CN1047607C - Water-soluble fluorescent dye - Google Patents
Water-soluble fluorescent dye Download PDFInfo
- Publication number
- CN1047607C CN1047607C CN94112746A CN94112746A CN1047607C CN 1047607 C CN1047607 C CN 1047607C CN 94112746 A CN94112746 A CN 94112746A CN 94112746 A CN94112746 A CN 94112746A CN 1047607 C CN1047607 C CN 1047607C
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- CN
- China
- Prior art keywords
- fluorescent dye
- coupling
- water
- acid
- aluminium
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/22—Monoazo compounds containing other metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The present invention relates to water soluble fluorescent dye which is azoic dye which has industrial practical value and contains a metal complex. A general formula (I) of the present invention discloses in the specification. In the formula (I), Ar and Ar' can be a benzene ring or a naphthalene ring, Ar and Ar' can be the same or can be different, R stands for H, OH, Cl, COOH and SO3H, R1 stands for H and OH, R2 stands for H and SO3H, R3 stands for H, Cl, CH3, COOH and SO3H, and Me can be metal aluminum, gallium, indium, etc. The fluorescent dye has a water soluble group. A benzenesulfonic acid (or benzene carboxylic acid) or naphthalenesulfonic acid (or naphthalene carboxylic acid) intermediate body which has amino and hydroxy is used as a diazo ingredient. Through diazotization, salification, accidental union and metal complexation, a series of water soluble fluorescent dye which has colors from yellow to purple is prepared.
Description
The invention belongs to the containing metal complexing azoic dyestuff of the industrial practicality of a class, its general formula is:
(I)
(I) Ar in the formula, Ar ' can be phenyl ring or naphthalene nucleus, and they can be identical or different; R=H, OH, Cl, COOH, SO
3H; R
1=H, OH; R
2=H, SO
3H; R
3=H, Cl, CH
3, COOH, SO
3H; Me can be metallic aluminium, gallium, indium etc.
Fluorescence dye is a kind of of functional dye, and it can give the gorgeous degree and the brightness of pollutant uniqueness, and in recent years, the fluorescence dye development is very rapid, but great majority are water-insoluble, are mainly used in high molecular polymers such as plastics, resin.Water miscible fluorescence dye then seldom, as for low price, have industrial applicibility just still less.Along with the raising of people's living standard, the enhancing of merchandise consciousness, the expansion of competition mechanism, people have all proposed higher demand to industrial art, environmental decoration, commodity packaging, advertisement and decoration etc.Fluorescence dye has become one of object of manufacturer's selection.At present, homemade kind is few, and mainly by import, general azoic dye does not have fluorescence, but (when OH) existing, then can generate the compound of band fluorescence with the complexing of metallic aluminium atom when there is hydroxyl at the ortho position of azo-group.This discovery is applied to this principle to measure in the fluorometric analysis content of metal ion at nineteen fifty-seven M.Ishibashi etc.It is that the azo-compound that the coupling component obtains is used for fluorometric analysis that Keiz o Hiraki in 1973 has further studied again with Resorcinol and Phloroglucinol monomethyl ether, and has studied their fluorescence property and produced the pairing pH value of maximum fluorescence intensity.After the Yamamoto gold equality people of Japan in 1991 finds schiff bases compounds and aluminium complexing, also can produce fluorescence, can be used for fluorometric analysis.
The above-mentioned dyestuff that these are generated when being used for fluorometric analysis, though fluorescence and color are arranged, can not be applied as the dyestuff of industrial practicality, because its Molecular Structure Design can not satisfy the requirement of dyestuff, for example: exist molecule little, low to coloring material avidity; Free amino on the structure, hydroxyl are many, cause light fastness poor; Owing to there is not water soluble group, shortcoming such as dyestuff is water insoluble.
The objective of the invention is requirement, adopt the used intermediate of synthetic dyestuff, contain water soluble group in the design molecular structure of dye, and can come synthesizing water-solubility metal complex fluorescence dye with the complexing of metallic aluminium atom according to practical dyestuff.
The present invention adopts the intermediate of hydroxy amino Phenylsulfonic acid (or benzene carboxylic acid) or naphthene sulfonic acid (or naphthalene monocarboxylic acid) as diazo component, through diazotization reaction, and the generation zinc salt, and then carry out coupled reaction with coupling component (benzene series, naphthalene system, heterogeneous ring compound), use aluminium salt (Al at last
3(SO
4)
318H
2O) complexing can make a series of by the water-soluble fluorescent dye of Huang to purple.
If make diazo component, carry out diazotization reaction earlier with 1-amino-2-naphthol-4-sulfonic acid:
Then, product is carried out acid out;
The acid out thing is dissolved into diazonium oxysome zinc salt with liquor zinci chloridi again:
Gained diazonium oxysome zinc salt and coupling component 1-(phenyl-4 '-sulfonic acid)-4 methylpyrazole ketone, coupling under alkaline condition can obtain containing the azoic dyestuff of free hydroxyl group, and is last, with Tai-Ace S 150 [Al
2(SO
4)
318H
2O] carry out metal complex, just make aluminiferous orange water-soluble fluorescent dye.
Red water-soluble fluorescent dye is to be diazo component with o-aminophenol-4-sulfonic acid, through diazotization, becomes zinc salt with zinc chloride, and again with coupling component beta naphthal-3, the coupling of 6-disulfonic acid is carried out the aluminium complexing with Tai-Ace S 150 at last and made.
In order to obtain the higher water-soluble dye of fluorescence intensity, diazo component has adopted hydroxy amino benzene, hydroxy amino Phenylsulfonic acid, three series of hydroxy amino naphthene sulfonic acid respectively, be respectively hydroxyl naphthalene, amino-phenol, hydroxyl naphthalene monocarboxylic acid, hydroxyl amino naphthene sulfonic acid and nitrogen-containing heterocycle compound with the coupling component, 24 monoazo-dyes have been synthesized with the aluminium complexing, the yield of dyestuff is generally 70～80%, and some dyestuff reaches as high as more than 90%.
From the fluorescence property of dyestuff and structural relation, find:
1. the fluorescence dye that two hydroxyls are arranged at neighbour, the ortho position of dyestuff azo-group, when forming complex compound with aluminium, the amino of azo-group contraposition more effectively strengthens fluorescence than hydroxyl.
2. contain sulfonic group (SO in the diazo component
3H) can significantly strengthen fluorescence.
Synthetic water-soluble fluorescent dye of the present invention, has higher vividness and brightness, and it is water-soluble good, the harm and the pollution on the environment that have needed organic solvent that human body is produced when having avoided water-insoluble fluorescence dye to use, more outstanding advantage is the dyestuff low price, easy to use, the coloring effect that is used for aspects such as finishing material, package packing supplies, stationery paper is good, and light fastness can reach more than 3 grades.
Embodiment 1
Take by weighing 0.02 mole 1-amino-2-naphthol-4-sulfonic acid, add water and 15% yellow soda ash and make its neutralization dissolving, add a spot of copper sulfate, be cooled to 15 ℃, add 0.025 mole 10% sodium nitrite solution, keep Starch iodide paper to be little indigo plant, reaction is 1 hour under room temperature, use the dilute sulphuric acid acid out then, filter, filter cake is dissolved into diazonium oxysome zinc salt with 15% zinc chloride again.
Again 2-amino-5-naphthols-7-sulfonic acid is dissolved with yellow soda ash, add diazonium oxysome zinc solution, transfer PH=9 with 15% yellow soda ash, in room temperature～55 ℃ coupling, terminal point to the diazonium salt disappearance, is used the dilute sulphuric acid acid out with oozing the check of circle method, filter, the dry product that gets, yield is 76%.
Is to be dissolved in water at 1: 6 dyestuff and Tai-Ace S 150 with mol ratio, transfers PH to be slightly acidic with acid, stirs down and is heated to 60～90 ℃, be incubated 1 hour, cooling, and filtration, drying gets dyestuff, and yield is 87%.
Embodiment 2
Take by weighing 0.02 mole Ortho-Aminophenol p-sulfonic acid, add 40 ml waters, stirring and dissolving, add 0.05 mole of Glacial acetic acid, be cooled to 6～7 ℃, add and dissolved 0.021 mole of good Sodium Nitrite, the little indigo plant of control starch potassium iodide paper, continue reaction, keep 8～10 ℃ of temperature, 1 hour, pH value is slightly acidic, add 0.01 mole of 10% liquor zinci chloridi, stirred 10 minutes, make the diazonium zinc solution.
Take by weighing 0.02 mole of beta naphthal-4-carboxylic acid, be dissolved in 40 milliliters of dilute sodium carbonate solution, make PH=8～9, slowly be added to diazonium liquid in the coupling solution, constantly add alkali and keep weakly alkaline, 10～15 ℃ of temperature were reacted 2 hours, check terminal point with oozing the circle method, add 10～15% salt then and saltout, filter drying, pulverize, yield is 85%.
The aluminium complexing is identical with embodiment 1.
Claims (3)
1. a class is characterized in that through the azoic dyestuff that diazotization, coupling make this azoic dyestuff is the water-soluble fluorescent dye of containing metal aluminium complexing, and its general formula is:
(I)
(I) Ar in the formula, Ar ' can be phenyl ring or naphthalene nucleus, and they can be identical or different; R=H, OH, Cl, COOH, SO
3H; R
1=H, OH; R
2=H, SO
3H; R
3=H, Cl, CH
3, COOH, SO
3H; Me can be aluminium (Al); This class dyestuff be with diazo component behind diazotization, salify with the coupling of coupling component, make with the complexing of aluminium salt at last.
2. according to the described azoic dyestuff of claim 1, it is characterized in that orange water-soluble fluorescent dye is is diazo component with 1-amino-beta naphthal-4 sulfonic acid, behind diazotization, acid out, be dissolved into diazonium oxysome zinc salt with zinc chloride, again with coupling component 1-(phenyl-4 '-sulfonic acid)-4-methylpyrazole ketone coupling, carry out the aluminium complexing with Tai-Ace S 150 at last and make.
3. according to the described azoic dyestuff of claim 1, it is characterized in that red water-soluble fluorescent dye is is diazo component with o-aminophenol-4-sulfonic acid, through diazotization, become zinc salt with zinc chloride, again with coupling component beta naphthal-3, the coupling of 6-disulfonic acid is carried out the aluminium complexing with Tai-Ace S 150 at last and is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112746A CN1047607C (en) | 1994-12-29 | 1994-12-29 | Water-soluble fluorescent dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112746A CN1047607C (en) | 1994-12-29 | 1994-12-29 | Water-soluble fluorescent dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125743A CN1125743A (en) | 1996-07-03 |
| CN1047607C true CN1047607C (en) | 1999-12-22 |
Family
ID=5036415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112746A Expired - Fee Related CN1047607C (en) | 1994-12-29 | 1994-12-29 | Water-soluble fluorescent dye |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1047607C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5170489B2 (en) * | 2003-12-09 | 2013-03-27 | 保土谷化学工業株式会社 | Sulphonic acid onium salt compound, method for producing the compound, photosensitive resin composition using the compound, and photosensitive material |
| CN103063662B (en) * | 2012-12-21 | 2014-12-24 | 内蒙古伊利实业集团股份有限公司 | Raw milk somatic cell test paper and preparation method thereof |
| CN104628669B (en) * | 2014-11-05 | 2016-07-06 | 九江善水科技有限公司 | A kind of oxysome and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052492A (en) * | 1988-10-20 | 1991-06-26 | 山道士有限公司 | fiber-reactive azo dyes |
-
1994
- 1994-12-29 CN CN94112746A patent/CN1047607C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052492A (en) * | 1988-10-20 | 1991-06-26 | 山道士有限公司 | fiber-reactive azo dyes |
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| Publication number | Publication date |
|---|---|
| CN1125743A (en) | 1996-07-03 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |