KR100485411B1 - Fiber-reactive Red Dyestuffs And Methods For Preparing Them - Google Patents

Abstract

The present invention relates to a dye compound represented by the following formula (1) capable of dyeing cellulose fiber material in red and a method for producing the same.

The dye according to the present invention dyes and prints textile materials, in particular, cellulose fiber materials according to color, to a deep red color, preferably scarlet red color, and has good absorption / fastness and fastness to light fastness and wet treatment. Very good

Description

Fiber-Reactive Red Dyestuffs And Methods For Preparing Them

The present invention relates to dyes capable of dyeing fibrous materials, in particular cellulose fibers in dark red, preferably scarlet, and methods for their preparation.

In the conventional dyeing method, when dyeing cellulose fiber material in scarlet, a method of dyeing a combination of red dye and yellow dye, or red dye and orange dye was common. But. A problem with this method is the fact that the reproducibility of the desired color is poor because the compatibility between the two dyes is generally poor. In particular, it is more problematic when trying to dye the vermilion at a high concentration, because not only compatibility between the two dyes but also the adhesion rate to the fibers in the high concentration region should be similar to each other.

Another serious problem in high concentration dyeing is the fact that when washing high dyed dyes, other fibers may be contaminated by unfixed dyes remaining in the dyes. In addition, in the high concentration of scarlet dyeing, as well as general dyes, high fastness to light or sweat is also required, so both dyes used in the formulation should have high fastness, but there is no dye that satisfies this.

Conventionally, monochloro triazine-based reactive dyes children. Reactive Red 120 Compounds

When a bifunctional reactive dye. children. Compounds of Reactive Red 195 were mainly used.

However, these dyes, as described above, do not exhibit a dark red color, in particular scarlet color, and at the same time do not satisfy sufficient directness, good dyeing rate, high reactivity, in particular high precision and the like.

Therefore, an object of the present invention is to solve such problems of the prior art and technical problems that have been requested from the past.

 That is, an object of the present invention is to have a high fixation rate and a high fiber-dye bond stability, at the same time can be easily washed dyes that are not fixed to the fiber, and excellent fiber reactivity red light (water and moisture fastness, etc.) Scarlet dye).

After numerous experiments and many years of research, the inventors have found that a new dye compound obtained by monochromating a red and yellow chromophore into a chlorotriazine ring, as shown in Formula 1, is dyed when compared to a combination of a conventional single chromophore. Not only is it excellent in wet washing and light fastness, but also has excellent build-up, and has good characteristics in wastewater treatment because there is not much residual liquid due to excellent adsorption and fixation, so that most of the above-mentioned objects can be solved. It was confirmed that the present invention was completed.

The fiber reactive red dye of the present invention according to this object has a structure of Formula (1).

Where

R ₁ is a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, an optionally substituted aryl group, or a hydrogen atom;

X ₁ and X ₂ are each independently halogen, hydroxy, carboxy, cyanine, a hydrogen atom, a sulfonic acid or an alkoxy group having 1 to 4 carbon atoms;

Y is halogen, hydroxyl, 3-carboxypyridin-1-yl, 3-carbamoylpyridin-1-yl, alkoxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted amino group Or an N-heterocycle group which may further contain a hetero atom;

Z is a group of formula (2);

n ₁ and n ₂ are each independently 0 to 4;

n ₃ is 0 or 1 and when n ₃ is 0,-(SO ₃ H) n ₃ is a hydrogen atom;

_{However, - (CH 2) n 1} -X 1 and - (CH ₂₎ n ₂ -X ₂ If is different from each other, n ₁ is O and X ₁ is a hydrogen atom; when n ₁ and n ₂ are each 0 and X ₁ is a hydrogen atom, X ₂ is not a hydrogen atom; When n ₁ is 0, n ₂ is 2 and X ₁ is hydrogen, X ₂ is not a carboxy group. Combinations excluded from the above are those which, through experimentation, have been found to be relatively poor in the rate of fixation and / or relative dye strength of the dyes.

Wherein U is a vinyl group or the general formula CH ₂ -CH ₂ -Q, wherein Q is a living group which can be removed under alkaline conditions. Preferred examples of such living groups are chlorine, acetoxy, benzoyloxy, phosphate, sulfato and the like.

Reactive dyes of the general formula (1) according to the present invention have a high reactivity, excellent fixing ability and very good build up ability, etc., compared to the conventional monochlorotriazine-based compound and vinyl sulfone-based compound, and is dark red, preferably Is characterized by expressing scarlet.

In Formula 1, more preferably, n ₁ is O, n ₂ is 2, X ₁ is a hydrogen atom, X ₂ is a hydroxy group.

In addition, in Y, preferable examples of the halogen include fluorine and chlorine, and preferred examples of the N-heterocyclo are morpholine, thiomorpholine, piperazine or piperidine radical, and the like. Preferred examples of the amino group are alkylamino, and examples of such alkylamino are N-mono- (C ₁ -C ₄ ) straight or branched alkyl in which unsubstituted or substituted alkyl residues are substituted with hydroxyl, sulfato or sulfur. Amino or N, N-di- (C ₁ -C ₄ ) straight or branched alkylamino, and the like, and more preferably, a group represented by the following general formula (3).

Wherein R ₁ is the same as in formula 1, and U is the same as in formula 2.

In Chemical Formula 2, more preferably, U is a vinyl group or β-sulfatoethyl.

Particularly preferred fiber reactive red dyes according to the present invention are compounds comprising a red chromophore and a yellow chromophore at the same time as in the following formulas 4a to 4e.

Wherein n ₁ , n ₂ , n ₃ , R ₁ , X ₁ , X ₂ and Y are the same as in formula (1), and U is the same as in formula (2).

Wherein n ₁ , n ₂ , n ₃ , R ₁ , X ₁ , X ₂ and Y are the same as in formula (1), and U is the same as in formula (2).

Wherein n ₃ , R ₁ , X ₁ and Y are the same as in formula (1), and U is the same as in formula (2).

Wherein n ₃ , R ₁ , X ₁ , X ₂ and Y are the same as in formula (1), and U is the same as in formula (2).

Wherein n ₃ , R ₁ , X ₁ and Y are the same as in formula (1), and U is the same as in formula (2).

The present invention also relates to a process for preparing the reactive dye of formula (I).

N ₁ , n ₂ , n ₃ , R ₁ , U, X ₁ , X ₂ , Y, Z, etc. in the following Chemical Formulas 5 to 17 are the same as defined in Chemical Formulas 1 and 2, unless otherwise noted. For convenience of explanation, the first to the formula 5 to 17 are as follows.

In the above formula, at least one of Y is a halogen atom, preferably chlorine or fluorine.

In the above formula, at least one of Y is a halogen atom, preferably chlorine or fluorine.

In the above formula, at least one of Y is a halogen atom, preferably chlorine or fluorine.

In the above formula, at least one of Y is a halogen atom, preferably chlorine or fluorine.

In the above formula, at least one of Y is a halogen atom, preferably chlorine or fluorine.

In the above formula, at least one of Y is a halogen atom, preferably chlorine or fluorine.

In the above formula, at least one of Y is a halogen atom, preferably chlorine or fluorine.

The first method (A) of preparing the compound of formula 1 is

(A-iii) diazotizing the compound of Formula 5 and coupling the compound of Formula 8 to prepare a compound of Formula 10;

(A-ii) diazotizing the compound of Formula 6 and coupling the compound of Formula 7 to prepare a compound of Formula 9; And,

(A-X) condensation of a compound of Formula 10 with a compound of Formula 9 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 1.

The diazotization / coupling reactions of step (A-iii) and step (A-ii), after diazotizing the compound of Formula 5 or Formula 6 with nitrous acid at -5-15 占 폚 and pH 0.5-2, Coupling of the compound of formula (8) or formula (7) is carried out by acid binder in an aqueous medium at -5 to 15 and pH 4 to 10.

The condensation reaction in the step (A-v),

(A-X ′) A compound of Formula 14 is prepared by a first condensation reaction of a compound of Formula 10 with 2,4,6-trihalogeno-s-triazine, and a compound of Formula 14 and Formula 9 Preparing a compound of formula 1 by a second condensation reaction of the compound,

(A-VII ") A compound of formula 12 is prepared by a first condensation reaction of a compound of formula 9 with 2,4,6-trihalogeno-s-triazine, and the compound of formula 12 and It is possible to prepare a compound of formula 1 by a second condensation reaction of the compound.

The first condensation reaction can be carried out in an organic medium, an aqueous medium, or an aqueous-organic medium, and a preferred example is carried out in the presence of an acid-binder in an aqueous medium. Preferred examples of the acid-binder include alkali metal carbonates, bicarbonates, hydroxides, alkaline earth metal carbonates, bicarbonates, hydroxides, alkali metal acetates, mixtures of two or more thereof, tertiary amines, and the like. have. Preferred examples of the alkali metal and alkaline earth metal include lithium, sodium, potassium, calcium, and the like, and preferred examples of the tertiary amine include pyridine, triethylamine, quinoline, and the like. The first condensation reaction is carried out at −10 to 40 ° C., more preferably at 0 to 10 ° C. and at pH 1.0 to 6.8.

The second condensation reaction, like the first condensation reaction, can be carried out in an organic medium, an aqueous medium, or an aqueous-organic medium, with preferred examples being 10-70 ° C. and pH 2.0-9.0 in the presence of an acid-binder in the aqueous medium. It may be carried out at 20 to 60 ℃ and pH 2.0 to 8.0 more preferably.

The second method (B) of preparing the compound of formula 1 is

(B-iii) diazotizing the compound of Formula 6 and coupling the compound of Formula 7 to prepare a compound of Formula 9;

(B-ii) condensing the compound of Formula 9 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 12;

(B-iii) condensing a compound of Formula 12 with a compound of Formula 8 to produce a compound of Formula 17;

And (B-VII) diazotizing the compound of Formula 5 and coupling the compound of Formula 17 to produce a compound of Formula 1.

The third method (C) for preparing the compound of formula 1 is

(C-VII) condensing the compound of Formula 8 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 13;

(C-ii) condensing a compound of Formula 13 with a compound of Formula 7 to produce a compound of Formula 15;

(C-VII) diazotizing the compound of Formula 5 and then coupling the compound of Formula 15 to prepare a compound of Formula 16; And,

And (C-VII) diazotizing the compound of Formula 6, followed by coupling reaction of the compound of Formula 16 to produce the compound of Formula 1.

The fourth method (D) for preparing the compound of formula 1 is

(D-iii) diazotizing the compound of Formula 5 and coupling the compound of Formula 8 to prepare a compound of Formula 10;

(D-ii) condensing the compound of Formula 10 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 14;

(D-iii) condensing the compound of Formula 14 with the compound of Formula 7 to prepare a compound of Formula 16; And,

And (D-VII) diazotizing the compound of Formula 6, followed by coupling reaction with the compound of Formula 16 to produce the compound of Formula 1.

Various methods for preparing the dye compound of Formula 1 in addition to the above-described methods (A to D) are possible, and even if there is no separate description, those skilled in the art to which the present invention pertains to the method described above It will be possible to fully recognize such methods. For example, a process of preparing the compound of Formula 11 may be preferentially performed by condensation reaction of the compound of Formula 7 with 2,4,6-trihalogeno-s-triazine.

The present invention also provides a method of dyeing cellulose fiber materials using the dye compound of formula (1).

The dye compounds of formula 1 according to the invention are suitable as dyes for dyeing and printing all types of cellulose fiber materials. Such cellulose fiber materials include, for example, natural cellulose fibers such as cotton, flax, and hemp, pulp and regenerated cellulose, and are particularly suitable for dyeing cotton. The dye compounds of formula 1 according to the invention are also suitable for dyeing or printing cellulose blend fabrics, for example cotton / polyester, cotton / nylon blend fabrics and the like.

In the dye solution, the amount of the reactive dye, such as the compound of formula 1, may vary depending on the desired degree of coloring. The dye compounds according to the invention can be used at 0.01 to 10% by weight, preferably 0.01 to 6% by weight, based on the fabric to be dyed.

The dye compounds of the formula (1) according to the invention are particularly suitable for dyeing by the absorption method.

The dyeing by the adsorption method generally has a weight ratio of water to dye in an aqueous medium of from 1: 2 to 1:60, preferably from 1: 5 to 1:20, from 20 to 105 ° C, preferably from 30 to 90 ° C, more Preferably it is performed at the temperature of 40-80 degreeC.

Another suitable dyeing method is pad dyeing, whereby the fabric is generally impregnated with an aqueous solution, saline solution, saline solution and the like. At this time, the pick-up is 20 to 150%, in particular 40 to 120%, preferably 50 to 100% by weight of the fiber material to be dyed. In some cases, the aqueous liquid already contains fixed alkalis or, after impregnation, the fiber material is treated with fixed alkalis. Suitable alkali metals are, for example, mixtures of sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium borate, aqueous ammonium, sodium trichloroacetate or sodium silicate solution. Preferred are alkali hydroxides and / or alkali carbonates, in particular sodium hydroxide and / or sodium carbonate.

Fixation can also be carried out, for example, by impregnating the fibrous material at a temperature of, for example, 100 to 120 ° C., through a thermal action such as steam, in particular saturated steam. According to the so-called cold pad-batch method, the dye is placed in a padder with alkali and stored and fixed at room temperature for several hours, for example 3 to 40 hours. After fixation, the dye or print is added with a dispersant if necessary and thoroughly washed.

The dyeings and printings obtained according to the present invention are excellent in build-up and leveling. In addition, the adherence is high, and non-fixed dyes can be easily washed off, and there is little difference between the degree of adsorption and the adherence, i.e., the loss of soap. Moreover, the dyeings and printings obtained are excellent in coloration, high in fiber-dye binding stability, and excellent in water fastness, wrinkles, ironing and rubbing such as fastness to washing, seawater, cross-dyeing and sweating, etc. As well as fastness to light, it also has excellent daylight fastness.

Although the specifics of the present invention will be described in detail with reference to the following Examples, the scope of the present invention is not limited thereto.

EXAMPLE

Example 1

Made by diazotizing 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene in a conventional manner, followed by coupling reaction with 1-amino-3- (N-hydroxyethyl) aminobenzene-4-sulfonic acid, To 100 g of an aqueous solution of 5.2 g of monoazo compound, 1.8 g of chlorocyanu was added and maintained at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 4.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was dissolved was added, and then maintained at 30 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 3.0 g of 2-amino-4,8-disulfonic acid and then maintained at pH 5.5 and 10 ° C. for 3 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters and then dried to obtain 12.5 g of a dye compound having the following formula.

This dye was dyed dark red (scarlet) in cellulose fibers and showed high light and wash fastnesses. The dyeing method 1, the dyeing method 2 and the printing method for confirming the wash fastness are as follows.

(Dyeing method 1)

2 g of the dye obtained above were dissolved in 400 g of water. This solution was added to 1500 g of a solution containing 53 g / 1 L of sodium chloride to prepare a salt bath. 100 g of cotton fabric were added into the dye bath at 40 ° C., and after 45 minutes, 100 g of a solution containing 16 g / 1 L sodium hydroxide and 20 g calcined sodium carbonate was added. In addition, the temperature of the salt bath was maintained at 40 ° C. for 45 minutes. The dyed fabric was then washed, soaped for 25 minutes upon boiling with a nonionic detergent, washed again and dried.

(Dyeing method 2)

2 g of the dye obtained above were dissolved in 400 g of water. To this solution was added to 1500 g of a solution containing 53 g / 1 L of sodium chloride to prepare a salt bath. 100 g of cotton fabric were added into the dyebath at 35 ° C., and after 20 minutes, 100 g of a solution containing 16 g / 1 L sodium hydroxide and 20 g calcined sodium carbonate was added. In addition, the temperature of the salt bath was maintained at 35 ° C. for 15 minutes. The temperature was then raised to 60 ° C. over 20 minutes and held at that temperature for an additional 35 minutes. The dyed fabric was washed, soaped for 25 minutes on boiling using a nonionic detergent, washed again and dried.

(Printing method)

3 g of the dye obtained above were scattered vigorously with 100 g of stock thickening comprising 50 g of sodium alginate thickener, 27.8 g of water, 20 g of urea, and 1.2 g of sodium m-nitrobenzenesulfonate. The cotton fabric was printed and dried with the printing paste obtained above. The printed cotton fabric was steamed at 102 DEG C for 2 minutes in saturated steam, then washed, optionally soaped at boiling, and washed once again to dry.

Example 2

Made by diazotizing 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene in a conventional manner, followed by coupling reaction with 1-amino-3- (N-hydroxyethyl) aminobenzene-4-sulfonic acid, To 100 g of an aqueous solution in which 5.5 g of monoazo compound was dissolved, 1.2 g of fluorocyanu was added and maintained at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 4.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was dissolved was added, and then maintained at 30 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 3.0 g of 2-amino-4,8-disulfonic acid and then maintained at pH 5.5 and 10 ° C. for 3 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters and then dried to obtain 9 g of a dye compound having the following formula.

This dye was dyed dark red (scarlet) in cellulose fibers and showed high light and wash fastness. The dyeing method for checking the washing fastness is the same as in Example 1.

Example 3

2.8 g of 4-sulfatoethylsulfone-1-aminobenzene was diazotized in a conventional manner and then coupled with 1-amino-3- (N, N-dihydroxyethyl) aminobenzene-4-sulfonic acid To 100 g of an aqueous solution of 5.2 g of monoazo compound, which was prepared, 1.8 g of chlorocyanu was added and maintained at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 4.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was dissolved was added, and then maintained at 30 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 3.0 g of 2-amino-4,8-disulfonic acid and then maintained at pH 5.5 and 10 ° C. for 3 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters and then dried to obtain 13.0 g of a compound of the following formula.

This dye was dyed dark red (scarlet) in cellulose fibers and showed high light and wash fastness. The dyeing method for checking the washing fastness is the same as in Example 1.

Example 4

2.8 g of 4-sulfatoethylsulfone-1-aminobenzene was diazotized in a conventional manner and then coupled with 1-amino-3- (N, N-dihydroxyethyl) aminobenzene-4-sulfonic acid To 100 g of an aqueous solution in which 5.2 g of the monoazo compound was dissolved, 1.8 g of fluorocyanu was added and maintained at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 4.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was dissolved was added, and then maintained at 30 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 3.0 g of 2-amino-4,8-disulfonic acid and then maintained at pH 5.5 and 10 ° C. for 3 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters and then dried to obtain 12.9 g of a dye compound having the following formula.

This dye was dyed dark red (scarlet) in cellulose fibers and showed high light and wash fastness. The dyeing method for checking the washing fastness is the same as in Example 1.

Example 5

Made by diazotizing 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene in a conventional manner, followed by coupling reaction with 1-amino-3- (N-hydroxyethyl) aminobenzene-4-sulfonic acid, To 100 g of an aqueous solution in which 5.2 g of the monoazo compound was dissolved, 1.8 g of chlorocyanu was added and maintained at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 4.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was dissolved was added, and then maintained at 30 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 3.0 g of 2-amino-4,8-disulfonic acid and then maintained at pH 5.5 and 10 ° C. for 3 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters and then dried to obtain 10 g of a dye compound having the following formula.

This dye was dyed dark red (scarlet) in cellulose fibers and showed high light and wash fastness. The dyeing method for checking the washing fastness is the same as in Example 1.

Comparative Example 1

5.5 g of monoazo compound prepared by diazotization of 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene in a conventional manner, followed by a coupling reaction with 1.8 g of 1,3-diaminobenzene-4-sulfonic acid. To 100 g of dissolved aqueous solution, 1.8 g of chlorocyanuls were added and maintained at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 4.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was dissolved was added, and then maintained at 30 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 3.0 g of 2-amino-4,8-disulfonic acid and then maintained at pH 5.5 and 10 ° C. for 3 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters and then dried to obtain 12.5 g of a dye compound of the following formula.

This dye was dyed red on cellulose fibers.

Comparative Example 2

Monoazo, prepared by diazotizing 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene in a conventional manner and then coupling reaction with 1.8 g of 1-amino-3-carboxyethylaminobenzene-4-sulfonic acid To 100 g of an aqueous solution of 5.5 g of compound, 1.8 g of chlorocyanu was added and maintained at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 4.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was dissolved was added, and then maintained at 30 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 3.0 g of 2-amino-4,8-disulfonic acid and then maintained at pH 5.5 and 10 ° C. for 3 hours to complete the reaction. The reaction solution was filtered to remove insoluble matters and then dried to obtain 11.5 g of a dye compound of the following formula.

This dye was dyed red on cellulose fibers.

[Examples 6 to 95]

Based on the examples, it was possible to synthesize the compounds described in Tables 1 to 13, and their specific preparation method can be sufficiently expected through the examples based on the chemical structure of the product, Detailed description will be omitted.

In addition, these compounds are dyes with very good fiber-reactive properties, and in particular, dyeing and printing of cellulosic fiber materials in dark red (scarlet) depending on the chromaticity by fixing methods commonly used in the field of fiber-reactive dyes It has been confirmed that it has excellent adsorption / settling rate and excellent fastness to light and wet treatment.

Example Red color matrix Coupler (Y) Yellow color development matrix 6 -Cl 7 -Cl 8 -Cl 9 -F 10 -F 11 -F 12 Morpholinyl

Example Red color matrix Coupler (Y) Yellow color development matrix 13 Morpholinyl 14 Morpholinyl 15 -3-sulfatoethylsulfone-1-aminobenzeneyl 16 -3-sulfatoethylsulfone-1-aminobenzeneyl 17 -3-sulfatoethylsulfone-1-aminobenzeneyl 18 4-sulfatoethylsulfone-1-aminobenzeneyl 19 4-sulfatoethylsulfone-1-aminobenzeneyl

Example Red color matrix Coupler (Y) Yellow color development matrix 20 4-sulfatoethylsulfone-1-aminobenzeneyl 21 -Cl 22 -Cl 23 -Cl 24 -F 25 -F 26 -F

Example Red color matrix Coupler (Y) Yellow color development matrix 27 Morpholinyl 28 Morpholinyl 29 Morpholinyl 30 -3-sulfatoethylsulfone-1-aminobenzeneyl 31 -3-sulfatoethylsulfone-1-aminobenzeneyl 32 -3-sulfatoethylsulfone-1-aminobenzeneyl 33 4-sulfatoethylsulfone-1-aminobenzeneyl

Example Red color matrix Coupler (Y) Yellow color development matrix 34 4-sulfatoethylsulfone-1-aminobenzeneyl 35 4-sulfatoethylsulfone-1-aminobenzeneyl 36 -Cl 37 -Cl 38 -Cl 39 -F 40 -F

Example Red color matrix Coupler (Y) Yellow color development matrix 41 -F 42 Morpholinyl 43 Morpholinyl 44 Morpholinyl 45 -3-sulfatoethylsulfone-1-aminobenzeneyl 46 -3-sulfatoethylsulfone-1-aminobenzeneyl 47 -3-sulfatoethylsulfone-1-aminobenzeneyl

Example Red color matrix Coupler (Y) Yellow color development matrix 48 4-sulfatoethylsulfone-1-aminobenzeneyl 49 4-sulfatoethylsulfone-1-aminobenzeneyl 50 4-sulfatoethylsulfone-1-aminobenzeneyl 51 -Cl 52 -Cl 53 -Cl 54 -F

Example Red color matrix Coupler (Y) Yellow color development matrix 55 -F 56 -F 57 Morpholinyl 58 Morpholinyl 59 Morpholinyl 60 -3-sulfatoethylsulfone-1-aminobenzeneyl 61 -3-sulfatoethylsulfone-1-aminobenzeneyl

Example Red color matrix Coupler (Y) Yellow color development matrix 62 -3-sulfatoethylsulfone-1-aminobenzeneyl 63 4-sulfatoethylsulfone-1-aminobenzeneyl 64 4-sulfatoethylsulfone-1-aminobenzeneyl 65 4-sulfatoethylsulfone-1-aminobenzeneyl 66 -Cl 67 -Cl 68 -Cl

Example Red color matrix Coupler (Y) Yellow color development matrix 69 -F 70 -F 71 -F 72 Morpholinyl 73 Morpholinyl 74 Morpholinyl 75 -3-sulfatoethylsulfone-1-aminobenzeneyl

Example Red color matrix Coupler (Y) Yellow color development matrix 76 -3-sulfatoethylsulfone-1-aminobenzeneyl 77 -3-sulfatoethylsulfone-1-aminobenzeneyl 78 4-sulfatoethylsulfone-1-aminobenzeneyl 79 4-sulfatoethylsulfone-1-aminobenzeneyl 80 4-sulfatoethylsulfone-1-aminobenzeneyl 81 -Cl 82 -Cl

Example Red color matrix Coupler (Y) Yellow color development matrix 83 -Cl 84 -F 85 -F 86 -F 87 Morpholinyl 88 Morpholinyl 89 Morpholinyl

Example Red color matrix Coupler (Y) Yellow color development matrix 90 -3-sulfatoethylsulfone-1-aminobenzeneyl 91 -3-sulfatoethylsulfone-1-aminobenzeneyl 92 -3-sulfatoethylsulfone-1-aminobenzeneyl 93 4-sulfatoethylsulfone-1-aminobenzeneyl 94 4-sulfatoethylsulfone-1-aminobenzeneyl 95 4-sulfatoethylsulfone-1-aminobenzeneyl

Example 96

Dye of Example 36, C.I. Reactive Red 120 Dye, C.I. Reactive Red 195 dyes, Comparative Example 1 and Comparative Example 2, using the method specified in the dyeing method 1, the dye was compared under the same conditions, the color difference of Gretag Macbeth (Gretag Macbeth) The relative dyeing intensities were measured and compared using a system. The results are shown in FIGS. 1 and 2.

As can be seen in FIGS. 1 and 2, the dye of Example 36 according to the present invention is a C.I. Reactive Red 120 Dye, C.I. It was confirmed that it exhibits excellent fixation rate and relative dye strength than the dyes of Reactive Red 195 dye, Comparative Example 1 and Comparative Example 2.

The novel compounds according to the invention are fibrous reactive dyes expressing dark red, in particular scarlet, which dye and print textile materials, in particular cellulose fiber materials, according to the chromaticity by a commonly used fixing method, It has a fixing rate and is excellent in light fastness and fastness to wet treatment.

1 is a comparative graph of fixation rates for dyes according to the invention and conventional dyes;

Figure 2 is a comparative graph of the relative dyeing intensity for the dye according to the invention and conventional dyes.

Claims (13)

A fiber reactive red dye having the structure of Formula 1. [Formula 1] Where R ₁ is a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, an optionally substituted aryl group, or a hydrogen atom; X ₁ and X ₂ are each independently halogen, hydroxy, carboxy, cyanine, a hydrogen atom, a sulfonic acid or an alkoxy group having 1 to 4 carbon atoms; Y is halogen, hydroxyl, 3-carboxypyridin-1-yl, 3-carbamoylpyridin-1-yl, alkoxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted amino group Or an N-heterocycle group which may further contain a hetero atom; Z is a group of formula (2); n ₁ and n ₂ are each independently 0 to 4; n ₃ is 0 or 1 and when n ₃ is 0,-(SO ₃ H) n ₃ is a hydrogen atom; _{However, - (CH 2) n 1} -X 1 and - (CH ₂₎ n ₂ -X ₂ If is different from each other, n ₁ is O and X ₁ is a hydrogen atom; when n ₁ and n ₂ are each 0 and X ₁ is a hydrogen atom, X ₂ is not a hydrogen atom; When n ₁ is 0, n ₂ is 2 and X ₁ is hydrogen, X ₂ is not a carboxy group. [Formula 2] Wherein U is a vinyl group or the general formula CH ₂ -CH ₂ -Q, wherein Q is a living group which can be removed under alkaline conditions. The fibrous reactive red dye according to claim 1, wherein n ₁ is O, n ₂ is 2, X ₁ is a hydrogen atom, and X ₂ is a hydroxy group. The fiber reactive red dye according to claim 1, wherein U is a vinyl group or β-sulfatoethyl. The compound of claim 1, wherein in Y, halogen is fluorine or chlorine, and N-heterocyclo is a morpholine, thiomorpholine, piperazine or piperidine radical, and the amino group is unsubstituted or alkyl N-mono- (C ₁ -C ₄ ) straight or branched alkylamino or N, N-di- (C ₁ -C ₄ ) straight or branched alkylamino moiety substituted with hydroxyl, sulfato or sulfur Fiber reactive red dye, characterized in that a group. The fibrous reactive red dye according to claim 1, which has a structure of formula 4a. [Formula 4a] Wherein n ₁ , n ₂ , n ₃ , R ₁ , X ₁ , X ₂ and Y are the same as in formula (1), and U is the same as in formula (2). The fibrous reactive red dye according to claim 1, which has a structure of formula 4b. [Formula 4b] Wherein n ₁ , n ₂ , n ₃ , R ₁ , X ₁ , X ₂ and Y are the same as in formula (1), and U is the same as in formula (2).  The fibrous reactive red dye according to claim 1, which has a structure of formula 4c. [Formula 4c] Wherein n ₃ , R ₁ and Y are the same as in formula 1, U is the same as in formula 2, X ₂ is halogen, hydroxy, cyanine, hydrogen, sulfonic acid or alkoxy group having 1 to 4 carbon atoms to be. The fibrous reactive red dye according to claim 1, which has a structure of formula 4d. [Formula 4d] Wherein n ₃ , R ₁ , X ₁ , X ₂ and Y are the same as in formula (1), and U is the same as in formula (2).  The fibrous reactive red dye according to claim 1, which has a structure of formula 4e. [Formula 4e] Wherein n ₃ , R ₁ and Y are the same as in formula 1, U is the same as in formula 2, X ₂ is halogen, hydroxy, cyanine, hydrogen, sulfonic acid or alkoxy group having 1 to 4 carbon atoms to be. (A-iii) diazotizing the compound of Formula 5 and coupling the compound of Formula 8 to prepare a compound of Formula 10; (A-ii) diazotizing the compound of Formula 6 and coupling the compound of Formula 7 to prepare a compound of Formula 9; And, (A-iii) condensing the compound of formula 10 and compound of formula 9 with 2,4,6-trihalogeno-s-triazine to prepare a compound of formula 1, Process for preparing a fiber reactive red dye compound of formula (1). [Formula 5] [Formula 6] [Formula 7] [Formula 8] [Formula 9] [Formula 10]  (B-iii) diazotizing the compound of Formula 6 and coupling the compound of Formula 7 to prepare a compound of Formula 9; (B-ii) condensing the compound of Formula 9 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 12; (B-iii) condensing a compound of Formula 12 with a compound of Formula 8 to produce a compound of Formula 17; (B-VIII) A method for preparing a fibrous reactive red dye compound of formula (I), comprising the step of diazotizing the compound of formula (5) and coupling the compound of formula (17) to produce a compound of formula (I). [Formula 12] [Formula 17] (C-VII) condensing the compound of Formula 8 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 13; (C-ii) condensing a compound of Formula 13 with a compound of Formula 7 to produce a compound of Formula 15; (C-VII) diazotizing the compound of Formula 5 and then coupling the compound of Formula 15 to prepare a compound of Formula 16; And, (C-iii) A method for preparing a fibrous reactive red dye compound of formula (I), comprising the step of diazotizing the compound of formula (6) and then coupling the compound of formula (16) to produce a compound of formula (1). . [Formula 13] [Formula 15] [Formula 16] (D-iii) diazotizing the compound of Formula 5 and coupling the compound of Formula 8 to prepare a compound of Formula 10; (D-ii) condensing the compound of Formula 10 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 14; (D-iii) condensing the compound of Formula 14 with the compound of Formula 7 to prepare a compound of Formula 16; And, (D-X) A method for preparing a fibrous reactive red dye compound of formula (I), comprising the step of diazotizing the compound of formula (6) and coupling the compound of formula (16) to produce a compound of formula (1). [Formula 14]