KR100485410B1 - Fiber-reactive Yellow Dyestuffs And Methods For Preparing Them - Google Patents

Abstract

The present invention relates to a fibrous reactive yellow dye of the formula: and simultaneously comprising two heteroamorphic or homogeneous monoazo dye radical components.

The dye according to the present invention dyes and prints the fibrous material, in particular, the cellulose fibrous material in dark yellow according to the hue, and has excellent absorption and fastening rate and excellent fastness to light and wet treatment.

Description

Fiber-Reactive Yellow Dyestuffs And Methods For Preparing Them

The present invention relates to a fiber reactive yellow dye comprising two heterogeneous or homogeneous monoazo dye radical components simultaneously and a process for producing the same.

Recently, dyeing using reactive dyes requires a more economical method in terms of the quality of the dyeing and the profitability of the dyeing process. Accordingly, there is a need for reactive dyes that have sufficient directness in dyeing operations and at the same time are very easy to wash unfixed dyes. As a result, there is still a need for novel reactive dyes having high fastness to light or sweat while meeting these conditions.

It is conventionally mainly monochloro triazine-based reactive dyes. I. Reactive Yellow 84 Compound

When a bifunctional reactive dye. The compound of I. Reactive Yellow 145 was used.

However, these dyes do not simultaneously satisfy sufficient directness, good dyeing rate, high reactivity, in particular high precision, and the like as described above.

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 provide a reactive dye having a high fixation rate and a high fiber-dye bonding stability, and at the same time, a dye that is not fixed to the fiber can be easily washed, and has excellent light and moisture fastness. It is.

After numerous experiments and many years of research, the inventors have found that a new dye compound obtained by monomerizing a heterochromic or homologous yellow chromophore as shown in the following formula (1) into a chlorotriazine ring is a monochloro including a conventional single yellow matrix. Compared to triazine-based or hetero-functional compounds, the dyeing process is not only excellent in wet washing and light fastness, but also excellent in build-up, and excellent in adsorption and fixation. Having the characteristics, it was confirmed that most of the above-mentioned objects can be solved, and the present invention has been completed.

The fiber reactive yellow dye of the present invention for this purpose has a structure of formula (1).

Where

D is a group of formula 2a or 2b having a yellow chromosome;

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 (3);

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.

Where

R ₂ is methyl, -NHCONH ₂ , or -NHCOT, wherein T is methyl, ethyl, -CH ₂ CH ₂ COOH or -CH = CHCOOH;

R ₃ is a hydrogen atom, lower alkyl or lower alkoxy;

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

Wherein X ₁ , X ₂ , Z, n ₁ , n ₂ , n ₃ are the same as in formula (1).

Wherein U is the same as in formula (2a).

Reactive dyes of the general formula (1) according to the present invention is characterized by having a high reactivity, excellent fixing ability and very good build up ability and the like compared to the conventional monochlorotriazine-based compound and vinyl sulfone-based compound.

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. a (C ₁ -C ₄₎ straight or alkylamino and the like in a side chain, more preferably a group of formula (4) amino or N, N- di.

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

In the above formula (2a), more preferably, U is a vinyl group or β-sulfatoethyl.

Particularly preferred fiber reactive yellow dyes according to the present invention are compounds comprising a first yellow chromophore and a second yellow chromophore at the same time as in the following formulas 5a to 5f.

Wherein A is ammonia or C ₁ -C ₃ alkyl; n ₁ , n ₂ , X ₁ , X ₂ and Y are the same as in formula (1); R ₃ and U are the same as in formula (2a).

Wherein A is the same as in formula 5a; U is the same as in formula (2a); X ₁ is the same as in formula (1).

Wherein A is the same as in formula 5a; U is the same as in formula (2a), X ₁ and X ₂ are the same as in formula (1).

Wherein n ₁ , n ₂ , X ₁ , X ₂ and Y are the same as in formula (1); U is the same as in formula (2a); X ₃ and X ₄ are each independently halogen, hydroxy, carboxy, cyanine, a hydrogen atom, a sulfonic acid or an alkoxy group having 1 to 4 carbon atoms; n ₃ and n ₄ are each independently 0 to 4; _{However, - (CH 2) n 3} -X 3 and - (CH ₂₎ n ₄ -X ₄ are different from one another, if n ₃ is O, and X ₃ is a hydrogen atom; when n ₃ and n ₄ are each 0 and X ₃ is a hydrogen atom, X ₄ is not a hydrogen atom; When n ₃ is 0, n ₄ is 2 and X ₃ is hydrogen, X ₄ is not a carboxy group.

Wherein n ₁ , n ₂ , X ₁ and X ₂ are the same as in formula (1); U is the same as in formula (2a); X ₃ is the same as in Formula 5d.

Wherein U is the same as in formula (1); X ₁ is the same as in formula (1); X ₃ is the same as in Formula 5d.

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

When the yellow chromophore (D) of Chemical Formula 1 is represented by dividing the dye compound of Formula 2a (Formula 16) and the method of preparing the dye compound of Formula 2b (Formula 18). Hereinafter, n ₁ , n ₂ , n ₃ , n ₄ , R ₁ , R ₂ , R ₃ , U, X ₁ , X ₂ , Y, Z, etc. in Chemical Formulas 6 to 18 are chemical formulas unless otherwise specified. Same as defined in 1 to 5b. For convenience of description, the following Chemical Formulas 6 to 18 are shown first.

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.

For the preparation of the compound of Formula 16 and the compound of Formula 18, the following two methods may be mentioned as preferable examples.

The first method (A) for preparing the compound of formula 16 is

(A-iii) diazotizing the compound of Formula 6 and coupling the compound of Formula 11 to prepare a compound of Formula 12;

(A-ii) diazotizing the compound of Formula 8 and coupling the compound of Formula 7 to prepare a compound of Formula 9; And,

(A-X) condensation of a compound of Formula 12 with a compound of Formula 9 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 16.

The diazotization / coupling reaction of step (A-iii) and step (A-ii), after diazotizing the compound of formula (6) or formula (8) with nitrous acid at -5-15 ° C and pH 0.5-2, Coupling of the compound of Formula 11 or Formula 7 is carried out by acid binders in an aqueous medium at -5 to 15 and at 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 12 with 2,4,6-trihalogeno-s-triazine, and a compound of Formula 14 and Formula 9 A method of preparing a compound of formula 16 by a second condensation reaction of a compound,

(A-VIII)) A compound of Formula 10 is prepared by a first condensation reaction of a compound of Formula 9 with 2,4,6-trihalogeno-s-triazine, and a compound of Formula 10 and Formula 12 It is possible to prepare a compound of formula 16 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 16 is

(B-VII) diazotizing the compound of Formula 8 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 10;

(B-iii) condensing the compound of Formula 10 with the compound of Formula 11 to prepare a compound of Formula 15;

And (B-VII) diazotizing the compound of Formula 6 and coupling the compound of Formula 15 to produce a compound of Formula 16.

As a method for preparing the dye compound of Formula 18, the following two methods can be exemplified.

The first method (C) of preparing the compound of formula 18 is

(C-VII) diazotizing the compound of Formula 6 and then coupling the compound of Formula 11 to prepare a compound of Formula 12;

(C-ii) condensing the compound of Formula 12 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 14; And,

(C-iii) condensing a compound of Formula 14 with a compound of Formula 12 to produce a compound of Formula 18.

The second method (D) of preparing the compound of formula 18 is

(D-VII) condensing the compound of Formula 11 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 13;

(D-ii) condensing a compound of Formula 13 with a compound of Formula 11 to produce a compound of Formula 17; And,

And (D-VII) diazotizing the compound of Formula 6, followed by coupling reaction of the compound of Formula 17 to prepare a compound of Formula 17.

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, the method (B) is to diazotize the compound of formula (7), and then to react the compound of formula (8) to produce a compound of formula (9), but in some cases to diazotize the compound of formula (8) Then, the compound of Chemical Formula 9 may be prepared by coupling reaction with the compound of Chemical Formula 7.

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

Chlorocyanulic 1.8 in 100 g of an aqueous solution of 4.1 g of monoazo compound prepared by diazotizing 4-aminobenzene-1,3-disulfonic acid in a conventional manner, followed by coupling reaction with 3-ureidoaminoaniline. g was added and condensation reaction was carried out at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 2.2 g of 1-amino-3- (2-hydroxyethyl) aminobenzene-4-sulfonic acid was dissolved was added, followed by condensation reaction at 30 ° C. and pH 5 for 3 hours. To this solution, a diazo solution of 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene was added, and then a coupling reaction was carried out at 10 DEG C and pH 5.5 for 3 hours. The reaction solution was filtered to remove insoluble matters and then dried to obtain 10.5 g of a compound of the following formula.

This dye was dyed yellow on cellulose fibers and showed high light and wash fastness. 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

Diazolation of 4-aminobenzene-1,3-disulfonic acid in a conventional manner, followed by coupling reaction with 3-ureidoaminoaniline, to dissolve 4.1 g of monoazo compound, in 100 g of aqueous solution of fluorocyanuls 1.4 g was added and condensation reaction was carried out at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 2.2 g of 1-amino-3- (2-hydroxyethyl) aminobenzene-4-sulfonic acid was added, followed by condensation reaction at 40 ° C. and pH 5 for 3 hours. To this solution, a diazo solution of 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene was added, and then a coupling reaction was carried out at 10 DEG C and pH 5.5 for 3 hours. The reaction solution was filtered to remove insoluble matters and then dried to obtain 10.3 g of a compound of the following formula.

This dye was dyed yellow on 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

Chlorocyanulic 1.8 in 100 g of an aqueous solution of 4.1 g of monoazo compound prepared by diazotizing 4-aminobenzene-1,3-disulfonic acid in a conventional manner, followed by coupling reaction with 3-ureidoaminoaniline. g was added and condensation reaction was carried out at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 2.2 g of 1-amino-3- (2-hydroxyethyl) aminobenzene-4-sulfonic acid was added, followed by condensation reaction at 40 ° C. and pH 5 for 3 hours. To this solution was added a diazo solution of 2.8 g of 3-sulfatoethylsulfone-1-aminobenzene, and then a coupling reaction was carried out at 10 DEG C and pH 5.5 for 3 hours. The reaction solution was filtered to remove insoluble matters and then dried to obtain 10.5 g of a compound of the following formula.

This dye was dyed yellow on 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

To 100 g of an aqueous solution of 5.5 g of monoazo compound prepared by diazotizing 2-aminonaphthalene-3,6,8-trisulfonic acid in a conventional manner and then coupling-coupling with 3-ureidoaminoaniline, 1.8 g chlorocyanuls were added and condensed at 5 ° C. and pH 5 for 3 hours. After the completion of the reaction, 20 g of an aqueous solution in which 1.8 g of 1,3-diaminobenzene-4-sulfonic acid was dissolved were added, followed by condensation reaction at 40 ° C. and pH 5 for 3 hours. To this solution, a diazo solution of 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene was added, and then a coupling reaction was performed at 10 DEG C and pH 5.5 for 3 hours. The reaction solution was filtered to remove insoluble matters and then dried to obtain 11.0 g of a compound of the following formula.

This dye was dyed yellow on cellulose fibers.

Comparative Example 2

To 100 g of an aqueous solution of 5.5 g of monoazo compound prepared by diazotizing 2-aminonaphthalene-3,6,8-trisulfonic acid in a conventional manner and then coupling-coupling with 3-ureidoaminoaniline, 1.8 g chlorocyanuls were added and condensed at 5 ° C. and pH 5 for 3 hours. After completion of the reaction, 20 g of an aqueous solution in which 2.6 g of 1-amino-3-carboxyethylaminobenzene-4-sulfonic acid was dissolved was added, followed by condensation reaction at 40 ° C. and pH 5 for 3 hours. To this solution, a diazo solution of 2.8 g of 4-sulfatoethylsulfone-1-aminobenzene was added, and then a coupling reaction was carried out at 10 DEG C and pH 5.5 for 3 hours. The reaction solution was filtered to remove insoluble matters and then dried to obtain 11.0 g of a compound of the following formula.

This dye was dyed yellow on cellulose fibers.

[Examples 4 to 137]

Based on the examples, it was possible to synthesize the compounds described in Tables 1 to 20, 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 cellulose fiber materials in dark yellow according to the chromaticity by fixing methods commonly used in the field of fiber-reactive dyes, It has been confirmed that the fastness to light fastness and wet treatment with a / fixation rate is very good.

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 4 -Cl 5 -Cl 6 -F 7 -F 8 -F 9 Morpholinyl 10 Morpholinyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 11 Morpholinyl 12 3-sulfatoethylsulfone-1-aminobenzeneyl 13 3-sulfatoethylsulfone-1-aminobenzeneyl 14 3-sulfatoethylsulfone-1-aminobenzeneyl 15 4-sulfatoethylsulfone-1-aminobenzeneyl 16 4-sulfatoethylsulfone-1-aminobenzeneyl 17 4-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 18 -Cl 19 -Cl 20 -Cl 21 -F 22 -F 23 -F 24 Morpholinyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 25 Morpholinyl 26 Morpholinyl 27 3-sulfatoethylsulfone-1-aminobenzeneyl 28 3-sulfatoethylsulfone-1-aminobenzeneyl 29 3-sulfatoethylsulfone-1-aminobenzeneyl 30 4-sulfatoethylsulfone-1-aminobenzeneyl 31 4-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 32 4-sulfatoethylsulfone-1-aminobenzeneyl 33 -Cl 34 -Cl 35 -Cl 36 -F 37 -F 38 -F

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 39 Morpholinyl 40 Morpholinyl 41 Morpholinyl 42 3-sulfatoethylsulfone-1-aminobenzeneyl 43 3-sulfatoethylsulfone-1-aminobenzeneyl 44 3-sulfatoethylsulfone-1-aminobenzeneyl 45 4-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 46 4-sulfatoethylsulfone-1-aminobenzeneyl 47 4-sulfatoethylsulfone-1-aminobenzeneyl 48 -Cl 49 -Cl 50 -Cl 51 -F 52 -F

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 53 -F 54 Morpholinyl 55 Morpholinyl 56 Morpholinyl 57 3-sulfatoethylsulfone-1-aminobenzeneyl 58 3-sulfatoethylsulfone-1-aminobenzeneyl 59 3-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 60 4-sulfatoethylsulfone-1-aminobenzeneyl 61 4-sulfatoethylsulfone-1-aminobenzeneyl 62 4-sulfatoethylsulfone-1-aminobenzeneyl 63 -Cl 64 -Cl 65 -Cl 66 -F

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 67 -F 68 -F 69 Morpholinyl 70 Morpholinyl 71 Morpholinyl 72 3-sulfatoethylsulfone-1-aminobenzeneyl 73 3-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 74 3-sulfatoethylsulfone-1-aminobenzeneyl 75 4-sulfatoethylsulfone-1-aminobenzeneyl 76 4-sulfatoethylsulfone-1-aminobenzeneyl 77 4-sulfatoethylsulfone-1-aminobenzeneyl 78 -Cl 79 -Cl 80 -Cl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 81 -F 82 -F 83 -F 84 Morpholinyl 85 Morpholinyl 86 Morpholinyl 87 3-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 88 3-sulfatoethylsulfone-1-aminobenzeneyl 89 3-sulfatoethylsulfone-1-aminobenzeneyl 90 4-sulfatoethylsulfone-1-aminobenzeneyl 91 4-sulfatoethylsulfone-1-aminobenzeneyl 92 4-sulfatoethylsulfone-1-aminobenzeneyl 93 -Cl 94 -Cl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 95 -Cl 96 -F 97 -F 98 -F 99 Morpholinyl 100 Morpholinyl 101 Morpholinyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 102 3-sulfatoethylsulfone-1-aminobenzeneyl 103 3-sulfatoethylsulfone-1-aminobenzeneyl 104 3-sulfatoethylsulfone-1-aminobenzeneyl 105 4-sulfatoethylsulfone-1-aminobenzeneyl 106 4-sulfatoethylsulfone-1-aminobenzeneyl 107 4-sulfatoethylsulfone-1-aminobenzeneyl 108 -Cl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 109 -Cl 110 -Cl 111 -F 112 -F 113 -F 114 Morpholinyl 115 Morpholinyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 116 Morpholinyl 117 3-sulfatoethylsulfone-1-aminobenzeneyl 118 3-sulfatoethylsulfone-1-aminobenzeneyl 119 3-sulfatoethylsulfone-1-aminobenzeneyl 120 4-sulfatoethylsulfone-1-aminobenzeneyl 121 4-sulfatoethylsulfone-1-aminobenzeneyl 122 4-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 123 -Cl 124 -Cl 125 -Cl 126 -F 127 -F 128 -F 129 Morpholinyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 130 Morpholinyl 131 Morpholinyl 132 3-sulfatoethylsulfone-1-aminobenzeneyl 133 3-sulfatoethylsulfone-1-aminobenzeneyl 134 3-sulfatoethylsulfone-1-aminobenzeneyl 135 4-sulfatoethylsulfone-1-aminobenzeneyl 136 4-sulfatoethylsulfone-1-aminobenzeneyl

Example 1st yellow color development matrix Coupler (Y) 2nd yellow color development matrix 137 4-sulfatoethylsulfone-1-aminobenzeneyl

Example 138

Dye of Example 48, C.I. Reactive Yellow 84 Dye, C.I. Reactive Yellow 145 dyes, dyes of Comparative Examples 1 and 2, were compared by dyeing under the same conditions using the method specified in the dyeing method 1, 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 48 according to the present invention is a C.I. Reactive Yellow 84 Dye, C.I. It was confirmed that exhibiting better fixing rate and relative dye strength than the reactive yellow 145 dye, the dyes of Comparative Example 1 and Comparative Example 2.

The novel compounds according to the invention are useful yellow expressing fibrous reactive dyes, which dye and print textile materials, in particular cellulose fiber materials, to dark yellow according to the chromaticity by means of commonly used fixing methods, It has a fixation 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 (14)

A fibrous reactive yellow dye having the structure of Formula 1. [Formula 1] Where D is a group of formula 2a or 2b having a yellow chromosome; 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, hydrogen, 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 (3); 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 2a] Where R ₂ is methyl, -NHCONH ₂ , or -NHCOT, wherein T is methyl, ethyl, -CH ₂ CH ₂ COOH or -CH = CHCOOH; R ₃ is a hydrogen atom, lower alkyl or lower alkoxy; U is a vinyl group or the general formula CH ₂ -CH ₂ -Q, where Q is a living group that can be removed under alkaline conditions. [Formula 2b] Wherein X ₁ , X ₂ , Z, n ₁ , n ₂ , n ₃ are the same as in formula (1). [Formula 3] Wherein U is the same as in formula (2a). The fibrous reactive yellow 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 yellow 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 yellow dye, characterized in that a group. The fibrous reactive yellow dye according to claim 1, which has a structure of formula 5a. [Formula 5a] Wherein A is ammonia or C ₁ -C ₃ alkyl; n ₁ , n ₂ , X ₁ , X ₂ and Y are the same as in formula (1); R ₃ and U are the same as in formula (2a).  The fibrous reactive yellow dye according to claim 1, which has a structure of formula 5b. [Formula 5b] Wherein A is the same as in formula 5a; U is the same as in formula (2a); X ₂ is halogen, hydroxy, cyanine, hydrogen, sulfonic acid or an alkoxy group having 1 to 4 carbon atoms. The fibrous reactive yellow dye according to claim 1, which has a structure of formula 5c. [Formula 5c] Wherein A is the same as in formula 5a; U is the same as in formula (2a), X ₁ and X ₂ are the same as in formula (1). The fibrous reactive yellow dye according to claim 1, which has a structure of formula 5d. [Formula 5d] Wherein n ₁ , n ₂ , X ₁ , X ₂ and Y are the same as in formula (1); U is the same as in formula (2a); X ₃ and X ₄ are each independently halogen, hydroxy, carboxy, cyanine, hydrogen, sulfonic acid or an alkoxy group having 1 to 4 carbon atoms; n ₃ and n ₄ are each independently 0 to 4; _{However, - (CH 2) n 3} -X 3 and - (CH ₂₎ n ₄ -X ₄ are different from one another, if n ₃ is O, and X ₃ is a hydrogen atom; when n ₃ and n ₄ are each 0 and X ₃ is a hydrogen atom, X ₄ is not a hydrogen atom; When n ₃ is 0, n ₄ is 2 and X ₃ is hydrogen, X ₄ is not a carboxy group.  The fibrous reactive yellow dye according to claim 1, which has a structure of formula 5e. [Formula 5e] Wherein n ₁ , n ₂ , X ₁ and X ₂ are the same as in formula (1); U is the same as in formula (2a); X ₄ is halogen, hydroxy, cyanine, hydrogen, sulfonic acid or an alkoxy group having 1 to 4 carbon atoms.  The fibrous reactive yellow dye according to claim 1, which has a structure of formula 5f. [Formula 5f] Wherein U is the same as in formula (1); X ₁ is the same as in formula (1); X ₄ is halogen, hydroxy, cyanine, hydrogen, sulfonic acid or an alkoxy group having 1 to 4 carbon atoms. (A-iii) diazotizing the compound of Formula 6 and coupling the compound of Formula 11 to prepare a compound of Formula 12; (A-ii) diazotizing the compound of Formula 7 and coupling the compound of Formula 8 to prepare a compound of Formula 9; And, (A-iii) condensation of the compound of formula 12 with the compound of formula 9 with 2,4,6-trihalogeno-s-triazine to prepare a compound of formula 16, Process for preparing a fiber reactive yellow dye compound of formula (16). [Formula 6] Wherein U is the same as in formula (2a). [Formula 7] Wherein R ₂ and R ₃ are the same as in formula (2a). [Formula 8] Wherein U is the same as in formula (2a). [Formula 9] Wherein R ₂ , R ₃ and U are the same as in Formula 2a. [Formula 11] Wherein n ₁ , n ₂ , X ₁ and X ₂ are the same as in formula (1). [Formula 12] Wherein n ₁ , n ₂ , n ₃ , X ₁ , X ₂ and Z are the same as in formula (1). [Formula 16] Wherein n ₁ , n ₂ , n ₃ , X ₁ , X ₂ , Y and Z are the same as in formula 1, and U is the same as in formula 2a. (B-VII) diazotizing the compound of Formula 8 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 10; (B-iii) condensing the compound of Formula 10 with the compound of Formula 11 to prepare a compound of Formula 15; (B-iii) A method of preparing a fibrous reactive yellow dye compound of formula (16), comprising diazolating a compound of formula (6) and coupling the compound of formula (15) to produce a compound of formula (16). [Formula 10] Wherein R ₂ , R ₃ and Y are the same as in formula (1), but Y is at least one of them is a halogen atom and U is the same as in formula (2a). [Formula 15] Wherein n ₁ , n ₂ , n ₃ , R ₂ , R ₃ , X ₁ , X ₂ and Y are the same as in formula 1, and U is the same as in formula 2a. (C-VII) diazotizing the compound of Formula 6 and then coupling the compound of Formula 11 to prepare a compound of Formula 12; (C-ii) condensing the compound of Formula 12 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 14; And, (C-iii) A method of preparing a fibrous reactive yellow dye compound of formula (18), comprising the step of condensing the compound of formula (14) with the compound of formula (12) to produce a compound of formula (18). [Formula 14] Wherein n ₁ , n ₂ , n ₃ , X ₁ , X ₂ , Y and Z are the same as in the general formula (1), but at least one of Y is a halogen atom. [Formula 18] Wherein n ₁ , n ₂ , n ₃ , R ₁ , R ₃ , X ₁ , X ₂ , Y and Z are the same as in formula (1). (D-VII) condensing the compound of Formula 11 with 2,4,6-trihalogeno-s-triazine to prepare a compound of Formula 13; (D-ii) condensing a compound of Formula 13 with a compound of Formula 11 to produce a compound of Formula 17; And, (D-iii) A method for preparing a fibrous reactive yellow dye compound of formula (18), comprising the step of diazotizing the compound of formula (6) and then coupling the compound of formula (17) to produce a compound of formula (17). [Formula 13] Wherein n ₁ , n ₂ , n ₃ , X ₁ , X ₂ and Y are the same as in the general formula (1), but at least one of Y is a halogen atom. [Formula 17] Wherein n ₁ , n ₂ , n ₃ , R ₁ , X ₁ , X ₂ and Y are the same as in formula (1).