synthesis Example 33 to obtain N-butyl-2- represented by the following formula (C22) Phenyl indole. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C22).

式（C22）

Formula (C22)

34-B. Synthesis of Orange Dye Compound (E-2) Using Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C22) instead of the compound of formula (C21). In addition, follow the synthesis example Steps 1 and 2 of 33 were similarly operated to obtain an orange dye compound (14.5 g, yield 62.1%) represented by the following formula (E-2). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 467 (M ⁺ )).

式（E-2）

Formula (E-2)

(Synthesis Example 35) [Synthesis of Red Dye Compound (D-7)] The red dye compound (D-7) is manufactured according to the following process.

35-A. Preparation of diazonium component solution (step 1) Add the 2-cyano group represented by the following formula (D7) to a mixture of concentrated sulfuric acid (7.5 g), acetic acid (15 g) and 43% nitrososulfuric acid (14.9 g) in the range of 20 to 25°C 4-Nitroaniline (8.15 g) was stirred at the same temperature for 2 hours to obtain a diazonium component solution.

式（D7）

Formula (D7)

35-B. Synthesis of Red Dye Compound (D-7) Using Coupling Reaction (Step 2) The preparation of the coupling agent component solution composed of the compound of formula (C18) was carried out in the same manner as in Synthesis Example 24. Triethylamine (30 g) is appropriately added to the above-mentioned coupling agent component solution in the range of 0 to 10°C, and the above-mentioned diazo component solution obtained in step 1 is added dropwise over 1 hour to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. A red dye compound (16.9 g, yield 68.9%) represented by the following formula (D-7) was obtained. The structure of the red dye compound was confirmed by LCMS analysis (m/z 492 (M ⁺ )).

式（D-7）

Formula (D-7)

(Synthesis example 36) [Synthesis of Purple Dye Compound (C-8)] The purple dye compound (C-8) is manufactured according to the following process.

The preparation of the coupling agent component solution composed of the compound of formula (C16) was carried out in the same manner as in Step 1 of Synthesis Example 16, and the preparation of the diazo component solution derived from the compound of formula (D1) was the same as that of Synthesis Example 1. Step 5 is performed in the same way. Triethylamine (32 g) is appropriately added to the above-mentioned coupling agent component solution in the range of 0 to 10°C, and the above-mentioned diazo component solution is added dropwise over 2 hours to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. The purple dye compound (6.14 g, yield 21.8%) represented by the following formula (C-8) was obtained. The molecular weight of the purple dye compound (m/z 563 (M ⁺ )) was analyzed by LCMS to confirm that its structure was the following formula (C-8).

式（C-8）

Formula (C-8)

(Synthesis Example 37) [Synthesis of Purple Dye Compound (C-9)] The purple dye compound (C-9) is manufactured according to the following process.

As the coupling agent component solution, the compound of the formula (C9) was used instead of the compound of the formula (C16), except that the operation was carried out in the same manner as in Synthesis Example 36 to obtain the purple dye compound represented by the following formula (C-9) ( 12.1 g). The structure of the purple dye compound was confirmed by LCMS analysis (m/z 731 (M ⁺ )).

式（C-9）

Formula (C-9)

(Synthesis example 38) [Synthesis of Purple Dye Compound (C-10)] The purple dye compound (C-10) is manufactured according to the following process.

Stir a mixture of sodium bromide (5.92 g), triethylamine (0.50 g), and DMF (80 g) in the range of 35 to 40°C for 15 minutes, add cuprous cyanide (5.0 g), and at the same temperature Stir for 15 minutes. The purple dye compound (C-9) (34.3 g) was added to this mixture, and the temperature was raised to 110°C and stirred for 1 hour. After cooling to 80°C, add a mixture of water (190 g) and sodium hypochlorite (18 g), stir at 70 to 80°C for 1 hour, and then cool to room temperature. The product was separated by filtration from the reaction mixture, washed with water, and dried at 60°C until the moisture became 1.0% by mass or less, to obtain a purple dye compound represented by the following formula (C-10) (20.4 g, yield Rate 64.2%). The structure of the purple dye compound was confirmed by LCMS analysis (m/z 678 (M ⁺ )).

式（C-10）

Formula (C-10)

(Synthesis Example 39) [Synthesis of Purple Dye Compound (C-11)] The purple dye compound (C-11) is manufactured according to the following process.

39-A. Preparation of diazonium component solution (step 1) Add 2-bromo-6-cyano-4-nitroaniline (11.1 g). 43% nitrososulfuric acid (15.6 g) was added to the mixture in the range of 20 to 25° C., and the mixture was stirred at the same temperature for 2 hours, thereby obtaining a diazo component solution.

式（D8）

Formula (D8)

39-B. Synthesis of Purple Dye Compound (C-11) Using Coupling Reaction (Step 2) The preparation of the coupling agent component solution composed of the compound of formula (C9) is the same as Steps 1 to 3 of Synthesis Example 9 Way to proceed. Triethylamine (20 g) is appropriately added to the above-mentioned coupling agent component solution in the range of 0 to 10°C, and the above-mentioned diazo component solution obtained in step 1 is added dropwise over 2 hours to carry out the coupling reaction. After stirring for 20 minutes in the range of 0 to 10°C, the product is separated by filtration from the reaction mixture, washed with methanol, then washed with water, and dried at 60°C until the moisture becomes 1.0% by mass or less. A purple dye compound (16.0 g, yield 45.0%) represented by the following formula (C-11) was obtained. The structure of the above-mentioned purple dye compound was ^{confirmed by LCMS analysis (m/z 711 (M +} )).

式（C-11）

Formula (C-11)

(Synthesis example 40) [Synthesis of Purple Dye Compound (C-12)] The purple dye compound (C-12) is manufactured according to the following process.

40-A. Synthesis of coupling agent compound C23 and preparation of coupling agent component solution (step 1) In Step 3 of Synthesis Example 9, except that 1-bromobutane (27.4 g) was used instead of 1-bromooctane, the operation was performed in the same manner as Steps 1 to 3 of Synthesis Example 9 to obtain the following formula (C23 ) Represented by N-[3-(N,N-dibutylamino)phenyl]octamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C23).

式（C23）

Formula (C23)

40-B. Synthesis of Purple Dye Compound (C-12) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C23) instead of the compound of formula (C9). In addition, follow the synthesis example Step 2 of 39 was performed in the same manner to obtain a purple dye compound (5.99 g, yield 20.0%) represented by the following formula (C-12). The structure of the purple dye compound was confirmed by LCMS analysis (m/z 599 (M ⁺ )).

式（C-12）

Formula (C-12)

(Synthesis example 41) [Synthesis of Purple Dye Compound (C-13)] The purple dye compound (C-13) is manufactured according to the following process.

As the coupling agent component solution, except that the compound of formula (C12) was used instead of the compound of formula (C9), the same procedure as in Step 2 of Synthesis Example 39 was carried out to obtain the purple color represented by the following formula (C-13) Dye compound (23.5 g, yield 75.0%). The structure of the purple dye compound was confirmed by LCMS analysis (m/z 627 (M ⁺ )).

式（C-13）

Formula (C-13)

(Synthesis example 42) [Synthesis of Purple Dye Compound (C-14)] The purple dye compound (C-14) is manufactured according to the following process.

As the coupling agent component solution, except that the compound of formula (C16) was used instead of the compound of formula (C9), the same procedure as in Step 2 of Synthesis Example 39 was carried out to obtain the purple color represented by the following formula (C-14) Dye compound (10.8 g, yield 39.8%). The structure of the purple dye compound was confirmed by LCMS analysis (m/z 543 (M ⁺ )).

式（C-14）

Formula (C-14)

(Synthesis example 43) [Synthesis of Purple Dye Compound (C-15)] The purple dye compound (C-15) is manufactured according to the following process.

In Synthesis Example 38, except that the violet dye compound (31.4 g) of formula (C-13) was used instead of the violet dye compound of formula (C-9), the same procedure as in Synthesis Example 38 was carried out to obtain the following formula (C-15) The purple dye compound (26.9 g, yield 93.7%) represented by (C-15). The structure of the purple dye compound was confirmed by LCMS analysis (m/z 574 (M ⁺ )).

式（C-15）

Formula (C-15)

(Synthesis example 44) [Synthesis of Purple Dye Compound (C-16)] The purple dye compound (C-16) is manufactured according to the following process.

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

式（C-16）

Formula (C-16)

(Synthesis Example 45) [Synthesis of yellow dye compound (G-3)] The yellow dye compound (G-3) is manufactured according to the following process.

In Synthesis Example 28, except that 2-ethylhexyl chloride (19.5 g) was used instead of n-octyl chloride, the same procedure as in Synthesis Example 28 was carried out to obtain the yellow color represented by the following formula (G-3) Dye compound (33.1 g, yield 87.3%). The structure of the yellow dye compound was confirmed by LCMS analysis (m/z 379 (M ⁺ )).

式（G-3）

Formula (G-3)

(Synthesis Example 46) [Synthesis of yellow dye compound (G-4)] The yellow dye compound (G-4) is manufactured according to the following process.

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

式（G-4）

Formula (G-4)

(Synthesis Example 47) [Synthesis of blue dye compound (B-9)] The blue dye compound (B-9) is manufactured according to the following process.

As the coupling agent component solution, the compound of formula (C23) was used instead of the compound of formula (C9), except that the operation was performed in the same manner as step 5 of Synthesis Example 9 to obtain the blue represented by the following formula (B-9) Color dye compound (9.12 g, yield 33.0%). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 553 (M ⁺ )).

式（B-9）

Formula (B-9)

(Synthesis example 48) [Synthesis of blue dye compound (B-10)] The blue dye compound (B-10) is manufactured according to the following process.

48-A. Synthesis of coupling agent compound C24 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 9, except that 2-ethylhexyl chloride (34.2 g) was used instead of n-octyl chloride, the operation was performed in the same manner as Steps 1 to 3 of Synthesis Example 9 to obtain the following formula ( C24) represented by N-[3-(N,N-dioctylamino)phenyl]-2-ethylhexamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C24).

式（C24）

Formula (C24)

48-B. Synthesis of Blue Dye Compound (B-10) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C24) instead of the compound of formula (C9), and in addition, synthesize Steps 4 and 5 of Example 9 were similarly operated to obtain a blue dye compound (19.0 g, yield 57.1%) represented by the following formula (B-10). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 665 (M ⁺ )).

式（B-10）

Formula (B-10)

(Synthesis Example 49) [Synthesis of orange dye compound (D-8)] The orange dye compound (D-8) is manufactured according to the following process.

As the coupling agent compound, N,N-diethylaniline (7.45 g) was used instead of the compound of formula (C18), except that it was operated in the same manner as in Synthesis Example 24 to obtain the following formula (D-8) The orange dye compound (15.2 g, yield 82.8%). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 367 (M ⁺ )).

式（D-8）

Formula (D-8)

(Synthesis example 50) [Synthesis of orange dye compound (D-9)] The orange dye compound (D-9) is manufactured according to the following process.

As the coupling agent compound, N,N-diethylaniline (7.45 g) was used instead of the compound of formula (C18), except that the same procedure as in Synthesis Example 31 was carried out to obtain the following formula (D-9) The orange dye compound (18.2 g, yield 80.0%). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 455 (M ⁺ )).

式（D-9）

Formula (D-9)

(Synthesis Example 51) [Synthesis of orange dye compound (D-10)] The orange dye compound (D-10) is manufactured according to the following process.

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

式（D-10）

Formula (D-10)

(Synthesis Example 52) [Synthesis of orange dye compound (D-11)] The orange dye compound (D-11) is manufactured according to the following process.

52-A. Synthesis of coupling agent compound C25 and preparation of coupling agent component solution (step 1) A mixture of aniline (18.6 g), acetic acid (50 g), cuprous chloride (1.3 g), and acrylonitrile (20 g) was heated to 110°C and stirred for 3 hours. After cooling to room temperature, toluene (100 g) and 10% sodium carbonate aqueous solution (150 g) were added to extract the organic layer. After washing the extract with saturated brine, the solvent was distilled off under reduced pressure, thereby obtaining N-cyanoethylaniline represented by the following formula (C25a) as a crude product (28.7 g, yield 98.2%).

式（C25a）

Formula (C25a)

(Step 2) The mixture of N-cyanoethylaniline (28.7 g), triethylamine (15 g), DMF (15 g) and 1-bromooctane (14.5 g) obtained in the above step was heated to 120°C, Stir at the same temperature for 3 hours, thereby obtaining N-cyanoethyl-N-octylaniline represented by the following formula (C25). Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C25).

式（C25）

Formula (C25)

52-B. Synthesis of Orange Dye Compound (D-11) Using Coupling Reaction (Step 3) As a coupling agent component solution, use the compound of formula (C25) instead of the compound of formula (C18). Otherwise, follow the synthesis example 30 The same operation was performed to obtain an orange dye compound (10.6 g, yield 52.0%) represented by the following formula (D-11). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 408 (M ⁺ )).

式（D-11）

Formula (D-11)

(Synthesis Example 53) [Synthesis of Red Dye Compound (C-17)] The red dye compound (C-17) is manufactured according to the following process.

53-A. Synthesis of coupling agent compound C26 and preparation of coupling agent component solution (step 1) Use 3'-aminoacetaniline (7.50 g) instead of N-(3-amino-4-methoxyphenyl)octamide and 1-bromoethane (27.3 g) instead of 1-bromooctane Except for this, the operation was performed in the same manner as in Step 4 of Synthesis Example 1 to obtain N-[3-(N,N-diethylamino)phenyl]acetamide represented by the following formula (C26). Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C26).

式（C26）

Formula (C26)

53-B. Synthesis of Red Dye Compound (C-17) by Coupling Reaction (Step 2) As the coupling agent compound, use the compound of formula (C26) instead of the compound of formula (C9). Otherwise, the same as Synthesis Example 17 The same operation was performed to obtain a red dye compound (11.8 g, yield 60.5%) represented by the following formula (C-17). The structure of the red dye compound was confirmed by LCMS analysis (m/z 390 (M ⁺ )).

式（C-17）

Formula (C-17)

(Synthesis Example 54) [Synthesis of Purple Dye Compound (F-2)] The purple dye compound (F-2) is manufactured according to the following process.

As the coupling agent compound, N,N-diethylaniline (7.45 g) was used instead of the compound of formula (C18), except that it was operated in the same manner as in Synthesis Example 29 to obtain the following formula (F-2) The purple dye compound (10.6 g, yield 59.6%). The structure of the purple dye compound was confirmed by LCMS analysis (m/z 356 (M ⁺ )).

式（F-2）

Formula (F-2)

(Synthesis Example 55) [Synthesis of blue dye compound (B-11)] The blue dye compound (B-11) is manufactured according to the following process.

As the coupling agent compound, the compound of the formula (C26) was used instead of the compound of the formula (C9), except that the operation was carried out in the same manner as in Steps 4 and 5 of Synthesis Example 9 to obtain the following formula (B-11) Blue dye compound (11.9 g, yield 57.6%). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 413 (M ⁺ )).

式（B-11）

Formula (B-11)

(Synthesis Example 56) [Synthesis of blue dye compound (A-9)] The blue dye compound (A-9) is manufactured according to the following process.

56-A. Synthesis of coupling agent compound C27 and preparation of coupling agent component solution (step 1) The N-(3-amino-4-methoxyphenyl)octamide (13.2 g), acetic acid (15 g), cuprous chloride (0.32 g), obtained in step 3 of Synthesis Example 1 A mixture of acrylonitrile (5.0 g) was heated to 110°C and stirred for 3 hours. After cooling to room temperature, toluene (50 g) and a 10% sodium carbonate aqueous solution (75 g) were added to extract the organic layer. After washing the extract with saturated brine, the solvent was distilled off under reduced pressure to obtain N-(3-cyanoethylamino-4 represented by the following formula (C27a) as a crude product -Methoxyphenyl)octamide (9.05 g, yield 57.0%).

式（C27a）

Formula (C27a)

(Step 2) Combine the N-(3-cyanoethylamino-4-methoxyphenyl)octamide (15.9 g), DMF (15 g) and diethyl sulfate (11.6 g) obtained in the above steps The mixture was heated to 90°C and stirred at the same temperature for 2 hours to obtain N-(3-N-ethyl-N-cyanoethylamino-4-methoxy represented by the following formula (C27) Phenyl) octamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C27).

式（C27）

Formula (C27)

56-B. Synthesis of Blue Dye Compound (A-9) by Coupling Reaction (Step 3) As a coupling agent component solution, use the compound of formula (C27) instead of the compound of formula (C1), in addition to the synthesis Steps 5 and 6 of Example 1 were similarly operated to obtain a blue dye compound (9.70 g, yield 31.4%) represented by the following formula (A-9). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 618 (M ⁺ )).

式（A-9）

Formula (A-9)

(Synthesis Example 57) [Synthesis of blue dye compound (A-10)] The blue dye compound (A-10) is manufactured according to the following process.

57-A. Synthesis of coupling agent compound C28 and preparation of coupling agent component solution (step 1) The N-(3-cyanoethylamino-4-methoxyphenyl)octamide (15.9 g), DMF (20 g) and triethylamine (12.6 g) A mixture of 1-bromooctane (29.0 g) is heated to 120°C and stirred for 8 hours to obtain N-(3-N-octyl-N-cyano group represented by the following formula (C28) Ethylamino-4-methoxyphenyl)octamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of formula (C28).

式（C28）

Formula (C28)

57-B. Synthesis of blue dye compound (A-10) by coupling reaction (Step 2) As a coupling agent component solution, use the compound of formula (C28) instead of the compound of formula (C1), and in addition, synthesize Steps 5 and 6 of Example 1 were similarly operated to obtain a blue dye compound (5.52 g, yield 15.7%) represented by the following formula (A-10). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 702 (M ⁺ )).

式（A-10）

Formula (A-10)

(Synthesis example 58) [Synthesis of blue dye compound (A-11)] The blue dye compound (A-11) is manufactured according to the following process.

58-A. Synthesis of coupling agent compound C29 and preparation of coupling agent component solution (step 1) The N-(3-amino-4-methoxyphenyl)octamide (13.2 g), DMF (15 g), triethylamine (15 g) and 2 obtained in step 3 of Synthesis Example 1 -The mixture of bromoethyl methyl ether (27.8 g) was heated to 110°C and stirred for 8 hours to obtain N-[3-N,N-(2-dimethoxy) represented by the following formula (C29) Ethyl)amino-4-methoxyphenyl]octamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of formula (C29).

式（C29）

Formula (C29)

(Step 2) As a coupling agent component solution, except that the compound of formula (C29) was used instead of the compound of formula (C1), the operation was carried out in the same manner as steps 5 and 6 of Synthesis Example 1 to obtain the following formula (A- 11) The indicated blue dye compound (6.58 g, yield 20.2%). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 653 (M ⁺ )).

式（A-11）

Formula (A-11)

(Synthesis example 59) [Synthesis of blue dye compound (A-12)] The blue dye compound (A-12) is manufactured according to the following process.

59-A. Synthesis of coupling agent compound C30 and preparation of coupling agent component solution (step 1) Use N-(3-amino-4-methoxyphenyl)acetamide (purchased as a commercial product) (9.0 g) instead of N-(3-amino-4-methoxyphenyl) For octamide, 1-bromobutane (27.4 g) was used instead of 1-bromooctane. The procedure was the same as Step 4 of Synthesis Example 1 except that 1-bromooctane was used to obtain N-[ represented by the following formula (C30) 3-(N,N-Dihexylamino)-4-methoxyphenyl]acetamide. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of formula (C30).

式（C30）

Formula (C30)

59-B. Synthesis of Blue Dye Compound (A-12) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C30) instead of the compound of formula (C1), in addition to the synthesis Steps 5 and 6 of Example 1 were similarly operated to obtain a blue dye compound (14.1 g, yield 49.9%) represented by the following formula (A-12). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 565 (M ⁺ )).

式（A-12）

Formula (A-12)

(Synthesis example 60) [Synthesis of blue dye compound (A-13)] The blue dye compound (A-13) is manufactured according to the following process.

60-A. Synthesis of coupling agent compound C31 and preparation of coupling agent component solution (step 1) Use N-(3-amino-4-methoxyphenyl)acetamide (purchased as a commercial product) (9.0 g) instead of N-(3-amino-4-methoxyphenyl) For octamide, 1-bromohexane (33.0 g) was used instead of 1-bromooctane, and the operation was carried out in the same manner as in Step 4 of Synthesis Example 1 except that 1-bromohexane (33.0 g) was used to obtain N-[ represented by the following formula (C31) 3-(N,N-Dihexylamino)-4-methoxyphenyl]acetamide. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C31).

式（C31）

Formula (C31)

60-B. Synthesis of Blue Dye Compound (A-13) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C31) instead of the compound of formula (C1), in addition to this, synthesize Steps 5 and 6 of Example 1 were similarly operated to obtain a blue dye compound (10.7 g, yield 34.5%) represented by the following formula (A-13). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 621 (M ⁺ )).

式（A-13）

Formula (A-13)

(Synthesis Example 61) [Synthesis of blue dye compound (A-14)] The blue dye compound (A-14) is manufactured according to the following process.

61-A. Synthesis of coupling agent compound C32 and preparation of coupling agent component solution (step 1) In step 1 of Synthesis Example 1, pentamethylene chloride (25.3 g) was used instead of n-octyl chloride, and in step 4, 1-bromoethane (27.3 g) was used instead of 1-bromooctane. In addition, with Steps 1 to 4 of Synthesis Example 1 were similarly operated to obtain N-[3-(N,N-diethylamino)-4-methoxyphenyl]pentanamide represented by the following formula (C32) . Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C32).

式（C32）

Formula (C32)

61-B. Synthesis of Blue Dye Compound (A-14) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C32) instead of the compound of formula (C1), and in addition, synthesize Steps 5 and 6 of Example 1 were similarly operated to obtain a blue dye compound (24.1 g, yield 87.5%) represented by the following formula (A-14). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 551 (M ⁺ )).

式（A-14）

Formula (A-14)

(Synthesis Example 62) [Synthesis of blue dye compound (A-15)] The blue dye compound (A-15) is manufactured according to the following process.

62-A. Synthesis of coupling agent compound C33 and preparation of coupling agent component solution (step 1) In step 1 of Synthesis Example 1, lauryl chloride (45.9 g) was used instead of n-octyl chloride, and in step 4, 1-bromoethane (27.3 g) was used instead of 1-bromooctane. In addition, with Steps 1 to 4 of Synthesis Example 1 were similarly operated to obtain N-[3-(N,N-diethylamino)-4-methoxyphenyl]dodecanoic acid represented by the following formula (C33) amine. Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C33).

式（C33）

Formula (C33)

62-B. Synthesis of Blue Dye Compound (A-15) Using Coupling Reaction (Step 2) As a coupling agent component solution, use formula (C33) instead of formula (C1). Otherwise, follow the steps of Synthesis Example 1 5 and 6 were operated in the same manner to obtain a blue dye compound (26.8 g, yield 82.6%) represented by the following formula (A-15). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 649 (M ⁺ )).

式（A-15）

Formula (A-15)

(Synthesis Example 63) [Synthesis of Red Dye Compound (C-18)] The red dye compound (C-18) is manufactured according to the following process.

63-A. Synthesis of coupling agent compound C34 and preparation of coupling agent component solution (step 1) In Step 3 of Synthesis Example 9, 1-bromohexane (33.0 g) was used instead of 1-bromooctane, and 3'-aminoacetaniline (7.50 g) was used instead of N-(3-aminophenyl) For octamide, the operation was performed in the same manner as in Step 3 of Synthesis Example 9 to obtain N-[3-(N,N-dihexylamino)phenyl]acetyl represented by the following formula (C34) amine. Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C34).

式（C34）

Formula (C34)

63-B. Synthesis of Red Dye Compound (C-18) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C34) instead of the compound of formula (C9). In addition, follow the synthesis example 17 The same operation was performed to obtain a red dye compound (20.1 g, yield 80.1%) represented by the following formula (C-18). The structure of the red dye compound was confirmed by LCMS analysis (m/z 502 (M ⁺ )).

式（C-18）

Formula (C-18)

(Synthesis example 64) [Synthesis of orange dye compound (D-12)] The orange dye compound (D-12) is manufactured according to the following process.

64-A. Synthesis of coupling agent compound C35 and preparation of coupling agent component solution (step 1) Use aniline (4.66 g) instead of N-(3-amino-4-methoxyphenyl)octamide, and use 1-bromohexane (33.0 g) instead of 1-bromooctane. In addition, with the synthesis Step 4 of Example 1 was similarly operated to obtain N,N-dihexylaniline represented by the following formula (C35). Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C35).

式（C35）

Formula (C35)

64-B. Synthesis of Orange Dye Compound (D-12) by Coupling Reaction (Step 2) As a coupling agent component solution, use the compound of formula (C35) instead of the compound of formula (C18). Otherwise, follow the synthesis example 24 The same operation was performed to obtain an orange dye compound (13.5 g, yield 56.4%) represented by the following formula (D-12). The structure of the orange dye compound was confirmed by LCMS analysis (m/z 479 (M ⁺ )).

式（D-12）

Formula (D-12)

(Synthesis Example 65) [Synthesis of orange dye compound (D-13)] The orange dye compound (D-13) is manufactured according to the following process.

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

式（D-13）

Formula (D-13)

(Synthesis Example 66) [Synthesis of blue dye compound (A-16)] The blue dye compound (A-16) is manufactured according to the following process.

66-A. Synthesis of coupling agent compound C8 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 1, 4-butoxyaniline (33.0 g) was used instead of p-anisidine, and propyl chloride (19.4 g) was used instead of n-octyl chloride. Otherwise, follow the steps of Synthesis Example 1. Operations 1 to 4 were performed in the same manner to obtain N-[3-(N,N-dioctylamino)-4-butoxyphenyl]propanamide represented by the following formula (C36). Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C36).

式（C36）

Formula (C36)

66-B. Synthesis of blue dye compound (A-16) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C36) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of Synthesis Example 1, and obtained the blue dye compound (6.45 g, yield 17.6%) represented by following formula (A-16). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 733 (M ⁺ )).

式（A-16）

Formula (A-16)

(Synthesis Example 67) [Synthesis of Red Dye Compound (C-19)] The red dye compound (C-19) is manufactured according to the following process.

67-A. Synthesis of coupling agent compound C37 and preparation of coupling agent component solution (step 1) In Step 1 of Synthesis Example 9, propylene chloride (19.4 g) was used instead of n-octyl chloride, and in Step 3 of Synthesis Example 9, 1-bromohexane (33.0 g) was used instead of 1-bromooctane, except Otherwise, it was operated in the same manner as Steps 1 to 3 of Synthesis Example 9 to obtain N-[3-(N,N-dihexylamino)phenyl]propanamide represented by the following formula (C37). Methanol (30 g) was added to the reaction mixture, and the mixture was cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C37).

式（C37）

Formula (C37)

67-B. Synthesis of red dye compound (C-19) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C37) obtained in step 1 instead of the compound of formula (C9), except Otherwise, the same operations as in Steps 1 and 2 of Synthesis Example 17 were performed to obtain a red dye compound (17.6 g, yield 68.2%) represented by the following formula (C-19). The structure of the red dye compound was confirmed by LCMS analysis (m/z 516 (M ⁺ )).

式（C-19）

Formula (C-19)

(Synthesis example 68) [Synthesis of Red Dye Compound (C-20)] The red dye compound (C-20) is manufactured according to the following process.

As the coupling agent component solution, except that the compound of formula (C12) was used instead of the compound of formula (C18), the operation was carried out in the same manner as Steps 1 and 2 of Synthesis Example 30 to obtain the following formula (C-20) The red dye compound (23.0 g, yield 87.7%). The structure of the red dye compound was confirmed by LCMS analysis (m/z 524 (M ⁺ )).

式（C-20）

Formula (C-20)

(Synthesis Example 69) [Synthesis of blue dye compound (A-17)] The blue dye compound (A-17) is manufactured according to the following process.

69-A. Synthesis of coupling agent compound C38 and preparation of coupling agent component solution (step 1) In step 1 of Synthesis Example 1, pentamethylene chloride (25.3 g) was used instead of n-octyl chloride, and in step 4, 1-bromohexane (33.0 g) was used instead of 1-bromooctane. In addition, with Steps 1 to 4 of Synthesis Example 1 were similarly operated to obtain N-[3-(N,N-dihexylamino)-4-methoxyphenyl]pentanamide represented by the following formula (C38) . Methanol (30 g) was added to the reaction mixture and cooled to 5°C, thereby obtaining a coupling agent component solution composed of a compound of formula (C38).

式（C38）

Formula (C38)

69-B. Synthesis of blue dye compound (A-17) by coupling reaction (step 2) As a coupling agent component solution, use the compound of formula (C38) obtained in step 1 instead of the compound of formula (C1), Except for this, it carried out similarly to the steps 5 and 6 of the synthesis example 1, and obtained the blue dye compound (15.3 g, yield 48.4%) represented by following formula (A-17). The structure of the blue dye compound was confirmed by LCMS analysis (m/z 663 (M ⁺ )).

式（A-17）

Formula (A-17)

The structural formulas of the dye compounds and conventional dye compounds described in the synthesis examples are shown in Tables 3-9.

式（A）

[table 3]

Formula (A)

式（B）

[Table 4]

Formula (B)

式（C）

[table 5]

Formula (C)

式（D）

[Table 6]

Formula (D)

式（E）

[Table 7]

Formula (E)

式（F）

[Table 8]

Formula (F)

式（G）

[Table 9]

Formula (G)

＜Dyeing example＞ Use only one of the dye compounds described in Tables 3 to 9 or the disperse dye compounds previously used for dyeing polyester fibers, etc., to dye polypropylene cloth or polyethylene cloth by the supercritical carbon dioxide dyeing method.

<Polypropylene dyeing example> [Dyeing example P1] Figure 1 shows the supercritical carbon dioxide dyeing device used for dyeing. The dyeing device consists of a liquid CO ₂ tank (1), filter (2), cooling jacket (3), cooler (4), high-pressure pump (5), preheater (6), pressure gauge (7 to 9) ), a magnetic drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).

Cut the polypropylene cloth and weigh about 50 to 70 g. From the inside, wind it on a stainless steel cylinder (21) with punching holes in the order of cotton cloth, polypropylene cloth, and cotton cloth, and then slowly fix it with cotton thread. The inner cotton cloth is a cushion cloth, and the outer cotton cloth is a cover cloth.

Fix the above-mentioned stainless steel cylinder wrapped with cloth samples (cotton cloth, polypropylene cloth, cotton cloth) in the pressure-resistant stainless steel tank (22), and set it to 0.3% by mass relative to the mass of polypropylene cloth in Synthesis Example 5 The obtained blue dye compound A-5 was wrapped in wipes and placed in the fluid passage on the upper part of the stainless steel cylinder. The volume of the pressure-resistant stainless steel tank is 2230 cm ³ . Close all the valves in the dyeing device, and heat to 120°C by the preheater.

After reaching the dyeing temperature, open the stop valves (14) and (16), and use a high-pressure pump with a cooling jacket to flow 1.13 kg of liquid carbon dioxide into the pressure-resistant stainless steel tank. After that, the stop valves (14) and (16) are closed, and the impeller and the magnetic drive part in the lower part of the pressure-resistant stainless steel tank are used for circulation. The rotation speed of the magnetic drive unit is 750 rpm, and the circulation direction is from the inner side to the outer side of the cylinder.

After reaching the specified temperature and pressure (120°C, 25 MPa) in the pressure-resistant stainless steel tank, maintain the temperature and pressure for 60 minutes to dye the polypropylene cloth. After dyeing, open the stop valve (18) and slowly open the needle valve to release the carbon dioxide in the pressure-resistant stainless steel tank and reduce the pressure in the pressure-resistant stainless steel tank from 25 MPa to atmospheric pressure. Continue to circulate until it reaches the critical pressure of carbon dioxide (about 8 MPa). Then take out the polypropylene dyed cloth in the pressure-resistant stainless steel tank.

[Staining examples P2 to P82, and staining examples P98 to P101] The blue dye compound A-5 described in the dyeing example P1 is changed to the dye compound described in Tables 3 to 9 or the disperse dye compound previously used for dyeing polyester fibers, etc., in addition to the dyeing example Polypropylene dyed cloth is obtained by the same dyeing sequence of P1. 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.

式（A）

[Table 10]

Formula (A)

式（B）

[Table 11]

Formula (B)

式（C）

[Table 12]

Formula (C)

式（D）

[Table 13]

Formula (D)

式（E）

[Table 14]

Formula (E)

式（F'）

[Table 15]

Formula (F')

式（G）

[Table 16]

Formula (G)

For the polypropylene dyed fabrics obtained in dyeing examples P1 to P82 and dyeing examples P98 to P101, the dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, rubbing fastness were performed Test and fastness test to hot pressing.

(1) Evaluation of dyeability The dyeability is visually evaluated by the Total K/S value obtained by color measurement of the dyed fabric and the dye residue after dyeing. The color measurement of the dyed cloth uses an integrating sphere spectrophotometer Color-Eye 5 (manufactured by GretagMacbeth), and the dyed cloth is pasted on white paper, and the observation light source is D65 with a 2 degree field of view.

(2) Light fastness test The light fastness test is carried out by the ultraviolet carbon arc lamp method in accordance with JIS L0842:2004. The outline of the test method is as follows. Using an ultraviolet fading tester U48 (manufactured by Suga Test Instruments Co., Ltd.), the dyed cloth was exposed for 20 hours at a black panel temperature of 63±3°C, and then the color change was judged.

(3) Sublimation fastness test The sublimation fastness test is carried out by the method in accordance with JIS L0854:2013. The outline of the test method is as follows. Clip the dyed cloth to the nylon cloth, and hold it at 120±2℃ for 80 minutes under a load of 12.5 kPa, and then determine the color change and contamination of the nylon cloth.

(4) Washing fastness test The washing fastness test is carried out by the method in accordance with JIS L0844:2011 (No. A-2). The outline of the test method is as follows. Attach a multi-fiber interwoven fabric to the dyed cloth, and wash it for 30 minutes at 50±2°C in the presence of soap to determine the color change and the contamination of the cotton and nylon parts of the multi-fiber interwoven fabric. In addition, the contamination of the residual liquid after washing is judged.

(5) Perspiration fastness test The sweat fastness test is carried out by the method in accordance with JIS L0848:2004. The outline of the test method is as follows. Attach the multi-fiber interwoven fabric to the dyed cloth, immerse it in acid artificial sweat or alkaline artificial sweat for 30 minutes, keep it at 37±2℃ for 4 hours under a load of 12.5 kPa, and then dry it below 60℃ to change it. Judgment of fading and contamination of the cotton part and nylon part of the multi-fiber interwoven fabric.

(6) Rubbing fastness test The rubbing fastness test is carried out according to the method of JIS L0849:2013. The outline of the test method is as follows. Using the rubbing fastness tester RT-300 (manufactured by Daiei Scientific Seiki Mfg. Co., Ltd.), apply a load of 2 N to the cotton cloth in a dry state or a cotton cloth in a wet state and rub the dyed cloth back and forth 100 times. Judgment of coloring.

(7) Fastness test to hot pressing The fastness test for hot pressing is carried out by the method in accordance with JIS L0850:2015 (A-2 Drying). The outline of the test method is as follows. Overlap the dyed cloth on the cotton cloth, and hold it under a load of 4±1 kPa for 15 seconds on a heating plate at 150°C, and then determine the color change and contamination of the cotton cloth.

The evaluation results of the dyeing examples of the compound of formula (A) are shown in Table 17 and Table 18.

[Table 17] Staining example P1 P2 P3 P4 P5 P6 P7 Synthesis example 5 6 3 4 7 1 8 Dye compound A-5 A-6 A-3 A-4 A-7 A-1 A-8 X _A NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ Y _A Br Br Br Br Br Br Br R _A1 C ₈ H ₁₇ C ₁₂ H ₂₅ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₈ H ₁₇ R _A2 C ₈ H ₁₇ C ₁₂ H ₂₅ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₈ H ₁₇ R _A3 CH ₃ CH ₃ C ₂ H ₅ Ethyl-pentyl C ₇ H ₁₅ C ₇ H ₁₅ C ₇ H ₁₅ R _A4 CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ C ₂ H ₅ Dyeability Total K/S 255 207 250 236 214 245 256 Dye residue none none none none none none none Light fastness 3 3 3 3-4 Less than level 3 3 3-4 Sublimation fastness 5 5 5 5 4 4-5 5 Washing fastness Fade 5 5 4-5 4-5 4 5 4-5 Pollution cotton 5 5 5 5 5 4-5 5 nylon 5 5 5 5 4-5 4-5 5 Residual liquid contamination 4-5 4-5 4-5 4-5 3 4 4-5 Fastness to sweat (acid) Fade 5 5 5 5 4-5 5 5 Pollution cotton 5 5 5 5 5 4-5 5 nylon 5 5 5 5 4-5 4-5 5 Sweat fastness (alkaline) Fade 5 5 5 5 4-5 5 5 Pollution cotton 5 5 5 5 5 4-5 5 nylon 5 5 5 5 4-5 4-5 5 Rubbing fastness Dry 5 5 5 5 4-5 5 5 Wet 5 5 5 5 4 5 5 Hot press 5 5 4-5 5 5 5 5

[Table 18] Staining example P8 P9 P10 P11 P12 P13 P14 P73 P74 P75 P76 P77 P98 P99 Synthesis example - - 56 57 58 - - 59 60 61 2 62 66 69 Dye compound A-X1 A-X2 A-9 A-10 A-11 A-X3 A-X4 A-12 A-13 A-14 A-2 A-15 A-16 A-17 X _A NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ Y _A Br Br Br Br Br Br Br Br Br Br Br Br Br Br R _A1 C ₂ H ₅ C ₂ H ₄ OCH ₃ C ₂ H ₅ C ₈ H ₁₇ C ₂ H ₄ OCH ₃ C ₂ H ₅ C ₃ H ₅ C ₄ H ₉ C ₆ H ₁₃ C ₂ H ₅ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₆ H ₁₃ R _A2 C ₂ H ₄ CN C ₂ H ₄ OCH ₃ C ₂ H ₄ CN C ₂ H ₄ CN C ₂ H ₄ OCH ₃ C ₂ H ₅ C ₃ H ₅ C ₄ H ₉ C ₆ H ₁₃ C ₂ H ₅ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₆ H ₁₃ R _A3 CH ₃ CH ₃ C ₇ H ₁₅ C ₇ H ₁₅ C ₇ H ₁₅ CH ₃ CH ₃ CH ₃ CH ₃ C ₄ H ₉ C ₄ H ₉ C ₁₁ H ₂₃ C ₂ H ₅ C ₄ H ₉ R _A4 CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ C ₄ H ₉ CH ₃ Dyeability Total K/S twenty four 66 93 78 146 62 71 211 258 168 174 237 263 233 Dye residue have have none have none have have none none have none none none none Light fastness Less than level 3 Less than level 3 3 3 Less than level 3 Less than level 3 Less than level 3 3-4 3-4 3-4 4-5 3-4 3-4 3 Sublimation fastness 5 5 4-5 5 5 4-5 4-5 4-5 4-5 4-5 5 4-5 5 5 Washing fastness Fade 5 4-5 4-5 4-5 5 5 5 5 4-5 4-5 Pollution cotton 4-5 4-5 4-5 4-5 5 4-5 5 5 5 5 nylon 4 4-5 4-5 4-5 5 4 5 5 4-5 5 Residual liquid contamination 4-5 4-5 4 3 4-5 3 4-5 4 4-5 4-5 Fastness to sweat (acid) Fade 5 4-5 4-5 5 5 5 5 5 5 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 5 5 Sweat fastness (alkaline) Fade 5 4-5 4-5 5 5 5 5 5 5 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 4-5 5 Rubbing fastness Dry 3-4 4 3 4-5 5 4 5 5 5 5 Wet 3 4 3-4 4-5 5 4 5 4-5 5 5 Hot press 5 5 5 5 5 5 5 5 5 5

_{Regarding the dyeability of the compound of formula (A), at least one of R A1} , R _A2 , and R _A3 used in dyeing examples P1 to P7 and P73 to P77, P98 and P99 is a compound having an alkyl group with 4 or more carbon atoms The dyeability is good.

However, the disperse dyes used in dyeing examples P8 to P14 that were previously used for dyeing polyester fibers, etc., that is, R _A1 , R _A2 , and R _{A3 are} all alkyl groups with less than 4 carbon atoms or have been treated with CN, OCH ₃ Or CH=CH ₂ substituted alkyl compounds have poor dyeability.

Moreover, regarding 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 with 4 or more carbon atoms is good.

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

[Table 19] Staining example P15 P16 P17 P18 P19 P20 P21 P22 P23 P24 P25 P78 Synthesis example 12 15 13 11 14 16 47 9 48 - 55 10 Dye compound B-4 B-7 B-5 B-3 B-6 B-8 B-9 B-1 B-10 B-X1 B-11 B-2 R _B1 C ₈ H ₁₇ Ethyl-hexyl C ₁₂ H ₂₅ C ₈ H ₁₇ C ₁₂ H ₂₅ C ₂ H ₅ C ₄ H ₉ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₄ OCH ₃ C ₂ H ₅ C ₈ H ₁₇ R _B2 C ₈ H ₁₇ Ethyl-hexyl C ₁₂ H ₂₅ C ₈ H ₁₇ C ₁₂ H ₂₅ C ₂ H ₅ C ₄ H ₉ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₄ OCH ₃ C ₂ H ₅ C ₈ H ₁₇ R _B3 CH ₃ CH ₃ CH ₃ C ₂ H ₅ C ₂ H ₅ C ₇ H ₁₅ C ₇ H ₁₅ C ₇ H ₁₅ Ethyl-pentyl CH ₃ CH ₃ C ₄ H ₉ Dyeability Total K/S 110 143 118 164 151 65 156 150 192 17 8 174 Dye residue none none none none none none none none none have have none Light fastness 6 6 5 6 5 6 6 6 6 Less than level 3 Less than level 3 6 Sublimation fastness 5 5 5 5 5 4-5 5 5 5 5 5 5 Washing fastness Fade 5 5 4-5 5 5 4-5 5 5 5 4-5 5 Pollution cotton 5 4-5 5 5 5 5 4-5 4-5 5 5 5 nylon 5 5 5 5 5 4-5 5 5 5 5 5 Residual liquid contamination 5 4 4-5 4-5 4-5 4-5 4-5 4-5 4-5 4-5 4 Fastness to sweat (acid) Fade 5 5 5 5 5 5 4-5 5 5 5 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 5 5 5 Sweat fastness (alkaline) Fade 4 5 5 5 5 5 4-5 5 5 5 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 5 5 5 Rubbing fastness Dry 5 4-5 5 5 4-5 5 5 5 5 5 5 Wet 4-5 4-5 4-5 5 4-5 4 4-5 4-5 5 5 5 Hot press 5 5 5 5 5 5 5 5 5 5 5

Regarding the dyeability of the compound of formula (B), R _B1 , R _B2 and R _B3 used in dyeing examples P15 to P23 and P78 are alkyl groups with 1 to 14 carbon atoms (wherein, R _B1 , R _B2 and R _{The compound in which at least one of B3} is an alkyl group with 4 to 14 carbons has good dyeability.

However, the disperse dyes used in dyeing examples P24 or P25, which were previously used for dyeing polyester fibers, etc., that is _{, compounds in which R B1} and R _B2 are alkyl groups substituted with OCH _{3 have poor dyeability.}

The evaluation results of the dyeing examples of the compound of formula (C) are shown in Table 20 and Table 21.

[Table 20] Staining example P26 P27 P28 P29 P30 P31 P32 P33 P34 P35 P36 P37 P38 P39 Synthesis example twenty two 20 twenty one 19 twenty three 17 41 42 40 39 36 43 44 38 Dye compound C-6 C-4 C-5 C-3 C-7 C-1 C-13 C-14 C-12 C-11 C-8 C-15 C-16 C-10 X _C Cl Cl Cl Cl Cl Cl CN CN CN CN NO ₂ CN CN CN Y _C H H H H H H Br Br Br Br Br CN CN NO ₂ R _C1 C ₄ H ₉ C ₈ H ₁₇ C ₁₂ H ₂₅ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₅ C ₄ H ₉ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ R _C2 C ₄ H ₉ C ₈ H ₁₇ C ₁₂ H ₂₅ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₅ C ₄ H ₉ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ C ₂ H ₅ C ₈ H ₁₇ R _C3 CH ₃ CH ₃ CH ₃ C ₂ H ₅ C ₇ H ₁₅ C ₇ H ₁₅ CH ₃ C ₇ H ₁₅ C ₇ H ₁₅ C ₇ H ₁₅ C ₇ H ₁₅ CH ₃ C ₇ H ₁₅ C ₇ H ₁₅ Dyeability Total K/S 154 182 193 242 137 146 127 100 147 165 199 92 86 178 Dye residue none none none none none none none none none none none none none none Light fastness 5 6 6 5 4 6 Less than level 3 Less than level 3 3 3 Less than level 3 Less than level 3 Less than level 3 Less than level 3 Sublimation fastness 2 3-4 4-5 4-5 3 4-5 5 4-5 5 5 4 5 5 5 Washing fastness Fade 5 5 5 4-5 5 5 4 5 4-5 4-5 5 4-5 3-4 5 Pollution cotton 3-4 4-5 5 5 3-4 5 5 5 5 5 5 5 3-4 5 nylon 3 4 4-5 4-5 3-4 5 5 4-5 5 5 4-5 5 4 5 Residual liquid contamination 1-2 5 4-5 4-5 2 4 4-5 3-4 4-5 4-5 3 3-4 2 5 Fastness to sweat (acid) Fade 5 5 5 4-5 5 5 5 5 5 5 5 5 4 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Sweat fastness (alkaline) Fade 5 5 5 4-5 5 5 5 5 5 5 5 5 4 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Rubbing fastness Dry 4 4-5 5 5 4-5 4-5 4-5 4 4-5 5 4-5 3-4 2-3 3-4 Wet 3-4 4-5 4 5 3-4 4-5 4 3 4 4-5 3 3 2-3 3-4 Hot press 4-5 5 5 5 5 5 5 5 5 5 5 5 5 5

[Table 21] Staining example P40 P41 P42 P43 P44 P45 P46 P79 P80 P100 P101 Synthesis example - - 53 - - - - 63 18 67 68 Dye compound C-X1 C-X2 C-17 C-X3 C-X4 C-X5 C-X6 C-18 C-2 C-19 C-20 X _C Cl Cl Cl CN CN NO ₂ CN Cl Cl Cl H Y _C H H H Br Br Br CN H H H H R _C1 C ₂ H ₄ OCOMe C ₂ H ₄ OCOMe C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₆ H ₁₃ C ₈ H ₁₇ C ₆ H ₁₃ C ₈ H ₁₇ R _C2 C ₂ H ₄ OCOMe C ₂ H ₄ OCOMe C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₆ H ₁₃ C ₈ H ₁₇ C ₆ H ₁₃ C ₈ H ₁₇ R _C3 CH ₃ C ₂ H ₅ CH ₃ CH ₃ C ₂ H ₅ CH ₃ CH ₃ CH ₃ C ₄ H ₉ C ₂ H ₅ CH ₃ Dyeability Total K/S twenty four twenty four 101 twenty three 35 59 8 211 193 204 192 Dye residue none none have have have have have none none none none Light fastness Less than level 3 Less than level 3 5 Less than level 3 Less than level 3 Less than level 3 Less than level 3 6 6 6 6 Sublimation fastness 4 4 2-3 4-5 3-4 5 4 4-5 4-5 4 Washing fastness Fade 4-5 5 5 5 5 Pollution cotton 4 5 5 5 5 nylon 2-3 5 5 5 5 Residual liquid contamination 2 3-4 4 3 4-5 Fastness to sweat (acid) Fade 4-5 5 5 5 5 Pollution cotton 4 5 5 5 5 nylon 4-5 5 5 5 5 Sweat fastness (alkaline) Fade 4 5 5 5 5 Pollution cotton 4-5 5 5 5 5 nylon 4 5 5 5 5 Rubbing fastness Dry 3-4 4-5 5 5 5 Wet 3-4 4-5 5 4-5 5 Hot press 4-5 5 5 5 5

_{Regarding the dyeability of the compound of formula (C), R C1} , R _C2 and R _C3 used in dyeing examples P26 to P39, P79, P80, P100 and P101 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein , _{At least one of R C1} , R _C2 and R _C3 is an alkyl group with 4 to 14 carbons) has good dyeability.

However, the dyeing properties of the disperse dyes used in dyeing examples P40 to P46, which were previously used for dyeing polyester fibers, etc., are poor.

Furthermore, regarding the fastnesses 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 each independently A compound representing an alkyl group having 1 to 14 carbon atoms (wherein _{at least one of R C1} , R _C2 and R _C3 is an alkyl group having 4 to 14 carbon atoms) is good.

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

[Table 22] Staining example P47 P48 P49 P50 P51 P52 P53 P54 P55 P56 P57 P58 P59 P60 P61 P81 P82 Synthesis example 26 twenty four 25 32 31 30 35 - 49 - 50 - 51 52 - 64 65 Dye compound D-3 D-1 D-2 D-6 D-5 D-4 D-7 D-X1 D-8 D-X2 D-9 D-X3 D-10 D-11 D-X4 D-12 D-13 X _D Cl Cl Cl Br Br H CN Cl Cl Br Br H H H CN Cl H Y _D Cl Cl Cl Br Br H H Cl Cl Br Br H H H H Cl H R _D1 C ₄ H ₉ C ₈ H ₁₇ C ₁₂ H ₂₅ C ₄ H ₉ C ₈ H ₁₇ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₄ CN C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₈ H ₁₇ C ₂ H ₅ C ₆ H ₁₃ C ₆ H ₁₃ R _D2 C ₄ H ₉ C ₈ H ₁₇ C ₁₂ H ₂₅ C ₄ H ₉ C ₈ H ₁₇ C ₈ H ₁₇ C ₈ H ₁₇ C ₂ H ₄ CN C ₂ H ₅ C ₂ H ₄ CN C ₂ H ₅ C ₂ H ₄ CN C ₂ H ₅ C ₂ H ₄ CN C ₂ H ₄ CN C ₆ H ₁₃ C ₆ H ₁₃ Dyeability Total K/S 133 117 131 126 117 149 211 6 54 30 72 17 63 90 14 145 178 Dye residue none none none none none none none have none have have none none have none have Light fastness 5 6 6 6 5 6 Less than level 3 Less than level 3 6 Less than level 3 6 6 3 Less than level 3 6 6 Sublimation fastness 2-3 4-5 5 3 5 3-4 4 5 2 3-4 2-3 1-2 3 3-4 4 3 Washing fastness Fade 4-5 4-5 5 5 5 5 4-5 4 4 4 5 5 5 Pollution cotton 4-5 5 5 4-5 5 5 5 4 4 3 5 5 5 nylon 3-4 5 4-5 4 5 5 4-5 2 2-3 1-2 3-4 5 4-5 Residual liquid contamination 2-3 4-5 4-5 2-3 4 4 4 4-5 3 2 2 4 3 Fastness to sweat (acid) Fade 4-5 5 5 5 5 5 5 5 5 5 5 5 5 Pollution cotton 4-5 5 5 5 5 5 5 4-5 4-5 4 5 5 5 nylon 4-5 5 5 5 5 5 5 4 4 3-4 5 5 5 Sweat fastness (alkaline) Fade 4-5 5 5 5 5 5 5 5 5 5 5 5 5 Pollution cotton 4-5 5 5 5 5 5 5 4-5 4-5 4 5 5 5 nylon 4-5 5 5 5 5 5 5 4 4 3-4 5 5 5 Rubbing fastness Dry 5 5 5 5 5 4-5 5 2-3 3 3 4 5 5 Wet 4-5 5 5 5 4-5 4-5 4-5 3 3-4 3 3-4 5 4-5 Hot press 5 5 5 5 5 5 5 4-5 5 4 5 5 5

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

However, the disperse dyes used in dyeing examples P54 to P59, and P61, which were previously used for dyeing polyester fibers, have poor dyeability.

Furthermore, regarding the fastnesses of the compound of formula (D), the compounds in which 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 are good.

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

[Table 23] Staining example P62 P63 P64 Synthesis example 34 33 - Dye compound E-2 E-1 E-X3 X _E Cl Cl Cl Y _E Cl Cl Cl R _E C ₄ H ₉ C ₈ H ₁₇ CH ₃ Dyeability Total K/S 77 84 20 Dye residue have none have Light fastness 5 6 Sublimation fastness 3 3 Washing fastness Fade 4 5 Pollution cotton 4-5 5 nylon 3-4 4-5 Residual liquid contamination 3-4 4-5 Fastness to sweat (acid) Fade 4 5 Pollution cotton 5 4-5 nylon 4-5 4-5 Sweat fastness (alkaline) Fade 4 5 Pollution cotton 5 5 nylon 4-5 4-5 Rubbing fastness Dry 5 5 Wet 4-5 4-5 Hot press 4-5 5

The dyeing on the compound of formula (E), the P62 or P63 staining embodiment used in the R _E is alkyl of 4 to 18 compounds of the good dyeability.

However, the dye compound previously used for dyeing polyester fibers and the like used in Dyeing Example P64 has poor dyeability.

Further, each of the compounds on fastness of formula (E), the hydrocarbon group having a carbon number R _E of the larger the better.

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

[Table 24] Staining example P65 P66 P67 Synthesis example 29 - 54 Dye compound F-1 F-X3 F-2 R _F1 C ₈ H ₁₇ C ₂ H ₅ C ₂ H ₅ R _F2 C ₈ H ₁₇ C ₂ H ₄ COOCH ₃ C ₂ H ₅ Dyeability Total K/S 204 62 61 Dye residue none none have Light fastness 5 Less than level 3 3 Sublimation fastness 4-5 3 3 Washing fastness Fade 5 4 Pollution cotton 4-5 4 nylon 5 2 Residual liquid contamination 4 3 Fastness to sweat (acid) Fade 5 4-5 Pollution cotton 5 5 nylon 5 4-5 Sweat fastness (alkaline) Fade 5 4-5 Pollution cotton 5 5 nylon 5 4-5 Rubbing fastness Dry 4-5 3 Wet 4 3 Hot press 5 5

Regarding the dyeability of the compound of formula (F), the dyeability of the compound in which R _F1 and R _F2 used in dyeing example P65 are independently an alkyl group with 4 to 14 carbon atoms has good dyeability.

However, the disperse dyes used in dyeing examples P66 or P67, which were previously used for dyeing polyester fibers, have poor dyeability.

In addition, with regard to the fastness of the compound of formula (F), the _{larger the carbon number of R F1} and R _F2 , the better the compound.

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

[Table 25] Staining example P68 P69 P70 P71 P72 Synthesis example 45 28 46 27 - Dye compound G-3 G-2 G-4 G-1 G-X5 R _G Ethyl-pentyl C ₇ H ₁₅ C ₈ H ₁₇ Hexyl-nonyl C ₃ H ₇ Dyeability Total K/S 38 39 39 40 12 Dye residue none none none none have Light fastness 5 4 4 5 4 Sublimation fastness 3-4 3-4 3-4 4-5 2 Washing fastness Fade 5 4-5 4-5 4-5 Pollution cotton 4 4-5 4-5 5 nylon 3-4 3-4 3-4 5 Residual liquid contamination 2-3 3 3 4-5 Fastness to sweat (acid) Fade 4 4 4-5 4-5 Pollution cotton 4-5 4-5 4-5 5 nylon 4-5 4-5 4-5 5 Sweat fastness (alkaline) Fade 4 4-5 4-5 4-5 Pollution cotton 4-5 4-5 5 5 nylon 4-5 4-5 4-5 5 Rubbing fastness Dry 2-3 4-5 4-5 5 Wet 2-3 4-5 4-5 5 Hot press 4-5 5 5 5

Regarding the dyeability of the compound of formula (G), the dyeing properties of the compound in which R _G is an alkyl group with 7 to 18 carbons used in dyeing examples P68 to P71 have good dyeability.

However, the dye compound previously used for dyeing polyester fibers and the like used in Dyeing Example P72 has poor dyeability.

Further, each of the compounds on fastness of formula (G), the carbon number of R _G of the larger the better.

＜Other polypropylene dyeing examples＞ Using a mixture of two or more dye compounds described in Tables 3 to 9 or a disperse dye compound previously used for dyeing polyester fibers, etc., the polypropylene fiber is dyed by the supercritical carbon dioxide dyeing method.

For the obtained dyed cloth, the dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, rubbing fastness were performed in the same way as the case of the polypropylene dyed cloth of the above-mentioned 1 dye compound. Test and fastness test to hot pressing. Dyeability is evaluated by visual inspection of Total K/S value, L ^* value, a ^* value, b ^* value and dye residue after dyeing obtained by color measurement of dyed cloth. In addition, the color measurement system of the dyed cloth uses an integrating sphere spectrophotometer Color-Eye 5 (manufactured by GretagMacbeth), and the dyed cloth is pasted on white paper, and the observation light source D65 is performed with a 2 degree field of view.

The evaluation results of the above-mentioned dyes are shown in Table 26 and Table 27.

[Table 26] Staining example P83 P84 P85 P86 P87 P88 P89 Dye compound A-1 1.00% omf 2.00% omf A-7 1.00% omf 0.50% omf B-4 2.00% omf 2.40% omf F-1 2.00% omf 1.00% omf 0.50% omf C-1 0.30% omf 0.60% omf C-4 0.60% omf 0.40% omf 0.60% omf 0.60% omf 0.30% omf D-1 1.40% omf 1.20% omf 1.40% omf 1.40% omf 0.70% omf 0.70% omf 1.40% omf Dye compound total 4.0% omf 4.0% omf 4.0% omf 4.0% omf 2.0% omf 2.0% omf 4.0% omf Dyeability L* 19.4 22.5 16.6 16.2 21.8 16.6 15.8 a* 8.2 10.5 5.8 3.4 7.7 2.6 1.6 b* 2.6 6.0 -0.5 -1.6 -2.2 -1.0 -0.2 Total K/S 501 407 612 634 359 624 716 Dye residue none none none none none none none Light fastness 5 5 Sublimation fastness 4 3-4 Washing fastness Fade 5 4-5 Pollution cotton 4-5 3-4 nylon 5 4 Liquid contamination 2-3 1-2 Fastness to sweat (acid) Fade 5 5 Pollution cotton 5 5 nylon 5 5 Sweat fastness (alkaline) Fade 5 5 Pollution cotton 5 5 nylon 5 5 Rubbing fastness Dry 4 2-3 Wet 4 2-3 Hot press 5 5

[Table 27] Staining example P90 P91 P92 P93 P94 P95 P102 P103 P104 P105 P106 P107 Dye compound A-3 1.00% omf 1.00% omf 0.50% omf 1.00% omf A-5 2.00% omf 1.00% omf 1.00% omf 1.00% omf 1.00% omf 1.00% omf 1.00% omf 1.00% omf C-3 0.60% omf 0.30% omf 0.30% omf 0.30% omf 0.30% omf 0.15% omf 0.30% omf 0.30% omf C-4 0.30% omf C-20 0.40% omf 0.40% omf 0.40% omf D-1 0.70% omf 0.70% omf 0.35% omf 0.60% omf D-4 1.40% omf 0.70% omf 0.70% omf 0.60% omf D-5 0.70% omf 0.70% omf 0.70% omf 0.60% omf Dye compound total 4.0% omf 2.0% omf 2.0% omf 2.0% omf 2.0% omf 1.0% omf 2.0% omf 2.0% omf 2.0% omf 2.0% omf 2.0% omf 2.0% omf Dyeability L* 15.7 15.2 16.5 15.5 16.0 18.5 16.7 16.5 16.4 16.4 15.3 16.6 a* 1.5 1.6 2.1 2.7 2.2 3.9 2.4 3.0 1.9 2.4 2.1 2.6 b* -0.8 -1.2 -2.6 -2.1 -2.8 -4.1 -3.0 -3.6 -3.1 -3.0 -3.3 -3.0 Total K/S 693 722 620 673 653 487 604 602 632 620 700 612 Dye residue none none none none none none none none none none none none Light fastness 5-6 5-6 5-6 6 5-6 6 6 5-6 5-6 5-6 Sublimation fastness 3-4 4-5 3-4 4-5 4-5 4-5 4-5 4-5 3-4 4-5 Washing fastness Fade 5 5 5 5 5 5 5 5 5 5 Pollution cotton 5 4-5 4-5 4-5 4-5 4-5 5 4-5 5 4-5 nylon 5 5 5 5 5 5 4-5 5 5 5 Liquid contamination 3-4 4 3-4 4 3 3-4 3-4 3 3-4 4 Fastness to sweat (acid) Fade 5 5 5 5 5 5 5 5 5 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 5 5 Sweat fastness (alkaline) Fade 5 5 5 5 5 5 5 5 5 5 Pollution cotton 5 5 5 5 5 5 5 5 5 5 nylon 5 5 5 5 5 5 5 5 5 5 Rubbing fastness Dry 3-4 4 3-4 3-4 3-4 4 4 3-4 3-4 4 Wet 3-4 4 3-4 3-4 3-4 4 4 3-4 3-4 4 Hot press 5 5 5 4-5 5 5 5 5 5 5

As shown in Table 26 and Table 27, when the orange dye, red dye, purple dye, and blue dye of the present invention obtained in dyeing examples P83 to P95 and P102 to P107 are used in combination, good dyeability and Black dyed cloth with good fastness.

<Polyethylene dyeing example> [Dyeing example E1] The supercritical carbon dioxide dyeing device used for dyeing is shown in FIG. 1. The dyeing device consists of a liquid CO ₂ tank (1), filter (2), cooling jacket (3), cooler (4), high-pressure pump (5), preheater (6), pressure gauge (7 to 9) ), a magnetic drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).

Cut the polyethylene cloth and weigh about 50 to 70 g. From the inside, wind it on a stainless steel cylinder (21) with punching holes in the order of cotton, polyethylene, and cotton from the inside, and then slowly fix it with cotton thread. The inner cotton cloth is a cushion cloth, and the outer cotton cloth is a cover cloth.

Fix the above-mentioned stainless steel cylinder wrapped with cloth samples (cotton cloth, polyethylene cloth, cotton cloth) in the pressure-resistant stainless steel tank (22), and set the weight of the polyethylene cloth to be equivalent to 0.3% by mass in Synthesis Example 5 The obtained blue dye compound A-5 was wrapped in wipes and placed in the fluid passage on the upper part of the stainless steel cylinder. The volume of the pressure-resistant stainless steel tank is 2230 cm ³ . Close all the valves in the dyeing device, and heat to 98°C by the preheater.

After reaching the dyeing temperature, open the stop valves (14) and (16), and use a high-pressure pump with a cooling jacket to flow 1.13 kg of liquid carbon dioxide into the pressure-resistant stainless steel tank. After that, the stop valves (14) and (16) are closed, and the impeller and the magnetic drive part in the lower part of the pressure-resistant stainless steel tank are used for circulation. The rotation speed of the magnetic drive unit is 750 rpm, and the circulation direction is from the inner side to the outer side of the cylinder.

After reaching the specified temperature and pressure (98°C, 25 MPa) in the pressure-resistant stainless steel tank, maintain the temperature and pressure for 60 minutes to dye the polyethylene cloth. After dyeing, open the stop valve (18) and slowly open the needle valve to release the carbon dioxide in the pressure-resistant stainless steel tank and reduce the pressure in the pressure-resistant stainless steel tank from 25 MPa to atmospheric pressure. Continue to circulate until it reaches the critical pressure of carbon dioxide (about 8 MPa). Then take out the polyethylene dyed cloth in the pressure-resistant stainless steel tank.

[Staining examples E2 to E14, and staining examples E18 to E20] The blue dye compound A-5 described in Dyeing Example E1 is changed to the dye compound described in Tables 3 to 9 or the disperse dye compound previously used for dyeing polyester fibers, etc., in addition to the same E1 the same dyeing sequence to obtain polyethylene dyed cloth. The dye compounds used in dyeing examples E1 to E14 and dyeing examples E18 to E20 are shown in Tables 28 to 32.

式（A）

[Table 28]

Formula (A)

式（B）

[Table 29]

Formula (B)

式（C）

[Table 30]

Formula (C)

式（D）

[Table 31]

Formula (D)

式（G）

[Table 32]

Formula (G)

The polyethylene dyed fabrics obtained in dyeing examples E1 to E14 and dyeing examples E18 to E20 were evaluated for dyeability, light fastness test, washing fastness test, sweat fastness test, and rubbing fastness test.

(1) Evaluation of dyeability The dyeability is visually evaluated by the Total K/S value obtained by color measurement of the dyed fabric and the dye residue after dyeing. The color measurement of the dyed cloth uses an integrating sphere spectrophotometer Color-Eye 5 (manufactured by GretagMacbeth), and the dyed cloth is pasted on white paper, and the observation light source is D65 with a 2 degree field of view.

(2) Light fastness test The light fastness test is carried out by the ultraviolet carbon arc lamp method in accordance with JIS L0842:2004. The outline of the test method is as follows. Using an ultraviolet fading tester U48 (manufactured by Suga Test Instruments Co., Ltd.), the dyed cloth was exposed for 20 hours at a black panel temperature of 63±3°C, and then the color change was judged.

(3) Washing fastness test The washing fastness test is carried out by the method in accordance with JIS L0844:2011 (No. A-2). The outline of the test method is as follows. Attach a multi-fiber interwoven fabric to the dyed cloth, and wash it for 30 minutes at 50±2°C in the presence of soap to determine the color change and the contamination of the cotton and nylon parts of the multi-fiber interwoven fabric. In addition, the contamination of the residual liquid after washing is judged.

(4) Perspiration fastness test The sweat fastness test is carried out by the method in accordance with JIS L0848:2004. The outline of the test method is as follows. Attach a multi-fiber interwoven fabric to the dyed cloth, immerse it in acid artificial sweat or alkaline artificial sweat for 30 minutes, keep it at 37±2°C for 4 hours under a load of 12.5 kPa, and then dry it at 60°C or less. Judgment of fading and contamination of the cotton part and nylon part of the multi-fiber interwoven fabric.

(5) Rubbing fastness test The rubbing fastness test is carried out according to the method of JIS L0849:2013. The outline of the test method is as follows. Using the rubbing fastness tester RT-300 (manufactured by Daiei Scientific Precision Manufacturing Co., Ltd.), apply a load of 2 N to the cotton cloth in a dry state or a cotton cloth in a wet state and rub the dyed cloth back and forth 100 times to carry out the treatment of the cotton cloth. Judgment of coloring.

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

[Table 33] Staining example E1 E2 E3 E4 E18 Synthesis example 5 3 4 60 66 Dye compound A-5 A-3 A-4 A-13 A-16 X _A NO ₂ NO ₂ NO ₂ NO ₂ NO ₂ Y _A Br Br Br Br Br R _A1 C ₈ H ₁₇ C ₈ H ₁₇ C ₈ H ₁₇ C ₆ H ₁₃ C ₈ H ₁₇ R _A2 C ₈ H ₁₇ C ₈ H ₁₇ C ₈ H ₁₇ C ₆ H ₁₃ C ₈ H ₁₇ R _A3 CH ₃ C ₂ H ₅ Ethyl-pentyl CH ₃ C ₂ H ₅ R _A4 CH ₃ CH ₃ CH ₃ CH ₃ C ₄ H ₉ Dyeability Total K/S 36 25 Not evaluated 37 40 Dye residue none none none none none Light fastness 4 3 5 3 3-4 Washing fastness Fade 5 5 5 5 4-5 Pollution cotton 5 5 5 5 5 nylon 5 5 5 5 5 Residual liquid contamination 4 4 5 4 4-5 Fastness to sweat (acid) Fade 5 5 5 5 5 Pollution cotton 5 5 5 5 5 nylon 5 5 5 5 5 Sweat fastness (alkaline) Fade 5 5 5 5 5 Pollution cotton 5 5 5 5 5 nylon 5 5 5 5 5 Rubbing fastness Dry 5 5 5 5 4-5 Wet 4-5 4-5 4-5 4-5 5

Regarding the dyeability of the compound of formula (A), R _A1 , R _A2 and R _A3 used in dyeing examples E1 to E4 and dyeing example E18 each independently represent an alkyl group having 1 to 14 carbon atoms or a carbon number of 1 to Compounds of 4 alkoxy or CN substituted alkyl with 1 to 14 carbons (wherein, _{at least one of R A1} , R _A2 and R _A3 is an alkyl with 4 to 14 carbons) has good dyeability.

In addition, with regard to the fastnesses of the compound of formula (A), X _A is a nitro group, Y _A is a bromine atom, and the _{larger the carbon number of R A1} , R _A2 and R _A3 , the better the compound.

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

[Table 34] Staining example E19 Synthesis example 48 Dye compound B-10 R _B1 C ₈ H ₁₇ R _B2 C ₈ H ₁₇ R _B3 Ethyl-pentyl Dyeability Total K/S twenty three Dye residue none Light fastness 5 Washing fastness Fade 5 Pollution cotton 5 nylon 5 Residual liquid contamination 5 Fastness to sweat (acid) Fade 5 Pollution cotton 5 nylon 5 Sweat fastness (alkaline) Fade 5 Pollution cotton 5 nylon 5 Rubbing fastness Dry 5 Wet 5

Regarding the dyeability of the compound of formula (B), R _B1 , R _B2 , and R _B3 used in dyeing example E19 are alkyl groups with 1 to 14 carbon atoms (wherein, at least one of _{R B1} , R _B2 and R _B3 Compounds with 4 to 14 carbon atoms have good dyeability.

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

[Table 35] Staining example E5 E6 E7 E20 Synthesis example 20 19 63 67 Dye compound C-4 C-3 C-18 C-19 X _C Cl Cl Cl Cl Y _C H H H H R _C1 C ₈ H ₁₇ C ₈ H ₁₇ C ₆ H ₁₃ C ₆ H ₁₃ R _C2 C ₈ H ₁₇ C ₈ H ₁₇ C ₆ H ₁₃ C ₆ H ₁₃ R _C3 CH ₃ C ₂ H ₅ CH ₃ C ₂ H ₅ Dyeability Total K/S twenty three 34 26 35 Dye residue none none none none Light fastness 5-6 6 5 5-6 Washing fastness Fade 4-5 4-5 4-5 4 Pollution cotton 4-5 5 5 5 nylon 5 5 5 5 Residual liquid contamination 3-4 4 3 4 Fastness to sweat (acid) Fade 4-5 4-5 5 4-5 Pollution cotton 5 5 5 5 nylon 5 5 5 5 Sweat fastness (alkaline) Fade 4-5 4-5 5 4-5 Pollution cotton 5 5 5 5 nylon 5 5 5 5 Rubbing fastness Dry 5 5 4-5 3-4 Wet 4-5 4-5 4 4

Regarding the dyeability of the compound of formula (C), R _C1 , R _C2 and R _C3 used in dyeing examples E5 to E7 and dyeing example E20 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein, R _C1 , _{At least one of R C2} and R _C3 is an alkyl group having 4 to 14 carbons) or X _C and Y _C each independently represent a hydrogen atom and a halogen atom, and R _C1 , R _C2 and R _C3 each independently represent a carbon number Compounds with 1 to 14 alkyl groups have good dyeability.

In addition, regarding the fastness of the compound of formula (C), X _C is a chlorine atom, Y _C is a hydrogen atom, and the _{larger the carbon number of R C1} , R _C2 , and R _C3 , the better the compound.

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

[Table 36] Staining example E8 E9 E10 E11 E12 E13 Synthesis example twenty four 31 30 64 65 49 Dye compound D-1 D-5 D-4 D-12 D-13 D-8 X _D Cl Br H Cl H Cl Y _D Cl Br H Cl H Cl R _D1 C ₈ H ₁₇ C ₈ H ₁₇ C ₈ H ₁₇ C ₆ H ₁₃ C ₆ H ₁₃ C ₂ H ₅ R _D2 C ₈ H ₁₇ C ₈ H ₁₇ C ₈ H ₁₇ C ₆ H ₁₃ C ₆ H ₁₃ C ₂ H ₅ Dyeability Total K/S twenty two twenty three twenty four 26 twenty three 17 Dye residue none none none none none none Light fastness 5 5-6 5 4 5 5 Washing fastness Fade 5 4-5 5 5 5 2 Pollution cotton 5 5 5 5 5 5 nylon 5 5 4-5 5 5 3-4 Residual liquid contamination 4 3 3-4 4 3 1-2 Fastness to sweat (acid) Fade 5 4-5 4-5 5 5 4 Pollution cotton 5 5 5 5 5 5 nylon 5 5 5 5 5 4-5 Sweat fastness (alkaline) Fade 5 4-5 4-5 5 5 4 Pollution cotton 5 5 5 5 5 5 nylon 5 5 5 5 5 4-5 Rubbing fastness Dry 5 5 5 5 5 2 Wet 4-5 4-5 4 4-5 4 3

Regarding the dyeability of the compound of formula (D), R _D1 used in dyeing examples E8 to E12 represents an alkyl group with 1 to 14 carbon atoms and R _D2 represents an alkyl group with 1 to 14 carbon atoms or the carbon number substituted with CN Compounds with 1 to 14 alkyl groups (wherein, when R _D2 is an alkyl group with 1 to 14 carbon atoms substituted by CN, R _D1 is an alkyl group with 4 to 14 carbon atoms), the dyeability is good.

However, the disperse dyes previously used for dyeing polyester fibers and the like used in dyeing example E13, that is _{, compounds in which both of R D1} and R _D2 are an alkyl group with a carbon number of 3 or less, have poor dyeability.

In addition, regarding the fastnesses 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 _D1 , R _The larger the carbon number of D2, the better the compound.

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

[Table 37] Staining example E14 Synthesis example 27 Dye compound G-1 R _G Hexyl-nonyl Dyeability Total K/S 19 Dye residue none Light fastness 6 Washing fastness Fade 5 Pollution cotton 5 nylon 5 Residual liquid contamination 4 Fastness to sweat (acid) Fade 5 Pollution cotton 5 nylon 5 Sweat fastness (alkaline) Fade 5 Pollution cotton 5 nylon 5 Rubbing fastness Dry 5 Wet 5

The dyeing on the compound of formula (G), the dye used in Example E14 of R _G is alkyl having 7 to 18 of the compounds of good dyeability.

Further, each of the compounds on fastness of formula (G), the carbon number of the hydrocarbon group R _G 15 were good.

＜Other polyethylene dyeing examples＞ Using a mixture of two or more of the dye compounds described in Tables 3 to 9 or the disperse dye compounds previously used for dyeing polyester fibers, etc., the polyethylene fiber is dyed by the supercritical carbon dioxide dyeing method.

For the obtained dyed cloth, evaluation of dyeability, light fastness test, washing fastness test, sweat fastness test, and rubbing fastness test were performed in the same manner as in the case of the polyethylene dyed cloth of the above-mentioned one dye compound. Table 38 shows the evaluation results of dyeing using the above-mentioned dyes. Dyeability is evaluated by visual inspection of Total K/S value, L ^* value, a ^* value, b ^* value and dye residue after dyeing obtained by color measurement of dyed cloth. In addition, the color measurement system of the dyed cloth uses an integrating sphere spectrophotometer Color-Eye 5 (manufactured by GretagMacbeth), and the dyed cloth is pasted on white paper, and the observation light source D65 is performed with a 2 degree field of view.

[Table 38] Staining example E15 E16 E18 Dye compound A-3 1.00% omf 2.00% omf A-5 1.00% omf C-3 0.30% omf 0.30% omf 0.60% omf D-4 0.70% omf 0.70% omf 1.40% omf Dye compound total 2.0% omf 2.0% omf 4.0% omf Dyeability L* 48.8 47.8 42.6 a* 4.6 3.0 5.2 b* -5.0 -6.3 -7.1 Total K/S 68 74 97 Dye residue none none none Light fastness 5-6 5-6 5 Washing fastness Fade 5 5 5 Pollution cotton 5 4-5 4-5 nylon 5 5 5 Liquid contamination 4 3-4 3-4 Fastness to sweat (acid) Fade 5 5 5 Pollution cotton 5 5 5 nylon 5 5 5 Sweat fastness (alkaline) Fade 5 5 5 Pollution cotton 5 5 5 nylon 5 5 5 Rubbing fastness Dry 4 4-5 2 Wet 3 4 3-4

As shown in Table 38, the orange dye, red dye, purple dye, and blue dye of the present invention obtained in dyeing examples E15, E16, and E18 are mixed. The user is a black dyed fabric with good dyeability and good fastness. .

As described above, the present invention is not limited to the above-mentioned embodiments, and the present invention also includes those obtained by appropriately combining or replacing the constitutions of the embodiments.

In addition, it is also possible to appropriately reorganize the combination or the sequence of steps in the embodiment based on the knowledge of the industry, or implement various design changes to the embodiment, and the embodiment with such changes may also be included in the scope of the present invention. . [Industrial availability]

The invention can be used for polyolefins used in clothing, underwear, hats, socks, gloves, sports clothing and other clothing, seat cushions and other vehicle interior materials, carpets, curtains, cushions, sofa covers, cushion covers, etc. Fiber dyeing.

1: Liquid CO ₂ gas tank 2: Filter 3: Cooling jacket 4: Cooler 5: High pressure pump 6: Preheater 7-9: Pressure gauge 10: Magnetic drive unit 11: DC motor 12, 13: Safety valve 14～18: Stop valve 19: Needle valve 20: Heater 21: Stainless steel cylinder 22: Pressure-resistant stainless steel tank

[Figure 1] Shows the supercritical carbon dioxide dyeing device used for dyeing.

Claims (12)

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

Formula (A) [In formula (A), X _A represents a nitro group, Y _A represents a halogen atom, and R _A1 , R _A2 and R _A3 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein, R _A1 , R _{At least one of A2} and R _A3 is an alkyl group with 4 to 14 carbons), R _A4 represents an alkyl group with 1 to 4 carbons],

Formula (B) [In formula (B), R _B1 , R _B2 and R _B3 each independently represent an alkyl group having 1 to 14 carbon atoms (wherein, _{at least one of R B1} , R _B2 and R _B3 is a carbon number of 4 To 14 alkyl)],

Formula (C) [In formula (C), X _C and Y _C represent hydrogen atom and halogen atom, halogen atom and nitro group, halogen atom and cyano group, cyano group and cyano group, nitro group and cyano group, hydrogen atom and Any combination of hydrogen atoms, R _C1 , R _C2 and R _C3 each independently represent an alkyl group with 1 to 14 carbons (wherein, _{at least one of R C1} , R _C2 and R _C3 is an alkane with 4 to 14 carbons base)],

Formula (D) [In formula (D), X _D and Y _D each independently represent a hydrogen atom, a halogen atom, or a cyano group, R _D1 represents an alkyl group having 1 to 14 carbons, and R _D2 represents a carbon number of 1 to 14 Or an alkyl group of 1 to 14 carbons substituted by CN; wherein _{at least one of R D1} and R _D2 is an alkyl of 4 to 14 carbons],

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

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

Formula (G) [In formula (G), _RG represents an alkyl group having 7 to 18 carbon atoms]. Such as the dye of claim 1, which is black and contains: At least one of purple or blue dye compounds. The above-mentioned purple or blue dye compounds contain compounds selected from the group consisting of compounds of general formula (A), compounds of general formula (B), compounds of general formula (C), and general formulas (F) more than one of the group consisting of compounds; The red dye compound contains at least one member selected from the group consisting of compounds of general formula (C) and compounds of general formula (D); and At least one of yellow or orange dye compounds, the yellow or orange dye compound contains selected from the group consisting of compounds of general formula (D), compounds of general formula (E) and compounds of general formula (G) More than one. Such as the dye of claim 2, which is black and contains: At least one of purple or blue dye compounds, the above-mentioned purple or blue dye compound contains a group selected from the group consisting of compounds of general formula (A), compounds of general formula (B) and compounds of general formula (F) More than one of them; The red dye compound of the compound of general formula (C); and The orange dye compound contains at least one member selected from the group consisting of compounds of general formula (D) and compounds of general formula (E). Such as the dye of claim 2 or 3, which contains: The blue dye compound of the compound of general formula (A), The red dye compound of the compound of general formula (C), and The orange dye compound of the compound of general formula (D). Such as the dye of any one of claims 2 to 4, which contains: The above-mentioned purple or blue dye compound in the range of 30 to 70% by mass, The above-mentioned red dye compound in the range of 5 to 25% by mass, and The yellow or orange dye compound in the range of 15 to 55% by mass. Such as the dye of claim 5, which contains: 40 to 60% by mass of the above-mentioned purple or blue dye compound, 5 to 25% by mass of the above-mentioned red dye compound, and 25 to 45% by mass of the yellow or orange dye compound. A dyeing method that uses supercritical carbon dioxide to dye polyolefin fibers, and includes the following steps: Dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the dye of any one of claims 1 to 6. The dyeing method of claim 7, wherein the dyeing step is performed at a pressure above 31°C and above 7.4 MPa. The dyeing method of claim 7 or 8, wherein the concentration of the dye relative to the fiber is in the range of 0.1 to 6.0 o.m.f. (on the mass of fiber, based on the fiber quality). The dyeing method according to any one of claims 7 to 9, wherein the polyolefin fiber is a polypropylene resin fiber. The dyeing method according to any one of claims 7 to 9, wherein the polyolefin fiber is a polyethylene resin fiber. A polyolefin fiber obtained by dyeing according to any one of claims 7 to 11.

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