EP0542677A1 - Storage-stable formulation of mixtures of optical brighteners - Google Patents

Storage-stable formulation of mixtures of optical brighteners Download PDF

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Publication number
EP0542677A1
EP0542677A1 EP92810830A EP92810830A EP0542677A1 EP 0542677 A1 EP0542677 A1 EP 0542677A1 EP 92810830 A EP92810830 A EP 92810830A EP 92810830 A EP92810830 A EP 92810830A EP 0542677 A1 EP0542677 A1 EP 0542677A1
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Prior art keywords
storage
weight
brightener
brightener formulation
stable
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German (de)
French (fr)
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EP0542677B1 (en
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Werner Dr. Fringeli
Josef Zelger
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BASF Schweiz AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/621—Optical bleaching or brightening in aqueous solvents with anionic brighteners
    • 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
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

Definitions

  • the present invention relates to storage-stable optical brightener formulations, a process for their preparation and their use.
  • Optical brighteners are usually marketed preferably in the form of aqueous solutions or suspensions.
  • aqueous solutions or suspensions e.g. the moist filter cake or the dry powder is slurried with water.
  • the suspensions thus obtained are then mixed with dispersing and thickening agents to increase homogeneity, wettability and stability.
  • An electrolyte is often added as a further auxiliary.
  • the auxiliaries used hitherto could not prevent sedimentation of the brighteners and / or a high increase in viscosity, especially at high storage temperatures, over a longer period of time.
  • Such formulations preferably contain anionic optical brighteners which contain at least one sulfonic acid residue.
  • optical brighteners are:
  • X and Y which may be the same or different and represent a secondary or tertiary amine or unsubstituted, mono- or di-substituted alkoxy
  • M represents a hydrogen atom or a salt-forming cation.
  • the secondary and tertiary amine are, for example, unsubstituted or mono- or polysubstituted phenylamine, morpholine, piperidine, methylamine, ethylamine, propylamine, butylamine, ⁇ -hydroxyethylamine, or substituted with C1-C4alkyl, C1-C4alkoxy, sulfo, halogen, cyano, or carboxy.
  • ⁇ -hydroxypropylamine ⁇ -cyano-ethylamine, dimethylamine, diethylamine, dipropylamine, bis- ⁇ -hydroxyethylamine, N-methyl-N-ethylamine, N-methyl-N- ⁇ -hydroxyethylamine, N-ethyl-N- ⁇ -hydroxyethylamine, N-methyl-N- ⁇ -hydroxypropylamine, N-ethyl-N- ⁇ -hydroxypropylamine, benzylamine, N- ⁇ -hydroxyethyl-benzylamine, cyclohexylamine, N-ethyl-cyclohexylamine, 2-methoxyethylamine, 2-ethoxyethylamine, N-methyl-2-methoxyethylamine and 3-methoxypropylamine in question.
  • unsubstituted, mono- or disubstituted alkoxy examples include methoxy, ethoxy, n-propoxy, i-propoxy, butoxy, ⁇ -hydroxy-ethoxy, ⁇ -methoxy-ethoxy, and ⁇ -ethoxy-ethoxy.
  • optical brighteners of the formula (1) in which X and Y, which may be identical or different, are a phenylamino group which is optionally mono- or di-substituted by alkyl radicals having 1 or 2 carbon atoms; the morpholino group; an alkylamino group having 1 to 4 carbon atoms, which may be substituted by hydroxyl radicals; or represent an alkoxy group having 1 to 4 carbon atoms; and M represents hydrogen or a salt-forming cation.
  • Optical brighteners of the formula (1) are furthermore preferred, in which X and Y, which may be identical or different, are phenylamino, morpholino, an alkylamino group having 1 to 4 carbon atoms, which may be substituted by hydroxyl radicals, and M is hydrogen or a salt-forming cation.
  • X and Y which may be identical or different, are phenylamino, morpholino, an alkylamino group having 1 to 4 carbon atoms, which may be substituted by hydroxyl radicals, and M is hydrogen or a salt-forming cation.
  • the morpholino and the N-methyl-N-ethanolamino groups are particularly preferred.
  • optical brighteners of the formulas (2) are examples wherein M represents an alkali metal ion, in the case of this optical brightener a content of 2 to 25% by weight, based on the total weight of the slurry, of a strong electrolyte is expediently present; and (3) where M denotes an alkali metal ion.
  • A is a sulfonic acid residue, hydrogen, C1-C4-alkyl, C1-C4-alkoxy or halogen and B is hydrogen, C1-C4-alkyl, C1-C4-alkoxy or halogen, with the condition that at least one substituent A is a sulfonic acid residue is and m, n, o, p independently of one another represent a number 1 or 2.
  • Particularly preferred compounds are compounds of the formulas and where A, B and n have the above meaning and M is a salt-forming cation.
  • halogens are fluorine, chlorine and bromine, but especially chlorine.
  • C1-C4 alkyl radicals are unbranched and branched alkyl radicals such as the methyl, ethyl, n- and iso-propyl, n-, sec- and tert-butyl radical. These C1-C4 alkyl radicals can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C1-C4 alkoxy, OH, halogen, sulfo or CN groups.
  • Salt-forming cations M are e.g. Alkali metal, ammonium or amine salt ions.
  • Amine salt ions are preferred those of the formula H+NR1R2R3 in which R1, R2 and R3 independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, halogenoalkyl or phenylalkyl or in which R1 and R2 together are the addition to a 5-7-membered saturated Represent nitrogen heterocycle, which may additionally contain a nitrogen or oxygen atom as a ring member, for example a piperidine, piperazine, pyrrolidine, imidazoline or morpholine ring, while R3 is hydrogen.
  • Preferred salt-forming cations are akali metal salts, Na+ and K+ being particularly preferred.
  • Preferred distyrylbiphenyl compounds of the formula (4) are those in which the cation M is an alkali metal, ammonium or amine ion, potassium and sodium being of particular importance for practical reasons.
  • Preferred mixtures each consist of 5 to 30% by weight, based on the total weight, but not more than 45% by weight, of two, three or four brighteners of the formulas (2), (3), (7) and (8) ,
  • the ratio of the optical brighteners to one another is between 1: 9 and 9: 1, preferably between 1: 4 and 4: 1.
  • electrolyte e.g. one or more alkali metal salts and salts of lower carboxylic acids
  • electrolytes are sodium chloride, sodium sulfate, sodium phosphate, sodium carbonate, sodium formate or one of the corresponding potassium salts and mixtures of these electrolytes.
  • Sodium chloride and the formates are preferred.
  • the amount of electrolyte can be 0.1 to 25% by weight, preferably 0.5 to 20% by weight and particularly preferably 0.5-15% by weight, based on the total weight of the formulation.
  • anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose, starch or from the heteropolysaccharides, with further monosaccharides such as e.g. Mannose and glucuronic acid can be included.
  • examples of anionic polysaccharides are sodium alginate, carboxymethylated guar, carboxymethyl cellulose, carboxymethyl starch, carboxymethylated locust bean gum and, particularly preferably, xanthan gum.
  • the amount of polysaccharide is 0.01 to 1% by weight, a range from 0.05 to 0.5% by weight being preferred and a range from 0.05-0.2% by weight being particularly preferred, in each case based on the total weight of the formulation. However, these ranges can be exceeded in the case of very highly concentrated or very low concentrated formulations.
  • the brightener formulation according to the invention can optionally contain additives; Preservatives such as chloroacetamide or aqueous formaldehyde solution, Mg / Al silicates, odor improvers and antifreezes may be mentioned as examples.
  • Mg / Al silicates examples are bentonite, montmorillonite, zeolites and highly disperse silicas. They are usually added in an amount of 0.2-1% by weight, based on the total weight of the brightener formulation.
  • Dispersants which can be used are those of the anionic or nonionic type. Examples include alkyl benzene, alkyl or Alkenylethersulfonatsalze, saturated or unsaturated fatty acids, alkyl or Alkylenethercarboxylsalze, sulfofatty or esters, Phosphatester, polyoxyethylene alkyl or alkenyl, polyoxyethylene alkyl vinyl ether, polyoxypropylene alkyl or alkenyl, Polyoxybutylenalkyl- or alkenyl ether, higher fatty acid or Alkylene oxide adducts, sucrose / fatty acid esters, fatty acid / glycol monoesters, alkylamine oxides and condensation products of aromatic sulfonic acids with formaldehyde as well as lignin sulfonates or mixtures of the above-mentioned dispersants.
  • condensation products of aromatic sulfonic acids with formaldehyde and lignin sulfonates are preferred.
  • Condensation products of naphthalene sulfonic acids with formaldehyde and ditolyl ether sulfonic acids with formaldehyde are particularly preferred.
  • the content of dispersant is 0.2 to 20% by weight, based on the total weight of the formulation, preferably 0.1 to 10% by weight and particularly preferably 0.2 to 5% by weight.
  • Formulations according to the invention are obtained by adding the moist presscakes or the dry powders of at least two anionic optical brighteners, which contain at least one sulfonic acid residue, in an amount of 15 to 45% by weight, preferably 15 to 40% by weight and particularly preferably 19 -40% by weight, based on the total weight of the formulation; with 0.01 to 1% by weight of anionic polysaccharide; 0.1 to 25% by weight electrolyte; 0.2 to 20 wt% dispersant; if necessary with further additives; and mixed with water and homogenized at room temperature.
  • the desired content of anionic optical brighteners in the suspension can be adjusted either by adding water, aqueous electrolyte, or further dry powder to the moist filter cake. This setting can be made before, during or after the addition of the anionic polysaccharide.
  • the new optical brightener formulations are used primarily in the incorporation into detergents, e.g. B. by inflowing the required amount of the optical brightener formulation according to the invention, from a container into a mixing device which contains a suspension of the detergent or the dispersant.
  • the present invention accordingly also relates to a process for the production of solid and liquid detergents, and to the detergents obtained thereafter, characterized in that e.g. a suspension for detergents of conventional detergents, mixed with an inventive suspension of brighteners, and dried.
  • the drying process can e.g. done by a spray drying process.
  • the brightener formulation according to the invention can be used for the production of liquid detergents.
  • Percentages refer to the total weight of the formulation.
  • the brightener formulations obtained remain liquid and, after standing for two months at -5 ° C., room temperature and 40 ° C., do not form any deposits.
  • the components listed in Table 2 are stirred with 1% by weight, based on the total weight of the brightener formulation, of the condensation product of ditolyl ether sulfonic acids with formaldehyde; 0.15% by weight of xanthan and water mixed and homogenized.
  • the brightener formulations remain liquid and do not form any deposits after standing for several weeks at room temperature and 40 ° C.
  • the brightener formulations remain liquid and do not form any deposits after standing for several weeks at room temperature and 40 ° C.

Abstract

Storage-stable formulations of mixtures of optical brighteners containing at least two anionic optical brighteners, which preferably contain at least one sulphonic acid radical; an anionic polysaccharide; dispersants and water and optionally also auxiliaries. These formulations are particularly suitable for the production of liquid detergents.

Description

Die vorliegende Erfindung betrifft lagerstabile optische Aufhellerformulierungen, ein Verfahren zu deren Herstellung, sowie deren Verwendung.The present invention relates to storage-stable optical brightener formulations, a process for their preparation and their use.

Üblicherweise werden optische Aufheller bevorzugt in Form wässriger Lösungen oder Suspensionen in den Handel gebracht. Hierzu werden z.B. die feuchten Filterkuchen oder auch die trockenen Pulver mit Wasser aufgeschlämmt. Die so erhaltenen Suspensionen werden dann mit Dispergier- und Verdickungsmitteln zur Erhöhung von Homogenität, Benetzbarkeit und Stabilität versetzt. Als weiteren Hilfsstoffen setzt man häufig noch einen Elektrolyten zu. Die bisher verwendeten Hilfsstoffe konnten jedoch ein Sedimentieren der Aufheller und/oder eine hohe Viskositätszunahme, insbesondere bei hohen Lagertemperaturen, nicht über einen längeren Zeitraum verhindern.Optical brighteners are usually marketed preferably in the form of aqueous solutions or suspensions. For this, e.g. the moist filter cake or the dry powder is slurried with water. The suspensions thus obtained are then mixed with dispersing and thickening agents to increase homogeneity, wettability and stability. An electrolyte is often added as a further auxiliary. However, the auxiliaries used hitherto could not prevent sedimentation of the brighteners and / or a high increase in viscosity, especially at high storage temperatures, over a longer period of time.

Es wurde nun überraschenderweise gefunden, dass man lagerstabile Formulierungen von konzentrierten, wässrigen Aufhellermischungen erhält, wenn man der wässrigen Suspension derartiger Aufhellermischungen geringe Mengen eines anionisches Polysaccharids, in Kombination mit Elektrolyten und Dispergiermittel, zumischt. Derartige Suspensionen setzen sich während der Lagerung kaum ab. Zusätzlich zu dem guten Sedimentationsverhalten bleiben die Suspensionen während der Lagerung homogen.It has now surprisingly been found that storage-stable formulations of concentrated, aqueous brightener mixtures are obtained if small amounts of an anionic polysaccharide, in combination with electrolytes and dispersants, are added to the aqueous suspension of such brightener mixtures. Such suspensions hardly settle out during storage. In addition to the good sedimentation behavior, the suspensions remain homogeneous during storage.

Die optischen Aufhellerformulierungen gemäss der Erfindung sind demnach gekennzeichnet durch einen Gehalt an:

  • a) 15 bis 45 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung einer Mischung von mindestens zwei anionischen optischen Aufhellern;
  • b) 0,1 bis 25 Gew. % bezogen auf das Gesamtgewicht der Aufhellerformulierung eines Elektrolyten oder eines Elektrolytengemisches;
  • c) 0,01 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung eines anionischen Polysaccharids;
  • d) 0,2 bis 20 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung eines oder mehrerer Dispergiermittel;
  • e) gegebenenfalls weitere Zusätze; und
  • f) den Rest auf 100 Gew. % Wasser.
The optical brightener formulations according to the invention are therefore characterized by a content of:
  • a) 15 to 45% by weight, based on the total weight of the brightener formulation, of a mixture of at least two anionic optical brighteners;
  • b) 0.1 to 25% by weight, based on the total weight of the brightener formulation of an electrolyte or an electrolyte mixture;
  • c) 0.01 to 1% by weight, based on the total weight of the brightener formulation of an anionic polysaccharide;
  • d) 0.2 to 20% by weight, based on the total weight of the brightener formulation of one or more dispersants;
  • e) if necessary, other additives; and
  • f) the rest to 100% by weight of water.

Diese neuen Formulierungen stellen Suspensionen dar und sind bei einer Temperatur von -5°C bis 40°C mindestens 6 Monate stabil.These new formulations are suspensions and are stable for at least 6 months at a temperature of -5 ° C to 40 ° C.

Vorzugsweise enthalten solche Formulierungen anionische optische Aufheller, die mindestens einen Sulfonsäurerest enthalten.Such formulations preferably contain anionic optical brighteners which contain at least one sulfonic acid residue.

Als optische Aufheller seien beispielsweise genannt :Examples of optical brighteners are:

a) Aufheller der Triazinreihe der Formel:a) Brightener of the triazine series of the formula:

Figure imgb0001

worin X und Y, die gleichartig oder verschieden sein können und ein sekundäres oder tertiäres Amin oder unsubstituiertes, mono- oder di-substituiertes Alkoxy bedeuten, und M ein Wasserstoffatom oder ein salzbildendes Kation bedeutet. Als sekundäres und tertiäres Amin kommen z.B. unsubstituiertes oder mit C₁-C₄Alkyl, C₁-C₄Alkoxy, Sulfo, Halogen, Cyano, oder Carboxy ein oder mehrfach substituiertes Phenylamin, Morpholin, Piperidin, Methylamin, Ethylamin, Propylamin, Butylamin, β-Hydroxy-ethylamin, β-Hydroxypropylamin, β-Cyano-ethylamin, Dimethylamin, Diethylamin, Dipropylamin, bis-β-Hydroxyethylamin, N-Methyl-N-ethylamin, N-Methyl-N-β-hydroxyethylamin, N-Ethyl-N-β-hydroxyethylamin, N-Methyl-N-β-hydroxypropylamin, N-Ethyl-N-β-hydroxypropylamin, Benzylamin, N-β-hydroxyethyl-benzylamin, Cyclohexylamin, N-Ethyl-cyclohexylamin, 2-Methoxy-ethylamin, 2-Ethoxy-ethylamin, N-Methyl-2-methoxyethylamin und 3-Methoxy-propylamin in Frage. Als Beispiele für unsubstituierte, mono- oder disubstituiertes Alkoxy seien Methoxy, Ethoxy, n-Propoxy, i-Propoxy, Butoxy, β-Hydroxy-ethoxy, β-Methoxy-ethoxy, und β-Ethoxy-ethoxy genannt. Von Interesse sind besonders optische Aufheller der Formel (1), worin X und Y, die gleichartig oder verschieden sein können, eine Phenylaminogruppe, welche gegebenenfalls durch Alkylreste mit 1 oder 2 Kohlenstoffatomen mono- oder di-substituiert ist; die Morpholinogruppe; eine Alkylaminogruppe mit 1 bis 4 Kohlenstoffatomen, die durch Hydroxylreste substituiert sein kann; oder eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen bedeuten; und M Wasserstoff oder ein salzbildendes Kation darstellt.
Figure imgb0001
wherein X and Y, which may be the same or different and represent a secondary or tertiary amine or unsubstituted, mono- or di-substituted alkoxy, and M represents a hydrogen atom or a salt-forming cation. The secondary and tertiary amine are, for example, unsubstituted or mono- or polysubstituted phenylamine, morpholine, piperidine, methylamine, ethylamine, propylamine, butylamine, β-hydroxyethylamine, or substituted with C₁-C₄alkyl, C₁-C₄alkoxy, sulfo, halogen, cyano, or carboxy. β-hydroxypropylamine, β-cyano-ethylamine, dimethylamine, diethylamine, dipropylamine, bis-β-hydroxyethylamine, N-methyl-N-ethylamine, N-methyl-N-β-hydroxyethylamine, N-ethyl-N-β-hydroxyethylamine, N-methyl-N-β-hydroxypropylamine, N-ethyl-N-β-hydroxypropylamine, benzylamine, N-β-hydroxyethyl-benzylamine, cyclohexylamine, N-ethyl-cyclohexylamine, 2-methoxyethylamine, 2-ethoxyethylamine, N-methyl-2-methoxyethylamine and 3-methoxypropylamine in question. Examples of unsubstituted, mono- or disubstituted alkoxy are methoxy, ethoxy, n-propoxy, i-propoxy, butoxy, β-hydroxy-ethoxy, β-methoxy-ethoxy, and β-ethoxy-ethoxy. Of particular interest are optical brighteners of the formula (1), in which X and Y, which may be identical or different, are a phenylamino group which is optionally mono- or di-substituted by alkyl radicals having 1 or 2 carbon atoms; the morpholino group; an alkylamino group having 1 to 4 carbon atoms, which may be substituted by hydroxyl radicals; or represent an alkoxy group having 1 to 4 carbon atoms; and M represents hydrogen or a salt-forming cation.

Ferner sind optische Aufheller der Formel (1) bevorzugt, worin X und Y, die gleichartig oder verschieden sein können, die Phenylamino-, die Morpholino-, eine Alkylaminogruppe mit 1 bis 4 Kohlenstoffatomen, die durch Hydroxylreste substituiert sein kann und M Wasserstoff oder ein salzbildendes Kation bedeuten. Besonders bevorzugt sind hierbei die Morpholino- und die N-Methyl-N-ethanolaminogruppe.Optical brighteners of the formula (1) are furthermore preferred, in which X and Y, which may be identical or different, are phenylamino, morpholino, an alkylamino group having 1 to 4 carbon atoms, which may be substituted by hydroxyl radicals, and M is hydrogen or a salt-forming cation. The morpholino and the N-methyl-N-ethanolamino groups are particularly preferred.

Als Beispiele seien die optischen Aufheller der Formeln (2)

Figure imgb0002

worin M ein Alkalimetallion bedeutet, wobei im Falle dieses optischen Aufhellers zweckmässig ein Gehalt von 2 bis 25 Gew.%, bezogen auf das Gesamtgewicht der Aufschlämmung an einem starken Elektrolyten vorhanden ist;
und (3)
Figure imgb0003
worin M ein Alkalimetallion bedeutet, genannt.The optical brighteners of the formulas (2) are examples
Figure imgb0002
wherein M represents an alkali metal ion, in the case of this optical brightener a content of 2 to 25% by weight, based on the total weight of the slurry, of a strong electrolyte is expediently present;
and (3)
Figure imgb0003
where M denotes an alkali metal ion.

b) Aufheller der Distilbenreihe, so zum Beispiel Verbindungen der Formel :b) brighteners of the distilbene series, for example compounds of the formula:

Figure imgb0004

wobei A ein Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen und B Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen bedeuten, mit der Bedingung, dass mindestens ein Substituent A ein Sulfonsäurerest ist und m, n, o, p unabhängig voneinander eine Zahl 1 oder 2 bedeuten.
Figure imgb0004
wherein A is a sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen and B is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, with the condition that at least one substituent A is a sulfonic acid residue is and m, n, o, p independently of one another represent a number 1 or 2.

Bevorzugt sind solche Verbindungen in denen o = 2 ist.Compounds in which o = 2 are preferred.

Besonders bevorzugte Verbindungen sind Verbindungen der Formeln

Figure imgb0005

und
Figure imgb0006
wobei A, B und n obige Bedeutung haben und M ein salzbildendes Kation ist.Particularly preferred compounds are compounds of the formulas
Figure imgb0005
and
Figure imgb0006
where A, B and n have the above meaning and M is a salt-forming cation.

Als Halogene kommen vor allem Fluor, Chlor und Brom in Frage, insbesondere jedoch Chlor.The most suitable halogens are fluorine, chlorine and bromine, but especially chlorine.

Als C₁-C₄-Alkylreste kommen unverzweigte und verzweigte Alkylreste wie der Methyl-, Ethyl-, n- und iso-Propyl, n-, sec- und tert.-Butylrest in Betracht. Diese C₁-C₄-Alkylreste können ihrerseits substituiert sein mit z.B. Aryl-(Phenyl-, Naphthyl-), C₁-C₄-Alkoxy-, OH-, Halogen-, Sulfo- oder CN-Gruppen.As C₁-C₄ alkyl radicals are unbranched and branched alkyl radicals such as the methyl, ethyl, n- and iso-propyl, n-, sec- and tert-butyl radical. These C₁-C₄ alkyl radicals can in turn be substituted with e.g. Aryl (phenyl, naphthyl), C₁-C₄ alkoxy, OH, halogen, sulfo or CN groups.

Salzbildende Kationen M sind z.B. Alkalimetall-, Ammonium- oder Aminsalzionen. Unter Aminsalzionen sind solche der Formel H⁺NR₁R₂R₃ bevorzugt, in denen R₁, R₂ und R₃ unabhängig voneinander Wasserstoff, Akyl, Alkenyl, Hydroxyalkyl, Cyanoalkyl, Halogenakyl oder Phenylalkyl bedeuten oder worin R₁ und R₂ zusammen die Ergänzung zu einem 5-7-gliedrigen gesättigten Stickstoffheterocyclus darstellen, der noch zusätzlich ein Stickstoff- oder Sauerstoffatom als Ringglied enthalten kann, beispielsweise einen Piperidin-, Piperazin-, pyrrolidin-, Imidazolin- oder Morpholinring, während R₃ für Wasserstoff steht. Bevorzugte salzbildende Kationen sind Akalimetallsalze, wobei Na⁺ und K⁺ besonders bevorzugt sind.Salt-forming cations M are e.g. Alkali metal, ammonium or amine salt ions. Amine salt ions are preferred those of the formula H⁺NR₁R₂R₃ in which R₁, R₂ and R₃ independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, halogenoalkyl or phenylalkyl or in which R₁ and R₂ together are the addition to a 5-7-membered saturated Represent nitrogen heterocycle, which may additionally contain a nitrogen or oxygen atom as a ring member, for example a piperidine, piperazine, pyrrolidine, imidazoline or morpholine ring, while R₃ is hydrogen. Preferred salt-forming cations are akali metal salts, Na⁺ and K⁺ being particularly preferred.

Bevorzugte Distyrylbiphenylverbindungen der Formel (4) sind solche in denen das Kation M ein Alkalimetall-, Ammonium-, oder Aminion ist, wobei aus praktischen Erwägungen Kalium und Natrium eine besondere Bedeutung haben.Preferred distyrylbiphenyl compounds of the formula (4) are those in which the cation M is an alkali metal, ammonium or amine ion, potassium and sodium being of particular importance for practical reasons.

Von praktischem Interesse sind dabei die Verbindungen

Figure imgb0007
Figure imgb0008
Figure imgb0009
worin M ein Alkalimetallion bedeutet.The connections are of practical interest
Figure imgb0007
Figure imgb0008
Figure imgb0009
wherein M represents an alkali metal ion.

Bevorzugte Mischungen bestehen aus je 5 bis 30 Gew.%, bezogen auf das Gesamtgewicht, zusammen aber nicht über 45 Gew.%, von zwei, drei oder vier Aufhellern der Formeln (2), (3), (7) und (8), wobei bei Zweiermischungen, die besonders bevorzugt sind, das Verhältnis der optischen Aufheller zueinander zwischen 1:9 und 9:1, vorzugsweise zwischen 1:4 und 4:1, liegt.Preferred mixtures each consist of 5 to 30% by weight, based on the total weight, but not more than 45% by weight, of two, three or four brighteners of the formulas (2), (3), (7) and (8) , In the case of two-component mixtures which are particularly preferred, the ratio of the optical brighteners to one another is between 1: 9 and 9: 1, preferably between 1: 4 and 4: 1.

Als Elektrolyt können z.B. ein oder mehrere Alkalimetallsalze sowie Salze niederer Carbonsäuren verwendet werden. Beispiele für Elektrolyte sind Natriumchlorid, Natriumsulfat, Natriumphosphat, Natriumcarbonat, Natriumformiat oder eines der entsprechenden Kaliumsalze sowie Mischungen dieser Elektrolyte. Bevorzugt sind hierbei Natriumchlorid sowie die Formiate. Die Menge an Elektrolyt kann 0,1 bis 25 Gew.%, vorzugsweise 0,5 bis 20 Gew.% und besonders bevorzugt 0,5-15 Gew.%, bezogen auf das Gesamtgewicht der Formulierung, betragen.As electrolyte e.g. one or more alkali metal salts and salts of lower carboxylic acids can be used. Examples of electrolytes are sodium chloride, sodium sulfate, sodium phosphate, sodium carbonate, sodium formate or one of the corresponding potassium salts and mixtures of these electrolytes. Sodium chloride and the formates are preferred. The amount of electrolyte can be 0.1 to 25% by weight, preferably 0.5 to 20% by weight and particularly preferably 0.5-15% by weight, based on the total weight of the formulation.

Die erfindungsgemäss verwendbaren anionischen Polysaccharide gehören zur Gruppe der modifizierten Polysaccharide, die sich von der Zellulose, Stärke oder von den Heteropolysacchariden ableiten lassen, wobei in den Seitenketten weitere Monosaccharide wie z.B. Mannose und Glucuronsäure enthalten sein können. Beispiele für anionische Polysaccharide sind Natriumalginat, Carboxymethyliertes Guar, Carboxymethylcellulose, Carboxymethylstärke, carboxymethyliertes Johannisbrotkernmehl und, besonders bevorzugt, Xanthan.The anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose, starch or from the heteropolysaccharides, with further monosaccharides such as e.g. Mannose and glucuronic acid can be included. Examples of anionic polysaccharides are sodium alginate, carboxymethylated guar, carboxymethyl cellulose, carboxymethyl starch, carboxymethylated locust bean gum and, particularly preferably, xanthan gum.

Die Menge an Polysaccharid beträgt 0,01 bis 1 Gew.%, wobei ein Bereich von 0,05 bis 0,5 Gew.% bevorzugt und ein Bereich von 0,05-0,2 Gew.% besonders bevorzugt ist, jeweils bezogen auf das Gesamtgewicht der Formulierung. Es können jedoch bei sehr hoch konzentrierten oder sehr niedrig konzentrierten Formulierungen diese Bereiche überschritten werden.The amount of polysaccharide is 0.01 to 1% by weight, a range from 0.05 to 0.5% by weight being preferred and a range from 0.05-0.2% by weight being particularly preferred, in each case based on the total weight of the formulation. However, these ranges can be exceeded in the case of very highly concentrated or very low concentrated formulations.

Gegebenenfalls kann die erfindungsgemässe Aufhellertormulierung Zusätze enthalten; exemplarisch seien Konservierungsmittel wie Chloracetamid oder wässrige Formaldehydlösung, Mg/Al-Silikate, Geruchsverbesserer und Gefrierschutzmittel genannt.The brightener formulation according to the invention can optionally contain additives; Preservatives such as chloroacetamide or aqueous formaldehyde solution, Mg / Al silicates, odor improvers and antifreezes may be mentioned as examples.

Beispiele für Mg/Al-Silikate sind Bentonit, Montmorillonit, Zeolithe und hochdisperse Kieselsäuren. Sie werden üblicherweise in einer Menge von 0,2-1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, zugesetzt.Examples of Mg / Al silicates are bentonite, montmorillonite, zeolites and highly disperse silicas. They are usually added in an amount of 0.2-1% by weight, based on the total weight of the brightener formulation.

Als Dispergiermittel können solche des anionischen oder nichtionischen Typs eingesetzt werden. Beispiele hierfür sind Alkylbenzolsulfonate, Alkyl- oder Alkenylethersulfonatsalze, gesättigte oder ungesättigte Fettsäuren, Alkyl- oder Alkylenethercarboxylsalze, Sulfofettsäuresalze oder Ester, Phosphatester, Polyoxyethylenalkyl- oder -alkenylether, Polyoxyethylen-alkylvinylether, Polyoxypropylenalkyl- oder -alkenylether, Polyoxybutylenalkyl- oder alkenylether, höhere Fettsäurealkanolamide oder Alkylenoxidaddukte, Sucrose/Fettsäureester, Fettsäure/Glykolmonoester, Alkylaminoxide und Kondensationsprodukte von aromatischen Sulfonsäuren mit Formaldehyd sowie Ligninsulfonaten oder Gemische aus den oben genannten Dispergiermitteln. Bevorzugt sind die Kondensationsprodukte von aromatischen Sulfonsäuren mit Formaldehyd sowie Ligninsulfonaten. Besonders bevorzugt sind Kondensationsprodukte von Naphthalinsulfonsäuren mit Formaldehyd sowie Ditolylethersulfosäuren mit Formaldehyd.Dispersants which can be used are those of the anionic or nonionic type. Examples include alkyl benzene, alkyl or Alkenylethersulfonatsalze, saturated or unsaturated fatty acids, alkyl or Alkylenethercarboxylsalze, sulfofatty or esters, Phosphatester, polyoxyethylene alkyl or alkenyl, polyoxyethylene alkyl vinyl ether, polyoxypropylene alkyl or alkenyl, Polyoxybutylenalkyl- or alkenyl ether, higher fatty acid or Alkylene oxide adducts, sucrose / fatty acid esters, fatty acid / glycol monoesters, alkylamine oxides and condensation products of aromatic sulfonic acids with formaldehyde as well as lignin sulfonates or mixtures of the above-mentioned dispersants. The condensation products of aromatic sulfonic acids with formaldehyde and lignin sulfonates are preferred. Condensation products of naphthalene sulfonic acids with formaldehyde and ditolyl ether sulfonic acids with formaldehyde are particularly preferred.

Der Gehalt an Dispergiermittel beträgt 0,2 bis 20 Gew.% bezogen auf das Gesamtgewicht der Formulierung, vorzugsweise 0,1 bis 10 Gew.% und besonders bevorzugt 0,2 bis 5 Gew. %.The content of dispersant is 0.2 to 20% by weight, based on the total weight of the formulation, preferably 0.1 to 10% by weight and particularly preferably 0.2 to 5% by weight.

Erfindungsgemässe Formulierungen erhält man, indem man die feuchten Presskuchen oder auch die trockenen Pulver von mindestens zwei anionischen optischen Aufhellern, die mindestens einen Sulfonsäurerest enthalten, in einer Menge von 15 bis 45 Gew.%, vorzugsweise 15 bis 40 Gew.% und besonders bevorzugt 19-40 Gew.%, bezogen auf das Gesamtgewicht der Formulierung; mit 0,01 bis 1 Gew.% anionischem Polysaccharid; 0,1 bis 25 Gew.% Elektrolyt; 0,2 bis 20 Gew.% Dispergiermittel; gegebenenfalls mit weiteren Zusätzen; sowie mit Wasser vermischt und bei Raumtemperatur homogenisiert.Formulations according to the invention are obtained by adding the moist presscakes or the dry powders of at least two anionic optical brighteners, which contain at least one sulfonic acid residue, in an amount of 15 to 45% by weight, preferably 15 to 40% by weight and particularly preferably 19 -40% by weight, based on the total weight of the formulation; with 0.01 to 1% by weight of anionic polysaccharide; 0.1 to 25% by weight electrolyte; 0.2 to 20 wt% dispersant; if necessary with further additives; and mixed with water and homogenized at room temperature.

Der gewünschte Gehalt an anionischen optischen Aufhellern, in der Suspension, kann entweder durch Zugabe von Wasser, wässrigem Elektrolyt, oder weiterem trockenen Pulver, zu dem feuchten Filterkuchen, eingestellt werden. Diese Einstellung kann vor, während oder nach Zusatz des anionischen Polysaccharids vorgenommen werden.The desired content of anionic optical brighteners in the suspension can be adjusted either by adding water, aqueous electrolyte, or further dry powder to the moist filter cake. This setting can be made before, during or after the addition of the anionic polysaccharide.

Verwendung finden die neuen optischen Aufhellerformulierungen vorallem in der Einarbeitung in Waschmittel, z. B. durch Einfliessenlassen der erforderlichen Menge der erfindungsgemässen optischen Aufhellerformulierung, aus einem Behälter in eine Mischvorrichtung, die eine Suspension des Waschmittels bzw. des Dispergiermittels enthält.The new optical brightener formulations are used primarily in the incorporation into detergents, e.g. B. by inflowing the required amount of the optical brightener formulation according to the invention, from a container into a mixing device which contains a suspension of the detergent or the dispersant.

Die vorliegende Erfindung betrifft demzufolge auch ein Verfahren zur Herstellung von festen und flüssigen Waschmitteln, sowie die danach erhaltenen Waschmittel, dadurch gekennzeichnet, dass man z.B. eine Suspension für Waschmittel üblicher Detergentien, mit einer erfindungsgemässen Suspension von Aufhellern, vermischt und trocknet. Der Trocknungsvorgang kann dabei z.B. durch ein Sprühtrocknungsverfahren erfolgen.The present invention accordingly also relates to a process for the production of solid and liquid detergents, and to the detergents obtained thereafter, characterized in that e.g. a suspension for detergents of conventional detergents, mixed with an inventive suspension of brighteners, and dried. The drying process can e.g. done by a spray drying process.

Weiterhin kann die erfindungsgemässe Aufhellerformulierung zur Herstellung von flüssigen Waschmitteln verwendet werden.Furthermore, the brightener formulation according to the invention can be used for the production of liquid detergents.

Die folgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken. Prozentangaben beziehen sich auf das Gesamtgewicht der Formulierung.The following examples illustrate the invention without restricting it. Percentages refer to the total weight of the formulation.

Beispiel 1:Example 1:

Unter Rühren bei 20°C werden die in Tabelle 1 angegebenen Komponenten vermischt und homogenisiert.The components listed in Table 1 are mixed and homogenized with stirring at 20 ° C.

Die erhaltenen Aufhellerformulierungen bleiben flüssig und bilden nach zweimonatigem Stehen bei -5°C, Raumtemperatur und 40°C keine Ablagerungen.

Figure imgb0010
The brightener formulations obtained remain liquid and, after standing for two months at -5 ° C., room temperature and 40 ° C., do not form any deposits.
Figure imgb0010

Beispiel 2:Example 2:

Unter Rühren werden die in Tabelle 2 angegebenen Komponenten mit 1 Gew. %, bezogen auf das Gesamtgewicht der Aufhellerformulierung, des Kondensationsproduktes von Ditolylethersulfosäuren mit Formaldehyd; 0,15 Gew. % Xanthan und Wasser vermischt und homogenisiert.The components listed in Table 2 are stirred with 1% by weight, based on the total weight of the brightener formulation, of the condensation product of ditolyl ether sulfonic acids with formaldehyde; 0.15% by weight of xanthan and water mixed and homogenized.

Die Aufhellerformulierungen bleiben flüssig und bilden nach mehrwöchigem Stehen bei Raumtemperatur und 40°C keine Ablagerungen.The brightener formulations remain liquid and do not form any deposits after standing for several weeks at room temperature and 40 ° C.

Beispiel 3:Example 3:

Unter Rühren werden
   20 Gew.% eines optischen Aufhellers der Formel (2);
   10 Gew.% eines optischen Aufhellers der Formel (7);
   1 Gew.% NaCl;
   0,5 Gew. % Bentonit;
   1 Gew.% des Kondensationsproduktes von Ditolylethersulfosäuren mit Formaldehyd;
   0,1 Gew.% Xanthan; und 67,4 Gew.% Wasser
   vermischt und homogenisiert.With stirring
20% by weight of an optical brightener of the formula (2);
10% by weight of an optical brightener of the formula (7);
1% by weight NaCl;
0.5% by weight bentonite;
1% by weight of the condensation product of ditolyl ether sulfonic acids with formaldehyde;
0.1% by weight xanthan; and 67.4 wt% water
mixed and homogenized.

Die Aufhellerformulierungen bleiben flüssig und bilden nach mehrwöchigem Stehen bei Raumtemperatur und 40°C keine Ablagerungen.

Figure imgb0011
The brightener formulations remain liquid and do not form any deposits after standing for several weeks at room temperature and 40 ° C.
Figure imgb0011

Claims (27)

Lagerstabile Aufhellerformulierung dadurch gekennzeichnet, dass sie a) 15 bis 45 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, einer Mischung von mindestens zwei anionischen optischen Aufhellern; b) 0,1 bis 25 Gew.% bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines Elektrolyten oder eines Elektrolytengemisches; c) 0,01 bis 1 Gew. %, bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines anionischen Polysaccharids; d) 0,2 bis 20 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines oder mehrerer Dispergiermittel; e) gegebenenfalls weitere Zusätze; und f) Wasser enthält. Storage-stable brightener formulation characterized in that it a) 15 to 45% by weight, based on the total weight of the brightener formulation, of a mixture of at least two anionic optical brighteners; b) 0.1 to 25% by weight, based on the total weight of the brightener formulation, an electrolyte or an electrolyte mixture; c) 0.01 to 1% by weight, based on the total weight of the brightener formulation, of an anionic polysaccharide; d) 0.2 to 20% by weight, based on the total weight of the brightener formulation, of one or more dispersants; e) if necessary, other additives; and f) contains water. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass der Gehalt an der Aufhellermischung 15 bis 40 Gew. % beträgt.Storage-stable brightener formulation according to claim 1, characterized in that the content of the brightener mixture is 15 to 40% by weight. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass sie zwei anionische optische Aufheller enthält.Storage-stable brightener formulation according to claim 1, characterized in that it contains two anionic optical brighteners. Lagerstabile Aufhellerformulierung gemäss Anspruch 3, dadurch gekennzeichnet, dass das Verhältnis der beiden anionischen optischen Aufheller zwischen 1:9 und 9:1 liegt.Storage-stable brightener formulation according to claim 3, characterized in that the ratio of the two anionic optical brighteners is between 1: 9 and 9: 1. Lagerstabile Aufhellerformulierung gemäss Anspruch 3, dadurch gekennzeichnet, dass das Verhältnis der beiden anionischen optischen Aufheller zwischen 1:4 und 4:1 liegt.Storage-stable brightener formulation according to claim 3, characterized in that the ratio of the two anionic optical brighteners is between 1: 4 and 4: 1. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass der Gehalt an Elektrolyt 0,5 bis 20 Gew.% beträgt.Storage-stable brightener formulation according to claim 1, characterized in that the electrolyte content is 0.5 to 20% by weight. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass der Gehalt an Polysaccharid 0,05 bis 0,5 Gew.% beträgt.Storage-stable brightener formulation according to claim 1, characterized in that the polysaccharide content is 0.05 to 0.5% by weight. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass der Gehalt an Dispergiermittel 0,1 bis 10 Gew. % beträgt.Storage-stable brightener formulation according to claim 1, characterized in that the content of dispersant is 0.1 to 10% by weight. Lagerstabile Aufhellerformulierung dadurch gekennzeichnet, dass sie a) 19 bis 40 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines Gemisches von mindestens zwei anionischen optischen Aufhellern; b) 0,5 bis 15 Gew.% bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines Elektrolyten oder eines Elektrolytengemisches; c) 0,05 bis 0,2 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines anionischen Polysaccharids; d) 0,2 bis 5 Gew.% bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines Dispergiermittels oder eines Dispergiermittelgemisches; e) gegebenenfalls weitere Zusätze; und f) Wasser enthält. Storage-stable brightener formulation characterized in that it a) 19 to 40% by weight, based on the total weight of the brightener formulation, of a mixture of at least two anionic optical brighteners; b) 0.5 to 15% by weight, based on the total weight of the brightener formulation, an electrolyte or an electrolyte mixture; c) 0.05 to 0.2% by weight, based on the total weight of the brightener formulation, of an anionic polysaccharide; d) 0.2 to 5% by weight, based on the total weight of the brightener formulation, of a dispersant or of a mixture of dispersants; e) if necessary, other additives; and f) contains water. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass sie als weitere Zusätze Mg/Al-Silikate in einer Menge von 0,2-1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, enthält.Storage-stable brightener formulation according to claim 1, characterized in that it contains, as further additives, Mg / Al silicates in an amount of 0.2-1% by weight, based on the total weight of the brightener formulation. Lagerstabile Aufhellerformulierung gemäss Anspruch 10, dadurch gekennzeichnet, dass als Mg/Al-Silikat Bentonit verwendet wird.Storage-stable brightener formulation according to claim 10, characterized in that bentonite is used as the Mg / Al silicate. Lagerstabile Aufhellerformulierung gemäss Anspruch 9, dadurch gekennzeichnet, dass das anionische Polysaccharid ein modifiziertes Polysaccharid ist, das sich von der Zellulose, Stärke oder von Heteropolysacchariden ableiten lässt.Storage-stable brightener formulation according to claim 9, characterized in that the anionic polysaccharide is a modified polysaccharide which can be derived from cellulose, starch or from heteropolysaccharides. Lagerstabile Aufhellerformulierung gemäss Anspruch 12, dadurch gekennzeichnet, dass das modifizierte Polysaccharid eine Zellulose-Grundstruktur hat.Storage-stable brightener formulation according to claim 12, characterized in that the modified polysaccharide has a cellulose basic structure. Lagerstabile Aufhellerformulierung gemäss Anspruch 13, dadurch gekennzeichnet, dass das anionische Polysaccharid Xanthan ist.Storage-stable brightener formulation according to claim 13, characterized in that the anionic polysaccharide is xanthan. Lagerstabile Aufhellerformulierung gemäss Anspruch 9, dadurch gekennzeichnet, dass das Dispergiermittel ein Kondensationsprodukt von aromatischen Sulfonsäuren mit Formaldehyd oder Gemischen davon ist.Storage-stable brightener formulation according to claim 9, characterized in that the dispersant is a condensation product of aromatic sulfonic acids with formaldehyde or mixtures thereof. Lagerstabile Aufhellerformulierung gemäss Anspruch 15, dadurch gekennzeichnet, dass das Dispergiermittel ein Kondensationsprodukt von Naphthalinsulfonsäuren mit Formaldehyd oder Ditolylethersulfosäuren mit Formaldehyd ist.Storage-stable brightener formulation according to claim 15, characterized in that the dispersant is a condensation product of naphthalene sulfonic acids with formaldehyde or ditolyl ether sulfonic acids with formaldehyde. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass einer der optischen Aufheller der Formel (1)
Figure imgb0012
 worin X und Y, die gleichartig oder verschieden sein können und einen sekundären oder tertiären Aminrest oder eine mono- oder di-substituierte Alkoxygruppe bedeuten, und M ein Wasserstoffatom oder ein salzbildendes Kation bedeutet, entspricht.Storage-stable brightener formulation according to claim 1, characterized in that one of the optical brighteners of the formula (1)
Figure imgb0012
 wherein X and Y, which may be the same or different and represent a secondary or tertiary amine radical or a mono- or di-substituted alkoxy group, and M represents a hydrogen atom or a salt-forming cation, corresponds. Lagerstabile Aufhellerformulierung gemäss Anspruch 17, dadurch gekennzeichnet, dass einer der optischen Aufheller der Formel (2) oder (3)
Figure imgb0013
Figure imgb0014
 entspricht, worin M ein Alkalimetallion bedeutet.Storage-stable brightener formulation according to claim 17, characterized in that one of the optical brighteners of the formula (2) or (3)
Figure imgb0013
Figure imgb0014
 corresponds in which M denotes an alkali metal ion. Lagerstabile Aufhellertormulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass einer der optischen Aufheller der Formel (4)
Figure imgb0015
 entspricht, worin
A einen Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen und
B Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen
bedeuten, mit der Bedingung, dass mindestens ein Substituent A ein Sulfonsäurerest ist und m, n, o, p unabhängig voneinander eine Zahl 1 oder 2 bedeuten.Storage-stable brightener formulation according to claim 1, characterized in that one of the optical brighteners of the formula (4)
Figure imgb0015
 corresponds to what
A is a sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen and
B is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen
mean, with the condition that at least one substituent A is a sulfonic acid residue and m, n, o, p independently of one another represent a number 1 or 2. Lagerstabile Aufhellerformulierung gemäss Anspruch 19, dadurch gekennzeichnet, dass einer der optischen Aufheller der Formel (7), (8) oder (9)
Figure imgb0016
Figure imgb0017
Figure imgb0018
 entspricht, worin M ein Alkalimetallion bedeutet.Storage-stable brightener formulation according to claim 19, characterized in that one of the optical brighteners of the formula (7), (8) or (9)
Figure imgb0016
Figure imgb0017
Figure imgb0018
 corresponds in which M denotes an alkali metal ion. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass sie je 5 bis 30 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines anionischen optischen Aufhellers der Formel (1) und (2)
Figure imgb0019
Figure imgb0020
 worin M ein Alkalimetallion bedeutet, enthält.Storage-stable brightener formulation according to claim 1, characterized in that it contains 5 to 30% by weight, based on the total weight of the brightener formulation, of an anionic optical brightener of the formula (1) and (2)
Figure imgb0019
Figure imgb0020
 wherein M represents an alkali metal ion. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass sie je 5 bis 30 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines anionischen optischen Aufhellers der Formel (7) und (3)
Figure imgb0021
Figure imgb0022
 worin M ein Alkalimetallion bedeutet, enthält.Storage-stable brightener formulation according to claim 1, characterized in that it contains 5 to 30% by weight, based on the total weight of the brightener formulation, of an anionic optical brightener of the formula (7) and (3)
Figure imgb0021
Figure imgb0022
 wherein M represents an alkali metal ion. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass sie je 5 bis 30 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, eines anionischen optischen Aufhellers der Formel (7) und (8)
Figure imgb0023
Figure imgb0024
 worin M ein Alkalimetallion bedeutet, enthält.Storage-stable brightener formulation according to claim 1, characterized in that it contains 5 to 30% by weight, based on the total weight of the brightener formulation, of an anionic optical brightener of the formula (7) and (8)
Figure imgb0023
Figure imgb0024
 wherein M represents an alkali metal ion. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekennzeichnet, dass sie a) je 5 bis 20 Gew.%, bezogen auf das Gesamtgewicht, von zwei, drei oder vier Aufhellern der Formeln (7), (8), (2) und (3)
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
 worin M Na⁺ oder K⁺ bedeutet; b) 0,5 bis 15 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, NaCl; c) 0,05 bis 0,2 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, Xanthan; d) 0,2 bis 5 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, Dispergiermittel; e) gegebenenfalls weitere Zusätze; und f) Wasser enthält. Storage-stable brightener formulation according to claim 1, characterized in that it a) 5 to 20% by weight, based on the total weight, of two, three or four brighteners of the formulas (7), (8), (2) and (3)
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
 wherein M is Na⁺ or K⁺; b) 0.5 to 15% by weight, based on the total weight of the brightener formulation, NaCl; c) 0.05 to 0.2% by weight, based on the total weight of the brightener formulation, xanthan; d) 0.2 to 5% by weight, based on the total weight of the brightener formulation, of dispersant; e) if necessary, other additives; and f) contains water. Lagerstabile Aufhellerformulierung gemäss Anspruch 24, dadurch gekennzeichnet, dass sie als weitere Zusätze 0,2-1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulierung, Bentonit enthält.Storage-stable brightener formulation according to claim 24, characterized in that it contains 0.2-1% by weight, based on the total weight of the brightener formulation, of bentonite as further additives. Verfahren zur Herstellung von lagerstabilen Aufhellerformulierungen gemäss Anspruch 1, dadurch gekennzeichnet, dass man die feuchten Presskuchen oder die trockenen Pulver der Aufheller gemäss Anspruch 1; den oder die Elektrolyten; ein anionisches Polysaccharid; Dispergiermittel und gegebenenfalls Mg/Al-Silikate mit Wasser vermischt und homogenisiert.A process for the preparation of storage-stable brightener formulations according to claim 1, characterized in that the moist press cake or the dry powder of the brightener according to claim 1; the electrolyte or electrolytes; an anionic polysaccharide; Dispersant and optionally Mg / Al silicates mixed with water and homogenized. Verwendung der lagerstabilen Aufhellerformulierungen gemäss Anspruch 1 zur Herstellung von Waschmitteln.Use of the storage-stable brightener formulations according to claim 1 for the production of detergents.
EP92810830A 1991-11-07 1992-10-28 Storage-stable formulation of mixtures of optical brighteners Expired - Lifetime EP0542677B1 (en)

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CH3245/91A CH682748A5 (en) 1991-11-07 1991-11-07 A storage-stable formulation of optical brightener.

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EP0808837A1 (en) * 1996-05-23 1997-11-26 Ciba SC Holding AG Stilbene compounds as fluorescent whitening agents, as UV absorbers and their use to increase the sun protection factor of textile material
EP0837124A2 (en) * 1996-10-15 1998-04-22 Ciba SC Holding AG Fluorescent whitening agent formulation
WO1999027059A1 (en) * 1997-11-22 1999-06-03 Henkel-Ecolab Gmbh & Co. Ohg Washing method and preparation for carrying out the same
WO2004085594A1 (en) * 2003-03-24 2004-10-07 Ciba Specialty Chemicals Holding Inc. Detergent compositions
WO2004111330A1 (en) * 2003-06-11 2004-12-23 Ciba Specialty Chemicals Holding Inc. Storage-stable fluorescent whitener formulations

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GB0100610D0 (en) * 2001-01-10 2001-02-21 Clariant Int Ltd Improvements in or relating to organic compounds
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ES2626605T3 (en) * 2011-01-20 2017-07-25 Huntsman Advanced Materials (Switzerland) Gmbh Formulations of fluorescent bleaching agents in dispersed form
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
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US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
CN103945828A (en) 2011-11-04 2014-07-23 阿克佐诺贝尔化学国际公司 Hybrid dendrite copolymers, compositions thereof and methods for producing the same
SG11201401383WA (en) 2011-11-04 2014-08-28 Akzo Nobel Chemicals Int Bv Graft dendrite copolymers, and methods for producing the same
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
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Cited By (11)

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Publication number Priority date Publication date Assignee Title
EP0604366A1 (en) * 1992-12-22 1994-06-29 Ciba-Geigy Ag Storage-stable formulation of mixtures of optical brighteners
US5429767A (en) * 1992-12-22 1995-07-04 Ciba-Geigy Corporation Storage-stable whitener formulation
EP0808837A1 (en) * 1996-05-23 1997-11-26 Ciba SC Holding AG Stilbene compounds as fluorescent whitening agents, as UV absorbers and their use to increase the sun protection factor of textile material
US6080208A (en) * 1996-05-23 2000-06-27 Ciba Specialty Chemicals Corporation Stilbene compounds and their use
EP0837124A2 (en) * 1996-10-15 1998-04-22 Ciba SC Holding AG Fluorescent whitening agent formulation
EP0837124A3 (en) * 1996-10-15 1999-01-20 Ciba SC Holding AG Fluorescent whitening agent formulation
WO1999027059A1 (en) * 1997-11-22 1999-06-03 Henkel-Ecolab Gmbh & Co. Ohg Washing method and preparation for carrying out the same
WO2004085594A1 (en) * 2003-03-24 2004-10-07 Ciba Specialty Chemicals Holding Inc. Detergent compositions
US7863236B2 (en) 2003-03-24 2011-01-04 Ciba Specialty Chemicals Corp. Detergent compositions
WO2004111330A1 (en) * 2003-06-11 2004-12-23 Ciba Specialty Chemicals Holding Inc. Storage-stable fluorescent whitener formulations
AU2004247892B2 (en) * 2003-06-11 2009-09-17 Basf Se Storage-stable fluorescent whitener formulations

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DK0542677T3 (en) 1996-04-01
CA2082202A1 (en) 1993-05-08
BR9204316A (en) 1993-05-11
NZ245027A (en) 1994-10-26
MX9206384A (en) 1993-05-01
EP0542677B1 (en) 1996-03-13
KR930010170A (en) 1993-06-22
CA2082202C (en) 2003-07-29
MY110095A (en) 1998-01-27
ES2084977T3 (en) 1996-05-16
CH682748A5 (en) 1993-11-15
JP3286358B2 (en) 2002-05-27
US5518657A (en) 1996-05-21
AU2820792A (en) 1993-05-13
JPH05239768A (en) 1993-09-17
ATE135423T1 (en) 1996-03-15
AU653271B2 (en) 1994-09-22
KR100249743B1 (en) 2000-03-15
DE59205674D1 (en) 1996-04-18
TW234145B (en) 1994-11-11

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