CN105542510B - Reactive black dye composition and dye product - Google Patents
Reactive black dye composition and dye product Download PDFInfo
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- CN105542510B CN105542510B CN201510571156.XA CN201510571156A CN105542510B CN 105542510 B CN105542510 B CN 105542510B CN 201510571156 A CN201510571156 A CN 201510571156A CN 105542510 B CN105542510 B CN 105542510B
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910006146 SO3M1 Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 abstract description 42
- 238000000034 method Methods 0.000 abstract description 21
- 239000003513 alkali Substances 0.000 abstract description 9
- 238000009980 pad dyeing Methods 0.000 abstract description 8
- 238000007639 printing Methods 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000000975 dye Substances 0.000 description 91
- 239000004744 fabric Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 17
- 238000005859 coupling reaction Methods 0.000 description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 150000003839 salts Chemical group 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000012752 auxiliary agent Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 235000010288 sodium nitrite Nutrition 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 239000000985 reactive dye Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- SRDOTWUOTQTGAK-UHFFFAOYSA-N C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 Chemical compound C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 SRDOTWUOTQTGAK-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- HFIYIRIMGZMCPC-UHFFFAOYSA-J chembl1326377 Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(N=NC=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1N=NC1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-UHFFFAOYSA-J 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WYSWTEPAYPNWDV-UHFFFAOYSA-M sodium;2,4-diaminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C(N)=C1 WYSWTEPAYPNWDV-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- Coloring (AREA)
Abstract
A reactive black dye composition and a dye product are disclosed, wherein the reactive black dye composition comprises a component A, a component B and a component C, the component A is selected from at least one compound shown in a formula (I), the component B is selected from at least one compound shown in a formula (II), the component C is selected from at least one compound shown in a formula (III) and/or a formula (IV), based on the component A, the component B and the component C, the weight part of the component A is 45-95 parts, the weight part of the component B is 5-55 parts, and the weight part of the component C is 0-40 parts. The reactive black dye product contains the reactive black dye composition, has the advantages of good deep dyeing property, excellent lifting force, high fixation rate, good compatibility, excellent color fastness, less dye consumption in the printing and dyeing process, easy washing, clear residual liquid, stable saline-alkali resistance and stable dyeing property, and is suitable for different processes such as dip dyeing, pad dyeing, printing and the like.
Description
(I) technical field
The invention relates to a reactive black dye composition and a dye product.
(II) background of the invention
The black dye is always the chromatogram with the largest dosage in the dye, and in the dyeing and printing of cotton fabrics, the black chromatogram accounts for about 50 percent of the total chromatogram, but the black reactive dye has not been a dye commodity which can be uniformly and completely absorbed in the wavelength range of 400-700 nm. The existing C.I. reactive black 5 accounts for a large proportion in a black color spectrum, but has the defects of small affinity to fibers, low color fixing rate, unsatisfactory blackness and the like, so that the good black reactive dye needs to be prepared by compounding multi-component dyes.
However, the existing reactive black dye color matching products still have the problems of weak deep dyeing property, low color fixing rate, difficult cleaning of dyed fabrics and the like in the practical application process, such as patents CN1195678A, CN103194091A, CN1858118A and the like. The reason is that the dye concentration used in deep-color dyeing is high, the amount of the floating dye is increased, the adsorption of the fiber to the dye has a saturation value, the dye concentration is generally not more than 10% of the saturation value of the dyeing, excessive dye cannot be dyed and fixed, the dye can be accumulated on the surface of the fabric, and if the dye is easy to wash, the wet treatment fastness of the dyed fabric is influenced, so that the dyeing performance is poor.
Disclosure of the invention
The invention aims to provide an active black dye composition and a dye product prepared from the active black dye composition, which have the advantages of good deep dyeing property, excellent lifting force, high fixation rate, good compatibility, excellent color fastness, less dye consumption in the printing and dyeing process, easiness in washing, residual liquid cleaning, stable saline-alkali resistance and stable dyeing property, and are suitable for different processes such as dip dyeing, pad dyeing, printing and the like.
The technical scheme adopted by the invention is as follows:
a reactive black dye composition comprises a component A, a component B and a component C, wherein the component A is selected from at least one compound shown as a formula (I), the component B is selected from at least one compound shown as a formula (II), the component C is selected from at least one compound shown as a formula (III) and/or a formula (IV), based on the component A, the component B and the component C, the weight part of the component A is 45-95 parts, the weight part of the component B is 5-55 parts, and the weight part of the component C is 0-40 parts:
in formula (I):
R1、R2、R3each independently is-H, -C1~C4Alkyl, -C1~C4Alkoxy or-SO3M1preferably-H, -CH3、-OCH3or-SO3M1;Y1is-CH ═ CH2or-C2H4OSO3M1;M1Is H or an alkali metal;
in formula (II):
The other isWherein R is13is-NHCONH2or-NHCOCH3;R14Is H or-OCH3;R15Is H, -OCH3or-SO3M2;M2Is H or an alkali metal;
in the formula (III):
R6、R7each independently is-H or-SO3M3,R8is-SO2Y2or-C1~C4Alkyl, preferably-SO2Y2or-CH3,Y2is-CH ═ CH2or-C2H4OSO3M3,M3Is H or an alkali metal;
in the formula (IV):
R9、R10each independently is-H, -C1~C4Alkyl, -C1~C4Alkoxy or-SO3M4preferably-H, -CH3、-OCH3or-SO3M4;R11is-H or-SO3M4;Y3is-CH ═ CH2or-C2H4OSO3M4;M4Is H or an alkali metal.
Preferably, based on the mass sum of the components A to C, the mass percentage of the component A is 45-95%, the mass percentage of the component B is 5-55%, and the mass percentage of the component C is 0-40%.
More preferably, the active black dye composition comprises a component A, a component B and a component C, wherein the mass percentage of the component A is 45-95%, the mass percentage of the component B is 5-55%, and the mass percentage of the component C is 0-40%.
Particularly preferably, the active black dye composition comprises a component A, a component B and a component C, wherein the mass percentage of the component A is 55-90%, the mass percentage of the component B is 5-40%, and the mass percentage of the component C is 0-35%.
Preferably, when the content of the component C in the reactive black dye composition is not 0, the content of the component C is 3-40% by mass, and more preferably 3-35% by mass.
Preferably, in said formula (I), -SO2Y1Is positioned para or meta to the azo group.
Preferably, in said formula (II), -SO2CH2CH2OSO3M2Is positioned para or meta to the azo group.
Preferably, in said formula (III), -SO2Y2Is positioned para or meta to the azo group.
Preferably, the alkali metal is Li, Na or K; more preferably, the alkali metal is Na or K; even more preferably M1~M4Each independently is preferably H or Na.
Specifically, the component A is preferably one of the following or a mixture of two or more thereof, wherein M is1Is H (free acid form) or Na (salt form):
specifically, the component B is preferably one of the following or a mixture of two or more thereof, wherein M is2Is H (free acid)Form) or Na (salt form):
specifically, the component C is preferably one of the following or a mixture of two or more thereof, wherein M is3、M4Is H (free acid form) or Na (salt form):
particularly preferably, the reactive black dye composition comprises a component A and a component B, wherein the content of the component C is 0, the mass percentage of the component A is 45-95% (more preferably 55-90%), and the mass percentage of the component B is 5-55% (more preferably 10-45%); wherein
The component A is at least one selected from the formulas (I-1) and (I-3);
the component B is at least one selected from the group consisting of the formulas (II-1), (II-5), (II-12) and (II-18).
Or particularly preferably, the reactive black dye composition comprises a component A, a component B and a component C, wherein based on the component A, the component B and the component C, the mass percentage of the component A is 45-95% (more preferably 55-90%), the mass percentage of the component B is 5-55% (more preferably 5-40%), and the mass percentage of the component C is 3-40% (more preferably 3-35%); wherein
The component A is at least one selected from the formulas (I-1) and (I-3);
the component B is at least one selected from the formulas (II-1), (II-5), (II-12) and (II-18);
the component C is at least one selected from the formulas (III-1), (III-2), (III-7), (IV-1) and (IV-3).
Or, more particularly, the reactive black dye composition comprises a component A, a component B and a component C, wherein the component A is 45-95% (more preferably 55-90%) by mass, the component B is 5-55% (more preferably 5-40%) by mass, and the component C is 3-40% (more preferably 3-35%) by mass; wherein
The component A is at least one selected from the formulas (I-1) and (I-3);
the component B is at least one selected from the formulas (II-1), (II-5), (II-12) and (II-18);
the component C is at least one selected from the formulas (III-1), (III-2), (III-7), (IV-1) and (IV-3).
The dye compounds of the formulae (I) to (IV) according to the invention can be used as free acids (M)1~M4is-H) or in the form of a salt, which does not affect the dyeing properties, but for the sake of preparation is preferably in the form of a salt, which may be an alkali metal salt (M)1~M4Is an alkali metal), particularly preferably a sodium or potassium salt (M)1~M4Na or K).
The reactive black dye compositions according to the invention, the dye compounds (I), (II), (III), (IV) used can be obtained by conventional methods, for example by synthesis using suitable components known to the person skilled in the art and using the necessary proportions by means of customary diazotization and coupling reactions, or by reference to the methods or approximations in patents CN101250334, CH695613, WO2013189817 and CN101284950, where the compounds (II) can also be prepared by the following methods:
diazotizing a compound shown in the formula (V), performing coupling reaction with a compound shown in the formula (VI), adding sodium nitrite and glacial hydrochloric acid, uniformly stirring, performing acid coupling reaction with a compound shown in the formula (VII), and adding a diazotized compound shown in the formula (VIII) to perform alkali coupling reaction to obtain a compound shown in the formula (II); or diazotizing the compound of the formula (VIII), carrying out acid coupling reaction on the diazotized compound of the formula (VIII) and the compound of the formula (VII) to obtain an acid coupling substance, diazotizing the compound of the formula (V), carrying out coupling reaction on the diazotized compound of the formula (V) and the compound of the formula (VI), and carrying out alkali coupling reaction on the diazotized compound of the formula (V) and the acid coupling substance to obtain the compound of the formula (II).
R12、R13、R14、R15、M2The definition of (A) is as above.
In the reactive black dye composition, phenolic hydroxyl groups in the formula (I) and/or the formula (IV) are easy to oxidize to form a quinone hydrazone structure, so that the dye compounds shown in the formula (I) and the formula (IV) can be respectively characterized by adopting the following structures:
the substituents in the above two formulae are defined as in formulae (I) and (IV).
The preparation method of the reactive black dye composition comprises the steps of mixing the dye component A, B, C according to the proportion, wherein the mixing can be carried out by adopting a conventional mechanical mode, for example in a mill, kneader or homogenizer, in which the individual dye compounds (I) to (IV) can be present in the form of powders, granules, aqueous solutions or synthetic solutions, when the individual dye compounds are mixed in the form of a synthesis solution, the isolation of the complex reactive black dyes according to the invention from the synthesis solution can be carried out by generally known methods, for example by salting out the dyes from the reaction medium with electrolytes, such as sodium chloride or potassium chloride, or the mixed solution is evaporated and spray dried, and thus, the dye component A, B, C and the dye composition thereof generally contain electrolyte salts (such as sodium chloride, sodium sulfate, etc.) which are conventional in reactive dyes.
When the active black dye composition is sold as a commodity or applied to textile material coloring, no auxiliary agent is added, and conventional auxiliary agents in the commodity dye, such as a cosolvent, a dispersing agent, an alkali-resistant auxiliary agent, a dust-proof agent, a surfactant, a buffering agent, an accelerating agent and the like, can also be added. Therefore, the invention also provides a reactive black dye product which contains the reactive black dye composition. Preferably, the reactive black dye product mainly comprises the reactive black dye composition and an auxiliary agent, and the weight ratio of the reactive black dye composition to the auxiliary agent is 100:0 to 45, preferably 100:0 to 40. The auxiliary agent is preferably one or the combination of any several of the following components: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), dispersant CNF (benzylnaphthalenesulfonate formaldehyde condensate), anhydrous sodium sulfate (industrial sodium sulfate). The auxiliary agents are all conventional types sold in the market.
The reactive black dye composition and the dye product are suitable for printing and dyeing of cellulose fibers, polyamide fibers and fabrics thereof, wherein the cellulose fibers are preferably cotton fibers or regenerated fibers, and can also comprise other plant fibers, such as hemp fibers or fabrics; the polyamide fiber is preferably an animal fiber material including a sheath, a wool or a silk, and a synthetic fiber material such as nylon 6 and nylon 66. When the reactive black dye product is used for printing and dyeing the fiber materials, the dyeing can be carried out according to a known reactive dye dyeing method, such as a common reactive dye dip dyeing method and a pad dyeing method, wherein the dip dyeing method is a method for dipping the fabric into a dye solution to gradually dye the fabric, and the procedures of dyeing, fixing color, washing, soaping, washing, dewatering, drying and the like are generally required.
The pad dyeing is a dyeing method that a fabric is soaked in a dye solution, then the fabric passes through a roller, the dye solution is uniformly rolled into the fabric, and then the fabric is steamed or hot-melted and the like, and generally the procedures of pad dyeing, drying- (pad fixing solution), steaming or baking, washing, soaping, washing, drying and the like are needed.
Generally, the dye usage amount is different due to different dyeing requirements on fabrics, when a dip dyeing method is used for dyeing, the dyeing depth (owf) is generally 0.1-10% (the dye accounts for the weight percent of the fabrics), the bath ratio is 1: 2-1: 60 (the weight ratio of the fabrics to the dye liquor is preferably 1: 10-1: 30), the initial dyeing temperature is controlled to be 30-60 ℃, the dyeing time is 10-30 minutes, the soaping temperature is 85-95 ℃, the soaping time is 10-15 minutes, the color fixing temperature is 60-100 ℃, the color fixing time is 10-50 minutes, and the color fixing pH value is 9-11. When the pad dyeing method is used for dyeing, the pad retention rate of the cellulose fiber is generally 60-80%, the steaming temperature is 100-103 ℃, and the steaming time is 1-3 minutes. In the pad dyeing method, a cold pad-batch dyeing method is frequently used at present, and a dye and an alkaline substance are introduced into a pad dyeing machine, coiled and stacked at room temperature for 2-30 hours for color fixation, and then thoroughly rinsed.
The invention has the following beneficial effects: the reactive black dye composition and the dye product have the advantages of good promotion, high fixation rate, good compatibility, easy washing, clear dyeing residual liquid, stable saline-alkali resistance, excellent color fastness and obvious cost advantage when being used for printing and dyeing fabrics, and are rare economical black dyes.
(IV) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
it is to be expressly noted that, for the sake of convenient and uniform characterization of the dye compounds, the individual monochromatic dyes of the color-matching components are present in the form of the free acids, whereas in the actual production process, the individual monochromatic components are usually present in the form of alkali metal salts, preferably lithium, sodium or potassium salts, particularly preferably sodium salts, and are used for dyeing in the form of their salts.
Compound of formula (ii) preparation example 1:
1. weighing 14.6g (0.02mol) of 53 percent sulfonated para-ester, adding water, pulping for 0.5h, slowly dropwise adding 5.06g (0.022mol) of 30 percent sodium nitrite solution under the conditions that the pH is 0.8-1.4 and the temperature is 14-17 ℃ to perform diazotization reaction, judging whether the sodium nitrite is excessive every 0.5h, reacting for 2h, and controlling the amino reagent to be not yellow at the reaction end point;
2. weighing 4.6g (0.02mol) of 65 percent meta-urea, slowly adding the meta-urea into the diazo component, adjusting the pH value to 4.5-5.0, carrying out coupling reaction for 2h at the temperature of 10-15 ℃, and finishing the reaction when the liquid phase purity reaches 80 percent;
3. adjusting the pH value of the coupling liquid to 6.5-6.7, adding 5.06g (0.022mol) of 30% sodium nitrite solution, uniformly stirring, slowly dripping into 5.9g (0.05mol) of 31% ice hydrochloric acid within 40-60min, continuously stirring for reacting for 3h, and judging whether the sodium nitrite is excessive every 0.5 h;
4. weighing 5.1g (0.02mol) of 82.5% sodium 2, 4-diaminobenzenesulfonate, adding into the reaction solution in the step 3, and controlling the pH to be 3-3.5 to perform acid coupling reaction for 2 hours;
5. weighing 28.7g (0.1mol) of para-ester with the content of 98%, 100mL of bottom water and 100g of ice, pulping for 1h, adding 15g (0.127mol) of 31% ice hydrochloric acid and 5.06g (0.022mol) of 30% sodium nitrite solution, reacting for 2h to obtain para-ester diazo, controlling potassium iodide test paper to slightly show blue, and eliminating sodium nitrite for later use;
6. adjusting the acid coupling product in the step 4 to perform alkali coupling reaction with the para-ester diazo in the step 5 under the conditions that the pH value is 5.0-5.5 and the temperature is 10-15 ℃, and obtaining the reactive dye compound (II-1), lambdamax=525nm。(M2Is H, i.e. the dye compound is represented in the form of the free acid)
Prepared according to the above preparation method using different diazo and coupling components, the following Table 1 can be prepared
Structure (M) shown in2Is H, i.e. the dye compound is represented in the free acid form):
TABLE 1
The structures shown in Table 2 below (M) were obtained by varying the coupling sequence and starting materials, respectively2Is H, i.e. the dye compound is represented in the free acid form):
TABLE 2
Example 23:
85 parts of the dye of the formula (I-3), 15 parts of the dye of the formula (II-1) and 20 parts of anhydrous sodium sulphate are mechanically mixed to obtain the composite dye, and the obtained composite dye is used for dyeing black cotton (M)1~M2Both H, i.e. the dye compound is represented in the free acid form).
Example 24:
20 parts of the dye of the formula (I-1), 45 parts of the dye of the formula (I-3), 25 parts of the dye of the formula (II-5), 10 parts of the dye of the formula (III-1) and 30 parts of anhydrous sodium sulphate are mechanically mixed, and the obtained composite dye is used for dyeing cotton to be black (M)1~M3Both H, i.e. the dye compound is represented in the free acid form).
Examples 25 to 72:
the dyes in the proportions listed in Table 3 were mechanically mixed and dyed black (M) in cotton1~M4Both H, i.e. the dye compound is represented in the free acid form).
TABLE 3
The application example is as follows:
the dry reactive black dyes prepared in the embodiments 23-72 of the invention are respectively dissolved in water, and 50g/L of anhydrous sodium sulphate is added to prepare dye liquor. The dyeing concentration is 4% (dye to cloth weight, if 100 parts of cotton cloth needs 4 parts of dye), the bath ratio is 1:20 (cloth weight (g): volume of dye liquor (ml)), the cotton cloth is placed into the bath for adsorption for 30 minutes at 60 ℃, soda (the amount is 15-20 g/L) is added for fixation for 45 minutes, and the dyed fabric is washed, soap boiled and dried to obtain the black dyed fabric. The dye has high fixation rate and low chroma of dyeing residual liquid.
(1) Color fastness
The fastness to washing is tested according to GB/T3921-2008, and the temperature is 60 ℃:
the original color change is more than or equal to 4-5 grades; staining is more than or equal to 4 grade
The rubfastness was tested according to ISO 105-X12:
dry friction: grade 4-5 or more; wet friction: not less than 3-4 grade
(2) Saline-alkali resistance: when the dye is used for dyeing, the salt dosage, the pH value and the strength are respectively increased, and the influence on color light is basically avoided, so that the salt and alkali resistance of the active black dye is stable.
Contrast staining experiment:
comparative example 1 according to example 15 of patent CN1195678A, the following two-component reactive black dye was prepared:
comparative example 2 the following two-component reactive black dye was prepared according to example 23 of patent CN 103194091A:
comparative example 3 according to example 1 of patent CN1858118A, the following three-component reactive black dye was prepared:
comparative example 4 the following three-component reactive black dye was prepared according to example 24 of patent CN 103194091A:
the results of selecting examples 23, 26, 27 and 41, which are the closest to comparative examples 1 to 4, for the lifting force (K/S values at different dyeing depths) comparison according to the method described in the application examples are shown in table 4 below:
TABLE 4
Depth of dyeing | 2.0% | 4.0% | 6.0% | 8.0% | 10.0% | 12.0% |
Example 1 | 14.58 | 27.83 | 34.85 | 41.79 | 43.18 | 46.02 |
Example 4 | 14.76 | 27.35 | 34.04 | 41.95 | 43.95 | 47.11 |
Example 5 | 14.46 | 27.81 | 34.75 | 41.31 | 43.59 | 46.62 |
Example 19 | 14.51 | 27.28 | 34.34 | 41.52 | 43.65 | 46.88 |
Comparative example 1 | 12.76 | 24.73 | 31.34 | 37.79 | 39.14 | 41.75 |
Comparative example 2 | 13.74 | 25.12 | 32.36 | 38.21 | 40.28 | 42.35 |
Comparative example 3 | 13.33 | 25.62 | 33.40 | 39.89 | 41.20 | 43.53 |
Comparative example 4 | 14.38 | 26.54 | 33.29 | 39.78 | 42.36 | 43.72 |
As can be seen from the above table, the deep dyeing property (lifting power) of the present invention is significantly better than that of the comparative example as the dyeing depth increases.
Claims (12)
1. A reactive black dye composition comprises a component A, a component B and a component C, wherein the component A is selected from at least one compound shown in a formula (I), the component C is selected from at least one compound shown in a formula (III) and/or a formula (IV), based on the component A, the component B and the component C, the component A is 45-95 parts by weight, the component B is 5-55 parts by weight, and the component C is 0-40 parts by weight:
in formula (I):
R1、R2、R3each independently is-H, -C1~C4Alkyl, -C1~C4Alkoxy or-SO3M1;Y1is-CH ═ CH2or-C2H4OSO3M1;M1Is H or an alkali metal;
in the formula (III):
R6、R7each independently is-H or-SO3M3,R8is-SO2Y2or-C1~C4Alkyl radical, Y2is-CH ═ CH2or-C2H4OSO3M3,M3Is H or an alkali metal;
in the formula (IV):
R9、R10each independently is-H, -C1~C4Alkyl, -C1~C4Alkoxy or-SO3M4;R11is-H or-SO3M4;Y3is-CH ═ CH2or-C2H4OSO3M4;M4Is H or an alkali metal; the component B is one of the following or more than two of the followingMixture of M in which2Is H or Na:
2. the reactive black dye composition according to claim 1, wherein: based on the sum of the components A to C, the mass percentage of the component A is 45-95%, the mass percentage of the component B is 5-55%, and the mass percentage of the component C is 0-40%.
6. the reactive black dye composition according to claim 5, wherein: the content of the component C in the reactive black dye composition is 0, and based on the component A and the component B, the reactive black dye composition comprises 45-95% of the component A and 5-55% of the component B: wherein
The component A is at least one selected from the formulas (I-1) and (I-3);
the component B is at least one selected from the group consisting of the formulas (II-1), (II-5), (II-12) and (II-18).
7. The reactive black dye composition according to claim 5, wherein: the reactive black dye composition comprises 45-95% of component A, 5-55% of component B and 3-40% of component C: wherein
The component A is at least one selected from the formulas (I-1) and (I-3);
the component B is at least one selected from the formulas (II-1), (II-5), (II-12) and (II-18);
the component C is at least one selected from the formulas (III-1), (III-2), (III-7), (IV-1) and (IV-3).
8. The reactive black dye composition according to claim 1, wherein: the active black dye composition comprises a component A, a component B and a component C, wherein based on the component A, the component B and the component C, the mass percentage of the component A is 45-95%, the mass percentage of the component B is 5-55%, and the mass percentage of the component C is 0-40%.
9. The reactive black dye composition according to claim 8, wherein: the active black dye composition is based on the component A, the component B and the component C, and consists of 45-95% of the component A, 5-55% of the component B and 3-40% of the component C: wherein
The component A is at least one selected from the formulas (I-1) and (I-3);
the component B is at least one selected from the formulas (II-1), (II-5), (II-12) and (II-18);
the component C is at least one selected from the formulas (III-1), (III-2), (III-7), (IV-1) and (IV-3).
10. The reactive black dye composition according to any one of claims 1 to 4 or 6 to 9, wherein: the phenolic hydroxyl of the dye compound shown in the formula (I) and/or the formula (IV) is oxidized to form a quinone hydrazone structure, and the quinone hydrazone structures of the dye compounds shown in the formula (I) and the formula (IV) are respectively shown as follows:
the substituents in the above two formulae are defined as in formulae (I) and (IV).
11. The reactive black dye composition according to claim 5, wherein: the phenolic hydroxyl of the dye compound shown in the formula (I) and/or the formula (IV) is oxidized to form a quinone hydrazone structure, and the quinone hydrazone structures of the dye compounds shown in the formula (I) and the formula (IV) are respectively shown as follows:
the substituents in the above two formulae are defined as in formulae (I) and (IV).
12. A reactive black dye preparation comprising the reactive black dye composition of claim 1.
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