Reactive dye composition and dye product

Abstract

The present invention discloses a reactive dye composition and a dye product. The reactive dye composition comprises component A, component B and component C, wherein the component A is selected from at least one of the dye compounds shown in formula (I), (II) and (III) and their alkali metal salts, the component B is selected from at least one of the dye compounds shown in formula (III) and their alkali metal salts, and the component C is selected from at least one of the dye compounds shown in formula (IV) and their alkali metal salts. The reactive dye composition and the dye product provided by the present invention are mainly coffee color or jujube red, and have the characteristics of good lifting power, dyeing rate, color fixation rate, and excellent friction resistance and water washing fastness.

Description

Technical Field

[0001] The invention relates to a reactive dye composition and a dye product. Background Art

[0002] Although the color spectrum of reactive dyes is relatively complete, dye suppliers have not yet found a suitable parent of coffee-colored dyes. Usually, they screen existing reactive dyes for those with similar performance as possible. Only dyes are mixed together. However, reactive dyes are sensitive to changes in dyeing reaction conditions, and the dyeing performance of each dye variety varies greatly, making it difficult to control the color. In particular, colors such as coffee color are tertiary colors, which are highly sensitive to color mixing. A slight change in the color of a dye component will cause a large change in the color hue of the color combination.

[0003] Currently, red 3BS, yellow 3RS, blue M2GE, yellow 3RS, and black B are commonly used to create coffee color, but due to the large differences in their performance, it is not easy to control the color light. Summary of the invention

[0004] To solve the above problems, the object of the present invention is to provide a reactive dye composition and a dye product, the color of which is mainly coffee or jujube red, and has the characteristics of good lifting power, dyeing rate, color fixation rate, and excellent friction resistance and water washing fastness.

[0005] In order to achieve the above-mentioned invention object, the present invention adopts the following technical scheme:

[0006] A reactive dye composition, comprising component A, component B and component C, wherein the component A is selected from at least one of dye compounds represented by formula (I), (II) and (III) and alkali metal salts thereof, the component B is selected from at least one of dye compounds represented by formula (II) and alkali metal salts thereof, and the component C is selected from at least one of dye compounds represented by formula (III) and alkali metal salts thereof; in the reactive dye composition, the mass percentage of component A is 25-85% (preferably 30-85%, more preferably 35-85%), the mass percentage of component B is 1-30% (preferably 1-25%, more preferably 1-20%), and the mass percentage of component C is 1-70% (preferably 1-65%, more preferably 5-60%);

[0007]

[0008] In the above formula (I):

[0009] D 1 , D 2 Each is independently a group represented by the following formula (a), (b) or (c):

[0010]

[0011] In the above formulas (a), (b), and (c): R 1 , R 2 , R 4 , R 5 , R 7 , R 8 Each R is independently H, C1-C4 alkyl, C1-C4 alkoxy or sulfonic acid; m=0-3, each R 3 Each is independently selected from an amino group, a sulfonic acid group, a urea group, a C1-C4 alkyl group, a C1-C4 alkanoylamino group or a C1-C4 alkoxy group; n=0-3, each R 6 Each independently selected from hydroxyl, amino or sulfonic acid group; X 1 , X 2 , X 3 Each is independently H, C1-C4 alkyl, C1-C4 alkoxy, -SO2Y 1 、-NHCO(CH2) p 2Y 2 or -CONH(CH2) q 2Y 3 , where p and q are 1 to 3 respectively; and D 1 , D 2 At least one of them contains a fiber-active group (i.e. -SO2Y 1 、-NHCO(CH2) p 2Y 2 or -CONH(CH2) q 2Y 3 ), where Y 1 ~Y 3 Each is independently -CH=CH2, -CH2CH2Cl or -C2H4OSO3H;

[0012] In the above formula (II):

[0013] R 9 ~R 12 are independently H, C1-C4 alkyl, C1-C4 alkoxy or sulfonic acid;

[0014] Y 4 , Y 5 Independently of each other, they are -CH=CH2 or -C2H4OSO3H;

[0015] In formula (III):

[0016] R 13 , R 14 Each is independently hydrogen, C1-C4 alkyl, C1-C4 alkoxy or sulfonic acid;

[0017] X 4 is halogen, preferably chlorine or fluorine;

[0018] Y 6 , Y 7 Independently of each other, they are -CH=CH2 or -C2H4OSO3H.

[0019] The reactive dye composition of the present invention may further include at least one of CI Reactive Yellow 145, CI Reactive Red 198, CI Reactive Orange 122, etc. as a coloring component, and the content of the coloring component does not exceed 30% of the total weight of the composition. Preferably, the reactive dye composition is composed of component A, component B and component C, wherein the mass percentage of component A is 25-85% (preferably 30-85%, more preferably 35-85%), the mass percentage of component B is 1-30% (preferably 1-25%, more preferably 1-20%), and the mass percentage of component C is 1-70% (preferably 1-65%, more preferably 5-60%).

[0020] In the present invention, the C1~C4 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; the C1~C4 alkoxy group can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.; the C1~C4 alkanoylamino group can be formylamino, acetylamino, n-propionylamino, isopropionylamino, n-butyrylamino, isobutyrylamino, tert-butyrylamino, etc.

[0021] In the actual synthesis, the sulfonic acid group and carboxyl group of the compounds of formula (I) to (III) described in the present invention exist in the form of sulfonic acid alkali metal salt or carboxylic acid alkali metal salt, and are used for dyeing in the form of salt, and sodium salt or potassium salt is particularly preferred.

[0022] As a preference, D 1 is a group represented by formula (a), wherein D 2 It is a group represented by formula (b) or formula (c).

[0023] Preferably, in the group represented by formula (b), m is 1 or 2.

[0024] Preferably, R 1 , R 2 , R 4 , R 5 , R 7 , R 8 are independently H, methyl, methoxy or sulfonic acid.

[0025] Preferably, each R 3 are independently methyl, sulfonic acid, urea or acetamido.

[0026] Preferably, each R 6 are independently hydroxyl or sulfonic acid groups;

[0027] As a preference, X 1 , X 2 , X 3 Independent of each other -SO2Y 1 , -NHCO(CH2) 1～3 2Y 2 or -CONH(CH2) 1～3 2Y 3 , where Y 1 ~Y 3 Each is independently -CH=CH2, -CH2CH2Cl or -C2H4OSO3H.

[0028] Preferably, R 9 ~R 14 Each is independently H, methyl, methoxy or sulfonic acid.

[0029] As a further preference, the component A is selected from at least one of the following compounds and their alkali metal salts:

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] In the present invention, it is particularly preferred that component A is selected from at least one of formula (I-1), (I-7), (I-17), (I-18), (I-21), (I-22), (I-24), (I-25) and alkali metal salts thereof.

[0044] As a further preference, the component B is selected from at least one of the following compounds and their alkali metal salts:

[0045]

[0046]

[0047] In the present invention, it is particularly preferred that the component B is at least one selected from the group consisting of formula (II-1), (II-2) and alkali metal salts thereof.

[0048] As a further preference, the component C is selected from at least one of the following compounds and their alkali metal salts:

[0049]

[0050]

[0051] In the present invention, it is particularly preferred that the component C is at least one selected from the group consisting of formula (III-1), (III-3) and alkali metal salts thereof.

[0052] It should be emphasized that the reactive dye compound (I) described in the present invention, the dye coupled at the ortho position of the phenolic hydroxyl group often exists in the form of a quinone hydrazone, that is, the dye of the general formula (I) contains a quinone hydrazone structure shown in the following formula (Ib) and / or (Ic) and / or (Id) and / or (Ie). Considering the writing habits of those skilled in the art, the writing form of the azo form is still used in the content of the invention and the examples, which does not affect the essence of the present invention:

[0053]

[0054] The substituents in formulas (Ib) to (Ie) are defined the same as in formula (I).

[0055] Preferably, the reactive dye composition comprises component A, component B and component C. Based on the sum of the masses of component A, component B and component C, the mass percentage of component A is 30-85%, the mass percentage of component B is 1-25%, and the mass percentage of component C is 1-65%.

[0056] As further preferred, the reactive dye composition consists of component A, component B and component C. Based on the sum of the masses of component A, component B and component C, the mass percentage of component A is 30-85%, the mass percentage of component B is 1-25%, and the mass percentage of component C is 1-65%.

[0057] In the present invention, it is particularly preferred that the reactive dye composition comprises component A, component B and component C, wherein component A is selected from at least one of the compounds represented by formula (I-1), (I-7), (I-17), (I-18), (I-21), (I-22), (I-24) and (I-25) and their alkali metal salts, component B is selected from at least one of the compounds represented by formula (II-1) and (II-2) and their alkali metal salts, component C is selected from at least one of the compounds represented by formula (III-1) and (III-3) and their alkali metal salts, the mass percentage of component A is 30-85% (preferably 35-85%), the mass percentage of component B is 1-25% (preferably 1-20%), and the mass percentage of component C is 1-65% (preferably 5-60%). More particularly, it is preferred that the reactive dye composition consists of component A, component B and component C.

[0058] The active dye composition of the present invention comprises a preparation method comprising mixing the dye components A, B and C according to the aforementioned ratio. The mixing can be carried out in a conventional mechanical manner, such as in a grinder, a kneader or a homogenizer. During the mixing process, the individual dye compounds (I) to (III) can be in the form of powder, granules, aqueous solution or synthetic solution. When the individual dye compounds are mixed in the form of a synthetic solution, the composite dark active dye of the present invention can be separated from the synthetic solution by a generally known method, such as using an electrolyte (such as sodium chloride or potassium chloride) to filter out the dye salt from the reaction medium, or evaporating and spray drying the mixed solution. Therefore, the dye components A, B, C and the dye composition thereof usually contain conventional electrolyte salts (such as sodium chloride, sodium sulfate, etc.) in active dyes.

[0059] When the active dye composition of the present invention is sold as a commodity or used for coloring textile materials, no auxiliary agent may be added, or conventional auxiliary agents in commercial dyes, such as cosolvents, dispersants, alkali-resistant auxiliary agents, dust-proof agents, surfactants, buffers and dyeing accelerators, may be added. Therefore, the present invention also provides an active dye product, which contains the active dye composition. Preferably, the active dye product contains the active dye composition and auxiliary agents, and the weight ratio of the active dye composition to the auxiliary agent is 100:0-45, preferably 100:0-40. The auxiliary agent is preferably one of the following or a combination of any several: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), diffusant CNF (benzylnaphthalenesulfonate formaldehyde condensate), and sodium sulfate (industrial sodium sulfate). The auxiliary agents are all commercially available conventional varieties.

[0060] The reactive dye product of the present invention is suitable for printing and dyeing cellulose fiber, polyamide fiber and fabrics thereof. Among them, the cellulose fiber is preferably cotton fiber or regenerated fiber, and of course it can also include other plant fibers, such as hemp fiber or fabric. Polyamide fiber preferably includes animal fiber materials including skin, hair or silk, and synthetic fiber materials, such as nylon 6, nylon 66, etc.

[0061] When the reactive dye product of the present invention is used to print and dye the above fiber materials, known reactive dyeing methods can be used, such as the commonly used reactive dyeing method and pad dyeing method. The aforementioned soaking dyeing method is to immerse the fabric in the dye solution so that the dye gradually dyes the fabric, and usually requires dyeing-fixing-washing-soap boiling-washing-dehydration-drying and other processes. The aforementioned pad dyeing method is to immerse the fabric in the dye solution first, then pass the fabric through a roller, roll the dye solution evenly into the fabric, and then steam or hot melt the dyeing method, and usually requires padding the dye solution-drying-(pad the fixation solution)-steaming or baking-washing-soap washing-washing-drying and other processes.

[0062] Usually, due to the different requirements for the coloring of fabrics, the amount of dye used will also be different. When using the exhaust dyeing method, the dyeing depth (owf) is generally 0.1% to 10% (the percentage of dye in the weight of the fabric), the bath ratio is 1:2 to 1:60 (the weight ratio of fabric to dye liquor, preferably 1:10 to 1:30), the initial dyeing temperature is controlled at 30 to 60°C, the dyeing time is 10 to 30 minutes, the soap boiling temperature is 85 to 95°C, the soap boiling time is 10 to 15 minutes, the color fixing temperature is 60 to 100°C, the color fixing time is 10 to 50 minutes, and the color fixing pH value is 9 to 11. When using the pad dyeing method for dyeing, the rolling rate of cellulose fiber is generally 60 to 80%, the steaming temperature is 100 to 103°C, and the steaming time is 1 to 3 minutes. Among the pad dyeing methods, the cold padding pile dyeing method is currently more commonly used, in which the dye and alkaline substance are introduced into the pad dyeing machine, and rolled and piled at room temperature for 2 to 30 hours for color fixing, and then thoroughly rinsed.

[0063] The beneficial effects of the present invention are mainly reflected in that the reactive dye composition and reactive dye product described in the present invention have the advantages of good lifting power, good color fixation rate, excellent water resistance and rubbing resistance color fastness when used for fabric printing and dyeing. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 It is the lifting force diagram of the reactive dye obtained in Examples 1 and 2 of the present invention.

[0065] Figure 2 1 is a graph showing the dye uptake of reactive dyes obtained in Examples 1 and 2 of the present invention.

[0066] Figure 3 It is a graph of the fixation rate of the reactive dyes obtained in Examples 1 and 2 of the present invention. DETAILED DESCRIPTION

[0067] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto. Any dye composition with similar properties obtained by changing the corresponding groups within the general formula of the present invention should be within the protection scope of the present invention.

[0068] For the convenience of writing, the structural formulas of all compounds in the examples are presented in the form of free acids, and their actual dyeing properties are equivalent to those of alkali metal salts (such as sodium salts, potassium salts, etc.).

[0069] Embodiment 1:

[0070] 80 parts of the dye compound of formula (I-1), 15 parts of the dye compound of formula (II-1), 5 parts of the dye compound of formula (III-1) and 15 parts of sodium sulfate are mechanically mixed to obtain a composite dye product which is used to dye cotton into a brown hue using a conventional dip dyeing method.

[0071]

[0072] Embodiment 2:

[0073] 45 parts of the dye compound of formula (I-1), 5 parts of the dye compound of formula (II-1), 50 parts of the dye compound of formula (III-1) and 15 parts of sodium sulfate are mechanically mixed to obtain a composite dye product which is used to dye cotton into a jujube red hue using a conventional dip dyeing method.

[0074]

[0075]

[0076] Example 3-63

[0077] According to the method described in Example 1 or 2, the dye compounds in the proportions listed in Table 1 and 10 parts of sodium sulfate are mechanically mixed, and the cotton is dyed into a coffee or reddish color according to the conventional reactive dyeing method.

[0078] Table 1

[0079]

[0080]

[0081]

[0082] Embodiment 64:

[0083] 75 parts of dye of formula (I-1), 15 parts of dye of formula (II-1), 5 parts of dye of formula (III-1) and 5 parts of CI Reactive Orange 122, as well as 5 parts of sodium sulfate and 5 parts of dispersant MF are mechanically mixed to obtain a composite dye which is used to dye cotton into a brown hue by conventional exhaust dyeing.

[0084] Embodiment 65:

[0085] 40 parts of dye of formula (I-1), 3 parts of dye of formula (II-1), 50 parts of dye of formula (III-1) and 7 parts of C.Ⅰ. Reactive Red 198, 5 parts of sodium sulfoxide and 5 parts of dispersant MF are mechanically mixed to obtain a composite dye which is used to dye cotton into a maroon hue by conventional immersion dyeing.

[0086] Application Example 1:

[0087] The dark reactive dye dry products obtained in Examples 1-64 and Comparative Example 1 were dissolved in water respectively, and 50 g / L of sodium sulfate was added to prepare a dyeing solution. The dyeing concentration was 4% (dye to cloth weight), the bath ratio was 1:20 (cloth weight in grams to dyeing solution volume in milliliters), and the cotton cloth was placed at 60°C for adsorption for 30 minutes, and alkali (sodium carbonate 20 g / L) was added for color fixation for 45 minutes. The dyed fabric was washed, soaped, and dried to obtain coffee to reddish red dyed fabric. The friction resistance and soaping fastness tests were carried out according to the methods in GB / T 3920-2008 and GB / T3921-2008, and the results are shown in Table 2:

[0088] Table 2

[0089]

[0090]

[0091]

[0092]

[0093] Application Example 2:

[0094] The reactive dyes prepared in Examples 1 to 2 of the present invention were tested for their lifting power, dye uptake and fixation rate according to the methods specified in GB / T 21875-2016 and GB / T 2391-2014. The results are as follows: Figure 1 , Figure 2 , Figure 3 As shown, the results show that the reactive dyes of the present invention have excellent performance.

Claims

1. A reactive dye composition, characterized in that: The reactive dye composition comprises component A, component B and component C, wherein the component A is selected from at least one of the dye compound represented by formula (I) and its alkali metal salt, the component B is selected from at least one of the dye compound represented by formula (II) and its alkali metal salt, and the component C is selected from at least one of the dye compound represented by formula (III) and its alkali metal salt; in the reactive dye composition, the mass percentage of component A is 25-85%, the mass percentage of component B is 1-30%, and the mass percentage of component C is 1-70%; In the above formula (I): D 1 , D 2 Each is independently a group represented by the following formula (a), (b) or (c): In the above formulas (a), (b), and (c): R 1 , R 2 , R 4 , R 5 , R 7 , R 8 Each R is independently H, C1-C4 alkyl, C1-C4 alkoxy or sulfonic acid; m=0-3, each R 3 Each is independently selected from an amino group, a sulfonic acid group, a urea group, a C1-C4 alkyl group, a C1-C4 alkanoylamino group or a C1-C4 alkoxy group; n=0-3, each R 6 Each independently selected from hydroxyl, amino or sulfonic acid group; X 1 , X 2 , X 3 Each is independently H, C1-C4 alkyl, C1-C4 alkoxy, -SO2Y 1 、-NHCO(CH2) p 2Y 2 or -CONH(CH2) q 2Y 3 , where p and q are 1 to 3 respectively; and D 1 , D 2 At least one of them contains fiber-active groups: -SO2Y 1 、-NHCO(CH2) p 2Y 2 or -CONH(CH2) q 2Y 3 , where Y 1 ~Y 3 Each is independently -CH=CH2, -CH2CH2Cl or -C2H4OSO3H; In the above formula (II): R 9 ~R 12 are independently H, C1-C4 alkyl, C1-C4 alkoxy or sulfonic acid; Y 4 , Y 5 Independently of each other, they are -CH=CH2 or -C2H4OSO3H; In formula (III): R 13 , R 14 Each is independently hydrogen, C1-C4 alkyl, C1-C4 alkoxy or sulfonic acid; X 4 is a halogen; Y 6 , Y 7 Independently of each other, they are -CH=CH2 or -C2H4OSO3H.

2. The reactive dye composition according to claim 1, wherein: The reactive dye composition consists of component A, component B and component C.

3. The reactive dye composition according to claim 1 or 2, wherein: In the reactive dye composition, the mass percentage of component A is 30-85%, the mass percentage of component B is 1-25%, and the mass percentage of component C is 1-65%.

4. The reactive dye composition according to claim 3, wherein: In the reactive dye composition, the mass percentage of component A is 35-85%, the mass percentage of component B is 1-20%, and the mass percentage of component C is 5-60%.

5. The reactive dye composition according to claim 1 or 2, wherein: The alkali metal salt is a sodium salt or a potassium salt.

6. The reactive dye composition according to claim 1 or 2, wherein: D 1 is a group represented by formula (a), wherein D 2 is a group represented by formula (b) or formula (c); In the group represented by formula (b), m is 1 or 2; R 1 , R 2 , R 4 , R 5 , R 7 , R 8 are independently H, methyl, methoxy or sulfonic acid; Each R 3 are independently methyl, sulfonic acid, urea or acetamido; Each R 6 are independently hydroxyl or sulfonic acid groups; X 1 , X 2 , X 3 Independent of each other -SO2Y 1 , -NHCO(CH2) 1～3 2Y 2 or -CONH(CH2) 1～3 2Y 3 , where Y 1 ~Y 3 Each is independently -CH=CH2, -CH2CH2Cl or -C2H4OSO3H; R 9 ~R 14 Each is independently H, methyl, methoxy or sulfonic acid; X 4 is chlorine or fluorine.

7. The reactive dye composition according to claim 1 or 2, wherein: The component A is selected from at least one of the following compounds and their alkali metal salts:

8. The reactive dye composition according to claim 1 or 2, wherein: The component B is selected from at least one of the following compounds and their alkali metal salts:

9. The reactive dye composition according to claim 1 or 2, wherein: The component C is selected from at least one of the following compounds and their alkali metal salts:

10. The reactive dye composition according to claim 1 or 2, wherein: The dye compound represented by formula (I) contains a quinone hydrazone structure represented by the following formula (Ib) and / or (Ic) and / or (Id) and / or (Ie): The substituents in formulas (Ib) to (Ie) are defined the same as in formula (I).

11. The reactive dye composition according to claim 1 or 2, wherein: In the reactive dye composition, component A is selected from at least one of the compounds represented by formula (I-1), (I-7), (I-17), (I-18), (I-21), (I-22), (I-24), (I-25) and their alkali metal salts, component B is selected from at least one of the compounds represented by formula (II-1) and (II-2) and their alkali metal salts, and component C is selected from at least one of the compounds represented by formula (III-1) and (III-3) and their alkali metal salts; 12. A reactive dye product comprising the reactive dye composition according to claim 1 or 2.

13. The reactive dye product according to claim 12, characterized in that: The reactive dye product contains the reactive dye composition and auxiliary agents, and the weight ratio of the reactive dye composition to the auxiliary agents is 100:0-45.

14. The reactive dye product according to claim 13, characterized in that: In the reactive dye product, the weight ratio of the reactive dye composition to the auxiliary agent is 100:0-40.

15. The reactive dye product according to any one of claims 12 to 14, characterized in that: The auxiliary agent is selected from the following one or any combination of the following: naphthalenesulfonic acid formaldehyde condensate, methylnaphthalenesulfonic acid formaldehyde condensate, diffusant CNF, and sodium sulfate.

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