TW526245B - Asymmetrical reactive red dye, composition containing the same and preparation method thereof - Google Patents

Abstract

A reactive red dye has a following formula (I), in which R, X, A and A' are defined as mentioned in the invention description document. This type of dye can be used for dyeing and printing cellulose fiber such as cotton, artificial cotton, linen and artificial linen. This invention also relates to a composition containing formula (I) and the preparation method of the composition.

Description

526245 A7 B7 V. Description of the invention [Background of the invention] The field of fejjj ^ The present invention relates to a reactive red dye, especially to a kind of asymmetric reactive red dye, and the present invention also relates to the A composition of a reactive red dye, and a method for preparing an asymmetric reaction 2 product. The red reactive dyes known in the prior art are known in US Patent Nos. 5,075,428, 5,359,042, and 5,354,849. [Summary of the Invention] The present invention provides a reactive red dye of formula XI, X.1

(Please read the notes on the back before filling this page} Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (I) Where: R represents a hydrogen atom or a dq alkyl group; X represents a fluorine, chlorine or bromine atom; A and A ' Each is different and represents a substituted or unsubstituted phenyl or naphthyl group, respectively, where the "substituents are selected from the group consisting of -s02Q, alkyl and Ci_C4 3 paper standard _iTcNS) A4 regulations 526245 A7 B7 5. Description of the invention (>) One or more of the alkoxy groups, Q represents -0H, -ch = ch2, -C2H40S03H or -C2H4CI ο the reactive red dye of formula (I) of the present invention Since each compound of formula (I) has an A substituent and an A 'substituent, and the a and A' substituents on the same compound of formula (I) must be different, the reactivity of the formula (I) is named Red dyes are "asymmetric" reactive red dyes. Regarding the substituted phenyl represented by A or A ’, the preferred one is the following substituted phenyl with sulfonic acid, (please read the precautions on the back before filling this page)

Z Among them, Z represents fluorene, a S02Q, a Crq alkyl group or a CVC4 alkoxy group, and Q represents a OH, a ch = ch2, a C2H4SO3H or a C2H4C1. Regarding A or A 'representing a substituted naphthyl group, the preferred one is a naphthyl group substituted with a sulfonic acid as follows,

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, where Z represents Η, a S02Q, Ci-Czl · alkyl, or Ci-q alkoxy group, and Q represents a OH, a CH = CH2, a C2H4〇S03H, or a C2H4C1 . The reactive red dye of the present invention can be used for dyeing to obtain various dyeing materials with good dyeing characteristics, especially in terms of detergency, leveling, and washing fastness. 4 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297). Mm) ho3s〆A—N = N,

N = N—A,, so3h co2r ho3s〆 526245 A7 B7 5. The invention description (3) has more excellent performance. The reactive red dye composition of the present invention comprises: a) a reactive red dye of formula (I), so3h ⑴ wherein X, R, A and A ′ are defined as above; b) the following formula (II) is reactive Red dye (please read the precautions on the back before filling this page)

H03S A—N Two N_

NH s〇3h

co2r

N = NA .NH N HObS ^^^^ SOsH Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (II) where X, R, A, and A are defined as above; and c) a reactive red dye of the following formula (ΙΓ) This paper size applies to China National Standard (CNS) Α4 size (210X 297 mm) J ^ 245

、 Explanation of invention (4 A7 B7

, ΝΗ NQH S03H C02R (ΙΓ)

The Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed X, R, A, and A. The reactive red dye composition of the present invention, as defined above, can be directly obtained in different proportions according to the amount of stone raw materials. According to the non-proportioned components, various dyeing / color-light two-color: objects' can also be obtained. Similarly, it has better performance in terms of detergency, leveling, and fastness to money. [Detailed description of the invention] The manufacturing method of the compound of formula VII of the present invention can be obtained by referring to the method of preparing the dye composition of the present invention described below. 'The method for preparing the dye composition of the present invention is quite special. In the present invention, the desired dye composition can be directly produced in the reaction process by controlling the ratio of raw materials. Generally, the manufacturing methods of the conventional dye compositions are mostly that the components of each composition are individually manufactured, and then blended according to a predetermined ratio to obtain the desired dye composition; and the preparation method of the dye composition of the present invention It's completely different. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) ----.----- t-shirt — C Please read the precautions on the back before filling in this page j,-口

Jm. 526245 A7 B7 reaction in the reactor, temperature V. Description of the invention (j) The dye composition of the present invention-An article can be produced by the following method:

Firstly, it is dissolved in a neutral aqueous solution at a temperature of 1-Cyclo-8-amino X ^^ A, A ^ 3,6 · 1, or hydroxy-8-aminonaphthalene-3,5-2% " ,, And then with the halogenated triazine well compound of the following formula (a),

(a) where X represents a fluorine, chlorine, or bromine atom, and U is between G ~ 3GC: 'is preferably controlled below 2 (rc, acid test is controlled to be acidic, and preferably controlled below 3, fully ㈣After the reaction is completed, the intermediate product of the following formula (b) can be obtained (please read the precautions on the back before filling this page)

X

so3h Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (b) where X is as defined above. Then, the azo salts of various A-NH2 and A, -NH2 compounds, where A and A 'are defined as described above, can be obtained by reacting with formula (b). 526245 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (t) A mixed solution of the intermediate product of formula (C) and the intermediate product of formula (d).

Where X, A and V are defined as above. Preferred examples of A-NH2 and A'-NH2 are aniline, 4-/?-Sulfate ethanesulfonyl aniline, 3-/?-Sulfate ethanesulfonyl aniline, 4- /? -Sulfate ethylsulfonyl-2-sulfonated aniline, aniline-2-sulfonic acid, aniline-3-sulfonic acid, aniline-4-carboxylic acid, aniline-2,4-dicarboxylic acid, aniline-2 , 5-Dicarboxylic acid, 2-Dimethyl-4-methylaniline, 2-sulfo-5-methylaniline, 2-sulfo-4-methoxyaniline, 2-sulfo-5-methoxy Aniline, 2-sulfonated 4-nitroaniline, 2-sulfonated 5-nitro-8 This paper is sized for China National Standard (CNS) A4 (210X 297 mm) (Please read the notes on the back first (Fill in this page again) 526245 A7 B7 V. Description of the invention (7) Aniline, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-I, 5-disulfonic acid, 2-aminonaphthalene-1, 6-disulfonic acid, 5-/?-Sulfatoethanesulfonyl-1-sulfonated-2-aminonaphthalene, 6-sulfate ethylphenoxy-1 -continuous-2 -amine Base tea. Continue to use the mixed solution containing the intermediate product of the formula (c) and the intermediate product of the formula (d) to perform synthesis reaction with 3,5-diaminobenzoic acid or alkyl 3,5-diaminobenzoic acid. The temperature is controlled between 20 ~ 80 ° C, preferably between 30 ~ 50 ° C, and the acid generated during the reaction is neutralized with an acid binder, and the acid-base hydrazone is controlled between 5 and 9 Between, it is best to control between 6 and 7, and fully stirred: fall. Suitable acid-binding agents are hydroxides, carbonates, or bicarbonates of metals, especially sodium, potassium, or lithium hydroxides, carbonates, or bicarbonates, which have more valences, especially sodium carbonates or carbonates. Hydrogen salts are more valuable. After the reaction is completed, a mixed solution containing a reactive red dye of the formula (I), a reactive red dye of the formula (II), and a reactive red dye of the formula (IΓ) can be obtained. (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

9 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 526245 A7 B7 V. Description of invention (2)

ho3s ^ A, —N = N.

N = N—A1, so3h co2r ho3s ^ (II,), so3h (Please read the notes on the back before filling this page) where X, R, A and A ’are defined as above. The dye and its composition of the present invention can be manufactured by the above method, and the reaction conditions used have been fully described in the previous description. Similarly, the dye can be purified by known methods, such as spraying. Dry or precipitate and filter. The reactive red dye of the formula (I) of the present invention is printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics. It can be used as a single pure compound and has excellent dyeing effect. The composition of the present invention containing the reactive red dye of the formula (I) also It has excellent dyeing effect. The composition containing the reactive red dye of formula (I) according to the present invention can dye red dyes of various shades according to different proportions, and has excellent dyeing effects. To Chen Ming. This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) A7 B7 V. Description of the invention (q) The reactive red dye of the present invention should be changed within a wide range. —Protection—'The ratio of the dye used can be in the clothes. (Please read the precautions on the back before filling in this page.) The fraction is 1%, and the maximum phase weight and quantity; the minimum relative The percentage by weight is 85%. The dyes of the present invention may be # 4 and may contain knife powder, granular, granular or water-like liquids, extinguishing agents, for example, retarders, leveling agents, solubilizer I surfactants, Buffering agents, dispersing agents, etc. The dyes of the present invention all contain anions such as sulfonic acid groups, which are expressed as free acids in this specification. However, when the invention is manufactured, purified, or used, it is often in the form of a water-soluble salt. Existence, especially their metal test salts, especially sodium salts, desalting salts or ammonium salts. The reactive red dye and its composition printed by the employee's cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs can be widely used for dyeing a wide range of textiles containing warp or amine groups, such as wool, silk: synthetic Polyamines and natural or synthetic fibers, such as cellulose fibers such as cotton, linen, rayon, and rayon, can also be used for dyeing blended or cross-woven fabrics of cellulose fibers with polyester fibers, polypropylene fibers, and other fibers. The dyeing method used is the method used when dyeing with reactive dyes. Take cellulose fiber as an example. Before, during or after dyeing, the dye will be treated with acid binding agents, such as caustic soda and sodium carbonate. , Sodium phosphate or sodium bicarbonate, and then add the necessary dyeing and finishing assistants. Generally speaking, the dyes of the present invention are substituted with 1,3-diaminobenzoic acid or 1,3-diaminobenzoic acid alkyl ester as the linking group, and the asymmetric Color masterbatch is used to synthesize dyes, and 11 paper sizes are applicable to Chinese National Standards (CNS) A4 specifications (210 X 297 mm) 526245 Μ —— ________ B7 V. Description of the invention (丨 0) The amount of the dye is used to directly produce the desired dye composition. Compared with the conventional phenylenediamine dyes, the dyes of the present invention have more excellent dyeing performance. The dye and the composition thereof of the present invention are a reactive dye with industrial value for cellulose fibers, and can obtain various dyes with good dyeing characteristics, especially in terms of detergency, leveling and washing fastness. Has excellent performance. For the convenience of further explanation, the following examples will be enumerated for a more detailed description. The following examples are specific illustrations of the present invention, but do not limit the scope of the present invention. The compounds are expressed in the form of a free acid, but the actual form may be a metal salt, more likely an alkali metal salt, especially It is a sodium salt. The parts or percentages used in the examples are based on weight unless otherwise specified. Example 1. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Disperse 18.5 g of trichlorotriazine wells in 14 ml of ice water, and then add 31.9 g of 1-amino-8-hydroxynaphthyl-3,6-disulfonic acid in 120 ml of water was stirred for 3 hours after the addition was completed to complete the reaction to form a solution (1). Then, in a conventional manner, 27.3 g of 2-amino theryl-1,5-disulfonic acid and 1.7 g of 2-aminobenzenesulfonic acid are subjected to an azo reaction to form an azo salt mixed solution, and then the above is added. The solution (1) after the reaction is completed, and the pH is controlled to be 3 hours below 6.0 ~ 7 · 0, the temperature is below 10 ° C, and the stirring is continued until the reaction is completed. 12 The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 stitches) 526245 A7 B7 • n = n, so3h

so3h V. Description of the invention (π whole and then add 7.6 grams of 3,5-diaminobenzoic acid, control ρΗ 値 at 60-7.0, temperature 30 ~ 40 ° C, and stir until the reaction is complete, you can get the formula, formula ( II-1) and a dye mixed solution composed of formula (Π-2); l max = 524 5nm, and its composition analyzed by HPLC is: formula (1-1): 2 · 92 (18.0)% Formula (II. 1): 78.00 (81.00)% and Formula (Π-2): [07 (1.00)%), red powder can be obtained after spray-drying, and red dyes with good fastness can be obtained by dyeing. (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs o3h

so3h (1-1) n = n. H03s-

(II-l) so3h 13

、 So3h C02H ho3s " This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 526245 A7 ^ _ B7 V. Description of the invention (H)

Example 2: 18.5 g of trichlorotriazine was uniformly dispersed in 14 ml of ice water, and then 31.9 g of 1-amino-8-hydroxynaphthyl-3,6-dioxane dissolved in 120 ml of water was added. The acid was stirred for 3 hours after the addition was completed to complete the reaction and form a solution (1). Then, in a conventional manner, 25.3 g of 2-aminonaphthyl-1,5-disulfonic acid and 2.9 g of 2-aminobenzenesulfonic acid are subjected to an azo reaction to form an azo salt mixed solution. After the reaction is completed (1), and the pH is controlled to be 6.0-7.0 and the temperature is below 10 ° C for three hours, continue to stir until the reaction is complete. 0 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Please fill in this page again) Then add 7.6 grams of 3,5-diaminobenzoic acid, control the pH to be between 6.0-7.0, temperature 30 ~ 40 ° C, and stir until the reaction is complete. The formula (i_ 1) can be obtained The dye mixed solution consisting of Formula (II-1) and Formula (II-2) 's max = 524.5nm, and its composition analyzed by HPLC is: Formula (ii): 26.34 (32.00)%, Formula ⑴-1) · 69.22 (64.00)% and formula (II-2): 4.44 (4.00)%. Red powder can be obtained after spray drying, and red dye with good fastness can be obtained by dyeing. 14 This paper size applies China's national standard (CNS) M Lin (21〇χ297 public envy) '— 526245 Α7 Β7 V. Description of the invention () 3) Example 3 (Please read the precautions on the back before filling this page ) Disperse 18.5 grams of trichlorotriazine wells in 140 ml of ice water, and then add 31.9 grams of aminohydroxynaphthyl-3,6-disulfonic acid dissolved in 120 ml of water. After the addition, stir 3 The reaction was allowed to complete in hours, forming a solution (a).

Then, according to a conventional method, 15.2 g of aminonaphthyl-fluorene disulfonic acid is subjected to an azo reaction with 8.7 g of 2-aminobenzenesulfonic acid to form an azo salt mixed solution. The solution (1) after the reaction is completed, and the pH is controlled to be between 3.0-7.0 and the temperature is below 10 ° C for three hours, and then the stirring is continued until the reaction is complete, and then 7.6 g of 3,5-diaminobenzoic acid is added. By controlling pH 値 at 6.0-7 · 〇, temperature 30 ~ 40 ° C, and stirring until complete reaction, dyes composed of formula (1-1), formula (Π-1) and formula (Π-2) can be obtained. Mixed solution, λ max = 520.0nm? The composition is analyzed by HPLC as: (48) (50 · 00)%, (11-1) · 19.29 (25.00)%, and (ΙΙ- 2): 29.43 (25.00)%, red powder can be obtained after spray-drying, and red dye with fastness can be obtained by dyeing. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Example 4. Disperse 18.5 g of trichlorotriazine wells in 140 ml of ice water, and then add 31.9 g of 1-amino-8-hydroxynaphthalene dissolved in 120 ml of water 3,6-disulfonic acid, stirred for 3 hours after the addition was complete to complete the reaction, forming a solution (a). Then, according to the conventional method, apply 6.1 grams of 2-aminonaphthyl-1,5-di 15 to the paper size to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 526245 A7 B7 5. Description of the invention ( A) The sulfonic acid is subjected to an azo reaction with 13.8 g of 2-aminobenzenesulfonic acid to form an azo salt mixed solution, and then the above-mentioned completed solution (1) is added, and the pH is controlled to be 6.0-7.0 at a temperature of 1 〇. 〇 After three hours, continue to stir until the reaction is complete. Then add 7.6 grams of 3,5-diaminobenzoic acid, control the pH to 6.0-7.0, temperature 30 ~ 40 ° C, and stir until the reaction is complete. The formula (μ!), Formula (ΙΙ-1) and A dye mixed solution composed of formula (II-2), λ max = 514 5 nm, and its composition analyzed by HPLC is: formula (1-1): 22 63 (32 〇)%, formula (11-1): 4.26 (4.00)% and formula (Π-2): 73.67 (64.00)%. After spray drying, a red powder can be obtained, and a red dye with good fastness can be obtained by dyeing. Example 5: Disperse 18-5 g of trichlorotriazine well in 14 ml of ice water, and then add 31.9 g of 1-amino-8-hydroxynaphthyl-3,6-disulfonic acid dissolved in 120 ml of water. 'Stir for 3 hours after the addition is complete to complete the reaction and form a solution (a). Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), and then use 25.3 g of 2-aminopyridyl-1,5-dicarboxylic acid and 2 · 9 grams of 2-aminobenzoic acid were reacted together to form an azo salt mixed solution, and the solution (1) was added, and the pH was controlled to be 6.0-7.0 and the temperature was below 10 ° C for three hours. After that, continue to stir until the reaction is complete, then add 8.3 g of methyl 3,5-diaminobenzoate, and control the pH. At this paper scale, apply Chinese National Standard (CNS) A4 specification (210X297). 526245 A7 B7 V. Description of the invention (β) 6.0-7.0, temperature 30 ~ 40 ° C, and stirred until the reaction is complete, a dye mixture composed of formula (I-2), formula (II-3) and formula (II-4) can be obtained Solution, λ max = 519.5 nm, and its composition was analyzed by HPLC as follows: formula (1-1): 3 0.75 (32.00) 〇 / 〇, formula (II-1): 64.16 (64.00)% and formula (II-2) : 5.08 (4.00)%, red powder can be obtained after spray drying, and red dye with good fastness can be obtained by dyeing. (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

so3h This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 526245 A7 B7 V. Description of the invention (b) Example 6 (Please read the precautions on the back before filling this page) Repeat Example 1 Step, to obtain the dye composition composed of formula (i), (ii) and (ii), and then perform the separation step in a conventional manner to obtain a reactive red fluorene of formula (M), which can be obtained by dyeing with good fastness. Red dye. Example 7: Repeat step 5 of Example 5 to obtain the formula (Π_3) and formula (11_4), and then use the conventional separation method to obtain the formula (1-2). Reactive red dye can be dyed to obtain a red dye with good fastness. Dyeing test: a) Take 1 part of the above dye and completely dissolve it in 1000 parts of distilled water to prepare a dye solution. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs b) Take two dyeing cups and rinse them with distilled water, pour 40 and 80 parts of the dye solution into the cups respectively, and finally add 4.8 parts of thenardite. c) Add 85 parts of each dyeing cup with distilled water. d) Add 320g / l soda ash to each dyeing cup. e) Take 2 parts of cotton plain woven fabrics, pre-wet them and put them in each dyeing solution. After the upper cover is locked, shake up and down to make the dyeing solution even. 18 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 526245 V. Description of the invention (卩 丨 A7 B7 2 = Wooden cup is placed in a 62-degree thermostatic bath, and the rotary knob is activated Lit / dish to 60 degrees and hold for 60 minutes, then, take out the cloth and rinse it with cold water, put it in a large steel basin, wash it with hot water for _ minutes, then put the cloth into a large steel basin containing 2g / I G, wash with stagnant water for 10 minutes. G) Remove the cloth and rinse it with cold water, then dehydrate and dry.

I [Effects of the invention] The dyes and their compositions described in the present invention can be widely used for dyeing a wide range of textiles containing 'industrial or amine groups', such as wool, silk, polyamines, and natural fibers. Synthetic fiber, such as cotton, linen, rayon and rayon, and also can be used for dyeing blended or cross-woven fabrics of cellulose fiber and rayon fiber, polypropylene fiber, and other fibers. Wanfa is a method used for dyeing reactive dyes. Take cellulose dyes as an example. 'Before, during or after dyeing, dyes will be treated with acid binding agents, such as burning, carbonic acid steel, phosphate steel or The bicarbonate steel, in the meantime, is matched with the dyeing and finishing auxiliaries required by the printing department of the Central Standards Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives. Generally speaking, the dye of the present invention is synthesized by using U-diaminobenzoic acid or U-diaminobenzoic acid alkyl ester instead of traditional phenylene diamine as a linking group, and then using an asymmetric color masterbatch to synthesize. dye. Compared with the conventional phenylene diamine dyes, the materials of the present invention have more excellent dyeing performance. The dye and its composition of the present invention are, for cellulose fibers, a paper with 19 paper sizes, applicable to the Chinese National Standard (CNS) M specification (210X 297 mm) 526245 5. Description of the invention ((f A7 B7 = straight Reactive dyes, can get a variety of good dyeing properties, dyeing properties and washing fastness more excellent performance. '上 迷' The invention can indeed use the disclosed structure to achieve the purpose of the invention, with novel Nature, progress, and industrial availability, but in accordance with the invention patent: 隹 ", the above disclosed, is a preferred embodiment, for example, the local • ^ 夂 more or know the technical ideas derived from the case Those who are familiar with this technology can easily infer the patent right of the case. 2f Read the notes on the back before filling out this page.) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. China National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

526245 A8 B8 C8 D8 6. Scope of patent application 1 · A reactive red dye of the following formula (I), Wherein: R represents a hydrogen atom or an alkyl group of CPC4; X represents a fluorine, chlorine or bromine atom; A and A 'are different, and represent a substituted or unsubstituted phenyl or naphthyl group, and the substituents thereon are It is selected from a S02Q, a CVC4 alkyl group or a CVC4 pitoxy group, and Q represents —OH, CH = CH2, —C2H4OSO3H, or —C2H4CI. 2. The dyestuff according to item 1 of the patent application, wherein X represents a chlorine atom. 3. If the dyestuff in the scope of the patent application is applied for, A or A ′ represents the following phenyl group substituted by sulfonic acid, (please read the precautions on the back before filling this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Z or the following naphthyl substituted by sulfonic acid, 21 paper sizes: Chinese National Standard (CNS) A4 specification (210X297) 526245 A8 B8 C8 D8 6. Scope of patent application Where 'Z represents fluorene, a SO2Q, C1-C4 alkyl or C1-C4 alkyl, and Q represents —OH, CH = CH2, —C2H4OSO3H or —. 4. If the dyestuff in the scope of patent application No. 1 is applied, where A represents the following phenyl group substituted with sulfonic acid, Z where 'Z represents H, a SO2Q, C1-C4 alkyl or C1-C4 alkyl, Q represents a 0H, a CH = CH2, a C2H4OSO3H or a C2H4CI; JL A' represents the following acid-substituted naphthalene base, Printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page), where Z is defined as before. 5. If the dyestuff in item 1 of the scope of patent application, the formula (I) is the following formula (1-1) 22 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 526245 A8 B8 C8 D8 6 · If you apply for dyeing materials in the scope of patent application, the formula is the following formula ho3s patent application scope (i-i). 1 (1-2) (1-2) compounds. 7 · A kind of reactive red dye composition, its composition includes: a) Formula ⑴ reactive red dye (please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 526245 A8 B8 C8 D3 VI. Scope of patent application (I) Where X, R, A and A 'are defined as the first scope of patent application scope Transported; b) The following formula (II) Reactive red dye gives a correction chapter (II) wherein X, R and A are as defined above; and c) a reactive red dye A of the following formula (IΓ), N = N. N = N—A, HO3S / v ▽ 'SO3H C02R H: 〇3S'v V, so3h -II! II ί I «1111 (Please read the precautions on the back before writing this page) 1¾ F then fill in the line · Printed by the Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ (ΙΓ) where X, R and A 'are as defined above. 8_ The reactive red dye composition according to item 7 of the application, wherein X represents a chlorine atom. 9 · If the reactive red dye composition in item 7 of the scope of patent application, where A or A 'represents the following 24 This paper size applies to the National Standard 0 (CNS) A4 specification (210 X 297 issued) 526245 A8 B8 C8 D8 Scope of patent application Z or the following (Please read the notes on the back before filling this page) Z Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economics, where Z represents Η, a S02Q, Crq alkyl, or Ci-q alkoxy group, and Q represents a OH, a CH = CH2, a C2H4OS03H, or a C2H4C1. 1 〇 If the reactive red dye composition according to item 7 of the patent application scope, wherein A represents the following phenyl group substituted with sulfonic acid, 503H, wherein Z represents fluorene, a S02Q, CKC4 alkyl or Crq alkoxy , Q represents a 0H, a ch = ch2, a C2H4SO3H or a C2H4C1; and A represents a sulfonic acid-substituted substituent, as follows, 25 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 8883 ABCD 526245 6. Scope of patent application Among them, z is defined as described above. 11 · The reactive red dye composition according to item 7 of the scope of the patent application, wherein the component a) is a reactive red dye of the following formula (1-1), , N = N. Ho3s so3h, its weight accounts for 1% to 85% of the total weight of the composition; component b) is a reactive red dye of the following formula (II-1) Please note the following on the back of 153 η Η Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (II-1) Its weight accounts for 1% to 85% of the total weight of the composition; and component c) is Reactive red dye of the following formula (II-2), This paper is applicable to 0 standard (CNS) A4 specifications (210 X 297 issued) 526245 A8 B8 C8 D8 VI. Patent application scope (II-2) Its weight accounts for 1% to 85% of the total weight of the composition between. 12. The reactive red dye composition according to item 7 of the application, wherein the component a) is a reactive red dye of the following formula (1-2), (Please read the precautions on the back before filling this page) Its weight accounts for 1% to 85% of the total weight of the composition; Component b) is a reactive red dye of the following formula (II-3), so3h so3h Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (II-3) Its weight accounts for 1% to 85% of the total weight of the composition; and component c) is the reactivity of the following formula (ΙΙ-4) Red dye, 27 This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 526245 A8 B8 C8 D8 Its weight accounts for 1 ° / of the total weight of the composition. Between 13 and 85% —a method for producing a reactive red dye composition as described in the scope of the patent application, which includes the following steps: 〇 1-chil-8-amino group Cai 3,6 _ Disulfonic acid or L aryl I amino group _ 3,5_ disulfonic acid and halogenated triazine compounds of the following formula &), D XX human N human X (a) where X represents fluorine, chlorine, or bromine The atomic reaction to obtain the intermediate product, 1 in the following formula (b) -------- ^ t ------ II -------% (Please read the precautions on the back before filling (This page) 526245 A8 B8 C8 D8 VI. Patent application scope (b) where X is defined as above; b) followed by azo salts of A-NH2 and A'_NH2 compounds, where A and A 'are defined as above, and formula (b ) Reaction to obtain a mixed solution containing the intermediate product of formula (c) and the intermediate product of formula (d); (Please read the precautions on the back first-install-^ write this page) Order Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Where X, A and A 'are as defined above; and c) continue to use the above mixed solution containing the intermediate product of formula (c) and intermediate product of formula (d) with 3,5-diaminobenzoic acid or 3,5 -Diaminobenzoic acid 29 This paper is sized for China National Standard (CNS) A4 (210X297 mm)-526245 A8, B8, C8, D8, and patented patented alkyl esters are synthesized to obtain a mixed solution containing a reactive red dye of formula (I), a reactive red dye of formula (Π), and a reactive red dye of formula (ΙΓ). For example, the manufacturing method of the scope of patent application No. 13 in which X represents 15. · For the manufacturing method of the scope of patent application No. 13 in which A or A represents phenyl substituted by sulfonic acid as follows, Z --------- 0-- (Please read the precautions on the back before filling out this page) or the following naphthyl substituted by sulfonic acid, Order printed by a member of the Central Bureau of Commerce of the Ministry of Economic Affairs and a consumer cooperative, where Z represents S, a S02Q, Ci-q alkyl, or CVC4 alkoxy group, and Q represents a 0H, a CH = CH2, a C2H4〇S03H, or a C2H4C1. 16. The manufacturing method according to item 13 of the scope of patent application, wherein A represents the following phenyl group substituted with sulfonic acid, o3h Z Among them, Z represents thorium, 〇2Q, C1-C4 alkyl or C1-C4 alkyl, 30 paper sizes are applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 526245 A8 B8 C8 D8 The scope of the patent application Q represents one OH, one CH = CH2, one C2H40S03H, or one (^ i4Cl; and A, represents the following naphthyl group substituted by sulfonic acid, Printed by the Employees 'Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, where' Z is defined as previously described. 11 3 This paper size applies to China National Standard (CNS) A4 (210X297 cm)