KR20210061621A - Azo based reactive-disperse dyes for supercritical fluid dyeing and supercritical fluid dyeing using the same - Google Patents

Abstract

The present invention relates to a novel azo-based reactive disperse dye for dyeing in a supercritical fluid, and a supercritical fluid dyeing method using the same. The azo-based reactive disperse dye for dyeing in a supercritical fluid according to the present invention has various colors and is excellent in color fastness to sunlight, fastness to washing, fastness to sweat, and various physical properties. Therefore, when dyeing a polyamide-based fiber, an animal fiber, a cellulose fiber, and the like in a supercritical fluid by using the azo-based reactive disperse dye for dyeing in a supercritical fluid of the present invention, it is not only environmentally friendly, but also reduces production costs.

Description

Azo-based reactive dispersion dye for supercritical fluid dyeing and supercritical fluid dyeing method using the same{AZO BASED REACTIVE-DISPERSE DYES FOR SUPERCRITICAL FLUID DYEING AND SUPERCRITICAL FLUID DYEING USING THE SAME}

The present invention relates to an azo-based reactive dispersion dye for dyeing a supercritical fluid and a method for dyeing a supercritical fluid using the same.

Due to the recent trend of increasing awareness of environmental pollution and strengthening regulations, the burden on companies for dyeing wastewater treatment is increasing, so development of a new clean dyeing process technology that can fundamentally reduce the dyeing wastewater itself is required. .

In 1991, Schollmeyer et al. announced a technology for dyeing fibers after dissolving dyes in supercritical carbon dioxide. By promoting the development of dyes for textile dyeing using 100% PET and Spandex blended textile materials, commercial disperse dyes that do not contain any surfactants, and global brands such as Nike and Adidas, use supercritical fluid dyeing. With the launch of the product, interest in supercritical fluid dyeing is increasing worldwide.

Studies on supercritical dyeing of polyamide fibers (nylon, etc.) and cellulose fibers (Cell-OH, cotton, etc.) include i) pretreatment of fibers with an expanding agent; ii) improved affinity with disperse dyes by modifying fibers; iii) use of co-solvents such as water, alcohols, acetone, DMSO and DMF to improve the solubility of dyes and reactivity with fibers; iv) Various methods have been attempted, such as the use of reactive disperse dyes that are capable of covalent bonding with fibers and are water-insoluble. Among these methods, i) and ii) require pretreatment, and iii) may cause environmental pollution due to the use of a co-solvent.

Currently, polyamide-based fibers (nylon, etc.) are mainly dyed with water-soluble acid dyes and metal-containing acid dyes containing heavy metals. Existing acid dyes contain harmful amines or heavy metals that are harmful to the environment and are water-soluble, so they are not suitable for dye residue baths. Highly colored dyeing wastewater can occur due to the presence of dye.

On the other hand, conventional acid dyes and reactive dyes have poor solubility in supercritical fluids.

On the other hand, reactive disperse dyes are water-insoluble dyes that have the characteristics of reactive dyes and disperse dyes at the same time, and have reactive groups that can react with nylon, silk and wool amino groups, and hydroxyl groups of cotton, allowing covalent bonding between dyes and fibers. Therefore, it is possible to greatly improve the fastness of washing, and excellent covering property, which is an advantage of disperse dyes, can be exhibited.

In recent years, attempts to dye polyamide-based fibers (such as nylon), cellulose fibers (such as cotton), and blended fibers using reactive disperse dyes have been actively made. However, it is still showing laboratory-level research results, and it has been reported that the dyeing rate and fastness are not satisfactory.

Since reactive disperse dyes are water-insoluble, although the possibility of applying supercritical dyeing is high, the development of reactive disperse dyes for supercritical fluid dyeing has not been made at all.

Therefore, the present inventors can be used for dyeing supercritical fluids such as polyamide-based fibers (nylon, etc.), animal fibers (silk, wool) and cellulose fibers (cotton, etc.), and light fastness, washing fastness, sweat fastness, and various physical properties. By developing this excellent azo-based reactive disperse dye for supercritical fluid dyeing, it is intended to provide an azo-based reactive disperse dye for supercritical fluid dyeing that is environmentally friendly and can reduce production costs.

Patent Document 1: U.S. Patent 7,938,865 Patent Document 2: U.S. Patent 5,578,088

The present invention provides an azo-based reactive dispersion dye for dyeing supercritical fluids that can be used for dyeing supercritical fluids such as polyamide fibers, animal fibers and cellulose fibers, and has excellent light fastness, washing fastness, sweat fastness, and general physical properties. do.

In addition, the present invention provides a supercritical fluid dyeing method using the azo-based reactive dispersion dye for supercritical fluid dyeing.

The present invention provides an azo-based reactive dispersion dye for dyeing supercritical fluids that can be used for dyeing supercritical fluids such as polyamide fibers, animal fibers and cellulose fibers, and has excellent light fastness, washing fastness, sweat fastness, and general physical properties. As a result, the azo-based reactive dispersion dye for supercritical fluid dyeing of the present invention is represented by the following formula (1).

[Formula 1]

(In Chemical Formula 1,

또는

이고;A is

or

ego;

L is C ₁ -C ₂₀ alkylene or C ₂ -C ₂₀ alkenylene;

R is hydrogen or C ₁ -C ₂₀ alkylcarbonyloxy;

R ₁ and R ₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or halogen;

R ₃ to R ₈ are independently of each other hydrogen, hydroxy, C ₁ -C ₂₀ alkyl, halo C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkylC ₆ -C ₂₀ aryl, C ₆ -C ₂₀ arylC ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxycarbonylC ₁ -C ₂₀ alkyl or -N(R')-CO-R'';

R'is hydrogen or C ₁ -C ₂₀ alkyl;

R'' is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₆ -C ₂₀ aryl;

However, when L is C ₁ -C ₂₀ alkylene, R is C ₁ -C ₂₀ alkylcarbonyloxy.)

The azo-based reactive dispersion dye for supercritical fluid dyeing according to an embodiment of the present invention may be represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,

L is C ₁ -C ₅ alkylene;

R ₁ is hydrogen, C ₁ -C ₁₀ alkoxy or halogen;

R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxy;

R ₃ and R ₄ are independently of each other C ₁ -C ₁₀ alkyl, haloC ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₁₀ alkylC ₆ -C ₁₂ aryl, C ₆ -C ₁₂ aryl C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxycarbonylC ₁ -C ₁₀ alkyl;

R ₆ is hydrogen, hydroxy or -N(R')-CO-R'';

R'is hydrogen or C ₁ -C ₁₀ alkyl;

R'' is C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl or C ₆ -C ₁₂ aryl.)

In Formulas 2 and 3 according to an embodiment of the present invention, L is C ₂ -C ₃ alkylene; R ₁ is hydrogen, C ₁ -C ₆ alkoxy or halogen; R ₂ is hydrogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy; R ₃ and R ₄ are independently of each other C ₁ -C ₆ alkyl, haloC ₁ -C ₆ alkyl, C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxycarbonylC ₁ -C ₆ Alkyl; R ₆ is hydrogen, hydroxy or -NH-CO-R'';R'' can be C ₁ -C ₆ alkyl or C ₂ -C ₃ alkenyl.

The azo-based reactive dispersion dye for supercritical fluid dyeing according to an embodiment of the present invention may be represented by the following formula (4).

[Formula 4]

(In Chemical Formula 4,

R ₁ is hydrogen, C ₁ -C ₁₀ alkoxy or halogen;

R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxy;

R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₁₀ alkyl, haloC ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₁₀ alkylC ₆ -C ₁₀ aryl or C ₆ -C ₁₂ arylC ₁ -C ₁₀ alkyl.)

_{R 1} in Formula 4 according to an embodiment of the present invention is hydrogen or C ₁ -C ₆ alkoxy; R ₂ is hydrogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy; R ₇ is C ₁ -C ₆ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkylC ₆ -C ₁₂ aryl or C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl; R ₈ may be hydrogen, C ₁ -C ₆ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkylC ₆ -C ₁₂ aryl or C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl.

The azo-based reactive dispersion dye for supercritical fluid dyeing according to an embodiment of the present invention may be exemplified by the following compounds, but is not limited thereto.

(The R ₁ is hydrogen, methoxy or bromo; R ₂ is hydrogen, methyl or methoxy; R ₆ is -NHCOCH ₃ or -NHCOCH=CH ₂ .)

In addition, the present invention provides a method of dyeing a fiber with a supercritical fluid using the azo-based reactive dispersion dye for dyeing a supercritical fluid of Formula 1 above.

In the supercritical fluid dyeing method according to an embodiment of the present invention, the fiber may be selected from polyamide fiber, animal fiber, cellulose fiber, and the like.

The azo-based reactive disperse dye for supercritical fluid dyeing according to the present invention can exhibit various colors, and fibers, especially polyamide fibers (nylon, etc.), animal fibers (silk, wool), and cellulose fibers ( By forming covalent bonds with fibers such as cotton, etc.), it has the advantage of not only showing improved dyeing properties, but also excellent all physical properties including light fastness, washing fastness, and sweat fastness.

In addition, the azo-based reactive disperse dye for supercritical fluid dyeing according to the present invention has excellent solubility properties for supercritical carbon dioxide, so that a dispersant is not required.

In addition, when dyeing supercritical fluids such as polyamide fibers, animal fibers and cellulose fibers by using the azo-based reactive dispersion dye for supercritical fluid dyeing of the present invention, it is not only environmentally friendly, but also it is possible to reduce production cost.

That is, when dyeing a supercritical fluid such as polyamide fiber (nylon, etc.), animal fiber (silk, wool) and cellulose fiber (cotton, etc.) using the azo-based reactive dispersion dye for supercritical fluid dyeing according to the present invention, water Since it does not use at all, there is no wastewater, and an economical and clean dyeing process that does not require a drying process even after dyeing is possible. In addition, the azo-based reactive dispersion dye that has not been used after dyeing can be recovered in a dried state and reused, and the used carbon dioxide can also be recycled by the recycling process design.

Hereinafter, the present invention will be described in detail. If there are no other definitions in the technical terms and scientific terms used at this time, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the subject matter of the present invention may be unnecessarily obscure in the following description. Description of known functions and configurations will be omitted.

The following terms used in the present specification are defined as follows, but these are merely exemplary, and are not intended to limit the present invention, application, or use.

The terms "substituent", "radical", "group", "moiety", and "fragment" can be used interchangeably.

The term "C _A -C _B "means "the number of carbons is A or more and B or less."

The term "alkylene" refers to a straight chain or branched saturated hydrocarbon divalent group consisting of only carbon and hydrogen atoms, specifically methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene, Including, but not limited to, hexylene, octylene, nonylene, and the like.

The term "alkenylene" refers to a straight-chain or branched unsaturated hydrocarbon divalent group containing one or more double bonds between two or more carbon atoms, specifically ethenylene (-CH=CH-), propenylene ( -CH=CH-CH ₂ -, -CH ₂ -CH=CH-, -CH=C(CH ₃ )-, -C(CH ₃ )=CH-), and the like, but are not limited thereto.

The term "alkyl" refers to a monovalent straight chain or branched saturated hydrocarbon radical consisting only of carbon and hydrogen atoms. The alkyl may have 1 to 20 carbon atoms, or 1 to 10 carbon atoms, or 1 to 6 carbon atoms. Examples of the alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and the like.

The term "alkoxy" is a *-O-alkyl radical, where "alkyl" is as defined above. Specific examples include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

The term "halo" or "halogen" denotes a halogen element and includes, for example, fluoro, chloro, bromo and iodo.

The term "haloalkyl" refers to an alkyl radical in which one or more hydrogen atoms are each substituted with a halogen atom, wherein'alkyl' and'halogen' are as defined above. For example, haloalkyl includes fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, perfluoroethyl, bromomethyl, bromoethyl, bromopropyl, and the like. have.

The term "hydroxy" means *-OH.

The term "aryl" is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and includes a single or fused ring system containing 4 to 7, preferably 5 or 6 ring atoms suitably in each ring. And, it includes a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

The term “arylalkyl” refers to an alkyl radical substituted with at least one aryl, wherein aryl is as defined above. Specific examples include, but are not limited to, benzyl and the like.

The term “alkylaryl” is an aryl radical substituted with at least one alkyl, including, but not limited to, tolyl and the like.

The term "alkylcarbonyloxy" refers to an *-OC(=O)alkyl radical, wherein'alkyl' is as defined above. Examples of such alkylcarbonyloxy radicals include methylcarbonyloxy, ethylcarbonyloxy, isopropylcarbonyloxy, propylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, t-butylcarbonyloxy, and the like. However, it is not limited thereto.

The term "alkoxycarbonyl" refers to a *-C(=O) alkoxy radical, wherein'alkoxy' is as defined above. Examples of such alkoxycarbonyl radicals include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, etc. It is not limited.

The term “alkoxycarbonylalkyl” refers to an alkyl radical substituted with alkoxycarbonyl, wherein “alkoxycarbonyl” is as defined above. Examples of such alkoxycarbonylalkyl radicals are methoxycarbonylmethyl, ethoxycarbonylmethyl, isopropoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxy Carbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl, isopropoxycarbonylethyl, propoxycarbonylethyl, butoxycarbonylethyl, isobutoxycarbonylethyl, t-butoxycarbonylethyl, etc. Including, but not limited to.

The term "reactive disperse dye" refers to a disperse dye containing a reactive group capable of covalently bonding with fibers in the molecular structure of the dye.

The present invention relates to an azo-based reactive dispersion dye for supercritical fluid dyeing that can be used for dyeing supercritical fluids such as polyamide fibers, animal fibers, and cellulose fibers, and has excellent light fastness, washing fastness, sweat fastness, and general physical properties. will be.

The azo-based reactive dispersion dye for supercritical fluid dyeing of the present invention is represented by the following formula (1).

[Formula 1]

(In Chemical Formula 1,

또는

이고;A is

or

ego;

L is C ₁ -C ₂₀ alkylene or C ₂ -C ₂₀ alkenylene;

R is hydrogen or C ₁ -C ₂₀ alkylcarbonyloxy;

R ₁ and R ₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or halogen;

R ₃ to R ₈ are independently of each other hydrogen, hydroxy, C ₁ -C ₂₀ alkyl, halo C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkylC ₆ -C ₂₀ aryl, C ₆ -C ₂₀ arylC ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxycarbonylC ₁ -C ₂₀ alkyl or -N(R')-CO-R'';

R'is hydrogen or C ₁ -C ₂₀ alkyl;

R'' is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₆ -C ₂₀ aryl;

However, when L is C ₁ -C ₂₀ alkylene, R is C ₁ -C ₂₀ alkylcarbonyloxy.)

The azo-based reactive dispersion dye for supercritical fluid dyeing of the present invention is a specific structure in which a sulfone group is introduced at the 3rd or 4th position with respect to the azo group (-N=N-) and a specific substituent is introduced at a specific position. It is very suitable for dyeing hydrophobic fibers such as polyamide fibers, animal fibers and cellulose fibers in a fluid dyeing process.

The compound of Formula 1 according to an embodiment may be preferably a compound represented by the following Formula 2 or Formula 3 in terms of solubility in a supercritical fluid, reactivity with fibers, and fastness.

[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,

L is C ₁ -C ₅ alkylene;

R ₁ is hydrogen, C ₁ -C ₁₀ alkoxy or halogen;

R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxy;

R ₃ and R ₄ are independently of each other C ₁ -C ₁₀ alkyl, haloC ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₁₀ alkylC ₆ -C ₁₂ aryl, C ₆ -C ₁₂ aryl C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxycarbonylC ₁ -C ₁₀ alkyl;

R ₆ is hydrogen, hydroxy or -N(R')-CO-R'';

R'is hydrogen or C ₁ -C ₁₀ alkyl;

R'' is C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl or C ₆ -C ₁₂ aryl.)

More specifically, in Formulas 2 and 3, L is C ₂ -C ₃ alkylene; R ₁ is hydrogen, C ₁ -C ₆ alkoxy or halogen; R ₂ is hydrogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy; R ₃ and R ₄ are independently of each other C ₁ -C ₆ alkyl, haloC ₁ -C ₆ alkyl, C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxycarbonylC ₁ -C ₆ Alkyl; R ₆ is hydrogen, hydroxy or -NH-CO-R'';R'' can be C ₁ -C ₆ alkyl or C ₂ -C ₃ alkenyl.

For example, in Formulas 2 and 3, L is ethylene; R ₁ is hydrogen or halogen; R ₂ is hydrogen; R ₃ and R ₄ are independently of each other C ₁ -C ₆ alkyl, C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxycarbonylC ₁ -C ₆ alkyl; R ₆ may be hydrogen, hydroxy, C ₁ -C ₅ alkylcarbonylamino or vinylcarbonylamino.

For example, in Formulas 2 and 3, L is ethylene; R ₁ is C ₁ -C ₄ alkoxy; R ₂ is C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; R ₃ and R ₄ are independently of each other C ₁ -C ₄ alkyl, C ₆ -C ₁₂ arylC ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxycarbonylC ₁ -C ₄ alkyl; R ₆ may be hydrogen, hydroxy, C ₁ -C ₄ alkylcarbonylamino or vinylcarbonylamino.

The compound of Formula 1 according to an embodiment may be preferably a compound represented by Formula 4 below in terms of solubility in a supercritical fluid, reactivity with fibers, and fastness.

[Formula 4]

(In Chemical Formula 4,

R ₁ is hydrogen, C ₁ -C ₁₀ alkoxy or halogen;

R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxy;

R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₁₀ alkyl, haloC ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₁₀ alkylC ₆ -C ₁₀ aryl or C ₆ -C ₁₂ arylC ₁ -C ₁₀ alkyl.)

More specifically, in Formula 4, R ₁ is hydrogen or C ₁ -C ₆ alkoxy; R ₂ is hydrogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy; R ₇ is C ₁ -C ₆ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkylC ₆ -C ₁₂ aryl or C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl; R ₈ may be hydrogen, C ₁ -C ₆ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkylC ₆ -C ₁₂ aryl or C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl.

For example, in Formula 4, R ₁ and R ₂ are hydrogen; R ₇ is C ₆ -C ₁₂ aryl or C ₁ -C ₄ alkylC ₆ -C ₁₂ aryl; R ₈ may be C ₁ -C ₄ alkyl or C ₆ -C ₁₂ arylC ₁ -C ₄ alkyl.

For example, in Formula 4, R ₁ is C ₁ -C ₆ alkoxy; R ₂ is C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy; R ₇ is C ₆ -C ₁₂ aryl or C ₁ -C ₄ alkylC ₆ -C ₁₂ aryl; R ₈ may be C ₁ -C ₄ alkyl or C ₆ -C ₁₂ arylC ₁ -C ₄ alkyl.

More preferably, the compound of Formula 1 may be specifically exemplified as the following compound, but the following compounds do not limit the present invention.

(The R ₁ is hydrogen, methoxy or bromo; R ₂ is hydrogen, methyl or methoxy; R ₆ is -NHCOCH ₃ or -NHCOCH=CH ₂ .)

The azo-based reactive dispersion dye for supercritical fluid dyeing according to an embodiment can be used for dyeing supercritical fluids such as polyamide fiber, animal fiber, and cellulose fiber, and has light fastness, washing fastness, sweat fastness, and various physical properties. It has an excellent advantage.

In addition, the present invention relates to a method of preparing an azo-based reactive dispersion dye for supercritical fluid dyeing of Formula 1, which may be prepared as shown in Reaction Schemes 1 and 2, but any possible method that can be recognized by those skilled in the art Of course, all are possible.

[Scheme 1]

[Scheme 2]

(In Reaction Schemes 1 and 2, L, R, and R ₁ to R ₈ are the same as defined in Formula 1.)

Hereinafter, the azo-based reactive dispersion dye for dyeing the supercritical fluid of Formula 1 will be described in detail.

The azo-based reactive dispersion dye according to an embodiment is

a) Disperse and stir the sulfonylaniline derivative of formula (a) in water, acetic acid, or a mixed solution of acetic acid and propionic acid, stirred, and then hydrochloric acid, sodium nitrite (NaNO ₂ ), or nitrosylsulfuric acid (HO ₃ SONO) Diazotizing by adding;

b) dissolving the aminobenzene derivative of formula b-1 in alcohol or acetone, or dissolving the 2-pyrazolin-5-one derivative of formula b-2 in an alkaline solution to prepare a coupler solution;

c) mixing and stirring the diazotized solution of step a) and the coupler solution of step b).

The sulfonylaniline derivative of Formula a and the aminobenzene derivative of Formula b-1 may be used in the same molar ratio, and the sulfonylaniline derivative of Formula a and the 2-pyrazolin-5-one derivative of Formula b-2 are the same. It can be used in a molar ratio.

In addition, after step c), d) neutralizing the solution of step c), filtering the solution, washing and drying with a solvent; may be further included. The solution of step c) may be neutralized with sodium acetate.

In addition, in the case of using a mixed solution of acetic acid and propionic acid in step a), it is preferable to use it in a volume ratio range of 3 to 5: 0.5 to 3, and maintaining the temperature at 0 to 10°C facilitates the diazo reaction well. To be able to.

In addition, in steps b) and c), the temperature is maintained in the range of -20 to 20°C, preferably 0 to 10°C, and efficient coupling when in the range of pH 1 to 5, preferably pH 1 to 2 The reaction is possible.

In the step b), the alcohol may be a C1-C4 lower alcohol such as methanol, ethanol, propanol, and butanol, preferably methanol or ethanol.

In the step b), the alkali solution is a solution obtained by dissolving an alkali metal salt in a solvent of water, alcohol or an aqueous alcohol solution, and the alkali metal salt may include a hydroxide, carbonate, hydrogen carbonate, etc. of an alkali metal such as sodium and potassium. Sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate can be used. The alcohol may be a C1-C4 lower alcohol such as methanol, ethanol, propanol or butanol, preferably methanol or ethanol.

Specifically, the alkali solution may be an aqueous solution of an alkali metal such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, and preferably an aqueous solution of sodium hydroxide or potassium hydroxide may be used.

In addition, the present invention provides a supercritical fluid dyeing method using the azo-based reactive dispersion dye for dyeing the supercritical fluid of Formula 1 above.

The azo-based reactive dispersion dye for supercritical fluid dyeing of Formula 1 is more suitable for supercritical fluid dyeing of polyamide-based fibers, animal fibers, and cellulose fibers.

When dyeing a supercritical fluid, the dyeing temperature substantially varies depending on the substrate to be dyed, but is generally in the range of 90 to 200°C, preferably 100 to 150°C, and the pressure should be at least _{so high that CO 2} exists in a supercritical state. . The pressure may preferably be in the range of 73 to 400 bar, preferably 150 to 300 bar.

In the following, for a detailed understanding of the present invention, the representative compounds of the present invention will be described in detail with reference to synthesis examples and examples, and the synthesis examples according to the present invention can be modified in various different forms, and the scope of the present invention It should not be construed as limited to the synthesis examples and examples described below. Synthesis examples and examples of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Tables 1 to 4 below describe the synthesis yield, molecular weight ( m/e ), maximum absorption wavelength (λ _max ) and molar absorption coefficient (ε) analysis data of the synthesized compound.

[Example 1] N -[3-hydroxy-4-[2-(4-vinylsulfonylphenyl)-diagenyl]phenyl]- N Preparation of -(2-ethoxy-2-oxoethyl)-glycine ethyl ester (1)

4-(vinylsulfonyl)aniline (A) (0.92 g, 5 mmol) was dispersed in (10 mL of acetic acid) and stirred at room temperature for 30, then concentrated hydrochloric acid (1.5 mL) was slowly added and the reaction mixture was 0 ~ 5 °C. Cooled to. Then, 3 N sodium nitrite (NaNO ₂ ) (1.8 mL, 5.4 mmol) was slowly added for 20 minutes, taking care not to exceed 5 ℃ of the reaction mixture, and the reaction mixture was stirred at 0~5 ℃ for 1 hour, and then sulfamic acid (0.05 g) was added to remove excess nitrous acid and the diazotization reaction was completed.

N-glycine ethyl ester (B) 1.4 g, and then completely dissolved, the diazotizing a (5 mmol) in 5 ml MeOH solution (a-2-oxoethyl 2-) - N - (3- hydroxy-phenyl) The reaction mixture was slowly added for 10 minutes, taking care not to increase the temperature of the reaction mixture, and stirred at 0-5° C. for 1.5 hours.

Sodium acetate (NaOAc) (1.5 g) was added to the reaction solution, and after stirring at room temperature for 30 minutes, the reaction solution was poured into distilled water (50 mL) and stirred for 1 hour. The resulting solid product was filtered and washed thoroughly with distilled water. , Washed with a small amount of methanol, dried and N -[3-hydroxy-4-[2-(4-vinylsulfonylphenyl)-diagenyl]phenyl] -N -(2-ethoxy-2-oxoethyl) -Glycine ethyl ester ( 1 ) was obtained.

[Examples 2 to 6]

It was carried out in the same manner as in Example 1, but instead of Compound A, an aminophenylvinylsulfone derivative or an aminophenyl-β-acetoxyethylsulfone derivative as shown in Table 1 was used as a diazo body, and Compound B was used as a coupler. Thus, azo-based reactive dispersion dyes for dyeing supercritical fluids of compounds 2 to 6 were obtained.

Example compound R ₁

R ₂ yield
(%) MS
( m/e ) λ _max ^*1
(nm) ε(×10 ^-4 )
(Lmol ^-1 cm ^-1 ) One One H 4-SO ₂ CH=CH ₂ H 93 475 456 4.28 2 2 H 3-SO ₂ CH=CH ₂ H 94 475 445 3.13 3 3 OCH ₃ 4-SO ₂ CH=CH ₂ OCH ₃ 90 535 478 3.49 4 4 OCH ₃ 4-SO ₂ CH=CH ₂ CH ₃ 83 519 468 3.64 5 5 Br 4-SO ₂ CH=CH ₂ H 90 554 475 3.49 6 6 H 4-SO ₂ CH ₂ CH ₂ OAc H 87 535 454 4.13 ^*1 UV measurement solvent: Acetone

[Examples 7 to 12]

It was carried out in the same manner as in Example 1, except that an aminophenylvinylsulfone derivative or an aminophenyl-β-acetoxyethylsulfone derivative as shown in Table 2 was used as a diazo, and N -ethyl- N- of Compound C (3-hydroxyphenyl)-glycine ethyl ester was used as a coupler to obtain azo-based reactive disperse dyes for dyeing supercritical fluids of compounds 7 to 12.

Example compound R ₁

R ₂ yield
(%) MS
( m/e ) λ _max ^*1
(nm) ε(×10 ^-4 )
(Lmol ^-1 cm ^-1 ) 7 7 H 4-SO ₂ CH=CH ₂ H 77 417 467 4.64 8 8 H 3-SO ₂ CH=CH ₂ H 44 417 455 3.91 9 9 OCH ₃ 4-SO ₂ CH=CH ₂ OCH ₃ 95 477 485 4.53 10 10 OCH ₃ 4-SO ₂ CH=CH ₂ CH ₃ 81 461 475 4.66 11 11 Br 4-SO ₂ CH=CH ₂ H 93 496 488 4.15 12 12 H 4-SO ₂ CH ₂ CH ₂ OAc H 96 477 465 4.54 ^*1 UV measurement solvent: Acetone

[Examples 13 to 19]

Compound 13 was carried out in the same manner as in Example 1, but using an aminophenylvinylsulfone derivative or an aminophenyl-β-acetoxyethylsulfone derivative as shown in Table 3 as a diazo body and a benzene derivative as a coupler. Azo-based reactive disperse dyes for dyeing supercritical fluids of to 19 were obtained.

Example compound R ₁

R ₂ R ₃ R ₄ yield
(%) MS
( m/e ) λ _max ^*1
(nm) ε(×10 ^-4 )
(Lmol ^-1 cm ^-1 ) 13 13 H 4-SO ₂ CH=CH ₂ H C ₂ H ₅ CH ₂ Ph 86 405 448 3.32 14 14 H 3-SO ₂ CH=CH ₂ H C ₂ H ₅ CH ₂ Ph 70 405 433 2.55 15 15 H 4-SO ₂ CH ₂ CH ₂ OAc H C ₂ H ₅ CH ₂ Ph 90 465 446 3.29 16 16 H 4-SO ₂ CH=CH ₂ H C ₄ H ₉ C ₄ H ₉ 76 399 464 3.53 17 17 H 3-SO ₂ CH=CH ₂ H C ₄ H ₉ C ₄ H ₉ 89 399 449 2.90 18 18 OCH ₃ 4-SO ₂ CH=CH ₂ OCH ₃ C ₄ H ₉ C ₄ H ₉ 57 459 474 3.07 19 19 OCH ₃ 4-SO ₂ CH=CH ₂ CH ₃ C ₄ H ₉ C ₄ H ₉ 82 443 462 3.34 ^*1 UV measurement solvent: Acetone

[Examples 20 to 29]

Conducted in the same manner as in Example 1, but using an aminophenylvinylsulfone derivative as shown in Table 4 below as a diazo body and using an amide derivative as a coupler, azo-based reactivity for dyeing supercritical fluids of compounds 20 to 29 A dispersion dye was obtained.

Example compound R ₁

R ₂ R ^a yield
(%) MS
( m/e ) λ _max ^*1
(nm) ε(×10 ^-4 )
(Lmol ^-1 cm ^-1 ) 20 20 H 4-SO ₂ CH=CH ₂ H CH ₃ 90 400 488 4.14 21 21 H 3-SO ₂ CH=CH ₂ H CH ₃ 64 400 473 3.66 22 22 OCH ₃ 4-SO ₂ CH=CH ₂ OCH ₃ CH ₃ 74 460 503 4.53 23 23 OCH ₃ 4-SO ₂ CH=CH ₂ CH ₃ CH ₃ 75 444 495 4.53 24 24 Br 4-SO ₂ CH=CH ₂ H CH ₃ 80 479 503 4.70 25 25 H 4-SO ₂ CH=CH ₂ H -CH=CH ₂ 90 412 490 4.13 26 26 H 3-SO ₂ CH=CH ₂ H -CH=CH ₂ 83 412 475 3.35 27 27 OCH ₃ 4-SO ₂ CH=CH ₂ OCH ₃ -CH=CH ₂ 80 472 507 4.39 28 28 OCH ₃ 4-SO ₂ CH=CH ₂ CH ₃ -CH=CH ₂ 85 456 499 4.37 29 29 Br 4-SO ₂ CH=CH ₂ H -CH=CH ₂ 53 491 504 3.69 ^*1 UV measurement solvent: Acetone

[Examples 30 to 33]

It was carried out in the same manner as in Example 1, except that an aminophenylvinylsulfone derivative as shown in Table 5 was used as a diazo body, and 3-methyl-1-phenyl-2-pyrazolin-5one of Compound D was used as a coupler. Was dissolved in an aqueous sodium hydroxide solution and used to obtain an azo-based reactive dispersion dye for dyeing a supercritical fluid of compounds 30 to 33.

Example compound R ₁

R ₂ yield
(%) MS
( m/e ) λ _max ^*1
(nm) ε(×10 ^-4 )
(Lmol ^-1 cm ^-1 ) 30 30 H 4-SO ₂ CH=CH ₂ H 90 368 385 2.74 31 31 H 3-SO ₂ CH=CH ₂ H 94 368 382 2.41 32 32 OCH ₃ 4-SO ₂ CH=CH ₂ OCH ₃ 93 428 425 2.58 33 33 OCH ₃ 4-SO ₂ CH=CH ₂ CH ₃ 87 412 411 2.82 ^*1 UV measurement solvent: Acetone

Hereinafter, the dyeing properties of the azo-based reactive dispersion dye for supercritical fluid dyeing prepared in the present invention were confirmed by Experimental Examples 1 to 4.

[Experimental Example 1] Dyeing Experiment

0.05 g (0.5% owf; On the Weight of Fiber. The amount of dye used relative to the weight of the dyed material) and nylon fiber (Nylon 100%, Double Pique) 10 g of a high pressure dyer with a capacity of 200 mL _{, cool the CO 2 with a cooler, and then inject the cooled CO 2} into the high pressure dye using a pressure pump, and then gradually increase the temperature to 120℃ to 250 Atm was maintained and supercritical fluid staining was performed for 2 hours.

[Experimental Example 2] Light fastness test (KS K ISO 105-B08: Xenon arc method)

The specimen is exposed to a xenon arc lamp under the specified conditions (chamber temperature: 43±3℃, black panel temperature: 63±3℃, relative humidity: 50±5%), and the degree of change of the test piece is compared with the standard gray color table for AATCC color change. It was determined by comparison.

[Experimental Example 3] Washing fastness test (KS K ISO 105-C06 A1S)

After inserting the attached white fabric (6 types of multi-fibre woven fabric) on the test piece and sewing the four sides, stainless steel was added to the standard detergent washing solution, and then washed, washed with water, dehydrated and dried under the specified conditions, and compared with the standard gray color table.

[Experimental Example 4] Sweat (acid and alkaline) fastness test (KS K ISO 105-E04)

After treating the test piece with artificial sweat solution, it was sandwiched between two plates, mounted on a sweat tester, left to stand for a certain period of time, dried, and compared with the standard gray color table for discoloration and the standard gray color table for contamination. Judged.

Table 6 below shows the results of the test results of the light fastness, washing fastness, and sweat (acid and alkaline) fastness of the supercritical fluid dyeing samples prepared in the present invention.

[Comparative Experimental Examples 1 to 2]

Supercritical fluid dyeing was performed in the same manner as in Experimental Example 1, except that an azo-based dispersion dye (C1 or C2) having the following structure was used, and fastness characteristics were evaluated in the same manner as in Experimental Examples 2 to 4.

compound Fastness daylight Washing (fading) Sweat (discoloration) acid Alkaline Example 1 One 4-5 4-5 4-5 4-5 Example 2 2 4 4-5 4-5 4-5 Example 7 7 4 4-5 4-5 4-5 Example 8 8 4 4-5 4-5 4-5 Example 12 12 4 4-5 4-5 4-5 Example 13 13 4-5 4-5 4-5 4-5 Example 14 14 4-5 4-5 4-5 4-5 Example 15 15 4-5 4-5 4-5 4-5 Example 16 16 4-5 4-5 4-5 4-5 Example 17 17 4-5 4-5 4-5 4-5 Example 18 18 4 4-5 4-5 4-5 Example 19 19 4-5 4-5 4-5 4-5 Example 20 20 4-5 4-5 4-5 4-5 Example 22 22 4 4-5 4-5 4-5 Example 23 23 4-5 4-5 4-5 4-5 Example 24 24 4 4-5 4-5 4-5 Example 25 25 4-5 4-5 4-5 4-5 Example 26 26 4 4-5 4-5 4-5 Example 27 27 4 4-5 4-5 4-5 Example 28 28 4 4-5 4-5 4-5 Example 29 29 4 4-5 4-5 4-5 Example 30 30 4 4-5 4-5 4-5 Example 31 31 4-5 4-5 4-5 4-5 Example 32 32 4 4-5 4-5 4-5 Example 33 33 4-5 4-5 4-5 4-5 Comparative Example 1 C1 1-2 4-5 4-5 4-5 Comparative Example 2 C2 1-2 4-5 4-5 4-5 Evaluation: 5. Very good 4. Excellent 3. Average 2. Slightly poor 1. Poor

As shown in Tables 1 to 5, the azo-based reactive disperse dye for supercritical fluid dyeing of the present invention synthesized using various diazo bodies and couplers has various colors of yellow, orange and red, satisfactory yield, and high mol. The extinction coefficient was shown.

In addition, as shown in Table 6, the dyed sample dyed with supercritical fluid using the azo-based reactive dispersion dye for supercritical fluid dyeing of the present invention exhibits excellent light fastness, washing fastness, and sweat (acid and alkaline) fastness. It was confirmed that it is effective for dyeing nylon fibers.

On the other hand, when supercritical fluid dyeing was performed using the previously known azo-based disperse dyes C1 and C2, it was observed that the light fastness characteristics of the dyed samples were reduced to grades 1-2.

Accordingly, it can be seen that the azo-based reactive dispersion dye for supercritical fluid dyeing of the present invention can be used as a dye for supercritical fluid dyeing such as polyamide fiber, animal fiber, and cellulose fiber.

Claims (8)

Azo-based reactive dispersion dye for dyeing supercritical fluids represented by the following formula (1):
[Formula 1]

(In Chemical Formula 1,
A is

or

ego;
L is C ₁ -C ₂₀ alkylene or C ₂ -C ₂₀ alkenylene;
R is hydrogen or C ₁ -C ₂₀ alkylcarbonyloxy;
R ₁ and R ₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy or halogen;
R ₃ to R ₈ are independently of each other hydrogen, hydroxy, C ₁ -C ₂₀ alkyl, halo C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkylC ₆ -C ₂₀ aryl, C ₆ -C ₂₀ arylC ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxycarbonylC ₁ -C ₂₀ alkyl or -N(R')-CO-R'';
R'is hydrogen or C ₁ -C ₂₀ alkyl;
R'' is C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₆ -C ₂₀ aryl;
However, when L is C ₁ -C ₂₀ alkylene, R is C ₁ -C ₂₀ alkylcarbonyloxy.) The method of claim 1,
Azo reactive disperse dyes for dyeing supercritical fluids represented by the following Chemical Formula 2 or Chemical Formula 3:
[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,
L is C ₁ -C ₅ alkylene;
R ₁ is hydrogen, C ₁ -C ₁₀ alkoxy or halogen;
R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxy;
R ₃ and R ₄ are independently of each other C ₁ -C ₁₀ alkyl, haloC ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₁₀ alkylC ₆ -C ₁₂ aryl, C ₆ -C ₁₂ aryl C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxycarbonylC ₁ -C ₁₀ alkyl;
R ₆ is hydrogen, hydroxy or -N(R')-CO-R'';
R'is hydrogen or C ₁ -C ₁₀ alkyl;
R'' is C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl or C ₆ -C ₁₂ aryl.) The method of claim 2,
L is C ₂ -C ₃ alkylene;
R ₁ is hydrogen, C ₁ -C ₆ alkoxy or halogen;
R ₂ is hydrogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;
R ₃ and R ₄ are independently of each other C ₁ -C ₆ alkyl, haloC ₁ -C ₆ alkyl, C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxycarbonylC ₁ -C ₆ Alkyl;
R ₆ is hydrogen, hydroxy or -NH-CO-R'';
R'' is a C ₁ -C ₆ alkyl or C ₂ -C ₃ alkenyl, azo reactive disperse dye for supercritical fluid dyeing. The method of claim 1,
Azo-based reactive disperse dyes for dyeing supercritical fluids represented by the following formula (4):
[Formula 4]

(In Chemical Formula 4,
R ₁ is hydrogen, C ₁ -C ₁₀ alkoxy or halogen;
R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxy;
R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₁₀ alkyl, haloC ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₁₀ alkylC ₆ -C ₁₀ aryl or C ₆ -C ₁₂ arylC ₁ -C ₁₀ alkyl.) The method of claim 4,
R ₁ is hydrogen or C ₁ -C ₆ alkoxy;
R ₂ is hydrogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;
R ₇ is C ₁ -C ₆ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkylC ₆ -C ₁₂ aryl or C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl;
R ₈ is hydrogen, C ₁ -C ₆ alkyl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkylC ₆ -C ₁₂ aryl or C ₆ -C ₁₂ arylC ₁ -C ₆ alkyl, supercritical fluid dyeing Azo-based reactive dispersion dye. The method of claim 1,
Azo-based reactive dispersion dye for dyeing supercritical fluids selected from the following compounds.

(The R ₁ is hydrogen, methoxy or bromo; R ₂ is hydrogen, methyl or methoxy; R ₆ is -NHCOCH ₃ or -NHCOCH=CH ₂ .) A method for dyeing fibers with a supercritical fluid using the azo-based reactive dispersion dye for dyeing a supercritical fluid according to any one of claims 1 to 6. The method of claim 7,
The fiber is one or two or more selected from polyamide fiber, animal fiber and cellulose fiber, supercritical fluid dyeing method.