CN102337040A - Preparation method of neutral metal complex dye - Google Patents
Preparation method of neutral metal complex dye Download PDFInfo
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- CN102337040A CN102337040A CN2011102041407A CN201110204140A CN102337040A CN 102337040 A CN102337040 A CN 102337040A CN 2011102041407 A CN2011102041407 A CN 2011102041407A CN 201110204140 A CN201110204140 A CN 201110204140A CN 102337040 A CN102337040 A CN 102337040A
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Abstract
The invention provides a preparation method of a neutral metal complex dye. The preparation method comprises the following steps of: (1) reacting dichromate with glucose under the action of acid to obtain a chromium complexing agent, wherein the dichromate is dichromate of an alkali metal; and (b) mixing the chromium complexing agent obtained in the step (a) with a monoazo dye solution and reacting to obtain the neutral metal complex dye. In the preparation method, a reaction product obtained by undergoing an oxidation-reduction reaction on dichromate and glucose is taken as a chromium complexing agent; the chromium complexing agent does not contain salicylic acid and is relatively clean; and no salicylic acid is left in the neutral metal complex dye obtained by reacting the chromium complexing agent with a monoazo dye, so that a fabric is not damaged when the neutral metal complex dye is applied to fabric dyeing. The neutral metal complex dye can be directly dried into powder with a spray drying method, and the neutral metal complex dye is not required to be separated from the solution with a salting-out method, so that the production of a large amount of dye waste water is avoided, and environmental pollution is avoided.
Description
Technical field
The invention belongs to the metallized dye technical field, relate in particular to a kind of preparation method of neutral premetallized dyes.
Background technology
Metallized dye is meant with the transition metal to be the coordination compound dyestuff that central ion, coloured dyestuff lewis' acid are ligand; It has that beautiful in colour, strong coloring force, photostabilization are good, good heat resistance, fastness advantages of higher, has a good application prospect in fields such as weaving, coating.Wherein, be that the azo metal complexdyes range of application that forms of ligand is the widest with the azoic dyestuff.
Press the molecular ratio of metal atom and part dyestuff; The azo metal complexdyes mainly is divided into 1: 1 type azo metal complexdyes and 1: 2 type azo metal complexdyes; 1: 1 type azo metal complexdyes is that a dye molecule and an atoms metal complexing form; Be matching stain, send Latin fast colo(u)r (Palatine Fast colours) like suitable and the indigo plant (Neolan) and the Baden, Germany aniline soda ash company (BASF) of Switzerland vapour crust laboratory (CIBA); 1: 2 type azo metal complexdyes is that two dye molecules and an atoms metal complexing form, and can in neutrality or slightly acidic solution, dye, and claims neutral premetallized dyes again.Whether identical by two molecular structure of dye, neutral premetallized dyes can be divided into symmetric neutral premetallized dyes and asymmetric neutral premetallized dyes again.Neutral premetallized dyes combines with fiber by means of hydrogen bond, Van der Waals force etc., does not damage fabric, does not also influence feel, has higher commercial value.
Prior art discloses multiple neutral premetallized dyes and preparation method thereof; Like 1: 1 type azo metal complexdyes and the azoic dyestuff generation neutral premetallized dyes that reacts; But this method generally is used to produce asymmetric neutral premetallized dyes, as application number be 200610059016.5 Chinese patent document disclosed with 1: 1 type azo chromium complexdyes and azoic dyestuff be 6.0～10.0 in the pH value, temperature is that reaction generates asymmetric neutral premetallized dyes under 60 ℃～90 ℃ the condition.Symmetric neutral premetallized dyes can be a raw material with complexing agent and azoic dyestuff; Synthetic in neutrality or weak basic condition; Be that 200610044571.0 Chinese patent document is a complexing agent with water-soluble aluminum salt or molysite like application number; React with azoic dyestuff, obtain symmetric neutral premetallized dyes.
Because Cr
3+Metal complex have satisfactory stability property, neutral premetallized dyes is generally with Cr
3+As central metal atom.Prior art is that complexing agent prepares neutral chromium complexdyes with Whitfield's ointment chromium generally, and residual in the neutral premetallized dyes that obtains have a Whitfield's ointment, can injure fabric when being used for textile dyeing.In addition, when being complexing agent, can produce the waste water from dyestuff that contains Whitfield's ointment, high chlorine root, high chroma in a large number, pollute the environment with Whitfield's ointment chromium.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of preparation method of neutral premetallized dyes, and anacidity is residual in the neutral premetallized dyes that preparation method provided by the invention obtains, and can not damage fabric.
The invention provides a kind of preparation method of neutral premetallized dyes, may further comprise the steps:
A) dichromate and glucose react under the effect of acid, obtain the chromium complexing agent, and said dichromate is alkali-metal dichromate;
B) the chromium complexing agent that said step a) is obtained mixes with monoazo-dyes solution, obtains neutral premetallized dyes after the reaction.
Preferably, in the said step a), said dichromate is sodium dichromate 99 or SRM 935a.
Preferably, in the said step a), said acid is acetic acid, hydrochloric acid, sulfuric acid or formic acid.
Preferably, in the said step a), the mass ratio of said dichromate, glucose and acid is (1～5): (0.5～3): (1～5).
Preferably, in the said step a), the temperature of said reaction is 90 ℃～120 ℃, and the time of said reaction is 4h～8h.
Preferably, in the said step b), said monoazo-dyes has formula (I) structure or formula (II) structure:
Wherein, R is halogen or the substituted phenyl of halogen;-R
1For-H ,-NH
2Or-NHCOCH
3-R
2For-NO
2,-CF
3,-CN ,-SO
3H ,-SO
2NH
2,-COOH or-COHN
2R
3Be alkyl or alkoxyl group.
Preferably, in the said step b), said monoazo-dyes has formula (I-a) structure or formula (II-a) structure:
Preferably, in the said step b), the temperature of said reaction is 90 ℃～120 ℃.
Preferably, in the said step b), the time of said reaction is 4h～5h.
Preferably, said step b) specifically comprises:
B1) the chromium complexing agent that said step a) is obtained mixes with monoazo-dyes solution, obtains neutral premetallized dyes solution after the reaction;
B2) with after the said neutral premetallized dyes solution spray drying, obtain neutral premetallized dyes.
Compared with prior art, the present invention is raw material, under the effect of acetic acid, prepares the chromium complexing agent with dichromate and glucose; With this chromium complexing agent and monoazo-dyes solution hybrid reaction, obtain neutral premetallized dyes then.The present invention is the chromium complexing agent with the reaction product that dichromate and glucose generation redox reaction obtain, and does not contain acid in the said chromium complexing agent, comparatively cleaning; Said chromium complexing agent and the monoazo-dyes anacidity that reacts in the neutral premetallized dyes that obtains is residual, when being used for coloration of textile materials, can not injure fabric.Further; When the reaction product that obtains with dichromate and glucose generation redox reaction is the chromium complexing agent; Can adopt spray-dired method directly neutral premetallized dyes to be dried to powder, need not to adopt the method for saltouing that neutral premetallized dyes is separated in solution, therefore; Can not produce a large amount of waste water from dyestuff, not pollute the environment.
Embodiment
The invention provides a kind of preparation method of neutral premetallized dyes, may further comprise the steps:
A) dichromate and glucose react under the effect of acid, obtain the chromium complexing agent, and said dichromate is alkali-metal dichromate;
B) the chromium complexing agent that said step a) is obtained mixes with monoazo-dyes solution, obtains neutral premetallized dyes after the reaction.
The present invention is the chromium complexing agent with the reaction product that dichromate and glucose generation redox reaction obtain, and does not contain acid in the said chromium complexing agent, comparatively cleaning; Said chromium complexing agent and the monoazo-dyes anacidity that reacts in the neutral premetallized dyes that obtains is residual, when being used for coloration of textile materials, can not injure fabric.
In the present invention, said dichromate is alkali-metal dichromate, is preferably sodium dichromate 99 or SRM 935a, more preferably sodium dichromate 99.
Redox reaction takes place in said dichromate and glucose under the effect of acid, obtain containing chromic chromium complexing agent, preferably includes following steps:
Dichromate is added to the water, adds fast glucose after being warming up to 60 ℃～70 ℃, add acid more fast, be warming up to 90 ℃～120 ℃ back flow reaction, obtain each complexing agent.
The present invention is preferably adding glucose within the 30min in the dichromate aqueous solution, more preferably add glucose within the 20min.
In the present invention, said acid can be organic acid or mineral acid, is preferably acetic acid, hydrochloric acid, sulfuric acid or formic acid, more preferably acetic acid.
In the present invention, the mass ratio of said dichromate, glucose and acid is preferably (1～5): (0.5～3): (1～5), more preferably (2～3): (1～2): (2～3).
The temperature of said dichromate and glucose generation redox reaction is preferably 90 ℃～120 ℃, more preferably 100 ℃～110 ℃; Time is preferably 4h～8h, more preferably 5h～7h.
Do not contain materials such as Whitfield's ointment in the chromium complexing agent that said dichromate and glucose generation redox reaction obtain, comparatively cleaning.
After obtaining the chromium complexing agent, said chromium complexing agent is joined in the monoazo-dyes solution, can obtain neutral premetallized dyes after the reaction.
In the present invention, the color of the neutral premetallized dyes that said monoazo-dyes has determined to obtain, it preferably has formula (I) structure or formula (II) structure:
Wherein, R is halogen or the substituted phenyl of halogen;-R
1For-H ,-NH
2Or-NHCOCH
3-R
2For-NO
2,-CF
3,-CN ,-SO
3H ,-SO
2NH
2,-COOH or-COHN
2R
3Be alkyl or alkoxyl group.
In the present invention, said monoazo-dyes can be for having the gray dyes of formula (I-a) structure:
Also can be for having the orange dye of formula (II-a) structure
It can also be monoazo-dyes with other structures, other colors.
The present invention does not have particular restriction to the source of said monoazo-dyes, preferably according to following method preparation:
Diazo component is joined in the mixing solutions of hydrochloric acid and water, add sodium nitrite solution under the stirring condition, obtain diazonium salt solution after the reaction;
Coupling component is dissolved in the alkali lye, adds said diazonium salt solution, obtain monoazo-dyes after the reaction.
At first diazo component is joined in the mixing solutions of hydrochloric acid and water; Behind dissolving, the suction strainer; The filtrating that obtains is cooled to below 5 ℃ with mixture of ice and water, and the temperature of said filtrating is controlled to be is lower than 5 ℃, pH value and is strongly-acid, under stirring condition, add sodium nitrite solution; Under 0 ℃～5 ℃ temperature, react 1h～2h, obtain diazonium salt solution.In the present invention, said diazo component is meant the raw material that can generate diazonium salt, can be phenol or fortified phenol.
Coupling component is dissolved in the alkali lye; After being cooled to 10 ℃～15 ℃; Add said diazonium salt solution, with alkali lye the pH value of the mixing solutions that obtains is adjusted to then and is alkalescence, can carry out the adjustment of pH value according to the character of diazo component of selecting for use and coupling component; Fully react 3h～4h down at 10 ℃～15 ℃, obtain monoazo-dyes solution.In the present invention, said coupling component is meant the raw material that can obtain monoazo-dyes with diazonium salt generation coupled reaction, can be phenol, naphthols, fortified phenol or substituted naphthol.
After obtaining monoazo-dyes solution, add said chromium complexing agent, obtain having the neutral premetallized dyes of formula (III) structure or formula (IV) structure after the reaction to said monoazo-dyes solution:
Wherein, M is a basic metal, is preferably sodium or potassium, more preferably sodium.
In the present invention, the temperature that said monoazo-dyes and said chromium complexing agent react is preferably 90 ℃～120 ℃, more preferably 100 ℃～110 ℃; Time is preferably 4h～5h, more preferably 4h.
After said monoazo-dyes and the reaction of said chromium complexing agent finish, obtain neutral premetallized dyes solution.Owing to do not contain the material that Whitfield's ointment etc. reduces the dyestuff performance in the said neutral premetallized dyes solution; The present invention need not to adopt the mode of saltouing that said neutral premetallized dyes is separated from solution, can directly adopt spray-dired mode directly to obtain the neutral premetallized dyes powder.Owing to can directly carry out spraying drying, therefore can not produce a large amount of dyeing waste-waters, not only can not cause environmental pollution, and can conservation.
After obtaining neutral premetallized dyes, to said neutral premetallized dyes dye experiment and fastness experiment, the result shows that the neutral premetallized dyes that the method that adopts invention to provide prepares has good dyeing behavior and fastness.
The present invention is the chromium complexing agent with the reaction product that dichromate and glucose generation redox reaction obtain, and does not contain acid in the said chromium complexing agent, comparatively cleaning; Said chromium complexing agent and the monoazo-dyes anacidity that reacts in the neutral premetallized dyes that obtains is residual, when being used for coloration of textile materials, can not injure fabric.Further; When the reaction product that obtains with dichromate and glucose generation redox reaction is the chromium complexing agent; Can adopt spray-dired method directly neutral premetallized dyes to be dried to powder, need not to adopt the method for saltouing that neutral premetallized dyes is separated in solution, therefore; Can not produce a large amount of waste water from dyestuff, not pollute the environment.
In order to further specify the present invention, the preparation method of neutral premetallized dyes provided by the invention is described in detail below in conjunction with embodiment.
Embodiment 1
It is that rising temperature for dissolving, suction strainer are cooled to the filtrating that obtains below 5 ℃ with frozen water in 30% the hydrochloric acid that 7.44g4-sulphonamide-2-amino-phenol is joined 39mL water and 7.6mL mass concentration; The solution that under stirring condition, 7mL is contained the 2.65g Sodium Nitrite joins in the said filtrating, is lower than under 5 ℃ the temperature to react 2h, obtains diazonium salt solution, and reaction formula is following:
2.16g yellow soda ash is dissolved in the 45mL water, adds the 3.8mL mass concentration then and be 30% sodium hydroxide solution, obtain alkali lye; 7.74g1-acetylaminohydroxyphenylarsonic acid 7-naphthols is dissolved in the said alkali lye, is cooled to 10 ℃～15 ℃ behind the suction strainer, obtain naphthol solution;
Said diazonium salt solution is joined in 1h～2h in the said naphthol solution; To use mass concentration be 30% sodium hydroxide solution is adjusted to 9～10 with the pH value of the mixing solutions that obtains; Under 10 ℃～15 ℃, react to the diazonium salt completely dissolve, obtain monoazo-dyes solution, reaction formula is following:
The 3g sodium dichromate 99 is joined in the 25mL water, be warming up to 70 ℃, add 1.6g glucose in the 10min, add 2.8g acetic acid then fast, be warming up to 100 ℃, insulation reaction 6h obtains the chromium complexing agent;
Said chromium complexing agent is joined in the said monoazo-dyes solution; Be warming up to 100 ℃; Insulation reaction 4h; Use the thin-layer chromatography detection reaction, to the monoazo-dyes completely dissolve, obtain neutral premetallized dyes solution, the developping agent of said thin-layer chromatography is that volume ratio is 10: 5: 5 benzene, methyl alcohol and a chloroform; After said neutral premetallized dyes solution spray drying, obtain the neutral grey dyestuff of chromium complexing, reaction formula is following:
Adopt said neutral premetallized dyes to dye and test and the fastness experiment, the result shows that the neutral premetallized dyes for preparing through method provided by the invention has good dyeing behavior and fastness.
Embodiment 2
It is that rising temperature for dissolving, suction strainer are cooled to the filtrating that obtains below 5 ℃ with frozen water in 30% the hydrochloric acid that 7.44g4-sulphonamide-2-amino-phenol is joined 39mL water and 7.6mL mass concentration; The solution that under stirring condition, 7mL is contained the 2.65g Sodium Nitrite joins in the said filtrating, is lower than under 5 ℃ the temperature to react 2h, obtains diazonium salt solution, and reaction formula is following:
4.5g yellow soda ash is dissolved in the 39mL water, adds the 6.6mL mass concentration then and be 30% sodium hydroxide solution, obtain alkali lye; 8.25g is dissolved in the said alkali lye the chlorine pyrazolone, is cooled to 10 ℃～15 ℃ behind the suction strainer, obtain chlorine pyrazolone solution;
Said diazonium salt solution is joined said in the chlorine pyrazolone solution; To use mass concentration be 30% sodium hydroxide solution is adjusted to 11.5～12.5 with the pH value of the mixing solutions that obtains; Under 10 ℃～15 ℃, react to the diazonium salt completely dissolve, obtain monoazo-dyes solution, reaction formula is following:
The 3g sodium dichromate 99 is joined in the 25mL water, be warming up to 70 ℃, add 1.6g glucose in the 10min, add 2.8g acetic acid then fast, be warming up to 100 ℃, insulation reaction 6h obtains the chromium complexing agent;
Said chromium complexing agent is joined in the said monoazo-dyes solution; Be warming up to 100 ℃; Insulation reaction 4h; Use the thin-layer chromatography detection reaction, to the monoazo-dyes completely dissolve, obtain neutral premetallized dyes solution, the developping agent of said thin-layer chromatography is that volume ratio is 10: 5: 5 benzene, methyl alcohol and a chloroform; After said neutral premetallized dyes solution spray drying, obtain neutral premetallized dyes, reaction formula is following:
Adopt said neutral premetallized dyes to dye and test and the fastness experiment, the result shows that the neutral premetallized dyes for preparing through method provided by the invention has good dyeing behavior and fastness.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a neutral premetallized dyes may further comprise the steps:
A) dichromate and glucose react under the effect of acid, obtain the chromium complexing agent, and said dichromate is alkali-metal dichromate;
B) the chromium complexing agent that said step a) is obtained mixes with monoazo-dyes solution, obtains neutral premetallized dyes after the reaction.
2. preparation method according to claim 1 is characterized in that, in the said step a), said dichromate is sodium dichromate 99 or SRM 935a.
3. preparation method according to claim 1 is characterized in that, in the said step a), said acid is acetic acid, hydrochloric acid, sulfuric acid or formic acid.
4. preparation method according to claim 1 is characterized in that, in the said step a), the mass ratio of said dichromate, glucose and acid is (1～5): (0.5～3): (1～5).
5. preparation method according to claim 1 is characterized in that, in the said step a), the temperature of said reaction is 90 ℃～120 ℃, and the time of said reaction is 4h～8h.
6. preparation method according to claim 1 is characterized in that, in the said step b), said monoazo-dyes has formula (I) structure or formula (II) structure:
Wherein, R is halogen or the substituted phenyl of halogen;-R
1For-H ,-NH
2Or-NHCOCH
3-R
2For-NO
2,-CF
3,-CN ,-SO
3H ,-SO
2NH
2,-COOH or-COHN
2R
3Be alkyl or alkoxyl group.
7. preparation method according to claim 6 is characterized in that, in the said step b), said monoazo-dyes has formula (I-a) structure or formula (II-a) structure:
8. preparation method according to claim 1 is characterized in that, in the said step b), the temperature of said reaction is 90 ℃～120 ℃.
9. preparation method according to claim 1 is characterized in that, in the said step b), the time of said reaction is 4h～5h.
10. preparation method according to claim 1 is characterized in that, said step b) specifically comprises:
B1) the chromium complexing agent that said step a) is obtained mixes with monoazo-dyes solution, obtains neutral premetallized dyes solution after the reaction;
B2) with after the said neutral premetallized dyes solution spray drying, obtain neutral premetallized dyes.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634235A (en) * | 2012-03-27 | 2012-08-15 | 河北永泰柯瑞特化工有限公司 | Neutral dye composition |
| CN104610777A (en) * | 2015-01-13 | 2015-05-13 | 青岛双桃精细化工（集团）有限公司 | Red complex dye used for wool/chinlon blend dyeing |
| CN105385186A (en) * | 2015-10-19 | 2016-03-09 | 广州市纬庆化工科技有限公司 | Migration-resistant red dye, preparation method therefor and application thereof |
| CN109575630A (en) * | 2018-11-20 | 2019-04-05 | 浙江劲光实业股份有限公司 | A kind of preparation method of rufous reactive dye |
| CN111519175A (en) * | 2020-06-09 | 2020-08-11 | 杭州朱炳仁文化艺术有限公司 | Processing method of golden yellow oxide film on surface of brass product |
| CN112409813A (en) * | 2020-11-17 | 2021-02-26 | 天津三环化工有限公司 | Preparation method of purple acid dye |
| CN113337140A (en) * | 2021-04-13 | 2021-09-03 | 武威合才化工有限责任公司 | Preparation method of solvent orange 62# dye |
| CN114525040A (en) * | 2022-02-16 | 2022-05-24 | 辽宁精化科技有限公司 | Red mordant dye and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427585A (en) * | 1981-07-27 | 1984-01-24 | Ciba-Geigy Corporation | 1:2 Chromium and cobalt complex dyes |
| CN101077937A (en) * | 2006-05-25 | 2007-11-28 | 青岛大学 | Environment-friendly type orange or brown neutral dye and preparation method thereof |
| CN101665628A (en) * | 2009-09-16 | 2010-03-10 | 大连理工大学 | Chrome complex dye as well as preparation method and applications thereof |
| KR20110052156A (en) * | 2009-11-12 | 2011-05-18 | 주식회사 디케이씨코포레이션 | Black acid dye composition |
-
2011
- 2011-07-20 CN CN2011102041407A patent/CN102337040A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427585A (en) * | 1981-07-27 | 1984-01-24 | Ciba-Geigy Corporation | 1:2 Chromium and cobalt complex dyes |
| CN101077937A (en) * | 2006-05-25 | 2007-11-28 | 青岛大学 | Environment-friendly type orange or brown neutral dye and preparation method thereof |
| CN101665628A (en) * | 2009-09-16 | 2010-03-10 | 大连理工大学 | Chrome complex dye as well as preparation method and applications thereof |
| KR20110052156A (en) * | 2009-11-12 | 2011-05-18 | 주식회사 디케이씨코포레이션 | Black acid dye composition |
Non-Patent Citations (2)
| Title |
|---|
| 付丽红 等: "葡萄糖还原重铬酸盐影响因素变化规律的研究", 《皮革化工》, vol. 18, no. 3, 31 December 2001 (2001-12-31), pages 1 - 5 * |
| 姚芝茂 等: "水热法还原铬酸钾/重铬酸钾制备水合氧化铬的实验", 《过程工程学报》, vol. 3, no. 1, 28 February 2003 (2003-02-28), pages 62 - 67 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634235A (en) * | 2012-03-27 | 2012-08-15 | 河北永泰柯瑞特化工有限公司 | Neutral dye composition |
| CN104610777A (en) * | 2015-01-13 | 2015-05-13 | 青岛双桃精细化工（集团）有限公司 | Red complex dye used for wool/chinlon blend dyeing |
| CN104610777B (en) * | 2015-01-13 | 2017-07-04 | 青岛双桃精细化工（集团）有限公司 | A kind of red composite dye for hair brocade blend dyeing |
| CN105385186A (en) * | 2015-10-19 | 2016-03-09 | 广州市纬庆化工科技有限公司 | Migration-resistant red dye, preparation method therefor and application thereof |
| CN109575630A (en) * | 2018-11-20 | 2019-04-05 | 浙江劲光实业股份有限公司 | A kind of preparation method of rufous reactive dye |
| CN111519175A (en) * | 2020-06-09 | 2020-08-11 | 杭州朱炳仁文化艺术有限公司 | Processing method of golden yellow oxide film on surface of brass product |
| CN112409813A (en) * | 2020-11-17 | 2021-02-26 | 天津三环化工有限公司 | Preparation method of purple acid dye |
| CN113337140A (en) * | 2021-04-13 | 2021-09-03 | 武威合才化工有限责任公司 | Preparation method of solvent orange 62# dye |
| CN114525040A (en) * | 2022-02-16 | 2022-05-24 | 辽宁精化科技有限公司 | Red mordant dye and preparation method thereof |
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Application publication date: 20120201 |