EP0385374A1 - Storage-stable brightener composition - Google Patents

Storage-stable brightener composition Download PDF

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Publication number
EP0385374A1
EP0385374A1 EP90103750A EP90103750A EP0385374A1 EP 0385374 A1 EP0385374 A1 EP 0385374A1 EP 90103750 A EP90103750 A EP 90103750A EP 90103750 A EP90103750 A EP 90103750A EP 0385374 A1 EP0385374 A1 EP 0385374A1
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Prior art keywords
brightener
storage
stable
formulation according
weight
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German (de)
French (fr)
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EP0385374B2 (en
EP0385374B1 (en
Inventor
Werner Dr. Fringeli
Josef Zelger
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BASF Schweiz AG
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Ciba Geigy AG
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Classifications

    • 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, aqueous, concentrated brightener formulations and a process for their preparation and their use.
  • optical brighteners are preferably marketed in the form of aqueous solutions.
  • the moist filter cake or the dry powder is slurried with water.
  • This suspension is mixed with dispersants and thickeners to increase homogeneity, wettability and stability.
  • An electrolyte is often added to these auxiliaries.
  • the additives used up to now could not prevent sedimentation of the brighteners over a longer period of time.
  • Such formulations preferably contain anionic optical brighteners which contain at least one sulfonic acid residue.
  • they are brighteners of the triazine series of the formula: 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 H represents a hydrogen atom or a salt-forming cation.
  • X1 and Y1 which may be the same or different, a phenylamino group which is optionally mono- or di-substituted by alkyl radicals with 1 or 2 carbon atoms, the morpholino group, an alkylamino group with 1 to 4 carbon atoms which may be substituted by hydroxyl radicals, represents an alkoxy group having 1 to 4 carbon atoms, and M represents hydrogen or a salt-forming cation.
  • X2 and Y2 which may be the same or different, the phenylamino, the 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.
  • X3 and Y3, which may be the same or different, represent a phenylamino, morpholino, the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation.
  • X4 and Y4 which may be the same or different, represent the morpholino or the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation.
  • M ' is an alkali metal ion, in the case of this optical brightener a content of 4 to 25% by weight, based on the total weight of the slurry, of a strong electrolyte is expediently present.
  • Optical brighteners from the distilbene series can also be used.
  • A sulfonic acid residue, hydrogen, C1-C4-alkyl, C1-C4-alkoxy or halogen
  • Particularly preferred compounds are compounds of the formula 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 alkyl, C1-C4 alkoxy, OH 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+NR8R9R10 in which R8, R9 and R10 independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or in which R8 and R9 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 R10 represents hydrogen.
  • Preferred distyrylbiphenyl compounds of the formula (X) 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.
  • the anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose. It can be etherified cellulose, but also heteropolysaccharides that contain other monosaccharides in the side chains, e.g. Mannose and glucuronic acid included.
  • the anionic polysaccharide is, for example, Na carboxymethyl cellulose and particularly preferably xanthan.
  • the amount of polysaccharide is preferably 0.01 to 1% by weight, with a range of 0.05-0.5% by weight being particularly preferred, 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 formulation can contain auxiliaries; electrolytes, preservatives such as chloroacetamide or aqueous formaldehyde solution and odor improvers may be mentioned as examples.
  • the electrolyte can be sodium chloride, sodium sulfate, sodium carbonate or one of the corresponding potassium salts or also mixtures of the aforementioned substances.
  • the amount of electrolyte can be 0.1 to 25% by weight, based on the total weight of the formulation, preferably 0.1 to 20% by weight.
  • Formulations according to the invention are obtained by mixing the moist filter cake or the dry powder of an anionic optical brightener, which preferably contains at least one sulfonic acid residue, in an amount of 10-60% by weight, based on the total weight of the formulation, with 0.01-1% by weight % anionic polysaccharide and water mixed and homogenized.
  • an anionic optical brightener which preferably contains at least one sulfonic acid residue
  • the desired content of anionic optical brightener in the suspension can be adjusted either by adding water, aqueous electrolyte, suspension 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 proportion of the anionic optical brightener is expediently 10 to 60%, preferably 15 to 40% by weight, based on the weight of the suspension.
  • the suspension is then mixed with the anionic polysaccharide until it is homogeneous.
  • the formulation can be incorporated into a detergent, e.g. by flowing the required amount of the suspension from a container into a mixing device which contains a suspension of the detergent or detergent.
  • the present invention accordingly also relates to a process for the production of detergents and the detergents obtained thereafter, characterized in that a suspension for detergents of conventional detergents is mixed and dried with a suspension of brighteners according to the invention.
  • the suspensions obtained are advantageously dried by subjecting them to a spray drying process.
  • the brightener formulation according to the invention can be used for the production of liquid detergents.
  • the properties of the brightener formulation correspond to those from Example 1.
  • the brightener formulation does not form any deposits after standing for several months at room temperature and 40 ° C.
  • the brightener formulation is stable on storage at room temperature and 40 ° C.
  • the suspension shows no deposits after standing for 3 months at room temperature.
  • the brightener formulation is stable on storage at room temperature and 40 ° C.

Abstract

The brightener compositions contain an anionic optic brightener which preferably contains at least one sulpho radical in an amount of 10-60% by weight, relative to the total weight of the composition, an anionic polysaccharide and water and, if desired, auxiliaries; these compositions are used for the preparation of detergents.

Description

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

Heutzutage werden optische Aufheller bevorzugt in Form wässriger Lösungen in den Handel gebracht. Hierzu wird der feuchte Filterkuchen oder auch das trockene Pulver mit Wasser aufgeschlämmt. Diese Suspension wird mit Dispergatoren und Verdickungsmitteln zur Erhöhung von Homogenität, Benetzbarkeit und Stabilität versetzt. Zu diesen Hilfsstoffen setzt man häufig noch einen Elektrolyten hinzu. Die bisher verwendeten Hilfsstoffe konnten jedoch ein Sedimentieren der Aufheller nicht über einen längeren Zeitraum verhindern.Nowadays, optical brighteners are preferably marketed in the form of aqueous solutions. For this purpose, the moist filter cake or the dry powder is slurried with water. This suspension is mixed with dispersants and thickeners to increase homogeneity, wettability and stability. An electrolyte is often added to these auxiliaries. However, the additives used up to now could not prevent sedimentation of the brighteners over a longer period of time.

Es wurde nun überraschenderweise gefunden, dass man lagerstabile, konzentrierte, wässrige Aufhellerformulierungen erhält, wenn man zu der wässrigen Suspension derartiger Aufheller ein anionisches Polysaccharid in geringen Mengen zugibt. 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, concentrated, aqueous brightener formulations are obtained by adding an anionic polysaccharide in small amounts to the aqueous suspension of such brighteners. Such suspensions hardly settle out during storage. In addition to the good sedimentation behavior, the suspensions remain homogeneous during storage.

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

  • a) 10 bis 60 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformu­lierung eines anionischen optischen Aufhellers,
  • b) 0,01 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformu­lierung eines anionischen Polysaccharids und
  • c) Wasser; sowie gegebenenfalls
  • d) Hilfsstoffe.
The formulations according to the invention are therefore characterized by a content of:
  • a) 10 to 60% by weight, based on the total weight of the brightener formulation of an anionic optical brightener,
  • b) 0.01 to 1% by weight, based on the total weight of the brightener formulation of an anionic polysaccharide and
  • c) water; and if necessary
  • d) auxiliary substances.

Diese Formulierungen stellen Suspensionen dar.These formulations represent suspensions.

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.

Beispielsweise handelt es sich um Aufheller der Triazinreihe der Formel:

Figure imgb0001
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 H ein Wasserstoffatom oder ein salzbildendes Kation bedeutet.For example, they are brighteners of the triazine series of the formula:
Figure imgb0001
 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 H represents a hydrogen atom or a salt-forming cation.

Von besonderem Interesse sind:

Figure imgb0002
worin X₁ und Y₁, 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, eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen bedeuten, und M Wasserstoff oder ein salzbildendes Kation darstellt.
Figure imgb0003
 worin X₂ und Y₂, 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.
Figure imgb0004
 worin X₃ und Y₃, die gleichartig oder verschieden sein können, eine Phenylamino-, Morpholino-, die N-Methyl-N-äthanolaminogruppe und M Wasserstoff oder ein salzbildendes Kation bedeuten.
Figure imgb0005
 worin X₄ und Y₄, die gleichartig oder verschieden sein können, die Morpholino- oder die N-Methyl-N-äthanolaminogruppe und M Wasserstoff oder ein salzbildendes Kation bedeuten.
Figure imgb0006
 worin M′ ein Alkalimetallion bedeutet, wobei im Falle dieses optischen Aufhellers zweckmässig ein Gehalt von 4 bis 25 Gew.%, bezogen auf das Gesamtgewicht der Aufschlämmung an einem starken Elektrolyten vorhanden ist.Of particular interest are:
Figure imgb0002
 wherein X₁ and Y₁, which may be the same or different, a phenylamino group which is optionally mono- or di-substituted by alkyl radicals with 1 or 2 carbon atoms, the morpholino group, an alkylamino group with 1 to 4 carbon atoms which may be substituted by hydroxyl radicals, represents an alkoxy group having 1 to 4 carbon atoms, and M represents hydrogen or a salt-forming cation.
Figure imgb0003
 wherein X₂ and Y₂, which may be the same or different, the phenylamino, the 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.
Figure imgb0004
 wherein X₃ and Y₃, which may be the same or different, represent a phenylamino, morpholino, the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation.
Figure imgb0005
 wherein X₄ and Y₄, which may be the same or different, represent the morpholino or the N-methyl-N-ethanolamine group and M is hydrogen or a salt-forming cation.
Figure imgb0006
 where M 'is an alkali metal ion, in the case of this optical brightener a content of 4 to 25% by weight, based on the total weight of the slurry, of a strong electrolyte is expediently present.

Weiterhin kann man optische Aufheller der Distilbenreihe einsetzen. So zum Beispiel Verbindungen der Formel

Figure imgb0007
wobei A = 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 = Sulfon­säurerest ist und m, n, o, p unabhängig voneinander eine Zahl 1 oder 2 bedeuten.Optical brighteners from the distilbene series can also be used. For example compounds of the formula
Figure imgb0007
 where A = sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen and B = hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, with the condition that at least one substituent A = Is sulfonic acid residue and m, n, o, p independently 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 Formel

Figure imgb0008
wobei A, B und n obige Bedeutung haben und M ein salzbildendes Kation ist.Particularly preferred compounds are compounds of the formula
Figure imgb0008
 where A, B and n have the above meaning and M is a salt-forming cation.

Von praktischem Interesse sind dabei die Verbindungen

Figure imgb0009
wobei M′ ein Alkalimetallion bedeutet.The connections are of practical interest
Figure imgb0009
 where M 'is an alkali metal ion.

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-Alkyl-, C₁-C₄-Alkoxy-, OH- 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 alkyl, C₁-C₄ alkoxy, OH or CN groups.

Salzbildende Kationen M sind z.B. Alkalimetall-, Ammonium- oder Amin­salzionen. Unter Aminsalzionen sind solche der Formel H⁺NR₈R₉R₁₀ bevor­zugt, in denen R₈, R₉ und R₁₀ unabhängig voneinander Wasserstoff, Alkyl, Alkenyl, Hydroxyalkyl, Cyanoalkyl, Halogenalkyl oder Phenylalkyl bedeuten oder worin R₈ und R₉ 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 R₁₀ für Wasserstoff steht.Salt-forming cations M are e.g. Alkali metal, ammonium or amine salt ions. Amine salt ions are preferred those of the formula H⁺NR₈R₉R₁₀ in which R₈, R₉ and R₁₀ independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or in which R₈ and R₉ 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 R₁₀ represents hydrogen.

Bevorzugte Distyrylbiphenylverbindungen der Formel (X) 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 (X) 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.

Die erfindungsgemäss verwendbaren anionischen Polysaccharide gehören zur Gruppe der modifizierten Polysaccharide, die sich von der Zellulose ableiten lassen. Es kann sich um veretherte Zellulose handeln, aber auch um Heteropolysaccharide, die in den Seitenketten weitere Monosaccharide wie z.B. Mannose und Glucuronsäure enthalten.The anionic polysaccharides which can be used according to the invention belong to the group of modified polysaccharides which can be derived from cellulose. It can be etherified cellulose, but also heteropolysaccharides that contain other monosaccharides in the side chains, e.g. Mannose and glucuronic acid included.

Das anionische Polysaccharid ist zum Beispiel Na-Carboxymethylcellulose und besonders bevorzugt Xanthan.The anionic polysaccharide is, for example, Na carboxymethyl cellulose and particularly preferably xanthan.

Die Menge an Polysaccharid beträgt vorzugsweise 0,01 bis 1 Gew.%, wobei ein Bereich von 0,05-0,5 Gew.% besonders bevorzugt ist, 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 preferably 0.01 to 1% by weight, with a range of 0.05-0.5% by weight being particularly preferred, 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 Formulierung Hilfsstoffe enthalten; exemplarisch seien genannt Elektrolyte, Konservierungsmittel wie Chloracetamid oder wässrige Formaldehydlösung und Geruchsverbesserer.If appropriate, the formulation can contain auxiliaries; electrolytes, preservatives such as chloroacetamide or aqueous formaldehyde solution and odor improvers may be mentioned as examples.

Der Elektrolyt kann Natriumchlorid, Natriumsulfat, Natriumcarbonat oder eines der entsprechenden Kaliumsalze sein oder auch Mischungen der vorgenannten Stoffe. Die Menge an Elektrolyt kann 0,1 bis 25 Gew.%, bezogen auf das Gesamtgewicht der Formulierung, vorzugsweise 0,1 bis 20 Gew.%, betragen.The electrolyte can be sodium chloride, sodium sulfate, sodium carbonate or one of the corresponding potassium salts or also mixtures of the aforementioned substances. The amount of electrolyte can be 0.1 to 25% by weight, based on the total weight of the formulation, preferably 0.1 to 20% by weight.

Erfindungsgemässe Formulierungen erhält man, indem man den feuchten Filterkuchen oder auch das trockene Pulver eines anionischen optischen Aufhellers, der vorzugsweise mindestens einen Sulfonsäurerest enthält, in einer Menge von 10-60 Gew.% bezogen auf das Gesamtgewicht der Formulie­rung mit 0,01 - 1 Gew.% anionischem Polysaccharid und Wasser vermischt und homogenisiert.Formulations according to the invention are obtained by mixing the moist filter cake or the dry powder of an anionic optical brightener, which preferably contains at least one sulfonic acid residue, in an amount of 10-60% by weight, based on the total weight of the formulation, with 0.01-1% by weight % anionic polysaccharide and water mixed and homogenized.

Der gewünschte Gehalt an anionischem optischen Aufheller in der Suspen­sion kann entweder durch Zugabe von Wasser, wässrigem Elektrolyt, Suspension oder weiterem trockenen Pulver zu dem feuchten Filterkuchen eingestellt werden. Diese Einstellung kann vor, während oder nach Zusatz des anionischen Polysaccharids vorgenommen werden. Der Anteil des anionischen optischen Aufhellers beträgt zweckmässig 10 bis 60 %, vorzugsweise 15 bis 40 Gew.%, bezogen auf das Gewicht der Suspension.The desired content of anionic optical brightener in the suspension can be adjusted either by adding water, aqueous electrolyte, suspension 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 proportion of the anionic optical brightener is expediently 10 to 60%, preferably 15 to 40% by weight, based on the weight of the suspension.

Die Suspension wird dann mit dem anionischen Polysaccharid vermischt, bis sie homogen ist.The suspension is then mixed with the anionic polysaccharide until it is homogeneous.

Die Formulierung kann in ein Waschmittel eingearbeitet werden, z.B. durch Einfliessenlassen der erforderlichen Menge der Suspension aus einem Behälter in eine Mischvorrichtung, die eine Suspension des Waschmittels bzw. des Detergenz enthält.The formulation can be incorporated into a detergent, e.g. by flowing the required amount of the suspension from a container into a mixing device which contains a suspension of the detergent or detergent.

Die vorliegende Erfindung betrifft demzufolge auch ein Verfahren zur Herstellung von Waschmitteln, sowie die danach erhaltenen Waschmittel, dadurch gekennzeichnet, dass man eine Suspension für Waschmittel üblicher Detergentien mit einer erfindungsgemässen Suspension von Aufhellern, vermischt und trocknet. Die erhaltenen Suspensionen werden vorteilhaft getrocknet, indem man sie einem Sprühtrocknungsverfahren unterwirft.The present invention accordingly also relates to a process for the production of detergents and the detergents obtained thereafter, characterized in that a suspension for detergents of conventional detergents is mixed and dried with a suspension of brighteners according to the invention. The suspensions obtained are advantageously dried by subjecting them to 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. Teile sind auf das Gewicht bezogen.The following examples illustrate the invention without restricting it. Parts are by weight.

Beispiel 1example 1

0,075 Teile Xanthan
0,2 Teile Chloracetamid
1,3 Teile Natriumsulfat und
5 Teile Natriumchlorid werden in
61 Teilen Wasser gelöst.
Unter Rühren werden in diese Lösung
32,5 Teile feuchter Presskuchen, enthaltend 12 Teile Wasser, 0,5 Teile Natriumchlorid und 20 Teile des optischen Aufhellers

Figure imgb0010
eingetragen und homogenisiert.0.075 parts of xanthan
0.2 parts chloroacetamide
1.3 parts of sodium sulfate and
5 parts of sodium chloride are in
61 parts of water dissolved.
Stir into this solution
32.5 parts of moist press cake, containing 12 parts of water, 0.5 parts of sodium chloride and 20 parts of the optical brightener
Figure imgb0010
 registered and homogenized.

Die weisse Aufhellerformulierung hat eine Viskosität von 108 cP (Haake VT 18, MVII, 22°C, D = 42 sec⁻¹) und bildet nach zweimonatigem Stehen bei -5°C, RT und 40°C keine Ablagerungen.The white brightener formulation has a viscosity of 108 cP (Haake VT 18, MVII, 22 ° C, D = 42 sec⁻¹) and forms no deposits after standing for two months at -5 ° C, RT and 40 ° C.

Beispiel 2Example 2

Wie im Beispiel 1 werden
0,075 Teile Xanthan
0,2 Teile Chloracetamid
1,3 Teile Natriumsulfat
5 Teile Natriumchlorid in
72 Teilen Wasser gelöst, mit
21,5 Teilen des trockenen Presskuchens, enthaltend 1,5 Teile Wasser und 20 Teile des optischen Aufhellers

Figure imgb0011
versetzt und unter Rühren homogenisiert.As in example 1
0.075 parts of xanthan
0.2 parts chloroacetamide
1.3 parts sodium sulfate
5 parts of sodium chloride in
72 parts of water dissolved, with
21.5 parts of the dry press cake, containing 1.5 parts of water and 20 parts of the optical brightener
Figure imgb0011
 added and homogenized with stirring.

Die Aufhellerformulierung entspricht in ihren Eigenschaften derjenigen aus Beispiel 1.The properties of the brightener formulation correspond to those from Example 1.

Beispiel 3Example 3

Wie in Beispiel 1 werden
0,1 Teile Chloracetamid
3,0 Teile Natriumchlorid
1,0 Teil Talgfettalkohol mit 11 Mol Ethylenoxid
0,3 Teile Xanthan in
37,5 Teilen Wasser gelöst, mit
58,1 Teilen des wasserfeuchten Filterkuchens, enthaltend 56 Teile Wasser und 44 Teile des optischen Aufhellers

Figure imgb0012
versetzt und unter Rühren homogenisiert.As in example 1
0.1 parts chloroacetamide
3.0 parts sodium chloride
1.0 part of tallow fatty alcohol with 11 moles of ethylene oxide
0.3 parts xanthan in
37.5 parts of water dissolved with
58.1 parts of the water-moist filter cake, containing 56 parts of water and 44 parts of the optical brightener
Figure imgb0012
 added and homogenized with stirring.

Die Aufhellerformulierung bildet nach mehrmonatigem Stehen bei Raum­temperatur und 40°C keine Ablagerungen.The brightener formulation does not form any deposits after standing for several months at room temperature and 40 ° C.

Beispiel 4Example 4

Wie in Beispiel 3 werden
0,1 Teile Chloracetamid
0,1 Teile Xanthan
3,0 Teile Natriumchlorid in
5,9 Teilen Wasser gelöst, mit
90,9 Teilen des wasserfeuchten Filterkuchens, enthaltend 56 Teile Wasser und 44 Teile des optischen Aufhellers der Formel (300), versetzt und unter Rühren homogenisiert.As in example 3
0.1 parts chloroacetamide
0.1 part xanthan
3.0 parts sodium chloride in
5.9 parts of water dissolved, with
90.9 parts of the water-moist filter cake, containing 56 parts of water and 44 parts of the optical brightener of the formula (300), were added and the mixture was homogenized with stirring.

Die Aufhellerformulierung ist bei Raumtemperatur und 40°C lagerstabil.The brightener formulation is stable on storage at room temperature and 40 ° C.

Beispiel 5Example 5

Wie in Beispiel 1 werden
0,5 Teile Formaldehyd (37 %) wässrig
2,0 Teile Na-Carboxymethylcellulose in
33,5 Teilen Wasser gelöst, mit
64,5 Teilen des wasserfeuchten Filterkuchens, enthaltend 53,5 Teile Wasser und 46,5 Teile des optischen Aufhellers der Formel

Figure imgb0013
versetzt und unter Rühren homogenisiert.As in example 1
0.5 parts of formaldehyde (37%) aqueous
2.0 parts Na carboxymethyl cellulose in
33.5 parts of water dissolved with
64.5 parts of the water-moist filter cake, containing 53.5 parts of water and 46.5 parts of the optical brightener of the formula
Figure imgb0013
 added and homogenized with stirring.

Die Suspension zeigt nach 3-monatigem Stehen bei Raumtemperatur keine Ablagerungen.The suspension shows no deposits after standing for 3 months at room temperature.

Beispiel 6Example 6

Wie in Beispiel 3 werden
0,1 Teile Chloracetamid
0,1 Teile Xanthan in
8,9 Teilen Wasser gelöst, mit
90,9 Teilen des wasserfeuchten Filterkuchens, enthaltend 56 Teile Wasser und 44 Teile des optischen Aufhellers der Formel (300), versetzt und unter Rühren homogenisiert.As in example 3
0.1 parts chloroacetamide
0.1 parts xanthan in
8.9 parts of water dissolved, with
90.9 parts of the water-moist filter cake, containing 56 parts of water and 44 parts of the optical brightener of the formula (300), were added and the mixture was homogenized with stirring.

Die Aufhellerformulierung ist bei Raumtemperatur und 40°C lagerstabil.The brightener formulation is stable on storage at room temperature and 40 ° C.

Claims (21)

1. Lagerstabile Aufhellerformulierung dadurch gekennzeichnet, dass sie a) 10 bis 60 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformu­lierung eines anionischen optischen Aufhellers, b) 0,01 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulie­rung eines anionischen Polysaccharids, und c) Wasser enthält. 1. Storage-stable brightener formulation characterized in that it a) 10 to 60% by weight, based on the total weight of the brightener formulation of an anionic optical brightener, b) 0.01 to 1% by weight, based on the total weight of the brightener formulation of an anionic polysaccharide, and c) contains water. 2. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, 15, 16 oder 17, dadurch gekennzeichnet, dass der Gehalt an Aufheller 15-40 Gew.% beträgt.2. Storage-stable brightener formulation according to claim 1, 15, 16 or 17, characterized in that the brightener content is 15-40% by weight. 3. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekenn­zeichnet, dass sie einen Elektrolyten enthält.3. Storage-stable brightener formulation according to claim 1, characterized in that it contains an electrolyte. 4. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, dadurch gekenn­zeichnet, dass der Gehalt an Elektrolyt 2 - 25 beträgt.4. Storage-stable brightener formulation according to claim 1, characterized in that the electrolyte content is 2-25. 5. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, 15, 16 oder 17, dadurch gekennzeichnet, dass der optische Aufheller der Formel
Figure imgb0014
 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 H ein Wasserstoffatom oder ein salzbildendes Kation bedeutet, entspricht.5. Storage-stable brightener formulation according to claim 1, 15, 16 or 17, characterized in that the optical brightener of the formula
Figure imgb0014
 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 H represents a hydrogen atom or a salt-forming cation, corresponds. 6. Lagerstabile Aufhellerformulierung gemäss Anspruch 5, dadurch gekenn­zeichnet, dass der optische Aufheller der Formel
Figure imgb0015
 worin X₂ und Y₂, 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, entspricht.6. Storage-stable brightener formulation according to claim 5, characterized in that the optical brightener of the formula
Figure imgb0015
 wherein X₂ and Y₂, which may be the same or different, the phenylamino, the 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, corresponds. 7. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, 15, 16 oder 17, dadurch gekennzeichnet, dass der optische Aufheller der Formel
Figure imgb0016
 wobei A = 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 = Sulfon­säurerest ist und m, n, o, p unabhängig voneinander eine Zahl 1 oder 2 bedeuten, entspricht.7. storage-stable brightener formulation according to claim 1, 15, 16 or 17, characterized in that the optical brightener of the formula
Figure imgb0016
 where A = sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen and B = hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, with the condition that at least one substituent A = Is sulfonic acid residue and m, n, o, p independently of one another represent a number 1 or 2, corresponds. 8. Lagerstabile Aufhellerformulierung gemäss Anspruch 7, dadurch gekenn­zeichnet, dass der optische Aufheller der Formel wobei A = Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen, B = Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen, n unabhängig voneinander eine Zahl 1 oder 2 und H ein salz­bildendes Kation bedeutet, entspricht.8. Storage-stable brightener formulation according to claim 7, characterized in that the optical brightener of the formula where A = sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, B = sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, n independently of one another a number 1 or 2 and H means a salt-forming cation. 9. Lagerstabile Aufhellerformulierung gemäss Anspruch 7, dadurch gekenn­zeichnet, dass der optische Aufheller der Formel
Figure imgb0018
 wobei A = Sulfonsäurerest, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen, B = Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen, n unabhängig voneinander eine Zahl 1 oder 2 und M ein salzbildendes Kation bedeutet, entspricht.9. Storage-stable brightener formulation according to claim 7, characterized in that the optical brightener of the formula
Figure imgb0018
 where A = sulfonic acid residue, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, B = hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, n is independently a number 1 or 2 and M. salt-forming cation means corresponds. 10. Lagerstabile Aufhellerformulierung gemäss Anspruch 5, dadurch gekenn­zeichnet, dass der optische Aufheller der Formel
Figure imgb0019
 entspricht, wobei M′ ein Alkalimetallion bedeutet.10. Storage-stable brightener formulation according to claim 5, characterized in that the optical brightener of the formula
Figure imgb0019
 corresponds, where M 'is an alkali metal ion. 11. Lagerstabile Aufhellerformulierung gemäss Anspruch 7, dadurch gekennzeichnet, dass der optische Aufheller der Formel
Figure imgb0020
 entspricht, wobei M′ ein Alkalimetallion bedeutet.11. Storage-stable brightener formulation according to claim 7, characterized in that the optical brightener of the formula
Figure imgb0020
 corresponds, where M 'is an alkali metal ion. 12. Lagerstabile Aufhellerformulierung gemäss Anspruch 1 oder 15, dadurch gekennzeichnet, dass das anionische Polysaccharid Xanthan ist.12. Storage-stable brightener formulation according to claim 1 or 15, characterized in that the anionic polysaccharide is xanthan. 13. Verfahren zur Herstellung von lagerstabilen Aufhellerformulierungen gemäss Anspruch 1 oder 15, dadurch gekennzeichnet, dass man zu dem feuchten Presskuchen oder dem trockenen Pulver des Aufhellers gemäss Anspruch 1 oder 15 ein anionisches Polysaccharid gibt, und mit Wasser vermischt und homogenisiert.13. A process for the preparation of storage-stable brightener formulations according to claim 1 or 15, characterized in that an anionic polysaccharide is added to the moist press cake or the dry powder of the brightener according to claim 1 or 15, and mixed and homogenized with water. 14. Verwendung der lagerstabilen Aufhellerformulierungen gemäss Anspruch 1 oder 15 zur Herstellung von Waschmitteln.14. Use of the storage-stable brightener formulations according to claim 1 or 15 for the production of detergents. 15. Lagerstabile Aufhellerformulierung dadurch gekennzeichnet, dass sie a) 10 bis 60 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformu­lierung eines anionischen optischen Aufhellers, b) 0,01 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulie­rung eines anionischen Polysaccharids, und c) Wasser sowie gegebenenfalls d) Hilfsstoffe enthält. 15. Storage-stable brightener formulation characterized in that it a) 10 to 60% by weight, based on the total weight of the brightener formulation of an anionic optical brightener, b) 0.01 to 1% by weight, based on the total weight of the brightener formulation of an anionic polysaccharide, and c) water and optionally d) contains auxiliary substances. 16. Lagerstabile Aufhellerformulierung gemäss Anspruch 15, dadurch gekennzeichnet, dass der Hilfsstoff ein Elektrolyt oder Elektrolyt­gemisch ist.16. Storage-stable brightener formulation according to claim 15, characterized in that the auxiliary is an electrolyte or electrolyte mixture. 17. Lagerstabile Aufhellerformulierung gemäss Anspruch 16, dadurch gekennzeichnet, dass der Gehalt an Elektrolyt 0,1 - 25 Gew.% beträgt.17. Storage-stable brightener formulation according to claim 16, characterized in that the electrolyte content is 0.1-25% by weight. 18. Lagerstabile Aufhellerformulierung gemäss Anspruch 1, 15, 16 oder 17, dadurch gekennzeichnet, dass das anionische Polysaccharid ein modifizier­tes Polysaccharid ist, das sich von der Zellulose ableiten lässt.18. Storage-stable brightener formulation according to claim 1, 15, 16 or 17, characterized in that the anionic polysaccharide is a modified polysaccharide which can be derived from the cellulose. 19. Lagerstabile Aufhellerformulierung gemäss Anspruch 18, dadurch gekennzeichnet, dass das modifizierte Polysaccharid eine veretherte Zellulose oder ein Heteropolysaccharid mit einer Zellulose-Grundstruktur ist.19. Storage-stable brightener formulation according to claim 18, characterized in that the modified polysaccharide is an etherified cellulose or a heteropolysaccharide with a cellulose basic structure. 20. Lagerstabile Aufhellerformulierung gemäss Anspruch 15, dadurch gekennzeichnet, dass sie a) 10 bis 60 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformu­lierung eines anionischen optischen Aufhellers der Formel
Figure imgb0021
 wobei M′ ein Alkalimetallion bedeutet, b) 0,01 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulie­rung Xanthan, und c) Wasser sowie gegebenenfalls d) einen Elektrolyten oder ein Elektrolytgemisch enthält. 20. Storage-stable brightener formulation according to claim 15, characterized in that it a) 10 to 60% by weight, based on the total weight of the brightener formulation of an anionic optical brightener of the formula
Figure imgb0021
 where M ′ is an alkali metal ion, b) 0.01 to 1% by weight, based on the total weight of the brightener formulation xanthan, and c) water and optionally d) contains an electrolyte or an electrolyte mixture. 21. Lagerstabile Aufhellerformulierung gemäss Anspruch 15, dadurch gekennzeichnet, dass sie a) 10 bis 60 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformu­lierung eines anionischen optischen Aufhellers der Formel
Figure imgb0022
Figure imgb0023
 wobei M′ ein Alkalimetallion bedeutet, b) 0,01 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Aufhellerformulie­rung Xanthan, und c) Wasser sowie gegebenenfalls d) einen Elektrolyten oder ein Elektrolytgemisch enthält. 21. Storage-stable brightener formulation according to claim 15, characterized in that it a) 10 to 60% by weight, based on the total weight of the brightener formulation of an anionic optical brightener of the formula
Figure imgb0022
Figure imgb0023
 where M ′ is an alkali metal ion, b) 0.01 to 1% by weight, based on the total weight of the brightener formulation xanthan, and c) water and optionally d) contains an electrolyte or an electrolyte mixture.
EP90103750A 1989-02-28 1990-02-26 Storage-stable brightener composition Expired - Lifetime EP0385374B2 (en)

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US5980904A (en) * 1998-11-18 1999-11-09 Amway Corporation Skin whitening composition containing bearberry extract and a reducing agent
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EP0577557A1 (en) * 1992-06-30 1994-01-05 Ciba-Geigy Ag Hydrates of 4,4'-Bis-(2-sulfostyryl)-biphenyl-disodium or -dipotassium salts
EP0884312A1 (en) * 1997-05-23 1998-12-16 Ciba SC Holding AG Triazinylaminostilbene compounds
US5980904A (en) * 1998-11-18 1999-11-09 Amway Corporation Skin whitening composition containing bearberry extract and a reducing agent
EP1300513A2 (en) * 2001-10-05 2003-04-09 Bayer Aktiengesellschaft Use of solid preparations of optical brighteners for optically brightening paper
EP1335001A1 (en) * 2001-10-05 2003-08-13 Bayer Aktiengesellschaft Solid whitener preparations
EP1300513A3 (en) * 2001-10-05 2007-04-04 Lanxess Deutschland GmbH Use of solid preparations of optical brighteners for optically brightening paper
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
EP2454356B1 (en) 2009-07-17 2017-03-01 Henkel AG & Co. KGaA Liquid detergent compositon comprising a polymer preventing graying

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DE59004269D1 (en) 1994-03-03
JPH02266000A (en) 1990-10-30
ES2048343T3 (en) 1994-03-16
US5076968A (en) 1991-12-31
ATE100484T1 (en) 1994-02-15
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ES2048343T5 (en) 2005-07-01

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