TWI274776B - Fiber reactive dyestuffs - Google Patents

Abstract

A fiber reactive dyestuff of the following formula (I), wherein the definition of D, R, R1, R2, X and Z have the same meaning as given in the description. The fiber reactive dyestuff of the present invention is suitable for dyeing and printing on cellulose fiber or fiber materials containing cellulose. Dyed material with various excellent properties in dyed color can be obtained, showing especially outstanding performance in the property of wash fastness, build-up and chlorine fastness.

Description

1274776 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a dye, particularly a fiber reactive dye having a low sleep test, which is suitable for cellulose color in an aqueous bath, and cellulose fiber printing. ^ [Prior Art]

Fiber reactive dyes have been used in the dyeing and finishing industry for many years, and their main feature is that there are reactive groups on the dye molecules that can react with groups on the fibers to form covalent bonds, such as 'in US Patent 4,703, 112, US 5, 484, 899, US 6,329, 514 and British Patent No. 1,353, 899' have disclosed fiber reactive dyes for use in dip dyeing, continuous dyeing or printing, which have excellent dyeing and finishing properties such as good dyeing and are widely dyed. Used throughout the industry. However, the development of reactive dyes today is oriented towards the economical demand of high fixation, high dyeing, and easy water washing. Therefore, in addition to having sufficient direct dyeing to increase the chance of fixing, the new generation of reactive dye H temples is not The fixed dye also needs to have excellent water-washing properties. The present inventors extensively studied reactive dyes which can satisfy the demand to solve the above problems. As a result, it has been found that the above problems can be solved by using a reactive azo dye of a quaternary ammonium salt group. The reactive groups of such quaternary ammonium salt groups temporarily enhance the directness of the dye and have a high affinity for the fibers. It has excellent water washability, biodegradability, good dyeing depth, high light 1274776 light fastness, high water wash fastness, high chlorine fastness, and excellent performance in other fastness tests. Has good combinability and fiber leveling. SUMMARY OF THE INVENTION The dye of the present invention is a fiber reactive dye of the following formula (I).

(I) where z is the formula below

S〇2-Y, (I)P wherein X is a halogen atom, a quaternary ammonium salt, a pyridine, a carboxypyridinium, and a °°3-carboxypyridin-l-yl and 4-carboxypyridin-l-yl, methylpyridinium or Amine σ σ ratio I274776 (carbamoylpyridinium); γ is an OH, vinyl or a CH2-CH2-W, where W is treated with a base

a group that can be removed, preferably, W is Cl, a 0S03H or

C〇〇H 1 is a repeating acid group, a Ci~4 alkyl group, (^~4 alkoxy group or a Ci~4 alkoxycarbonyl group; P is 0, 1, 2 or 3; Q is -S02-Y, -CONH -(CH2)n-S02-Y,

~(〇). a (CH2)m-CONH-(CH2)n-S〇2-Υ, or a ΝΗ-CO-Τ, wherein γ is as defined above, Τ is α, /3·halopropionyl or Α-haloacryloyl, η and m are each independently an integer from 1 to 6; p is as defined above; 〇 is 〇, 1, 2 or 3; R, Ri and R2 are mutually independent hydrogen atoms, ^~4 alkyl, or by halogen atom, hydroxyl group, cyano, Cw alkoxy, (: 丨~4 alkoxycarbonyl, carboxyl, sulfonate, or sulfate) Substituted by sulfato) (^~4 alkyl; when R is a hydrogen atom, then X is a quaternary ammonium salt, a ruthenium, a 4-wei group; a ratio of sigma-1 or fluorenyl ruthenium; When it is -CH2CH2COOH, the shell 1J X is a quaternary salt, a ruthenium ratio π, a methylpyridine or an aminopyridylpyridine; and D is a chromophore having a reactive group or a reactive group, wherein the reactive group may be Each of the one or more independently selected from the Q group as defined above, the chromophore is selected from one of the group consisting of: formazan chromophore, anthraquinone, 酉太花Green, three . ^ Well dioxane, monoazo group, polyazo or metal complex azo group-yl 71274776 preceding the chromophore are described as follows: (a) formazan chromophore Can (formazan chromophore)

or

Where P and Ο are defined as above; (b) anthraquinone

Wherein G is a phenylene substituted by a Cm or a carboxylic acid group. • (c) a phthalocyanine; (S〇2W)〇

Pc S〇2- NH-E—where Pc is copper phthalocyanine or nickel phthalocyanine, W is -OH and/or -NH2, and E is phenylene or ethylene ( Ethylene) ; o is defined as above; (d) triphenyl dioxin (triphendioxazine) 8 1274776

Cl

E is defined as above; (e) monoazo (monoazo)

OH

Ho3s^^^ 9 1274776

OH

(Y — 〇 2s) 0

(H〇3S)f \ I )m 1 II (Y-〇2S)0

-N=N

10 1274776 h〇3s

(S〇3H)〇

(NHR5)p so3h

P

Or 11 1274776 (S03H)

N=N

R9 Ο^Ν"^ΟΗ Rs wherein R3 is Cw alkyl, Cw alkoxy, carboxyl, sulfonic acid or -S02-Y, Y is as defined above;

R>4 is C 1~4 alkyl 'C 1~4 alkoxy' amine group, acetylamino group, ureido or sulfo group; R5 is Ci~4 decyloxy group Or benzoyl; R6 is <^~4 alkyl or carboxyl; R7 and 8 are Ci~4 alkyl, R9 is hydrogen, amine hydrazine or sulfomethyl; wherein m, η, 〇 and p are defined as above; (f) polyazo

OH

12 1274776

(Rio)c or (HObS)^ Λ (Y-02S) Γ~:ί—Ν:

,(R3> q N=N-

JL (〇H) t

P (S〇3H)r (S〇3H) u where

Rio is Cl~4 alkyl, Cl~4 alkoxy, Weiyl, feldspar, acetyl, acetamido, ureido or a S02-Y; 9, 1*, 8, 1 And 11 are each independently selected from 0, 1, 2 or 3; R3, Y, m, η, 〇 and p are as defined above; or (g) a metal complex azo group. D can be more specifically listed as follows...

13 1274776

14 1274776

15 1274776

OH _ k

OH NHCOCH2CH3

SO3H

S03H 16 1274776

N=N- S03H pH NH2

S03H

H〇3SOH2CH2〇

n

n

•NH2 NHCCXH3

OCH3 N=N—^-NH2 NHCOCH3

17 1274776

C— CH3 N=N-CH

NH2

H00C

XX

H03s N=N

NH2 NT OH H03S.

S03H

HOOC

S03H

HOOC

NH2

Nh2

18 1274776

19 1274776

20 1274776

0—Cu-Ο C^jtn=nt^X^ ho3s into 〆^^νη2 so2ch2ch2oso3h 21 1274776

22 1274776

H2n^y^.so3h — N=N— 0 ooc

Nh2 The reactive dye of the formula (I) of the fiber-reactive dye of the present invention is preferably a reactive dye of the following formula (la).

NH — R

(I)P (la) wherein D, X, Q, I, R, 1, R2 and p are as defined above. The reactive dye of the formula (I) of the fiber-reactive dye of the present invention is particularly preferably a reactive dye of the following formula (lb). 23 1274776

NH-R

(lb) where 0, 乂, (^, 1, 11, and 卩 are as defined above.

The reactive dye of the formula (I) of the fiber-reactive dye of the present invention is particularly preferably a reactive dye of the following formula (Ic).

NH — R

Wherein D, X, R and Y are as defined above.

/ (1) a fiber-reactive dye of the formula (I), wherein Z is preferably

-S〇2-Y

(I)P wherein I, p and Y are as defined above. The fiber reactive dye of the formula (I) of the present invention, wherein the hydrazine is more preferably 24 1274776

-〇Q wherein I, p and Q are as defined in the above formula (I). The fiber-reactive dye of the formula (I) of the present invention, wherein X is preferably a quaternary ammonium salt, pyridine, 4-carboxypyridine-1-yl, methylpyridine or amidoxime. A fiber-reactive dye of the formula (I) of the present invention, wherein W is preferably chlorine

Atom, an oso3h

The fiber-reactive dye of the formula (I) of the present invention, wherein Q is preferably -S02-Y or a CONH-(CH2)n-S02-Y, wherein η and Y are as defined above. A preferred embodiment of the fiber-reactive dye of the formula (I) of the present invention is as shown in the following formula (1)

a reactive dye of so2c2h4oso3h; the following formula (2) 25 1274776 〇-cooh OH NH-^/ N N=^

NHCH2CH2〇H S03H

NH

so3H

r^yVN=N

N^N y~ SO2C2H4OSO3H

Reactive dye of H03S (2); the following formula (3)

Reactive dye; the following formula (4)

Reactive dye of SO3H (4); the following formula (5) 26 1274776

(5) a reactive dye; the following formula (6)

Reactive dye; the following formula (7)

a reactive dye for SO2C2H4OSO3H; as shown in the following formula (8) 27 1274776

a reactive dye; and the following formula (9)

HO3S

(9) Reactive dye. For the convenience of description, the compounds are all expressed in the form of free acid in the specification, but the dyes in the present invention are often in the form of water-soluble salts when they are manufactured or used, and suitable salts may be alkali metals or alkaline earth metals. An ammonium salt or an organic amine salt, preferably a sodium salt, a potassium salt, a rumulin salt, a salt or a triethanolamine salt. [Embodiment] The dye of the present invention can be prepared by a known method, and the reaction sequence of the preparation thereof is not strictly restricted, and the chromophore can be prepared first, and then the desired dye can be synthesized; In the preparation process of the dye, the chromophore is synthesized. For example, the chromophore is prepared first, and then the dye is synthesized. For example, the following method can be exemplified. 28 1274776 a, take the following formula (A) The compound is first subjected to a first condensation reaction with a halotriazine of the following formula @), and the obtained product is subjected to a second condensation reaction with a compound of D-NHR2 (D& R2 as defined above), and then the obtained product Further coupling with the diazonium salt of Z_NH2, and finally selecting the appropriate compound X, and then performing the third condensation reaction with the obtained product to obtain the dye of the formula (1);

Similarly, it is also possible to first take D_NHR2 (I^R2 is defined as the above compound, and the first condensation reaction is carried out with three teeth of the following formula (B), and the obtained product is subjected to a second condensation with the compound of the following formula (4). The reaction 'then the product is then subjected to a coupling reaction with an azo salt of ζ·ΝΗ2 (as defined above), and finally an appropriate compound hydrazine is selected, and a third condensation reaction with the obtained product is carried out to obtain the formula (1). dye.

(I) wherein Hal is halogen, and Ri and R2 are as defined above, b, first taking Z-NH2 such as fluorine, chlorine or bromine atoms, x, z, d, r, (z is as defined above) of the azo salt, Coupling a compound of formula (A) according to 29 1274776, and then subjecting the resulting product to a first condensation reaction with a halotriazole well of the formula, the resulting product is subjected to a second time with a compound of D_NHR2 (D and R2 as defined above) The condensation reaction, and finally the appropriate compound X is selected, and the obtained product is subjected to a third condensation reaction to obtain the dye of the formula (I); in addition, the compound d_NHR2 (d& R2 is defined as described above) may also be taken first. The first condensation reaction is carried out in the three wells of the formula (B), and the product is subjected to a coupling reaction with the azo salt of z-nh2 (Z as defined above), such as the compound of the formula (4). The second condensation reaction, and finally the appropriate compound x is selected, and the obtained product is subjected to a third condensation reaction to obtain the dye of the formula (I).

NH — R

· · X, Z, D, R, heart and R2 are defined as above; 1 Take the compound of formula (A), first with the three teeth of formula (8). The product obtained by the reaction is subjected to a second condensation reaction with D-NHR2 (defined as D and R2), and then the appropriate compound X is selected to carry out a third condensation reaction with the obtained product, and finally the t product. The coupling reaction with diazonium salt of Ζ·ΝΗ2 can be carried out to obtain the dye of formula (I); likewise, D-NHR2 can be taken first (D&R2 is defined as described above) 30 1274776 The first condensation reaction of the cargo, The second condensation is carried out to carry out the second compound with the obtained product, and the first obtained product is carried out with the three wells of the following formula (B) to be further reacted with the compound of the following formula (A), and then The dye of the formula (I) can be obtained by selecting an appropriate compound X to react with the resulting di- bis group, and finally obtaining the product for coupling reaction with the diazonium salt of Ζ_ΝΗ2. Two or two undercondensation reactions, the violent media, you are also π

NH — R

Wherein X, Ζ, D, R, Ri and R2 are as defined above. The preparation of the dye of the present invention is carried out by a conventional reaction condition such as a coupling reaction, which is carried out at a slightly acidic to neutral acid value and at a temperature of 0 to 25 C; The first condensation reaction is carried out at an acidic to neutral pH value, such as a pH of 1 to 7 and _· at a low temperature, such as 〇~l〇°C; and a second time with a brine well The condensation reaction is carried out between a slightly acidic to a neutral pH, for example, an acid value of 4.5 to 7.5 'and a medium temperature of, for example, 30 to 60 ° C; and! The third condensation reaction carried out by the three wells is between the micro acid to the neutral acid test, for example, a pH of 4.5 to 7.5, and a high temperature, for example, a temperature of 70 to i ° ° C. The dyes of the present invention are suitable for use in the dyeing or printing of fibrous materials, especially cellulosic fibrous materials, and fibrous materials comprising cellulosic fibers. The fiber material is not particularly limited and may be a natural or regenerated cellulose fiber, such as cotton, hemp, linen, hemp, ramie, mucus snail, η, η fiber material containing cellulose fibers. The dyes of the invention are also = dyed and printed on fiber blended fabrics containing hydroxyl fibers. 7 Applicable - The dyes of the present invention can be fixed to the fibers in a variety of ways, in the form of aqueous dye solutions and printing pastes. It is dyed and printed by special dyeing, dyeing, printing and dyeing. The dyeing or printing of the present invention can be carried out according to the conventional and conventional methods. The exhausting dyeing method is a well-known inorganic neutral salt (such as anhydrous sodium sulfate and sodium chloride) and a well-known acid. Knot 8 / / σ MC such as sodium carbonate, sodium bismuth oxide) used alone or in combination. The use of inorganic neutral salts and bases is not critical, and inorganic neutral salts and bases can be added to the dye bath once or in divided portions by conventional methods. In addition, it is also possible to add a dyeing aid (such as a leveling agent, a retarding agent, etc.) according to a conventional method, and the dyeing temperature is usually between 4 ° C and 90 ° C, preferably 4 (TC - 70 ° C). Cold press dyeing is a substance to be dyed, which is padded with well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium chloride) and well-known acid binders (such as sodium carbonate, sodium hydroxide). The resulting material is dyed in a roll form at room temperature. The continuous dyeing method is to mix a known acid binder (such as sodium carbonate or sodium hydrogencarbonate) with a padding solution, and to dye the dye according to the usual method. The material is padded, • the resulting material is then dried or steam-fixed; the two-bath padding process is dyed with the dye _, and then the well-known inorganic neutral salt (such as sodium sulphate or Sodium citrate), it is best to dry or steam-fix the treated material according to the usual method. 32 1274776 The company = \ printing method, for example, there is a single-phase printing method, which contains a well-known acid, ... 丨 (such as carbonic acid) Printing paste of sodium hydrogen) printed on the substance to be printed, = dry or steamed solid color ♦ two-phase printing Containing the embossed goods, the immersed material is immersed in high temperature (9 〇 or above (such as; sodium) and well-known acid binder (such as oxychloride: sodium 5, ,, 谷谷液Fixing color. The method according to the invention is not limited to the dyeing or printing method of the preceding column. The dye of the invention is a kind of reaction with industrial value for the cellulose fiber, and has excellent fixing ability. , and has excellent dyeing depth, high liquid absorption capacity, and is suitable for dyeing in a wide temperature range. Therefore, it is also suitable for dyeing cotton/polyester blended fabrics. The dyes of the present invention are also suitable for printing and dyeing, especially Suitable for cotton or blended fabrics containing wool or silk. Dyeing and printing on cellulose fiber materials can obtain a variety of dyeing properties with good dyeing properties; especially in dyeing depth, washing fastness and chlorine fastness, High quality dyeing, printing or pressing products are obtained. 'For the sake of further explanation, the following examples will be more specifically described, but the scope of the present invention will not be limited thereby, The form of the acid is indicated, but the actual form may be a metal salt, more likely a metal salt, especially a sodium salt. Unless otherwise stated, the parts or percentages used in the examples are in weight' The temperature is in degrees Celsius, c. Example 1 7-Amino-1,3,6•trisulphonyl-naphthalene 33 1274776

(7-amino-l,3,6-trisulfonic acid-naphthalene) 19.17 parts are uniformly dispersed in 70 parts of water, 4.3 parts of soda ash (Na2C03) is adjusted to be neutral and fully soluble, and then 3.6 parts of sodium nitrite is added. And 15 parts of 32% hydrochloric acid aqueous solution is subjected to diazotization reaction at 5 to 10 ° C, and further, 7 parts of m-Aminophenyl urea is uniformly dispersed in 50 parts of water, and then added to The diazonium salt component is kept at a temperature of 8 to 10 ° C, and the acid-base value is adjusted to 5 to 7 with a soda lye aqueous solution to carry out a coupling reaction. After the reaction is completed, 9.5 parts of cyanuric chloride dispersed in ice water is added. To the above solution, and maintain the temperature at 5~8 ° C, the acid-base value is 5~7, and the reaction is complete, then 2,4 _diamino-1 -phenylphosphinic acid (2,4-diamino-1) _benzenesulfonic acid) 12.8 parts was added to the above reaction solution, and maintained at a pH of 5 to 7, at a temperature of 40 to 60 ° C, after the reaction was completed, 6.8 parts of 4-carboxypyridinium was added to the above reaction solution. And maintain the acid value of 5~7, the temperature is 80~100 °C, and the reaction is completely cooled to 7~10 °C. Then, 18 parts of 2-sulfonic acid-4-(2-sulfatoethylsulfonyl)aniline was diazotized by a known method. The diazonium salt was added to the above solution, and the pH was adjusted to 6.0, after the reaction was over. The resulting solution is desalted and spray-dried to obtain a dye of the following formula (1), which is dyed to obtain a golden yellow dye having excellent properties. 34 1274776

So2c2h4oso3h 1)

· Example 2 Place 1_amino-3,6-disulfonic acid-8-hydroxy-naphthalene 15.6 parts in 20 parts of water, adjust the pH to 6.5-7.0 to fully dissolve, and then reduce the temperature of the solution to At 5 ° C, 6.7 parts of acetic anhydride was added and stirred until the reaction was completed. In addition, 11.2 parts of tonic acid (2-amino-naphthyl sulfonic acid) is diazotized by a conventional method, and then the above solution is poured into the diazotization solution, and Adjust the pH to 7~8, confirm the reaction is complete, adjust the pH to 12~13 and warm to 70~90 °C until the reaction is complete, then add 50 parts of sodium chloride and adjust the pH to 6 · 8~7 · 2 after the transition. The filtrate was dissolved in 1, hydrazine water, and then quickly added to 8.7 parts of melamine chloride solution which had been dispersed in 30 parts of ice water, and the pH was maintained at 6-7, and the temperature was 5-8. °C, etc. After confirming the completion of the reaction, add 4-amino-2-(2-hydroxyethyl)amino benzene sulfonic acid 1.6. And maintain the acidity of 5~7, and raise the temperature to 40~60 °C. After the reaction is complete, add 6.8 parts of 3-carboxypyridinium to the above reaction solution and keep the acidity at 35 1274776. It is 5~7, the temperature is 80~100 °C, and the reaction is completely cooled to 7~10 °C. Further, 18 parts of 2-sulfonic acid 4-(2-sulfatoethylsulfonyl)aniline is added to the above solution by diazotization of the diazo salt by a known method, and the pH is adjusted to 6.0, after the reaction is over. The resulting solution is desalted and spray-dried to obtain a dye of the following formula (2), which is dyed to obtain a pink dye having excellent properties. C^cooh

Example 3 19.7 parts of 7-amino-l,3,6-trisulfonic acid-naphthalene was uniformly dispersed in 70 parts of water to 4.3 The soda ash (Na2C03) adjusts the acid-base value to be neutral and fully soluble, and further adds 3.6 parts of sodium nitrite and 15 parts of 32% hydrochloric acid aqueous solution to carry out diazotization reaction at 5 to 10 ° C, and further, the m-amino group Benzene urea (m-Aminophenylurea) 7.8 ^ parts are uniformly dispersed in 50 parts of water, then added to the above diazonium salt component ', and kept at a temperature of 8 to 10 ° C, and then adjusted with a soda aqueous solution to have a pH value of 5~ 7 The coupling reaction is carried out, and after the reaction is completed, 9.5 parts of melamine chloride dispersed in ice water is added to the above solution, and kept at a temperature of 5 to 8 36 1274776 C, and the acid value is 5 to 7, and the reaction is completed. 12.87 parts of 4-amino-2-(2-war acid) and ethylamine benzenesulfonic acid were added to the above reaction solution, and maintained at an acid-base value of 5 to 7, at a temperature of 40 to 60 ° C, and the reaction was completed. Afterwards, 6.74 parts of 3-*-aminomethylcarbazine ratio was added. (3-carbamoylpyridinium) is added to the above reaction solution, and maintained at a pH of 5 to 7, at a temperature of 80 to 10 ° C, and after the reaction is completed, the temperature is lowered to 7 to 10 ° C. The weight of 18 parts of 2-sulfonic acid-4(2-sulfatoethylsulfonyl)aniline was diazotized by a known method. The nitrogen salt was added to the above solution, and the pH value was adjusted to 6.0, and the reaction was completed. The resulting solution is desalted and spray-dried to obtain a dye of the following formula (3), which is dyed to obtain a golden yellow dye having excellent properties.

In the following Examples 4 to 13, in general, the following reactive dyes (4) to (13) can be prepared according to the procedures described in Example 1, Example 2 and Example 3, so that the dyes are good. Fastness. Example 4 37 1274776

(4) Example 5

(5) Xin Lu Example 6

(6) Example 7 38 1274776

(8) Example 9

(9) 39 1274776 Example ίο so3h ho3s

NHC2H4COOH so3h

Ν. Ν (NHCONH2 Ν=Ν—(( —SO2C2H4OSO3H ho3s

COOH

(10) Example 11

·· (11) Example 12 40 1274776

C2H5

(12) Example 13

SO2C2H4OSO3H (13) Example 14

Take 100 parts of urea, 10 parts of m-nitrobenzene sulfonic acid sodium salt, 20 parts of baking soda, 55 parts of sodium alginate, and 815 parts of warm water, 1000 parts in total. Paste paste. Three parts of the dye prepared in Example 1 were taken and sprinkled into 100 parts of the above-mentioned auxiliary paste, and quickly mixed. The 100 degree twill print screen of lOOmesh is covered on a suitable size of mercerized cotton twill, and the above paste is placed on the screen and scraped. 41 1274776 The scraped cloth was placed in a 65 aC oven for 5 minutes to dry; the dried cloth was placed in a steamer and steamed at atmospheric pressure saturated steam at 102~l〇5 °C for 10 minutes. Then, the obtained golden yellow dye is first washed with cold water, then washed with boiling hot water for 10 minutes' and then soaped with boiling non-ionic detergent for 1 minute. Finally, it is washed once with cold water, and dried to obtain golden yellow. The dye has excellent dyeing and coloring rate. Example 15 3 parts of the dye prepared in Example 1 was dissolved in 100 ml of water to prepare 30 parts/boost dye solution; 25 ml of alkali solution was used (using caustic soda 38QBe' 15 ml/liter and Glauber's salt 3 The mixture is added to the dyeing solution and uniformly stirred. The mixed solution is poured into a roller (R〇Her) dyeing machine, and then the cotton fabric is subjected to roller dyeing and then wound into a shaft shape. This form of cotton fabric was stored at room temperature for 4 hours. Then, the obtained golden yellow dye is first washed with cold water, then washed with boiling hot water for 10 minutes, then soaped with boiling non-ionic detergent for 10 minutes, and finally washed again with cold water, and dried to obtain golden yellow dye. Excellent dyeing and coloring. Example 10 0.25 parts of the dye prepared in Example 1 was dissolved in 25 ml of water to prepare a mother liquid, 40 ml of the above mother liquid was placed in a dyeing bottle, and then 2 parts of cotton fabric was placed, and then 2.4 parts of Glauber's salt was added, and finally Place 2.5 ml of 32% soda solution; place the dye bottle in a horizontal shaker at 60 ° C for 60 minutes. Then, the obtained golden yellow dye is first washed with cold water, then washed with hot water for 1 〇 minutes, then boiled with non-ionic detergent for 2 minutes, and finally washed with cold water - times, dried. The golden yellow dye obtained afterwards has excellent dyeing and coloring rate. Example 17 0.25 parts of the dye prepared in Example 2 was dissolved in 25 ml of water to prepare a mother liquid, 40 ml of the above mother liquid was placed in a dyeing bottle, and then 2 parts of cotton fabric was placed, and then 2.4 parts of Glauber's salt was added, and finally Put into a 32% soda solution φ # 2·5 ml; place the dye bottle in a 60 ° C horizontal shake dyeing machine and keep it for 60 minutes. Then, the obtained pink dye is first washed with cold water, then washed with boiling hot water for 10 minutes, then soaped with boiling non-ionic detergent for 1Q minutes, and finally washed again with cold water, and the pink dye obtained after drying. Excellent dyeing and coloring. Example 18 0.25 parts of the dye prepared in Example 3 was dissolved in 250 ml of water to make a mother liquid, 40 ml of the above mother liquid was placed in a dyeing bottle, and then 2 parts of cotton fabric was placed, and then 2.4 parts of Glauber's salt was added, and finally Place 2.5 ml of 32% soda solution; place the dye bottle in a horizontal shaker at 60 ° C for 60 minutes. Then, the obtained golden yellow dye is first washed with cold water, then washed with boiling hot water for a minute, then washed with boiling non-ionic detergent for 1 minute, and finally washed again with cold water, and the gold obtained after drying. Yellow dyes have excellent dyeing and coloring. The fiber reactive dye of the present invention is a general-purpose dye composition which can be applied to cellulose fiber dyeing, and the dyeing method used is a method used for dyeing a reactive dye such as dip dyeing, printing or continuous dyeing. And has very special excellent characteristics. The series of fiber reactive dyes described in the present invention are commercially available water-soluble dyes, and can obtain various dyeing materials with good dyeing properties, especially in washing property, dyeing depth, leveling property, washing fastness, and light fastening. Excellent performance in terms of degree, friction fastness, ironing fastness and fastness to chlorine bleaching. In summary, the present invention exhibits characteristics that are different from conventional techniques in terms of purpose, technique, and efficacy, or in terms of its technical level and R&D design. It is to be noted that the various embodiments described above are merely illustrative, and the scope of the invention is intended to be limited by the scope of the application. [Simple diagram description] None _Lu [Main component symbol description] None 44

Claims (1)

-1274776 (〇)〇-(CH2)m-CONH-(CH2)„ I ～~NH—CO — T, where Y is as defined above, T is propionic acid or propylene, η and m Each is independently an integer from 1 to 6; ρ is as defined above; 〇 is 〇, 1, 2 or 3; &, 1 and 112 are mutually independent hydrogen atoms, 〇1 to 4 alkyl groups, or dentate atoms, hydroxyl groups, cyano groups, Ci~4 alkoxy groups, Ci~4 alkoxycarbonyl groups, carboxyl groups, sulfonic acid groups Or a sulfate group substituted (^~4 alkyl group; when R is a hydrogen atom, then X is a quaternary ammonium salt, pyridine, 'carboxy π-pyridyl group or methyl σ ratio bite; when R is -CH2CH2COOH , X is a quaternary ammonium salt, pyridine, picoline or amine methapicyl pyridine; D is a chromophore with or without a reactive group, wherein the reactive group may be one or more independent Is selected from the group consisting of Q groups as defined above, the chromophore group being selected from one of the following groups: a scorpion chromophore, brewing, ugly green, triphenyl sulphur well, monoazo group, a polyazo group, and a metal complex azo group; and when Z is When the -S02-Y, (I)P substituent is substituted, the definition of P is as described above, and D is a chromophore. 2. For example, the fiber-reactive dye of claim 1 of the patent scope, wherein the scorpion chromophore is 46 1274776 Where p and Ο are as defined above. 3. For fiber-reactive dyes according to item 1 of the patent application, wherein the 〇 NH-G— Wherein G is a phenylene substituted with a Cw alkyl group or a sulfo group. 4. A fiber-reactive dye as claimed in claim 1 of the patent scope, wherein (S〇2W)0 S02 - NH-E - wherein Pc is copper S sapogenyl or nickel S sapphire; W is - 〇H or -NH2; E is phenylene or ethylene; 〇 is as defined above. 5. For fiber-reactive dyes according to item 1 of the patent application, wherein the triphenyl oxoxium well is 47 1274776 Cl Cl I H〇3Wn^ | r"V〇vr S〇3H 1 1 h2n u Ding JN Cl NH — E or Cl Wherein E is as defined above. 6. A fiber reactive dye according to claim 1 wherein the monoazo group is 48 1274776 OH (Y-〇2S)0 (Y—〇2S)〇 (H03S)- (Y-〇2s)0 (s〇3h)0 N=N OH (NHR5)p H03S 49 1274776 TSlOolTL λλτιτ χτττπ Wherein R3 is Ci~4 alkyl, Cm alkoxy, carboxyl, sulfonic acid or -S02-Y, Υ is as defined above; R4 is Ci~4 alkyl, Ci~4 alkoxy, amine, ethyl Alkyl, sulfhydryl or terminic, R5 is Ci~4 alkoxy or phenylhydrazine; R6 is Cm alkyl or carboxyl; R7 and R8 are mutually independent Cm alkyl; R9 is hydrogen, amine Formamidine, or sulfomethyl; m, n, oxime and p are as defined above. 7. For fiber reactive dyes as claimed in item 1 of the patent scope, 50 1274776 Azo is OH (H〇3S) S03H ho3s s〇3h 10 (H〇3S) 丨m (H〇3Sfe Nh2 oh (S〇3H)f N=N hq3s (H03s)q (Y—〇2S)p -N=N (〇H) (SO3H) or tu wherein R10 is Ci~4 alkyl, Cm alkoxy, carboxyl, sulfonate, acetyl, acetyl, ureido or -S〇2- Y; 9, 1*, 3, 1 and 11 are each independently selected from 0, 1, 2, and 3; 51 1274776 R3, Y, m, n, 〇 and p are as defined above. 8. The fiber-reactive dye according to claim 1, wherein the formula (I) is a reactive dye of the following formula (la) Wherein D, X, Q, I, R, 1, R2 and p are as defined above. 9. The fiber reactive dye according to claim 1, wherein the formula (I) is a reactive dye of the following formula (lb) (I)P (lb) wherein D, X, Q, I, R and p are as defined above. 10. The fiber-reactive dye according to claim 1, wherein the formula (I) is a reactive dye of the following formula (Ic) 52 J274776 D-NH- N. NH — R S〇3H -NH N 丫N X S〇2-Y so3H (Ic) wherein D, X, R and Y are as defined above. 11. The fiber reactive dye Z as in claim 1 of the patent scope is Q wherein Ι, ρ and Q are as defined above. 12. A fiber-reactive dye as claimed in claim 1 wherein -so factory 、 , (I)P where I, p and Y are as defined above. 13. The fiber-reactive dye according to claim 1, wherein X is a quaternary ammonium salt, a pyridine, a 4-carboxypyridine-1-yl group, a mercaptopyridine or an amine gf group. 14. A fiber-reactive dye as claimed in claim 1, wherein 53 J274776 w is a gas atom, a 〇S03H or N C〇〇H 15. The fiber-reactive dye of claim 1, wherein Q is a S〇2-Y or a CONH-(CH2)n-S〇2-Y, wherein η and Y are as defined above . 16. The fiber reactive dye according to claim 1, wherein the formula (I) is as follows: (1) 1) Reactive dyes. among them 17. The fiber reactive dye according to claim 1 of the patent application formula (I) is the following formula (2) C^c〇〇h 54 (2) -1274776 Reactive dye. 18. The fiber reactive dye according to claim 1, wherein the formula (I) is as follows (3) Reactive dye. 19. The fiber-reactive dye according to claim 1, wherein the formula (I) is as follows: (4) Reactive dye. 20. The fiber-reactive dye of claim 1, wherein the formula (I) is as follows: (5) 55 • 1274776 Reactive dye. 2 1. The fiber-reactive dye according to claim 1, wherein the formula (I) is as follows (6) (6) Reactive dye. 22. The fiber reactive dye according to claim 1, wherein the formula (I) is as follows (7) 56 J274776 Reactive dye. 23. The fiber reactive dye according to claim 1, wherein the formula (I) is as follows (8) Reactive dye. 24. The fiber reactive dye according to claim 1, wherein the formula (I) is as follows (9) Reactive dye. 57