CN1296438C - Black and active dye - Google Patents
Black and active dye Download PDFInfo
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- CN1296438C CN1296438C CNB2005100471354A CN200510047135A CN1296438C CN 1296438 C CN1296438 C CN 1296438C CN B2005100471354 A CNB2005100471354 A CN B2005100471354A CN 200510047135 A CN200510047135 A CN 200510047135A CN 1296438 C CN1296438 C CN 1296438C
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- Prior art keywords
- dye
- acid
- component
- black
- dyestuff
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- 239000000975 dye Substances 0.000 claims abstract description 67
- -1 polyazo Polymers 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229940072033 potash Drugs 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 24
- 230000008878 coupling Effects 0.000 abstract description 22
- 238000010168 coupling process Methods 0.000 abstract description 22
- 238000004043 dyeing Methods 0.000 abstract description 19
- 239000000835 fiber Substances 0.000 abstract description 18
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000004744 fabric Substances 0.000 abstract description 6
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 abstract description 3
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 239000004952 Polyamide Substances 0.000 abstract 1
- 150000001448 anilines Chemical class 0.000 abstract 1
- 238000010014 continuous dyeing Methods 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000000985 reactive dye Substances 0.000 abstract 1
- 125000004964 sulfoalkyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 11
- 239000012954 diazonium Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000001989 diazonium salts Chemical class 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004218 Orcein Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 3
- 235000019248 orcein Nutrition 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 1
- IHDBZCJYSHDCKF-UHFFFAOYSA-N 4,6-dichlorotriazine Chemical compound ClC1=CC(Cl)=NN=N1 IHDBZCJYSHDCKF-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- UMJJNXFVAMHNIE-UHFFFAOYSA-N ClCC[Na] Chemical compound ClCC[Na] UMJJNXFVAMHNIE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 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
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009981 jet dyeing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000344 soap Substances 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
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Coloring (AREA)
Abstract
The present invention provides the black composite reactive dye composed of three primary color components, which comprises a diazo component, a blue disazo dye, a red disazo dye and a yellow disazo or polyazo dye, wherein the ethylene series arylamine or an aniline derivative is taken as the diazo component, the H-acid of the blue disazo dye is a coupling component, one or more than one sulfoalkyl J acid or carboxymethyl J acid derivative of the red disazo dye is the coupling component, and one or more than one 3, 5-diaminobenzoic acid or sulfoalkyl derivative of the yellow disazo or the polyazo dye is the coupling component. The dye is suitable for intermittent and continuous dyeing for cellulose fiber, protein fiber and polyamide fiber and fiber mixed fabrics thereof. The dyeing fabric has excellent blackness, level dyeing property and lifting force.
Description
Technical field
The present invention relates to the composition and the synthesis technique of a multi-component dark black active dyestuff.It is close to the colouring speed of fiber that its characteristics are to form each component of this dyestuff, and coloured fibre has good pitch black degree, level-dyeing property and good fastness.This dyestuff is applicable to cellulosic fibre, protein fibre and tynex dip-dye, pad dyeing-decatize, pad dyeing-bake and pad dyeing-bank up and jet dyeing.
Background technology
Black dyes is to use the look kind more, that output is bigger in the dyestuff.Wherein the C.I. reactive black 5 is the reactive dyestuffs kind of global current output maximum.But as black dyes, its pitch black degree is not enough.Korea S went into the pitch black degree that following orange component is improved dyeing back fiber with the complementary color principle with assembly in 1988, made the output of reactive black turn over liter at double.Simultaneously, become the first sign of improving the reactive black quality by the commercialization of dyes technology.
Although the composite reactive black output that obtains of above-mentioned dyestuff has reached ten thousand tons of meters, this pieces together the union dyeing material and exists following critical defect: (1) pitch black degree is still not ideal enough, does not reach black degree; (2) both water-soluble reaching have than big difference the cellulosic fibre substantivity, the dyeing behavior compatibleness is poor: fiber affinity is also differed bigger, and orange O1 dyestuff is higher to fiber affinity, is adsorbed onto on the fiber earlier, cause different period coloured light differences in the dyeing course, easily cause the look flower; When adding the alkali fixation, orange component easily precipitation is separated out, and causes color spot especially; (3) both reactivities have difference.Orange component has the dichlorotriazine active group, and speed of response is higher than reactive black 5 (B1).
Over past ten years, mainly be in the adjustment of dark blue composite dye structure and each component ratio of mixture for the improvement of reactive black.The inventor proposed at " dyestuff and dyeing " magazine in 2004: under the theoretical direction of the supramolecular chemistry of dyestuff, the introducing substituting group makes the highest absorption red shift of absorption curve and increases water soluble group and introduce character and the suitable active group of quantity in red, orange component in dark blue component, adapt with fixing property, improve the dyeing compatibleness with the avidity of dark blue component.In the domestic and international patent in recent years the improvement of black and active dye is carried out according to above-mentioned thinking just.Wherein relatively success as US6537332, propose with above-mentioned cyan dye B1 and following orchil R1 and composite pitch black degree and all good reactive black of level-dyeing property of obtaining of orange dye O2 among the USP5849887.
Other provides the close patent of invention of black and active dye composition to also have CN195678A, WO2004069937, US6160101 etc.
Summary of the invention
The purpose of this invention is to provide one group the polycomponent black composite active dye that good dyeing behavior, pitch black degree, level-dyeing property and lifting force are good, synthetic conveniently, raw material is easy to get is arranged.At least by following general formula (1), (2), (3) are dark blue, red, Yellow active dye is formed.Its dyeing behavior is characterised in that each component dyestuff good and compatibleness and lifting force.Its DYED FABRICS has excellent pitch black degree and painted level-dyeing property.
The constitutional features of dyestuff of the present invention is that the structure of three primary colors component dyestuff has very approaching wetting ability/lipophilicity, wherein: be contained in the navy tetrazo type reactive dyestuffs shown in the formula (1):
With contain the tetrazo type reactive dyestuffs shown at least a formula (2):
With contain tetrazo shown at least a formula (3) or trisazo-type reactive dyestuffs:
Above-mentioned general formula (1), (2) are in (3);
X=H or
Group on Y=vinyl or the ethyl β position can come off under alkaline condition and generate the group of vinyl sulfone(Remzaol,
As chlorine, beta-hydroxyethyl sulfuric ester, especially good is vinyl sulfone(Remzaol and beta-hydroxyethyl sulfuric ester;
Z=hydrogen, CH
2SO
3M, CH
2CH
2SO
3M or CH
2COOM;
W=CH
2SO
3M, CH
2CH
2SO
3M or CH
2COOM;
M=hydrogen or basic metal are as lithium, sodium and potassium;
R
1～R
12=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or chlorine;
R
13, R
14=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, carboxyl, sulfonic group or sulfuric acid ester ethyl sulfone.
As the active diazo component of blue or green, red, yellow dye as:
Or the vinyl sulfone(Remzaol derivative 01V-13V of compound 01-13
The general structure of red component dyestuff (2) is:
(2) used coupling component is (30):
In the formula
W=CH
2SO
3M, CH
2CH
2SO
3M or CH
2COOM;
M=hydrogen or alkalimetal ion are as lithium, potassium, sodium ion;
This compound (30) is made by J acid and sodium hydroxymethane sulfonate, chloroethyl sodium sulfonate or chloroacetate reaction.For example the available methylol sulfonic acid of sulphur methyl J acid is azochlorosulfonate methyl agent.The latter then can very easily be got by formaldehyde and sodium bisulfite addition smoothly.
(2) contain R on the ring in
5, R
6, R
7, R
8Substituent active diazo component can be some among 01-13 or the 01V-13V in the top literary composition.
The general formula of synthetic dyestuff (3) is:
(3) used coupling component is 3 in, the 5-Diaminobenzoic acid derivatives:
Z=hydrogen or AlkSO in the formula
3M
Alk=methylene radical or ethylene group;
M=hydrogen or lithium, potassium, sodium metal ion.
R in the diazo component
9, R
10, R
11, R
12Substituent active diazo component can be some among 01-13 or the 01V-13V in the top literary composition.X can be H ((3) are disazo dyess) or contain R
13, R
14The ring diazo component (trisazo dye) can be in the top literary composition 01,02 or 21-29 in some.
In three kinds of component dyestuffs, raw material is easy to get, the cyan component commonly used (1) of better performances is as 101,102, and 103 etc.:
The red component commonly used (2) of better performances is as 201,202, and 203,204,205 etc.:
The yellow color component of better performances (3) is as following dyestuff (301)-(308) etc.
The preparation method of dyestuff (1) be with H acid with etc. the diazonium salt of mol ratio beta-hydroxyethyl sulfone sulfate ester aniline derivative under the condition of pH＜2, carry out earlier a coupling obtain in the middle of dyestuff, again under pH=4～7 conditions and the diazonium salt of another part beta-hydroxyethyl sulfone sulfate ester aniline derivative carry out the secondary coupling and obtain dyestuff (1).The diazonium salt of twice coupling can be identical, also can be different.Under the identical situation of the diazo component of twice coupling, the H acid solution can be added drop-wise in the diazonium liquid that two moles doazo reaction finishes, control by pH and finish twice coupling.Permission slightly adjusts in the proportioning of diazo component and coupling component, to adjust the coloured light of dark blue component.Can be directly after coupling finishes or desalt through membrane sepn and to carry out spraying drying after concentrating and obtain solid dye (1).
The preparation method of dyestuff (2) carries out diazotization (mixture of also available two kinds of components in case of necessity) with any arylamine among compound 01-13 or the 01V-13V, under the condition of pH＜2, carry out earlier a coupling with corresponding coupling component then, and then under pH=4～7 conditions, carry out the secondary coupling, reaction solution can be directly or membrane sepn desalt and carry out spraying drying after concentrating and obtain solid dye (2).
The preparation method of dyestuff (3) carries out diazotization with the arbitrary arylamine among the compound 21-31, then with 3,5-diaminobenzoic acid or derivatives thereof is under promoter effect, under pH＜3.2 conditions, carry out the coupling first time, and then and compound 01-13 or 01V-13V in any arylamine diazonium salt (can be the mixture of two kinds of components in case of necessity) time carry out the coupling second time in pH＜4, time carry out coupling for the third time in pH＜6.3, reaction solution is saltoutd after acidifying, and drying obtains solid dye (3).
Blue or green: red: the weight percent of yellow three primary colors component is 50～90: 25～5: 25～5.
Composite active dye can be with structure the dyestuff shown in (1), (2), (3) in specified ratio mechanical means mixed preparing, also can do by the water-soluble back spray of proportioning.
Black composite active dye of the present invention is suitable for dying natural fiber, as cotton, fiber crops, regenerated fibre, is applicable to protein fibre and tynex too.Above-mentioned textile fiber can take various forms, as fiber, yarn, fabric or tricot.Dip-dye is after pollutant is adsorbed in the dye bath of specified mix, to use the alkaline purification fixation again, and dyeing and color fixing temperature are 50～70 ℃, the level-dyeing property of this dyestuff, lifting force are good, the compatibleness of three components is good, and coloured light is more stable in the dyeing course, and has good pitch black degree.
Among the following embodiment, as do not have especially and indicate, hundred mass fractions (with g or kg metering) are rolled in being of referring to.
Embodiment
Embodiment 1
Synthesizing of sodium hydroxymethane sulfonate:
In the 500ml there-necked flask, 104g sodium bisulfite (1mol) is used the 150ml water dissolution, under 35 ℃, drip 88g36% formaldehyde solution (1.05mol), in stirring reaction 3-5 below 50 ℃ hour.In 60-70 ℃ of following decompression dehydration 100ml, obtain concentrated solution.With the concentrated solution cooling, add a certain amount of recrystallisation solvent, under 0-5 ℃, left standstill crystallization 5 hours, filter, filter cake 30ml absolute ethanol washing, drying gets 125g sodium hydroxymethane sulfonate white solid.
Embodiment 2
Synthesizing of sulfomethylation J acid:
In the 500ml there-necked flask, 23.9gJ acid is scattered in the 200ml water, uses 20%Na
2CO
3Solution is regulated pH to 6-7, adds the 15g sodium hydroxymethane sulfonate, in reacting 3-6h below 50 ℃, gets sulfomethylation J acid solution, content 〉=95% (HPLC) of wherein sulfomethylation J acid in the organism.
Embodiment 3
Synthesizing of orchil 201:
56.2g para-ester and 13g sulfuric acid are mixed, add the 350g mixture of ice and water, making beating 30min, 0-5 ℃ drips 47g30%NaNO down
2Solution keeps NaNO in dropping and the reaction process
2Excessive.Drip the back and continue stirring reaction 2h, excessive N aNO
2Destroy with thionamic acid, get the para-ester diazonium salt.
The para-ester diazonium salt is joined in the sulfomethylation J acid solution of embodiment 2, control pH≤2 down at 0-5 ℃, coupled reaction 3h is transferred to pH 5-6 again, and coupled reaction 3h is concentrated with the dye solution of gained, fries and does, and pulverizes, and gets the 125g dye powder.
Embodiment 4
Synthesizing of yellow dyes 301
17.2g Sulphanilic Acid is used 23g 30%NaNO about 5 ℃
2Solution, 20g 36% concentrated hydrochloric acid carry out diazotization.Reaction is finished with thionamic acid or the unnecessary NaNO of urea destruction
2The 0.5g dispersion agent is joined in the diazonium liquid, and after stirring, with 3,5-diaminobenzoic acid 15.5g dissolves in the 100ml6% hydrochloric acid soln, cools to the coupling component solution that obtains about 5 ℃ and is added in the above-mentioned diazonium salt, carries out a coupling.Control reaction solution pH≤3, complete to a coupling.56.2g the diazonium salt solution that para-ester is made is added drop-wise in the above-mentioned coupling solution, at room temperature, pH progressively brings up to 6.0-6.2, to reacting completely.The dye solution acidifying is saltoutd with NaCl.Filtration cakes torrefaction is pulverized, and gets the about 112g of pale brown look dye powder.
Embodiment 5
70g dyestuff (101), 15g dyestuff (201), 15g dyestuff (301) and appropriate amount of addition agent are carried out dry powder blend in tempering tank, or common dissolving back spraying drying, and the black dyes that obtains dyes the cotton aterrimus that is.Have good dyeing ability and satisfied dyefastness.
But other dyestuff synthetic method reference example 1-5
Embodiment 6-20
The dye set of embodiment 6-20 becomes to see Table 1, is undertaken by embodiment 5 similar methods.Form by following dyestuff and all can obtain all excellent reactive black of coloured light and dyeing behavior.
The dyestuff of embodiment 6-20 is formed
| Sequence number | Cyan dye 1 | Orchil 2 | Yellow (orange) look dyestuff 3 | Weight ratio: green grass or young crops: red: yellow (orange) |
| 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 | 101 101 101 101 103 103 101 101 102 101 101 102 101 101 101 | 201 205 201 202 201 201 201 201 205 203 201 205 201 204 201 | 306 306 302 302 308 301 302 305 306 301 307 302 304 301 308 | 65∶15∶25 62∶15∶17 70∶15∶15 65∶10∶25 60∶20∶20 65∶17∶1/8 75∶10∶25 75∶15∶10 60∶10∶30 73∶5∶22 60∶20∶20 65∶25∶10 70∶15∶15 60∶18∶22 65∶15∶20 |
Embodiment 21
The 100g cotton by the black dyes that embodiment 5-20 obtains, is pressed fabric and is weighed 2%, is in 20: 1 the dye bath containing 50g/L Sodium sulfate anhydrous.min(99), bath raio, and 60 ℃ of absorption 30min down add soda ash (consumption 15-20g/L) fixation 45min.DYED FABRICS is through washing, soap boiling, drying.The black cotton that obtains has the black and the satisfied Exposure to Sunlight and the moisture resistant fastness of homogeneous.
Claims (1)
1. compound black and active dye of being made up of blue or green, red and yellow three primary colors is characterized in that this dyestuff is made up of (1), (2), (3) general structure:
In above-mentioned general formula (1), (2), (3):
R
1～R
12=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or chlorine atom;
X=H or
R
13, R
14=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, carboxyl, sulfonic group or sulfuric acid ester ethyl sulfone;
Y=vinyl or beta-hydroxyethyl sulfuric ester;
Z=hydrogen, CH
2SO
3M, CH
2CH
2SO
3M or CH
2COOM;
W=CH
2SO
3M, CH
2CH
2SO
3M or CH
2COOM;
M=hydrogen or lithium, sodium, potash metal ion;
In above-mentioned compound black and active dye, (1): (2): the weight percent of (3) is 50～90: 25～5: 25～5.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100471354A CN1296438C (en) | 2005-08-30 | 2005-08-30 | Black and active dye |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100471354A CN1296438C (en) | 2005-08-30 | 2005-08-30 | Black and active dye |
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| CN1296438C true CN1296438C (en) | 2007-01-24 |
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Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107501996A (en) * | 2017-09-07 | 2017-12-22 | 上海万得化工有限公司 | A kind of synthetic method of black and active dye compound |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5445654A (en) * | 1992-11-28 | 1995-08-29 | Hoechst Aktiengesellschaft | Black dye mixtures of fiber-reactive azo dyes and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material |
| US5565553A (en) * | 1993-10-07 | 1996-10-15 | Ciba-Geigy Corporation | Disazo dyes with a vinylsulfonyl type fiber-reactive radical substituted diazo component and a 2-sulfophenylene middle component carrying a fiber-reactive radical in the 5-position |
| CN1136057A (en) * | 1995-05-18 | 1996-11-20 | 大连理工大学 | Activated black dye |
| CN1616552A (en) * | 2004-09-22 | 2005-05-18 | 上海科华染料工业有限公司 | Composite active black dye |
-
2005
- 2005-08-30 CN CNB2005100471354A patent/CN1296438C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5445654A (en) * | 1992-11-28 | 1995-08-29 | Hoechst Aktiengesellschaft | Black dye mixtures of fiber-reactive azo dyes and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material |
| US5565553A (en) * | 1993-10-07 | 1996-10-15 | Ciba-Geigy Corporation | Disazo dyes with a vinylsulfonyl type fiber-reactive radical substituted diazo component and a 2-sulfophenylene middle component carrying a fiber-reactive radical in the 5-position |
| CN1136057A (en) * | 1995-05-18 | 1996-11-20 | 大连理工大学 | Activated black dye |
| CN1616552A (en) * | 2004-09-22 | 2005-05-18 | 上海科华染料工业有限公司 | Composite active black dye |
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