WO2019020122A1 - 一种活性藏青至黑色染料组合物及染料制品 - Google Patents

一种活性藏青至黑色染料组合物及染料制品 Download PDF

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WO2019020122A1
WO2019020122A1 PCT/CN2018/097754 CN2018097754W WO2019020122A1 WO 2019020122 A1 WO2019020122 A1 WO 2019020122A1 CN 2018097754 W CN2018097754 W CN 2018097754W WO 2019020122 A1 WO2019020122 A1 WO 2019020122A1
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component
formula
group
independently
dye composition
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PCT/CN2018/097754
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English (en)
French (fr)
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王晓红
陈浩兵
李世华
汪仁良
周俊峰
张桂香
高怀庆
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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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Priority to US16/632,207 priority Critical patent/US10954392B2/en
Publication of WO2019020122A1 publication Critical patent/WO2019020122A1/zh

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive 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
    • C09B62/503Reactive 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
    • C09B62/507Azo dyes
    • C09B62/513Disazo or polyazo dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046Mixtures of two or more azo dyes
    • C09B67/0047Mixtures of two or more reactive azo dyes
    • C09B67/005Mixtures of two or more reactive azo dyes all the reactive groups being not directly attached to a heterocyclic system
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046Mixtures of two or more azo dyes
    • C09B67/0055Mixtures of two or more disazo dyes
    • C09B67/0057Mixtures of two or more reactive disazo dyes
    • C09B67/0059Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/38General 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
    • D06P1/384General 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/24Polyamides; Polyurethanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/24Polyamides; Polyurethanes
    • D06P3/248Polyamides; Polyurethanes using reactive dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34Material containing ester groups
    • D06P3/52Polyesters
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58Material containing hydroxyl groups
    • D06P3/60Natural or regenerated cellulose
    • D06P3/66Natural or regenerated cellulose using reactive dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58Material containing hydroxyl groups
    • D06P3/60Natural or regenerated cellulose
    • D06P3/66Natural or regenerated cellulose using reactive dyes
    • D06P3/666Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/70Material containing nitrile groups

Definitions

  • the present invention relates to a reactive dye composition and a dye preparation, and more particularly to an active navy to black dye composition and dye preparation suitable for printing with nitrogen-containing and/or hydroxyl-containing fibrous materials.
  • Reactive black KNB has become the most widely used black reactive dye due to its low price, good fastness and easy washing.
  • the dye has low directness to fiber, and the dyeing rate and fixing rate are not high.
  • an object of the present invention is to provide an active navy to black dye composition and a dye product, which have the advantages of good washing fastness, high fixing rate and exhaustion rate, good lifting power, and dyeing residue. It is suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials and their blended fabrics.
  • the present invention adopts the technical solution as follows:
  • the present invention provides an active navy to black dye composition
  • component A is selected from one or more dye compounds of formula (I)
  • component B is selected from the group consisting of One or more dye compounds as shown in formula (II); based on said component A and component B, component A has a mass percentage of 5 to 50%, and component B has a mass percentage 50 to 95%;
  • D 1 and D 2 are each independently a group represented by the following formula (a) or (b) or (c);
  • the C 1 -C 4 linear or branched alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl or the like;
  • the C 1 ⁇ C 4 alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like;
  • a C 1 The alkanoylamino group of -C 4 may be a formylamino group, an acetylamino group, a n-propionylamino group, an isopropionylamino group, a n-butyrylamino group, an isobutyrylamino group, a t-butyrylamino group or the like.
  • the active navy to black dye composition comprises component A and component B, wherein component A is selected from one or more dye compounds of formula (IA), component B is selected from the group consisting of Or a plurality of dye compounds as shown in formula (II); based on said 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%;
  • D 1 and D 2 are each independently a group represented by the following formula (a) or (b) or (c);
  • D 1 and D 2 are all derived from a group of the formula (a), and the substituents may be the same or different; or D 1 is selected from the group represented by the formula (a), and D 2 is selected from the formula (b) or the formula (c) The group shown.
  • R 1 , R 2 , R 4 , R 5 , R 7 and R 8 are each independently preferably H, a methyl group, a methoxy group or a sulfonic acid group.
  • each of R 3 is each independently preferably a methyl group, a sulfonic acid group, a urea group or an acetylamino group.
  • each of R 9 , R 10 , R 11 and R 12 is independently preferably H, a methyl group, a methoxy group or a sulfonic acid group.
  • the active navy to black dye composition consists of component A and component B.
  • the active na[o] to black dye composition may further comprise a component C selected from one or more compounds of the formulae (III) to (VI), wherein the composition,
  • the mass of component C is from 1 to 50%, preferably from 5 to 40%, based on the total mass of component A and component B,
  • R 13 , R 14 , R 15 and R 16 are each independently H, a C 1 -C 4 linear or branched alkyl group, a C 1 -C 4 alkoxy group, a carboxyl group or a sulfonic acid group, wherein R 13 to R Each of 16 is preferably independently H, methyl, methoxy, carboxyl or sulfonic acid;
  • alkanoylamino group a C 1 -C 4 alkoxy group or a hydroxyl group, preferably having a number of substituents of 1-2, each substituent being independently selected from the group consisting of an amino group, a sulfonic acid group, a urea group, and an acetyl group.
  • Each of e, f, and g is independently 0-3, and each of R 21 , R 22 , and R 23 is independently a C 1 -C 4 linear or branched alkyl group, a C 1 -C 4 alkoxy group or a sulfonic acid group. Preferred as methyl, methoxy or sulfonic acid;
  • X 4 is hydrogen or carboxyl;
  • each R 24 is independently a C 1 -C 4 linear or branched alkyl group, a C 1 -C 4 alkoxy group or a sulfonic acid group, preferably a methyl group, a methoxy group or a sulfonic acid group.
  • a group; i 1-3
  • each R 25 is independently selected from amino, sulfonate, ureido, C 1 -C 4 alkanoyl, C 1 -C 4 alkoxy or hydroxy, preferably amino, sulfonate Acid group or acetylamino group;
  • component C is selected from at least one dye represented by formula (III) and/or formula (IV), wherein a and b are both 0, or one of a, b is 0, and the other is 1, c. Is 1, d is 0 or 1.
  • the active na[o] to black dye composition of the present invention preferably comprises the following dye components:
  • Component A a dye selected from at least one formula (I), wherein D 1 and D 2 are each independently a group represented by the formula (a), and each substituent may be the same or different; or D 1 is a formula a group represented by (a), D 2 is a group represented by formula (b) or formula (c); and at least one of D 1 and D 2 contains -SO 2 Y 1 ;
  • Component B selected from at least one dye represented by formula (II);
  • Component C selected from at least one dye of the formula (III) and/or formula (IV), wherein a and b are both 0, or one of a, b is 0, the other is 1, c is 1 , d is 0 or 1.
  • the active navy to black dye composition consists of component A, component B and component C.
  • the active navy to black dye composition of the present invention preferably consists of the following dye components:
  • Component A a dye selected from at least one formula (I), wherein D 1 and D 2 are each independently a group represented by the formula (a), and each substituent may be the same or different; or D 1 is a formula a group represented by (a), D 2 is a group represented by formula (b) or formula (c); and at least one of D 1 and D 2 contains -SO 2 Y 1 ;
  • Component B selected from at least one dye represented by formula (II);
  • Component C selected from at least one dye of the formula (III) and/or formula (IV), wherein a and b are both 0, or one of a, b is 0, the other is 1, c is 1 , d is 0 or 1.
  • the component A is preferably one of the following or a mixture of two or more thereof:
  • the component A is more preferably at least one of the formulae (I-1) to (I-63), (I-88), and (I-89), and still more preferably, the formula (I-1) to (I- 21), at least one of (I-27) to (I-33), (I-41) to (I-63), (I-88), and (I-89), and still more preferably a formula ( I-1), (I-3), (I-4), (I-31), (I-32), (I-41), (I-48), (I-51), (I- At least one of 52), (I-55), (I-88), and more particularly preferably at least one of the formulae (I-31), (I-32), (I-51), and (I-52) One.
  • the component B is preferably one of the following or a mixture of two or more thereof:
  • Component B is particularly preferably a formula (II-1), a formula (II-3) or a combination thereof.
  • the component C is preferably one of the following or a mixture of two or more thereof:
  • Component C is more preferably one or more of the formulae (III-1) to (III-31), (IV-1) to (IV-9), and still more preferably, the formula (III-1), (III- 2), at least one of (III-4), (IV-1), (IV-3).
  • the dye composition comprises component A and component B:
  • Component A selected from the group consisting of formula (I-1), (I-3), (I-4), (I-31), (I-32), (I-41), (I-48), At least one of the dyes of I-51), (I-52), (I-55) and (I-88), more particularly preferably of the formulae (I-31), (I-32), (I- At least one of 51) and (I-52) a dye;
  • the component A is more preferably at least one of the formulae (I-1) to (I-63), (I-88), and (I-89), and still more preferably, the formula (I-1) to (I- 21), at least one of (I-27) to (I-33), (I-41) to (I-63), (I-88), and (I-89), and still more preferably a formula ( I-1), (I-3), (I-4), (I-31), (I-32), (I-41), (I-48), (I-51), (I- At least one of 52), (I-55), (I-88), and more particularly preferably at least one of the formulae (I-31), (I-32), (I-51), and (I-52) One.
  • Component B selected from the group consisting of the dyes of the formula (II-1) and/or (II-3);
  • the mass percentage of the component A is preferably from 5 to 50%, and the mass percentage of the component B is preferably from 50 to 95%, based on the sum of the masses of the components A to B.
  • the dye composition comprises component A, component B and component C:
  • Component A selected from the group consisting of formula (I-1), (I-3), (I-4), (I-31), (I-32), (I-41), (I-48), At least one of the dyes of I-51), (I-52), (I-55) and (I-88), more particularly preferably of the formulae (I-31), (I-32), (I- At least one of 51) and (I-52) a dye;
  • Component B selected from the group consisting of the dyes of the formula (II-1) and/or (II-3);
  • Component C at least one selected from the group consisting of the dyes of the formulae (III-1), (III-2), (III-4), (IV-1), (IV-3);
  • the mass percentage of the component A is 5 to 50%
  • the mass percentage of the component B is 50 to 95%
  • the mass of the component C is the component A and 1 to 50% of the total mass of component B.
  • the active na[o] to black dye compositions of the present invention are all known dyes, which can be synthesized by a conventional method, for example, by using a suitable group well known to those skilled in the art.
  • the fractions and the necessary ratios are prepared by means of the usual diazotization reaction and coupling reaction, or by the method of the patents CN101250334A, CN1163291A, CN105176139A or the like.
  • the compound of the formula (I) can also be prepared according to the conventional diazo, coupling method of the reactive dye, for example:
  • 3,5-dihydroxybenzoic acid is added with water and beaten, and the beaten 3,5-dihydroxybenzoic acid solution is subjected to stepwise coupling with one of the diazonium salts obtained in the step (1) as needed, preferably in the first coupling.
  • the coupling reaction is carried out at a pH of from 3 to 4.5, at a temperature of from 0 to 30 ° C (preferably from 0 to 20 ° C), and the reaction is stopped by monitoring the free 3,5-dihydroxybenzoic acid below 3% by HPLC; Further, if necessary, a second coupling is performed with one of the diazonium salts obtained in the step (1).
  • the pH When the second coupling is performed, it is preferred to control the pH to be 5.0 to 8.0 and the temperature to be 0 to 30 ° C (preferably 0 to 20 ° C).
  • the coupling reaction is carried out, and it is monitored by HPLC that the coupling product is less than 3%, and the second coupling reaction is completed to obtain the reactive dye compound (I); wherein 3,5-dihydroxybenzoic acid is used for two couplings.
  • the molar ratio of the diazonium salt is controlled to be 1: (0.95-1.2), preferably 1: (0.98-1.08); or further alkalized to adjust the pH value of 10-11 to form a vinyl sulfone, and then acidify;
  • the dye compound monomer ortho-coupled in the phenolic hydroxyl group is often present in a stable state of the steroid, that is, the dye of the formula (I).
  • a dye substantially containing a steroid structure represented by the following formula (Ia) and/or formula (Ib) and/or (Ic) and/or (Id), and a dye of the formula (II), (IV) substantially contains the following formula ( The steroid structures shown in IIa) and (IVa), in view of the writing habits of those skilled in the art, still use the written form of the azo body in the content of the invention and the examples, which does not affect the essence of the invention:
  • each monochromatic dye compound is characterized by its free acid form, and in the actual synthesis process, usually its alkali metal salt (such as sodium or potassium salt) Preparation and separation in the form of, and also in the form of its salt for dyeing, which is also well known to those skilled in the art, that is, the carboxyl group in the formula (I) to the formula (VI), the sulfonic acid group may be a carboxylic acid Sodium, sodium sulfonate is present in the form.
  • alkali metal salt such as sodium or potassium salt
  • the active navy to black dye composition of the present invention is prepared by mixing the dye components A, B or A, B, C according to the foregoing ratio, and mixing can be carried out by a conventional mechanical means, such as in a grinder. In a kneading machine or a homogenizer, during the mixing process, the individual dye compounds (I) to (VI) may be present in the form of powder, granule, aqueous solution or synthetic solution.
  • Separation of the composite active navy to black dye of the present invention from a synthetic solution can be carried out by a generally known method, for example, by filtering an acid salt from a reaction medium with an electrolyte such as sodium chloride or potassium chloride, or mixing
  • an electrolyte such as sodium chloride or potassium chloride
  • the solution is evaporated, spray dried, and therefore, the dye components A, B, C and their dye compositions usually contain conventional electrolyte salts (such as sodium chloride, sodium sulfate, etc.) in the reactive dye.
  • the active navy to black dye composition of the present invention can be used as a commercial product, and can be added without adding an auxiliary agent, and can also be added to a conventional auxiliary agent in a commercial dye, such as a cosolvent, a dispersant, an alkali-resistant auxiliary, and dustproof. Agents, surfactants, buffers and dyes. Accordingly, the present invention also provides an active navy to black dye preparation comprising the active navy to black dye composition.
  • the active navy to black dye preparation contains the active navy to black dye composition and an auxiliary.
  • the weight of the adjuvant does not exceed 45%, preferably no more than 40% by weight of the active navy to black dye composition.
  • the auxiliary agent is preferably one or a combination of any one of the following: a naphthalenesulfonic acid formaldehyde condensate (NNO), a methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), and a diffusing agent CNF (benzyl naphthalenesulfonate).
  • NNO naphthalenesulfonic acid formaldehyde condensate
  • a methylnaphthalenesulfonic acid formaldehyde condensate disersant MF
  • CNF benzyl naphthalenesulfonate
  • Formaldehyde condensate Yuanming powder (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium hydrogencarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener, and the like.
  • the auxiliaries are all commercially
  • the active navy to black dye preparation of the present invention is suitable for printing with nitrogen-containing and/or hydroxyl-containing fiber materials, which may be cellulose fibers, polyamide fibers and fabrics thereof.
  • the cellulose fibers are preferably cotton fibers or recycled fibers, and of course may include other vegetable fibers such as hemp fibers or fabrics;
  • the polyamide fibers preferably include animal fiber materials including skin, wool or silk, and synthetic Fiber material such as nylon 6, nylon 66.
  • the above-mentioned fibrous material is printed by using the active navy to black dye preparation of the present invention, it can be carried out according to a known reactive dye dyeing method, such as a commonly used reactive dye dip dyeing method and pad dyeing method, and the dip dyeing method is
  • a known reactive dye dyeing method such as a commonly used reactive dye dip dyeing method and pad dyeing method
  • the dip dyeing method is
  • the method of immersing the fabric in the dyeing liquid to gradually dye the dye to the fabric usually requires a process of dyeing-fixing-washing-soap-washing-dehydration-drying.
  • the padding is a method of first immersing the fabric in a dyeing solution, then passing the fabric through a roll, uniformly rolling the dye solution into the interior of the fabric, and then treating by steaming or hot-melting, usually by dipping and dyeing.
  • the amount of dye used will vary depending on the dyeing requirements on the fabric.
  • the dyeing depth (owf) is generally 0.1% to 10% (dye is percentage by 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 control 30 ⁇ 60°C, dyeing time 10 ⁇ 30 minutes, soap boiling temperature 85 ⁇ 95°C, soaping time 10 to 15 minutes, the fixing temperature is 60 to 100 ° C, the fixing time is 10 to 50 minutes, and the fixing pH is 9 to 11.
  • the rolling rate of the cellulose fibers is generally 60 to 80%
  • the steaming temperature is 100 to 103 ° C
  • the steaming time is 1 to 3 minutes.
  • the cold-rolling pile dyeing method is used more frequently, and the dye and the alkaline substance are introduced into the pad dyeing machine, and are piled up for 2 to 30 hours at room temperature for fixing, and then thoroughly rinsed. .
  • the beneficial effects of the invention are mainly embodied in: the active navy to black dye composition and the product of the invention, which have good lifting property, good compatibility, dyeing rate and fixing color when used for printing and dyeing nitrogen-containing and/or hydroxyl-containing fiber materials.
  • the rate is high, the dye residue is clear, and the washing fastness is excellent.
  • Figure 1 is a 1H NMR spectrum of the orange reactive dye compound (I-1) obtained in Example 1;
  • Embodiments 2 to 30 are identical to Embodiments 2 to 30:
  • step 1 154g (0.1mol) of 3,5-dihydroxybenzoic acid was added to 200g of water for beating, pH was adjusted to 8.0-9.0 with soda ash, temperature was 20-25 ° C, and the beaten 3,5-dihydroxybenzoic acid solution was added.
  • the pH is controlled at 4.0 with 30% liquid alkali
  • the temperature is controlled at 0-20 ° C
  • the reaction is 0.5-2.5 h
  • the free 3,5-two is controlled by HPLC.
  • the diazonium solution of the chromophore 1 prepared in the step (1) is added to the chromophore 2, the pH is controlled at 5.0-8.0 with 30% liquid alkali, the temperature T is controlled at 0-20 ° C, and the further coupling reaction is 0.5-10 h.
  • the dye in terms of free sulfonic acid has the most accurate molecular mass number M of 980.0, and the hydrogen spectrum is characterized by [ 1 H NMR (DMSO-d6) [3.61-3.74 ppm 4H (m), 3.96-4.04 ppm 4H (m), 6.22 Ppm 1H(s), 7.48-8.20ppm 8H(m), 8.40ppm 1H(s), 9.02ppm 1H(s), 11.1ppm 1H(s)]
  • the dye of the formula (I-1), 75 parts of the dye of the formula (II-3) and 10 parts of the powder are mechanically mixed, and the obtained composite dye is dyed with black by conventional dyeing method, and is resistant to washing and staining.
  • It is a nylon, polyester, acrylic fiber staining fastness of 4 to 5 or more (refer to ISO 105 C10-2006), excellent lifting power and fixing rate (refer to GB/T21875-2016 and GB/T2391-2014).
  • the dye of the formula (I-31), 65 parts of the dye of the formula (II-3) and 10 parts of the Ming powder are mechanically mixed, and the obtained composite dye is dyed with black by conventional dyeing method, and is resistant to washing and staining.
  • It is a nylon, polyester, acrylic fiber staining fastness of 4 to 5 or more (refer to ISO 105 C10-2006), excellent lifting power and fixing rate (refer to GB/T21875-2016 and GB/T2391-2014).
  • the method of dyeing cotton is black, and it is resistant to washing and staining, especially the nylon, polyester and acrylic fibers have a color fastness of 4 to 5 or more (refer to ISO 105 C10-2006), and the lifting power and fixing rate are excellent (refer to GB/T21875-2016). And GB/T2391-2014).
  • the method of dyeing cotton is black, and it is resistant to washing and staining, especially the nylon, polyester and acrylic fibers have a color fastness of 4 to 5 or more (refer to ISO 105 C10-2006), and the lifting power and fixing rate are excellent (refer to GB/T21875-2016). And GB/T2391-2014).
  • the dyed cotton is dark black, resistant to washing and staining, especially nylon, polyester and acrylic.
  • the color fastness is above 4 ⁇ 5 (refer to ISO 105 C10-2006), and the lifting power and fixing rate are excellent (refer to GB/T21875- 2016 and GB/T2391-2014).
  • the composite dyed cotton is dark black, resistant to washing and staining, especially nylon, polyester and acrylic.
  • the color fastness is above 4 ⁇ 5 (refer to ISO 105 C10-2006), and the lifting power and fixing rate are excellent (refer to GB/ T 21875-2016 and GB/T2391-2014).
  • the dyes listed in Tables 7 and 8 are mechanically mixed according to the conventional dyeing method of reactive dyes, and the dyed cotton is navy to black, and is resistant to washing and staining, especially nylon and polyester.
  • Acrylic fiber has a color fastness of 4 to 5 or more (refer to ISO 105 C10-2006), excellent lifting power (refer to standard GB/T 21875-2016), excellent lifting power and fixing rate (refer to GB/T 21875-2016) And GB/T2391-2014).
  • Comparative Example 1 According to Example 2 in Patent CN1858118, the following three components of the reactive black dye were prepared:
  • the active black dyes obtained in Examples 91 to 96 (closest) and Comparative Examples 1 and 2 were each dissolved in water, and 50 g/L of Yuanming powder was added to prepare a dyeing solution.
  • the color fastness test was carried out according to the method of ISO 105 C10-2006. The results are shown in Table 9:
  • the reactive dyes obtained in the representative examples 91 to 96 of the present invention and the comparative examples 1 and 2 were tested for their lifting power according to the method specified in the standard GB/T 21875-2016 standard, and found in Examples 91-96.
  • the reactive dye has a significantly better lifting power than the comparative examples 1 to 2. Under the same dyeing conditions, the amount of dye can be saved by 5 to 15%, and the economy is remarkable.
  • Example Example 91 Example 92 Example 93 Example 94 Example 95
  • Example 96 Comparative example 1 Comparative example 2 Fixing rate 76.1% 75.9% 75.2% 76.5% 75.7% 76.3% 71.6% 70.5%
  • the dye of the present invention is significantly superior to the comparative example, and it has a significant improvement in color fastness, lift and fixation rate for the industry.

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Abstract

一种活性藏青至黑色染料组合物,包括组分A和组分B,组分A选自一种或多种化合物(Ⅰ),组分B选自一种或多种化合物(II);其中D1、D2各自独立为式(a)或(b)或(c)所示的基团;R1-R12彼此独立为H、C1~C4烷基、C1~C4烷氧基或磺酸基;m、n=0-3,每个R3各自独立选自氨基、磺酸基、脲基、C1~C4的烷酰氨基、C1~C4烷氧基或C1~C4烷氧基,每个R6各自独立选自羟基、氨基或磺酸基;X1-X3彼此独立为H、C1~C4烷基、C1~C4烷氧基、-SO2Y1、-NHCO(CH2)pSO2Y2或-CONH(CH2)qSO2Y3,且D1、D2中至少有一个含有纤维活性基团,p、q=1-3,Y1~Y5各自独立为-CH=CH2、-C2H4OSO3H或-CH2CH2Cl。一种活性藏青至黑色染料制品,含有所述染料组合物,具有耐水洗牢度佳、固色率及吸尽率高、提升力好、染色残夜清等特点。 (I), (II), (a), (b), (c)

Description

一种活性藏青至黑色染料组合物及染料制品 (一)技术领域
本发明涉及一种活性染料组合物及染料制品,特别涉及一种适用于含氮和/或含羟基纤维材料印染的活性藏青至黑色染料组合物及染料制品。
(二)背景技术
活性黑KNB由于价格低廉,牢度良好和易洗涤性,已成为黑色活性染料中用量最大的品种,但该染料对纤维的直接性不高,上染率和固色率不高,针对活性黑KNB的缺点,近年来染料研究者在活性黑色染料的研发方面做了大量的工作。现有的活性黑染料拼色产品在实际应用过程中仍然存在提升力不佳、上染率和固色率不高、染色织物不易清洗等问题,如专利CN102245712A、CN1730566A、CN1745147A等。
(三)发明内容
为解决上述问题,本发明的目的在于提供一种活性藏青至黑色染料组合物及染料制品,具有耐水洗牢度佳、固色率及吸尽率高、提升力好、染色残夜清等特点,适用于含氮和/或含羟基纤维材料及其混纺织物的印染。
为实现上述发明目的,本发明采用技术方案如下:
本发明提供了一种活性藏青至黑色染料组合物,包括组分A和组分B,其中组分A选自一种或多种如式(Ⅰ)所示的染料化合物,组分B选自一种或多种如式(Ⅱ)所示的染料化合物;基于所述的组分A和组分B,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%;
Figure PCTCN2018097754-appb-000001
式(Ⅰ)中:
D 1、D 2各自独立为下式(a)或(b)或(c)所示的基团;
Figure PCTCN2018097754-appb-000002
Figure PCTCN2018097754-appb-000003
上式(a)~(c)中:R 1、R 2、R 4、R 5、R 7、R 8彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;m=0-3,每个R 3各自独立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或C 1~C 4烷基;n=0-3,每个R 6各自独立选自氨基、羟基或磺酸基;X 1、X 2、X 3彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基、-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3,且D 1、D 2中至少有一个含有纤维活性基团,即-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3,其中p=1-3,q=1-3,Y 1~Y 3各自独立为-CH=CH 2、-C 2H 4OSO 3H或-CH 2CH 2Cl;
式(Ⅱ)中:
R 9、R 10、R 11、R 12彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;Y 4、Y 5各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl。
本发明中,所述的C 1~C 4直链或支链烷基可以是甲基、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;所述的C 1~C 4的烷酰氨基可以是甲酰氨基、乙酰氨基、正丙酰氨基、异丙酰氨基、正丁酰氨基、异丁酰氨基、叔丁酰氨基等。
作为优选,所述活性藏青至黑色染料组合物,包括组分A和组分B,其中组分A选自一种或多种如式(ⅠA)所示的染料化合物,组分B选自一种或多种如式(Ⅱ)所示的染料化合物;基于所述的组分A和组分B,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%;
Figure PCTCN2018097754-appb-000004
式(ⅠA)中:
D 1、D 2各自独立为下式(a)或(b)或(c)所示的基团;
Figure PCTCN2018097754-appb-000005
Figure PCTCN2018097754-appb-000006
上式(a)、(b)、(c)中:R 1、R 2、R 4、R 5、R 7、R 8彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;m=0-3,每个R 3各自独立选自磺酸基、脲基或C 1~C 4的烷酰氨基;n=0-3,每个R 6各自独立选自羟基或磺酸基;X 1、X 2、X 3彼此独立为-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3,其中p=1-3,q=1-3,Y 1~Y 3各自独立为-CH=CH 2、-C 2H 4OSO 3H或-CH 2CH 2Cl;
式(Ⅱ)中:
R 9、R 10、R 11、R 12彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;Y 4、Y 5各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl。
进一步,D 1、D 2皆来自通式(a)的基团,取代基可相同或不同;或者D 1选自式(a)所示的基团,D 2选自式(b)或式(c)所示的基团。
进一步,R 1、R 2、R 4、R 5、R 7、R 8彼此独立优选为H、甲基、甲氧基或磺酸基。
进一步,每个R 3各自独立优选为甲基、磺酸基、脲基或乙酰氨基。
进一步,R 9、R 10、R 11、R 12各自独立优选为H、甲基、甲氧基或磺酸基。
进一步,所述的活性藏青至黑色染料组合物,由组分A和组分B组成。
进一步,所述的活性藏青至黑色染料组合物,还可以包括组分C,组分C选自一种或多种如式(Ⅲ)~(Ⅵ)所示的化合物,所述组合物中,组分C的质量占组分A和组分B总质量的1~50%,优选为5~40%,
Figure PCTCN2018097754-appb-000007
Figure PCTCN2018097754-appb-000008
式(Ⅲ)中:
R 13、R 14、R 15、R 16彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基、羧基或磺酸基,其中,R 13~R 16各自独立优选为H、甲基、甲氧基、羧基或磺酸基;Y 6、Y 7各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;a为0或1;b为0或1;c、d彼此独立为0或1,优选为1;每个D 3、D 4彼此独立为取代的苯基、未取代的苯基、取代的萘基或未取代的萘基,所述的取代的苯基和取代的萘基的取代基个数分别为1-3个,每个取代基各自独立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或羟基,优选取代基个数分别为1-2个,每个取代基各自独立选自氨基、磺酸基、脲基、乙酰氨基、甲氧基或羟基;
式(Ⅳ)中:
R 17~R 20彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基,其中,R 17~R 20各自独立优选为H、甲基、甲氧基或磺酸基;s=0-1,Y 8、Y 9各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;
式(Ⅴ)中:
e、f、g各自独立为0-3,每个R 21、R 22、R 23各自独立为C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基,优选为甲基、甲氧基或磺酸基;X 4为氢或羧基;Y 10、Y 11各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;
式(Ⅵ)中:
h=0-2,每个R 24各自独立为C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基,优选为甲基、甲氧基或磺酸基;i=1-3,每个R 25各自独立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或羟基,优选氨基、磺酸基或乙酰氨基;Y 12为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl。
更进一步,组分C选自至少一种式(Ⅲ)和/或式(Ⅳ)所示的染料,其中a、b同为0,或a、b之一为0,另一为1,c为1,d为0或1。
再更进一步,本发明所述的活性藏青至黑色染料组合物,优选包含以下染料组分:
组分A:选自至少一种式(Ⅰ)的染料,其中,D 1、D 2彼此独立为通式(a)所示的基团,各取代基可相同或不同;或者D 1为式(a)所示的基团,D 2为式(b)或式(c)所示的基团;且D 1、D 2中至少有一个含-SO 2Y 1
组分B:选自至少一种式(Ⅱ)所示的染料;
组分C:选自至少一种式(Ⅲ)和/或式(Ⅳ)所示的染料,其中a、b同为0,或a、b之一为0,另一为1,c为1,d为0或1。
更进一步,所述的活性藏青至黑色染料组合物,由组分A、组分B和组分C组成。
再更进一步,本发明所述的活性藏青至黑色染料组合物,优选由以下染料组分组成:
组分A:选自至少一种式(Ⅰ)的染料,其中,D 1、D 2彼此独立为通式(a)所示的基团,各取代基可相同或不同;或者D 1为式(a)所示的基团,D 2为式(b)或式(c)所示的基团;且D 1、D 2中至少有一个含-SO 2Y 1
组分B:选自至少一种式(Ⅱ)所示的染料;
组分C:选自至少一种式(Ⅲ)和/或式(Ⅳ)所示的染料,其中a、b同为0,或a、b之一为0,另一为1,c为1,d为0或1。
具体的,所述组分A优选为下列之一或其中两种以上的混合物:
Figure PCTCN2018097754-appb-000009
Figure PCTCN2018097754-appb-000010
Figure PCTCN2018097754-appb-000011
Figure PCTCN2018097754-appb-000012
Figure PCTCN2018097754-appb-000013
Figure PCTCN2018097754-appb-000014
Figure PCTCN2018097754-appb-000015
Figure PCTCN2018097754-appb-000016
Figure PCTCN2018097754-appb-000017
Figure PCTCN2018097754-appb-000018
Figure PCTCN2018097754-appb-000019
Figure PCTCN2018097754-appb-000020
Figure PCTCN2018097754-appb-000021
Figure PCTCN2018097754-appb-000022
Figure PCTCN2018097754-appb-000023
其中,组分A更优选式(I-1)~(I-63)、(I-88)、(I-89)中的至少一种,更进一步优选式(I-1)~(I-21)、(I-27)~(I-33)、(I-41)~(I-63)、(I-88)、(I-89)中的至少一种,再更进一步优选式(I-1)、(I-3)、(I-4)、(I-31)、(I-32)、(I-41)、(I-48)、(I-51)、(I-52)、(I-55)、(I-88)中的至少一种,更特别优选式(I-31)、(I-32)、(I-51)及(I-52)中的至少一种。
具体的,所述组分B优选为下列之一或其中两种以上的混合物:
Figure PCTCN2018097754-appb-000024
Figure PCTCN2018097754-appb-000025
组分B特别优选式(Ⅱ-1)、式(Ⅱ-3)或其组合。
具体的,所述组分C优选为下列之一或其中两种以上的混合物:
Figure PCTCN2018097754-appb-000026
Figure PCTCN2018097754-appb-000027
Figure PCTCN2018097754-appb-000028
Figure PCTCN2018097754-appb-000029
Figure PCTCN2018097754-appb-000030
Figure PCTCN2018097754-appb-000031
Figure PCTCN2018097754-appb-000032
Figure PCTCN2018097754-appb-000033
Figure PCTCN2018097754-appb-000034
Figure PCTCN2018097754-appb-000035
Figure PCTCN2018097754-appb-000036
Figure PCTCN2018097754-appb-000037
Figure PCTCN2018097754-appb-000038
组分C更优选式(Ⅲ-1)~(Ⅲ-31)、(Ⅳ-1)~(Ⅳ-9)中的一种或多种,更进一步优选式(Ⅲ-1)、(Ⅲ-2)、(Ⅲ-4)、(Ⅳ-1)、(Ⅳ-3)中的至少一种。
本发明特别优选所述的染料组合物包括组分A和组分B:
组分A:选自式(I-1)、(I-3)、(I-4)、(I-31)、(I-32)、(I-41)、(I-48)、(I-51)、(I-52)、(I-55)及(I-88)所示染料中的至少一种,更特别优选式(I-31)、(I-32)、(I-51)及(I-52)所示染料中的至少一种;
其中,组分A更优选式(I-1)~(I-63)、(I-88)、(I-89)中的至少一种,更进一步优选式(I-1)~(I-21)、(I-27)~(I-33)、(I-41)~(I-63)、(I-88)、(I-89)中的至少一种,再更进一步优选式(I-1)、(I-3)、(I-4)、(I-31)、(I-32)、(I-41)、(I-48)、(I-51)、(I-52)、(I-55)、(I-88)中的至少一种,更特别优选式(I-31)、(I-32)、(I-51)及(I-52)中的至少一种。
组分B:选自式(Ⅱ-1)和/或(Ⅱ-3)所示染料;
基于所述组分A~B质量之和,组分A的质量百分含量优选为5~50%,组分B的质量百分含量优选为50~95%。
本发明还特别优选所述的染料组合物包括组分A、组分B和组分C:
组分A:选自式(I-1)、(I-3)、(I-4)、(I-31)、(I-32)、(I-41)、(I-48)、(I-51)、(I-52)、(I-55)及(I-88)所示染料中的至少一种,更特别优选式(I-31)、(I-32)、(I-51)及(I-52)所示染料中的至少一种;
组分B:选自式(Ⅱ-1)和/或(Ⅱ-3)所示染料;
组分C:选自式(Ⅲ-1)、(Ⅲ-2)、(Ⅲ-4)、(Ⅳ-1)、(Ⅳ-3)所示染料中的至少一种;
基于所述组分A~B质量之和,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%,组分C的质量为组分A和组分B总质量的1~50%。
本发明所述的活性藏青至黑色染料组合物,所使用的染料化合物(Ⅱ)~(Ⅵ)均为已知染料,可通过常规方法合成得到,例如通过使用本领域技术人员熟知的合适的组分和使用必要的比例借助于通常的重氮化反应和偶合反应合成,或参照专利CN101250334A、CN1163291A、CN105176139A中的方法或近似的方法制备。
所述的式(I)化合物也可按照活性染料常规的重氮、偶合方法进行制备,例如:
(1)重氮化:将下式(a0)、式(b0)和/或式(c0)所示的化合物各自与水、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);重氮终点到后,用氨基磺酸消除过量的亚硝酸钠,重氮液保存备用;其中,式(a0)、式(b0)或式(c0)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):(1-1.02)。
(2)偶合反应:
将3,5-二羟基苯甲酸加水打浆,打浆好的3,5-二羟基苯甲酸溶液视需要与步骤(1)获得的其中一种重 氮盐进行分步偶合,第一次偶合时优选控制PH值在3~4.5、温度在0-30℃(优选为0-20℃)进行偶合反应,用HPLC监测游离3,5-二羟基苯甲酸在3%以下时停止反应;然后一次偶合产物再视需要与步骤(1)获得的其中一种重氮盐进行第二次偶合,第二次偶合时,优选控制PH值在5.0~8.0、温度在0-30℃(优选为0-20℃)进行偶合反应,用HPLC监测到一次偶合产物在3%以下,则第二次偶合反应完成,即可得到活性染料化合物(Ⅰ);其中,3,5-二羟基苯甲酸与两次偶合采用的重氮盐的摩尔比分别控制为1:(0.95-1.2),优选为1:(0.98-1.08);或进一步加碱调PH值10~11水解成乙烯砜的形式,再酸化;
Figure PCTCN2018097754-appb-000039
所述的式(a0)、(b0)、(c0)中各取代基定义同式(Ⅰ)。
需要强调的是,本发明所述的活性藏青至黑色染料组合物中,在酚羟基邻位偶合的染料化合物单体,经常以醌腙体的稳定态存在,亦即通式(Ⅰ)的染料实质含有下式(Ⅰa)和/或式(Ⅰb)和/或(Ⅰc)和/或(Ⅰd)所示的醌腙体结构、通式(Ⅱ)、(Ⅳ)的染料实质含有下式(Ⅱa)、(Ⅳa)所示的醌腙体结构,考虑到本领域技术人员的书写习惯,在发明内容和实施例部分仍采用了偶氮体的书写形式,这并不影响本发明的实质:
Figure PCTCN2018097754-appb-000040
Figure PCTCN2018097754-appb-000041
上述式(Ia)~(Id)中取代基的定义同式(I),式(IIa)和(IVa)中取代基的定义分别同式(II)和(IV)。
另外,本发明所述的活性藏青至黑色染料组合物,各单色染料化合物皆以其自由酸的形式进行表征,而在实际合成过程中,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)~式(Ⅵ)中的羧基、磺酸基可以羧酸钠、磺酸钠的形式存在。
本发明所述的活性藏青至黑色染料组合物,其制备方法包括将染料组分A、B或者A、B、C按照前述配比进行混合,混合可采用常规的机械方式进行,如在研磨机、捏合机或均质机中进行,混合过程中,单个染料化合物(Ⅰ)~(Ⅵ)可以粉状、粒状、水溶液或合成溶液形式存在,当单个染料化合物以合成溶液的形式拼混时,从合成溶液分离本发明所述的复合活性藏青至黑色染料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,或将混合溶液蒸发、喷雾干燥,因此,染料组分A、B、C及其染料组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)。
本发明所述的活性藏青至黑色染料组合物,作为商品出售时,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藏青至黑色染料制品,其含有所述的活性藏青至黑色染料组合物。优选的,所述的活性藏青至黑色染料制品中,含有所述的活性藏青至黑色染料组合物和助剂。所述助剂的重量不超过活性藏青至黑色染料组合物重量的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。
本发明所述的活性藏青至黑色染料制品,适用于含氮和/或含羟基纤维材料的印染,所述含氮和/或含羟基纤维材料可以是纤维素纤维、聚酰胺纤维及其织物,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藏青至黑色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。
本发明的有益效果主要体现在:本发明活性藏青至黑色染料组合物和制品,用于含氮和/或含羟基纤维材料印染时,具有提升性好、配伍性好、上染率和固色率高、染色残液清、水洗牢度优异等特点。
(四)附图说明
图1是实施例1制得的橙色活性染料化合物(I-1)的1HNMR谱图;
图2是实施例1制得的橙色活性染料化合物(I-1)的LC-MS谱图。
图3为实施例1制得的化合物(I-31)的1H NMR谱图;
图4为实施例1制得的化合物(I-31)的13C NMR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,凡在本发明通式范围内,通过相应基团变换得到的具有相似性能的染料组合物,皆应在本发明保护范围之类。
实施例1
1)重氮化:将100g水、100g冰投入32.5g(0.2mol)克里西丁对位酯(2-甲氧基-5甲基对位酯)打浆1h,再加40g 31%盐酸(含HCl 0.34mol),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,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,重氮液保存备用。
2)一次偶合:将15.4g(0.1mol)3,5-二羟基苯甲酸加入200g水中打浆,打浆完毕将0.1mol克里西丁对位酯重氮液加入3,5-二羟基苯甲酸溶液中,同时用30%液碱控制pH在4.0,温度控制在0-20℃,反应0.5~2h,用HPLC控制游离3,5-二羟基苯甲酸在3%以下即到终点,否则,延长反应时间到终点,得到的一次偶合物备用。
3)二次偶合:将0.1mol克里西丁对位酯重氮液加入一次偶合物中,用30%液碱控制pH在5.0-8.0,温度T控制在0-20℃,反应0.5~2h,用HPLC控制游离3,5-二羟基苯甲酸在3%以下即到终点,干燥,得到橙色活性染料化合物(I-1),水溶液中λ max=465nm。
Figure PCTCN2018097754-appb-000042
实施例2~30:
参照实施例1所述的双偶氮染料制备方法,经分步偶合,可分别制得下表1和表2中所示结构的染料化合物:
表1
Figure PCTCN2018097754-appb-000043
Figure PCTCN2018097754-appb-000044
Figure PCTCN2018097754-appb-000045
表2
Figure PCTCN2018097754-appb-000046
Figure PCTCN2018097754-appb-000047
Figure PCTCN2018097754-appb-000048
实施例31
1)重氮化:
将28.1g(0.1mol)对位酯(对-β-羟乙基砜硫酸酯苯胺)投入100g水、100g冰中打浆约1h,再加20g31%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,得到的对位酯重氮液保存备用。
将36.1g(0.1mol)磺化对位酯(2-磺酸-4-β-羟乙砜硫酸酯苯胺)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,得到的磺化对位酯重氮液保存备用。
取上述0.1mol的磺化对位酯重氮液加入到15.1g(0.1mol)间脲(间脲基苯胺)中,用30%液碱控制pH在4.0-6.0,温度T控制在0-20℃,偶合反应0.5-2h,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(若不到则继续反应至终点),得色基1,向该色基1中加入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1-2h,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,得到色基1的重氮液保存备用。
2)偶合:
首先将154g(0.1mol)3,5-二羟基苯甲酸加入200g水中进行打浆,用纯碱调pH=8.0-9.0,温度20-25℃,将打浆好的3,5-二羟基苯甲酸溶液加入到步骤1)中得到的0.1mol对位酯重氮液中,用30%液碱控制pH在4.0,温度控制在0-20℃,反应0.5-2.5h,用HPLC控制游离3,5-二羟基苯甲酸在3%以下即到终点,得下式(A)所示的色基2,氢谱表征[ 1HNMR(DMSO-d6)[3.68-3.71ppm 2H(t),3.98-4.01ppm 2H(t),6.42ppm1H(s),6.62ppm 1H(s),7.96-7.97ppm 2H(d),8.05-8.07ppm 2H(d)]。
Figure PCTCN2018097754-appb-000049
将步骤(1)中制得的色基1的重氮液加入到色基2中,用30%液碱控制pH在5.0-8.0,温度T控制在0-20℃,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-31),水溶液中λmax=485nm,质谱(ESI-MS)m/z(-):325.84([M-3H] 3-/3)、488.96([M-2H] 2-/2)、978.89([M-H] -1)。染料(以游离磺酸计)最丰精确分子质量数M为980.0,氢谱表征为[ 1HNMR(DMSO-d6)[3.61-3.74ppm 4H(m),3.96-4.04ppm 4H(m),6.22ppm 1H(s),7.48-8.20ppm 8H(m),8.40ppm 1H(s),9.02ppm 1H(s),11.1ppm 1H(s)]
Figure PCTCN2018097754-appb-000050
实施例32~90:
参照实施例31所述的偶氮染料制备方法,按需经分步重氮和偶合反应,可分别制得下表3-7中所示结构的染料化合物。
表3
Figure PCTCN2018097754-appb-000051
Figure PCTCN2018097754-appb-000052
Figure PCTCN2018097754-appb-000053
Figure PCTCN2018097754-appb-000054
Figure PCTCN2018097754-appb-000055
表4
Figure PCTCN2018097754-appb-000056
Figure PCTCN2018097754-appb-000057
Figure PCTCN2018097754-appb-000058
表5
Figure PCTCN2018097754-appb-000059
Figure PCTCN2018097754-appb-000060
Figure PCTCN2018097754-appb-000061
表6
Figure PCTCN2018097754-appb-000062
Figure PCTCN2018097754-appb-000063
表7
Figure PCTCN2018097754-appb-000064
Figure PCTCN2018097754-appb-000065
实施例91:
将25份式(I-1)的染料、75份式(Ⅱ-3)的染料和10份元明粉进行机械混合,得到的复合染料采用常规浸染法染棉为黑色,耐水洗沾色特别是锦纶、涤纶、腈纶沾色牢度达4~5级以上(参照ISO 105 C10-2006),提升力及固色率优异(参照GB/T21875-2016及GB/T2391-2014)。
Figure PCTCN2018097754-appb-000066
实施例92:
将35份式(I-31)的染料、65份式(Ⅱ-3)的染料和10份元明粉进行机械混合,得到的复合染料采用常规浸染法染棉为黑色,耐水洗沾色特别是锦纶、涤纶、腈纶沾色牢度达4~5级以上(参照ISO 105 C10-2006),提升力及固色率优异(参照GB/T21875-2016及GB/T2391-2014)。
Figure PCTCN2018097754-appb-000067
实施例93:
将30份式(I-31)的染料、5份式(Ⅰ-4)的染料、65份式(Ⅱ-3)的染料和10份元明粉进行机械混合,得到的复合染料采用常规浸染法染棉为黑色,耐水洗沾色特别是锦纶、涤纶、腈纶沾色牢度达4~5级以上(参照ISO 105 C10-2006),提升力及固色率优异(参照GB/T21875-2016及GB/T2391-2014)。
Figure PCTCN2018097754-appb-000068
实施例94:
将30份式(I-31)的染料、5份式(Ⅰ-3)的染料、65份式(Ⅱ-3)的染料和10份元明粉进行机械混合,得到的复合染料采用常规浸染法染棉为黑色,耐水洗沾色特别是锦纶、涤纶、腈纶沾色牢度达4~5级以上(参照ISO 105 C10-2006),提升力及固色率优异(参照GB/T21875-2016及GB/T2391-2014)。
Figure PCTCN2018097754-appb-000069
Figure PCTCN2018097754-appb-000070
实施例95:
将20份式(I-31)的染料、65份式(Ⅱ-3)的染料、15份式(Ⅲ-1)的染料和10份元明粉进行机械混合,得到的复合染料采用常规浸染法染棉为深黑色,耐水洗沾色特别是锦纶、涤纶、腈纶沾色牢度达4~5级以上(参照ISO 105 C10-2006),提升力及固色率优异(参照GB/T21875-2016及GB/T2391-2014)。
Figure PCTCN2018097754-appb-000071
实施例96:
将20份式(I-31)的染料、65份式(Ⅱ-3)的染料、10份式(Ⅳ-1)的染料和10份元明粉和10份分散剂MF进行机械混合,得到的复合染料染棉为深黑色,耐水洗沾色特别是锦纶、涤纶、腈纶沾色牢度达4~5级以上(参照ISO 105 C10-2006),提升力及固色率优异(参照GB/T 21875-2016及GB/T2391-2014)。
Figure PCTCN2018097754-appb-000072
Figure PCTCN2018097754-appb-000073
实施例97~286
按照实施例91或实施例96所述的方法,机械混合表7和8中所列配比的染料,按照活性染料常规染色法,染棉为藏青至黑色,耐水洗沾色特别是锦纶、涤纶、腈纶沾色牢度达4~5级以上(参照ISO 105 C10-2006),提升力优异(参照标准GB/T 21875-2016),提升力及固色率优异(参照GB/T 21875-2016及GB/T2391-2014)。
表7
Figure PCTCN2018097754-appb-000074
Figure PCTCN2018097754-appb-000075
Figure PCTCN2018097754-appb-000076
Figure PCTCN2018097754-appb-000077
Figure PCTCN2018097754-appb-000078
表8
Figure PCTCN2018097754-appb-000079
Figure PCTCN2018097754-appb-000080
Figure PCTCN2018097754-appb-000081
对比例1:按照专利CN1858118中的实施例2,制备如下三组分的活性黑染料:
Figure PCTCN2018097754-appb-000082
对比例2:按照专利CN1730566中的实施例6,制备如下三组分的活性黑染料:
Figure PCTCN2018097754-appb-000083
应用实施例1:
将实施例91~96(最接近)与对比例1、2得到的活性黑染料干品分别溶解在水中,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,得到藏青至黑色染织物。参照ISO 105 C10-2006的方法进行耐洗色牢度测试,结果如表9:
表9
Figure PCTCN2018097754-appb-000084
应用实施例2:
将本发明中代表性的实施例91~96、对比实施例1~2中制得的活性染料按照标准GB/T 21875-2016标准中所规定的方法测试其提升力,发现实施例91-96的活性染料,提升力明显好于对比例1~2,在同等染色条件下,可节约染料用量5~15%,经济性显著。
应用实施例3
将本发明中实施例91-96、对比实施例1-2中制得的活性染料按照GB/T2391-2014标准中所规定的方法测试固色率,所得结果如表10所示:
表10
实施例 实施例91 实施例92 实施例93 实施例94 实施例95 实施例96 对比例1 对比例2
固色率 76.1% 75.9% 75.2% 76.5% 75.7% 76.3% 71.6% 70.5%
综上所述,本发明的染料明显优于对比实施例,对于本行业而言,其在色牢度、提升力及固色率方面有显著的改善。

Claims (17)

  1. 一种活性藏青至黑色染料组合物,包括组分A和组分B,其中组分A选自一种或多种如式(Ⅰ)所示的染料化合物,组分B选自一种或多种如式(Ⅱ)所示的染料化合物;基于所述的组分A和组分B,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%;
    Figure PCTCN2018097754-appb-100001
    式(Ⅰ)中:
    D 1、D 2各自独立为下式(a)或(b)或(c)所示的基团;
    Figure PCTCN2018097754-appb-100002
    上式(a)~(c)中:R 1、R 2、R 4、R 5、R 7、R 8彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;m=0-3,每个R 3各自独立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或C 1~C 4烷基;n=0-3,每个R 6各自独立选自氨基、羟基或磺酸基;X 1、X 2、X 3彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基、-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3,且D 1、D 2中至少有一个含有纤维活性基团,即-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3,其中p=1-3,q=1-3,Y 1~Y 3各自独立为-CH=CH 2、-C 2H 4OSO 3H或-CH 2CH 2Cl;
    式(Ⅱ)中:
    R 9、R 10、R 11、R 12彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;Y 4、Y 5各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl。
  2. 如权利要求1所述的活性藏青至黑色染料组合物,其特征在于:所述组合物包括组分A和组分B, 其中组分A选自一种或多种如式(IA)所示的染料化合物,组分B选自一种或多种如式(Ⅱ)所示的染料化合物;基于所述的组分A和组分B,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%;
    Figure PCTCN2018097754-appb-100003
    式(IA)中:
    D 1、D 2各自独立为下式(a)或(b)或(c)所示的基团;
    Figure PCTCN2018097754-appb-100004
    上式(a)、(b)、(c)中:R 1、R 2、R 4、R 5、R 7、R 8彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;m=0-3,每个R 3各自独立选自磺酸基、脲基或C 1~C 4的烷酰氨基;n=0-3,每个R 6各自独立选自羟基或磺酸基;X 1、X 2、X 3彼此独立为-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3,其中p=1-3,q=1-3,Y 1~Y 3各自独立为-CH=CH 2、-C 2H 4OSO 3H或-CH 2CH 2Cl;
    式(Ⅱ)中:
    R 9、R 10、R 11、R 12彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;Y 4、Y 5各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl。
  3. 如权利要求1或2所述的活性藏青至黑色染料组合物,其特征在于:D 1、D 2皆选自通式(a)的基团,取代基可相同或不同;或者D 1选自式(a)所示的基团,D 2选自式(b)或式(c)所示的基团。
  4. 如权利要求1所述的活性藏青至黑色染料组合物,其特征在于:所述组分A为下列之一或其中两种以上的混合物:
    Figure PCTCN2018097754-appb-100005
    Figure PCTCN2018097754-appb-100006
    Figure PCTCN2018097754-appb-100007
    Figure PCTCN2018097754-appb-100008
    Figure PCTCN2018097754-appb-100009
    Figure PCTCN2018097754-appb-100010
    Figure PCTCN2018097754-appb-100011
    Figure PCTCN2018097754-appb-100012
    Figure PCTCN2018097754-appb-100013
    Figure PCTCN2018097754-appb-100014
    Figure PCTCN2018097754-appb-100015
    Figure PCTCN2018097754-appb-100016
    Figure PCTCN2018097754-appb-100017
    Figure PCTCN2018097754-appb-100018
    Figure PCTCN2018097754-appb-100019
  5. 如权利要求1或2所述的活性藏青至黑色染料组合物,其特征在于:组分A选自式(I-1)~(I-63)、(I-88)、(I-89)中的至少一种,优选式(I-1)~(I-21)、(I-27)~(I-33)、(I-41)~(I-63)、(I-88)、(I-89)中的至少一种,进一步优选式(I-1)、(I-3)、(I-4)、(I-31)、(I-32)、(I-41)、(I-48)、(I-51)、(I-52)、(I-55)、(I-88)中的至少一种,更特别优选式(I-31)、(I-32)、(I-51)及(I-52)中的至少一种。
  6. 如权利要求1或2所述的活性藏青至黑色染料组合物,其特征在于:所述组分B为下列之一或其中两种以上的混合物:
    Figure PCTCN2018097754-appb-100020
    Figure PCTCN2018097754-appb-100021
  7. 如权利要求1或2所述的活性藏青至黑色染料组合物,其特征在于:所述的活性藏青至黑色染料组合物由组分A和组分B组成。
  8. 如权利要求1或2所述的活性藏青至黑色染料组合物,其特征在于:所述的活性藏青至黑色染料组合物还包括组分C,组分C选自一种或多种如式(Ⅲ)~(Ⅵ)所示的化合物,所述组合物中,组分C的质量占组分A和组分B总质量的1~50%,
    Figure PCTCN2018097754-appb-100022
    Figure PCTCN2018097754-appb-100023
    式(Ⅲ)中:
    R 13、R 14、R 15、R 16彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基、羧基或磺酸基;Y 6、Y 7各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;a为0或1;b为0或1;c、d彼此独立为0或1;每个D 3、D 4彼此独立为取代的苯基、未取代的苯基、取代的萘基或未取代的萘基,所述的取代的苯基和取代的萘基的取代基个数分别为1-3个,每个取代基各自独立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或羟基;
    式(Ⅳ)中:
    R 17~R 20彼此独立为H、C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;s=0-1,Y 8、Y 9各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;
    式(Ⅴ)中:
    e、f、g各自独立为0-3,每个R 21、R 22、R 23各自独立为C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;X 4为氢或羧基;Y 10、Y 11各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;
    式(Ⅵ)中:
    h=0-2,每个R 24各自独立为C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基;i=1-3,每个R 25各自独 立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或羟基;Y 12为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl。
  9. 如权利要求8所述的活性藏青至黑色染料组合物,其特征在于:组分C选自至少一种式(Ⅲ)和/或式(Ⅳ)所示的染料,其中a、b同为0,或a、b之一为0,另一为1,c为1,d为0或1。
  10. 如权利要求8所述的活性藏青至黑色染料组合物,其特征在于:所述的活性藏青至黑色染料组合物包含以下染料组分:
    组分A:选自至少一种式(Ⅰ)的染料,其中,D 1、D 2彼此独立为通式(a)所示的基团,各取代基可相同或不同;或者D 1为式(a)所示的基团,D 2为式(b)或式(c)所示的基团;且D 1、D 2中至少有一个含-SO 2Y 1
    组分B:选自至少一种式(Ⅱ)所示的染料;
    组分C:选自至少一种式(Ⅲ)和/或式(Ⅳ)所示的染料,其中a、b同为0,或a、b之一为0,另一为1,c为1,d为0或1。
  11. 如权利要求8所述的活性藏青至黑色染料组合物,其特征在于:所述组分C为下列之一或其中两种以上的混合物:
    Figure PCTCN2018097754-appb-100024
    Figure PCTCN2018097754-appb-100025
    Figure PCTCN2018097754-appb-100026
    Figure PCTCN2018097754-appb-100027
    Figure PCTCN2018097754-appb-100028
    Figure PCTCN2018097754-appb-100029
    Figure PCTCN2018097754-appb-100030
    Figure PCTCN2018097754-appb-100031
    Figure PCTCN2018097754-appb-100032
    Figure PCTCN2018097754-appb-100033
    Figure PCTCN2018097754-appb-100034
    Figure PCTCN2018097754-appb-100035
    Figure PCTCN2018097754-appb-100036
  12. 如权利要求8~11之一所述的活性藏青至黑色染料组合物,其特征在于:所述的活性藏青至黑色染料组合物由组分A、组分B和组分C组成。
  13. 如权利要求4所述的活性藏青至黑色染料组合物,其特征在于:所述的染料组合物包括组分A和组分B,其中:
    组分A:选自式(Ⅰ-1)、(Ⅰ-3)、(Ⅰ-4)、(Ⅰ-31)、(Ⅰ-32)、(Ⅰ-41)、(Ⅰ-48)、(Ⅰ-51)、(Ⅰ-52)、(Ⅰ-55)、(I-88)所示染料中的至少一种,更特别优选式(Ⅰ-31)、(Ⅰ-32)、(Ⅰ -51)及(Ⅰ-52)所示染料中的至少一种;
    组分B:选自式(Ⅱ-1)和/或(Ⅱ-3)所示染料;
    基于所述组分A~B质量之和,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%;
    Figure PCTCN2018097754-appb-100037
  14. 如权利要求4所述的活性藏青至黑色染料组合物,其特征在于:所述的染料组合物包括组分A、组分B和组分C,其中:
    组分A:选自式(Ⅰ-1)、(Ⅰ-3)、(Ⅰ-4)、(Ⅰ-31)、(Ⅰ-32)、(Ⅰ-41)、(Ⅰ-48)、(Ⅰ-51)、(Ⅰ-52)、(Ⅰ-55)及(I-88)所示染料中的至少一种,更特别优选式(Ⅰ-31)、(Ⅰ-32)、(Ⅰ-51)及(Ⅰ-52)所示染料中的至少一种;
    组分B:选自式(Ⅱ-1)和/或(Ⅱ-3)所示染料;
    组分C:选自式(Ⅲ-1)、(Ⅲ-2)、(Ⅲ-4)、(Ⅳ-1)、(Ⅳ-3)所示染料中的至少一种;
    基于所述组分A~B质量之和,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%,组分C的质量为组分A和组分B总质量的1~50%;
    Figure PCTCN2018097754-appb-100038
    Figure PCTCN2018097754-appb-100039
  15. 如权利要求1或2所述的活性藏青至黑色染料组合物,其特征在于:通式(Ⅰ)的染料含有下式(Ⅰa)和/或式(Ⅰb)和/或(Ⅰc)和/或(Ⅰd)所示的醌腙体结构,通式(Ⅱ)的染料含有下式(Ⅱa)所示的醌腙体结构:
    Figure PCTCN2018097754-appb-100040
    Figure PCTCN2018097754-appb-100041
    上述式(Ia)~(Id)中取代基的定义同式(I),式(IIa)中取代基的定义同式(II)。
  16. 如权利要求8所述的活性藏青至黑色染料组合物,其特征在于:通式(Ⅳ)的染料含有下式(Ⅳa)所示的醌腙体结构:
    Figure PCTCN2018097754-appb-100042
    上述式(IVa)中取代基的定义同式(IV)。
  17. 一种活性藏青至黑色染料制品,其含有权利要求1或2所述的活性藏青至黑色染料组合物。
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