CN1235979C - Cationic dye - Google Patents
Cationic dye Download PDFInfo
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- CN1235979C CN1235979C CN 02120187 CN02120187A CN1235979C CN 1235979 C CN1235979 C CN 1235979C CN 02120187 CN02120187 CN 02120187 CN 02120187 A CN02120187 A CN 02120187A CN 1235979 C CN1235979 C CN 1235979C
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Abstract
The invention provides a cationic dye which excels in dyeing speed and degree of exhaustion and which gives a dyed product having superior fastness to light and humidity. The novel cationic dye is represented by general formula (1) [wherein n is 1, 2 or 3; D is a coloring matter matrix selected from azo, anthraquinone and phthalocyanine coloring matters; R<0> is an aminoethylsulfonylphenyl group represented by general formula (2) (wherein R<a> and R<b> are independently of each other a hydrogen, halogen, 1-3C alkyl, and 1-3C alkoxy, and R<1a> and R<1b> are independently of each other a 1-4C alkyl, 1-3C hydroxyalkyl and aminoalkyl); and R<0> may be identical or different if n is 2 or 3].
Description
Technical field
The present invention relates to new cationic dyestuff, in more detail, relate to the rate of dyeing and the outstanding cationic dyestuff of colour fastness that in dye matrix, have imported amino-ethyl alkylsulfonyl phenyl.
Background technology
Various natural and synthetic dyestuff in the past use in the dyeing of various filamentary materials, leather, paper, paper pulp etc.As these dyestuffs, use mostly azo bond as the azoic dyestuff of dye matrix, quinoid structure as benzoquinones type dyes such as the naphthoquinones of dye matrix, anthraquinones, phthalocyanine structure is as the phthalocyanine pigment of dye matrix.
Summary of the invention
These normally used dyestuffs, dyeing property such as dyeing kinetics, rate of dyeing, colour fastness to light, moistening colour fastness etc. reach the material of certain level, remaining quantity reaches zero in dyeing waste-water, be that to reach 100% be difficult to rate of dyeing, and be difficult to because it thoroughly decomposes, in wastewater treatment, cause big load.
On the other hand, rationalization such as in dyeing industry, the special requirement dyeing time is short, the wastewater treatment load alleviates, urgent expectation exploitation dyeing kinetics and rate of dyeing height, and the good dyestuff of various colour fastness of product dyed thereby.Particularly, in the dyeing of paper, paper pulp etc., from the storage of paper, to viewpoints such as the corrodibility of installations, wastewater treatments, the acid papermaking method of using Tai-Ace S 150 from the solidifying of dyestuff or cementing agent etc. is rapidly to the neutral paper process conversion of not using Tai-Ace S 150, and present neutral paper process is just becoming main flow.But in neutral paper process, former dyeing speed is slow and rate of dyeing is also low, and the product dyed thereby that therefore obtains high density is difficult to.And dyestuff also remains in the waste water in a large number.In addition, these dyestuffs are beyond thought little for the rate of dyeing of bleached pulp particularly, and undyed dyestuff is remaining in a large number in dyeing waste-water.In addition, in the dyeing of other materials, for example, there is the limit of nature in rate of dyeing when wool, thin,tough silk, leather, wooden silk floss etc. were dyed heavy colour separately with anionic property dyestuffs such as direct dyestuff or matching stains in the past, if dye the above degree of saturated dyeing, undyed dyestuff can be remaining in a large number in the waste water, and color dyeing is difficult.
The objective of the invention is, can obtain particularly fast to the dyeing kinetics of paper, paper pulp, and rate of dyeing height, dyeing time shortens or alleviates the rationalization such as load of wastewater treatment, or for the material of anionic property dyeings such as direct dyestuff or matching stain also salify rapidly, obtain high gloss and have the product dyed thereby of outstanding moistening colour fastness, colour fastness to light in high density, have the new cationic dyestuff of good dyeing property and colour fastness.
Present inventor etc.; carried out deep research for achieving the above object; it found that; from azoic dyestuff; import the dye composition of amino-ethyl alkylsulfonyl phenyl in the dye matrix of selecting in the group that anthraquinone dye and phthalocyanine pigment are formed; for paper; the dyeing kinetics of paper pulp is fast; and rate of dyeing height; and the fast light and moistening colour fastness of product dyed thereby is outstanding; in addition; even by the material of anionic property dyeings such as direct dyestuff or matching stain; for example; wool; thin,tough silk; leather; when using in surface (chromatography) dyeing of wood silk floss etc., a small amount of use also can be rapidly and the anionic dyestuff salify, compares with the situation of independent use anionic property dyestuff; discovery can be in high far away concentration; obtain high gloss, and fast light and moistening colour fastness outstanding product dyed thereby, and finished the present invention.
The present invention is, the cationic dyestuff shown in the following general formula (1),
D-(R
0)
n (1)
[in the formula, n is 1,2 or 3, and D represents to be selected from the dye matrix in the group that azoic dyestuff, anthraquinone dye and phthalocyanine pigment form, R
0Represent the amino-ethyl alkylsulfonyl phenyl shown in the following general formula (2)
[in the formula, R
aAnd R
bRepresent the alkyl of hydrogen, halogen, carbonatoms 1～3, the alkoxyl group of carbonatoms 1～3 respectively independently, R
1aAnd R
1bRepresent the alkyl of hydrogen, carbonatoms 1～4, the hydroxyalkyl of carbonatoms 1～3, the aminoalkyl group shown in the following formula respectively independently,
(Z here,
aThe alkylidene group of expression carbonatoms 1～4, R
2aAnd R
2bRepresent the alkyl of hydrogen, carbonatoms 1～3, the hydroxyalkyl of carbonatoms 1～3 respectively independently)], n is 2 or 3 o'clock, R
0Can be identical or different respectively].
In the cationic dyestuff of this law, in the aforementioned formula (1), D has 1 azo bond at least (azoic dyestuff N=N-), atomic group is that to have the anthraquinone dye of quinoid structure and atomic group be to have the dye matrix of selecting in the group that the phthalocyanine pigment of phthalocyanine structure forms from the atomic group that constitutes dye composition.
In the aforementioned formula of azo dyestuff cpds (1), the dye matrix that D represents can be the compound shown in the following formula
X(-N＝N-)
p
(here, X represents the dye matrix skeleton, and p is 1～5 integer) ,-N=N-key can be present in skeleton X end, skeleton X inside or be present in two aspects.
As the compound of the skeleton X that constitutes above-mentioned azo dyestuff cpds, for example can enumerate, coupling composition shown in following general formula (3)～(10) or naphthols AS belong to soaker and have the compound of similar structures.
In the above-mentioned general formula (3), R
5Expression amino or hydroxyl, R
6The alkoxyl group of expression hydroxyl, carbonatoms 1～3 or-NHR
10(R here
10Expression hydrogen, the alkyl of carbonatoms 1～3, ethanoyl, carbonylamino, benzoyl), R
7Alkyl, the alkoxyl group of carbonatoms 1～3, hydroxyl, carboxyl, nitro, the halogeno-group of expression carbonatoms 1～3.
In above-mentioned general formula (4), (6) and (7), R
8Alkyl, ethanoyl or the carbonylamino of representing hydrogen, carbonatoms 1～3 respectively, the R in the general formula (4)
9Expression hydrogen or hydroxyl.
In the above-mentioned general formula (5), Z
bExpression singly-bound (-) ,-CO-or alkylidene group.
In above-mentioned general formula (9) and (10), R
3Alkyl, carbonyl or the methyl carbonyl (カ Le ボ メ チ Le) of representing hydrogen, carbonatoms 1～3 respectively, R
4aAnd R
4bRepresent the alkyl of hydrogen, halogen, carbonatoms 1～3 or the alkoxyl group of carbonatoms 1～3 respectively independently.
In above-mentioned general formula (6) and (7), Y represents following (a) or (b) shown in group.
In the above-mentioned formula (a), R
11And R
12Represent halogen, hydroxyl, carboxyl, alkyl, alkoxyl group or nitro independently, in the formula (b), R
11Identical with (a), R
13aAnd R
13bThe alkyl of representing hydrogen or carbonatoms 1～3 respectively independently.
In the aforementioned formula (1),, can enumerate 1,4-diamino-anthraquinone-2-sulfonic acid etc. as the anthraquinone dye compound that constitutes the dye matrix shown in the D.In addition, as the phthalocyanine pigment compound, can enumerate CuPc etc.
As the amino-ethyl alkylsulfonyl phenyl that imports in the above-mentioned dye matrix, the R in the aforementioned formula (2)
1aAnd R
1bPreferable methyl, ethyl, hydroxyethyl, aminoalkyl group, preferred aminoalkyl group is Z in the formula
aBe ethylidene (dimethylene), propylidene (trimethylene), R
2aAnd R
2bBe methyl, ethyl.And R
aAnd R
bPreferable methyl, methoxyl group.
Cationic dyestuff compound shown in the aforementioned formula of the present invention (1), available known method is easily made.Azo dyestuff cpds can pass through, for example, and with following general formula (11)
(in the formula, R
a, R
b, R
1aAnd R
1bIdentical with aforementioned definitions) shown in amine known method diazotization, then combine preparation by known coupled reaction with the compound of the formation azo-compound skeleton X shown in aforementioned formula (3)～(9).In addition; the amine diazotization of compound of skeleton X that contains the formation azo dyestuff cpds of sulfato (ス Le Off ア ト) ethylsulfonyl; then combine by known coupled reaction with the compound shown in aforementioned formula (3)～(9); then; after for example various alkylamines such as ethamine, diethylamine or diethylamino ethamine combine, by the known method Processing of Preparation.
The anthraquinone dye compound can pass through, and makes the sulfato ethylsulfonyl of the anthraquinone derivative that contains the sulfato ethylsulfonyl combine preparation with for example various alkylamines such as ethamine, diethylamine or diethylamino ethamine.In addition, phthalocyanine pigment can directly combine with the amine shown in the above-mentioned general formula (11) by the sulfonic group that imports in phthalocyanine derivates and preparation easily.
The concrete example and the tone thereof of the cationic dyestuff compound shown in the aforementioned formula of the present invention (1) are as shown in table 1.
Table 1
Table 1 (continuing)
Table 1 (continuing)
Table 1 (continuing)
Cationic dyestuff compound of the present invention can be made Powdered or particulate state after the drying, but is preferably dissolved in the dense liquid state that forms in organic acid and/or the water-miscible organic solvent.
As organic acid, for example can enumerate formic acid, acetate, lactic acid, citric acid, oxyacetic acid, methylsulfonic acid etc.Group is water-miscible organic solvent, for example can enumerate ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, the molten acyl agent of methyl, Trivalin SF, methyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triglycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, thioglycol, butyrolactone, N-N-methyl-2-2-pyrrolidone N-, dimethyl formamide, methane amide, N,N-DIMETHYLACETAMIDE etc.
Preferred these organic acids and water-soluble solvent mix use more than 2 kinds.
Embodiment
Below, the present invention will be described in more detail by embodiment.
In addition, " part " among the embodiment and " % " are unless to specialize be weight basis.
The azo dyestuff cpds of embodiment 1 compound sequence number 3
In 28.1 parts water-soluble 100 parts of 4-(β-sulfato ethylsulfonyl) aniline, under agitation be added dropwise to 28.0 parts of 2 '-dimethyl aminoethyls-2-diethylamino ethamine, add 4.0 parts in sodium hydroxide then, 70 ℃ of reactions 1 hour.Reaction is finished postcooling to room temperature, filters the resultant of separating out, and obtains in the aforementioned formula (11) R
2aBe-C
2H
4N (C
2H
5)
2, R
2bBe-C
2H
4N (CH
3)
2The amine of following formula (12).
With 37.0 parts of gained amine after 32.0 parts of 150 parts in water and concentrated hydrochloric acids fully stir,, remain on temperature below 10 ℃ then and it is added into 4.0 parts in m-phenylenediamine-18.8 parts of 4-sulfonic acid and sodium hydroxide is dissolved in the coupling composition in 100 parts in the water 5～10 ℃ of diazotization with 25.0 parts of 4N Sodium Nitrites.Finish coupled reaction after being adjusted to pH5.0 with aqueous sodium hydroxide solution, reaction is finished the back and is saltoutd for 50 parts with sodium-chlor, the resultant that filtration is separated out, and drying obtains the azo dyestuff cpds of the compound sequence number 3 shown in the following formula (13).
The gained azo dyestuff cpds is easily molten in water, and paper is dyed reddish yellow (red flavor ガ カ っ yellow).This product dyed thereby shows good colour fastness to light and moistening colour fastness, and enhancing is outstanding in the dyeing of neutral papermaking, and confirming does not have painted to waste water fully.
The azo dyestuff cpds of embodiment 2 compound sequence numbers 9
In 28.1 parts water-soluble 100 parts of 4-(β-sulfato ethylsulfonyl) aniline; after 20.0 parts of hydrochloric acid fully stir;, then it is added into 5.3 parts in 23.9 parts of 2-amido-8-naphthol-6-sulfonic acids and yellow soda ash and is dissolved in the solution in 150 parts in the water 5～10 ℃ of diazotization with 25 parts of 4N Sodium Nitrites.Finish coupled reaction after being adjusted to pH4.0 with aqueous sodium carbonate.
Under agitation be added dropwise to 2 in this reaction solution, two (N, the N-dimethylethyl amine) 20.7 parts of 2 '-imino-add behind 6.0 parts in the sodium hydroxide 70 ℃ of reactions 1 hour.After reaction solution is cooled to normal temperature, adds sodium-chlor and saltout for 50.0 parts, filter the resultant of separating out, obtain 130 parts of the filter cakes of the azo dyestuff cpds of the compound sequence number 9 shown in the following formula (14).
In 130 parts of the filter cakes of gained azo dyestuff cpds, add 120 parts in 150 parts of acetate and water, obtain containing the strong solution of dye composition 15%.This dyestuff is dyed paper blue redness a little.This product dyed thereby shows good colour fastness to light and moistening colour fastness, and enhancing is outstanding in the dyeing of neutral papermaking, and confirming does not have painted to waste water fully.
The anthraquinone dye compound of embodiment 3 compound sequence numbers 12
With 60.3 parts water-soluble 500 parts of vinyl sulphone type chemically-reactive dyess (C.I. reactive blue 19), add 26.1 parts of 2 '-dimethyl aminoethyls-3-dimethylamino propylamine, add 4.0 parts in sodium hydroxide then, 60 ℃ of reactions 1 hour.After reaction solution is cooled to normal temperature, filter the resultant of separating out, obtain 98 parts of wet cakes.
In 98 parts of gained wet cakes, add 172 parts in 180 parts of acetate and water, obtain containing the strong solution of the anthraquinone dye compound 15% of the compound sequence number 12 shown in the following formula (15).
The gained dyestuff is dyed distinct blueness with paper.This product dyed thereby shows good colour fastness to light and moistening colour fastness, and enhancing is outstanding in the dyeing of neutral papermaking, and confirming does not have painted to waste water fully.
The sodium salt of the azo dyestuff cpds of embodiment 4 compound sequence numbers 15
In 28.1 parts water-soluble 100 parts of 4-(β-sulfato ethylsulfonyl) aniline; after 20.0 parts of hydrochloric acid fully stir; with 25 parts of 4N Sodium Nitrites 5～10 ℃ of diazotization; add 1-amino-8-naphthol-3 then; 34.1 parts of 6-sulfonic acid list sodium salts; reacted 3 hours at 10～15 ℃ after being adjusted to pH2, finish coupled reaction.
Add 2 in this reaction solution, 8.0 parts in 20.7 parts of 2 '-imino-s two (N, N-dimethyl amine) and sodium hydroxide were 70 ℃ of reactions 1 hour.Obtain the solution of the azo dyestuff cpds shown in the following formula (16).
In 33.7 parts water-soluble 100 parts of 4-(β-sulfato ethylsulfonyl) aniline, under agitation be added dropwise to 13.0 parts of the aqueous solution of dimethyl amine 50%, further add 5.0 parts in sodium hydroxide, 60 ℃ of reactions 1 hour.Reaction solution is cooled to normal temperature, filters the crystallization of separating out, obtain R in the general formula (11)
1aAnd R
1bAll be 45.0 parts of the wet cakes of amine shown in the following formula (17) of methyl.
In 45.0 parts of the wet cakes of gained amine, add 30.0 parts of concentrated hydrochloric acids, after fully stirring, with 25.0 parts of 4N Sodium Nitrites 5～10 ℃ of diazotization.With 1 hour this azo-compound is added dropwise in the azo dyestuff cpds solution that obtains in advance then, when being adjusted to pH9, carries out coupling at 10～15 ℃ with 10% aqueous sodium hydroxide solution.After coupled reaction is finished, filter the resultant separate out, obtain 160 parts of the wet cakes of sodium salt of the azo dyestuff cpds of the compound sequence number 15 shown in the following formula (18).
Add 200 parts in 280 parts of acetate and water in 160 parts of gained wet cakes, preparation contains the strong solution of above-mentioned dye composition 15%.
The gained azo dyestuff cpds is dyed bluish black (blue or green flavor ガ カ っ black) with paper.This product dyed thereby shows good colour fastness to light and moistening colour fastness, and enhancing is outstanding in the dyeing of neutral papermaking, and confirming does not have painted to waste water fully.
Dyeing example 1
LBKP to 25 ° of SR of beating degree: NBKP (=50: add 20 parts of 10% aqueous solution of the azo dyestuff cpds of the compound sequence number 3 that embodiment 1 obtains in the pulp that paper pulp 50) 500 parts (100 parts of dry weights) and water are 3000 parts, stirred 5 minutes.Add aqueous sodium carbonate then pH is adjusted to 7.0.
Adding cationic starch (CATOF, prince's Na シ ョ Na Le (strain) system) in this slurry stirs after 5 minutes for 0.5 part, add alkyl ketene bi-polymer analogy class sizing agent (Ha one コ Application 40B, デ ィ ッ Network Ha one キ ュ レ ス (strain) system) 0.1 part (being scaled solid formation branch), restir 10 minutes.Further add entry and dilute for 6500 parts, carry out papermaking with ordinary method.It is painted to confirm that paper waste does not have fully, and gained dye paper look valency is to have red yellow, has good color of sunshine fastness and moistening colour fastness.
Dyeing example 2
15.0 parts of (7.5 parts of dry weights of pig leather with chrome tanning system, 100mm (W) * 200mm (L) * 0.8mm (t)) puts into rotary-type staining trough (round shape of internal diameter 200mm φ * height 60mmh), make 38.0 parts of waters carry out washing operation 2 times in 10 minutes therein, pig leather is washed 40 ℃ of rotations.
The pig leather of cleaning after handling is taken out from staining trough, be reentered in the rotary-type staining trough of the same type, inject 4.5 parts of direct dyestuff (C.I. directly deceives 169) 10% solution, in 40 ℃ of rotations dyeing in 30 minutes.Then, add 1.1 parts of fatting agents (シ Application コ リ Application L, Ji Chuan system oil (strain) system), carried out stuffing in 60 minutes 40 ℃ of rotations again, append 0.2 part in formic acid afterwards, rotate and solidified dyestuff in 20 minutes.Take out painted pig leather, 38.0 parts of waters carried out water treatment in 10 minutes 40 ℃ of rotations in aforementioned rotary-type staining trough.
Then, take out pig leather, be reentered into aforementioned staining trough rotary-type staining trough of the same type in, 3.5 parts of 10% aqueous solution of the black dyes strong solution of the azoic dyestuff sodium salt of the compound sequence number 15 that 23.0 parts in injection water and embodiment 4 obtain, dyeed in 20 minutes 40 ℃ of rotations, then append 0.04 part in formic acid, being further rotated 20 minutes solidifies dyestuff, carry out so-called padding (chromatography dyeing), pig leather is taken out from staining trough, with above-mentioned carry out water treatment equally after, with seasoning in 15 hours.
This painted pig leather is compared with the pig leather that only uses substantive dyestuff or acid dyeing, can dye the black of high density far away, does not have ooze out (color to other materials shifts) of dyestuff, and moistening colour fastness is outstanding, and the color of sunshine fastness is also outstanding.In addition, do not see the painted of padding liquid yet.
Cationic dyestuff of the present invention, all high with respect to dyeing kinetics, rate of dyeing and the dyeing concentration of base material, use its product dyed thereby that obtains and dyeing base material to have outstanding fast light and moistening colour fastness.
In addition, it is painted to use the dyeing waste liquid of cationic dyestuff of the present invention not see, is colourless, therefore can not cause very big burden to liquid waste disposal, the dyeing engineering is rationalized, and also had very big advantage in environment protection.
The invention provides new cationic dyestuff, its industry meaning, particularly the meaning in dyestuff and dyeing field is great.
Claims (3)
1. the cationic dyestuff shown in the following general formula (1),
D-(R
0)
n (1)
In the formula, n is 1,2 or 3, and D represents to be selected from the dye matrix of azoic dyestuff, anthraquinone dye and phthalocyanine pigment, and when D was azoic dyestuff, this dye matrix with formula X (N=N-)
pExpression, wherein X represents the dye matrix skeleton, p is 1～5 integer, and X represents with following general formula (3), (5), (9), (10):
In the formula, R
3Alkyl, carbonyl or the methyl carbonyl of expression hydrogen, carbonatoms 1～3, R
4aAnd R
4bRepresent the alkyl of hydrogen, halogen, carbonatoms 1～3 or the alkoxyl group of carbonatoms 1～3 respectively independently, R
5Expression amino or hydroxyl, R
6The alkoxyl group of expression hydroxyl, carbonatoms 1～3 or-NHR
10, R here
10Expression hydrogen, the alkyl of carbonatoms 1～3, ethanoyl, carbonylamino, benzoyl, R
7The alkyl of expression carbonatoms 1～3, alkoxyl group, hydroxyl, carboxyl, nitro or the halogen of carbonatoms 1～3, Z
bThe expression singly-bound ,-CO-or alkylidene group,
R
0Represent the amino-ethyl alkylsulfonyl phenyl shown in the following general formula (2),
In the formula, R
aAnd R
bRepresent the alkyl of hydrogen, carbonatoms 1～3 or the alkoxyl group of carbonatoms 1～3 respectively independently, but R
aAnd R
bCan not be the alkoxyl group of carbonatoms 1～3 simultaneously, R
1aAnd R
1bRepresent the alkyl of hydrogen, carbonatoms 1～4, the hydroxyalkyl of carbonatoms 1～3, the aminoalkyl group shown in the following formula respectively independently,
Here, Z
aThe alkylidene group of expression carbonatoms 1～4, R
2aAnd R
2bRepresent the alkyl of hydrogen, carbonatoms 1～3, the hydroxyalkyl of carbonatoms 1～3 respectively independently,
N is 2 or 3 o'clock, R
0Can be identical or different respectively.
2. the cationic dyestuff of claim 1 record, the R in its formula of (2)
1aAnd R
1bBe methyl, ethyl, hydroxyethyl or aminoalkyl group.
3. the cationic dyestuff of claim 2 record, wherein in described aminoalkyl group, the Z in the formula
aBe ethylidene or propylidene, R
2aAnd R
2bBe methyl or ethyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001155043A JP4820016B2 (en) | 2001-05-24 | 2001-05-24 | New cationic dye |
| JP155043/01 | 2001-05-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1388183A CN1388183A (en) | 2003-01-01 |
| CN1235979C true CN1235979C (en) | 2006-01-11 |
Family
ID=18999292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02120187 Expired - Lifetime CN1235979C (en) | 2001-05-24 | 2002-05-24 | Cationic dye |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4820016B2 (en) |
| CN (1) | CN1235979C (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB923148A (en) * | 1960-03-24 | 1963-04-10 | Ici Ltd | New anthraquinone dyestuffs |
| FR1370455A (en) * | 1962-10-03 | 1964-08-21 | Hoechst Ag | Basic phthalocyanine dyes and their preparation process |
| DE3734528A1 (en) * | 1987-10-13 | 1989-05-03 | Hoechst Ag | USE OF COLORING AGENTS FOR RECORDING LIQUIDS |
| WO1999001510A1 (en) * | 1997-07-03 | 1999-01-14 | Avecia Limited | Monoazo dyes and inks containg them |
| ES2192516T3 (en) * | 1999-09-27 | 2003-10-16 | Ciba Sc Holding Ag | AZOIC COLORS OF COPPER COMPLEX, OBTAINING AND USING THEMSELVES. |
-
2001
- 2001-05-24 JP JP2001155043A patent/JP4820016B2/en not_active Expired - Fee Related
-
2002
- 2002-05-24 CN CN 02120187 patent/CN1235979C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002348492A (en) | 2002-12-04 |
| JP4820016B2 (en) | 2011-11-24 |
| CN1388183A (en) | 2003-01-01 |
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Granted publication date: 20060111 |