CN105542510A - Reactive black dye composition and dye product - Google Patents
Reactive black dye composition and dye product Download PDFInfo
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- CN105542510A CN105542510A CN201510571156.XA CN201510571156A CN105542510A CN 105542510 A CN105542510 A CN 105542510A CN 201510571156 A CN201510571156 A CN 201510571156A CN 105542510 A CN105542510 A CN 105542510A
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- black dye
- active black
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Links
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229910052728 basic metal Inorganic materials 0.000 claims description 11
- 150000003818 basic metals Chemical class 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 17
- 238000009980 pad dyeing Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 238000007639 printing Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 99
- 239000002253 acid Substances 0.000 description 18
- 239000004744 fabric Substances 0.000 description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 241000219146 Gossypium Species 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000006193 diazotization reaction Methods 0.000 description 5
- 239000000344 soap Substances 0.000 description 4
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZSBCZEFDYNLRQQ-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid;sodium Chemical compound [Na].NC1=CC=C(S(O)(=O)=O)C(N)=C1 ZSBCZEFDYNLRQQ-UHFFFAOYSA-N 0.000 description 1
- WODGMMJHSAKKNF-UHFFFAOYSA-N 2-methylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WODGMMJHSAKKNF-UHFFFAOYSA-N 0.000 description 1
- 0 C*C(C(N)=CC(*)=C[*@@](*=C(C(*)=CC(C**(C)c1c(*)cc(*)cc1)=C1C=CC(*)=C)C1=*)I)=CC Chemical compound C*C(C(N)=CC(*)=C[*@@](*=C(C(*)=CC(C**(C)c1c(*)cc(*)cc1)=C1C=CC(*)=C)C1=*)I)=CC 0.000 description 1
- 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
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 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
- 238000005097 cold rolling Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010016 exhaust dyeing Methods 0.000 description 1
- 239000002657 fibrous material Substances 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
- 239000012943 hotmelt Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- ZNRSXPDDVNZGEN-UHFFFAOYSA-K trisodium;chloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O ZNRSXPDDVNZGEN-UHFFFAOYSA-K 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- Coloring (AREA)
Abstract
The invention relates to a reactive black dye composition and a dye product. The reactive black dye composition includes, by weight, 45-95 parts of a component A, 5-55 parts of a component B and 0-40 parts of a component C, the component A is selected from at least one compound represented by formula (I), the component B is selected from at least one compound represented by formula (II), and the compound C is selected from at least one compound represented by formula (III) and/or formula (IV). The reactive black dye product includes the reactive black dye composition. The product has the advantages of good deep dyeing property, excellent lifting force, high color fixing rate, good compatibleness, excellent color fastness, realization of less dye dosage, easy water washing and clear raffinate in the printing and dyeing process, stable saline-alkaline resistance, stable dyeing performance, and suitableness for dip dyeing, pad dyeing, printing and other technologies.
Description
(1) technical field
The present invention relates to a kind of active black dye composition and dye preparations.
(2) background technology
Black dyes is the chromatogram that in dyestuff, consumption is maximum always, in the dyeing and stamp of cotton fabric, black chromatogram account for about 50% of whole chromatogram, but black and active dye does not still have so far, and energy in 400 ~ 700nm wavelength region is even, the dyestuff commodity of hypersorption.C.I. reactive black 5 accounts for very large proportion in black chromatogram now, but there is the shortcomings such as little to fiber affinity, degree of fixation is low, pitch black degree is undesirable, and the black and active dye that therefore will obtain just must form with multi-component dyes is composite.
But existing reactive black dye colorant match product still exists in actual application that depth is strong and degree of fixation is not high, the DYED FABRICS not problem such as easy cleaning, as patent CN1195678A, CN103194091A, CN1858118A etc.This is because deep color dyeing dye strength used is high, loose colour amount of dye increases, and fiber is to the saturation value that is adsorbed with of dyestuff, dye strength is generally no more than 10% of dyeing saturation value, excessive dyestuff can not go up dye and set, can pile up, if easy cleaning is bad at fabric face, the wet colour fastness of dyeing and weaving thing certainly will be affected, thus cause dyeing behavior not good enough.
(3) summary of the invention
The dye preparations that the object of the present invention is to provide a kind of active black dye composition and obtained by it, depth is good, lifting force is excellent, degree of fixation is high, and compatibleness is good, and colour fastness is excellent, few, the easy washing of dyeing process dye dosage, raffinate are clear, Salt And Alkali Tolerance stable performance, dyeing behavior is stablized, and is applicable to the different process such as dip-dye, pad dyeing and stamp.
The technical solution used in the present invention is:
A kind of active black dye composition, comprise component A, B component and component C, described component A is selected from the compound shown at least one formula I, described B component is selected from the compound shown at least one formula II, described component C is selected from the compound shown at least one formula III and/or formula IV, based on described component A, B component and component C, the weight part of component A is 45 ~ 95 parts, the weight part of B component is 5 ~ 55 parts, and the weight part of component C is 0 ~ 40 part:
In formula I:
R
1, R
2, R
3respective independence is-H ,-C
1~ C
4alkyl ,-C
1~ C
4alkoxyl group or-SO
3m
1, be preferably-H ,-CH
3,-OCH
3or-SO
3m
1; Y
1for-CH=CH
2or-C
2h
4oSO
3m
1; M
1for H or basic metal;
In formula II:
R
4, R
5in both, one is
wherein R
12for H ,-OCH
3or-SO
3m
2;
Another be
wherein R
13for-NHCONH
2, or-NHCOCH
3; R
14for H or-OCH
3; R
15for H ,-OCH
3or-SO
3m
2; M
2for H or basic metal;
In formula III:
R
6, R
7respective independence is-H or-SO
3m
3, R
8for-SO
2y
2or-C
1~ C
4alkyl, is preferably-SO
2y
2or-CH
3, Y
2for-CH=CH
2or-C
2h
4oSO
3m
3, M
3for H or basic metal;
In formula IV:
R
9, R
10respective independence is-H ,-C
1~ C
4alkyl ,-C
1~ C
4alkoxyl group or-SO
3m
4, be preferably-H ,-CH
3,-OCH
3or-SO
3m
4; R
11for-H or-SO
3m
4; Y
3for-CH=CH
2or-C
2h
4oSO
3m
4; M
4for H or basic metal.
Preferably, based on described component A ~ C quality sum, the mass percentage of component A is 45 ~ 95%, the mass percentage of B component be 5 ~ 55%, component C mass percentage be 0 ~ 40%.
More preferably, described active black dye composition is made up of component A, B component and component C, and wherein, the mass percentage of component A is 45 ~ 95%, the mass percentage of B component be 5 ~ 55%, component C mass percentage be 0 ~ 40%.
Particularly preferred, described active black dye composition is made up of component A, B component and component C, and the mass percentage of component A is 55 ~ 90%, the mass percentage of B component be 5 ~ 40%, component C mass percentage be 0 ~ 35%.
Preferably, when component C content in described active black dye composition is not 0, the mass percentage of component C is 3-40%, is more preferably 3-35%.
Preferably, in described formula I ,-SO
2y
1be positioned at contraposition or a position of azo group.
Preferably, in described formula II ,-SO
2cH
2cH
2oSO
3m
2be positioned at contraposition or a position of azo group.
Preferably, in described formula III ,-SO
2y
2be positioned at contraposition or a position of azo group.
Preferably, described basic metal is Li, Na or K; Preferred, described basic metal is Na or K; Further preferred M
1~ M
4independently be preferably H or Na separately.
Concrete, described component A is preferably one of following or wherein two or more mixtures, wherein M
1for H (free acid form) or Na (form of salt):
Concrete, described B component is preferably one of following or wherein two or more mixtures, wherein M
2for H (free acid form) or Na (form of salt):
Concrete, described component C is preferably one of following or wherein two or more mixtures, wherein M
3, M
4for H (free acid form) or Na (form of salt):
Particularly preferred, active black dye composition of the present invention comprises following component A and B component, wherein the content of component C is 0, the mass percentage of component A is 45 ~ 95% (being more preferably 55 ~ 90%), and the mass percentage of B component is 5 ~ 55% (being more preferably 10 ~ 45%); Wherein
Component A is selected from least one in formula (I-1), (I-3);
B component is selected from least one in formula (II-1), (II-5), (II-12), (II-18).
Or it is particularly preferred, active black dye composition of the present invention comprises following component A, B component and component C, based on component A, B component and component C, the mass percentage of component A is 45 ~ 95% (being more preferably 55 ~ 90%), the mass percentage of B component is 5 ~ 55% (being more preferably 5 ~ 40%), and the mass percentage of component C is 3 ~ 40% (being more preferably 3 ~ 35%); Wherein
Component A is selected from least one in formula (I-1), (I-3);
B component is selected from least one in formula (II-1), (II-5), (II-12), (II-18);
Component C is selected from least one in formula (III-1), (III-2), (III-7), (IV-1), (IV-3).
Or, particularly preferred, active black dye composition of the present invention is made up of following component A, B component and component C, the mass percentage of component A is 45 ~ 95% (being more preferably 55 ~ 90%), the mass percentage of B component is 5 ~ 55% (being more preferably 5 ~ 40%), and the mass percentage of component C is 3 ~ 40% (being more preferably 3 ~ 35%); Wherein
Component A is selected from least one in formula (I-1), (I-3);
B component is selected from least one in formula (II-1), (II-5), (II-12), (II-18);
Component C is selected from least one in formula (III-1), (III-2), (III-7), (IV-1), (IV-3).
The dye composition of formula I ~ formula IV of the present invention, can free acid (M
1~ M
4for-H) or the form of salt exist, there is no impact to its dyeing behavior, just in order to easy to prepare, preferably exist in a salt form, described salt can be an alkali metal salt (M
1~ M
4for basic metal), be particularly preferably sodium salt or sylvite (M
1~ M
4for Na or K).
Active black dye composition of the present invention, the dye composition (I) used, (II), (III), (IV) obtain by ordinary method, such as by using suitable component well known to those skilled in the art and using necessary ratio by means of common diazotization reaction and coupled reaction synthesis, or with reference to the method in patent CN101250334, CH695613, WO2013189817 and CN101284950 or the preparation of approximate method, wherein compound (II) is also prepared by following methods:
Coupled reaction is carried out with formula VI compound by after formula (V) compound diazotization, add Sodium Nitrite and cryosel acid stirs, carry out acid with formula (VII) compound occasionally to react, add formula (VIII) compound after diazotization again and carry out the even reaction of alkali, obtain formula II compound; Or, by carrying out with formula (VII) compound after formula (VIII) compound diazotization, acid is even reacts to obtain acidic coupling object, coupled reaction is carried out with formula VI compound by after (V) compound diazotization, carry out alkali more occasionally to react with acidic coupling object, obtain formula II compound.
R
12, R
13, R
14, R
15, M
2definition the same.
In active black dye composition of the present invention, phenolic hydroxyl group oxidizable formation quinone hydrazone structure in formula I and/or formula IV, therefore, the dye composition shown in formula I and formula IV also can adopt following structure to characterize respectively:
The same formula I of each substituent definition, (IV) in above-mentioned two formulas.
Active black dye composition of the present invention, its preparation method comprises dye component A, B, C mixes according to aforementioned proportioning, mixing can adopt conventional mechanical system to carry out, as at shredder, carry out in kneader or clarifixator, in mixing process, single dye composition (I) ~ (IV) can powdery, granular, the aqueous solution or resulting solution form exist, when the form blending of single dye composition with resulting solution, be separated composite active black dye of the present invention from resulting solution to be undertaken by generally known method, such as use ionogen (as sodium-chlor or Repone K) to be saltoutd by dyestuff from reaction medium to leach, or mixing solutions is evaporated, spraying dry, therefore, dye component A, B, C and dye composite thereof include electrolytic salt conventional in reactive dyestuffs usually (as sodium-chlor, sodium sulfate etc.).
Active black dye composition of the present invention, as commodity selling or be applied to textile materials painted time, can not auxiliary agent be added, also can add the conven-tional adjuvants in commercial dye, as solubility promoter, dispersion agent, alkali resistance auxiliary agent, dust-proofing agent, tensio-active agent, buffer reagent and dyeing accelerant etc.Therefore, present invention also offers a kind of reactive black dye goods, it contains described active black dye composition.Preferably, in described reactive black dye goods, main containing described active black dye composition and auxiliary agent, the weight ratio of described active black dye composition and auxiliary agent is 100:0 ~ 45, preferred 100:0 ~ 40.The preferred following a kind of or several arbitrarily combination of described auxiliary agent: naphthalene sulfonic acidformaldehyde condensation product (NNO), condensation compound of methyl naphthalene sulfonic acid and formaldehyde (Dispersant MF), dispersing agent CNF (benzyl naphthalenesulfonate formaldehyde condensation compound), Sodium sulfate anhydrous.min(99) (industrial sulphuric acid sodium).Described auxiliary agent is commercially available conventional variety.
Active black dye composition of the present invention and dye preparations, be applicable to the printing and dyeing of cellulosic fibre, tynex and fabric thereof, wherein, the preferred cotton fibre of cellulosic fibre or regenerated fibre, certainly other vegetative fiber can also be comprised, as bast-fibre or fabric; Tynex preferably includes skin, hair or silk at interior animal fiber material, and the filamentary material such as nylon 6, nylon66 fiber of synthesis.Adopt reactive black dye goods of the present invention print and dye above-mentioned filamentary material time, can carry out in accordance with known reactive dyes dyeing method, as conventional reactive dyestuffs in exhaustion staining and pad dyeing staining, described exhaust dyeing be by textile impregnation in dye liquor, make dyestuff go up the method for dyeing and weaving thing gradually, usually need the operations such as dyed-fixation-washing-soap boiling-washing-dehydration-oven dry.
Described pad dyeing be then first textile impregnation in dye liquor, then fabric is made to pass through roll, dye liquor is evenly rolled into fabric, again through the dyeing process of the process such as decatize or hot melt, usually need through padding dye liquor-oven dry-(padding fixation liquid)-decatize or bake-wash-soap-wash-operation such as to dry.
Usually, due to the difference that dyeing pool on fabric requires, dyestuff usage quantity also can be different, when using dip method dyeing, dye level (owf) is generally 0.1% ~ 10% (dyestuff accounts for fabric weight per-cent); bath raio 1:2 ~ 1:60 (fabric and dye liquor weight ratio; preferably 1:10 ~ 1:30); just dye temperature controls 30 ~ 60 DEG C, dyeing time 10 ~ 30 minutes, soap boiling temperature 85 ~ 95 DEG C; 10 ~ 15 minutes soap boiling time; color fixing temperature 60 ~ 100 DEG C, 10 ~ 50 minutes fixation time, fixation pH value 9 ~ 11.When using pad dyeing method dyeing, the pick-up of cellulosic fibre is generally 60 ~ 80%, steam temperature 100 ~ 103 DEG C, steaming time 1 ~ 3 minute.In pad dyeing method, morely at present use cold-rolling heap staining method, dyestuff and alkaline matter are incorporated in pad fix machine, and at room temperature clot is banked up and carried out fixation in 2 ~ 30 hours, carries out thorough rinsing afterwards.
Beneficial effect of the present invention is mainly reflected in: active black dye composition of the present invention and dye preparations, during for fabric printing, have enhancing good, degree of fixation is high, and compatibleness is good, be easy to washing, dyeing residual liquid is clear, Salt And Alkali Tolerance stable performance, and colour fastness is excellent, cost advantage is obvious, is rare economical black dyes.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
It should be noted that, for making the sign of dye composition convenient and unified, each monogenetic dyestuff in colorant match component all presents with the form of free acid, but in actual production processing, each monochromatic component usually in alkali metal salt, the form of preferred lithium salts, sodium salt or sylvite, particularly preferably the form of sodium salt exists, and in its salt form for dyeing.
Formula II compound prepares embodiment 1:
1, take content be 53% sulfonation para-ester 14.6g (0.02mol) add water making beating 0.5h, under pH is 0.8-1.4, temperature 14-17 DEG C condition, slowly drips 30% sodium nitrite solution 5.06g (0.022mol) carries out doazo reaction, judge that whether sub-sodium is excessive every 0.5h, reaction 2h, control of reaction end point amino agents not displaing yellow;
2, taking content is urea 4.6g (0.02mol) between 65%, slowly joins in above-mentioned diazo component, regulates pH to 4.5-5.0, coupled reaction 2h under 10-15 DEG C of condition, and survey liquid phase purity reaches 80% and namely reacts end;
3, the pH of above-mentioned coupling solution is regulated to be 6.5-6.7, add 30% sodium nitrite solution 5.06g (0.022mol) to stir, slowly be added dropwise in 5.9g (0.05mol) 31% cryosel acid in 40-60min, and continuous stirring reaction 3h, judge that whether Sodium Nitrite is excessive every 0.5h;
4, take content be 82.5% 2,4-diamino benzene sulfonic acid sodium 5.1g (0.02mol) join in the reaction solution of step 3, control pH 3 ~ 3.5 carries out that acid is even reacts 2h;
5, para-ester 28.7g (0.1mol), end water 100mL and ice 100g that content is 98% is taken, making beating 1h, then the acid of 15g (0.127mol) 31% cryosel is added, 30% sodium nitrite solution 5.06g (0.022mol), reaction 2h, obtain para-ester diazonium, control the micro-aobvious blueness of potassium iodide starch paper, eliminate Sodium Nitrite for subsequent use;
6, the even product of the acid in regulating step 4 carries out alkali and occasionally reacts under pH=5.0-5.5, temperature 10-15 DEG C condition with the para-ester diazonium in step 5, obtain reactive dye compound (II-1), λ
max=525nm.(M
2for H, namely dye composition represents with the form of free acid)
According to above-mentioned preparation method, adopt different diazonium and coupling component preparation, following table 1 can be obtained respectively
Shown in structure (M
2for H, namely dye composition represents with the form of free acid):
Table 1
Coupling order and raw material are changed and can obtain the structure (M shown in following table 2 respectively
2for H, namely dye composition represents with the form of free acid):
Table 2
Embodiment 23:
The dyestuff of the dyestuff of 85 parts of formulas (I-3), 15 parts of formulas (II-1) and 20 parts of Sodium sulfate anhydrous.min(99) are carried out mechanically mixing, and the composite dye dye obtained is cotton is black (M
1~ M
2be H, namely dye composition represents with the form of free acid).
Embodiment 24:
The dyestuff of the dyestuff of the dyestuff of 20 parts of formulas (I-1), 45 parts of formulas (I-3), 25 parts of formulas (II-5), the dyestuff of 10 parts of formulas (III-1) and 30 parts of Sodium sulfate anhydrous.min(99) are carried out mechanically mixing, and the composite dye dye obtained is cotton is black (M
1~ M
3be H, namely dye composition represents with the form of free acid).
Embodiment 25 ~ 72:
The dyestuff of listed proportioning in mechanically mixing table 3, dye cotton is black (M
1~ M
4be H, namely dye composition represents with the form of free acid).
Table 3
Application Example:
Get the reactive black dye dry product that the embodiment of the present invention 23 ~ 72 is obtained respectively, be dissolved in respectively in water, add Sodium sulfate anhydrous.min(99) 50g/L and be configured to dye liquor.(dyestuff is to cloth weight for dyeing concentration 4%, as 100 parts of cottons need dyestuff 4 parts); bath raio 1:20 (cloth heavy (g): dye liquor volume (ml)); adsorb 30 minutes at inserting 60 DEG C, cotton; add soda ash (consumption 15 ~ 20g/L) fixation 45 minutes; DYED FABRICS, through washing, soap boiling, drying, obtains black dyeing and weaving thing.Dye fixing rate is high, and dyeing residual liquid colourity is low.
(1) colour fastness
Its washing fastness is tested, 60 DEG C according to GB/T3921-2008:
Former state variable color >=4-5 level; Staining >=4 grade
Its fastness to rubbing is tested according to ISO105-X12:
Metal to-metal contact: >=4-5 level; Wet friction: >=3-4 level
(2) Saline alkali tolerance: during above-mentioned dyeing, respectively along with increase, the increase of power part of salt consumption, pH value, does not substantially affect coloured light, reactive black dye Salt And Alkali Tolerance of the present invention stable performance is described.
Counterstain is tested:
Comparative example 1, according to the embodiment 15 in patent CN1195678A, is prepared as follows the reactive black dye of two components:
Comparative example 2, according to the embodiment 23 in patent CN103194091A, is prepared as follows the black dyestuff of two composition activities:
Comparative example 3, according to the embodiment 1 in patent CN1858118A, is prepared as follows the reactive black dye of three components:
Comparative example 4, according to the embodiment 24 in patent CN103194091A, is prepared as follows three components reactive black dye:
According to the method described in above-mentioned Application Example, to choose in the present invention immediate embodiment 23, embodiment 26, embodiment 27, embodiment 41 with comparative example 1 ~ 4 to carry out lifting force (the K/S value under the coloured differently degree of depth) and contrast, result is as follows in table 4:
Table 4
| Dye level | 2.0％ | 4.0％ | 6.0％ | 8.0％ | 10.0％ | 12.0％ |
| Embodiment 1 | 14.58 | 27.83 | 34.85 | 41.79 | 43.18 | 46.02 |
| Embodiment 4 | 14.76 | 27.35 | 34.04 | 41.95 | 43.95 | 47.11 |
| Embodiment 5 | 14.46 | 27.81 | 34.75 | 41.31 | 43.59 | 46.62 |
| Embodiment 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 seen from the above table, along with the increase of dye level, depth of the present invention (lifting force) is significantly better than comparative example.
Claims (11)
1. an active black dye composition, comprise component A, B component and component C, described component A is selected from the compound shown at least one formula I, described B component is selected from the compound shown at least one formula II, described component C is selected from the compound shown at least one formula III and/or formula IV, based on described component A, B component and component C, the weight part of component A is 45 ~ 95 parts, the weight part of B component is 5 ~ 55 parts, and the weight part of component C is 0 ~ 40 part:
In formula I:
R
1, R
2, R
3respective independence is-H ,-C
1~ C
4alkyl ,-C
1~ C
4alkoxyl group or-SO
3m
1; Y
1for-CH=CH
2or-C
2h
4oSO
3m
1; M
1for H or basic metal;
In formula II:
R
4, R
5in both, one is
wherein R
12for H ,-OCH
3or-SO
3m
2; Another be
wherein R
13for-NHCONH
2, or-NHCOCH
3; R
14for H or-OCH
3; R
15for H ,-OCH
3or-SO
3m
2; M
2for H or basic metal;
In formula III:
R
6, R
7respective independence is-H or-SO
3m
3, R
8for-SO
2y
2or-C
1~ C
4alkyl, Y
2for-CH=CH
2or-C
2h
4oSO
3m
3, M
3for H or basic metal;
In formula IV:
R
9, R
10respective independence is-H ,-C
1~ C
4alkyl ,-C
1~ C
4alkoxyl group or-SO
3m
4; R
11for-H or-SO
3m
4; Y
3for-CH=CH
2or-C
2h
4oSO
3m
4; M
4for H or basic metal.
2. active black dye composition as claimed in claim 1, it is characterized in that: based on described component A ~ C quality sum, the mass percentage of component A is 45 ~ 95%, the mass percentage of B component be 5 ~ 55%, component C mass percentage be 0 ~ 40%.
3. active black dye composition as claimed in claim 1 or 2, is characterized in that: described component A is one of following or wherein two or more mixture, wherein M
1for H or Na:
4. the active black dye composition as described in one of claims 1 to 3, is characterized in that: described B component is one of following or wherein two or more mixture, wherein M
2for H or Na:
5. the active black dye composition as described in one of Claims 1 to 4, is characterized in that: described component C is one of following or wherein two or more mixture, wherein M
3, M
4for H or Na:
6. active black dye composition as claimed in claim 5, it is characterized in that: in described active black dye composition, the content of component C is 0, based on described component A and B component, it comprises the component A of 45 ~ 95% and the B component of 5 ~ 55%: wherein
Component A is selected from least one in formula (I-1), (I-3);
B component is selected from least one in formula (II-1), (II-5), (II-12), (II-18).
7. active black dye composition as claimed in claim 5, is characterized in that: described active black dye composition based on described component A, B component and component C, comprise the component A of 45 ~ 95%, the B component of 5 ~ 55% and 3 ~ 40% component C: wherein
Component A is selected from least one in formula (I-1), (I-3);
B component is selected from least one in formula (II-1), (II-5), (II-12), (II-18);
Component C is selected from least one in formula (III-1), (III-2), (III-7), (IV-1), (IV-3).
8. active black dye composition as claimed in claim 1, it is characterized in that: described active black dye composition is made up of component A, B component and component C, based on described component A, B component and component C, the mass percentage of component A is 45 ~ 95%, the mass percentage of B component be 5 ~ 55%, component C mass percentage be 0 ~ 40%.
9. active black dye composition as claimed in claim 8, is characterized in that: described active black dye composition based on described component A, B component and component C, by the component A of 45 ~ 95%, the B component of 5 ~ 55% and 3 ~ 40% component C form: wherein
Component A is selected from least one in formula (I-1), (I-3);
B component is selected from least one in formula (II-1), (II-5), (II-12), (II-18);
Component C is selected from least one in formula (III-1), (III-2), (III-7), (IV-1), (IV-3).
10. the active black dye composition as described in one of claim 1 ~ 9, it is characterized in that: the phenolic hydroxyl group oxidation of formula I and/or the dye composition shown in formula IV forms quinone hydrazone structure, and the quinone hydrazone structure of the dye composition shown in formula I, formula IV is as follows respectively:
The same formula I of each substituent definition, (IV) in above-mentioned two formulas.
11. 1 kinds of reactive black dye goods, containing, for example active black dye composition according to claim 1.
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