TWI304831B - Reaction dye composition and their use - Google Patents

Description

1304831 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to reactive dye compositions suitable for dyeing cellulosic fibers and materials containing cellulosic fibers, and to their use, particularly in relation to 5 amine-containing groups. Reactive dye compositions of reactive red dyes and their use. [Prior Art] Reactive dyes are often used for dyeing cellulose fibers such as cotton yarns and rayon fibers. It is known that dyeing of a cellulose fiber material using a reactive dye uses a red, yellow, and blue reactive dye as a dye for the three primary colors. A method of adding and dyeing at various ratios is useful. 15 However, the application of reactive dyes today is directed to the need for one-color dyeing and finishing. However, when the dyes used as the dyes for the three primary colors have different affinities, reactivity, dyeing speeds or temperature dependences, There is a problem of so-called leveling property in which stains are generated in the middle of dyeing, or a problem such as so-called dye reproducibility which causes chromatic aberration between dyeing batches when slight variations occur in dyeing conditions. Regarding the leveling property or dye reproducibility, in recent years, with the variety or type of fiber materials, and the simplification of the operation of the dyeing and finishing factory for shortening the dyeing time, it is also strongly desired to have a uniform dyeing. Good reactive dye for sexual or dye reproducibility. Although various discussions have been made to solve the problem of _ _ (4) Japanese franchise, " " Limming book]', but still not satisfactory results. Inventors' intent to study various problems in the dyeing and printing process, and found that a reactive red dye containing a specific structure can be used with 20 1304831, and a specific reactive yellow dye and/or The reactive dye composition of the specific reactive blue dye is such that the dyes constituting the dye compositions have the same affinity and dyeing speed, and the cellulose fibers can be dyed with good dyeability and reproducibility. 5 methods, and finally completed the present invention. SUMMARY OF THE INVENTION The present invention provides a reactive dye composition, and the use of the reaction > dye composition for dyeing and printing, can be used to reproduce cellulose fibers or cellulose fiber-containing woven fiber materials based on excellent Sex, detergency, good dyeing, high fastness and good reproducibility, and improve the color success rate. The reactive dye composition of the present invention comprises: (a) at least one reactive red dye having an amido substituent represented by the following formula (1) 15 in an amount of from 1 to 99% by weight;

(1) wherein R is a Ci~4 alkyl group which is unsubstituted or substituted by a hydroxy group, a sulfonic acid group, a carboxyl group or a halogen atom, or an unsubstituted or a carboxylic acid group, a carboxylic acid group, a slow group or a phenyl group 20 1304831 Sub-substituted phenyl;

Ri and R2 are independent of each other, hydrogen atom, acid group, 'sub or unsubstituted or hydroxy

Ri and Κ·3 are hydrogen atoms, X is a halogen atom, -〇r4, , -OR4, >

(CH2)m—COISTH—(CH2)n—S02—γ or —nh-CO—, wherein Υ is vinyl or a CH 2 —CH 2 — u ' where υ is a group that can be removed by treatment with a base of ' Τ为〇:, halopropionyl or haloacryloyl, m are each independently an integer from i to 6, 〇 is 〇, 1 '2 or 3; and (b) content 99 to 1 weight percent of at least one reactive yellow dye selected from the following color index: CI Reactive Yellow No. 145 and 15 CI Reactive Yellow No. 176, and/or at least one color selected from the following # Index Reactive blue dye: CI Reactive Blue No. 194, CI Reactive Blue No. 221, and CI Reactive Blue No. 222. The reactive dye composition of the present invention, wherein the component (a) dye is preferably contained in an amount of from 1 to 80% by weight, and the component (b) dye is preferably present in an amount of from 99 to 20% by weight. The reactive dye composition of the present invention, wherein the reactive red dye is a compound of the formula (la): 1304831

Q (la) wherein R, Ri, R2, R3, X and Q define a reactive red dye as in the above formula (1). The reactive red dye of formula (1), more preferably the formula (lb) compound: 5

H03S

so3H

X NH

Q (lb) wherein R, X and Q define a reactive red dye as in the above formula (1). Specific examples of the compound of the formula (lb) include a compound of the following formula (2) to formula (6). Φ ho3soh2ch2co2s

So3h oh nhcoch3 丄丄 H03S" so3h 9 (2) -ο

(3) ο

Cl -o

1304831 H03S0H2CH2C02S ho3soh2ch2co2s •5

H03SOH2CH2C02S

H03SOH2CH2C02S NH· IIΝγΝ .N, ,S03H OH NHCOCHs1丄 -N=N— HO3S"

SO3H, cr (6) The reactive dye composition of the present invention may be in the form of an acid or a salt, particularly an alkali metal and an alkaline earth metal salt, preferably in the form of an alkali metal salt. 10 1304831 The invention also provides a method of dyeing or printing a cellulosic fibrous material comprising treating a fibrous material with an aqueous solution comprising a composition of a reactive dye of formula (1) wherein the cellulosic fibrous material, such as cotton. [Embodiment]

For the preparation of the reactive dye of the component (a) of the reactive dye composition of the present invention, reference may be made to the disclosure of European Patent No. 36,582 and U.S. Patent No. 4,667,022, the disclosure of which is incorporated herein by reference. A reactive dye of the formula (1) is prepared. It is prepared by acid-to-neutral acid (pH=3-7) for an amine compound of the following formula (A) and a trihalogen triazine compound of the following formula (B).

Condensation reaction is carried out at φ and low temperature (0-l(TC), wherein R! is defined as the reactive dye of the above formula (1), and Hal is a halogen such as a fluorine, gas or bromine atom. (C) an amine compound between slightly acidic to basic pH values 'e.g., pH 5.0 to 9.0, and 20 to 6 (condensation at TC temperature, 11 20 1304831

Q Κ2ΗΝγ^\ (C)

Wherein R2, R3 and Q are as defined by the reactive dye of the above formula (1), and then with the compound of the following formula (D)

H-X Φ) 10

The compound of the following formula (E) can be obtained by condensing a reaction at an acidic pH value, for example, pH = 3 to 6, and at a temperature of 60 to 100 ° C, wherein X is as defined by the reactive dye of the above formula (1).

(E) Finally, the compound of formula (E) is diazo 12 15 1304831 at a temperature of -10 to 20 ° C, and then the naphthol compound of the following formula (F) is at a temperature of -10 to 50 ° C. Preferably, at 0 to 30 ° C, the control of the acid value is from 1 to 7, preferably, at 1 to 5, a coupling reaction can be carried out to form a reactive dye of the formula (1),

ROCHN OH

(F) wherein R, R2, R3, X and Q are as defined in the above formula (1). The red reactive dye represented by the formula (1) is not particularly limited, but is preferably. It is a dye represented by the following formulas (2) to (6) in a free acid form.

15

Ho3soh2ch2co2s

13 (3) 1304831 ho3soh2ch2co2s

Cl (4)

H03SOH2CH2C02S

H03SOH2CH2C02S

(6) 10 The component (b) of the reactive dye composition of the present invention, the yellow reactive dye mentioned therein, and/or the blue reactive dye are commercially available products, and are used by Taiwan Yongguang Chemical Industry Co., Ltd. Produced by. The dye composition of the present invention, based on the total weight of the dye, wherein (a) the dye content is from 1 to 99 weight percent (wt%), and (b) the dye content is from 99 15 to 1 weight percent (wt%). Preferably, (a) the dye content is from 1 to 80 weight percent (wt%), and (b) the dye content is from 99 to 20 weight percent 1304831 5

10 15 # 20 (Wt%). In the dye composition of the present invention, the method of adding each dye is not particularly limited. For example, a method of separately producing various dyes, followed by addition, a method of adding a reaction liquid at the time of production, and then drying the composition as a composition, and dissolving various dyes in a dye bath, and setting each of the above in the dye bath A method in which the composition has the same composition. The mixing ratio of the red reactive dye and the yellow reactive dye and/or the blue reactive dye at this time is added in accordance with the desired color, and is not particularly limited, and if necessary, the composition of the present invention is also It may contain well-known additives such as a concentration regulator, a dispersant, a leveling agent, a precipitation inhibitor, a metal ion blocking agent, a reduction inhibitor, or a conventional dyeing agent. In the above, in the case where the dyes, the dyeing liquid, and the printing paste are directly added to each of the dyes of the reactive dye composition of the present invention, and the above-mentioned one is added; when the dyeing is performed, the dyes are dissolved, Tim makes an appropriate decision based on the foregoing. The amount of each of the emollients can also be used in the present invention for convenience of explanation. In the specification, the formula (4) indicates that the dye in the present invention is present in the acid form, and the "H" in the salt or the salt in the salt is used. In particular, a bismuth metal salt such as sodium cesium or a sodium salt is preferred. The lithium salt, potassium salt or ammonium salt, the dye composition of the present invention, which is suitable for the fiber material, and the cellulose fiber material, especially the cellulose material, are not particularly limited, and include the color of the sky and the color. Cellulose fiber such as cotton fiber, flax, hemp, cellulose fiber, case L liquid helium, or fiber 15 1530431

10 15

20 fiber material of plain fiber. In the present invention, the dyeing method itself is well known, and dyeing is carried out by a conventionally known or conventional method, for example, according to the method described later. Exhaustion dyeing is carried out in a dye solution using well-known inorganic neutral salts (such as anhydrous sodium sulphate and sodium chloride) and well-known curing agents (such as sodium carbonate, sodium hydroxide) alone or in combination. The amount of inorganic neutral salt and test is not very important. Inorganic neutral salts and bases can be added to the dye bath once or in portions according to conventional methods. In addition, dyeing assistants (such as leveling agents, retarding agents, etc.) may be added according to a conventional method, and the dyeing temperature is usually from 40 ° C to 90 ° C, preferably. The dyeing temperature is 50 ° C ~ 70 ° C. The dye bath ratio is usually 1: 5 to 1: 50 (infected matter: staining solution). The cold batch-up dyeing method is a substance to be dyed, using well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium chloride) and well-known acid binders (such as sodium citrate, hydrogen peroxide). Sodium) padding, and then the resulting material is wound into a roll at room temperature for dyeing. The continuous dyeing method is dyeing by single bath dyeing, mixing with a well-known alkali fixing agent (such as sodium carbonate or sodium hydrogencarbonate) and a padding solution, and the material to be dyed is padded by a usual method, and then the obtained substance is obtained. Drying or steam curing; two-bed padding is a dyeing of the material to be dyed, followed by well-known inorganic neutral salts (such as anhydrous sodium sulfate and gasification) and well-known curing agents ( For treatment with sodium hydroxide or sodium citrate, it is preferred to dry or steam solidify the treated material in the usual manner. Textile printing methods, such as single-phase printing 16 1304831, with well-known alkali fixing agents (such as sodium bicarbonate)

On the substance to be printed, 'and dry or steam-fixed; the two-phase printing P contains the printed matter f, and the resultant f is immersed in the high temperature state C ^ 5

10 or more) Fixes only in a solution containing an inorganic neutral salt (such as sodium chloride) and a well-known curing agent (such as 1 !: sodium natrate). The method according to the invention is not a dyeing or printing method. The dye composition of the present invention has good affinity, reactivity and redness, and makes cellulose fibers or fiber materials containing (10) vitamins reproducible, level-sensitive, detergency and various fastnesses. Dyeing, and improve the color success rate of one color, and has high fixation rate and easy water washing. For the sake of further explanation, the following examples will be described in more detail. The following examples are illustrative of the invention, and the scope of the invention is not limited by i5 s. The compounds of the formula are in the form of a dissociated acid form; usually 15 they are isolated in the form of their metal salt and used in dyeing in their salt form. The following examples are illustrative of the invention, and parts and rupees are by weight unless otherwise indicated. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters. 20 Example 1 0.03 parts The following dye compositions are provided: Red reactive dyes (2) Dye 25 Yellow reactive dyes 17 1304831 CI Reactive Yellow 145 0.03 parts · Blue reactive dye CI Reactive Blue 221 〇_14 parts Dissolve the above dye composition in 1000 parts of water, add 2 parts of Glauber's salt and 100 parts of unsilked cotton cloth, and heat the mixture to 3 〇 from room temperature. Minutes reached 6 ° C, after which 10 parts of soda ash were added and continued to hold for 6 〇 t for t hours. During the dyeing process, the samples were regularly sampled, and the fabric exhibited the same gray color tone, showing excellent compatibility. After the dyeing was completed, it was washed with water, soaped and dried to obtain a light gray fabric with excellent level dyeing. Example 2 0.2 parts 0.2 parts 〇·28 parts Provided as a dye composition Red reactive dye Dye of formula (3) 15 Yellow reactive dye CI Reactive Yellow 176 P Blue reactive dye CI Reactive Blue 221 Combination of the above dyes Dissolve in 1000 parts of water, add 3 parts of Mang 20% and 1 part of 0 pieces of unsilked cotton cloth, keep the dye solution at 60 °c for 30 minutes, then add 15 parts of soda ash, continue to keep 6 〇t for dyeing i After the completion of the dyeing, washing, washing and drying were carried out to obtain a light fading fabric. Repeat the dyeing process multiple times. The resulting fabrics all fall within 〇·5, and the performance is highly current, and the secondary color ratio is higher than 9〇%. 18 1304831 Example 3 The following dye compositions are provided: Red reactive dyes Dye of formula (2) 0.2 parts of yellow reactive dye CI Reactive Yellow 145 0.2 parts of blue reactive dye CI Reactive Blue 194 0.28 parts of the above dye composition Dissolve in 1000 parts of water, add 3 parts of Glauber's salt and 100 parts of unsilked cotton cloth. Stir the mixture from room temperature for 3 〇 minutes to 6 °C, then add 15 parts of soda ash and continue to keep 6 〇〇c for dyeing. After the dyeing is completed, the water is washed, rinsed and dried. The dye compound has high fixation rate, is not easy to wash with HI, and has good wet fastness. The obtained fabric has excellent reproducibility and leveling property. One color versus color. 15 20 Example 4 The following dye compositions are provided: Red reactive dyes Dye of formula (3) 0.2 parts of yellow reactive dye CI Reactive Yellow 176 0.2 parts of blue reactive dye CI Reactive Blue 222 〇.28 parts of the above dyes The composition is dissolved in 1000 parts of water, and then 3 parts of Glauber's salt and 100 parts of unsilked cotton cloth are added. The dyeing solution is heated from room temperature for 3 minutes to reach 19 25 1304831 6 ° C, and then 15 parts of soda ash is added to continue to maintain 60 °. C dyeing] hourly 'after dyeing' is washed, soaped and dried, the dye composition has high fixation rate, the unfixed part is easy to be washed, and the wet fastness is good, and the obtained fabric has excellent reproducibility and dyeing. Sex and one-time color. Example 5 〇·4 parts The following dye compositions were provided: Red reactive dye ► Dye of formula (4) 10 Yellow reactive dye

Blue reactive dye 0.3 parts C.I. Reactive Blue 221 Λ . 0.3 parts 15

The above dye composition is dissolved in 1000 parts of water, and then 3 〇 wide-nitrogen and 100 parts of non-silk cotton cloth are added, and the dyeing solution is stirred for 30 minutes at room temperature for two minutes and 60 C, and then 15 parts of soda ash is added to continue to maintain 6 〇 ° c dyeing for 1 hour, after the dyeing is completed, washing, soaping and drying, the dye composition has high fixation rate, the unfixed part is easy to be washed, and the wet fastness is good, and the obtained fabric has excellent reproducibility. Dyeing and one-time color. EXAMPLES The following dye compositions were provided: Red reactive dye 20 l3〇4831 Dye of formula (5) 0.3 parts of yellow reactive dye CI Reactive Yellow 176 〇·4 parts of blue reactive dye 5 CI Reactive Blue 221 0.3 parts The above dye composition is dissolved in 1000 parts of water, and then 30. of Glauber's salt and 100 parts of unsilked cotton cloth' dyeing solution are stirred from room temperature for 3 minutes to reach 6 ° C, and then 15 parts of soda ash is added to continue to maintain 60 °. c dyeing, small φ when 'staining is finished', washing, soaping and drying, the dye composition has a high fixation rate of 1°, the unfixed part is easy to be washed, and the wet fastness is good, and the obtained fabric is excellent. Reproducibility, levelness and primary color. Example 7 The following dye compositions were provided: 15 Red reactive dyes Dye yellow reactive dyes of formula (6) CI Reactive Yellow 176 Blue reactive dyes 20 CI Reactive Blue 221 0.3 parts 0.4 parts 0.3 parts The above dye composition Dissolve in 1000 parts of water, add 3 parts of thenurethane and 100 parts of non-silk cotton cloth, the dyeing solution is stirred at room temperature for 3 minutes to reach 6 ° C, then add 15 parts of soda ash, continue to maintain 6 (rc for dyeing i After the dyeing is completed, the water is washed, soaped and dried. The dye composition has a high fixing rate, the unfixed part is easy to be washed, and the wet fastness is good. The obtained fabric is 21 l3〇4831 and has excellent reproducibility. , level dyeability and primary color matching. Comparative Example 1' provides the following dye composition: red reactive dye

〇·〇3 copies 0.03 parts 0.14 parts 10

15 Yellow reactive dye CI Reactive Yellow 145 Blue reactive dye CI Reactive Blue 221 The above dye composition is dissolved in 1000 parts of water, then 2 parts of Glauber's salt and 100 parts of unsilked cotton cloth are added, and the dyeing solution is stirred from room temperature. After 〇 minutes reached 60 C, then add soda ash, continue to maintain 6 (rc for dyeing 丄 hours. Timed sampling during the dyeing process, found that the fabric gradually changed from yellow-green to gray' indicates that the red dye dyes the fabric at a slower rate than yellow And the blue sound of the material, the compatibility is not good. After the color is completed, the water-washing, soaping and drying, the light gray fabric of the ^ shows the unevenness of the local red streaks. Comparative Example 2 provides the following dye composition : Red reactive dye 22 1304831 5

10

15

Yellow reactive dye C.I. Reactive Yellow 176 Blue reactive dye

S〇2C2H4〇S03H 0.2 parts 0.2 parts CI Reactive Blue 194 0 28 f. Dissolve the above dye composition in 1 part water, add 3 parts of thenardite and 100 parts of unsilked cotton cloth, and keep the dye solution 6 (rc Stir for 3 minutes, then add I5 parts of soda ash 'continue to maintain 6 〇t for i hours, after dyeing is completed, wash, 4 wash and dry, the resulting light brown fabric. Repeat the dyeing process multiple times, the resulting fabrics each other Comparing Ac is greater than !·〇, in the poor current, the first color ratio is less than 7〇%. The invention-series dye combination is a general-purpose dye composition, which can be applied to the dyeing of cellulose fiber (4) The method is a method used in the general reaction of a steep dye* color, such as dip dyeing, printing or continuous dyeing, and has a particularly excellent characteristic. 〃 The series of dye compositions described in the present invention are commercially valuable white water-soluble dyes. The composition can be used for reproducibility, leveling property, detergency and various kinds of materials by using the dye composition of the present invention in a balanced affinity, reactivity, (iv) vitamins or fiber materials containing cellulose. Strong The shoulders have a good water color processing' and have a very good performance in the success rate of the secondary color. ' 23 20 1304831 In summary, the present invention can achieve the object of the invention by the disclosed technical idea, and is novel. , Progressive and available for industrial use, and in accordance with the requirements of the invention patents. However, the above disclosures are preferred embodiments, and those who are partially modified or modified from the technical ideas of the case are familiar with the 5 techniques. It is easy to infer, and does not deviate from the scope of patent rights in this case. [Simple description of the schema]

1[Main I want to explain the symbols of the pieces] !〇 No » 24

Claims (1)

1304831 Announcement No. 10, the scope of application of the patent: 1 A reactive dye composition comprising: (a) at least one of from 1 to 99% by weight of hydrazine containing an amido substituent as shown in the following formula (1) Reactive red dye, (1) wherein R is unsubstituted or substituted by a hydroxy, sulfonate, carboxyl or dentate atom An alkyl group, or a phenyl group which is unsubstituted or substituted by a hydroxyl group, a sulfonic acid group, a carboxyl group or a dentate atom; Ri and R2 are independently of each other a hydrogen atom or an unsubstituted or a hydroxyl group, a sulfonic acid group, a carboxyl group or a cyano-substituted Ci4 alkyl group; R3 is a hydrogen atom, a sulfonic acid group, c "alkyl group or a % alkoxy group; X is a halogen atom, - 〇r4, 15 - wherein L is a hydrogen atom or a Ci4 alkyl group; Y, -CONH-(CH2)n~s〇2_Y, -(〇) - »υ2 - Υ ' — (ο (CH2)m- CONH- (CH2)n - SO v 屮, 2' b〇2-Y or ~NH-CO-T,. Y is vinyl or a CH2 - CH2~U, basin * T ϋ where U is a group treated with a base of 25 1304831' T is α, θ-halopropi〇nyi or α-haloacryloyl, and η and m are each independently an integer of 1 to 6, and 〇 is 〇, 1, 2 or 3; b) at least one reactive yellow dye selected from the following 5 color index: 99 Reactive Yellow No. 145 and CI Reactive Yellow No. 176, and/or at least one selected from the following Color-reactive blue dye: CI Reactive Blue No. 194, CI Reactive Blue No. 221, and CI Reactive Blue No. 222. ί 2. The dye composition of claim 1, wherein 10 parts (a) The dye content is 1 to 80% by weight, and the component (b) has a dye content of 99 to 20% by weight. 3. The dye composition of claim i, wherein the formula (1) is ( La) compound: Wherein R, Ri, Rz, &, X and Q are as defined in the scope of the patent application. 4. The dye composition of claim 3, wherein formula 20 is a compound of formula (lb): 26 1304831 (lb) wherein R, X and Q are as defined in item 1 of the scope of the patent application. 5. The dye composition of claim 4, wherein formula (lb) is a compound of formula (2). Ho3soh2ch2co2s S. 3h (2) 10 6. The dye composition of claim 4, wherein the formula (lb) is a compound of the formula (3). Ho3soh2ch2co2s (3) The dye composition of claim 4, wherein the formula (lb) is a compound of the formula (4). 27 15 J304831 (4) The dye composition of claim 4, wherein the formula (lb) is a compound of the formula (5). _ 9. The dye composition of claim 4, wherein the formula (^b) is a compound of the formula (6). 〇 (6) 28