EP0765964A2 - Storage stable liquid formulations containing optical brighteners - Google Patents
Storage stable liquid formulations containing optical brighteners Download PDFInfo
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- EP0765964A2 EP0765964A2 EP96113235A EP96113235A EP0765964A2 EP 0765964 A2 EP0765964 A2 EP 0765964A2 EP 96113235 A EP96113235 A EP 96113235A EP 96113235 A EP96113235 A EP 96113235A EP 0765964 A2 EP0765964 A2 EP 0765964A2
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- Prior art keywords
- brightener
- acid
- formulations according
- stable liquid
- brighteners
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/607—Optical bleaching or brightening in organic solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/927—Polyacrylonitrile fiber
Definitions
- Brighteners for textiles are usually marketed as aqueous formulations.
- Brighteners for polyacrylonitrile use aqueous solutions which contain the cationic compound in the form of a salt, e.g. formates, acetates, lactates, sulfates, etc.
- These formulations are always acidic for stabilization and contain so-called adjusting agents as stabilizers to avoid precipitation during storage. Acidic settings of pH ⁇ 4 can lead to corrosion. In spite of adjusting agents, with these watery settings with a water content of 20 to 90%, clouding and browning and possibly odor formation can be observed after prolonged storage.
- the invention thus relates to liquid brightener formulations which essentially consist of a basic brightener, an aprotic polar organic solvent and an acid.
- Brighteners from the group of pyrazolines, benzimidazole-benzoxazolyls, (benzo) furanyl-benzimidazolyls, furan-bis-benzimidazolyls, naphthalimides or coumarins are particularly suitable for this.
- the brighteners can be used in the form of the amine base, but it is also possible to use these brighteners in the form of their acid addition salts or as real quaternary ammonium salts.
- Suitable pyrazoline brighteners are described, inter alia, in EP-A-0 234 176 and in EP-A-0 396 503 (formulas I to VI).
- possible cationic pyrazoline brighteners are also described in "Rev. Prog. Coloration” Vol 17, 39-55 (1987). There you will also find examples of cationic brighteners from the series of benzimidazolyl-benzoxazolyl compounds, (benzo) furanyl-benzimidazole compounds, coumarin compounds and naphthalimide compounds.
- Suitable solvents for the formulations according to the invention are organic aprotic polar solvents such as, for example, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1-methoxypropanol, acetone and other solvents of this type.
- Preferred solvents are those which are suitable for dissolving polyacrylonitrile, such as, for example, Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, dimethyl carbonate or mixtures thereof.
- Suitable acids are all those which are sufficiently soluble in the solvent, such as, for example, mono- or poly-basic alkanoic acids, hydroxyalkanoic acids, alkanesulfonic acids, arylsulfonic acids, hydrogen chloride, phosphoric acid, sulfuric acid, phosphorous acid. Acid anhydrides such as sulfur dioxide are also suitable. Preferred acids are formic, citric, acetic and lactic acid and mixtures thereof. Mixtures of acids are also possible, for example a mixture of formic acid and lactic acid.
- the brightener formulations normally do not contain any further additives, but the high solubility means that additional additives can be incorporated, which can be advantageous for later use.
- additional additives can be incorporated, which can be advantageous for later use.
- Representative here are e.g. Cationic or nonionic plasticizers, retarders or fungicides mentioned, or also reducing sulfur compounds, as described in EP-A-0 396 503.
- the amount of acid is chosen so that a pH of 0.1 to 9, preferably 4.5 to 8.5, in particular 5 to 7 is achieved.
- the preferred pH in each case also depends on the nature of the brightener. For example, it must be taken into account here that certain pyrazoline brighteners already decompose at pH values below 2. All mentioned pH values were determined with a Mettler Delta 320 pH electrometer.
- the proportion of the optical brightener in the formulations according to the invention can vary within wide limits up to the saturation limit of the respective brightener in the formulation. Concentrations of 5 to 60, preferably 5 to 30% by weight of optical brightener are preferred.
- the formulations according to the invention are prepared by simply mixing or stirring the individual components, the order of addition being uncritical. Usually you will stir the optical brightener into the solvent and adjust the desired pH with the acid. In order to accelerate the mixing process, the solvent can also be slightly warmed up to approx. 50 ° C, generally one works at room temperature.
- the formulations according to the invention are clear solutions which are distinguished by a high storage stability. In addition, much higher concentrations of optical brightener can be achieved in this way than with conventional aqueous formulations. They are used to lighten polyacrylonitrile fibers and are preferably used when spinning these fibers in the gel phase.
- the formulations according to the invention can be used undiluted or after dilution with water. Even in one Dilution with water in a ratio of 1:10 6 -10 7 gives clear aqueous solutions without precipitation.
- the brightener formulation can also be prepared without acid and this acid-free formulation can be placed in an aqueous bath which contains the necessary amount of acid.
- Example 3 The procedure is as in Example 3. However, N, N-dimethylacetamide is used as the solvent. To adjust the pH to 6, 29 g of lactic acid are added. A clear, bright, storage-stable setting is obtained which, even after 14 days at 40 ° C., shows no clouding and does not darken.
- a brightener salt of the formula 5 g are mixed with 20 ml of DMF. A slurry with a pH of 2.19 is obtained. After adding 6.5 g of HCOOH, a dark, clear, stable solution with a pH of 1.52 is obtained. If water is used instead of DMF, a thickened slurry with pH 1.35 is obtained first. A solution of pH 1.12 is obtained by adding 6.5 g of HCOOH.
- Example 7 The procedure is as in Example 7. The solution obtained is 5 min. stirred with 1 g Na 2 S 2 O 4 . The solid substance is then filtered off. A greenish, stable brightener setting is obtained.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Medicinal Preparation (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
Description
Optische Aufheller für Textilien werden meist als wäßrige Einstellungen in den Handel gebracht. Bei Aufhellern für Polyacrylnitril verwendet man wäßrige Lösungen, welche die kationische Verbindung in Form eines Salzes, wie z.B. eines Formiates, Acetates, Lactates, Sulfates u.a., enthalten. Diese Formulierungen sind zur Stabilisierung immer sauer eingestellt und enthalten, um Ausfällungen bei der Lagerung zu vermeiden, noch sog. Stellmittel als Stabilisatoren. Saure Einstellungen von pH < 4 können zu Korrosionen führen. Trotz Stellmittel beobachtet man bei diesen wäßrigen Einstellungen mit einem Wassergehalt von 20 bis 90 % bei längerem Lagern Austrübungen und Verbräunungen und möglicherweise Geruchsbildung. Derartige Zusatzstoffe sind jedoch immer problematisch, da es bei Recycling von Aufhellerflotten oder Aufhellerbädern im "never-dried-Prozeß" zu einer Anreicherung dieser Stoffe kommen kann, was höhere Anforderungen an eine Entsorgung stellt. Wäßrige Einstellungen haben auch den Nachteil, daß sie in Konzentrationen über 30 % Aktivsubstanz viskos und damit schlechter handhabbar werden.Optical brighteners for textiles are usually marketed as aqueous formulations. Brighteners for polyacrylonitrile use aqueous solutions which contain the cationic compound in the form of a salt, e.g. formates, acetates, lactates, sulfates, etc. These formulations are always acidic for stabilization and contain so-called adjusting agents as stabilizers to avoid precipitation during storage. Acidic settings of pH <4 can lead to corrosion. In spite of adjusting agents, with these watery settings with a water content of 20 to 90%, clouding and browning and possibly odor formation can be observed after prolonged storage. Such additives are always problematic, however, since recycling of brightener liquors or brightener baths in the "never-dried process" can lead to an accumulation of these substances, which places higher demands on disposal. Aqueous settings also have the disadvantage that they become viscous in concentrations above 30% active substance and are therefore difficult to handle.
Es wurde nun gefunden, daß man unter Verzicht auf solche Stellmittel aus basischen optischen Aufhellern, die für die Aufhellung von Polyacrylnitrilfasern verwendet werden, stabile flüssige Formulierungen herstellen kann, die in wäßriger Verdünnung nicht ausfallen, wenn man diese Aufheller in einem aprotischen polaren organischen Lösemittel in Gegenwart einer Säure löst.It has now been found that by dispensing with such adjusting agents from basic optical brighteners which are used for the brightening of polyacrylonitrile fibers, stable liquid formulations can be prepared which do not precipitate out in aqueous dilution if these brighteners are used in an aprotic polar organic solvent Presence of an acid dissolves.
Gegenstand der Erfindung sind somit flüssige Aufhellerformulierungen, die im wesentlichen aus einem basischen Aufheller, einem aprotischen polaren organischen Lösemittel und einer Säure bestehen.The invention thus relates to liquid brightener formulations which essentially consist of a basic brightener, an aprotic polar organic solvent and an acid.
Als basische Aufheller kommen hier alle bekannten Vertreter dieser Klasse in Frage, wie sie insbesondere zum Aufhellen von Polyacrylnitril genommen werden. Besonders geeignet hierfür sind Aufheller aus der Gruppe der Pyrazoline, Benzimidazol-benzoxazolyle, (Benzo)furanyl-benzimidazolyle, Furan-bis-benzimidazolyle, Naphthalimide oder Cumarine. Erfindungsgemäß können die Aufheller in Form der Aminbase eingesetzt werden, ebenso ist es aber auch möglich, diese Aufheller in der Form ihrer Säureadditionssalze oder als echte quartäre Ammoniumsalze zu verwenden.All known representatives of this class come into question as basic brighteners, as are used in particular for brightening polyacrylonitrile. Brighteners from the group of pyrazolines, benzimidazole-benzoxazolyls, (benzo) furanyl-benzimidazolyls, furan-bis-benzimidazolyls, naphthalimides or coumarins are particularly suitable for this. According to the invention, the brighteners can be used in the form of the amine base, but it is also possible to use these brighteners in the form of their acid addition salts or as real quaternary ammonium salts.
Geeignete Pyrazolin-Aufheller sind unter anderem beschrieben in EP-A-0 234 176 und in EP-A-0 396 503 (Formeln I bis VI). Darüberhinaus sind in Frage kommende kationische Pyrazolin-Aufheller auch beschrieben in "Rev. Prog. Coloration" Vol 17, 39-55 (1987). Dort finden sich auch Beispiele für kationische Aufheller aus der Reihe der Benzimidazolyl-benzoxazolyl-Verbindungen, (Benzo)furanyl-benzimidazol-Verbindungen, Cumarin-Verbindungen und Naphthalimid-Verbindungen.Suitable pyrazoline brighteners are described, inter alia, in EP-A-0 234 176 and in EP-A-0 396 503 (formulas I to VI). In addition, possible cationic pyrazoline brighteners are also described in "Rev. Prog. Coloration" Vol 17, 39-55 (1987). There you will also find examples of cationic brighteners from the series of benzimidazolyl-benzoxazolyl compounds, (benzo) furanyl-benzimidazole compounds, coumarin compounds and naphthalimide compounds.
Als Lösemittel für die erfindungsgemäßen Formulierungen kommen organische aprotische polare Lösemittel in Frage wie zum Beispiel Dimethylformamid, Dimethylsulfoxyd, N-Methylpyrrolidon, 1-Methoxypropanol, Aceton und andere Lösemittel dieser Art. Bevorzugt sind diejenigen Lösemittel, die sich zum Lösen von Polyacrylnitril eignen, wie z.B. Dimethylformamid, Dimethylacetamid, Dimethylsulfoxid, N-Methylpyrrolidon, Dimethylcarbonat oder deren Mischungen.Suitable solvents for the formulations according to the invention are organic aprotic polar solvents such as, for example, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1-methoxypropanol, acetone and other solvents of this type. Preferred solvents are those which are suitable for dissolving polyacrylonitrile, such as, for example, Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, dimethyl carbonate or mixtures thereof.
Als Säuren eignen sich alle diejenigen, die in dem Lösemittel ausreichend löslich sind, wie z.B. ein- oder mehr-basische Alkansäuren, Hydroxyalkansäuren, Alkansulfosäuren, Arylsulfosäuren, Chlorwasserstoff, Phosphorsäure, Schwefelsäure, Phosphorige Säure. Geeignet sind auch Säureanhydride, wie z.B. Schwefeldioxid. Bevorzugte Säuren sind Ameisen-, Citronen-, Essig- und Milchsäure und Mischungen davon. Auch Mischungen von Säuren sind möglich, beispielsweise eine Mischung aus Ameisensäure und Milchsäure.Suitable acids are all those which are sufficiently soluble in the solvent, such as, for example, mono- or poly-basic alkanoic acids, hydroxyalkanoic acids, alkanesulfonic acids, arylsulfonic acids, hydrogen chloride, phosphoric acid, sulfuric acid, phosphorous acid. Acid anhydrides such as sulfur dioxide are also suitable. Preferred acids are formic, citric, acetic and lactic acid and mixtures thereof. Mixtures of acids are also possible, for example a mixture of formic acid and lactic acid.
Die Aufhellerformulierungen enthalten normalerweise keine weiteren Zusatzstoffe, jedoch können durch das hohe Lösevermögen noch zusätzliche Additive eingearbeitet werden, welche für die spätere Verwendung von Vorteil sein können. Stellvertretend seien hier z.B. kationische oder nichtionische Weichmacher, Retarder oder Fungizide erwähnt, oder auch reduzierend wirkende Schwefelverbindungen, wie sie in EP-A-0 396 503 beschrieben sind.The brightener formulations normally do not contain any further additives, but the high solubility means that additional additives can be incorporated, which can be advantageous for later use. Representative here are e.g. Cationic or nonionic plasticizers, retarders or fungicides mentioned, or also reducing sulfur compounds, as described in EP-A-0 396 503.
Die Menge an Säure wird so gewählt, daß ein pH-Wert von 0,1 bis 9, vorzugsweise von 4,5 bis 8,5, insbesondere von 5 bis 7 erreicht wird. Der jeweils bevorzugte pH-Wert ist auch abhängig von der Natur des Aufhellers. Beispielsweise ist hier zu berücksichtigen, daR sich bestimmte Pyrazolin-Aufheller bei pH-Werten unter 2 bereits zersetzen. Alle genannten pH-Werte wurden mit einem Mettler Delta 320 pH-Elektrometer bestimmt. Der Anteil des optischen Aufhellers in den erfindungsgemäßen Formulierungen kann in breiten Grenzen schwanken bis hin zum Sättigungsgrenzwert des jeweiligen Aufhellers in der Formulierung. Bevorzugt sind Konzentrationen von 5 bis 60, vorzugsweise 5 bis 30 Gew.-% an optischem Aufheller.The amount of acid is chosen so that a pH of 0.1 to 9, preferably 4.5 to 8.5, in particular 5 to 7 is achieved. The preferred pH in each case also depends on the nature of the brightener. For example, it must be taken into account here that certain pyrazoline brighteners already decompose at pH values below 2. All mentioned pH values were determined with a Mettler Delta 320 pH electrometer. The proportion of the optical brightener in the formulations according to the invention can vary within wide limits up to the saturation limit of the respective brightener in the formulation. Concentrations of 5 to 60, preferably 5 to 30% by weight of optical brightener are preferred.
Die Herstellung der erfindungsgemäßen Formulierungen erfolgt durch einfaches Mischen oder Verrühren der einzelnen Komponenten, wobei die Reihenfolge der Zugabe unkritisch ist. Üblicherweise wird man den optischen Aufheller in das Lösemittel einrühren und mit der Säure den gewünschten pH-Wert einstellen. Um den Mischvorgang zu beschleunigen, kann man das Lösemittel auch leicht erwärmen bis ca. 50°C, im allgemeinen arbeitet man bei Raumtemperatur.The formulations according to the invention are prepared by simply mixing or stirring the individual components, the order of addition being uncritical. Usually you will stir the optical brightener into the solvent and adjust the desired pH with the acid. In order to accelerate the mixing process, the solvent can also be slightly warmed up to approx. 50 ° C, generally one works at room temperature.
Die erfindungsgemäßen Formulierungen sind klare Lösungen, die sich durch eine hohe Lagerstabilität auszeichnen. Außerdem lassen sich auf diesem Weg sehr viel höhere Konzentrationen an optischem Aufheller erzielen als bei den herkömmlichen wäßrigen Formulierungen. Sie dienen zum Aufhellen von Polyacrylnitrilfasern und werden vorzugsweise beim Verspinnen dieser Fasern in der Gelphase eingesetzt. Man kann die erfindungsgemäßen Formulierungen unverdünnt oder nach Verdünnung mit Wasser verwenden. Selbst in einer Verdünnung mit Wasser im Verhältnis von 1:106-107 erhält man klare wäßrige Lösungen ohne Niederschläge. Alternativ zu der zuvor beschriebenen Verfahrensweise kann man auch so vorgehen, daß man die Aufhellerformulierung ohne Säure herstellt und diese säurefreie Formulierung in ein wäßriges Bad gibt, das die notwendige Menge an Säure enthält.The formulations according to the invention are clear solutions which are distinguished by a high storage stability. In addition, much higher concentrations of optical brightener can be achieved in this way than with conventional aqueous formulations. They are used to lighten polyacrylonitrile fibers and are preferably used when spinning these fibers in the gel phase. The formulations according to the invention can be used undiluted or after dilution with water. Even in one Dilution with water in a ratio of 1:10 6 -10 7 gives clear aqueous solutions without precipitation. As an alternative to the procedure described above, the brightener formulation can also be prepared without acid and this acid-free formulation can be placed in an aqueous bath which contains the necessary amount of acid.
30 g einer Aminbase mit der Formel
15 g der Aufhellerbase aus Beispiel 1 werden in einer Mischung aus 6 g HCOOH und 50 ml Wasser gelöst. Die Lösung wird mit Wasser auf 100 ml verdünnt und filtriert. Bereits nach 24-stündigem Stehen bei 40°C bildet sich ein leichter Bodensatz.15 g of the brightener base from Example 1 are dissolved in a mixture of 6 g of HCOOH and 50 ml of water. The solution is diluted to 100 ml with water and filtered. After standing at 40 ° C for 24 hours, a light sediment forms.
30 g der Aminbase aus Beispiel 1 werden mit 105 g N-Methylpyrrolidon verrührt und mit 22 g Milchsäure auf pH 6,0 eingestellt. Es wird eine lagerstabile, klare, helle Einstellung erhalten welche auch nach 14 Tagen bei 40°C keine Eintrübung zeigt und nicht nachgedunkelt ist.30 g of the amine base from Example 1 are stirred with 105 g of N-methylpyrrolidone and adjusted to pH 6.0 with 22 g of lactic acid. A storage-stable, clear, bright setting is obtained which, even after 14 days at 40 ° C., shows no cloudiness and is not darkened.
Es wird wie bei Beispiel 3 gearbeitet. Als Lösungsmittel wird jedoch N,N-Dimethylacetamid verwendet. Zur Einstellung des pH-Wertes von 6 werden 29 g Milchsäure zugesetzt. Man erhält eine klare, helle, lagerstabile Einstellung, welche auch nach 14 Tagen bei 40°C keine Eintrübung zeigt und nicht nachdunkelt.The procedure is as in Example 3. However, N, N-dimethylacetamide is used as the solvent. To adjust the pH to 6, 29 g of lactic acid are added. A clear, bright, storage-stable setting is obtained which, even after 14 days at 40 ° C., shows no clouding and does not darken.
Es wird wie unter Beispiel 1 beschrieben gearbeitet, jedoch wird eine Aufhellerbase der Formel
7,5 g der Aminbase aus Beispiel 1 werden in 52 g DMF eingerührt. Man erhält eine trübe Lösung, welche durch Zugabe von Eisessig bereits bei pH 8,3 klar wird. Bei einer Gesamtzugabe von 6,28 g Eisessig stellt sich ein pH von 6,42 ein. Es wird eine helle, klare, lagerstabile Lösung erhalten, welche auch nach 14 tägigem Stehen bei 40°C keine Eintrübung oder Verbräunung zeigt.7.5 g of the amine base from Example 1 are stirred into 52 g of DMF. A cloudy solution is obtained, which becomes clear at pH 8.3 by adding glacial acetic acid. With a total addition of 6.28 g of glacial acetic acid, the pH is 6.42 on. A bright, clear, storage-stable solution is obtained which, even after standing for 14 days at 40 ° C., shows no clouding or browning.
75 g der Aminbase aus Beispiel 1 wurden in 75 ml DMF eingerührt und mit 50 g HCOOH auf pH 3,2 eingestellt. Man erhält eine klare, lagerstabile Einstellung, welche deutlich geringer viskos ist als eine analoge Formulierung auf Wasserbasis mit einem Gehalt an Aminbase von 35 %.75 g of the amine base from Example 1 were stirred into 75 ml of DMF and adjusted to pH 3.2 with 50 g of HCOOH. A clear, storage-stable setting is obtained, which is significantly less viscous than an analogous water-based formulation with an amine base content of 35%.
5 g eines Aufhellersalzes der Formel
100 g Milchsäure werden mit 13,5 g der Aufhellerbase aus Beispiel 1 versetzt. Nach 1-wöchigem Stehen bei Raumtemperatur sind davon 11 g in Lösung gegangen. Durch Zugabe von 5 g DMF lassen sich die restlichen 2,5 g der ungelösten Aminbase sehr leicht auflösen.100 g of lactic acid are mixed with 13.5 g of the brightener base from Example 1. After standing for 1 week at room temperature, 11 g of which are in solution went. The remaining 2.5 g of the undissolved amine base can be very easily dissolved by adding 5 g of DMF.
Es wird wie unter Beispiel 7 gearbeitet. Die erhaltene Lösung wird 5 min. mit 1 g Na2S2O4 verrührt. Anschließend wird von der Festsubstanz abfiltriert. Man erhält eine grünliche, stabile Aufhellereinstellung.The procedure is as in Example 7. The solution obtained is 5 min. stirred with 1 g Na 2 S 2 O 4 . The solid substance is then filtered off. A greenish, stable brightener setting is obtained.
In 135 g N-Methylpyrrolidon werden 15 g Citronensäure, 2 g Ameisensäure und 15 g der Aufhellerbase aus Beispiel 1, eingerührt. Man erhält eine helle, stabile Einstellung.15 g of citric acid, 2 g of formic acid and 15 g of the brightener base from Example 1 are stirred into 135 g of N-methylpyrrolidone. You get a bright, stable setting.
Polyacrylnitrilfaser-Gewebe wird mit der Einstellung nach Beispiel 6 im Ausziehverfahren aufgehellt und gegen eine mit gleichem Gehalt an Wirksubstanz versehene wäßrige Einstellung (pH 2,7; HCOOH) verglichen.
- Rezeptur:
- 1 g/l eines nichtionischen Netzmittels,
HCOOH pH 3,
0,4 % Einstellung nach Beispiel 6 bzw. analoge wäßrige Formulierung,
Flottenverhältnis 1 : 30
30 min. bei 95°C - Ergebnis:
- Man erhält mit der erfindungsgemäßen Einstellung gleich gute Weißeffekte wie mit der analogen herkömmlichen wäßrigen Einstellung.
- Recipe:
- 1 g / l of a nonionic wetting agent,
HCOOH pH 3,
0.4% setting according to Example 6 or analogous aqueous formulation,
Fleet ratio 1: 30
30 min. at 95 ° C - Result:
- With the setting according to the invention, the same good white effects are obtained as with the analogous conventional aqueous setting.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19531265A DE19531265A1 (en) | 1995-08-25 | 1995-08-25 | Storage-stable liquid brightener formulations |
| DE19531265 | 1995-08-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0765964A2 true EP0765964A2 (en) | 1997-04-02 |
| EP0765964A3 EP0765964A3 (en) | 1998-03-25 |
Family
ID=7770346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96113235A Withdrawn EP0765964A3 (en) | 1995-08-25 | 1996-08-19 | Storage stable liquid formulations containing optical brighteners |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5904739A (en) |
| EP (1) | EP0765964A3 (en) |
| JP (1) | JPH09118835A (en) |
| KR (1) | KR970011155A (en) |
| CN (1) | CN1149091A (en) |
| CA (1) | CA2184032A1 (en) |
| DE (1) | DE19531265A1 (en) |
| MX (1) | MX9603631A (en) |
| TR (1) | TR199600680A2 (en) |
| TW (1) | TW345602B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087754C (en) * | 1999-12-03 | 2002-07-17 | 杭州华洋化工有限公司 | Powdered fluorescent composition as whitening agent |
| CN1119440C (en) * | 2000-12-27 | 2003-08-27 | 天津南开戈德集团有限公司 | Ultraviolet fluorescent fiber making method |
| DE10208773A1 (en) * | 2002-02-28 | 2003-09-04 | Clariant Gmbh | Aqueous liquid formulations of pyrazoline brighteners |
| EP1752453A1 (en) * | 2005-08-04 | 2007-02-14 | Clariant International Ltd. | Storage stable solutions of optical brighteners |
| CN101932567B (en) * | 2007-12-12 | 2013-01-23 | 科莱恩金融(Bvi)有限公司 | Storage stable solutions of fluorescent whitening agent |
| CN107245873A (en) * | 2016-07-04 | 2017-10-13 | 如皋长江科技产业有限公司 | A kind of chemical fibre auxiliary agent of whitening type |
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| DE1594858A1 (en) * | 1965-09-03 | 1972-03-09 | Ciba Geigy Ag | Process for the continuous optical brightening of fiber material made from incompletely acylated cellulose |
| US4001138A (en) * | 1973-12-19 | 1977-01-04 | Ciba-Geigy Corporation | Stable solutions of fluorescent brighteners |
| US4031273A (en) * | 1974-09-03 | 1977-06-21 | Ciba-Geigy Corporation | Continuous process for optical brightening |
| EP0044061A1 (en) * | 1980-07-16 | 1982-01-20 | Hoechst Aktiengesellschaft | Process for the dyeing in a gel state of fibrous articles spun from acrylonitrile polymer solutions in organic solvents |
| US4559150A (en) * | 1982-08-11 | 1985-12-17 | Ciba Geigy Corporation | Stable composition for treating textile substrates |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5725365A (en) * | 1980-07-22 | 1982-02-10 | Showa Kagaku Kogyo Kk | Dyestuff salt-containing fluorescent brightener composition |
| US4508900A (en) * | 1980-11-03 | 1985-04-02 | Hoechst Aktiengesellschaft | Cationic compounds of the naphthalimide series, process for their preparation and their use |
| US4816590A (en) * | 1985-12-04 | 1989-03-28 | Ciba-Geigy Corporation | Pyrazoline compounds and method of whitening |
| ES2078331T3 (en) * | 1989-05-02 | 1995-12-16 | Ciba Geigy Ag | AQUEOUS BLEACHING FORMULATIONS, STABLE ON STORAGE. |
-
1995
- 1995-08-25 DE DE19531265A patent/DE19531265A1/en not_active Withdrawn
-
1996
- 1996-08-19 EP EP96113235A patent/EP0765964A3/en not_active Withdrawn
- 1996-08-22 JP JP8221442A patent/JPH09118835A/en not_active Withdrawn
- 1996-08-23 KR KR1019960034951A patent/KR970011155A/en not_active Application Discontinuation
- 1996-08-23 CA CA002184032A patent/CA2184032A1/en not_active Abandoned
- 1996-08-23 MX MX9603631A patent/MX9603631A/en not_active Application Discontinuation
- 1996-08-23 CN CN96111498A patent/CN1149091A/en active Pending
- 1996-08-23 TR TR96/00680A patent/TR199600680A2/en unknown
- 1996-08-26 US US08/702,884 patent/US5904739A/en not_active Expired - Fee Related
- 1996-08-26 TW TW085110357A patent/TW345602B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1594858A1 (en) * | 1965-09-03 | 1972-03-09 | Ciba Geigy Ag | Process for the continuous optical brightening of fiber material made from incompletely acylated cellulose |
| US4001138A (en) * | 1973-12-19 | 1977-01-04 | Ciba-Geigy Corporation | Stable solutions of fluorescent brighteners |
| US4031273A (en) * | 1974-09-03 | 1977-06-21 | Ciba-Geigy Corporation | Continuous process for optical brightening |
| EP0044061A1 (en) * | 1980-07-16 | 1982-01-20 | Hoechst Aktiengesellschaft | Process for the dyeing in a gel state of fibrous articles spun from acrylonitrile polymer solutions in organic solvents |
| US4559150A (en) * | 1982-08-11 | 1985-12-17 | Ciba Geigy Corporation | Stable composition for treating textile substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| TR199600680A2 (en) | 1997-03-21 |
| DE19531265A1 (en) | 1997-02-27 |
| MX9603631A (en) | 1997-05-31 |
| JPH09118835A (en) | 1997-05-06 |
| CA2184032A1 (en) | 1997-02-26 |
| US5904739A (en) | 1999-05-18 |
| EP0765964A3 (en) | 1998-03-25 |
| TW345602B (en) | 1998-11-21 |
| CN1149091A (en) | 1997-05-07 |
| KR970011155A (en) | 1997-03-27 |
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