TWI335927B - - Google Patents

Description

1335927 IX. INSTRUCTIONS: * TECHNICAL FIELD OF THE INVENTION The present invention relates to a reactive yellow dye composition which can improve the dyeing depth, detergency, washing fastness and the like of existing yellow reactive dyes. [Prior Art] A conventional yellow dye such as C_I. Reactlve Yell〇w 1〇7 ' c丄

Reactive Yellow 145 or CI Reactive Yellow 176 are all single reactive yellow dyes. In order to improve the dyeing depth of traditional yellow dyes, 10 is based on a reactive yellow dye and is compatible with orange, yellow or other color systems. A dye that constitutes a highly dyed deep yellow dye composition. The reactive yellow dye main body used in the conventional yellow dye, for example, a reactive yellow dye of the following formula (丨).

SUMMARY OF THE INVENTION The present invention provides a reactive yellow dye composition suitable for dyeing leather, wool, silk, nylon, cellulose fibers, and cellulosic fiber blends or fabrics. 5 1335927 The reaction-reactive yellow dye composition of the present invention mainly comprises the following components (A) and component (B). The component (A) is an azo reactive dye represented by the following formula (I) or formula (II), which is contained in an amount of 98 to 50% by weight, and is selected from the following formula (I) or formula (II).

So3h (1) The same or different substituents Cl-4 leukoxene and CW4 alkoxy group, wherein '(Ri)o-3 is independently selected from 0 to 3 phases selected from the group consisting of halogen, suspending, and tartaric acid groups (SUlf) 〇), the group formed; 10

R2 is a group consisting of Η, c〇CH3 and CONH2; Q is -NH-CO-CH(Hal)-CH2(Hal), -NH-CO~C(Hal)=CH2 or -so2-y ' Wherein γ is -CH2Ch2〇s〇3h, _CH=CH2 or -CH2CH2U, and U is a group which can be removed by alkali treatment; Hal is a halogen;

Ν=Ν 15 H, methyl, wherein R7 and R8 are independent and separately selected

The group consisting of COOH, -〇CH3, -0C2H5, -S03H, -C1 and -S02Y' where Y is the same as defined above.

6 (II) (II) The group consisting of COCH3 and CONH2; thiol, -OCH3, -oc#, 8〇311 and -(:1 consisting of h is selected from the group consisting of η selected from η; Since the group consisting of the following formula (Da), -ea (Da) where the team). _3 is the same as the azo reactive dye represented by the above formula (1);

N. ^10 VN~D>

N wherein U is selected from the group consisting of hydrazine, methyl and ethyl; selected from the group consisting of the following formula (D-b),

(Db) wherein (RMQ is the same as defined in the azo reactive dye represented by the above formula (1). The component (8) is at least 2 to 5 重量% by weight of the azo selected from the following formula (ΠΙ) Reactive dye, , 1335927

Hy

2 N = N-

〇3 n=n-d2

(III) wherein R is H or a carboxyl group (COOH);

X is the same as defined above for the azo-reactive dye of the formula (I); wherein the X substituent is preferably a hydrogen atom; Z is Η, -CH2SO3H, -CH2CH2S03H'-ch2cooh or -ch2ch2cooh; 02 and 03 Individually independent and separately selected from the group consisting of the following formula (Da) or (Db), 10 (Rl) 0-3

Delay 1) 0-3 • (D-a) (D-b) wherein (1^)()_3 and Q are the same as the azo reactive dyes represented by the above formula (1). The dye composition of the present invention, wherein the substituent of 15 (1) 0-3 of the azo reactive dye of the formula (I), preferably 0 to 3 identical or different substituents are selected from the group consisting of: sulfonic acid a group consisting of a base, a methyl group, and a methoxy group. In the dye composition of the present invention, the Q substituent of the azo reactive dye of the formula (I) is preferably -S02-Y, wherein Y is -ch2ch2oso3h, -ch=ch2 or -ch2ch2u, and U is treated by alkali. The leaving group. As for the U substituent 8 1335927

The combination of -n-r5 and quaternary salt % is preferably selected from the group consisting of: Cl, 〇; § j j j j 成 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中The dye composition of the present invention, wherein the DA03 substituent of the azo reactive dye of the formula (IV) is preferably independently selected from the group consisting of the following formula (D-b), respectively.

(R-l)〇-3 10

15

Let (RA·3 be 0 to 3 identical or different substituents selected from the group consisting of: sulfonic acid methyl and methoxy; Q ^ -NH-CO-CH(Hal)-CH2( Hal) ^ -NH-CO-C(Hal)=CH2 or S02 γ wherein γ is -ch2ch2oso3h, -ch=ch2 or -CH2CH2U, U is a group which can be removed by alkali treatment; Hal is halogen. 'Q is preferably -S〇2-Y, wherein Y is -CH2cH2〇s〇3H, _CH=CH2 or CH2CH2U, U is a group which can be removed by treatment; it is a halogen. Among the azo-reactive dyes, (10) the treatable leaving group (IV) is preferably selected from

Cl ' -oso3h

Quaternary ammonium salt

- N, a group of R5~, wherein R4, 5, and the core are each independently and are respectively Cl 4 alkyl. Specific examples of the azo reactive dye of the formula (1) in the dye composition of the present invention are, for example, the following formula (1), formula (2) and a compound of the formula, but are not limited to the specific compound. 9 20 1335927

HO3SOC2H4O2S

N

=N

H2N

SO2C2H4OSO3H (2)

H03SOC2H402S

N = N

CH3COHN

S03H ^>-NH2

(3) Specific examples of the azo-reactive dye of the formula (II) in the dye composition of the present invention are, for example, but not limited to, the compounds of the following formula (4).

10 (4) 1335927 Specific examples of the azo-reactive dye of the formula (III) in the dye composition of the present invention are, for example, but not limited to, the compounds of the following formula (5), formula (6) and formula (7). So3h

rK rH

H03S0H4C202S—d λ— N = N

H2n"^V^nh2 N II N

SO2C2H4OSO3H 5 (5)

Nh2

N

S02C2H4〇S03H (6)

11 10 (7) 1335927 The proportion of the dye component used in the dye composition of the present invention, the ratio of the components of the various dyes can be freely changed, and is not limited. In general, the minimum relative weight percentage is 2% 'the maximum relative weight percentage is 98%; the content of the component (A) of the present invention is preferably 7 to 98 weight percent, and 5 the component (B) The content of the component (A) of the present invention is preferably from 80 to 95% by weight, and the content of the component (B) is preferably from 20 to 5% by weight. The dye molecule of the present invention is represented by a free acid form, but is not limited thereto. It may be a salt type when it is implemented, for example, an alkali metal, an alkaline earth metal 10 or an ammonium salt, and particularly a sodium salt 'potassium salt. Lithium or ammonium salts are preferred. The dye composition of the invention can be applied to cellulose fibers such as cotton, rayon, hemp and artificial hemp, dyeing of polyamide fibers such as wool, silk and nylon, and dyeing of blended or woven fabrics, and can obtain various dyeing materials with good dyeing properties. . The dye composition of the present invention has excellent dyeing depth, detergency, and sunlight fastness. It can be used as a color matching composition with other color dyes. [Embodiment] The compound of the formula (I) in the composition of the present invention can be synthesized by the following method: First, the amine compound of the following formula (a) is subjected to diazotization, followed by an acid test with an amine compound of the formula (b): The compound of the formula (1) of the present invention can be obtained by a coupling reaction at a pH of 1 to 7 and a temperature of 0 to 3 (TC). 12 1335927

"中(Ri)." R2 Q, X are defined as described above. For example, in the German Patent Gazette

No. 91 1427 discloses a preparation method of the formula (1), and a preparation method of the formula (3) is disclosed in German Patent Publication No. DE 3134357. The compound of the formula (Π) in the composition of the present invention can be synthesized by the following method: First, the amine compound of the following formula (4) is subjected to diazotization, followed by the amine compound of the following formula (d) at an acidic pH value of pH=1_7 and temperature 〇~ The (p) compound of the present invention can be obtained by carrying out a coupling reaction at 3 Torr. 10 D-NH2

(c)

Hr3n (p) wherein R3, R9, and D are as defined above. ❻) and trichloro-triazine in the pH value ρ Η = 1-7 and the temperature 〇 ~ 25. (: After the condensation reaction is carried out, HNRmD is further added to the compound, wherein Rw'D is defined as described above, and the condensation reaction is carried out at a pH of 6-8 and a temperature of 25 to 60 ° C to obtain the present invention 13 15 1335927 Formula (II). The preparation method of the formula (4) is disclosed, for example, in the Japanese Patent Publication No. JP561 1 8974. The compound of the formula (III) in the composition of the present invention can be synthesized by the following method: First, the following formula (e) The amine compound is subjected to diazotization, followed by coupling reaction with an amine compound of the following formula (f) at an acidic pH value such as pH = l-3, and at a temperature of 〇3 to 3 ° C. Then again with the following formula (g) A diazonium salt of an amine compound, wherein a coupling reaction is carried out between an acid to a neutral acid-base value, for example, a pH of 3.0 to 7.0, and a temperature of 〇30 to 30 T: to obtain a compound of the formula (ΙΠ) of the present invention, but Because of the difference in raw materials and reaction conditions, the bonding position selected by Ds-NH2 will be different. The definitions of R, X, Z, D2 and D3 are as described above. D3—NH〗 15 d2-nh2 R 1 (e) (f) nh2 (g) The dye composition of the present invention can be formulated by various methods, for example, separately. The individual dyes' are then mixed in a suitable mixer, for example in a transfer barrel or in a suitable mill, such as a ball and sand mill. The above method also uses agitation to mix individual dyes to form The dye liquid is mixed; or the individual dyes are mixed during the dyeing or printing process. The form of the reactive yellow dye composition of the present invention is not particularly limited, and is a powdery, granular or liquid state. The reactive yellow dye composition of the present invention Medium, 14 20 1335927 Optionally, inorganic salts such as sodium sulphate and gasification 1 may be optionally used, and the dispersing agent may be, for example, no tea acid _ road condensation product, methyl cyano acid- hydrazine The condensation product, the alanine-naphthalene compound, etc.; the dustproofing agent can be 1 such as p-benzoic acid, and the pH buffering agent can be 5, for example, acetamidine and sodium silicate. And a water softener A, such as a polyacrylate, etc.; or a conventional dyeing agent, etc. The reactive yellow dye composition of the present invention is suitable for leather, wool, stupid silk, 'Nylon, cellulose fiber and fiber Blended or woven fabric of plain fiber material Color, but not limited to, wherein the cellulose fiber material is not specifically limited to 'contains natural or regenerated cellulose fibers, such as pure cotton fiber, flax, hemp, ramie or mucilage. The invention is applicable to various habits Known dyeing methods 'but not limited to this, such as dip dyeing, continuous dyeing, cold press dyeing and printing, more suitable for dyeing' can also be applied to the dye component of digital inkjet printing ink. The composition is a wood color which is blended or blended with cellulose fibers and cellulose fibers, and is a kind of reactive yellow dye with industrial value, which has good dyeing and leveling property, and has good dye stability. Sexual, quality dyeing, printing or dyeing products. ° For the convenience of further description, the following examples will be given to more specific descriptions of 20. The following examples illustrate the scope of the patent application of the present invention. Wherein the compound is expressed in the form of a free acid, but the actual form may be a metal salt, more likely an alkali metal salt 'especially a sodium salt, unless otherwise stated, otherwise the parts or percentages used in the examples are In weight, the temperature is in degrees Celsius. C is the unit. 15 1335927 Preparation Example 1 28.1 parts of 1-aminobenzene-4-β-sulfatoethylsulfone was dissolved and dispersed in 200 parts of ice water, followed by 24 parts of 32%. The aqueous solution of HCl was thoroughly stirred therein, and then a further 7.0 parts of an aqueous solution of sodium nitrite was added, followed by stirring at 〇 to 5 ° C until diazotization was completed. Then add 9.4 parts of 2,4-diamino-1-sulfonic benzene compound, adjust the pH to 2.5~3.0 with sodium bicarbonate at a temperature of 0-1 0 °C. After stirring for 3 hours, the pH was adjusted to 5-6 with sodium hydrogencarbonate at a temperature of 10-15 ° C, and the mixture was stirred until the 10 coupling reaction was completed. Finally, the gasification sodium salt is added and the mixture is taken out to obtain a compound of the following formula (2).

SO2C2H4OSO3H 15 Preparation Example 2 36.1 parts of 1-aminobenzene-2-sulfonic acid-4-β-sulfato-ethylsulfone was dissolved and dispersed in In 200 parts of ice water, 24 parts of 32% aqueous hydrochloric acid solution was added, followed by thorough stirring, followed by the addition of 7.0 parts of an aqueous solution of sodium nitrite, and then stirring was continued at a temperature of 0 to 5 ° C to complete diazotization. Next, 15.2 parts of a powder of 3,5-diaminobenzoic acid was added, and the reaction mixture 16 1335927 was mixed to complete the coupling reaction. Finally, salting out of the gasified sodium is carried out, and the mixture is removed by filtration to obtain the following formula (in-1 conjugate).

(ΙΙΙ-1) 5 Take 28.1 parts of 1-aminobenzene-4-p-sulfatoethylsulfone dissolved and dispersed in 200 parts of ice water, and add 24 parts of 32% hydrochloric acid. After the aqueous solution was stirred thoroughly, 7.0 parts of an aqueous solution of sodium nitrite was added, followed by stirring at a temperature of 0 to 5 ° C until diazotization was completed. Next, the compound of the formula (III-1) obtained above is added, and the pH is adjusted to 3.5 to 5.0 with sodium hydrogencarbonate, and the mixture is stirred at a temperature of 5 to 15 ° C to complete the coupling reaction. Finally, gasification nanosaltration is added, and the mixture is removed by filtration to obtain a compound of the following formula (5).

N

SO2C2H4OSO3H 15 Preparation Example 3 17 (5) 1335927 17.3 parts of 1-aminobenzene-2-sulfonic acid was dissolved and dispersed in 200 parts of ice water, followed by 24 parts of 32% HC1. The aqueous solution was thoroughly stirred therein, followed by the addition of 7 parts of an aqueous solution of sodium nitrite, and then stirring was continued at 0 to 5 ° C until diazotization was completed. Next, 15.2 parts of 3,5-diaminobenzoic acid powder was added, and the reaction mixture was stirred until the coupling reaction was completed. Finally, salting out with sodium chloride is added, and the mixture is removed by filtration to obtain the compound (III-2).

(III-2) Dissolve and disperse 28.1 parts of 1-aminobenzene-4-β-sulfate ethanesulfonate in 200 parts of ice water, then add 24 parts of 32% aqueous HCl solution and stir well, then add 7 parts of an aqueous solution of sodium nitrite was then continuously stirred at 0 to 5 ° C until diazotization was completed. Next, the compound (III-2) is added, and the mixture is stirred with sodium hydrogen carbonate to adjust the pH to 3.5 at a temperature of 10 to 15 ° C to complete the coupling reaction. Finally, gasification sodium is added to the salting out, and the mixture is removed by filtration to obtain the compound (6). 18 1335927

NH2

SO2C2H4OSO3H (6) Preparation Example 4 72.2 parts of 1-aminobenzene-2-sulfonic acid -4-β-5 sulfatoethylsulfone was dissolved and dispersed in 2000 parts of ice water, and 48 parts of 32% aqueous hydrochloric acid solution was added thereto, followed by stirring, followed by addition of 14.0 parts. An aqueous solution of sodium nitrate was then continuously stirred at a temperature of 0 to 5 ° C until diazotization was completed. Then, 10.8 parts of m-phenylenediamine powder was added, and the reaction mixture was stirred for 3 hours, and the pH was adjusted to 10 3.5 to 6.0 with sodium hydrogencarbonate, and the mixture was stirred at a temperature of 5-15 ° C. Until the coupling reaction is completed. Finally, gasification sodium salting is further added, and the mixture is removed by filtration to obtain a compound of the following formula (7).

(7) Example 1 19 15 1335927 95% of the dye of the formula (1) and 5% of the dye of the formula (5) were mixed with each other to obtain a uniform dye composition. Example 2 to Example 33 The procedure of Example 1 was repeated, respectively, with a reactive dye as shown in Table 1, and the components and weight percentages as shown in Table 1 were mixed with each other to obtain a uniform dye composition. Table 1 Example ------------- 1 Group composition and weight percentage component (A) Group composition (B) 1 Formula (1) 95% Formula (5) 5% 2 Formula (1 90% Formula (5) 10% 3 Formula (1) 85% Formula (5) 15% 4 Formula (1) 95% Formula (6) 5% 5 Formula (1) 90% Formula (6) 10% 6 (1) 85% Formula (6) 15% 7 Formula (1) 95% ^ Formula (7) 5% 8 Formula (1) 90% Formula (7) 10% 9 --- ——------- Formula (1) 85% Formula (7) 15 % 10 Formula (2) 95% Formula (5) 5% ---- 》 20 1335927 11 Formula (2) 90% Formula (5) 10% 12 Formula (2) 85% Formula (5) 15% 13 Formula ( 2) 95% Formula (7) 5% 14 Formula (2) 90% Formula (7) 10% 15 Formula (2) 85% Formula (7) 15% 16 Formula (3) 95% Formula (5) 5% 17 Formula (3) 90% Formula (5) 10% 18 Formula (3) 85% Formula (5) 15% 19 Formula (3) 95% Formula (6) 5% 20 Formula (3) 90% Formula (6) 10 % 21 Formula (3) 85% Formula (6) 15% 22 Formula (3) 95% Formula (7) 5% 23 Formula (3) 90% Formula (7) 10% 24 Formula (3) 85% Formula (7) 15% 25 Formula (4) 95% Formula (5) 5% 26 Formula (4) 90% Formula (5) 10% 27 Formula (4) 85% Formula (5) 15% 28 Formula (4) 95% Formula (6) 5% 29 (4) 90% (6) 10% 21 1335927 30 (4) 85% r*—-— (6) 15% 31 type (4) 95% type (7) 5% 32 type (4) 90% type (7) 10% 33 type (4) 85% type (7) 15% ¥ color s type test example 1: take example 1 The dye composition was subjected to a dyeing test by the following dyeing method. A yellow dyeing product excellent in fastness can be obtained. 5 I. Dip Dyeing: Take 1 part of the above mixed dye mixture, completely dissolve in 100 parts of distilled water, and prepare a dye solution. Then, take two dyes and rinse them with distilled water. Inject 20 parts and 40 parts of the dye solution respectively. In the cup, finally add 4.8 parts of Glauber's salt, then add the dyeing solution of each dyeing cup to the total amount of 75 parts with distilled water, and then add 5 parts of 320 g/L of soda ash to each dyeing cup. Take 4 parts of cotton flat woven cloth and put it into each dyeing liquid. After locking the upper cover, shake it up and down to make the dye uniform. Then, put the dyeing cup into the thermostat bath at 62 °C and start the rotary button for 5 minutes. After heating to 60 C, keep it for 60 minutes. Then, take out the cloth and rinse it with cold water. Put it in a large steel basin, wash it with boiling water for 10 minutes, then put the cloth into a large steel basin containing 2g/1 15 soaping agent. In the middle, the soap was washed with boiling water for 10 minutes, and then the cloth was taken out and rinsed with cold water, and then dehydrated and dried. Second, printing and dyeing: Take 100 parts of urea, 1 part of sodium nitrobenzoate, 2 parts of baking soda, 55 parts of sodium alginate and 815 parts of warm water in a container to make a paste, and mix and finish 22 1335927 Fully uniform, formulated into auxiliary paste, taking 46 parts of auxiliary paste and 4 parts of dye to prepare a color paste. Then, a 100-mesh printing screen is applied to a suitable size of mercerized cotton cloth, and then the color paste is separately applied over the screen plate, and then the color paste is evenly coated on the top with a rubber blade. The shaved 5 cloth was placed in an oven at 65 ° C for 5 minutes. The dried cloth was taken out and placed in a steamer and steamed at a saturated steam of 102 ° C - 105 ° C for 10 minutes. As with the dip dyeing method, it is dehydrated and dried after being washed with cold water, hot water and soap. Lu 3. Continuous dyeing: Take 3 parts of dye, 0.4 parts of sodium alginate and 46.6 parts of distilled water, and mix them to make a dyeing solution. After the preparation of the dyeing solution is completed, the pressure dyeing solution is immediately pressed on the dyeing machine, the temperature of the dyeing solution can not exceed 3 degrees, and the pressure-absorbing rate of 7〇% of the pressed color cloth passes through the oven at 65 °C. After drying for 5 minutes, the dried cloth is steamed through a steamer at a saturated steam of 1 ° C - 105 ° C for 40 seconds. Then, as in the dip dyeing method, it is subjected to cold water washing, hot water washing and soaping, and then dehydrated and dried. 15 Dyeing Test Examples 2 to 33: Φ The procedure of Example 1 was repeated, and the reactive dye composition of Example 2 to Example 36 shown in Table 1 was substituted, and the fiber dyeing test described in the dyeing test 1 was repeated. Various yellow dyeing products excellent in fastness were obtained. 20 Solubility Test Examples 1 to 33: 36 sets of dye compositions of Examples 1 to 36 were taken, respectively, in the following 150 g/liter solubility test. 23 1335927 Take a 7_5 wound quantitative dye' Add 50 parts of steamed water in a 25-inch beaker, use a glass rod to be aged, then heat (4) and heat for 5 minutes. Take T〇Y〇 N. · 1 The paper and the funnel are pre-wet and then pumped, and the dissolved test solution is quickly poured into the air. Take out the natural wind of the crepe paper and dry it. As a result, it was judged that the dye-free residue adhered to the crepe paper, and the solubility test was passed. As a result of the test, 36 sets of dye compositions, such as Examples (1) to (36), all passed the solubility test, indicating that the solubility was good. Comparative Test Examples 1 to 3: 10 The single yellow dyes of the above formula 〇), formula (3) and formula (4) were respectively taken, and the dye staining test described in the dyeing s test 1 was repeated. Various yellow dyed products can be obtained. Comparison of dyeing test results: 15 Appearance strength: Generally known dyeing and finishing technology, the definition of appearance strength is basically based on the spectrophotometer measuring color sample in the range of visible light 3〇〇-700nm, the color sample is measured by illumination The absorption and reflection values of the color samples, that is, the reflectance and the K/S value. Generally speaking, the method of expressing strength has two kinds of chromatic intensity and appearance strength. Chromaticity: The ratio of the K/S value of the maximum absorption wavelength of visible light at 300-700 nm. Appearance strength: the sum of the K/S values of visible light 300-700nm. The results of the dyeing test are shown in Tables 2 to 5 below. Table 2 24 1335927 Dyeing Test No. Dye Appearance Strength Comparison Test Example 1 Formula (1) 100% Dyeing Test Example 1 Example 1 113.111% Dyeing Test Example 2 Example 2 115.694% Dyeing Test Example 3 Example 3 124.464% Dyeing Test Example 7 Example 7 110.621% Dyeing Test Example 8 Example 8 124.529% Dyeing Test Example 9 Example 9 134.867% Table 3 Dyeing Test No. Dye Appearance Strength Comparison Test Example 2 Formula (2) 100% Dyeing Test Example 10 Example 10 121.11% Dyeing Test Example 11 Example 11 142.49% Dyeing Test Example 12 Example 12 157.18% Dyeing Test Example 13 Example 13 135.41% Dyeing Test Example 14 Example 14 150.52% Dyeing Test Example 15 Example 15 173.07% Table 4 25 1335927 Dyeing test number 'Dye appearance strength comparison used Test Example 3 Formula (3) 100% Dyeing test Example 16 Example 16 114.317% Dyeing test Example 17 Example 17 125.720% Dyeing test Example 18 Example 18 135.676% Dyeing test Example 22 Example 22 117.283% Dyeing test Example 23 Example 23 137.375% Dyeing test Example 24 Example 24 143.860% Table 5 staining Comparison of Dye Appearance Strength of Test No. Test Example 4 Formula (4) 100% Dyeing Test Example 25 Example 25 102.171% Dyeing Test Example 26 Example 26 114.223% Dyeing Test Example 27 Example 27 119.023% Dyeing Test Example 3 1 Example 31 119.023% Dyeing Test Example 32 Example 32 125.738% Dyeing Test Example 33 Example 33 135.584% 26 1335927 The present invention is not limited to the above-described embodiments, but is intended to be illustrative only and the claimed scope of claims is The above is in accordance with the above embodiment. 5 [Simple diagram description] None [Main component symbol description] None 10

27

Claims (1)

927 X. Patent application scope: 1. A reactive yellow dye composition comprising: (A) at least 98 to 50% by weight of a kind selected from the group consisting of azo as shown in (1) or (II) Reactive dye, Wherein (R))o·3 are individually independent to 3 identical or self: dentate, carboxyl, sulfonic acid, Cw alkyl and C group; 10 different substituents selected I.4 The composition is selected from the group consisting of Η, c〇ch3 and CONH2m; Q is -NH-C0_CH(Hal)_CH2(Hal), _NH c〇-c(Hai)=cH2 :S〇2 Y, wherein Y 疋-CH2CH2〇S〇3h, -CH=CH2 or -CH2CH2U, ϋ is a group which can be removed by alkali treatment; Ha丨 is dentate; Ν=Ν wherein R·7 and Rs are each independently selected from the group consisting of Ηmethyl, c〇〇h, _〇CH3, _〇C2H5, —s〇3H c1AS〇2Y, where γ is as defined above the same; NH-W 28 丄 927 (ιι) where R3 is a group consisting of H, C〇CH3 and conh2; thiol, _OCH3, _〇C2H5, -s〇3H^Ο consisting of D series selected from the group consisting of a group of the formula (D_a), (Da) wherein (Ri )〇·3 is the same as the azo reactive dye represented by the above formula (1): N 10 W is γΝ Cl ίο ND, wherein R 10 is selected from a hydrogen atom a group consisting of a methyl group and an ethyl group; D! is selected from the group consisting of the following formula (Db), (^1) 0-3 (Db) 15 wherein (R)) 3 and Q are the same as defined in the azo reactive dye represented by the above formula (1); and (B) at least one selected from the group consisting of 2 to 5 重量% by weight The azo reactive dye shown in (III), 29 2 丄jjjyz/ Where R is H or a carboxyl group; X is the same as the azo reactive dye represented by the above formula (1); z is Η, a CH2S〇3H, ~CH2CH2S〇3H, _Ch2C〇〇h or -ch2ch2cooh; D2 and Da are individually and separately selected, Including the base 10 of the following formula (Da) or (Db) Which is the same (^ΐ)〇-3 (D_a) (Db) (Us and Q are defined by the azo reactive dyes of the above formula (1), 2. The dye composition as described in the scope of the patent application, wherein The (Ri) 〇3 of the azo reactive dye of the formula (I) is a group of ruthenium to three identical or different substituents selected from the group consisting of a sulfonic acid group, a methyl group and a methoxy group. The dye composition as described in the scope of claim 2, wherein the Q substituent of the azo reactive dye of the formula (1) is _s〇2_Y, wherein γ is -ch2ch2oso3h, -CH=CH2 or -ch2ch2u, U is The dye composition described in claim 3, wherein the alkali-removable group 11 is selected from the group consisting of: 3 COOH - A and quaternary salt '~ group consisting of c, _4 alkyl. 5 R6 are independent and ▲ 5 · The dye composition described in the first paragraph of the patent scope ' The D substituent group ' of the azo reactive dye is selected from the group consisting of the following formula (Da) 10 (Da) wherein (the 0-3 series is 0 to 3 identical or different substituents selected from the group, a group consisting of a methoxy group and a methoxy group. 6. A dye composition as described in the scope of the application, wherein R Ν Ν Ν Cl is an azo reactive dye of the formula (II) wherein R 1 〇 is selected from the group consisting of a group consisting of a hydrogen atom 'mercapto group and an ethyl group. D, selected from the group consisting of the following formula (D_b), #1) 0-3 Q 31 15 (1) 5927 (Db) wherein (R 1) 0-3 is 0 to 3 identical or different substituents selected from the group consisting of: acid group, methyl group and methoxy group; Q is - NH-CO-CH(Hal)-CH2(Hal), -NH-CO-C(Hal)=CH2 or -S02-Y, where γ is a ch2ch2oso3h, -CH=CH2 or -CH2CH2U, and U is treated with a base a group that can be removed; Hal is a halogen. 7. The dye composition according to claim 6 of the patent application, wherein the q of the azo reactive dye of the formula (II) is -s〇2_Y, wherein γ is -CH2CH20S03H, -CH=CH2 or -CH2CH2U , U is a group which can be removed by alkali treatment; Hal is a element. 8. The dye composition according to claim 7, wherein in the azo reactive dye of the formula (II), the group U which can be removed by the treatment is selected from: a, -oso3h, —N—R5 and the quaternary salt ～ The group consisting of R4, Rs, and R0 are each independently and are respectively _€14 alkyl. 9. The dye composition according to claim 1, wherein the A and A substituents of the azo reactive dye of the formula (III) are individually independent and are respectively selected from the group consisting of the following formula (Da) or (Db) ), the group, For 1) 0-3 ... (D_a) (Db) 20 wherein (Rl) 〇 _3 is 〇 to 3 identical or different substituents selected from the group consisting of: sulfo, methyl and methoxy The group formed; 32 cut 5927 Q is -NH-CO-CH(Hal)-CH2(Hal) '-NH-CO-C(Hal)=CH2 or -S02-Y ' which makes γ a Ch2CH2〇s 〇3H, —ch=CH2 or -CH2CH2U, U is a group which can be removed by treatment; Hai is a halogen. 10. The dye composition as claimed in claim 9, wherein the Q system of the azo reactive dye of the formula (II) is -s〇2-γ, wherein Y is -CH2CH2〇S03H, -CH= CH^-CH2CH2U, U is a group which can be removed by alkali treatment; Hal is a dentate. 11. The dye composition as described in the first aspect of the patent application, wherein the azo reactive dye of the formula (III), the base group 10-N-R5 and the quaternary ammonium salt which can be removed by alkali treatment The family consisting of 乂 is selected from the group consisting of: ci, -oso3h, and ^^COOH group, wherein R4, R5, and Re are each independently and are respectively -Gw. 12. The dye composition as described in the scope of the patent application, wherein the X substituent of the azo reactive dye of the formula (III) is a hydrogen atom. The dye composition according to the invention of claim 1, wherein the azo reactive dye of the formula (I) is a compound of the following formula (1) H03SOC2H402S The dye composition of claim i, wherein the oxime reactive dye of the formula (I) is a compound of the formula: A 33 1335927 SO-, Η HO3SOC2H4O2S SO2C2H4OSO3H (2) 〇 The dye composition according to claim 1, wherein the azo reactive dye of the formula (I) is a compound of the following formula (3): so3h HO3SOC2H4O2S CH3COHN (3). 16. The dye composition of claim 1, wherein the azo reactive dye of the formula (II) is a compound of the following formula (4): 10 The azo reactive dye of the formula (III) is a compound of the following formula (5): 34 1335927 _ SO2C2H4OSO3H (5). 18. The dye composition according to claim 1, wherein the azo reactive dye of the formula (III) is a compound of the following formula (6): so3h / COOH ^n=nyS H2N/^fXNH2 N N The dye composition according to claim 1, wherein the azo reactive dye of the formula (III) is a compound of the following formula (7): 35 1335927 SO2C2H4OSO3H (7). 20. The dye composition of claim 1, wherein the component (A) is present in an amount of from 70 to 98% by weight, and the component (B) is in an amount of from 30 to 2% by weight. 21. The dye composition according to claim 1, wherein the component (A) is contained in an amount of from 80 to 95% by weight, and the component (B) is contained in an amount of from 20 to 5% by weight. 36