WO2022134532A1 - 一种活性染料化合物及其制备方法和应用 - Google Patents

一种活性染料化合物及其制备方法和应用 Download PDF

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WO2022134532A1
WO2022134532A1 PCT/CN2021/104710 CN2021104710W WO2022134532A1 WO 2022134532 A1 WO2022134532 A1 WO 2022134532A1 CN 2021104710 W CN2021104710 W CN 2021104710W WO 2022134532 A1 WO2022134532 A1 WO 2022134532A1
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formula
reactive dye
dye compound
iib
iic
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PCT/CN2021/104710
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French (fr)
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何旭斌
王专
何权辉
赵朋
沈建良
方舒逸
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浙江科永化工有限公司
上海科华染料工业有限公司
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Publication of WO2022134532A1 publication Critical patent/WO2022134532A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
    • C09B62/006—Azodyes
    • C09B62/01—Disazo or polyazo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group

Definitions

  • the present invention relates to a reactive dye compound, in particular to a reactive dye compound and its preparation method and its application in the printing and dyeing of cellulose fibers, polyamide fibers and their fabrics.
  • the extension of the dye-conjugated system is beneficial to improve the directness of the dye, thereby improving its dyeing rate and color fixing rate.
  • new polyazo reactive dyes in the prior art such as published patents CN1266869A, CN105694530A, CN101319096A, etc., due to the increase of the conjugated system, the exhaustion rate and the color fixation rate have improved a lot, but the resistance to washing and The rubbing fastness is not good, especially the color fastness to washing and staining can not meet the production requirements well.
  • the inventors developed a new polyazo reactive dye structure, using 3,5-diaminobenzoic acid as the coupling component, and carried out in-depth and meticulous research on this compound, based on a large number of experiments. , and obtained polyazo reactive dyes with excellent properties such as rubbing resistance and washing fastness.
  • the first object of the present invention is to provide a reactive dye compound with novel structure and excellent performance.
  • the second object of the present invention is to provide a preparation method of reactive dye compounds.
  • the third object of the present invention is to provide the application of the reactive dye compounds in the printing and dyeing of cellulose fibers, polyamide fibers or fabrics thereof.
  • the present invention provides a reactive dye compound, which is a compound represented by the following formula (I) or an alkali metal salt thereof:
  • D 1 and D 2 are each independently a group represented by the following formula (a) or (b):
  • R 1 and R 2 are each independently hydrogen, oxygen, -COR 7 , C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted by hydroxyl, sulfonic acid or carboxyl, wherein R 7 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl or -NH 2 ;
  • R 3 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxyl or sulfonic acid group;
  • R 4 -R 6 are each independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or sulfonic acid group;
  • the C 1 -C 4 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; the C 1 -C 4 The alkoxy group can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.
  • D 1 and D 2 are both groups represented by formula (a) or (b). More preferably, D 1 and D 2 are both groups represented by formula (a).
  • R 1 and R 2 are each independently hydrogen, -COR 7 , wherein R 7 is methyl or -NH 2 .
  • R 3 is hydrogen, methyl, methoxy, carboxyl or sulfonic acid.
  • R 4 to R 6 are each independently hydrogen, methyl, methoxy or sulfonic acid group.
  • group represented by formula (a) is selected from one of the following groups:
  • the group represented by formula (b) is selected from one of the following groups:
  • the present invention specifically recommends that the compound represented by the formula (I) is selected from one of the following structures:
  • the compound represented by the formula (I) is selected from one of the compounds represented by the formulae (I-1) to (I-28) and the formulae (I-48) to (I-55).
  • the compound represented by the formula (I) is selected from (I-1), (I-2), (I-4), (I-5), (I-6), (I-7) ) at least one of them.
  • the reactive dye compound of the present invention can be the alkali metal salt of the compound represented by the formula (I). form exists.
  • the alkali metal salt is a sodium salt or a potassium salt.
  • the present invention provides a preparation method of the reactive dye compound, comprising:
  • arylamine compounds represented by formula (IIa), formula (IIb) and/or formula (IIc) are respectively diazotized to obtain their respective diazonium salts as required;
  • 3,5-diaminobenzoic acid is added to water and beating, and the beating solution is first coupled with the diazonium salt of the aromatic amine compound represented by formula (IIa) in step (1), and then with formula (IIb)
  • the diazonium salt of the arylamine compound shown or the diazonium salt of the arylamine compound shown by the formula (IIc) is coupled for the second time, and then it is coupled with the diazonium salt of the arylamine compound shown by the formula (IIb) or the formula (IIb).
  • the diazonium salt of the aromatic amine compound shown in (IIc) is coupled for the third time to obtain the reactive dye compound;
  • the concrete synthesis step of described reactive dye compound is as follows:
  • the detection end point of the ethanol solution that is, the end point is reached if the color does not change within 5s
  • the excess sodium nitrite is eliminated with sulfamic acid, and the formula (IIa), formula (IIb) or formula (IIc) is obtained, respectively.
  • the diazo liquid of the arylamine compound shown is preserved for subsequent use; wherein, the mol ratio of the arylamine compound shown in formula (IIa), formula (IIb) or formula (IIc) to hydrochloric acid and sodium nitrite is 1:(1- 3): (1-1.1), preferably 1: (1-1.8): (1-1.05);
  • the diazo liquid of formula (IIb) or the diazo liquid of formula (IIc) obtained in step (1) is added to the coupling product 1, and the pH is controlled at 5.0-8.0 with liquid caustic soda or baking soda, and the temperature is controlled at 0- At 20°C, carry out the second coupling reaction, test the diazonium with H acid test solution, the infiltration circle is colorless, that is, the diazonium has reacted completely to the end point, and the coupling product 2 is obtained;
  • the diazo liquid of formula (IIb) or the diazo liquid of formula (IIc) obtained in step (1) is added to the coupling product 2, and the pH is controlled at 5.0-8.0 with liquid caustic soda or baking soda, and the temperature is controlled at 0 -20°C, carry out the third coupling reaction, test the diazo with H acid test solution, the infiltration circle is colorless, that is, the diazo has reacted completely to the end point, and the reactive dye compound can be obtained;
  • the molar ratio of the aromatic amine compound represented by formula (IIa), formula (IIb) or formula (IIc) to 3,5-diaminobenzoic acid is controlled to be (0.95-1.2): 1, preferably (0.98-1.08): 1.
  • the second coupling reaction and the third coupling reaction can be combined into one coupling reaction, that is, the second coupling reaction and
  • the third coupling reaction is changed to: then add the diazo liquid of the aromatic amine compound represented by the formula (IIb) or the diazo liquid of the aromatic amine compound represented by the formula (IIc) obtained in step (1) to the coupling product 1 , use liquid caustic soda or baking soda to control pH at 5.0-8.0 and temperature at 0-20°C, carry out the second coupling reaction, test diazonium with H acid test solution, the infiltration circle is colorless, that is, diazonium has reacted completely At the end point, the reactive dye compound can be obtained, wherein the molar ratio of the aromatic amine compound represented by formula (IIb) or formula (IIc) to 3,5-diaminobenzoic acid is controlled to be (1.9-2.4): 1 , preferably (1.96-2.16
  • the reactive dye compound of the present invention is also allowed to have by-products with a content of not more than 30% in the preparation process.
  • the by-products can be directly used for the processing of commercial dyes without separation, including but not limited to the following structures.
  • the reactive dye compounds of the present invention are usually prepared and isolated in the form of their alkali metal salts (such as sodium or potassium salts) in the actual synthesis process, and are also used for dyeing in the form of their salts, which is also the present invention.
  • alkali metal salts such as sodium or potassium salts
  • the carboxyl and sulfonic acid groups in formula (I) can exist in the form of alkali metal salts of carboxylic acids (such as sodium carboxylate) and alkali metal salts of sulfonic acids (such as sodium sulfonate).
  • the reactive dye compounds of the present invention may exist in the form of powders, granules, aqueous solutions or synthetic solutions, and the isolation of the reactive dye compounds of the present invention from synthetic solutions can be carried out by generally known methods, such as with electrolytes (such as sodium chloride) or potassium chloride) from the reaction medium, the dye is salted out and filtered out, or the solution is evaporated and spray-dried. Therefore, the dye compound usually contains conventional electrolyte salts (such as sodium chloride, sodium sulfate, etc.) in reactive dyes.
  • electrolytes such as sodium chloride
  • potassium chloride potassium chloride
  • the present invention provides the application of the reactive dye compound in the printing and dyeing of cellulose fibers, polyamide fibers or fabrics thereof.
  • the present invention also provides a reactive dye preparation, which contains the reactive dye compound.
  • the reactive dye product contains the reactive dye compound and auxiliary agent, wherein the weight of the auxiliary agent does not exceed 45% of the weight of the reactive dye compound, preferably does not exceed 40%.
  • auxiliary agent is preferably one or any combination of the following: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersing agent MF), diffusing agent CNF (benzylnaphthalenesulfonate) Formaldehyde condensate), Yuanming powder (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener, etc.
  • the auxiliary agents are all commercially available conventional varieties.
  • the reactive dye compounds and reactive dye products of the present invention are suitable for the printing and dyeing of cellulose fibers, polyamide fibers and their fabrics, wherein the cellulose fibers are preferably cotton fibers or regenerated fibers, and of course other vegetable fibers can also be included, Such as hemp fibers or fabrics; polyamide fibers preferably include animal fiber materials including leather, wool or silk, as well as synthetic nylon 6, nylon 66 and other fiber materials.
  • the reactive dye compound or reactive dye product of the present invention to print and dye the above-mentioned fiber material, it can be carried out according to the known reactive dye dyeing method, such as the commonly used reactive dye dyeing method and pad dyeing method.
  • the method of immersing the fabric in the dye solution to gradually dye the fabric with the dye usually requires the processes of dyeing, color fixing, water washing, soaping, water washing, dehydration, and drying.
  • the said pad dyeing is a dyeing method in which the fabric is first immersed in the dye liquor, and then the fabric is passed through the rollers, the dye liquor is evenly rolled into the fabric, and then the dyeing method is processed by steaming or hot melting. Liquid-drying-(paddle fixing solution)-steaming or baking-washing-soap washing-washing-drying and other processes.
  • the amount of dye used will also be different.
  • the dyeing depth (owf) is generally 0.1% to 10% (dye accounts for the weight of the fabric), and the bath ratio is 1: 2 ⁇ 1:60 (weight ratio of fabric to dye liquor, preferably 1:10 ⁇ 1:30)
  • initial dyeing temperature is controlled at 30 ⁇ 60°C
  • dyeing time is 10 ⁇ 30 minutes
  • soap cooking temperature is 85 ⁇ 95°C
  • fixing temperature 60-100°C fixing time 10-50 minutes
  • fixing pH 9-11 the padding rate of cellulose fibers is generally 60-80%
  • the steaming temperature is 100-103°C
  • the steaming time is 1-3 minutes.
  • the cold pad stack dyeing method is more commonly used at present.
  • the dyes and alkaline substances are introduced into the pad dyeing machine, and they are rolled and stacked at room temperature for 2 to 30 hours to fix the color, and then thoroughly rinsed. .
  • the beneficial effects of the present invention are as follows: the reactive dye compound of the present invention has novel structure, good washing fastness and rubbing fastness, and good bonding stability with fibers, and is suitable for cotton, rayon, silk, Dyeing and printing of fibers such as wool.
  • Fig. 1 is the mass spectrum of compound (I-1) prepared in Example 1:
  • FIG. 2 is a mass spectrum of the chromophore (A) prepared in Example 1.
  • FIG. 2 is a mass spectrum of the chromophore (A) prepared in Example 1.
  • the reactive dye compounds of the present invention are prepared and isolated in the form of their sodium salts in the actual synthesis process described in the examples, and are also used for dyeing in the form of sodium salts, but for the convenience of writing, in the examples All chemical formulas of the reactive dye compounds are embodied in the form of free acid, and their substantial dyeing properties are equivalent to the form of sodium salt.
  • para-ester p- ⁇ -hydroxyethylsulfone sulfate aniline
  • hydrochloric acid containing HCl 0.3mol
  • 20- Add 48g 30% sodium nitrite solution containing 0.208mol of sodium nitrite
  • control pH 0.5-2.0
  • formaldehyde detects the end point (that is, no discoloration within 5s). After the diazo end point is reached, the excess sodium nitrite is eliminated with sulfamic acid, and the obtained para-ester diazo liquid is stored for later use.
  • Amino-2-aminobenzenesulfonic acid diazo liquid is added to the beaten 3,5-diaminobenzoic acid solution, the pH is controlled at 5-5.5 with 30% liquid alkali, the temperature is controlled at 5-10 °C, and the reaction is 0.5- In 2.5h, the free 3,5-diaminobenzoic acid was controlled by HPLC to reach the end point below 3%, and the chromophore represented by the following formula (A) was obtained, and the mass spectrum was shown in FIG. 2 .
  • the mass spectrum of compound (I-1) is shown in Fig. 1 .
  • the reactive dyes prepared in Examples 1-66 of the present invention and Comparative Examples 1-3 were taken, respectively dissolved in water, and 50 g/L of Yuanming powder was added to prepare a dye liquor.
  • Dyeing concentration 4% (dye to cloth weight), bath ratio 1:20 (cloth weight in grams to dye liquor volume in milliliters), put into cotton cloth at 60°C for adsorption for 30 minutes, add alkali (sodium carbonate 20g/L) to fix the color 45 minutes.
  • the dyed fabrics are washed, soaped and dried to obtain yellow to orange dyed fabrics. According to the methods in ISO 105 C10-2006 and ISO 105 X12, the color fastness to washing and rubbing fastness were tested respectively. The results are shown in Table 2:
  • the reactive dye compounds of the present invention have obvious improvements in color fastness to washing and rubbing fastness compared with the existing dyes.

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Abstract

本发明提供了一种活性染料化合物及其制备方法和应用，所述活性染料化合物是结构如下式(Ⅰ)所示的化合物或者其碱金属盐，式(Ⅰ)中，D1、D2各自独立为下式(a)或(b)所示的基团。本发明提供了所述活性染料化合物在纤维素纤维、聚酰胺纤维及其织物印染中的应用。本发明的活性染料化合物结构新颖，耐水洗牢度和耐摩擦牢度好，与纤维结合稳定性好，适用于棉、人造棉、丝绸、羊毛等纤维的染色和印花。

Description

一种活性染料化合物及其制备方法和应用 (一)技术领域
本发明涉及一种活性染料化合物，特别涉及一种活性染料化合物及其制备方法和在纤维素纤维、聚酰胺纤维及其织物印染中的应用。
(二)背景技术
染料共轭系统的延伸有利于提高染料的直接性，从而提高其上染率和固色率。现有技术中开发多偶氮新型活性染料的报道也不少，如公开专利CN1266869A、CN105694530A、CN101319096A等，由于共轭系统的增加，竭染率和固色率提高了不少，但耐水洗和耐摩擦牢度欠佳，特别是耐水洗沾色牢度不能很好地满足生产要求。
为解决上述问题，本发明人开发了新的多偶氮活性染料结构，采用3,5-二氨基苯甲酸为偶合组分，并对该化合物进行了深入细致的研究，在大量实验的基础上，获得了耐摩擦、耐水洗牢度等性能俱佳的多偶氮活性染料。
(三)发明内容
本发明的第一个目的在于提供结构新颖、性能优异的活性染料化合物。
本发明的第二个目的是提供一种活性染料化合物的制备方法。
本发明的第三个目的是提供所述活性染料化合物在纤维素纤维、聚酰胺纤维或其织物印染中的应用。
下面对本发明所采用的技术方案进行具体说明。
第一方面，本发明提供了一种活性染料化合物，其是结构如下式(Ⅰ)所示的化合物或者其碱金属盐：
Figure PCTCN2021104710-appb-000001
式(Ⅰ)中：
D 1、D 2各自独立为下式(a)或(b)所示的基团：
Figure PCTCN2021104710-appb-000002
上式(Ⅰ)、式(a)和(b)中：
R 1、R 2各自独立为氢、氧、-COR 7、C 1～C 4烷基或被羟基、磺酸基或羧基取代的C 1～C 4烷基，其中R 7为C 1～C 4烷基、C 2～C 4烯基或-NH 2；
R 3为氢、C 1～C 4烷基、C 1～C 4烷氧基、羧基或磺酸基；
R 4～R 6各自独立为氢、C 1～C 4烷基、C 1～C 4烷氧基或磺酸基；
X 1、X 2各自独立为-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3，其中Y 1～Y 3各自独立为-CH＝CH 2、-CH 2CH 2OSO 3H或-CH 2CH 2Cl，p＝1-3，q＝1-3。
本发明中，所述的C 1～C 4烷基可以是甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等；所述的C 1～C 4烷氧基可以是甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、叔丁氧基等。
作为优选，D 1、D 2同时为式(a)或(b)所示的基团。进一步优选D 1、D 2同时为式(a)所示的基团。
作为优选，R 1、R 2各自独立为氢、-COR 7，其中R 7为甲基或-NH 2。
作为优选，R 3为氢、甲基、甲氧基、羧基或磺酸基。
作为优选，R 4～R 6各自独立为氢、甲基、甲氧基或磺酸基。
作为优选，X 1、X 2各自独立为-SO 2Y 1、-NHCOCH 2CH 2SO 2Y 2或-CONHCH 2CH 2SO 2Y 3，其中Y 1～Y 3各自独立为-CH＝CH 2或-CH 2CH 2OSO 3H。
作为进一步的优选，式(a)所示的基团选自下列基团之一：
Figure PCTCN2021104710-appb-000003
作为进一步的优选，式(b)所示的基团选自下列基团之一：
Figure PCTCN2021104710-appb-000004
本发明具体推荐所述式(I)所示的化合物选自下列结构之一：
Figure PCTCN2021104710-appb-000005
Figure PCTCN2021104710-appb-000006
Figure PCTCN2021104710-appb-000007
Figure PCTCN2021104710-appb-000008
Figure PCTCN2021104710-appb-000009
Figure PCTCN2021104710-appb-000010
Figure PCTCN2021104710-appb-000011
Figure PCTCN2021104710-appb-000012
Figure PCTCN2021104710-appb-000013
Figure PCTCN2021104710-appb-000014
Figure PCTCN2021104710-appb-000015
Figure PCTCN2021104710-appb-000016
Figure PCTCN2021104710-appb-000017
Figure PCTCN2021104710-appb-000018
Figure PCTCN2021104710-appb-000019
Figure PCTCN2021104710-appb-000020
Figure PCTCN2021104710-appb-000021
本发明进一步优选所述式(I)所示的化合物选自式(Ⅰ-1)～(Ⅰ-28)、式(Ⅰ-48)～(Ⅰ-55)所示的化合物之一。
更进一步优选，所述式(I)所示的化合物选自(Ⅰ-1)、(Ⅰ-2)、(Ⅰ-4)、(Ⅰ-5)、(Ⅰ-6)、(Ⅰ-7)中 的至少一种。
本发明所述的活性染料化合物可以是式(I)所示化合物的碱金属盐，此时式(Ⅰ)中的羧基、磺酸基以羧酸的碱金属盐、磺酸的碱金属盐的形式存在。作为优选，所述的碱金属盐为钠盐或钾盐。
第二方面，本发明提供了一种所述活性染料化合物的制备方法，包括：
(1)重氮化：
根据需要将式(Ⅱa)、式(Ⅱb)和/或式(Ⅱc)所示的芳胺化合物分别进行重氮化，得到各自的重氮盐；
(2)偶合反应：
将3,5-二氨基苯甲酸加水打浆，打浆好的溶液与步骤(1)中的式(Ⅱa)所示的芳胺化合物的重氮盐进行第一次偶合，接着再与式(Ⅱb)所示的芳胺化合物的重氮盐或式(Ⅱc)所示的芳胺化合物的重氮盐进行第二次偶合，然后再与式(Ⅱb)所示的芳胺化合物的重氮盐或式(Ⅱc)所示的芳胺化合物的重氮盐进行第三次偶合，即得到所述的活性染料化合物；
Figure PCTCN2021104710-appb-000022
上述式(Ⅱa)～式(Ⅱc)各取代基定义同式(Ⅰ)。
作为优选，所述活性染料化合物的具体合成步骤如下：
(1)重氮化：
根据需要将式(Ⅱa)、式(Ⅱb)和/或式(Ⅱc)所示的芳胺化合物各自与水、冰一起打浆1～2h，打浆完成后加入一定量的盐酸，然后在20-30min内加入亚硝酸钠溶液，控制pH＝0.5-3.0(优选为0.5-2.0)、温度T＝0-30℃(优选为0-20℃)进行重氮化反应，用4-二甲氨基苯甲醛的乙醇溶液检测终点(即5s内不变色则到达终点)；重氮终点到后，用氨基磺酸消除过量的亚硝酸钠，分别得到式(Ⅱa)、式(Ⅱb)或式(Ⅱc)所示的芳胺化合物的重氮液保存备用；其中，式(Ⅱa)、式(Ⅱb)或式(Ⅱc)所示的芳胺化合物各自与盐酸、亚硝酸钠的摩尔比为1:(1-3):(1-1.1)，优选为1:(1-1.8):(1-1.05)；
(2)偶合反应：
首先将3,5-二氨基苯甲酸加水溶解，控制pH为8.0-12.0，温度为15-25℃；将溶解好的3,5-二氨基苯甲酸溶液加入上述步骤(1)制得的式(Ⅱa)所示的芳胺化合物的重氮液中，用液碱或小苏打控制控制pH为2.0-6.0，温度为0-20℃，进行第一次偶合反应，用H酸试液测试重氮，渗圈处无色即重氮已反应完全到终点，得到偶合产物1；
接着将步骤(1)得到的式(Ⅱb)的重氮液或式(Ⅱc)的重氮液加入到偶合产物1中，用液碱或小苏打控制pH在5.0-8.0、温度控制为0-20℃，进行第二次偶合反应，用H酸试液测试重氮，渗圈处无色即重氮已反应完全到终点，得到偶合产物2；
然后再将骤(1)得到的式(Ⅱb)的重氮液或式(Ⅱc)的重氮液加入到偶合产物2中，用液碱或小苏打控制pH在5.0-8.0、温度控制为0-20℃，进行第三次偶合反应，用H酸试液测试重氮，渗圈处无色即 重氮已反应完全到终点，即可得到活性染料化合物；
其中，每次偶合中，控制式(Ⅱa)、式(Ⅱb)或式(Ⅱc)所示的芳胺化合物与3,5-二氨基苯甲酸的摩尔比为(0.95-1.2)：1，优选(0.98-1.08)：1。
进一步，如果D 1、D 2同时为式(a)或(b)所示的基团，则第二次偶合反应和第三次偶合反应可合并成一次偶合反应，即第二次偶合反应和第三次偶合反应改为：再将步骤(1)得到的式(Ⅱb)所示的芳胺化合物的重氮液或式(Ⅱc)所示的芳胺化合物的重氮液加入到偶合产物1中，用液碱或小苏打控制pH在5.0-8.0、温度控制为0-20℃，进行第二次偶合反应，用H酸试液测试重氮，渗圈处无色即重氮已反应完全到终点，即可得到所述的活性染料化合物，其中控制式(Ⅱb)或式(Ⅱc)所示的芳胺化合物与3,5-二氨基苯甲酸的摩尔比为(1.9-2.4)：1，优选(1.96-2.16)：1。
本发明所述的活性染料化合物，在其制备过程中，还允许存在含量不超过30％的副产物，所述的副产物可不分离，直接用于商品染料的加工，包括且不限于以下结构的化合物或混合物：
Figure PCTCN2021104710-appb-000023
上述副产物中，各取代基定义同前述式(Ⅰ)。
本发明所述的活性染料化合物，在实际合成过程中，通常以其碱金属盐(如钠盐或钾盐)的形式进行制备和分离，并且也以其盐的形式用于染色，这也是本领域技术人员所熟知的，亦即式(Ⅰ)中的羧基、磺酸基可以羧酸的碱金属盐(如羧酸钠)、磺酸的碱金属盐(如磺酸钠)的形式存在。
本发明所述的活性染料化合物可以粉状、粒状、水溶液或合成溶液形式存在，从合成溶液分离本发明所述的活性染料化合物，可用普遍已知的方法进行，例如用电解质(如氯化钠或氯化钾)从反应介质中将染料盐析滤出，或将溶液蒸发、喷雾干燥，因此，染料化合物通常包含有活性染料中常规的电解质盐(如氯化钠、硫酸钠等)。
第三方面，本发明提供了所述活性染料化合物在纤维素纤维、聚酰胺纤维或其织物的印染中的应用。
本领域公知，本发明的活性染料化合物中，当Y 1～Y 3为-C 2H 4OSO 3H或-CH 2CH 2Cl时，在通常的活性染料染色应用中，β-羟乙砜基硫酸酯(-SO 2C 2H 4OSO 3H)或β-氯乙基砜(-SO 2C 2H 4Cl)在碱性介质中经消除反应生成乙烯砜基(-SO 2CH＝CH 2)，然后与纤维素纤维经亲核加成反应，形成共价键。
本发明所述的活性染料化合物，作为商品出售或者应用时，可以不加入助剂，也可以加入商品染料中的常规助剂，如助溶剂、分散剂、耐碱性助剂、防尘剂、表面活性剂、缓冲剂和促染剂等。因此，本发明还提供了一种活性染料制品，其含有所述的活性染料化合物。优选的，所述的活性染料制品中，含有所述的活性染料化合物以及助剂，其中助剂的重量不超过活性染料化合物重量的45％，优选不超过40％。所述 的助剂优选下列一种或任意几种的组合：萘磺酸甲醛缩合物(NNO)、甲基萘磺酸甲醛缩合物(分散剂MF)、扩散剂CNF(苄基萘磺酸盐甲醛缩合物)、元明粉(工业硫酸钠)、木质素磺酸盐、醋酸钠、碳酸氢钠、柠檬酸钠、磷酸二氢钠、磷酸氢二钠、增稠剂等。所述助剂均为市售常规品种。
本发明所述的活性染料化合物和活性染料制品，适用于纤维素纤维、聚酰胺纤维及其织物的印染，其中，纤维素纤维优选棉纤维或再生纤维，当然也可包括其它的植物性纤维，如麻类纤维或织物；聚酰胺纤维优选包括皮、毛或丝在内的动物性纤维材料，以及合成的尼龙6、尼龙66等纤维材料。采用本发明所述的活性染料化合物或活性染料制品印染上述纤维材料时，可遵照已知的活性染料染色方法进行，如常用的活性染料浸染染色法和轧染染色法，所述的浸染染色是将织物浸渍于染液中，使染料逐渐上染织物的方法，通常需经染色－固色－水洗－皂煮－水洗－脱水－烘干等工序。
所述的轧染则是先把织物浸渍于染液中，然后使织物通过轧辊，把染液均匀轧入织物内部，再经汽蒸或热熔等处理的染色方法，通常需经浸轧染液－烘干－(浸轧固色液)－汽蒸或焙烘－水洗－皂洗－水洗－烘干等工序。
通常，由于织物上染色泽要求的不同，染料使用量也会有所不同，使用浸染法染色时，染色深度(owf)一般为0.1％～10％(染料占织物重量百分比)，浴比1:2～1:60(织物与染液重量比，优选1:10～1:30)，初染温度控制30～60℃，染色时间10～30分钟，皂煮温度85～95℃，皂煮时间10～15分钟，固色温度60～100℃，固色时间10～50分钟，固色pH值9～11。使用轧染方法染色时，纤维素纤维的轧余率一般为60～80％，汽蒸温度100～103℃，汽蒸时间1～3分钟。轧染方法中，目前较多使用的是冷轧堆染色法，将染料和碱性物质引入到轧染机中，并在室温下打卷堆置2～30小时进行固色，之后进行彻底漂洗。
与现有技术相比，本发明的有益效果在于：本发明的活性染料化合物结构新颖，耐水洗牢度和耐摩擦牢度好，与纤维结合稳定性好，适用于棉、人造棉、丝绸、羊毛等纤维的染色和印花。
(四)说明书附图
图1为实施例1制得的化合物(Ⅰ-1)的质谱图：
图2为实施例1制得的色基(A)的质谱图。
(五)具体实施方式
下面结合具体实施例对本发明作进一步描述，但本发明的保护范围并不仅限于此：
本发明所述的活性染料化合物，在实施例所述的实际合成过程中，以其钠盐的形式进行制备和分离，并且也以钠盐的形式用于染色，但是为方便撰写，实施例中的活性染料化合物的所有化学式皆以自由酸的形式体现，其实质染色性能等同钠盐的形式。
实施例1
(1)重氮化：
将23.0g(0.1mol)4-乙酰氨基-2-氨基苯磺酸投入100g水、100g冰中打浆约1h，再加20g 31％盐酸(含HCl 0.17mol)，在20-30min内加入24g 30％亚硝酸钠液(含亚硝酸钠0.104mol)，控制pH＝0.5-2.0、温度T＝0-20℃进行重氮化反应1～2小时，用4-二甲氨基苯甲醛的乙醇溶液检测终点(即5s内不变色)。重氮终点到后，用氨基磺酸消除过量的亚硝酸钠，得到的4-乙酰氨基-2-氨基苯磺酸重氮液保存备用。
将56.2g(0.2mol)对位酯(对-β-羟乙基砜硫酸酯苯胺)投入200g水、200g冰中打浆约1h，再加 35g 31％盐酸(含HCl 0.3mol)，在20-30min内加入48g 30％亚硝酸钠液(含亚硝酸钠0.208mol)，控制pH＝0.5-2.0、温度T＝0-20℃进行重氮化反应1～2小时，用4-二甲氨基苯甲醛的乙醇溶液检测终点(即5s内不变色)。重氮终点到后，用氨基磺酸消除过量的亚硝酸钠，得到的对位酯重氮液保存备用。
(2)偶合：
首先将15.2g(0.1mol)3,5-二氨基苯甲酸加入200g水中进行打浆，用纯碱调pH＝8.0-9.0，温度20-25℃，将步骤(1)中得到的0.1mol 4-乙酰氨基-2-氨基苯磺酸重氮液加入到打浆好的3,5-二氨基苯甲酸溶液中，用30％液碱控制pH在5-5.5，温度控制在5-10℃，反应0.5-2.5h，用HPLC控制游离3,5-二氨基苯甲酸在3％以下即到终点，得下式(A)所示的色基，质谱图如图2所示。
Figure PCTCN2021104710-appb-000024
再将步骤(1)中制得的对位酯重氮液加入到式(A)所示的色基中，用30％液碱控制pH在5-5.5，温度控制在5-10℃，进一步偶合反应0.5-10h，用H酸试液测试重氮，渗圈处无色即重氮反应完全到终点，得到橙色活性染料化合物(Ⅰ-1)，水溶液中λmax＝420nm。化合物(Ⅰ-1)的质谱图如图1所示。
Figure PCTCN2021104710-appb-000025
实施例2～66：
参照实施例1所述的偶氮染料制备方法，采用本领域熟知的中间体原料，经分步重氮和偶合反应，可分别制得下表1中所示结构的染料化合物。
表1
Figure PCTCN2021104710-appb-000026
Figure PCTCN2021104710-appb-000027
Figure PCTCN2021104710-appb-000028
Figure PCTCN2021104710-appb-000029
Figure PCTCN2021104710-appb-000030
Figure PCTCN2021104710-appb-000031
Figure PCTCN2021104710-appb-000032
Figure PCTCN2021104710-appb-000033
Figure PCTCN2021104710-appb-000034
Figure PCTCN2021104710-appb-000035
Figure PCTCN2021104710-appb-000036
Figure PCTCN2021104710-appb-000037
Figure PCTCN2021104710-appb-000038
Figure PCTCN2021104710-appb-000039
Figure PCTCN2021104710-appb-000040
Figure PCTCN2021104710-appb-000041
Figure PCTCN2021104710-appb-000042
对比例1
按照专利CN1266869A中实施例38的方法，制备如下式(1)所示结构的活性染料化合物：
Figure PCTCN2021104710-appb-000043
对比例2
按照专利CN105694530A中实施例1的方法，制备如下式(2)所示结构的活性染料化合物：
Figure PCTCN2021104710-appb-000044
对比例3
按照专利CN101319096A中实施例1的方法，制备如下式(3)所示结构的活性染料化合物：
Figure PCTCN2021104710-appb-000045
应用实施例1
取本发明实施例1～66、对比例1～3制得的活性染料，分别溶解在水中，加入元明粉50g/L配置成染液。染色浓度4％(染料对布重)，浴比1:20(布重克数对染液体积毫升数)，置入棉布60℃下吸附30分钟，加碱(碳酸钠20g/L)固色45分钟。染色织物经水洗、皂煮、干燥，得到黄色至橙色染织物。按ISO 105 C10-2006、ISO 105 X12中的方法分别进行耐洗沾色牢度和摩擦牢度测试，结果如表2：
表2
Figure PCTCN2021104710-appb-000046
Figure PCTCN2021104710-appb-000047
由表2可知，本发明所述的活性染料化合物相较于现有染料，在水洗沾色牢度和摩擦牢度上有明显改善。

Claims (12)

  1. 一种活性染料化合物，其是结构如下式(Ⅰ)所示的化合物或者其碱金属盐：
    Figure PCTCN2021104710-appb-100001
    式(Ⅰ)中：
    D 1、D 2各自独立为下式(a)或(b)所示的基团：
    Figure PCTCN2021104710-appb-100002
    上式(Ⅰ)、式(a)和(b)中：
    R 1、R 2各自独立为氢、氧、-COR 7、C 1～C 4烷基或被羟基、磺酸基或羧基取代的C 1～C 4烷基，其中R 7为C 1～C 4烷基、C 2～C 4烯基或-NH 2；
    R 3为氢、C 1～C 4烷基、C 1～C 4烷氧基、羧基或磺酸基；
    R 4～R 6各自独立为氢、C 1～C 4烷基、C 1～C 4烷氧基或磺酸基；
    X 1、X 2各自独立为-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3，其中Y 1～Y 3各自独立为-CH＝CH 2、-CH 2CH 2OSO 3H或-CH 2CH 2Cl，p＝1-3，q＝1-3。
  2. 如权利要求1所述的活性染料化合物，其特征在于：D 1、D 2同时为式(a)或(b)所示的基团。
  3. 如权利要求1所述的活性染料化合物，其特征在于：D 1、D 2同时为式(a)所示的基团。
  4. 如权利要求1-3之一所述的活性染料化合物，其特征在于：R 1、R 2各自独立为氢、-COR 7，其中R 7为甲基或-NH 2；R 3为氢、甲基、甲氧基、羧基或磺酸基。
  5. 如权利要求1或2所述的活性染料化合物，其特征在于：R 4～R 6各自独立为氢、甲基、甲氧基或磺酸基；X 1、X 2各自独立为-SO 2Y 1、-NHCOCH 2CH 2SO 2Y 2或-CONHCH 2CH 2SO 2Y 3，其中Y 1～Y 3各自独立为-CH＝CH 2或-CH 2CH 2OSO 3H。
  6. 如权利要求1所述的活性染料化合物，其特征在于：式(a)所示的基团选自下列基团之一：
    Figure PCTCN2021104710-appb-100003
    Figure PCTCN2021104710-appb-100004
  7. 如权利要求1所述的活性染料化合物，其特征在于：式(b)所示的基团选自下列基团之一：
    Figure PCTCN2021104710-appb-100005
  8. 如权利要求1所述的活性染料化合物，其特征在于：所述式(I)所示的化合物选自下列结构之一：
    Figure PCTCN2021104710-appb-100006
    Figure PCTCN2021104710-appb-100007
    Figure PCTCN2021104710-appb-100008
    Figure PCTCN2021104710-appb-100009
    Figure PCTCN2021104710-appb-100010
    Figure PCTCN2021104710-appb-100011
    Figure PCTCN2021104710-appb-100012
    Figure PCTCN2021104710-appb-100013
    Figure PCTCN2021104710-appb-100014
    Figure PCTCN2021104710-appb-100015
    Figure PCTCN2021104710-appb-100016
    Figure PCTCN2021104710-appb-100017
    Figure PCTCN2021104710-appb-100018
    Figure PCTCN2021104710-appb-100019
    Figure PCTCN2021104710-appb-100020
    Figure PCTCN2021104710-appb-100021
    Figure PCTCN2021104710-appb-100022
    Figure PCTCN2021104710-appb-100023
  9. 如权利要求1-3之一所述的活性染料化合物，其特征在于：所述的碱金属盐为钠盐或钾盐。
  10. 一种如权利要求1所述的活性染料化合物的制备方法，包括：
    (1)重氮化：
    根据需要将式(Ⅱa)、式(Ⅱb)和/或式(Ⅱc)所示的芳胺化合物分别进行重氮化，得到各自的重氮盐；
    (2)偶合反应：
    将3,5-二氨基苯甲酸加水打浆，打浆好的溶液与步骤(1)中的式(Ⅱa)所示的芳胺化合物的重氮盐进行第一次偶合，接着再与式(Ⅱb)所示的芳胺化合物的重氮盐或式(Ⅱc)所示的芳胺化合物的重氮盐进行第二次偶合，然后再与式(Ⅱb)所示的芳胺化合物的重氮盐或式(Ⅱc)所示的芳胺化合物的重氮盐进行第三次偶合，即得到所述的活性染料化合物；
    Figure PCTCN2021104710-appb-100024
    上述式(Ⅱa)～式(Ⅱc)各取代基定义同式(Ⅰ)。
  11. 如权利要求10所述的制备方法，其特征在于：所述活性染料化合物的具体合成步骤包括：
    (1)重氮化：
    根据需要将式(Ⅱa)、式(Ⅱb)和/或式(Ⅱc)所示的芳胺化合物各自与水、冰一起打浆1～2h，打浆完成后加入一定量的盐酸，然后在20-30min内加入亚硝酸钠溶液，控制pH＝0.5-3.0、温度T＝0-30℃进 行重氮化反应，用4-二甲氨基苯甲醛的乙醇溶液检测终点；重氮终点到后，用氨基磺酸消除过量的亚硝酸钠，分别得到式(Ⅱa)、式(Ⅱb)或式(Ⅱc)所示的芳胺化合物的重氮液保存备用；其中，式(Ⅱa)、式(Ⅱb)或式(Ⅱc)所示的芳胺化合物各自与盐酸、亚硝酸钠的摩尔比为1:(1-3):(1-1.1)；
    (2)偶合反应：
    首先将3,5-二氨基苯甲酸加水溶解，控制pH为8.0-12.0，温度为15-25℃；将溶解好的3,5-二氨基苯甲酸溶液加入上述步骤(1)制得的式(Ⅱa)所示的芳胺化合物的重氮液中，用液碱或小苏打控制控制pH为2.0-6.0，温度为0-20℃，进行第一次偶合反应，用H酸试液测试重氮，渗圈处无色即重氮已反应完全到终点，得到偶合产物1；
    接着将步骤(1)得到的式(Ⅱb)的重氮液或式(Ⅱc)的重氮液加入到偶合产物1中，用液碱或小苏打控制pH在5.0-8.0、温度控制为0-20℃，进行第二次偶合反应，用H酸试液测试重氮，渗圈处无色即重氮已反应完全到终点，得到偶合产物2；
    然后再将骤(1)得到的式(Ⅱb)的重氮液或式(Ⅱc)的重氮液加入到偶合产物2中，用液碱或小苏打控制pH在5.0-8.0、温度控制为0-20℃，进行第三次偶合反应，用H酸试液测试重氮，渗圈处无色即重氮已反应完全到终点，即可得到活性染料化合物；
    其中，每次偶合中，控制式(Ⅱa)、式(Ⅱb)或式(Ⅱc)所示的芳胺化合物与3,5-二氨基苯甲酸的摩尔比为(0.95-1.2)：1。
  12. 如权利要求1所述的活性染料化合物在纤维素纤维、聚酰胺纤维或其织物的印染中的应用。
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918245A (zh) * 2004-02-13 2007-02-21 西巴特殊化学品控股有限公司 活性染料混合物及其用途
CN103703083A (zh) * 2011-08-04 2014-04-02 亨斯迈先进材料（瑞士）有限公司 活性染料的混合物及其用途
CN104059387A (zh) * 2014-07-10 2014-09-24 浙江瑞华化工有限公司 复合黑色活性染料组合物、其用途和由其制成的纤维或纤维的纺织物
CN104059000A (zh) * 2014-07-10 2014-09-24 浙江瑞华化工有限公司 一种活性染料及其制备方法和用途
CN105778561A (zh) * 2016-03-17 2016-07-20 浙江瑞华化工有限公司 一种黑色活性染料组合物及其制备方法和用途
CN112574592A (zh) * 2020-12-26 2021-03-30 浙江科永化工有限公司 一种活性藏青至黑色染料组合物及染料制品
CN112679987A (zh) * 2020-12-26 2021-04-20 浙江科永化工有限公司 一种活性藏青至黑色染料组合物及染料制品
CN112679984A (zh) * 2020-12-26 2021-04-20 浙江科永化工有限公司 一种活性染料化合物及其制备方法和应用
CN112679988A (zh) * 2020-12-26 2021-04-20 浙江科永化工有限公司 一种活性藏青至黑色染料组合物及染料制品

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107501997A (zh) * 2017-07-28 2017-12-22 浙江科永化工有限公司 一种活性藏青至黑色染料组合物及染料制品
CN108102423B (zh) * 2017-12-18 2020-06-26 浙江瑞华化工有限公司 一种黑色活性染料组合物及其制备方法和用途

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918245A (zh) * 2004-02-13 2007-02-21 西巴特殊化学品控股有限公司 活性染料混合物及其用途
CN103703083A (zh) * 2011-08-04 2014-04-02 亨斯迈先进材料（瑞士）有限公司 活性染料的混合物及其用途
CN104059387A (zh) * 2014-07-10 2014-09-24 浙江瑞华化工有限公司 复合黑色活性染料组合物、其用途和由其制成的纤维或纤维的纺织物
CN104059000A (zh) * 2014-07-10 2014-09-24 浙江瑞华化工有限公司 一种活性染料及其制备方法和用途
CN105778561A (zh) * 2016-03-17 2016-07-20 浙江瑞华化工有限公司 一种黑色活性染料组合物及其制备方法和用途
CN112574592A (zh) * 2020-12-26 2021-03-30 浙江科永化工有限公司 一种活性藏青至黑色染料组合物及染料制品
CN112679987A (zh) * 2020-12-26 2021-04-20 浙江科永化工有限公司 一种活性藏青至黑色染料组合物及染料制品
CN112679984A (zh) * 2020-12-26 2021-04-20 浙江科永化工有限公司 一种活性染料化合物及其制备方法和应用
CN112679988A (zh) * 2020-12-26 2021-04-20 浙江科永化工有限公司 一种活性藏青至黑色染料组合物及染料制品

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