The present invention relates to a reactive dye composition and dye product thereof, especially a reactive navy to black dye composition suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials, and dye product thereof.
Reactive black dye KNB has become the most widely used reactive black dye due to its low price, good fastnesses and easy washing. However, the dye has low substantivity to fiber, and its dye-uptake and degree of fixation are not high. Aiming at the shortcomings of the reactive black dye KNB, dye researchers have done a lot of work in the research and development of reactive black dyes in recent years. In the actual application process, existing composite reactive black products, such as described in patents CN100582168A, CN1730566A, and the like, still have problems such as poor build-up and not good fastness to washing.
To solve the above problems, the object of the present invention is to provide a reactive navy to black dye composition and dye product thereof with properties such as good fastness to washing, high degree of fixation and good build-up, which is suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials and blended fabrics thereof.
In order to achieve the above object, the present invention adopts the technical solution as follows: The present invention provides a reactive navy to black dye composition, comprising component A and component B, wherein component A is one or more selected from the group consisting of dye compounds of formula (I) and alkali metal salts thereof, and component B is one or more selected from the group consisting of dye compounds of formula (II) and alkali metal salts thereof; based on component A and component B, component A has a mass percentage of 5% to 50%, and component B has a mass percentage of 50% to 95%,
In the present invention, the C1˜C4 alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; the C1˜C4 alkoxy may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.
Further, both D1 and D2 are preferably the group of formula (a) or (b).
More further, both D1 and D2 are preferably the group of formula (a).
Further, R1 and R2 are each independently preferably hydrogen or —COR7, in which R7 is methyl or —NH2.
Further, R3 is preferably hydrogen, methyl, methoxy, carboxyl or sulfo.
Further, R4˜R6 are each independently preferably hydrogen, methyl, methoxy or sulfo.
Further, X1 and X2 are each independently preferably —SO2Y1, —NHCOCH2CH2SO2Y2 or —CONHCH2CH2SO2Y3, wherein Y1˜Y3 are each independently —CH═CH2 or —CH2CH2OSO3H.
Further, R8—R11 are each independently preferably hydrogen, methyl, methoxy or sulfo.
Further, Y4 and Y5 are each independently preferably —CH═CH2 or —CH2CH2OSO3H.
As the first preferred solution of the present invention, the reactive navy to black dye composition consists of component A and component B.
As the second preferred solution of the present invention, the reactive navy to black dye composition also comprises component C, and component C is one or more selected from the group consisting of compounds of formulae (III)˜(IV) and alkali metal salts thereof, in the composition, the mass of component C is 1% to 50%, preferably is 1% to 40%, of the total mass of component A and component B:
Further, the reactive navy to black dye composition of the present invention preferably comprises the following components:
Further, the reactive navy to black dye composition consists of component A, component B and component C.
More further, the reactive navy to black dye composition of the present invention preferably consists of the following dye components:
As the third preferred solution of the present invention, the dye composition also comprises component D, component D is one or more selected from the group consisting of dye compounds of formulae (V)˜(VII) and alkali metal salts thereof, in the composition, the mass of component D is 1% to 50%, preferably is 1% to 40%, of the total mass of component A and component B:
Further, component D is at least one selected from the group consisting of dyes of formula (VI) and alkali metal salts thereof.
Further, the reactive navy to black dye composition consists of component A, component B and component D.
More further, the reactive navy to black dye composition of the present invention preferably consists of the following dye components:
As the fourth preferred solution of the present invention, the dye composition also comprises component C and component D, and component C is one or more selected from the group consisting of compounds of formulae (III)˜(IV) and alkali metal salts thereof, in the composition, the mass of component C is 1% to 50%, preferably is 1% to 40%, of the total mass of component A and component B; component D is one or more selected from the group consisting of dye compounds of formulae (V)˜(VII) and alkali metal salts thereof, in the composition, the mass of component D is 1% to 50%, preferably is 1% to 40%, of the total mass of component A and component B:
the groups in formulae (III)˜(VII) are defined as above.
Further, the reactive navy to black dye composition consists of component A, component B, component C and component D.
Further, component C is at least one selected from the group consisting of dye compounds of formula (III) and/or formula (IV) and alkali metal salts thereof, wherein both a and b are 0, or one of a and b is 0 while the other is 1, c is 1, and d is 0 or 1.
Further, component D is at least one selected from the group consisting of dye compounds of formula (VI) and alkali metal salts thereof.
More further, the reactive navy to black dye composition of the present invention preferably comprises the following components:
Even more further, the reactive navy to black dye composition consists of component A, component B, component C and component D, wherein
Besides component A, component B, component C and component D, the reactive navy to black dye composition of the present invention may also comprises one or more conventional shade-adjusting dye components such as C.I. reactive yellow 145, C.I. reactive red 194, C.I. reactive red 195 and C.I. reactive red 198, and the total amount of the conventional dye component(s) is not more than 30% of the total mass of component A, component B, component C and component D.
Specifically, component A is preferably at least one selected from the group consisting of dye compounds of the following formulae (I-1)˜(I-66) and alkali metal salts thereof:
Further, component A is preferably at least one selected from the group consisting of compounds of formulae (I-1)˜(I-28) and (I-48)˜(I-55) and alkali metal salts thereof.
More further, component A is preferably at least one selected from the group consisting of compounds of formulae (I-1), (I-2), (I-4), (I-5), (I-6) and (I-7) and alkali metal salts thereof.
Specifically, component B is preferably at least one selected from the group consisting of the following compounds and alkali metal salts thereof:
Further, component A is preferably at least one selected from the group consisting of compounds of formulae (II-1) and (II-3) and alkali metal salts thereof.
Specifically, component C is preferably at least one selected from the group consisting of the following compounds and alkali metal salts thereof:
Further, component C is preferably at least one selected from the group consisting of compounds of formulae (III-1)˜(III-33) and (IV-1)˜(IV-10) and alkali metal salts thereof. More further, component C is preferably at least one selected from the group consisting of compounds of formulae (II-1), (II-2), (III-4), (IV-1) and (IV-3) and alkali metal salts thereof.
Specifically, component D is at least one selected from the group consisting of the following compounds and alkali metal salts thereof:
Further, component D is preferably at least one selected from the group consisting of compounds of formulae (VI-1), (VI-3), (VI-4), (VI-26), (VI-27), (VI-31), (VI-38), (VI-41), (VI-42), (VI-45) and (VI-54) and alkali metal salts thereof.
More further, component D is preferably at least one selected from the group consisting of compounds of formulae (VI-26), (VI-27), (VI-41) and (VI-42) and alkali metal salts thereof.
The dye composition of the present invention particularly preferably comprises component A and component B, wherein
Particularly preferably, the dye composition of the present invention comprises component A, component B and component C, wherein
Particularly preferably, the dye composition of the present invention comprises component A, component B and component D, wherein
Particularly preferably, the dye composition of the present invention comprises component A, component B, component C and component D, wherein
In the reactive navy to black dye composition of the present invention, the dye compounds of formulae (II)˜(VI) used are all known dyes, and can be synthesized by conventional methods, for example, synthesized by using suitable components well known to those skilled in the art in necessary proportions by means of conventional diazotization and coupling reactions, or prepared according to the methods described in the applications CN101250334A, CN105176139A, CN 105524485A, CN1266869A and CN109971208A or the like.
The reactive dye compound of formula (I) can also be prepared by diazotization and coupling reactions commonly used in reactive dyes, for example:
Further, if both D1 and D2 are the group of formula (a) or (b), the second coupling reaction and the third coupling reaction can be merged into one coupling reaction, that is, the diazonium solution of formula (Ib) or (Ic) prepared in step (1) is added to coupling product 1, the pH is controlled to be between 5.0 and 8.0 with liquid alkali or baking soda, the temperature is controlled to be between 0° C. and 20° C., and the second coupling reaction is carried out, the second reaction solution is tested with H acid test solution, if the bleed circle is colorless, it means that the diazonium is reacted completely to the end point, thereby obtaining the reactive dye compound of formula (I) of the present invention; wherein, the molar ratio of the compound of formula (Ib) or (Ic) to 3,5-diaminobenzoic acid is (1.9-2.4):1, preferably is (1.96-2.16):1.
It should be emphasized that, in the reactive navy to black dye composition of the present invention, the dye compounds coupled at the ortho-position of the phenolic hydroxyl, often exist in a stable state of quinohydrazone, that is, the dye of the general formulae (VI) substantially contains a quinohydrazone structure of the following formulae (VIa) and/or (VIb) and/or (VIc) and/or (VId), and the dyes of the general formulae (II) and (IV) substantially contain a quinohydrazone structure of the following formulae (IIa) and (IVa), respectively. Considering the writing habits of those skilled in the art, azo-form is also used as the written form in the summary of the invention and the examples, which does not affect the essence of the present invention:
the definitions of the substituents of the above formulae (IIa) and (IVa) are respectively the same as those of formula (II) and (IV), and the definitions of the substituents of formulae (VIa)˜(VId) are the same as those of formula (VI).
In addition, in the reactive navy to black dye composition of the present invention, component A is at least one selected from the group consisting of compounds of formula (I) and alkali metal salts thereof, component B is at least one selected from the group consisting of compounds of formula (II) and alkali metal salts thereof, component C is at least one selected from the group consisting of compounds of formulae (III)˜(IV) and alkali metal salts thereof, and component D is at least one selected from the group consisting of compounds of formulae (V)˜(VII) and alkali metal salts thereof; when the compound is alkali metal salt, the carboxyl groups and sulfonic acid groups in formulae (I)˜(VII) exist in the form of alkali metal salt of carboxylic acid or sulfonic acid. Preferably, the alkali metal salt is sodium salt or potassium salt. It is known by all the person skilled in the art that dye compounds in the form of free acid and dye compounds in the form of alkali metal salt (such as sodium salt, potassium salt, etc.) have the same dyeing properties and that the structural formula of each single color dye compound is generally expressed in the form of free acid. However, in the actual synthesis process, they are usually prepared and isolated in the form of alkali metal salt (such as sodium or potassium salt) and also used for dyeing in the form of salt, which is also well known to those skilled in the art.
The preparation method of the reactive navy to black dye composition of the present invention comprises mixing the dye components according to the said ratio. The mixing can adopt a conventional mechanical means, such as performing in a grinder, a kneading machine or a homogenizer. In the mixing process, the individual dye compound may be present in the form of powder, granule, an aqueous solution or a synthetic solution. When the individual dye compound is mixed in the form of the synthetic solution, separation of the reactive navy to black dye composition of the present invention from the synthetic solution can be carried out by a generally known method, for example, the dye is salted out and filtered from a reaction medium with an electrolyte salt (such as sodium chloride or potassium chloride), or the mixture is evaporated and spray dried. Hence, the dye components and their dye compositions generally contain the conventional electrolyte salt(s) (such as sodium chloride, sodium sulfate, etc.) commonly appearing in reactive dyes.
When sold as a commodity or used directly, the reactive navy to black dye composition of the present invention can be without an auxiliary, and can also be added with an auxiliary commonly used in commercial dyes, such as a cosolvent, a dispersant, an alkali-resistant auxiliary, a dustproof agent, a surfactant, a buffer, and an accelerant. Therefore, the present invention also provides a reactive navy to black dye product comprising the reactive navy to black dye composition. Preferably, the reactive navy to black dye product contains the reactive navy to black dye composition and an auxiliary. The weight of the auxiliary does not exceed 45%, preferably 40% of the weight of the reactive navy to black dye composition. The auxiliary is preferably one or more selected from the group consisting of the following compounds: a naphthalene sulfonic acid/formaldehyde condensation product (NNO), a methylnaphthalenesulfonic acid/formaldehyde condensation product (dispersant MF), a diffusing agent CNF (benzylnaphthalenesulfonate/formaldehyde condensation product), Yuanming powder (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium hydrogencarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, a thickener, and the like. All the auxiliaries are commercially available conventional products.
The reactive navy to black dye product of the present invention is suitable for dyeing and printing of nitrogen-containing and/or hydroxyl-containing fiber materials, which may be cellulose fibers, polyamide fibers and fabrics thereof. Wherein, the cellulose fibers are preferably cotton fibers or regenerated fibers, and of course may include other vegetable fibers such as hemp fibers or fabrics thereof; the polyamide fibers preferably include animal fiber materials including skin, wool or silk, and synthetic fiber materials such as nylon 6 and nylon 66. When the above-mentioned fiber materials are dyed and printed by using the reactive navy to black dye product of the present invention, it can be carried out according to known reactive dye dyeing and printing methods, such as a commonly used reactive dye dip dyeing method and pad dyeing method, and the dip dyeing method is a method of immersing a fabric into a dyeing solution to gradually dye the fabric, which usually needs to go through the processes of dyeing-fixing-washing-soaping-washing-dehydration-drying and so on.
The pad dyeing method is a method of firstly immersing the fabric into a dyeing solution, then passing the fabric through a roll, uniformly rolling the dyeing solution into the interior of the fabric, and then treating the fabric by steaming, hot-melting or other treatments, which usually needs to go through the processes of padding with a dye solution-drying-(padding with a fixing solution)-steaming or curing-washing-soaping-washing-drying and so on.
Generally, due to different requirements for the dyed color of the fabrics, the usage amount of dyes is different. When dyed by dip dyeing, the dyeing depth (owf) is generally between 0.1% and 10% (which means the weight of the dye accounts for 0.1%˜-10% of the weight of the fabric), the bath ratio is 1:2 to 1:60 (the bath ratio is defined as the weight ratio of the fabric to the dyeing solution, and preferably is 1:10 to 1:30), the initial dyeing temperature is controlled to be between 30° C. and 60° C., the dyeing time is 10 minutes to 30 minutes, the soaping temperature is 85° C. to 95° C., the soaping time is 10 minutes to 15 minutes, the fixing temperature is 60° C. to 100° C., the fixing time is 10 minutes to 50 minutes, and the fixing pH is 9 to 11. When dyed by the pad dyeing method, the pickup of cellulose fiber is generally 60% to 80%, the steaming temperature is 100° C. to 103° C., and the steaming time is 1 minute to 3 minutes. In padding methods, cold pad-batch dyeing method is widely used, in which a dye and an alkaline substance are introduced into a pad dyeing machine, batched onto a roll and the roll which is covered is turned slowly for 2 hours to 30 hours at room temperature for fixation, and then thoroughly rinsed.
The advantages of the present invention are mainly embodied in that when used for dyeing and printing of nitrogen-containing and/or hydroxyl-containing fiber materials, the reactive navy to black dye composition and product of the present invention have the properties of good build-up, good compatibility, high degree of fixation and color fastness, especially excellent fastness to washing, and the like.
The present invention will be further described in conjunction with the specific examples, but the scope of protection of the present invention is not limited thereto:
The dye compounds used in the examples of the present invention were prepared and separated in the form of their sodium salt in the actual synthesis process, and are also used for dyeing in the form of sodium salt, but for the convenience of writing, all the chemical formulae of the dye compounds in the examples are expressed in the form of free acid, and their substantial dyeing properties are equivalent to the form of sodium salt.
(1) Diazotization:
23.0 g (0.1 mol) of 4-(acetylamino)-2-amino-benzenesulfonic acid were added into 100 g of water and 100 g of ice, beaten for about 1 h, added with 20 g of 31% hydrochloric acid (containing 0.17 mol of HCl), and added with 24 g of a 30% sodium nitrite solution (containing 0.104 mol of sodium nitrite) within 20 min to 30 min. The diazotization reaction was carried out for 1˜2 hours by controlling pH at between 0.5 and 2.0 and temperature T at between 0° C. and 20° C., and the end point of the reaction was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (ie, if no color change within 5 s, the end point was reached). After the diazotization, excess sodium nitrite was eliminated with sulfamic acid, and the diazonium solution of 4-(acetylamino)-2-amino-benzenesulfonic acid was obtained and stored for use.
56.2 g (0.2 mol) of para-ester (p-β-hydroxyethylsulfone sulfate aniline) were added into 200 g of water and 200 g of ice, beaten for about 1 h, added with 35 g of 31% hydrochloric acid (containing 0.3 mol of HCl), and added with 48 g of a 30% sodium nitrite solution (containing 0.208 mol of sodium nitrite) within 20 min to 30 min. The diazotization reaction was carried out for 1˜2 hours by controlling pH at between 0.5 and 2.0 and temperature T at between 0° C. and 20° C., and the end point of the reaction was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (ie, if no color change within 5 s, the end point was reached). After the diazotization, excess sodium nitrite was eliminated with sulfamic acid, and the diazonium solution of the para-ester was obtained and stored for use.
(2) Coupling Reaction:
15.2 g (0.1 mol) of 3,5-dihydroxybenzoic acid were added to 200 g of water for beating, the pH of the solution was controlled to be between 8.0 and 9.0, and the temperature of the solution was controlled to be between 20° C. and 25° C. After the beating, the diazonium solution of 0.1 mol 4-(acetylamino)-2-amino-benzenesulfonic acid obtained in step (1) was added to the 3,5-dihydroxybenzoic acid solution. The pH was controlled to be between 5 and 5.5 with 30% liquid alkali, the temperature was controlled to be between 5° C. and 10° C., the reaction was carried out for 0.5˜2 h, and when the content of the free 3,5-dihydroxybenzoic acid was detected to be below 3% by HPLC, the reaction reached the end point, thereby obtaining chromophore of the following formula (A) whose mass spectrum is shown in
The diazonium solution of the para-ester obtained in step (1) was added to the chromophore of formula (A), the pH was controlled to be between 5 and 5.5 with 30% liquid alkali, and the temperature T was controlled to be between 5° C. and 10° C., the coupling reaction was further carried out for 0.5 h to 10 h. The reaction solution was tested with H acid test solution, if the bleed circle was colorless, it meant that the diazonium had been reacted completely to the end point, thereby obtaining an orange reactive dye compound (I-1) whose λmax is 420 nm in water. And the mass spectrum of the compound (I-1) is shown in
Referring to the preparation method of the azo dye described in example 1, the dye compounds of the structures shown in the following table 1 were respectively obtained by stepwise diazotization and coupling reactions using raw materials of intermediates well known in the art.
25 parts of the dye of formula (I-1), 75 parts of the dye of formula (II-1) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye composition dyed cotton black by conventional dip dyeing, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).
20 parts of the dye of formula (I-1), 76 parts of the dye of formula (II-3), 4 parts of the dye of formula (VI-26) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye composition dyed cotton black by conventional dip dyeing, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).
22 parts of the dye of formula (I-1), 75 parts of the dye of formula (II-3), 3 parts of the dye of formula (IV-1) and 10 parts of sodium sulfate powder were mechanically mixed, and the obtained dye composition dyed cotton dark black by conventional dip dyeing, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).
21 parts of the dye of formula (I-1), 76 parts of the dye of formula (II-3), 1 part of the dye of formula (IV-1), 2 parts of the dye of formula (VI-26), 10 parts of sodium sulfate powder and 10 parts of dispersant MF were mechanically mixed, and the obtained dye composition dyed cotton dark black, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).
17 parts of the dye of formula (I-1), 68 parts of the dye of formula (II-3), 7 parts of the dye of formula (IV-1), 8 parts of the dye of formula (VI-26), 10 parts of sodium sulfate powder and 10 parts of dispersant MF were mechanically mixed, and the obtained dye composition dyed cotton dark black, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).
20 parts of the dye of formula (I-1), 70 parts of the dye of formula (II-1), 10 parts of the dye of formula (III-1), 10 parts of sodium sulfate powder and 10 parts of dispersant MF were mechanically mixed, and the obtained dye composition dyed cotton dark black, and the color fastness to washing of the dyeings, especially on nylon and wool was not lower than grade 4 (referring to ISO 105 C10-2006), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).
According to the method described in one of examples 67-72, the dyes with listed ratio in Table 2 were mechanically mixed, and the obtained dye mixture dyed cotton navy to black by the conventional reactive dyeing method, and the color fastness to washing of the dyeings especially on nylon and wool was not lower than grade 4 (referring to ISO 105 C10-2006), and the build-up was excellent (referring to GB/T21875-2016), and the build-up and degree of fixation were excellent (referring to GB/T21875-2016 and GB/T2391-2014).
2
The dried reactive black dyes obtained in examples 67-72 (closest to the prior art) and comparative examples 1 and 2 were respectively dissolved in water and added with sodium sulfate powder with a final concentration of 50 g/L to prepare a dyeing solution. The dyeing concentration (dye to cloth weight) was set at 4%, the bath ratio (gram weight of cloth to milliliter volume of dyeing solution) was set at 1:20, cotton was placed in the bath for adsorption at 60° C. for 30 minutes, alkali (sodium carbonate 20 g/L) was added for dye fixation for 45 minutes, the dyed fabric was washed with water, soaped, and dried to obtain a navy to black dyed fabric. Tests of fastnesses to washing, perspiration and rubbing were carried out according to methods in ISO 105 C10, ISO 105-E04 and ISO 105 X12. The results are shown in table 2:
The build-up property of the reactive dyes obtained in the representative examples 67-72 of the present invention and comparative examples 1 and 2 was tested according to a method specified in the GB/T 21875-2016 standard, and it was found that the build-up of the reactive dyes of examples 67-72 was obviously better than that of the comparative examples 1 and 2, and that under the same dyeing conditions, the amount of the dye can be reduced by 5% to 15%, which led to remarkable economic effect.
The degree of fixation of the reactive dyes obtained in examples 67˜72 of the present invention and comparative examples 1˜2 was tested according to the method specified in GB/T2391-2014 standard, and the results are shown in Table 3:
In summary, the dyes of the present invention are significantly superior to those of the comparative examples, and for the industry it has a significant improvement in fastness, build-up and degree of fixation.
Number | Date | Country | Kind |
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202011570956.7 | Dec 2020 | CN | national |
Filing Document | Filing Date | Country | Kind |
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PCT/CN2021/104713 | 7/6/2021 | WO |