CN102993774A - Stable thick aqueous composition for stilbene derivative - Google Patents
Stable thick aqueous composition for stilbene derivative Download PDFInfo
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- CN102993774A CN102993774A CN 201210345236 CN201210345236A CN102993774A CN 102993774 A CN102993774 A CN 102993774A CN 201210345236 CN201210345236 CN 201210345236 CN 201210345236 A CN201210345236 A CN 201210345236A CN 102993774 A CN102993774 A CN 102993774A
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- waterborne compositions
- amino
- stibene
- disulfonic acid
- triazinyl
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Abstract
The present invention provides a stable thick aqueous composition for a stilbene derivative. 4,4'-bis(2-anilino-4-methoxyl-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid thick aqueous composition which is expected to be used at a dyeing working site, has an excellent saving stability at low temperature and high temperature, and has an excellent stability when being diluted by using hard water is looked for. The present invention provides the 4,4'-bis(2-anilino-4-methoxyl-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid aqueous composition which is obtained by adding alkanolamine, water, and glycol and/or urea used as optional components into the 4,4'-bis(2-anilino-4-methoxyl-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid.
Description
Technical field
The present invention relates to be used for 4,4 '-two (2-anilino-4-methoxyl group-1,3,5-triazines base-6-is amino) stibene-2 of white dyes etc., the dense thick waterborne compositions of 2 '-disulfonic acid.More specifically, the present invention relates to this good waterborne compositions of stability in storage and dilution stability.
Background technology
From the angle of the ease of use of white dyes, compare with powder, liquid product in metering, add, with the mixing of other medicaments in the use of being more convenient for, in recent years, the white dyes that can obtain from the market nearly all changes into the liquid state product.But, still have solvability in water, storage stability, stable low when liquid product dilute thereby have to use the white dyes of powder product.
Generally speaking, the lysate of white dyes etc. stable bad is following aspect mostly: when the existence of the inorganic salt of association causes low temperature owing to making or the stability during high temperature reduce, thereby crystallization etc.In order to prevent above-mentioned situation, known have by reducing the method that the inorganic salt that contain in the aqueous solution improve the stability of solution with semi-permeable membranes.That is, for example, disclose in Japanese kokai publication sho 58-65760 communique, the Japanese kokai publication sho 60-158266 communique by make the method for the dense thick aqueous solution with the salt concn in the semi-permeable membranes reduction aqueous solutions of optical brighteners.
In addition, as the method for not using semi-permeable membranes, for example, the metal-salt that discloses the insoluble or insoluble by making the stibene derivative in the Japanese kokai publication sho 58-222156 communique is removed the method that insoluble substance is made the stable and dense thick aqueous solution of stibene derivative with rudimentary azanol reaction and from this reaction mixture in the presence of carbanion.In addition, disclose in the Japanese kokai publication sho 57-123262 communique such as following technology: in the aqueous solution of the sodium salt of stibene derivative, add the tetraalkyl ammonium compounds such as tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, make sodium salt form tetraalkylammonium salt, solvability is improved.In addition, in the Japanese kokai publication sho 62-273266 communique, modification method as the disclosed method of Japanese kokai publication sho 57-123262 communique, following method is disclosed: the sodium salt of stibene derivative is become the salt that tetraalkyl ammonium compound with hydroxyl for example forms with choline, use filter-pressing device to carry out desalination, then, add the solubility promoters such as urea, thereby make the stable dense thick aqueous solution of stibene derivative.In No. 4179584 communiques of Japanese Patent and No. 4111405 communiques of Japanese Patent all less than about 4,4 '-two (2-anilino-4-methoxyl group-1,3,5-triazines base-6-is amino) stibene-2, the record of the dense thick waterborne compositions of 2 '-disulfonic acid.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 58-222156 communique
Patent documentation 2: Japanese kokai publication sho 57-123262 communique
Patent documentation 3: Japanese kokai publication sho 62-273266 communique
Patent documentation 4: Japanese JP 7-91485 communique
Patent documentation 5: No. 4179584 communiques of Japanese Patent
Patent documentation 6: No. 4111405 communiques of Japanese Patent
Summary of the invention
Invent problem to be solved
Expectation by simple method obtain stability in storage, dilution stability good, contain 4,4 '-two (2-anilino-4-methoxyl group-1,3,5-triazines base-6-is amino) stibene-2, the waterborne compositions of 2 '-disulfonic acid.
For the method for dealing with problems
The inventor conducts in-depth research in order to address the above problem, and the result has finished the present invention.Namely, the present invention relates to 4,4 '-two (2-anilinos-4-methoxyl group-1,3 of in the situation of not using semi-permeable membranes etc., obtaining by adding specific stablizer, 5-triazinyl-6-is amino) stibene-2, the stable dense thick waterborne compositions of 2 '-disulfonic acid.The present invention relates to following 1) ~ 4).
1) a kind of 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2, the waterborne compositions of 2 '-disulfonic acid, it passes through to 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2, add alkanol amine, water and obtain as the glycols of optional member and/or urea in 2 '-disulfonic acid.
2) such as above-mentioned 1) described 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2, the waterborne compositions of 2 '-disulfonic acid, wherein, 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2,2 '-disulfonic acid is by adding mineral acid in an alkali metal salt of this compound or alkaline-earth metal salt brine solution, time carry out acid out in pH1 ~ 3 and will separating out the crystallization that the suspension liquid of crystallization filters, washes this compound that obtains.
3) such as above-mentioned 1) or 2) described waterborne compositions, wherein, in the waterborne compositions 4,4 '-two (2-anilino-4-methoxyl group-1,3,5-triazines base-6-is amino) stibene-2, the concentration of 2 '-disulfonic acid is 10 ~ 30%, be 5 ~ 30% as the thanomin of alkanol amine or the concentration of Propanolamine, the concentration of glycols is 0 ~ 40%, and the concentration of urea is 0 ~ 30%.
4) such as above-mentioned 1) ~ 3) in each described waterborne compositions, wherein, the alkalimetal ion in the waterborne compositions and/or the concentration of alkaline-earth metal ions are below the 1000ppm.
The invention effect
Of the present invention 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2, even the dense thick waterborne compositions of 2 '-disulfonic acid is preserved also stable under low temperature, hot conditions, and namely use the high water dilution of hardness also to have stability, for example, extremely useful in situation about using as the white dyes waterborne compositions, thus also high in industrial value.
Embodiment
Waterborne compositions of the present invention is described.
4,4 '-two (2-anilino-4-methoxyl group-1,3,5-triazines base-6-is amino) stibene-2,2 '-disulfonic acid (the following compound (1) that sometimes is denoted as) and salt thereof is as C.I. white dyes 90 and known, and sold in market.In addition, can also make according to known document.Namely, for example, in the presence of suitable alkali, make cyanuric chloride and the methyl alcohol reaction that waits molar equivalent, make resulting compound in the presence of same alkali with the diamino stibene derivatives reaction that waits molar equivalent, make resulting compound in the presence of same alkali with the aniline reaction of 2 molar equivalents, thus, can make compound (1).
In addition, the crystallization of the compound that contains in the waterborne compositions of the present invention (1) can be by following method manufacturing: the thick purification thing of this compound that obtains with commercially available product or by above-mentioned manufacture method is made the aqueous solution of an alkali metal salt or alkaline earth salt by ordinary method, then add mineral acid described later, making pH is 1 ~ 3, acid out goes out the crystallization of compound (1) thus, the suspension liquid that generates is filtered, and the crystallization that obtains is washed.
Waterborne compositions of the present invention is by adding alkanol amine, water in the compound that as above obtains (1) and obtaining as glycols and/or the urea of optional member.
An alkali metal salt refers to the negatively charged ion of compound (1) and the salt that alkalimetal ion (alkali metal cation) forms, and as alkalimetal ion, can enumerate: lithium ion, sodium ion, potassium ion etc.
Alkaline earth salt refers to the negatively charged ion of compound (1) and the salt that alkaline-earth metal ions (alkaline earth metal cation) forms, and as alkaline-earth metal ions, can enumerate: magnesium ion, calcium ion, barium ion etc.
Mineral acid can be enumerated such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid etc.
As the alkanol amine that contains in the waterborne compositions of the present invention, so long as then be not particularly limited by fatty compounds amino and that hydroxyl replaces, as long as and can replace, the position of substitution and replacement number also are not particularly limited.As this alkanol amine, can enumerate: thanomin (such as monoethanolamine, diethanolamine, trolamine etc.), Propanolamine (such as single Propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine etc.) etc.
Glycols as containing as optional member in the waterborne compositions of the present invention can use commercially available commodity, can enumerate such as ethylene glycol, Diethylene Glycol, triethylene glycol, poly(oxyethylene glycol) 400 etc.
The concentration of the compound (1) in the preferred waterborne compositions of the present invention be about 10% ~ about 30%, the concentration of alkanol amine be about 5% ~ about 30%, the concentration of glycols be about 0% ~ about 40%, the concentration of urea is about 0% ~ about 30%.In addition, the alkalimetal ion in the preferred waterborne compositions of the present invention and/or the concentration of alkaline-earth metal ions add up to below the 1000ppm.
Waterborne compositions of the present invention can use when for example cellulosic fibre material being dyeed.For example, can be used for utilize the dyeing that common dyeing condition that paper, paper pulp are dyeed carry out, the surface coated dyeing that comprises size press method, coating method or in add dyeing etc.In addition, this waterborne compositions can be used for the dyeing that utilizes common dyeing condition to carry out as fiber such as cotton, the artificial silk etc. of the natural or man-made cellulose fibers of cellulosic fibre material or cellulose, such as dip-dye, continuous dyeing or the method for printing and dyeing etc. can obtain daylight and the strong product dyed thereby of washing.
In order to regulate tone or to regulate fastness, dyeing property etc., can in waterborne compositions of the present invention, mix other dyestuffs and use.In addition, can add other dyestuffs when dyeing uses.Similarly, the pigment beyond also can mixing colouring agent etc. uses.In addition, can add dyeing medicament etc. in when dyeing uses.
Embodiment
By following embodiment the present invention is at length described.In an embodiment, part expression weight part, % represents % by weight, ppm (PPM) represents ppm by weight.
[embodiment 1]
In the sodium salt of 100 parts of compounds (1), add 4000 parts of water and heating, make it 90 ℃ ~ 95 ℃ lower dissolvings.After crystallization is dissolved fully, add 7.6 parts of sulfuric acid, make compound (1) carry out acid out.Filter out crystallization, water fully washs this crystallization, thereby inorganic salt are washed out.Obtain the crystallization of 105 parts of moisture compounds (1).Add 123 parts of Diethylene Glycols, 100 parts of urea, 50 parts of trolamines and suitable quantity of water in this crystallization, obtain the waterborne compositions of 480 parts of compounds (1).The concentration of the compound in this waterborne compositions (1) is 20%.
Utilize ion chromatography that this waterborne compositions is analyzed, the result, sodium ion is 450ppm, and calcium ion is 290ppm, and magnesium ion is 55ppm.
[embodiment 2]
Add 123 parts of Diethylene Glycols, 100 parts of urea, 50 parts of diethanolamine and suitable quantity of water in the water-containing crystal that obtains to 105 parts of operations by similarly to Example 1, obtain the waterborne compositions of 480 parts of compounds (1).The concentration of the compound in this waterborne compositions (1) is 20%.
[embodiment 3]
Add 123 parts of ethylene glycol, 100 parts of urea, 50 parts of diethanolamine and suitable quantity of water in the water-containing crystal that obtains to 105 parts of operations by similarly to Example 1, obtain the waterborne compositions of 480 parts of compounds (1).The concentration of the compound in this waterborne compositions (1) is 20%.
[embodiment 4]
Add 123 parts of poly(oxyethylene glycol) 400,100 parts of urea, 50 parts of diethanolamine and suitable quantity of water in the water-containing crystal that obtains to 105 parts of operations by similarly to Example 1, obtain the waterborne compositions of 480 parts of compounds (1).The concentration of the compound in this waterborne compositions (1) is 20%.
[embodiment 5 ~ 13]
According to the composition shown in following table 1 and the table 2, add each composition in the water-containing crystal that obtains to the operation by similarly to Example 1, adding entry, to make total amount be 100 parts, obtains waterborne compositions.Numerical value all represents % by weight.
[table 1]
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Compound (1) | 15 | 20 | 20 | 20 | 20 |
| MEA | 5 | ||||
| DEA | 10 | ||||
| TEA | 10 | ||||
| DIPA | 10 | ||||
| TIPA | 10 | ||||
| EG | 10 | ||||
| DEG | 10 | 15 | 10 | ||
| TEG | 15 | ||||
| PEG4 | |||||
| Urea | 10 | 15 | 10 | 15 |
[table 2]
| Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |
| Compound (1) | 20 | 20 | 30 | 5 |
| MEA | 5 | |||
| DEA | 15 | 25 | ||
| TEA | 10 | |||
| DIPA | ||||
| TIPA | ||||
| EG | 10 | |||
| DEG | 8 | |||
| TEG | ||||
| PEG4 | 40 | |||
| Urea | 5 | 25 | 5 |
MEA: monoethanolamine
DEA: diethanolamine
TEA: trolamine
DIPA: diisopropanolamine (DIPA)
TIPA: tri-isopropanolamine
EG: ethylene glycol
DEG: Diethylene Glycol
TEG: triethylene glycol
PEG4: poly(oxyethylene glycol) 400
[comparative example 1]
In the sodium salt of 100 parts of compounds (1), add 4000 parts of water and heating, make it 90 ℃ ~ 95 ℃ lower dissolvings.After crystallization is dissolved fully, add 7.6 parts of sulfuric acid, make compound (1) carry out acid out.Filter out the crystallization of separating out, obtain the crystallization of 108 parts of moisture compounds (1).Directly add 124 parts of Diethylene Glycols, 101 parts of urea, 50 parts of trolamines and suitable quantity of water in this crystallization, obtain the waterborne compositions of 485 parts of compounds (1).The concentration of the compound in this waterborne compositions (1) is 20%.
Utilize ion chromatography that this waterborne compositions is analyzed, the result, sodium ion is 2200ppm, and calcium ion is 290ppm, and magnesium ion is 65ppm.
[comparative example 2]
Add 123 parts of Diethylene Glycols, 100 parts of urea, 50 parts of trolamines and 110 parts of water in the sodium salt of 100 parts of compounds (1) and stir, but not fully dissolving.
[comparative example 3]
The aqueous sodium hydroxide solution that adds 1 part 17.4% in 100 parts of waterborne compositions that obtain by embodiment 1.
[comparative example 4]
The sodium chloride aqueous solution that adds 1 part 25.5% in 100 parts of waterborne compositions that obtain by embodiment 1.
[test example 1]
The waterborne compositions that obtains among the embodiment 1 ~ 13-5 ℃ and 40 ℃ of lower preservations 1 month, is not had crystallization etc. to separate out, thereby is stable.-5 ℃ of lower preservations, the result is all at 1 ~ 3 day crystallization with the waterborne compositions of comparative example 1, comparative example 3, comparative example 4 that obtained solution.
[test example 2]
0.0441g Calcium Chloride Powder Anhydrous and 0.0339g Magnesium Chloride Anhydrous are dissolved in the pure water of 1000ml, make simulation hard water.Use this simulation hard water with 32 times of each waterborne compositions dilutions of embodiment 1 ~ 13 and comparative example 1, comparative example 3, comparative example 4, estimate the stability under the room temperature.
The waterborne compositions that obtains among the embodiment 1 ~ 13 is crystallization not all, thereby is stable.The waterborne compositions of comparative example 1, comparative example 3, comparative example 4 is crystallization within just dilution is afterwards to several hours all, thereby unstable.
Claims (4)
1. one kind 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2, the waterborne compositions of 2 '-disulfonic acid, it passes through to 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2, add alkanol amine, water and obtain as the glycols of optional member and/or urea in 2 '-disulfonic acid.
2. as claimed in claim 14,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2, the waterborne compositions of 2 '-disulfonic acid, wherein, 4,4 '-two (2-anilinos-4-methoxyl group-1,3,5-triazinyl-6-is amino) stibene-2,2 '-disulfonic acid is by adding mineral acid in an alkali metal salt of this compound or alkaline-earth metal salt brine solution, time carry out acid out in pH1 ~ 3 and will separating out the crystallization that the suspension liquid of crystallization filters, washes this compound that obtains.
3. waterborne compositions as claimed in claim 1 or 2, wherein, in the waterborne compositions 4,4 '-two (2-anilino-4-methoxyl group-1,3,5-triazines base-6-is amino) stibene-2, the concentration of 2 '-disulfonic acid is 10 ~ 30%, be 5 ~ 30% as the thanomin of alkanol amine or the concentration of Propanolamine, the concentration of glycols is 0 ~ 40%, and the concentration of urea is 0 ~ 30%.
4. such as each described waterborne compositions in the claim 1 ~ 3, wherein, the alkalimetal ion in the waterborne compositions and/or the concentration of alkaline-earth metal ions are below the 1000ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011201287A JP2013060558A (en) | 2011-09-15 | 2011-09-15 | Concentrated aqueous composition of stilbene derivative |
| JP2011-201287 | 2011-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102993774A true CN102993774A (en) | 2013-03-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210345236 Pending CN102993774A (en) | 2011-09-15 | 2012-09-17 | Stable thick aqueous composition for stilbene derivative |
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|---|---|
| JP (1) | JP2013060558A (en) |
| CN (1) | CN102993774A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483868A (en) * | 2013-09-11 | 2014-01-01 | 山西青山化工有限公司 | Acid resistance type disulfonic acid liquid fluorescent whitening agent preparation method |
-
2011
- 2011-09-15 JP JP2011201287A patent/JP2013060558A/en not_active Withdrawn
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2012
- 2012-09-17 CN CN 201210345236 patent/CN102993774A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483868A (en) * | 2013-09-11 | 2014-01-01 | 山西青山化工有限公司 | Acid resistance type disulfonic acid liquid fluorescent whitening agent preparation method |
| CN103483868B (en) * | 2013-09-11 | 2015-05-27 | 山西青山化工有限公司 | Preparation method for acid resistance type disulfonic acid liquid fluorescent whitening agent |
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| Publication number | Publication date |
|---|---|
| JP2013060558A (en) | 2013-04-04 |
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Application publication date: 20130327 |