TWI239984B - Disazo reactive dyestuffs containing the quaternary groups and their use - Google Patents

Abstract

The present invention provides disazo reactive dyestuffs containing the quaternary group compounds of the general formula (1), wherein R, (W)0-3, (W5)0-3, Y1 and Y2 are defined the same as the specification. The dyes of the invention are distinguished by high fixation and a very good build-up. They are distinguished also by high washing off and a low nylon stain, and they have fiber-reactive properties and are very highly suitable for dyeing and printing of materials containing either cellulose fibers, such as cotton, synthetic cotton, hemp, and synthetic hemp, or amide containing fibres such as wool and nylon.

Description

! 239984 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a novel reactive dye, a bisazo-reactive azo dye containing a quaternary salt group, and fiber dyeing and printing in an aqueous bath. In particular, it is applicable to cellulose 10 [Prior art] British Patent No. 952,123 has disclosed the following formula (A), but the reactive dye has poor dyeing and dyeing properties. Reactive dye

(A) British Patent No. 1,349,168 has disclosed the reaction wood of the following formula (B) ', but the affinity and reactivity of the reactive dye are not good.

W a 「n =

nh2 w n = n-a2 ((S〇3H) r (X) n (X) ^ i

R (HOsS) !!!! (B) U.S. Patent No. 5,817,779 has disclosed compounds of formula (C) 20 1239984 for the preparation of co-wood applications 'which has high reactivity and good fixation in dyeing applications' but this Reactive dyes are said to have low affinity and poor washability. ,

n = n £ mn = n3-Dj 5 10 15 e (C) κ is on the market 'due to the poor quality of dyes and the economic efficiency of the dyeing method'. The use of reactive dyes for dyeing is in practical need, so ^ Improved properties, especially new reactive dyes in application are still urgently needed. In reactive dyeing applications, reactive dyes that can fully and easily wash off unsettled parts are also needed. It should also have excellent coloring rate and high reflectance. Central Asia spreads dyes with a southern coloration. Conventional dyes do not satisfy all the properties in this requirement. ^ Two ^ The problem that needs to be solved is to find a novel and improved reactivity for fiber materials: printing and dyeing with high above-mentioned characteristics. Those who dye ifpti have extensively researched reactive dyes that can meet the needs to solve ammonium rhenium. '. As a matter of fact, the above problems can be borrowed by using-including seasonings: = tenderness of the base group (pyndlni °), fiber = decomposability, bi-irradiation. It has easy-washability, bio-cota fastness, high light fastness, high water-wash fastness, and also has excellent performance in terms of its strength / beam, and also has good combinability and fiber. Leveling and non-dichroic properties [Abstract] The present invention relates to a dye and its application, a kind of quaternary ammonium salt bisazo reactivity of the following formula (1)

R 疋 gas atom, C " sulfonic acid group or CN4 carboxylic acid group; R is preferably a hydrogen atom or CN4 alkyl carboxylic acid group; (wk3 疋 0 to 3 same or different selected from the acid group (W) 0 ~ 3 is preferably 0 to 3, which are the same or different, and are selected from the group consisting of sulfonate ㈣f〇), methyl (, ~ 3 疋 0 to 3 same or different groups selected from the group consisting of sulfonic acid group, C " alkyl group or alkoxy group; (w,) 0 to 3, preferably 0 to 3 same or different groups The same group selected from the group consisting of sulfo, sulfo, methyl and methoxy; Yl depleted A is independently _CH = CH2, _CH2CH2〇s〇3H4 20 Cli2CH2-U, and Υι and Y2 At least one must be; preferably 'Y! Is -CH2CH2-U, Y2g-CH = CH2 or -CH2CH20S03H; U is one of the following formulae (2a), (2b), (2c), (2d) or (2e) Group 1239984-%-R2 R3

COOH (2a) (2c) ^ y〇NH2 XH3 (2d) or or (2c) group; ⑽ 5 10 and Xinming are 炫 xuanyl: preferably ^ and ^ are methyl. :: Mingzhi quaternary ammonium salt bisazo-reactive dye type ⑴ can be presented in the form of acid, 1 = 'especially metal test and soil test metal salts. In use, the form of alkali metal salts is preferred. The quaternary ammonium bisazo reactive dye of the present invention is preferably a reactive dye of formula (1), which is a reactive dye of the following formula (la). ~

(la), R, YjnY2 are defined as above. The quaternary ammonium bisazo-reactive dye of the present invention is particularly preferably a reactive slag of formula (1), which is a reactive dye of the following formula (lb). 1239984

Yi ~ 02s? 〇3Η

/, Medium 11, Ym and Y2 are defined as above. The present invention also relates to a method for dyeing or printing a cellulose fiber material, which comprises treating the fiber material with an aqueous solution such as the formula (1) and a reactive dye thereof, wherein the cellulose fiber material such as cotton is used. [Application method] 10 The quaternary ammonium salt bisazo reactive dye of the present invention is prepared by the formula (1). The reactive dye can be synthesized by conventional methods. For example, the following synthesis method is used to prepare the reactive formula (1). dye. The preparation is carried out by diazotizing the amine compound of the following formula (a), and then testing the acid value with the amine compound of the following formula (b) to a weakly acidic acid (pH == 2_5)

/ (W) 〇 ~ 3 ⑷ and coupling reaction at low temperature (0-10 ° C). And then with the diazonium salt of an amine compound of the formula 1239984

(C) The reaction between formula (1) 5 of the present invention can be obtained by performing a coupling reaction between a slightly acidic value and an acidic value, for example, an acidic value of 4.0 to 8.0, and a temperature of 20 to 60 ° C. dye. In the aforementioned preparation procedure, the compound of formula (c) and the compound of formula (b) can be reacted first and then with the compound of formula (a) by changing the reaction order. Similarly, a reactive dye of formula (1) can be obtained. The compound of the formula (a) may be exemplified by the following examples: 10 ho3soh2ch2co2s h2n ho3soh2ch2co2s guang nh2 ho3soh2ch2co2s- — 广 > —nh2 so3h

_nh2 ho3soh2ch2co2s (Ύ, ho3soh2ch2co2s, so3h h2n, nh2, H03S0H2CH2C02S /

so3h so3h -nh2 • nh2 ho3soh2ch2co2s ho3soh2ch2co2s 10 1239984 H03S0H2CH2C02S / so3H V -nh2 HO3SOH2CH2CO2S— so3h rV -nh2 so3h, ho3s / ^^ so3h so3h hs

H03SOH2CH2C02S -nh2 -nh2 h2ohco2s 0CH3 nh2

H03SOH2CH2C02S

nh2 och3

H03SOH2CH2C02S so3h nh2 ho3soh2ch2co2s

H03SOH2CH2C02S

och3 0CH3 HO3SOH2CH2CO2S— ^ nh2 h3co ho3soh2ch2co2s

nh2 11 1239984

f ^ r -νη2 h3c tx

_nh2 H3C—N-H2CH2C02S ’h3c〆

The compound of formula (b) can be exemplified as follows: nh2

so3h nh2

nhch2cooh

so3h

so3H

NHCH2CH2COOH 12 1239984 nh2

nh2

k NHCH2CH2CH2COOH nhch2ch2ch2ch2cooh

so3h, so3H nh2

nh2

NHCH2SO3H NHCH2CH2CH2SO3H

so3H, so3H

nh2

'NHCH2CH2CH2CH2S03H S03H and so on. The compounds of the formula (c) can be exemplified as follows: ho3soh2ch2co2s h2n ho3soh2ch2co2s ^^ ρΝΗ2 H03SOH2CH2C02S-

so3H

, Ho3soh2ch2co2s so3h

nh2

H03S0H2CH2C02S, v NH2 HO3SOH2CH2CO2S H2NVs / ^] / Xy S〇3 ^ 13 1239984 h2c = hco2s h2c = hco2s so3h

nh2

H03SOH2CH2C02S 0CH3 so3h ho3soh2ch2co2s

nh2

-nh2 nh2 OCH3 ， H03S0H2CH2C02S // // 0CH3 HO3SOH2CH2CO2S—nh2 h3co

14 1239984

nh2 h3c h3c 」waiter-h2ch2co2s h3c〆 h2noc so3h

nh2 a h2ch2co2s a h2ch2co2s

HOOC

—H2ch2co2s

nh2, etc. 5 The quaternary ammonium bisazo reactive dye of the present invention can be produced by the above-mentioned method, and the reaction situation has been fully described in the above description. The dye of the present invention can be obtained by spray method, sedimentation method or filter press method, and the type of the dye is powder, fine powder, granule or liquid state, and additives such as retarder, leveling agent, accelerator, interface Active agent or dispersant. 10 The dye of the present invention contains at least one anionic group, such as a sulfonic acid group. For convenience, the description is shown in the free acid form. The dyes of the present invention exist in the form of water-soluble salts when manufactured in large quantities. In particular, alkali metal salts such as sodium salts, sodium salts, potassium salts or beryllium salts are preferred. The dyes of the present invention can also be mixed with each other to form a composition and can be formulated by various methods, such as formulating different dyes and then mixing them; the mixing method is performed in a suitable mixer, such as a jog drum; Or in a suitable mill, such as a ball and sand mill, which are also 15 1239984 5 10 15 20 by stirring to make them a dye liquid and mixing each dye in the preparation method to control the reaction conditions so that = 备 = 生 if 相 如 > ^ At the same time you express your heart, you can produce products; you can also mix dyeing or printing dyes. Go down and make individual flowers. Two ::: t materials can be used for dyeing and printing of cellulose fiber materials; the conventional example of the bucket is naturally occurring cellulose fibers, such as cotton, cotton, and hemp ', as well as cellulose and recycled fiber blending. Fabric dyeing and printing. π-based fibers. The dyes of the present invention fix the fibers in various ways, especially in the form of stock solutions and printing pastes. And dyeing and printing by means of dip dyeing, continuous dyeing, cold second: ρ wood. The dyes of the present invention are characterized by being easily decomposable, low in salt, low in inspection, and capable of dyeing, and excellent in dyeing depth, and at the same time have a high absorption of M mm. f Resolution, and it is compatible with the wide range of warm and blue colors, so it is also suitable for cotton / polyester blended fabrics. The dye mixture of the invention is also suitable for printing and dyeing, especially for cotton or silk blended fabrics and For use in D / C one-bath staining applications. The dyeing and printing on the cellulose fiber material of the dye of the present invention have high directness, high dyeing depth, excellent transferability, and high fiber / ㈣ stability in acid test. The light and moisture resistance of the dyed articles produced in light fastness, sweat fastness, wet fastness, such as fastness, peroxide wash fastness, sweat fastness and acid fastness They are all very good in terms of fastness, especially in terms of fastness to rubbing, fastness to ironing, and fastness to chlorine bleaching. _ 16 1239984 For the convenience of further description, the following embodiments will be enumerated for a more detailed description. The following examples illustrate the present invention, and the scope of patent application of the present invention is not limited by this. The compounds represented by the general formula are in the dissociated acid form; usually they are isolated in the form of their metal salts and used in the form of their salts for dyeing. The starting compounds of the dissociated acid form mentioned in the following examples can also be used immediately in the synthesis or in their salt form (preferably alkali metal salts such as sodium or potassium salts) for synthesis. The following examples illustrate the invention. Unless otherwise specified, parts and percentages are based on weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters. Example 1 36 · 1 part of 1-aminobenzene-2-sulfonic acid-4-β-sulfate sulfonium sulfonate 15 (l-aminobetizenelsulfonic add bucket p-Suifatoethylsulfone) was dissolved and dispersed in 150 parts of ice water , Adjust the pH to 13 with 45% liquid alkali, and keep the pH stable and stir for b minutes until the reaction mixture completes the ethyleneization reaction, then adjust the acid test value to 5.0 to 6.0 with 32% hydrochloric acid solution, and then add 12.7 parts of nicotinate (nicotinate ), Heating and maintaining the temperature at 600 ° C and stirring the mixture for two hours and 20 to complete the reaction. Finally, it is added by gasification sodium salting out, filtered out, and the compound formula (P-1) can be recovered. ^ 17 1239984

nh2 Dissolve and disperse 19.4 parts of compound (P-1) in 150 parts of ice water, then add 12.6 5 parts of 32% aqueous hydrochloric acid solution and stir thoroughly, then add 3.7 parts of sodium nitrite aqueous solution, and then add 0 to 5 Continue stirring at ° C until complete diazotization. Next, 9.5 parts of 2,4-diaminobenzenesulphonic acid powder was added, and the pH was adjusted slowly with sodium bicarbonate to 3.5, and the mixture was stirred at room temperature until the coupling reaction was completed. Then, add 14.1 parts of the diazonium salt of 1-aminobenzene-4-P-sulfatoethylsulfone to the reaction solution, and slowly adjust the pH value to 5.0 to 6.0 with soda ash and stir Until the reaction is complete. Finally, the gaseous sodium is added for salting out, and filtered out to obtain the compound formula (3).

15 (3) Example 2 Dissolve and disperse 20.6 parts of 2-aminonaphthalene-1 -sulfonic acid-6-β-sulfosulfoethanesulfonate (2-aminonaphthalene-l-sulfonic acid_6-P-sulfatoethylsulfone) in 20 parts 150 parts of ice water, followed by adding 12.6 parts of 32% aqueous hydrochloric acid solution to 18, 18,39,984 parts and stirring, and then adding 3.6 parts of sodium nitrite aqueous solution, and then continuously stirring at 0 to 5 ° C to complete the diazotization. Next, 9.5 parts of 2,4-diaminobenzenesulphonic acid powder was added, and the pH was adjusted slowly with sodium carbonate to 3.5, and the mixture was stirred at room temperature until the coupling reaction was completed. Add ice to cool to 0 ° C, adjust the pH to 13 with 45% liquid alkali, and keep the pH stable for 15 minutes, then adjust the pH to 5.0 to 6.0 with 32% hydrochloric acid solution, and then add 6.4 parts of nicotine acid (11 丨(: (^ 1 ^ 6), heat and keep the temperature at 60 ° C and stir the mixture for two hours to complete the reaction, and cool to 20 ° C until use.

10 Then, add 14.1 parts of the diazonium salt of 1-aminobenzene-4-β-sulfatoethylsulfone (l-aminobenzene-4-p_sulfatoethylsulfone) to the above-mentioned reserve 15 reaction solution, and slowly adjust the acid and base with soda ash The value was stirred to 5.0 to 6.0 until the reaction was complete. Finally, sodium chloride is added for salting out, and it is filtered out to obtain the compound formula (4). HOOC < x n-h2ch2co2s

so3h

S02C2H40S03H (4) Example 3 19 20 1239984 Dissolve and disperse 19.4 parts of compound (P-1) in 150 parts of ice water, then add 12.6 parts of 32% aqueous hydrochloric acid solution and stir the mixture, then add 3.7 parts of nitrous acid Aqueous sodium solution, then continuously stirred at 0 to 5 ° C until complete diazotization. Next, 9.5 parts of 2,4-diaminobenzenesulphonic acid 5 (2,4-diaminobenzenesulphonic acid) powder were added, and the pH was adjusted slowly with sodium bicarbonate to 3.5, and the mixture was stirred at room temperature until the coupling reaction was completed. Then, 15.4 parts of the diazonium salt of l-Aminobenzene-4-p-nicotinic ethylsulfone was forcefully poured into the above reaction solution, and the acid was slowly adjusted with soda ash The base number is stirred from 5.0 to 6.0 until the reaction is completed. Finally, sodium chloride is added for salting out, and it is filtered out to obtain the compound formula (5).

(5)

15 Example 4 Dissolved 14.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone (l-aminobenzene-3-p-sulfatoethylsulfone) in 150 parts of ice water, and then added 12.6 parts of 32% The hydrochloric acid aqueous solution was fully stirred therein, followed by 3.6 parts of an aqueous sodium nitrite solution, and then continuously stirred at 0 to 5 ° C until the diazotization was completed. Next, 9.5 parts of 2,4-diaminobenzenesulphonic acid powder was added, and the pH was adjusted slowly with sodium bicarbonate to 3.5, and the mixture was stirred at room temperature until the coupling reaction was completed. After 20 1239984, '15 .4 parts of 1-Aminobenzene-4-P-nicotinic ethylsulfone diazonium salt was forcefully poured into the above reaction solution, and Soda ash slowly adjust the pH value to 5.0 to 6.0 and stir until the reaction is complete. Finally, sodium chloride is added for salting out, and the mixture is filtered and taken out to obtain the compound of formula (6).

10 Examples 5 to 19 In general, according to the steps described in Application Example 1, Example 2, Example 3, and Example 4, the following reactive dyes can be prepared to dye cotton fibers with a specific hue and have good Fastness. 15 Example 5 The compound of formula (7) is golden yellow.

20 Example 6 The compound of formula (8) is orange. 21 1239984

Example 7 5 The compound of formula (9) is orange.

10 Example 8 The compound of formula (10) is orange. h3c h3c-W ~ h2ch2co2s h3c

S02CH2CH20S03H (10)

Example 9 15 The compound of formula (11) is orange.

22 1239984 Example ο As compound formula (12), it is orange.

(12) Example 11 The compound of formula (13) is orange.

Example 12 The compound of formula (14) is orange.

15 Example 13 The compound of formula (15) is orange. 23 1239984

(15) Example 14 The compound of formula (16) is orange.

(16)

Example 15 10 The compound of formula (17) is orange.

so3h (17)

Example 16 15 The compound of formula (18) is orange.

Example 17 24 (18) 1239984 According to the compound formula (19), the color is orange.

H〇3SOH2CH2C02S

N = N NH2

S03H N = N NH2

(19) 5 Example 18 The compound of formula (20) is orange.

10 Example 19 The compound of formula (21) is orange. h2c = hco2s

N = N

(21) 15 Example 20 Firstly, 100 parts of urea, 10 parts of reduction inhibitor, 20 parts of baking soda, 55 parts of sodium alginate, and 1,000 parts of warm water (1,000 parts in total) were stirred to obtain an auxiliary paste; take 3 parts of the example 1 The prepared dye was sprinkled on the above-mentioned 100 parts of the auxiliary paste, and quickly stirred. Cover with a mesh of 45 degree twill printing screen 25 1239984 over a suitable size of mercerized cotton twill. After the color paste has been applied, place the good cloth in a hungry oven for 5 minutes to dry; The well-dried cloth was put into a plug phase and steamed in a cavity of 10 ~ 10 cavities with atmospheric pressure for 10 minutes. After that, the obtained orange dye was washed with cold water, washed with boiling hot water for 10 minutes, and boiled for 5 minutes with soap and then washed with cold water for one time, and dried. The obtained orange dye has excellent characteristics. Example 21: The dye prepared in Example 3 was dissolved in 100 ml of water to prepare 10 30 parts / pressurization dye solution; an alkaline agent was used (using caustic soda ml / liter and thenardite 30 parts / liter) Add it to the press dyeing solution (the amount of alkali agent is 1/4 of the press dyeing solution—) and stir uniformly. The resulting mixed solution is poured into the roller press dyeing, and then the cotton fabric is subjected to roller press dyeing. Roll into a shaft. The cotton fabric in this form was stored at room temperature for 4 hours. After that, the obtained orange dye was washed with cold water 15 for 10 minutes with boiling hot water, soaped with boiling non-ionic detergent for 10 minutes, and then washed with cold water one time and dried. The obtained orange dye has excellent characteristics. Example 22 20 Take 0.25 parts of the dye prepared in Example 1 and dissolve it in 250 ml of water, which is called mother liquor (0.1%). Take 40 ml of 0.1% mother liquor in a dyeing bottle, put 2 parts of cotton fabric, and then put Add 2.4 parts of thenardite, and then put 2.5 ml of 32% soda ash solution; put the dyeing bottle in a 6 (TC horizontal shaking dyeing machine, and keep it for 60 minutes. After that, the obtained orange dye is first washed with cold water, Wash with boiling water for 10 minutes, wash with cold boiling water for 10 minutes, and wash with cold water once, and dry 26! 239984. The obtained orange dye has excellent characteristics. Example 23 0.25 parts of the dye prepared in Example 2 was dissolved in 250 ml of water, and 5 was referred to as the mother liquor (0.1%). 40 ml of the mother liquor was collected in a dyeing bottle, and 2 parts of cotton Then put 2.4 parts of thenardite into the fabric, and then put 2.5 ml of 32% soda ash solution; put the dyeing bottle in a horizontal shaking dyeing machine at 60 ° C, and keep it for 60 minutes. Wash with boiling hot water for 10 minutes, soap with boiling non-ionic detergent for 10 minutes, rinse once with cold water, and dry for 10 minutes. The prepared orange dye has excellent characteristics. Example 24 Take 0.25 parts of the dye prepared in Example 3 and dissolve it in 25 ml of water, which is called mother liquor (0.1%). Take 0.1 ml of 40% mother liquor in In the dyeing bottle, put 2 parts of cotton 15 fabric, and then put 2 · 4 parts of thenardite, and then put 2.5 ml of 32% soda ash solution; put the dyeing bottle in a horizontal shaking dyeing machine at 60 ° C, and keep the temperature for 6 After 0 minutes, the obtained orange dye was washed with cold water, washed with boiling hot water for 10 minutes, soaped with boiling non-ionic detergent for 10 minutes, #washed with cold water once, and dried. The dyed material has excellent characteristics. 20 Example 25 Take 0.25 parts of the material prepared in Example 4 and dissolve it in 25 ml of water, which is called mother liquor (0.1%). Take 40 ml of 0.1% mother liquor in a dyeing bottle. Put 2 parts of cotton fabrics, then 2.4 parts of Amanite Shaw, and then put 32% pure test solution. Ml; put 25 dyeing bottles into 6 (TC horizontal shake plate dyeing machine, and keep for 60 minutes. After that, 27 1239984 ^ gold steam colored wood was washed with cold water, 10 minutes with boiling hot water, and 10 minutes with non-ionic detergents. The bell is washed again with cold water, dried, and dried. The obtained golden-yellow dye has excellent characteristics. 5. The series of quaternary ammonium salt bisazoazo dyes of the present invention is a general-purpose, wood-based composition. It can be used for cellulose fiber dyeing, and the dyeing method used is the method used when dyeing with reactive dyes, such as dip dyeing, wood printing or continuous dyeing, and has very special excellent properties. A series of quaternary ammonium salt bisazo azo dyes are water-soluble dyes with commercial value, which can obtain a variety of dyeing properties ^ 10 dyes, especially in the cleaning, deep dyeing, leveling, washing fastness, sunlight Very good performance in terms of fastness, rubbing fastness, ironing fastness and chlorine bleaching fastness. The above embodiments are merely examples for the convenience of description. The scope of the claims of the present invention shall be based on the scope of the patent application, rather than being limited to the above embodiments. 28 1239984 [Simplified description of the diagram] None [Description of the main component symbols]

Claims (1)

1239984 10. Scope of patent application: 1, a kind of quaternary ammonium salt bisazo reactive dye of the formula (1), R is a nitrogen atom, a Cy alkanesulfonic acid group, or a Ci 4 alkanocarboxylic acid group; (W) 0 to 3 are 0 to 3 identical or different groups selected from a sulfonic acid group, an alkyl group, or a c! 10 (W ') o ~ 3 are 0 to 3 groups which are the same or different and are selected from the group consisting of sulfonic acid group, ci4 alkyl group or Cl-4 alkoxy group; Υι and Y2 are each independently · CHcCH〗, -CH2CH20S03H, or -CH2CH2-U, and at least one of ^ and ^ must be _CH2CH2-U; ϋ is the following formula (2a), (2b), (2c), (2d) or (2e): 15 _ ^ ΟΟΝΗ2 (2d) or (2e); and R !, R2 and R ^ C14 alkyl. 30 1239984 • For example, the quaternary ammonium salt bisazo reactive dye of the scope of the patent application of Shenyang; ,, where R is a hydrogen atom or a cN4 alkylcarboxylic acid group. For example, please apply the quaternary ammonium salt bisazo reactive dye in the scope of the patent; //, in (w) 0 ~ 3 疋 〇 to 3 same or different selected from the group consisting of sulfonate () methyl and hydrazone (W,) 0 ~ 3 are 0 to 3 groups which are the same or different and are far from sulfo, sulfonyl and fluorenyl groups. ， 4 · The quaternary ammonium salt bisazo reactive dyes in item 1 of the patent application, where I and m3 are methyl. ίο 5. If a quaternary ammonium salt bisazo reactive dye 'in the scope of the application for patent,' where U is a group of the following formula (2b) or (2e) (yOOH-(2b) or 6. The first item in the scope of patent application, which is -CH2CH2-U, -CH2CH2〇S〇3H 〇 (2c) ο quaternary ammonium salt bisazo reactive dye I is -ch = ch2 or 15 The quaternary ammonium salt bisazo reactive dye of the scope of application for patent No. 6 wherein U is a group of the following formula (2b) or (2c)-# ~ Λ — ^ γο〇Η w ⑽ or w / (2c). 8 · The quaternary ammonium salt bisazo reactive dye as in item 1 of the patent application, wherein formula (1) is a reactive dye of the following formula, 20 Y1-〇2S S〇sH NH, Ν = Ν- 〆r ^ Sr-N = N-_XT ^ Tij- (s〇3fX〇2-Y, NHR S03H 3Η) 〇 ~ 2 Υ2 31 1239984 where (la) R is a hydrogen atom and ci4 alkanesulfonic acid Group or ci4 alkyl carboxylic acid group; γι and each independently are -CH = CH2, -CH2CH20S03H or CH2CH2_U, and ya! At least one of Y2 must be -CH2CH2-U; U is a group of the following formula (2a), (2b), (2c), (2d) or (2e): WRlt ~ 〇⑽,-(2a) (2c ) 15 0CH3 0〇TCONH2 (2d) or W / (2e); Ri, R2 and R3 are alkyl groups. 9. The quaternary ammonium salt bisazo reactive dye according to item 8 of the application, wherein R is a hydrogen atom or a c14 alkyl carboxylic acid group. • The quaternary ammonium salt bis-azo reactive dyeing of the patent claim No. 8 in which Ri, R2 and R3 are methyl. n • If the quaternary ammonium salt is bisazo reactive dyes in the scope of patent application No. 8 in which U is a group of the formula (2b) or (2C): W (2b) or-(2c) ^ The quaternary ammonium salt bisazo reactive dyeing of item 8, in which the L series is, and the Υ2 series is _CH = CH2 or -CH2CH2 0S〇3H 〇 quaternary ammonium salt bisazo reaction of claim 12 Dye materials_ (y: 〇〇H 32 20 1239984 materials where U is a group of the following formula (2b) or (2c): — ^ V〇〇H (2b) or (2c) 14. The quaternary ammonium salt bisazo reactive dyeing in the range item 8 wherein the formula (1 a) is as follows: (4) HOOC 5 4 a h2ch2co2s so3h NH〇 Ν = Ν Ν = Ν- νη2 so2ch2ch2oso3h so3h (4) reactive dye. 15. If the quaternary ammonium salt bisazo reactive dyestuff of item 1 of the scope of patent application 'is used, wherein the formula (1) is a reactive dye of the following formula (lb), (lb) where R is a fluorene atom, a C1-4 alkanesulfonic acid group, or a 4 alkanocarboxylic acid group; 15 γι and Y2 are each independently _CH = CH2, -CH2cH2〇s〇3H, and γ 丨 and γ 2 at least one must be g-CH2CH2-U; 11 is a group of the formula (2a), (2b), (2c), (2d) or (2e): 33 1239984 ίο-^ 3CH3 __gT ^ CONH2 (2d) or W / (2e); and Ri, R2, and H3 are c "4 alkyl groups. Material i claims% patent scope of the quaternary ammonium salt bisazo reactivity In Ran, R and R are hydrogen atom or retarded acid group. Roughly applied ^ month δ month patent scope No. 15 quarterly salt double-coupled IL reactive dye village, R, R, RjR3 system is fluorenyl MA declares that the quaternary ammonium salt bisazo reactive dye of item 15 of the patent scope, '', is a group of the following formula (2b) or (2c) ~ ^ 3 — # ύ〇〇η 19 (2b) or w / (2c) 〇., # Shi Shenming patent scope item 15 quaternary ammonium salt bisazo reactive dye, in which L is -CH2CHW, -CH2CH2〇S3H 〇Y2 is -ch = ch2 or 15 materials, ⑽reactivity * .❹⑽) or -〇_ u (2c). For example, if the scope of the patent application is the 15th item, the formula (lb) is the following formula ('3) the 15th quaternary ammonium double Nitrogen reactive dye r h2ch2co2 n = n NH so3h 'tl so2ch2ch2oso3h 34 (3) 1239984 reactive dye. 22. The quaternary ammonium salt bisazo reactive dye according to item 15 of the application, wherein the formula (lb) is the following formula (5) HOOC N-H2CH2C02: so3h N = N NH. N = N— nh2 \ so2ch2ch2—n y S03H COOH (5) Of reactive dyes. 23. The quaternary salt bisazo reactive dye according to item 15 of the application, wherein the formula (lb) is the following formula (18) 10 35