KR102124599B1 - Azo based disperse dyes for supercritical fluid dyeing and method for preparing the same - Google Patents

Abstract

The present invention relates to a new azo-based dispersion dye for supercritical fluid dyeing and a method for manufacturing the same, and the azo-based dispersion dye for various colors of supercritical fluid dye prepared according to the present invention has light fastness, wash fastness, sweat fastness, and various properties. Excellent physical properties.
Therefore, by using the azo-based disperse dye for supercritical fluid dyeing of the present invention, it is not only environmentally friendly when dyeing supercritical fluids such as polyester fibers, synthetic fibers, and polyester blended fibers, but also can reduce production costs.

Description

AZO BASED DISPERSE DYES FOR SUPERCRITICAL FLUID DYEING AND METHOD FOR PREPARING THE SAME

The present invention relates to azo-based dispersion dyes for supercritical fluid dyeing and synthesis thereof.

Due to the recent increase in awareness of environmental pollution and the strengthening of regulations, the burden of the company on the treatment of dyed wastewater is increasing, and thus it is required to develop a new clean dyeing process technology that can fundamentally reduce dyed wastewater itself. . As part of this, as global brands such as Nike and Adidas recently released clothing products using supercritical fluid dyeing, interest in supercritical fluid dyeing is increasing worldwide.

In 1991, Schollmeyer et al. published a technique for dyeing fibers after dissolving dyes in supercritical carbon dioxide. In 2011, DyeCoo of the Netherlands, which succeeded in commercializing the supercritical fluid dyeing machine, and Huntsman of Germany, a dye maker, have entered into a supercritical fluid through business cooperation By promoting the development of dyes for textile dyeing using, we developed a commercial dispersion dye capable of dyeing 100% PET and Spandex blended fiber materials, which is different from the current dyes dyed in water, and contains only pure dyes without any surfactant. have.

Dyestuffs for supercritical fluid dyeing have been partially developed and supplied by Huntsman and Colourtex of India, but there are no developments for dyestuffs for supercritical fluid dyeing in Korea.

Accordingly, the present inventors can be used for supercritical fluid dyeing such as polyester fiber, synthetic fiber, and polyester blend fiber, and azo-based disperse dyes for supercritical fluid dyeing with excellent light fastness, wash fastness, sweat fastness, and various properties. It is intended to provide azo-based disperse dyes for supercritical fluid dyeing, which are not only environmentally friendly, but also capable of reducing production costs.

Patent Document 1: U.S. Patent 8,409,300 Patent Document 2: US Patent 9,376,570

The present invention can be used for supercritical fluid dyeing such as polyester fiber, synthetic fiber, and polyester blended fiber, and azo-based disperse dye for supercritical fluid dyeing having excellent light fastness, wash fastness, sweat fastness and various physical properties and its Provide synthetic methods.

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

The present invention can be used for supercritical fluid dyeing such as polyester fiber, synthetic fiber, and polyester blend fiber, and provides azo-based disperse dyes for supercritical fluid dyeing with excellent light fastness, wash fastness, sweat fastness, and various physical properties By doing, the azo-based dispersion dye for supercritical fluid dyeing of the present invention is represented by the following formula (1).

[Formula 1]

(In the formula 1,

또는

이고;A is

or

ego;

R ₁ and R ₂ are different from each other and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen, cyano or SO ₂ F;

R ₃ and R ₄ are each independently hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen, cyano or SO ₂ F;

R ₅ and R ₆ are each independently a hydrogen atom, hydroxy, acetamide, (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

R ₇ and R ₈ are each independently a hydrogen atom, hydroxy, acetamide, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

However, when R ₈ is a hydrogen atom or acetamide, R ₂ is necessarily SO ₂ F, and when R ₄ is (C ₁ -C ₂₀ )alkyl, R ₈ must be hydroxy or (C ₁ -C ₂₀ )alkoxycarbo Neiloxy.)

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

In addition, the present invention is a) by dispersing the amine derivative of the formula (4) in a solution selected from water, acetic acid or a mixed solution of acetic acid and propionic acid, followed by stirring, then hydrochloric acid, sodium nitrite (NaNO ₂ ) or nitrosylsulfuric acid (HO ₃ SONO) to diazotize; b) dissolving an aryl derivative of Formula 5 in alcohol or acetone to prepare a coupler solution; And c) mixing and agitating the diazotized solution of step a) and the coupler solution of step b) to provide a method for producing azo-based dispersion dyes for supercritical fluid dyeing of Chemical Formula 1.

[Formula 1]

[Formula 4]

[Formula 5]

(In the formulas 1, 4 and 5,

또는

이고; A is

or

ego;

R ₁ and R ₂ are different from each other and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen, cyano or SO ₂ F;

R ₃ and R ₄ are each independently hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen, cyano or SO ₂ F;

R ₅ and R ₆ are each independently a hydrogen atom, hydroxy, acetamide, (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

R ₇ and R ₈ are each independently a hydrogen atom, hydroxy, acetamide, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

However, when R ₈ is a hydrogen atom or acetamide, R ₂ is necessarily SO ₂ F, and when R ₄ is (C ₁ -C ₂₀ )alkyl, R ₈ must be hydroxy or (C ₁ -C ₂₀ )alkoxycarbo Neiloxy.)

Azo-based dispersion dyes for dyeing supercritical fluids of various colors according to the present invention are excellent in light fastness, wash fastness, and properties. In addition, the azo-based disperse dye for supercritical fluid dyeing according to the present invention has excellent solubility properties for supercritical carbon dioxide, so a dispersant is unnecessary.

Therefore, by using the azo-based disperse dye for supercritical fluid dyeing of the present invention, it is not only environmentally friendly when dyeing supercritical fluids such as polyester fibers, synthetic fibers, and polyester blended fibers, but also can reduce production costs.

That is, when the supercritical fluid is dyed to a polyester fiber, a synthetic fiber, and a polyester blended fiber using the azo-based disperse dye for supercritical fluid dyeing according to the present invention, no waste water is generated because water is not used at all. An economical and clean dyeing process that requires no drying after dyeing is possible. In addition, after dyeing, the unused dispersion dye can be recovered and reused in a dried state, and the used carbon dioxide can also be recycled by the recycling process design.

Hereinafter, the present invention will be described in detail. At this time, unless there are other definitions in the technical terms and scientific terms used, those skilled in the art to which this invention belongs have meanings that are commonly understood, and the following description may unnecessarily obscure the subject matter of the present invention. Descriptions of known functions and configurations will be omitted.

The term "alkyl" described in the specification refers to a monovalent straight-chain or ground saturated hydrocarbon radical consisting only of carbon and hydrogen atoms, examples of such alkyl radicals being methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl , Pentyl, hexyl, octyl, dodecyl, and the like.

The term "alkoxy" described in the specification means a monovalent radical in which oxygen and alkyl are bonded together, where "alkyl" is as defined above. Examples of such alkoxy include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

The term "haloalkyl" described in the specification means an alkyl radical substituted with a halogen atom as defined above, and examples of haloalkyl include fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, and difluoroethyl , Bromopropyl, and the like.

The term "aryl" described in the specification is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and is preferably a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring. It includes a system, and 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" described in the specification means an alkyl radical substituted with an aryl radical as defined above. Examples of such arylalkyl radicals include, but are not limited to, benzyl and the like.

The present invention can be used for supercritical fluid dyeing such as polyester fiber, synthetic fiber and polyester blend fiber, and relates to azo-based disperse dyes for supercritical fluid dyeing having excellent light fastness, wash fastness, sweat fastness, and various physical properties will be.

The azo-based dispersion dye for supercritical fluid dyeing of the present invention is represented by the following Chemical Formula 1.

[Formula 1]

(In the formula 1,

또는

이고;A is

or

ego;

R ₁ and R ₂ are different from each other and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen, cyano or SO ₂ F;

R ₃ and R ₄ are each independently hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen, cyano or SO ₂ F;

R ₅ and R ₆ are each independently a hydrogen atom, hydroxy, acetamide, (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

R ₇ and R ₈ are each independently a hydrogen atom, hydroxy, acetamide, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

However, when R ₈ is a hydrogen atom or acetamide, R ₂ is necessarily SO ₂ F, and when R ₄ is (C ₁ -C ₂₀ )alkyl, R ₈ must be hydroxy or (C ₁ -C ₂₀ )alkoxycarbo Neiloxy.)

The compound of Formula 1 according to an embodiment may be a compound represented by Formula 2 in the aspect of having excellent solubility in a supercritical fluid.

[Formula 2]

(In the formula 2,

R ₁ and R ₂ are different from each other and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen, cyano or SO ₂ F;

R ₃ is hydrogen or halogen;

R ₅ and R ₆ are each independently (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl;

R ₈ is a hydrogen atom, hydroxy, acetamide or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

However, when R ₈ is a hydrogen atom or acetamide, R ₂ is necessarily SO ₂ F.)

The compound of Formula 1 according to an embodiment may be a compound represented by Formula 3 in the aspect of having excellent solubility in a supercritical fluid.

[Formula 3]

(In the formula 3,

R ₄ is a hydrogen atom, nitro, acetyl, (C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxy;

R ₅ and R ₆ are each independently (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl;

R ₈ is a hydrogen atom, hydroxy, acetamide or (C ₁ -C ₂₀ )alkoxycarbonyloxy;

However, when R ₄ is (C ₁ -C ₂₀ )alkyl, R ₈ is necessarily hydroxy or (C ₁ -C ₂₀ )alkoxycarbonyloxy.)

More specifically, in Formula 2, R ₁ and R ₂ are different from each other, and hydrogen, amide, nitro, acetyl, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy, halogen, cyano, or SO ₂ F; R ₃ is hydrogen or halogen; R ₅ and R ₆ are each independently (C ₁ -C ₁₀ )alkyl, halo(C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl(C ₁ -C ₁₀ )alkyl, hydroxy(C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxycarbonylmethyl; R ₈ is a hydrogen atom, hydroxy, acetamide or (C ₁ -C ₁₀ )alkoxycarbonyloxy; However, when R ₈ is a hydrogen atom or acetamide, R ₂ is preferably a compound of which SO ₂ F.

More specifically, R ₄ in Chemical Formula 3 is a hydrogen atom, nitro, acetyl, (C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxy; R ₅ and R ₆ are each independently (C ₁ -C ₁₀ )alkyl, halo(C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl(C ₁ -C ₁₀ )alkyl, hydroxy(C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxycarbonylmethyl; R ₈ is a hydrogen atom, hydroxy, acetamide or (C ₁ -C ₁₀ )alkoxycarbonyloxy; However, when R ₄ is (C ₁ -C ₁₀ )alkyl, R ₈ is preferably a hydroxy or (C ₁ -C ₁₀ )alkoxycarbonyloxy compound.

Preferably, the compound of Chemical Formula 2 may be a compound represented by Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c in terms of having excellent fastness when supercritical fluid is dyed.

[Formula 2a]

[Formula 2b]

[Formula 2c]

(In the formulas 2a to 2c,

R ₁ and R ₂ are different from each other,

R ₁ is hydrogen, nitro, halogen or cyano;

R ₂ is amide, nitro, acetyl, (C ₁ -C ₆ )alkyl, (C ₁ -C ₆ )alkoxy, halogen or SO ₂ F;

R ₃ is hydrogen or halogen;

R ₅ and R ₆ are each independently (C ₁ -C ₆ )alkyl, (C ₆ -C ₁₂ )aryl(C ₁ -C ₆ )alkyl, hydroxy(C ₁ -C ₆ )alkyl or (C _1- C ₆ )alkoxycarbonylmethyl;

R'is (C ₁ -C ₆ )alkyl;

R ₈ is hydrogen or acetamide.)

Preferably, the compound of Formula 3 may be a compound represented by the following Formula 3a or Formula 3b in terms of having excellent fastness when supercritical fluid dyeing.

[Formula 3a]

[Formula 3b]

(In the formulas 3a and 3b,

R ₄ is (C ₁ -C ₆ )alkyl;

R ₅ and R ₆ are each independently (C ₁ -C ₆ )alkyl, hydroxy(C ₁ -C ₆ )alkyl or (C ₁ -C ₆ )alkoxycarbonylmethyl;

R'is (C ₁ -C ₆ )alkyl.)

More preferably, the compound of Formula 2 may be specifically exemplified as the following compound, but the following compound is not intended to limit the present invention.

(R ₁ and R ₂ above are different from each other, R ₁ is hydrogen, nitro, halogen or cyano; R ₂ is amide, nitro, acetyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy , Butoxy, halogen or SO ₂ F; R ₃ is hydrogen or halogen.)

More preferably, the compound of Formula 3 may be specifically exemplified as the following compound, but the following compound is not intended to limit the present invention.

(R ₄ above is methyl, ethyl, propyl or butyl.)

The azo-based disperse dye for supercritical fluid dyeing according to an embodiment has excellent solubility in supercritical fluid, and thus can be used for dyeing supercritical fluids such as polyester fibers, synthetic fibers, and polyester blend fibers. It has the advantages of fastness, wash fastness, fastness to sweat and excellent physical properties.

In addition, the present invention relates to a method for preparing an azo-based dispersion dye for supercritical fluid dyeing of Chemical Formula 1, and may be prepared as shown in Reaction Scheme 1 below, but any possible method recognized by those skilled in the art is possible. Of course.

[Scheme 1]

(In Scheme 1 above, A and R ₅ to R ₈ are the same as defined in Formula 1.)

That is, the azo-based dispersion dye for supercritical fluid dyeing of Chemical Formula 1 may be prepared by including the following steps:

a) Dispersing and stirring the amine derivative of the following formula 4 in a solution selected from water, acetic acid or a mixed solution of acetic acid and propionic acid, and then adding hydrochloric acid, sodium nitrite (NaNO ₂ ) or nitrosylsulfuric acid (HO ₃ SONO) Diazoizing by;

b) preparing a coupler solution by dissolving the aryl derivative of Formula 5 in alcohol or acetone;

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

The amine derivative of Formula 4 and the aryl derivative of Formula 5 may be used in a molar ratio of 1:1.

In addition, after step c), d) neutralizing the solution of step c), followed by filtration, washing and drying with a solvent. The solution of step c) can be neutralized with sodium acetate.

In addition, when using a mixed solution of acetic acid and propionic acid in the step a), it is preferable to use in a volume ratio range of 3 to 5: 0.5 to 3, and maintaining the temperature at 0 to 10° C. makes diazo reaction smoothly. Make it possible.

In addition, in step b) and c), the temperature is preferably maintained in the range of -20 to 20°C, preferably 0 to 10°C, in terms of efficient coupling reaction.

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

The following scheme 2 shows the scheme of formula 2, and the scheme 3 below shows the scheme of formula 3.

[Scheme 2]

[Scheme 3]

(In Schemes 2 and 3, R ₁ to R ₄ , R ₅ , R ₆ and R ₈ are the same as defined in Formulas 1 to 3.)

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

The azo-based dye for supercritical fluid dyeing of Chemical Formula 1 is suitable for supercritical fluid dyeing of polyester fibers, synthetic fibers, and polyester blend fibers.

The dyeing temperature during the supercritical fluid dyeing is substantially different 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 high enough that at least CO ₂ exists in a supercritical state. . The pressure can preferably range from 73 to 400 bar, preferably from 150 to 300 bar.

Hereinafter, for a detailed understanding of the present invention, a representative compound of the present invention will be described in detail with reference to synthetic examples and examples. The synthetic examples according to the present invention may be modified in various other forms, and the scope of the present invention Should not be construed as being limited to the synthetic examples and examples described below. The synthetic examples and examples of the present invention are provided to more fully describe the present invention to those skilled in the art.

In Tables 1 to 5, synthesis yield, molecular weight ( m/e ), and maximum absorption wavelength (λ _max ) and molar absorption coefficient (ε) analysis data of the UV-VIS-NIR spectrum of the synthesized compound are described.

[ Synthetic example 1-1] N -[3- Hydroxy -4-[2-(4- Nitrophenyl )- Diazen ]Phenyl]- N -(2-ethoxy-2-oxoethyl)-glycine Of ethyl ester (1) Produce

4-Nitroaniline (A) (0.69 g, 5 mmol) was dispersed in acetic acid (10 mL) and stirred at room temperature for 30 minutes, concentrated hydrochloric acid (1.5 mL) was slowly added and the reaction was cooled to 0-5°C. . Then, 3 N sodium nitrite (NaNO ₂ ) (1.8 mL, 5.4 mmol) was slowly added for 20 minutes, taking care not to exceed the temperature of the reactant at 5° C., and the reactant was stirred at 0 to 5° C. for 1 hour, followed by sulfamic acid (0.05 g) was added to remove excess nitrite and to complete the diazoization reaction.

N - (ethoxy-2-oxo-ethyl 2-) - N - (3- hydroxyphenyl) glycine ethyl ester (B) (1.4 g, 5 mmol) to dissolve completely and 0 ℃ in MeOH (5 mL) After maintaining, the reactant was slowly added to the diazo solution for 10 minutes while being careful not to raise the temperature of the reactant and stirred at 0-5°C for 1.5 hours.

After adding sodium acetate (NaOAc) (1.5 g) to the reaction solution and stirring at room temperature for 30 minutes, the reaction solution was poured into distilled water (50 mL) and stirred for 1 hour to filter the solid product obtained, washed thoroughly with distilled water, , Washed with a small amount of methanol and dried to give N -[3-hydroxy-4-[2-(4-nitrophenyl)-diazenyl]phenyl] -N -(2-ethoxy-2-oxoethyl)-glycine Ethyl ester ( 1 ) was obtained.

[ Synthetic example 1-2 ~ 1-10]

In the same manner as in Synthesis Example 1-1, Compound B was used as a coupler, but instead of Compound A, an aniline derivative as shown in Table 1 was used to prepare an azo-based dye for supercritical fluid dyeing of Compounds 2 to 10. Got.

[Table 1]

[ Synthetic example 2-1 ~ 2-10]

It was carried out in the same manner as in Synthesis Example 1-1, using an aniline derivative as shown in Table 2 below as a diazo body and N -ethyl- N- (3-hydroxyphenyl)-glycine ethyl ester of compound C as a coupler Used as to obtain azo-based dispersion dye for supercritical fluid dyeing of compounds 11 to 20.

[Table 2]

[ Synthetic example 3-1 ~ 3-10]

It was carried out in the same manner as in Synthesis Example 1-1, using an aniline derivative as shown in Table 3 as a diazo body and 3-[bis(2-hydroxyethyl)amino]phenyl-carbonate ethyl ester of Compound D. It was used as a coupler to obtain an azo-based dispersion dye for supercritical fluid dyeing of compounds 21 to 30.

[Table 3]

[ Synthetic example 4-1 ~ 4-3]

The supercritical fluid staining of compounds 31 to 33 was carried out in the same manner as in Synthesis Example 1-1, using a sulfonylfluor group-substituted aniline derivative as shown in Table 4 as a diazo body and an aryl derivative as a coupler. Azo-based disperse dyes were obtained.

[Table 4]

[ Synthetic example 5-1 ~ 5-3]

In the same manner as in Synthesis Example 1-1, 3-amino-5-methylisoxazole (E) as shown in Table 5 below was used as a diazo body, and an aryl derivative was used as a coupler to obtain compounds 34 to 36. An azo-based dispersion dye for supercritical fluid dyeing was obtained.

[Table 5]

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

[Experimental Example 1] Dyeing experiment

Azo-based disperse dye for supercritical fluid dye prepared in an embodiment of the present invention 0.05 g (0.5% owf; On the Weight of Fiber. amount of dye used for the weight of the object) and polyester fiber (Polyester Knit) 10 g was added to a high-pressure dyeing machine with a volume of 200 mL, CO ₂ was cooled with a cooler, and then injected using a pressure pump, and then slowly heated to 120° C. to maintain the high-pressure dyeing machine at 250 atm and supercritical fluid staining for 2 hours. Did.

[Experimental Example 2] Light fastness experiment (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°C, black panel temperature: 63±3°C, relative humidity: 50±5%), and the standard gray color for AATCC fading fading It was judged by comparison.

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

After attaching the attached white cloth (six types of multi-sum orthogonal fabric) to the test piece and sewing the four sides, stainless steel was added to the standard detergent washing solution, and then washed, washed, dehydrated and dried under the prescribed conditions, and then compared with the standard gray color.

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

After treating the test piece with artificial sweat solution, insert it between two plates, mount it on a sweat tester, leave it for a certain period of time, and then dry it to compare the degree of contamination of the faeces and attached whites with the standard gray color table for color fading and the standard gray color table for staining. It was judged.

Examples 1 to 17 of Table 6 below describe the results of the light fastness, wash fastness, and sweat (acid and alkali) fastness test results of the supercritical fluid staining sample.

[Comparative Experimental Examples 1 to 2]

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

[Table 6]

As shown in Table 1 to Table 5, the azo-based dispersion dye for supercritical fluid dyeing of the present invention synthesized using various diazo bodies and couplers has various colors of yellow, orange, red, magenta and purple, satisfactory Yield and high molar extinction coefficient.

In addition, as shown in Table 6, the supercritical fluid-dyed dyeing sample using the azo-based dispersion dye for supercritical fluid dyeing of the present invention exhibits excellent sunlight fastness, wash fastness, and sweat (acid and alkali) fastness to poly It was confirmed that it is effective for dyeing of ester fibers.

On the other hand, when supercritical fluid dyeing was performed using the well-known azo-based disperse dyes C1 and C2, it was observed that the fastness characteristics of the stained samples were deteriorated.

Accordingly, the azo-based dispersion dye for supercritical fluid dyeing of the present invention can be provided as a dye for supercritical fluid dyeing such as polyester fiber, synthetic fiber, and polyester blend fiber.

Claims (11)

Azo-based disperse dyes for supercritical fluid dyeing represented by the following Chemical Formula 1:
[Formula 1]

(In the formula 1,
A is

or

ego;
R ₁ and R ₂ are different from each other and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen or cyano;
R ₃ and R ₄ are each independently hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen or cyano;
R ₅ and R ₆ are each independently hydroxy, acetamide, (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl , Hydroxy(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy, wherein R ₅ and R ₆ At least one of hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl;
R ₇ is a hydrogen atom;
R ₈ is hydroxy, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;
However, when R ₄ is (C ₁ -C ₂₀ )alkyl, R ₈ is necessarily hydroxy or (C ₁ -C ₂₀ )alkoxycarbonyloxy.) According to claim 1,
Azo-based dispersion dye for supercritical fluid dyeing represented by the following Chemical Formula 2:
[Formula 2]

(In the formula 2,
R ₁ and R ₂ are different from each other and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen or cyano;
R ₃ is hydrogen or halogen;
R ₅ and R ₆ are each independently (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl, wherein at least one of R ₅ and R ₆ is hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl;
R ₈ is hydroxy or (C ₁ -C ₂₀ )alkoxycarbonyloxy.) According to claim 1,
Azo-based dispersion dye for supercritical fluid dyeing represented by the following Chemical Formula 3:
[Formula 3]

(In the formula 3,
R ₄ is a hydrogen atom, nitro, acetyl, (C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxy;
R ₅ and R ₆ are each independently (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl, wherein at least one of R ₅ and R ₆ is hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl;
R ₈ is hydroxy or (C ₁ -C ₂₀ )alkoxycarbonyloxy.) According to claim 2,
R ₁ and R ₂ are different from each other, and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy, halogen or cyano; R ₃ is hydrogen or halogen; R ₅ and R ₆ are each independently (C ₁ -C ₁₀ )alkyl, halo(C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl(C ₁ -C ₁₀ )alkyl, hydroxy(C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxycarbonylmethyl, wherein at least one of R ₅ and R ₆ is hydroxy(C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxycarbonyl Methyl; R ₈ is hydroxy or (C ₁ -C ₁₀ ) alkoxycarbonyloxy, azo-based dispersion dye for supercritical fluid dyeing. According to claim 3,
R ₄ is a hydrogen atom, nitro, acetyl, (C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxy; R ₅ and R ₆ are each independently (C ₁ -C ₁₀ )alkyl, halo(C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl(C ₁ -C ₁₀ )alkyl, hydroxy(C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxycarbonylmethyl, wherein at least one of R ₅ and R ₆ is hydroxy(C ₁ -C ₁₀ )alkyl or (C ₁ -C ₁₀ )alkoxycarbonyl Methyl; R ₈ is hydroxy or (C ₁ -C ₁₀ ) alkoxycarbonyloxy, azo-based dispersion dye for supercritical fluid dyeing. According to claim 2,
An azo-based dispersion dye for supercritical fluid dyeing represented by the following Chemical Formula 2a or Chemical Formula 2b.
[Formula 2a]

[Formula 2b]

(In the above formula 2a and 2b,
R ₁ and R ₂ are different from each other,
R ₁ is hydrogen, nitro, halogen or cyano;
R ₂ is amide, nitro, acetyl, (C ₁ -C ₆ )alkyl, (C ₁ -C ₆ )alkoxy or halogen;
R ₃ is hydrogen or halogen;
R ₅ and R ₆ are each independently (C ₁ -C ₆ )alkyl, (C ₆ -C ₁₂ )aryl(C ₁ -C ₆ )alkyl, hydroxy(C ₁ -C ₆ )alkyl or (C _1- C ₆ )alkoxycarbonylmethyl, wherein at least one of R ₅ and R ₆ is hydroxy(C ₁ -C ₆ )alkyl or (C ₁ -C ₆ )alkoxycarbonylmethyl;
R'is (C ₁ -C ₆ )alkyl.) According to claim 3,
An azo-based dispersion dye for supercritical fluid dyeing represented by the following Chemical Formula 3a or Chemical Formula 3b.
[Formula 3a]

[Formula 3b]

(In the formulas 3a and 3b,
R ₄ is (C ₁ -C ₆ )alkyl;
R ₅ and R ₆ are each independently (C ₁ -C ₆ )alkyl, hydroxy(C ₁ -C ₆ )alkyl or (C ₁ -C ₆ )alkoxycarbonylmethyl, wherein at least R ₅ and R ₆ are One is hydroxy(C ₁ -C ₆ )alkyl or (C ₁ -C ₆ )alkoxycarbonylmethyl;
R'is (C ₁ -C ₆ )alkyl.) The method of claim 6,
Azo-based dispersion dye for supercritical fluid dyeing selected from the following compounds.

(R ₁ and R ₂ above are different from each other, R ₁ is hydrogen, nitro, halogen or cyano; R ₂ is amide, nitro, acetyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy , Butoxy or halogen; R ₃ is hydrogen or halogen.) The method of claim 7,
Azo-based dispersion dye for supercritical fluid dyeing selected from the following compounds.

(R ₄ above is methyl, ethyl, propyl or butyl.) A supercritical fluid dyeing method using an azo-based dispersion dye for supercritical fluid dyeing according to any one of claims 1 to 9. a) Dispersing and stirring the amine derivative of the following formula 4 in a solution selected from water, acetic acid or a mixed solution of acetic acid and propionic acid, and then adding hydrochloric acid, sodium nitrite (NaNO ₂ ) or nitrosylsulfuric acid (HO ₃ SONO) Diazoizing by;
b) preparing a coupler solution by dissolving the aryl derivative of Formula 5 in alcohol or acetone;
c) a step of mixing and stirring the diazotized solution of step a) and the coupler solution of step b);
[Formula 1]

[Formula 4]

[Formula 5]

(In the formulas 1, 4 and 5,
A is

or

ego;
R ₁ and R ₂ are different from each other and are hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen or cyano;
R ₃ and R ₄ are each independently hydrogen, amide, nitro, acetyl, (C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxy, halogen or cyano;
R ₅ and R ₆ are each independently hydroxy, acetamide, (C ₁ -C ₂₀ )alkyl, halo(C ₁ -C ₂₀ )alkyl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl , Hydroxy(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy, wherein R ₅ and R ₆ At least one of hydroxy(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl;
R ₇ is a hydrogen atom;
R ₈ is hydroxy, (C ₁ -C ₂₀ )alkoxycarbonyl(C ₁ -C ₂₀ )alkyl or (C ₁ -C ₂₀ )alkoxycarbonyloxy;
However, when R ₄ is (C ₁ -C ₂₀ )alkyl, R ₈ is necessarily hydroxy or (C ₁ -C ₂₀ )alkoxycarbonyloxy.)