Brown reactive dye composition, brown reactive dye and preparation method thereof

Abstract

The invention discloses a brown reactive dye composition, a brown reactive dye and a preparation method thereof, and belongs to the technical field of dyestuff, the brown reactive dye can be directly used for brown dyeing production, then dyes with other colors are added for fine adjustment according to needed colors, colored light adjustment becomes easy, the production operation procedure can be simplified, and the production cost is reduced. Moreover, front and back color differences and left, middle and right color differences of the dyed cloth can be reduced, the colored light stability of dyeing is improved, and the rate of dyed certified products is increased. Compared with the conventional color matching method, the reactive brown dye disclosed by the invention has the advantages that the cold and hot color change and the dry and wet color change are small (namely, the color stability is better).

Description

Technical Field

[0001] The invention relates to the technical field of dyes, in particular to a brown reactive dye composition, a brown reactive dye and a preparation method thereof. Background Art

[0002] Reactive dyes are a type of reactive dye that can form covalent bonds with fibers through chemical reactions. They have many advantages, such as complete color spectrum, bright colors, good level dyeing, simple process, and low price. In recent years, with the enhancement of people's environmental awareness and the improvement of living standards, people have higher requirements for the quality and types of dyed fabrics, and they prefer natural fibers such as cotton, linen, and silk. The main dye variety for dyeing these natural fibers is reactive dyes, which makes reactive dyes one of the most important dye categories today.

[0003] At present, printing and dyeing factories often use brown, red and blue reactive dyes to make brown, which is difficult to adjust the color. In addition, the performance of the components used for the color matching is often quite different. After the color matching, hue fluctuations are likely to occur during the dyeing process, resulting in color differences between the front and back of the dyed fabric and between the left, middle and right sides of the fabric. Summary of the invention

[0004] The embodiment of the present invention provides a brown reactive dye composition, a brown reactive dye and a preparation method thereof. After the dye composition of the present invention is applied to dyeing, in addition to ensuring various fastnesses, compared with traditional brown dyes, it effectively solves the color difference between the edge and the center and the cold and hot color change problems in the dyeing process, meets the current printing and dyeing needs, and has broad application prospects. The contents of the present invention are as follows: The first object of the present invention is to provide a brown reactive dye composition, which comprises 10-20 parts by weight of component A as shown in formula (I), 40-65 parts by weight of component B as shown in formula (II), and 20-40 parts by weight of component C as shown in at least one of formula (III) or (IV); (I); (II); (III); (IV); Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15is any one of -H, (C1-C4) alkyl, (C1-C4) alkoxy and -SO3M, y1 and y2 are any one of -CH=CH2 and -C2H4OSO3M, y3 is any one of -H, -SO2CH=CH2 and SO2C2H4OSO3M, and M is any one of -H and alkali metal. The reactive brown dye composition of the present invention, the dye component AC used can be obtained by conventional methods, for example, by using suitable components well known to those skilled in the art and using necessary proportions by means of conventional diazotization reaction and coupling reaction.

[0005] Wherein component A is at least one of formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5), formula (I-6), formula (I-7) and formula (I-8), wherein M1 is H (in free acid form) or Na (in salt form): (Ⅰ-1); (I-2); (I-3); (I-4); (I-5); (I-6); (I-7); (Ⅰ-8).

[0006] Wherein component B is at least one of formula (II-1), formula (II-2), formula (II-3), formula (II-4), formula (II-5), formula (II-6), formula (II-7) and formula (II-8), wherein M is H (in free acid form) or Na (in salt form): (Ⅱ-1); (Ⅱ-2); (II-3); (II-4); (II-5); (II-6); (II-7); (Ⅱ-8).

[0007] Wherein component C is at least one of formula (III-1), formula (III-2), formula (III-3), formula (III-4), formula (IV-1), formula (IV-2), formula (IV-3) and formula (IV-4), wherein M is H (in free acid form) or Na (in salt form): (III-1); (III-2); (III-3); (III-4); (IV-1); (IV-2); (IV-4). Whether M is H (free acid form) or Na (salt form) has no effect on its dyeing properties. It is usually prepared in the form of Na (salt form) just for the convenience of preparation. Ordinary technicians in this field can also acidify it into the free acid form.

[0008] In some embodiments of the present invention, component A in the brown reactive dye composition of the present invention is synthesized by diazotization reaction and coupling reaction.

[0009] In some embodiments of the present invention, the specific preparation method of component A in the brown reactive dye composition of the present invention is: add hydrochloric acid and 30wt% sodium nitrite solution to the para-ester compound raw material at a temperature of 0-5°C for diazotization reaction to obtain a diazonium salt solution of the para-ester compound, and first couple H acid with a 2-fold molar ratio of the para-ester diazonium salt solution at pH <2.0 and a temperature of 10°C, then control the temperature to 8-10°C, adjust the pH value to 3.0-3.5, and stir for 0.5-1h, continue to adjust the pH value to 5.0-6.5, maintain the temperature at 10-15°C, and then react for 3-4h, further concentrate and dry to obtain component A.

[0010] The second object of the present invention is to provide a brown reactive dye, which comprises a brown reactive dye composition and an auxiliary agent.

[0011] In some embodiments of the present invention, the auxiliary agents in the brown reactive dye of the present invention include auxiliary solvents, dispersants, alkali-resistant auxiliary agents, dust-proof agents, surfactants, buffers, and dyeing accelerators.

[0012] The third purpose of this part is to provide a method for preparing a brown reactive dye, the technical point of which is that component A, component B and component C are mixed according to a ratio, impurities and salts are removed therefrom, and then placed in an auxiliary agent and spray-dried to obtain the brown reactive dye composition.

[0013] In some embodiments of the present invention, the mixing method in the preparation method of the brown reactive dye of the present invention is: mixing by mechanical means.

[0014] In some embodiments of the present invention, the mechanical method in the preparation method of the brown reactive dye of the present invention is mixing in a mixer.

[0015] In some embodiments of the present invention, the mixing method in the preparation method of the brown reactive dye of the present invention is: mixing in a solution.

[0016] At least one of the above technical solutions adopted in the embodiments of the present invention can achieve the following beneficial effects: The active brown dye of the present invention can be directly used in the production of brown dyeing, and then other color dyes can be added according to the required color for fine adjustment, so that the color adjustment becomes easy, which can not only simplify the production operation procedure and improve the production efficiency, but also reduce the color difference between the front and back and the left, middle and right of the dyed cloth, improve the color stability of the dyeing, and improve the rate of dyeing genuine products. The active brown dye of the present invention has smaller cold and hot color change and dry and wet color change of brown than the conventional color matching method (that is, the color stability is better). Implementation

[0017] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Example

[0018] A brown reactive dye composition, comprising 20 kg of component A as shown in formula (I), 40 kg of component B as shown in formula (II), and 40 kg of component C as shown in at least one of formula (III) and formula (IV), wherein the weight ratio of the components of formula (III) to formula (IV) is 1:1; (I); (II); (III); (IV); Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R15 It is any one of -H, (C1-C4) alkyl, (C1-C4) alkoxy and -SO3M, y1 and y2 are any one of -CH=CH2 and -C2H4OSO3M, y3 is any one of -H, -SO2CH=CH2 and SO2C2H4OSO3M, and M is any one of -H and alkali metal.

[0019] Wherein component A is of formula (I-3), wherein M1 is H (in free acid form) or Na (in salt form): (Ⅰ-3).

[0020] Component B is of formula (II-3), wherein M is H (in free acid form) or Na (in salt form): (Ⅱ-3).

[0021] Component C is a mixture of formula (III-2) and formula (IV-2), wherein M is H (in free acid form) or Na (in salt form): (III-2); (Ⅳ-2).

[0022] Wherein, component A is synthesized through diazotization reaction and coupling reaction.

[0023] Among them, the specific preparation method of component A is: add hydrochloric acid and 30wt% sodium nitrite solution to the para-ester compound raw material at a temperature of 0-5°C for diazotization reaction to obtain a diazonium salt solution of the para-ester compound, and first couple H acid with a 2-fold molar ratio of the para-ester diazonium salt solution at pH <2.0 and a temperature of 10°C, then control the temperature to 8-10°C, adjust the pH value to 3.0-3.5, and stir for 0.5-1h, continue to adjust the pH value to 5.0-6.5, maintain the temperature at 10-15°C, and react for 3-4h, and further concentrate and dry to obtain component A.

[0024] According to the formula of the above composition, the brown reactive dye of the present invention comprises a brown reactive dye composition and an auxiliary agent.

[0025] Among them, the auxiliary agents in brown reactive dyes include auxiliary solvents, dispersants, alkali-resistant auxiliary agents, dust-proof agents, surfactants, buffers, and dyeing accelerators.

[0026] The preparation method of the brown reactive dye of this embodiment comprises mixing component A, component B and component C according to the above ratio, removing impurities and salt therefrom, placing in an auxiliary agent and spray drying to obtain the brown reactive dye composition.

[0027] Wherein, the mixing method in the preparation method of brown reactive dye is: mixing by mechanical means.

[0028] Among them, the mechanical method in the preparation method of brown reactive dye is mixing in a mixer. Example

[0029] A brown reactive dye composition, comprising 15 kg of component A as shown in formula (I), 50 kg of component B as shown in formula (II) and 30 kg of component C as shown in formula (III); (I); (II); (III); Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 It is any one of -H, (C1-C4) alkyl, (C1-C4) alkoxy and -SO3M, y1 and y2 are any one of -CH=CH2 and -C2H4OSO3M, y3 is any one of -H, -SO2CH=CH2 and SO2C2H4OSO3M, and M is any one of -H and alkali metal.

[0030] Component A is of formula (I-1), wherein M1 is H (in free acid form) or Na (in salt form): (III); Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 It is any one of -H, (C1-C4) alkyl, (C1-C4) alkoxy and -SO3M, y1 and y2 are any one of -CH=CH2 and -C2H4OSO3M, y3 is any one of -H, -SO2CH=CH2 and SO2C2H4OSO3M, and M is any one of -H and alkali metal.

[0031] Component A is of formula (I-1), wherein M1 is H (in free acid form) or Na (in salt form): (Ⅰ-1).

[0032] Component B is of formula (II-1), wherein M is H (in free acid form) or Na (in salt form): (Ⅱ-1).

[0033] Component C is of formula (III-1), wherein M is H (in free acid form) or Na (in salt form): (III-1).

[0034] Wherein, component A is synthesized through diazotization reaction and coupling reaction.

[0035] Among them, the specific preparation method of component A is: add hydrochloric acid and 30wt% sodium nitrite solution to the para-ester compound raw material at a temperature of 0-5°C for diazotization reaction to obtain a diazonium salt solution of the para-ester compound, and first couple H acid with a 2-fold molar ratio of the para-ester diazonium salt solution at pH <2.0 and a temperature of 10°C, then control the temperature to 8-10°C, adjust the pH value to 3.0-3.5, and stir for 0.5-1h, continue to adjust the pH value to 5.0-6.5, maintain the temperature at 10-15°C, and react for 3-4h, and further concentrate and dry to obtain component A.

[0036] According to the formula of the above composition, the brown reactive dye of the present invention comprises a brown reactive dye composition and an auxiliary agent.

[0037] Among them, the auxiliary agents in brown reactive dyes include auxiliary solvents, dispersants, alkali-resistant auxiliary agents, dust-proof agents, surfactants, buffers, and dyeing accelerators.

[0038] The preparation method of the brown reactive dye of this embodiment comprises mixing component A, component B and component C according to the above ratio, removing impurities and salt therefrom, placing in an auxiliary agent and spray drying to obtain the brown reactive dye composition.

[0039] Wherein, the mixing method in the preparation method of brown reactive dye is: mixing in solution. Example

[0040] A brown reactive dye composition, comprising 10 kg of component A as shown in formula (I), 65 kg of component B as shown in formula (II) and 25 kg of component C as shown in formula (IV); (I); (II); (IV); Among them, R1, R2, R3, R4, R5, R6, R7, R 12 , R 13 , R 14 , R 15It is any one of -H, (C1-C4) alkyl, (C1-C4) alkoxy and -SO3M, y1 and y2 are any one of -CH=CH2 and -C2H4OSO3M, y3 is any one of -H, -SO2CH=CH2 and SO2C2H4OSO3M, and M is any one of -H and alkali metal.

[0041] Wherein component A is of formula (I-2), wherein M1 is H (in free acid form) or Na (in salt form): (Ⅰ-2).

[0042] Component B is of formula (II-2), wherein M is H (in free acid form) or Na (in salt form): (Ⅱ-2).

[0043] Wherein component C is of formula (IV-1), wherein M is H (in free acid form) or Na (in salt form): (Ⅳ-1).

[0044] Wherein, component A is synthesized through diazotization reaction and coupling reaction.

[0045] Among them, the specific preparation method of component A is: add hydrochloric acid and 30wt% sodium nitrite solution to the para-ester compound raw material at a temperature of 0-5°C for diazotization reaction to obtain a diazonium salt solution of the para-ester compound, and first couple H acid with a 2-fold molar ratio of the para-ester diazonium salt solution at pH <2.0 and a temperature of 10°C, then control the temperature to 8-10°C, adjust the pH value to 3.0-3.5, and stir for 0.5-1h, continue to adjust the pH value to 5.0-6.5, maintain the temperature at 10-15°C, and react for 3-4h, and further concentrate and dry to obtain component A.

[0046] According to the formula of the above composition, the brown reactive dye of the present invention comprises a brown reactive dye composition and an auxiliary agent.

[0047] Among them, the auxiliary agents in brown reactive dyes include auxiliary solvents, dispersants, alkali-resistant auxiliary agents, dust-proof agents, surfactants, buffers, and dyeing accelerators.

[0048] The preparation method of the brown reactive dye of this embodiment comprises mixing component A, component B and component C according to the above ratio, removing impurities and salt therefrom, placing in an auxiliary agent and spray drying to obtain the brown reactive dye composition.

[0049] Wherein, the mixing method in the preparation method of brown reactive dye is: mixing by mechanical means.

[0050] Among them, the mechanical method in the preparation method of brown reactive dye is mixing in a mixer.

[0051] Wherein, the mixing method in the preparation method of brown reactive dye is: mixing in solution.

[0052] Test example The present invention adopts the method of pad dyeing to carry out testing: The present invention adopts the printing method to test the product: Fabric:20 S x16 S 128×60 pure cotton yarn (pre-treated by singeing, bleaching, mercerizing, etc.).

[0053] Dye solution preparation: prepare the brown reactive dyes prepared in Examples 1-3 and Comparative Example 1 (traditional three-color brown) to prepare dye solutions with an active dye content of 20 g / L, wherein the fixing solution includes 200 g / L of sodium chloride, 20 g / L of sodium carbonate and 5 g / L of sodium hydroxide.

[0054] Padding and drying: adjust the padding rate to 60-65%; put the cotton yarn card into the padding machine with the front side facing downwards during padding; pad three pieces of cloth for each standard sample and test sample, mark them, and hang them in an oven at 70-75℃ to dry for 8 minutes.

[0055] Immerse in fixing solution: After the cloth sample is immersed in the fixing solution for 2 seconds, it is spread flat on a double-layer film with the front side facing upwards (the 6 cloth samples of the standard sample and the test sample are placed in order). Use a glass rod to gently scrape off the bubbles and excess fixing solution in the film, so that the amount of liquid on the cloth sample is about 90%.

[0056] Steaming: Place the film sample in an oven at 160°C, start timing when observing the bubbling of the film from outside the glass door, take out the film sample immediately after 60 seconds and put it into cold water, and then take the fabric sample out of the film and put it into cold water.

[0057] Cleaning: Wash with warm water, boil with soap (bath ratio 1:100, time 3min), wash with clean water, use a roller to remove excess water, and dry (ironing with the front side facing down, ironing the reverse side, and ironing slowly to dry).

[0058] The following standards were used for testing: Dyeing Standard Depth Color Chart——GB / T4841.1-19841 / 1 Color fastness to washing——GB / T3921-2008 Color fastness to perspiration——GB / T3922-1995 Color fastness to rubbing——GB / T3920-2008 Color fastness to chlorinated water——GB / T8433-1998 (effective chlorine solution is 20mg / L) Color fastness to artificial light - GB / T8427-2008 (Method 3, xenon arc lamp), test results are shown in Table 1:

[0059] The test comparison results of the brown reactive dyes prepared in Examples 1-3 and the product of Comparative Example 1 (traditional three-color brown) in actual factory production are as follows: Fabric:20 S x16 S 128×60 pure cotton yarn (pre-treated by singeing, bleaching, mercerizing, etc.).

[0060] Dye solution preparation: prepare the brown reactive dyes prepared in Examples 1-3 and Comparative Example 1 (traditional three-color brown) to prepare dye solutions with an active dye content of 20 g / L, wherein the fixing solution includes 200 g / L of sodium chloride, 20 g / L of sodium carbonate and 5 g / L of sodium hydroxide.

[0061] Pad dyeing process: semi-finished fabric → pad dye solution → drying → pad fixation solution → steaming → washing → soaping → washing → drying. Note: The larger the DE value measured by the datacolor 600 computer colorimeter, the greater the color difference. From the test data of actual application, it can be seen that the color difference between the front and back and the left, middle and right of the reactive brown pad-dyed cloth of the present invention is significantly improved.

[0064] Compared with the traditional method of producing brown dyeing by combining three dyes into one brown color, the active brown dye of the present invention can be directly used for continuous roller dyeing and brown dyeing production. When necessary, dyes of other colors can be added according to the required color for fine adjustment, so that the color adjustment becomes easy, which can not only simplify the production operation procedures and improve production efficiency, but also reduce the color difference between the front and back and the left, middle and right of the dyed cloth, improve the color stability of the dyeing, and improve the rate of genuine dyeing. In addition, the active brown dye of the present invention has smaller cold and hot color changes and dry and wet color changes than the brown of the conventional color combination method (that is, the color stability is better), thereby improving the quality indicators of the dyed products.

[0065] The above description is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A brown reactive dye composition, characterized in that, The invention comprises 10-20 parts by weight of component A as represented by formula (I), 40-65 parts by weight of component B as represented by formula (II), and 20-40 parts by weight of component C as represented by at least one of formula (III) or (IV); （Ⅰ）； （Ⅱ）； （Ⅲ）； （Ⅳ）； Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 It is any one of -H, (C1-C4) alkyl, (C1-C4) alkoxy and -SO3M, y1 and y2 are any one of -CH=CH2 and -C2H4OSO3M, y3 is any one of -H, -SO2CH=CH2 and SO2C2H4OSO3M, and M is any one of -H and alkali metal.

2. The brown reactive dye composition according to claim 1, characterized in that The component A is synthesized through diazotization reaction and coupling reaction.

3. The brown reactive dye composition according to claim 2, characterized in that The specific preparation method of the component A is as follows: add hydrochloric acid and 30wt% sodium nitrite solution to the para-ester compound raw material at a temperature of 0-5°C for diazotization reaction to obtain a diazonium salt solution of the para-ester compound, and carry out a coupling reaction with H acid and a 2-fold molar ratio of the para-ester diazonium salt solution at pH <2.0 and a temperature of 10°C, then control the temperature to 8-10°C, adjust the pH value to 3.0-3.5, and stir for 0.5-1h, continue to adjust the pH value to 5.0-6.5, maintain the temperature at 10-15°C, react for 3-4h, and further concentrate and dry to obtain component A.

4. A brown reactive dye, characterized in that The invention comprises the brown reactive dye composition according to any one of claims 1 to 3 and an auxiliary agent.

5. The brown reactive dye according to claim 4, characterized in that The auxiliary agents include auxiliary solvents, dispersants, alkali-resistant auxiliary agents, dust-proof agents, surfactants, buffers, and dyeing accelerators.

6. The method for preparing a brown reactive dye according to claim 4, wherein The method comprises mixing component A, component B and component C according to a proportion, removing impurities and salt therefrom, placing the components in an auxiliary agent and spray drying the components to obtain the brown active dye composition.

7. The method for preparing a brown reactive dye according to claim 6, wherein The mixing method is: mixing by mechanical method.

8. The method for preparing a brown reactive dye according to claim 7, wherein The mechanical method is mixing in a blending machine.

9. The method for preparing a brown reactive dye according to claim 6, wherein The mixing method is: mixing in a solution.

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