EP0327927A2 - Detergent additive - Google Patents

Detergent additive Download PDF

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Publication number
EP0327927A2
EP0327927A2 EP89101618A EP89101618A EP0327927A2 EP 0327927 A2 EP0327927 A2 EP 0327927A2 EP 89101618 A EP89101618 A EP 89101618A EP 89101618 A EP89101618 A EP 89101618A EP 0327927 A2 EP0327927 A2 EP 0327927A2
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EP
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Prior art keywords
detergent additive
water
polymer component
additive according
acid
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EP89101618A
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German (de)
French (fr)
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EP0327927A3 (en
Inventor
Jochen Dr. Jacobs
Rudolf Weber
Winfried Pochandke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0327927A2 publication Critical patent/EP0327927A2/en
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to a detergent additive which counteracts the dye and brightener transfer from colored or lightened textiles to white or colored or non-lightened textiles during the washing together.
  • DE-OS 29 16 656 describes detergents with an addition of cationic alkylpyridinium salts to prevent the transfer of optical brighteners from brightener-containing laundry items to brightener-free laundry items during washing. From DE-AS 12 24 698 it is known that treatment of textiles which have undergone a color shift due to brightener transfer, with solutions of tertiary or quaternary organic nitrogen bases or their salts, can effect a color regeneration.
  • DE-OS 35 19 012 relates to detergents containing polymer constituents based on polyvinylpyrrolidone and water-soluble cationic compounds and other usual detergent constituents. These detergents are very valuable in terms of their discoloration-inhibiting effect.
  • a detergent additive containing at least partially water-soluble polymer constituents based on N-vinylpyrrolidone and / or N-vinylimidazole and / or N-vinyloxazolidone and / or water-soluble and / or water-insoluble cationic compounds significantly improves the described odor formation problem causes.
  • Such detergent additives also tend to develop less unpleasant odors in connection with conventional detergent components than do the detergents according to the teaching of DE-OS 35 19 012.
  • the detergent additive contains the zinc salts which are known per se for eliminating unpleasant odors Ricinoleic acid (see. Fats, soaps, paint 75, 1973, page 647 ff) contains.
  • the detergent additive is in particulate form, preferably in the form of granules. The particle size distribution is expediently adjusted to approximately the particle size distribution of the detergent to which this additive is to be added, as a result of which segregation phenomena can be avoided during storage, transport and handling.
  • the detergent additive additionally contains a polymer component containing acid groups.
  • a polymer component containing acid groups alone, ie without the simultaneous presence of zinc salts of ricinoleic acid, already reduces the odor problem; on the other hand, the joint use of zinc salts of ricinoleic acid and polymer constituents containing acid groups brings about a surprisingly greater reduction in the problem of gnawing than would have been expected after the sum of the individual active substances used to improve the odor.
  • the polymer component containing acid groups is particularly effective if it is present on the surface of the particulate detergent additive, in particular if it at least partially covers the surface of the detergent additive.
  • the polymer component containing acid groups is preferably polyacrylic acid or a copolymer containing polyacrylic acid.
  • a polymer constituent is, for example, the product known as "Schlichte S" ( R ) from Badische Anilin and Sodafabrik, Ludwigshafen, Federal Republic of Germany, which is known for the sizing of fully synthetic fibers.
  • Suitable copolymers based on polyacrylic acid are obtained by copolymerization, for example with methacrylic acid, maleic acid, fumaric acid, the copolymers also being partially esterified or in salt form. It is essential for suitable copolymers that they still contain free acid groups and are expediently film-forming and water-soluble.
  • Detergent additives according to the invention optionally contain 0.1 to 2% by weight of zinc salts of ricinoleic acid and optionally 1 to 10% by weight, preferably 2 to 5% by weight, of acid groups of the polymer components.
  • Suitable water-insoluble quaternary ammonium compounds are the compounds known as textile plasticizers of the quaternary type derived from ammonia or imidazoline. These are primarily compounds with two long-chain, preferably saturated aliphatic radicals each having 14 to 26, in particular essentially 16 to 20, carbon atoms and at least one quaternary nitrogen atom in the molecule.
  • the long-chain aliphatic radicals can be straight-chain or branched and can accordingly be derived from fatty acids or from fatty amines, Guerbetamines or from alkylamines obtainable from the reduction of nitroparaffins.
  • quaternary ammonium compounds are, in particular, derivatives of ammonia, ie the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for example, the compounds distearyldimethylammonium chloride or ditalgalkyldimethylamminium chloride or methosulfate.
  • quaternary ammonium compounds are obtained by reacting 1 mol of a Aminoalkylethylendiamins Hydroxyalkylethylendiamin or with 2 moles of a long-chain C 2 to C 26 -Fettsäkure or ester imidazoline compounds available, which are then converted by alkylation into the quaternary ImidazolidiumENSen.
  • the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization.
  • chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are therefore suitable as anions, as is the case with the water-soluble quaternary ammonium compounds.
  • Suitable water-soluble quaternary ammonium compounds are dioctyldimethylammonium chloride, octyldodecyldimethylammonium chloride, hexadecyltrimethylammonium chloride or bromide, methylditalgalkylhydroxypropylammonium chloride, tallow alkyltrimethylammonium chloride, octadecyldimethylammonium hydrogen sulfate.
  • the alkyl group of the alkylpyrridinium salt which can also be used as a water-soluble cationic compound, contains 10 to 18, in particular 12 to 16, carbon atoms in the alkyl group.
  • Suitable anions are, for example, the chloride or hydrogen sulfate anion.
  • the polymer component based on N-vinylpyrrolidone can be a homopolymer of N-vinylpyrrolidone or a copolymer of N-vinylpyrrolidone with a molecular weight in the range from about 10,000 to about 1,000,000. Particularly suitable homopolymers have a molecular weight of approximately 15,000 to approximately 700,000. In copolymers which are suitable for the detergent additives according to the invention, the proportion of N-vinylpyrrolidone is at least about 50% of the copolymer. Suitable comonomers are, for example, acrylonitrile and maleic anhydride. The preferred molecular weight of suitable copolymers is in the range of about 20,000 to about 200,000.
  • the for the polymer component based on N- The information given for vinylpyrrolidone also applies analogously to polymer components based on N-vinylimidazole and N-vinyloxazolidone.
  • the water-soluble polymer component based on polyvinylpyrrolidone is present in a large excess over the cationic compound;
  • Detergent additives with a water-soluble polymer component based on polyvinylpyrrolidone and cationic compounds in a weight ratio of 10: 1 to 50: 1, in particular in a weight ratio of 30: 1 to 40: 1, are particularly preferred.
  • Another object of the present invention is a method for producing a detergent additive, as described above.
  • This process comprises intimately mixing a mixture of the water-soluble polymer constituent based on polyvinylpyrrolidone and the cationic compound and, if appropriate, the zinc salt of ricinoleic acid with the addition of water in a mixing unit, preferably granules being formed, then the resulting mixture with optionally heated air dries to a free-flowing product, which is optionally mixed in the fluidized bed with a solution of the acid component-containing polymer component by spraying and, if necessary, dried again with heated air if necessary.
  • a mixing unit preferably granules being formed
  • Granulation conditions can be achieved that the detergent additive according to the present invention has a particle size distribution which corresponds approximately to the particle size distribution of the detergent to which the detergent additive is to be added.
  • the mixing unit which is used to mix the discoloration-inhibiting active ingredients and, if appropriate, the odor-improving additives is, for example, a fluidized bed mixer or preferably a mixing granulator in which the formation of the optional particulate detergent additive according to the invention takes place.
  • a polymer component containing acid groups is used as an odor-improving additive, and the detergent additive according to the invention is added to it in the form of an aqueous solution
  • the water contained in the detergent additive is mixed after mixing in the mixing unit and / or after spraying on the solution containing the acid groups
  • Another object of the present invention is a detergent which contains a detergent additive according to the invention.
  • Detergents which have optimal properties with regard to their discoloration-inhibiting action and their freedom from unpleasant odors preferably contain 0.5 to 10, in particular 1 to 5% by weight of the detergent additives described above.
  • Such detergents not only have excellent discoloration-inhibiting effects, but they can also be perfumed with customary fragrances of a desired fragrance.
  • the dry granules in the fluidized bed were then mixed with an aqueous 20% by weight solution of a low molecular weight polyacrylic acid ("Schlichte S " (R) , from BASF, Ludwigshafen, Federal Republic of Germany ) within 18 minutes at an air temperature of 70 ° C. Germany) sprayed that the granules contained about 3 wt .-% polyacrylic acid.
  • the detergent additive according to the invention thus obtained weighed 440 g per liter and contained about 12% by weight of water.
  • a mixture of 63.4% by weight of the polyvinylpyrrolidone from Example 1, 3.73% by weight of the imidazolinium salt / silica / nonionic surfactant mixture from Example 1 was mixed in a fluidized bed mixer and 32.8% by weight of water at 70 ° C. in the course of 10 minutes.
  • the granules containing about 9.3% by weight of water were then sprayed with 2% by weight of polyacrylic acid (as a 20% by weight solution) as in Example 1.

Abstract

A detergent additive containing at least partly water-soluble polymer components based on N-vinylpyrrolidone or N-vinylimidazole or N-vinyloxazolidone in combination with water-soluble or water-insoluble cationic compound has a discoloration-inhibiting effect and has a neutral odour even in contact with alkaline detergent components. The insensitivity of an additive of this type to strongly alkaline detergent components can be further increased by including in the additive polymer components with acidic groups or zinc ricinoleates.

Description

Die vorliegende Erfindung betrifft einen Waschmittelzusatz, der der Farbstoff- und Aufhellerübertragung von farbigen bzw. aufgehellten Textilien auf weiße oder farbige bzw. nichtaufgehellte Textilien während des gemeinsamen Waschens entgegenwirkt.The present invention relates to a detergent additive which counteracts the dye and brightener transfer from colored or lightened textiles to white or colored or non-lightened textiles during the washing together.

Die Übertragung von Farbstoffen, zu der im folgenden auch die Aufheller gezählt werden, bei der gemeinsamen Wäsche von farbigen und weißen bzw. hellfarbigen Textilien, ist ein seit langem bekanntes Problem, für das es bereits einige Lösungsvorschläge gibt, die aber alle nicht voll befriedigen können, weil sie gegenüber einer Reihe von Farbstoffen bzw. Textilien nur eine geringe Wirkung aufweisen, oder sie wirken der Übertragung von entweder nur dem Farbstoff oder nur dem Aufheller entgegen. Aus der DE-AS 22 32 353 ist ein Waschmittel bekannt, dessen verfärbungsinhibierender Zusatz Polymerbestandteile auf Basis von Polyvinylpyrrolidon sind. Die DE-OS 29 16 656 beschreibt Waschmittel mit einem Zusatz an kationischen Alkylpyridiniumsalzen zur Verhinderung der Übertragung optischer Aufheller von aufhellerhaltigen Wäschestücken auf aufhellerfreie Wäschestücke während des Waschens. Aus der DE-AS 12 24 698 ist bekannt, daß man durch eine Behandlung von Textilien, die durch Aufhellerübertragung eine Farbtonverschiebung erfahren haben, mit Lösungen von tertiären oder quartären organischen Stickstoffbasen oder deren Salzen eine Farbtonregenerie rung bewirken kann. Gegenstand der DE-OS 35 19 012 sind Waschmittel mit einem Gehalt an Polymerbestandteilen auf Basis von Polyvinylpyrrolidon und wasserlöslichen kationischen Verbindungen sowie sonstigen üblichen Waschmittelbestandteilen. Hinsichtlich ihrer verfärbungsinhibierenden Wirkung sind diese Waschmittel sehr wertvoll. Allerdings neigen die verfärbungsinhibierenden Wirkstoffe dieser Waschmittel vor allem in Kombination mit den übrigen Waschmittelbestandteilen zur Ausbildung unangenehmer Gerüche, wodurch deren universelle Verwendung beeinträchtigt wird. Dies gilt auch für die ebenfalls als verfärbungsinhibierend bekannten Wirkstoffe Polyvinylimidazol (DE-OS 28 14 287) und Polyvinyloxazolidon (DE-OS 28 14 329).The transfer of dyes, to which the brighteners are also to be counted, when washing colored and white or light-colored textiles together, has been a problem that has been known for a long time, for which there are already some proposed solutions, but not all of them can fully satisfy , because they have only a slight effect on a number of dyes or textiles, or they counteract the transfer of either only the dye or only the brightener. A detergent is known from DE-AS 22 32 353, the discoloration-inhibiting addition of which are polymer components based on polyvinylpyrrolidone. DE-OS 29 16 656 describes detergents with an addition of cationic alkylpyridinium salts to prevent the transfer of optical brighteners from brightener-containing laundry items to brightener-free laundry items during washing. From DE-AS 12 24 698 it is known that treatment of textiles which have undergone a color shift due to brightener transfer, with solutions of tertiary or quaternary organic nitrogen bases or their salts, can effect a color regeneration. DE-OS 35 19 012 relates to detergents containing polymer constituents based on polyvinylpyrrolidone and water-soluble cationic compounds and other usual detergent constituents. These detergents are very valuable in terms of their discoloration-inhibiting effect. However, the discoloration-inhibiting active ingredients of these detergents, especially in combination with the other detergent constituents, tend to form unpleasant odors, thereby impairing their universal use. This also applies to the active substances polyvinylimidazole (DE-OS 28 14 287) and polyvinyloxazolidone (DE-OS 28 14 329), which are also known to inhibit discoloration.

Es wurde nun gefunden, daß ein Waschmittelzusatz mit einem Gehalt an wenigstens teilweise wasserlöslichen Polymerbestandteilen auf Basis von N-Vinylpyrrolidon und/oder N-Vinylimidazol und/oder N-Vinyloxazolidon und/oder wasserlöslichen und/oder wasserunlöslichen kationischen Verbindungen eine deutliche Verbesserung des beschriebenen Geruchsbildungsproblems bewirkt. Derartige Waschmittelzusätze neigen auch in Verbindung mit üblichen Waschmittelbestandteilen deutlich weniger zur Ausbildung unangenehmer Gerüche als es die Waschmittel nach der Lehre der DE-OS 35 19 012 tun. Obwohl schon die separate Zubereitungsform in Form eines Waschmittelzusatzes der als Verfärbungsinhibitoren für sich und auch in Kombination bekannten Wirkstoffe schon eine deutliche Verminderung des Geruchproblems bewirkt, läßt sich das Geruchsproblem noch weiter vermindern, wenn der Waschmittelzusatz die an sich zur Beseitigung von unangenehmen Gerüchen bekannten Zinksalze der Ricinol säure (vgl. Fette, Seifen, Anstrichmittel 75, 1973, Seite 647 ff) enthält. In einer bevorzugten Ausführungsform liegt der Waschmittelzusatz teilchenförmig, vorzugsweise als Granulat vor. Zweckmäßigerweise stellt man die Teilchengrößenverteilung etwa auf die Teilchengrößeverteilung des Waschmittels, dem dieser Zusatz zugefügt werden soll, ein, wodurch sich bei Lagerung Transport und Handhabung Entmischungserscheinungen vermeiden lassen.It has now been found that a detergent additive containing at least partially water-soluble polymer constituents based on N-vinylpyrrolidone and / or N-vinylimidazole and / or N-vinyloxazolidone and / or water-soluble and / or water-insoluble cationic compounds significantly improves the described odor formation problem causes. Such detergent additives also tend to develop less unpleasant odors in connection with conventional detergent components than do the detergents according to the teaching of DE-OS 35 19 012. Although the separate form of preparation in the form of a detergent additive, the active ingredients known as discoloration inhibitors per se and also in combination, already brings about a significant reduction in the odor problem, the odor problem can be further reduced if the detergent additive contains the zinc salts which are known per se for eliminating unpleasant odors Ricinoleic acid (see. Fats, soaps, paint 75, 1973, page 647 ff) contains. In a preferred embodiment, the detergent additive is in particulate form, preferably in the form of granules. The particle size distribution is expediently adjusted to approximately the particle size distribution of the detergent to which this additive is to be added, as a result of which segregation phenomena can be avoided during storage, transport and handling.

Eine weitere Verringerung des Geruchsproblems kann man erzielen, wenn der Waschmittelzusatz zusätzlich einen Säuregruppen enthaltenden Polyermerbestandteil enthält. Der Zusatz eines Säuregruppen enthaltenden Polymerbestandteils bewirkt für sich allein, d.h. auch ohne die gleichzeitige Anwesenheit von Zinksalzen der Ricinolsäure bereits eine Verringerung des Geruchsproblems; die gemeinsame Verwendung von Zinksalzen der Ricinolsäure und Säuregruppen enthaltender Polymerbestandteile bewirkt dagegen eine überraschend stärkere Verringerung des Gruchsproblems, als es nach der Summe der einzelnen zur Geruchsverbesserung eingesetzten Wirkstoffe zu erwarten gewesen wäre. Der Säuregruppen enthaltende Polymerbestandteil ist besonders wirksam, wenn er an der Oberfläche des teilchenförmigen Waschmittelzusatzes angereichert vorliegt, insbesondere wenn er die Oberfläche des Waschmittelzusatzes wenigstens teilweise bedeckt. Der Säuregruppen enthaltende Polymerbestandteil ist vorzugsweise Polyacrylsäure oder ein Polyacrylsäure enthaltendes Copolymerisat. Ein derartiger Polymerbestandteil ist beispielsweise das zum Schlichten von vollsynthetischen Fasern bekannt Produkt auf Acrylsäurebasis "Schlichte S"(R) der Firma Badische Anilin und Sodafabrik, Ludwigshafen, Bundesrepublik Deutschland. Geeignete Copolymerisate auf Basis von Polyacrylsäure erhält man durch Copolymerisation, beispielsweise mit Methacrylsäure, Maleinsäure, Fumarsäure, wobei die Copolymerisate auch teilweise verestert sein oder in Salzform vorliegen können. Wesentlich ist für geeignete Copolymerisate, daß sie noch freie Säuregruppen enthalten und zweckmäßigerweise filmbildend und wasserlöslich sind.A further reduction in the odor problem can be achieved if the detergent additive additionally contains a polymer component containing acid groups. The addition of a polymer component containing acid groups alone, ie without the simultaneous presence of zinc salts of ricinoleic acid, already reduces the odor problem; on the other hand, the joint use of zinc salts of ricinoleic acid and polymer constituents containing acid groups brings about a surprisingly greater reduction in the problem of gnawing than would have been expected after the sum of the individual active substances used to improve the odor. The polymer component containing acid groups is particularly effective if it is present on the surface of the particulate detergent additive, in particular if it at least partially covers the surface of the detergent additive. The polymer component containing acid groups is preferably polyacrylic acid or a copolymer containing polyacrylic acid. Such a polymer constituent is, for example, the product known as "Schlichte S" ( R ) from Badische Anilin and Sodafabrik, Ludwigshafen, Federal Republic of Germany, which is known for the sizing of fully synthetic fibers. Suitable copolymers based on polyacrylic acid are obtained by copolymerization, for example with methacrylic acid, maleic acid, fumaric acid, the copolymers also being partially esterified or in salt form. It is essential for suitable copolymers that they still contain free acid groups and are expediently film-forming and water-soluble.

Erfindungsgemäße Waschmittelzusätze enthalten gegebenenfalls 0,1 bis 2 Gew.-% von Zinksalzen der Ricinolsäure und gegebenenfalls 1 bis 10 Gew.-%, vorzugsweise 2 bis 5 Gew.-% Säuregruppen enthaltender Polymerbestandteile.Detergent additives according to the invention optionally contain 0.1 to 2% by weight of zinc salts of ricinoleic acid and optionally 1 to 10% by weight, preferably 2 to 5% by weight, of acid groups of the polymer components.

Die als verfärbungsinhibierender Wirkstoff in dem erfindungsgemäßen Waschmittelzusatz enthaltenen kationischen Verbindung können wasserlöslich oder wasserunlöslich sein. Als wasserlösliche kationische Verbindungen kommen quartäre Ammoniumverbindungen entweder a) der Formel I

  • R1 mR2 nN 0 x8 (1)
in der R1 eine Alkyl- oder Alkenyl- oder Acyloxyethyl- oder Hydroxyalkylgruppe mit 8 bis 20 Kohlenstoffen oder eine Benzylgruppe ist, R2 eine Alkylgruppe mit 1 bis 4 Kohlenstoffatome ist, mit der Maßgabe, daß wenn R1 8 bis 12 Kohlenstoffatome hat, m = 1 oder 2 ist und n = 3 oder 2 ist und wenn R1 14 bis 20 Kohlenstoffatome hat, m = 1 und n = 3 ist und X⊖ein Anion ist, das die Elektroneutralität der quartären Ammoniumverbindung herstellt oder b) der Formell II
Figure imgb0001
in der R3 Wasserstoff oder eine gegebenenfalls substituierte Alkylgruppe mit 1 bis 18 Kohlenstoffatomen, R4 eine Alkyl- oder Alkenylgruppe mit 10 bis 20 Kohlenstoffatomen oder eine Alkyl- oder Alkenylamidoethylgruppe mit 10 bis 20 Kohlenstoffatomen in der Alkyl- oder Alkenylgruppe und R5 eine Alkyl- oder Alkenylgruppe mit 10 bis 20 Kohlenstoffatomen ist und X die obengenannte Bedeutung hat, oder c) ein C10- bis C18-Alkylpyridiniumsalz infrage.The cationic compound contained as a discoloration-inhibiting active ingredient in the detergent additive according to the invention can be water-soluble or water-insoluble. Quaternary ammonium compounds are either a) of the formula I as water-soluble cationic compounds
  • R 1 m R 2 n N 0 x8 (1)
in which R 1 is an alkyl or alkenyl or acyloxyethyl or hydroxyalkyl group with 8 to 20 carbons or a benzyl group, R 2 is an alkyl group with 1 to 4 carbon atoms, with the proviso that when R 1 has 8 to 12 carbon atoms, m = 1 or 2 and n = 3 or 2 and when R 1 has 14 to 20 carbon atoms, m = 1 and n = 3 and X⊖ is an anion which produces the electroneutrality of the quaternary ammonium compound or b) the formula II
Figure imgb0001
 in which R 3 is hydrogen or an optionally substituted alkyl group with 1 to 18 carbon atoms, R 4 is an alkyl or alkenyl group with 10 to 20 carbon atoms or an alkyl or alkenylamidoethyl group with 10 to 20 carbon atoms in the alkyl or alkenyl group and R 5 is an alkyl - or alkenyl group having 10 to 20 carbon atoms and X has the meaning given above, or c) a C 10 - to C 18 -alkylpyridinium salt in question.

Als wasserunlösliche quartären Ammoniumverbindungen kommen die als Textilweichmacher bekannten Verbindungen vom Typ der quartären von Ammoniak oder Imidazolin abgeleiteten Ammoniumverbindungen infrage. Dies sind vor allem Verbindungen mit zwei langkettigen, vorzugsweise gesättigten aliphatischen Resten mit je 14 bis 26, insbesondere im wesentlichen 16 bis 20 Kohlenstoffatomen und wenigstens einem quartären Stickstoffatom im Molekül. Die langkettigen aliphatischen Reste können geradkettig oder verzweigt sein und dementsprechend von Fettsäuren, bzw. von Fettaminen, Guerbetaminen oder aus den Reduktion von Nitroparaffinen erhältlichen Alkylaminen abstammen. Bei diesen quartären Ammoniumverbindungen handelt es sich insbesondere um Derivate des Ammoniaks, d.h. um die durch Alkylierung von langkettigen sekundären Aminen erhältlichen quartären Salze, wie z.B. die Verbindungen Distearyldimethylammoniumchlorid bzw. Ditalgalkyldimethylamminiumchlorid oder -methosulfat. Andere geeignete quartäre Ammoniumverbindungen sind die durch Umsetzung von 1 Mol eines Aminoalkylethylendiamins oder Hydroxyalkylethylendiamin mit 2 Mol einer langkettigen C,2-bis C26-Fettsäkure oder der Ester erhältlichen Imidazolinverbindungen, die anschließend durch Alkylierung in die quartären Imidazolidiumverbindungen übergeführt werden. In allen diesen quartären Ammoniumverbindungen besteht das Anion im allgemeinen aus dem Säurerest, der aus dem bei der Quarternierung verwendeten Alkylierungsmittel entstanden ist. Beispielsweise kommt als Anion daher wie auch bei den wasserlöslichen quartären Ammoniumverbindungen Chlorid, Bromid, Methylsulfat, Ethylsulfat, Methan-, Ethan oder Toluolsulfonat in Betracht. Beispiele für geeignete wasserlösliche quartäre Ammoniumverbindungen sind Dioctyldimethylammoniumchlorid, Octyldodecyldimethylammoniumchlorid, Hexadecyltrimethylammoniumchlorid oder -bromid, Methylditalgalkylhydroxypropylammoniumchlorid, Talgalkyltrimethylammoniumchlorid, Octadecyldimethylammoniumhydrogensulfat. Die Alkylgruppe des ebenfalls als wasserlösliche kationische Verbindung einsetzbaren Alkylpyrridiniumsalze enthält 10 bis 18, insbesonder 12 bis 16 Kohlenstoffatome in der Alkylgruppe. Geeignete Anionen sind beispielsweise das Chlorid- oder das Hydrogensulfatanion.Suitable water-insoluble quaternary ammonium compounds are the compounds known as textile plasticizers of the quaternary type derived from ammonia or imidazoline. These are primarily compounds with two long-chain, preferably saturated aliphatic radicals each having 14 to 26, in particular essentially 16 to 20, carbon atoms and at least one quaternary nitrogen atom in the molecule. The long-chain aliphatic radicals can be straight-chain or branched and can accordingly be derived from fatty acids or from fatty amines, Guerbetamines or from alkylamines obtainable from the reduction of nitroparaffins. These quaternary ammonium compounds are, in particular, derivatives of ammonia, ie the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for example, the compounds distearyldimethylammonium chloride or ditalgalkyldimethylamminium chloride or methosulfate. Other suitable quaternary ammonium compounds are obtained by reacting 1 mol of a Aminoalkylethylendiamins Hydroxyalkylethylendiamin or with 2 moles of a long-chain C 2 to C 26 -Fettsäkure or ester imidazoline compounds available, which are then converted by alkylation into the quaternary Imidazolidiumverbindungen. In all of these quaternary ammonium compounds, the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization. For example, chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are therefore suitable as anions, as is the case with the water-soluble quaternary ammonium compounds. Examples of suitable water-soluble quaternary ammonium compounds are dioctyldimethylammonium chloride, octyldodecyldimethylammonium chloride, hexadecyltrimethylammonium chloride or bromide, methylditalgalkylhydroxypropylammonium chloride, tallow alkyltrimethylammonium chloride, octadecyldimethylammonium hydrogen sulfate. The alkyl group of the alkylpyrridinium salt, which can also be used as a water-soluble cationic compound, contains 10 to 18, in particular 12 to 16, carbon atoms in the alkyl group. Suitable anions are, for example, the chloride or hydrogen sulfate anion.

Der Polymerbestandteil auf Basis von N-Vinylpyrrolidon kann ein Homopolymer aus N-Vinylpyrrolidon oder ein Copolymer von N-Vinylpyrrolidon mit einem Molgewicht im Bereich von etwa 10.000 bis etwa 1.000.000 sein. Besonders geeignete Homopolymere haben ein Molgewicht von etwa 15.000 bis etwa 700.000. In Copolymeren, die für die erfindungsgemäßen Waschmittelzusätze geeignet sind, beträgt der Anteil an N-Vinylpyrrolidon wenigstens etwa 50 % des Copolymeren. Geeignete Comonomere sind beispielsweise Acrylnitril und Maleinsäureanhydrid. Das bevorzugte Molgewicht von geeignetem Copolymeren liegt im Bereich von etwa 20.000 bis etwa 200.000. Die für den Polymerbestandteil auf Basis von N-Vinylpyrrolidon gemachten Angaben gelten sinngemäß auch für Polymerbestandteile auf Basis von N-Vinylimidazol und N-Vinyloxazolidon.The polymer component based on N-vinylpyrrolidone can be a homopolymer of N-vinylpyrrolidone or a copolymer of N-vinylpyrrolidone with a molecular weight in the range from about 10,000 to about 1,000,000. Particularly suitable homopolymers have a molecular weight of approximately 15,000 to approximately 700,000. In copolymers which are suitable for the detergent additives according to the invention, the proportion of N-vinylpyrrolidone is at least about 50% of the copolymer. Suitable comonomers are, for example, acrylonitrile and maleic anhydride. The preferred molecular weight of suitable copolymers is in the range of about 20,000 to about 200,000. The for the polymer component based on N- The information given for vinylpyrrolidone also applies analogously to polymer components based on N-vinylimidazole and N-vinyloxazolidone.

In besonders bevorzugten Waschmittelzusätzen liegt der wasserlösliche Polymerbestandteil auf Basis von Polyvinylpyrrolidon in großem Überschuß gegenüber der kationischen Verbindung vor; Waschmittelzusätze mit einem wasserlöslichen Polymerbestandteil auf Basis von Polyvinylpyrrolidon und kationischen Verbindungen in einem Gewichtsverhältnis von 10 : 1 bis 50 : 1, insbesondere im Gewichtsverhältnis von 30 : 1 bis 40 : 1 sind besonders bevorzugt.In particularly preferred detergent additives, the water-soluble polymer component based on polyvinylpyrrolidone is present in a large excess over the cationic compound; Detergent additives with a water-soluble polymer component based on polyvinylpyrrolidone and cationic compounds in a weight ratio of 10: 1 to 50: 1, in particular in a weight ratio of 30: 1 to 40: 1, are particularly preferred.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines Waschmittelszusatzes, wie er zuvor beschrieben wurde. Dieses Verfahren umfaßt, daß man ein Gemisch des wasserlösichen Polymerbestandteils auf Basis von Polyvinylpyrrolidon und der kationischen Verbindung sowie ggf. des Zinksalzes der Ricinolsäure unter Zusatz von Wasser in einem Mischaggregat innig vermischt, wobei sich vorzugsweise ein Granulat ausbildet, anschließend das erhaltene Gemisch mit ggf. erhitzter Luft zu einem rieselfähigen Produkt trocknet, das man ggf. in der Wirbelschicht mit einer Lösung des Säuregruppen enthaltenden Polymerbestandteils durch Aufsprühen versetzt und ggf. erneut mit ggf. erhitzter Luft trocknet. Durch geeignete Einstellung der Misch-bzw. Granulierbedingungen kann man erreichen, daß der Waschmittelzusatz gemäß der vorliegenden Erfindung eine Teilchengrößenverteilung aufweist, die in etwa der Teilchengrößenverteilung des Waschmittels entspricht, dem der Waschmittelzusatz zugesetzt werden soll. Das Mischaggregat, das zur Mischung der verfärbungsinhibierenden Wirkstoffe und ggf. der geruchsverbessernden Zusatzstoffe verwendet wird, ist beispielsweise ein Wirbelschichtmischer oder vorzugsweise ein Mischgranulator, in dem sich die Bildung des ggf. teilchenförmigen Waschmittelzusatzes gemäß der Erfindung vollzieht. Verwendet man als geruchsverbessernden Zusatz eine Säuregruppen enthaltenden Polymerbestandteil, und setzt diesen in Form einer wäßrigen Lösung den erfindungsgemäßen Waschmittelzusatz zu, ist es zweckmäßig, daß man das im Waschmittelzusatz enthaltende Wasser nach dem Mischen im Mischaggregat und/oder nach dem Aufsprühen der Lösung des Säuregruppen enthaltenden Polymerbestandteils durch Einblasen von ggf. bis auf 80 °C erhitzter Luft bis auf einen Restwassergehalt von maximal 15 Gew.-%, bezogen auf den Waschmittelzusatz, entfernt.Another object of the present invention is a method for producing a detergent additive, as described above. This process comprises intimately mixing a mixture of the water-soluble polymer constituent based on polyvinylpyrrolidone and the cationic compound and, if appropriate, the zinc salt of ricinoleic acid with the addition of water in a mixing unit, preferably granules being formed, then the resulting mixture with optionally heated air dries to a free-flowing product, which is optionally mixed in the fluidized bed with a solution of the acid component-containing polymer component by spraying and, if necessary, dried again with heated air if necessary. By suitable adjustment of the mixing or. Granulation conditions can be achieved that the detergent additive according to the present invention has a particle size distribution which corresponds approximately to the particle size distribution of the detergent to which the detergent additive is to be added. The mixing unit which is used to mix the discoloration-inhibiting active ingredients and, if appropriate, the odor-improving additives is, for example, a fluidized bed mixer or preferably a mixing granulator in which the formation of the optional particulate detergent additive according to the invention takes place. If a polymer component containing acid groups is used as an odor-improving additive, and the detergent additive according to the invention is added to it in the form of an aqueous solution, it is expedient that the water contained in the detergent additive is mixed after mixing in the mixing unit and / or after spraying on the solution containing the acid groups Polymer component removed by blowing in air possibly heated up to 80 ° C to a residual water content of at most 15 wt .-%, based on the detergent additive.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Waschmittel, das einen erfindungsgemäßen Waschmittelzusatz enthält. Waschmittel, die hinsichtlich ihrer verfärbungsinhibierenden Wirkung and ihrer Freiheit von störenden Gerüchen optimale Eigenschaften haben, enthalten vorzugsweise 0,5 bis 10, insbesondere 1. bis 5 Gew.-% der oben beschriebenen Waschmittelzusätze. Derartige Waschmittel weisen nicht nur ausgezeichnete verfärbungsinhibierende Wirkungen auf, sondern sie lassen sich auch mit üblichen Duftstoffen einer gewünschten Duftrichtung parfümieren.Another object of the present invention is a detergent which contains a detergent additive according to the invention. Detergents which have optimal properties with regard to their discoloration-inhibiting action and their freedom from unpleasant odors preferably contain 0.5 to 10, in particular 1 to 5% by weight of the detergent additives described above. Such detergents not only have excellent discoloration-inhibiting effects, but they can also be perfumed with customary fragrances of a desired fragrance.

BeispieleExamples Beispiel 1example 1

In einem 130 I - Pflugscharmischer (Fa. Lödige, Paderbon, Bundesrepublik Deutschland) wurden 24,95 kg Polyvinylpyrrolidon, Molgewicht ca. 40 000, und 1,45 kg Methyl-i-talgalkylamidoethyl-2-talgalkylimidazo- liniummethosulfat auf Trägerkieselsäure (65 Gew.-% Imidazoliniumverbindung, 28 Gew.-% Kieselsäure, 7 Gew.-% nichtionisches Tensid, "Rewoquat 1806"(R) Fa. Rewo, Steinau, Bundesrepublik Deutschland) 5 Minuten lang bei laufendem Mischer und Messerkränzen homogenisiert. Anschließend wurden bei weiter laufendem Mischer 4,67 kg Wasser aufgesprüht. Das resultierende feinteilige feuchte Granulat wurde dann in der Wirbelschicht mit 70 ° C heißer Luft auf einen Wassergehalt von ca. 8 Gew.-% getrocknet.In a 130 l ploughshare mixer (Lödige, Paderbon, Federal Republic of Germany), 24.95 kg of polyvinylpyrrolidone, molecular weight approx. 40,000, and 1.45 kg of methyl i-tallow alkylamidoethyl-2-tallow alkyl imidazoline methosulfate on supported silica (65 wt % Imidazolinium compound, 28% by weight silica, 7% by weight nonionic surfactant, "Rewoquat 1806" (R) from Rewo, Steinau, Federal Republic of Germany) homogenized for 5 minutes with the mixer and knife rings running. Then 4.67 kg of water were sprayed on while the mixer was still running. The resulting finely divided moist granules were then dried in the fluidized bed with hot air at 70 ° C. to a water content of approximately 8% by weight.

Anschließend wurde das trockene Granulat in der Wirbelschicht innerhalb von 18 Minuten bei einer Lufttemperatur von 70 °C mit soviel eine wäßrigen, 20 gew.-%igen Lösung einer niedermolekularen Polyacrylsäure ("Schlichte S"(R), Fa. BASF, Ludwigshafen, Bundesrepublik Deutschland) besprüht, daß das Granulat ca. 3 Gew.-% Polyarcylsäure enthielt. Der so erhaltene erfindungsgemäße Waschmittelzusatz wog 440 g pro I und enthielt ca. 12 Gew.-% Wasser.The dry granules in the fluidized bed were then mixed with an aqueous 20% by weight solution of a low molecular weight polyacrylic acid ("Schlichte S " (R) , from BASF, Ludwigshafen, Federal Republic of Germany ) within 18 minutes at an air temperature of 70 ° C. Germany) sprayed that the granules contained about 3 wt .-% polyacrylic acid. The detergent additive according to the invention thus obtained weighed 440 g per liter and contained about 12% by weight of water.

Beispiel 2Example 2

In einem Wirbelschichtmischer wurde ein Gemisch aus 63,4 Gew.-% des Polyvinylpyrrolidons aus Beispiel 1, 3,73 Gew.-% des Imidazoliniumsalz/Kieselsäure/nichtionisches Tensid-Gemisches von Beispiel 1 und 32,8 Gew.-% Wasser bei 70 C innerhalb von 10 Minuten granuliert. Das ca. 9,3 Gew.-% Wasser enthaltende Granulat wurde dann mit 2 Gew.-% Polyacrylsäure (als 20 gew.-%ige Lösung) wie in Beispiel 1 besprüht.A mixture of 63.4% by weight of the polyvinylpyrrolidone from Example 1, 3.73% by weight of the imidazolinium salt / silica / nonionic surfactant mixture from Example 1 was mixed in a fluidized bed mixer and 32.8% by weight of water at 70 ° C. in the course of 10 minutes. The granules containing about 9.3% by weight of water were then sprayed with 2% by weight of polyacrylic acid (as a 20% by weight solution) as in Example 1.

Beispiel 3Example 3

In einem Wirbelmischer wurde bei 20 ° C innerhalb von 60 Minuten ein Gemisch aus 61,28 Gew.-% des Polyvinylpyrrolidons aus Beispiel 1, 3,60 Gew.-% des Imidazoliniumsalz/Kieselsäure/nichtionisches Tensid-Gemisches von Beispiel 1, 0,92 Gew.-% eines Zinricinoleats mit geringen Anteilen Talkum ("Grillocin P 176"(R), Fa. Grillo, Duisburg, Bundesrepublick Deutschland) und 34,2 Gew.-% Wasser granuliert. Anschließend wurde auf einen Wassergehalt von 3,7 Gew.-% getrocknet und mit 2 Gew.-% Polyacrylsäure, wie in den Beispielen 1 und 2 beschrieben, besprüht.A mixture of 61.28% by weight of the polyvinylpyrrolidone from Example 1, 3.60% by weight of the imidazolinium salt / silica / nonionic surfactant mixture from Example 1, 0 was mixed in a vortex mixer at 20 ° C. within 60 minutes. 92% by weight of a zinricinoleate with small proportions of talc ("Grillocin P 176" ( R ), from Grillo, Duisburg, Federal Republic of Germany) and 34.2% by weight of water granulated. The mixture was then dried to a water content of 3.7% by weight and sprayed with 2% by weight of polyacrylic acid, as described in Examples 1 and 2.

Beispiel 4Example 4

Versetzte man pulverförmige Waschmittel mit einem Gehalt an 20 bis 50 Gew.-% alkalischen Builderbestandteilen mit 0,5 bis 8,5 Gew.-% der Produckte aus den Beispielen 1 bis 3, stellte man auch nach längerer Lagerung auch bei erhöhter Temperatur keine Bildung unangenehmer Gerüche fest. Das gleiche gilt für die Lagerung der erfindungsgemäßen Waschzusätze selbst. Ähnliche Ergebnisse erhielt man, wenn man als kationische Verbindung wasserunlösliches Distearyldimethylammoniumchlorid, wasserlösliches C14-Alkylpyridiniumchlorid oder wasserlösliches Cetyltrimethylammoniumbromid einsetzte.If powdery detergents containing 20 to 50% by weight of alkaline builder constituents were mixed with 0.5 to 8.5% by weight of the products from Examples 1 to 3, no formation was formed even after prolonged storage, even at elevated temperature unpleasant smells. The same applies to the storage of the washing additives according to the invention itself. Similar results were obtained if water-insoluble distearyldimethylammonium chloride, water-soluble C 14 -alkylpyridinium chloride or water-soluble cetyltrimethylammonium bromide was used as the cationic compound.

VergleichsbeispielComparative example

Setzte man den Waschmitteln von Beispiel 4 mengengleich Polyvinylpyrrolidon und kationische Verbindungen ohne die erfindungsgemäßen Aufbereitungsmaßnahmen zu, bildeten sich bei Lagerung nach kurzer Zeit unangenehme Gerüche, die man als "dumpf" und "aminisch" bezeichnen kann aus. Die verfärbungsinhibierende. Wirkung der Waschmittels von Beispiel 4 und des Vergleichsbeispiels war vergleichbar gut.If polyvinylpyrrolidone and cationic compounds were added to the detergents of Example 4 in equal quantities without the preparation measures according to the invention, unpleasant odors formed after storage, which can be described as "dull" and "aminic". The discoloration-inhibiting. Effect of the detergents from Example 4 and the comparative example was comparably good.

Hinsichtlich der Geruchsverbesserung vergleichbare Ergebnisse erhielt man, wenn man statt Polyvinylpyrrolidon Polymerbestandteile auf Basis von N-Vinylimidazol und N-Vinyloxazolidon einsetzte. Die Waschkraft aller Waschmittel wies keine signifikanten Unterschiede auf.Comparable results regarding the improvement in odor were obtained if, instead of polyvinylpyrrolidone, polymer components based on N-vinylimidazole and N-vinyloxazolidone were used. The washing power of all detergents showed no significant differences.

Claims (12)

1. Waschmittelzusatz, gekennzeichnet durch einen Gehalt an wenigstens teilsweise wasserlöslichen Polymerbestandteilen auf Basis von N-Vinylpyrrolidon und/öder N-Vinylimidazol und/oder N-Vinyloxazolidon und/oder wasserlöslichen und/ oder wasserunlöslichen kationischen Verbindungen.1. Detergent additive, characterized by a content of at least partially water-soluble polymer components based on N-vinylpyrrolidone and / or N-vinylimidazole and / or N-vinyloxazolidone and / or water-soluble and / or water-insoluble cationic compounds. 2. Waschmittelzusatz nach Anspruch 1, dadurch gekennzeichnet, daß er teilchenförmig, vorzugsweise als Granulat, vorliegt.2. Detergent additive according to claim 1, characterized in that it is in particulate form, preferably in the form of granules. 3. Waschmittelzusatz nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß er zusätzlich einen Säuregruppen enthaltenden Polymerbestandteil enthält.3. Detergent additive according to one of claims 1 or 2, characterized in that it additionally contains a polymer component containing acid groups. 4. Waschmittelzusatz nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Säuregruppen enthaltende Polymerbestandteil an der Oberfläche des teilchenförmigen Waschmittelzusatzes angereichert vorliegt, vorzugsweise die Oberfläche wenigstens teilweise bedeckt.4. Detergent additive according to one of claims 1 to 3, characterized in that the polymer component containing acid groups is present enriched on the surface of the particulate detergent additive, preferably at least partially covering the surface. 5. Waschmittelzusatz nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Säuregruppen enthaltende Polymerbestandteil Polyacrylsäure oder ein Polyacrylsäure enthaltendes Co-Polymerisat ist.5. Detergent additive according to one of claims 1 to 4, characterized in that the acid component-containing polymer component is polyacrylic acid or a copolymer containing polyacrylic acid. 6. Waschmittelzusatz nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß er 1 bis 10, vorzugsweise 2 bis 5 Gew.-%, des Säuregruppen enthaltenden Polymerbestandteils enthält.6. Detergent additive according to any one of claims 1 to 5, characterized in that it contains 1 to 10, preferably 2 to 5 wt .-%, of the acid component-containing polymer component. 7. Waschmittelzusatz nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß er zusätzlich ein Zinksalz der Ricinolsäure enthält.7. Detergent additive according to one of claims 1 to 6, characterized in that it additionally contains a zinc salt of ricinoleic acid. 8. Waschmittelzusatz nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß er (i) den wasserlöslichen Polymerbestandteil auf Basis von N-Vinylpyrrolidon und (ii) die kationische Verbindung in einem Gew.-Verhältnis von (i) : (ii) = 10 : 1 bis 50 : 1, vorzugsweise von 30 : 1 bis 40 : 1 enthält. 8. detergent additive according to any one of claims 1 to 7, characterized in that it (i) the water-soluble polymer component based on N-vinylpyrrolidone and (ii) the cationic compound in a weight ratio of (i): (ii) = 10: 1 to 50: 1, preferably from 30: 1 to 40: 1. 9. Verfahren zur Herstellung eines Waschmittelzusatzes nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man ein Gemisch des wasserlöslichen Polymerbestandteils auf Basis von N-Vinylpyrrolidon und der kationischen Verbindung sowie ggf. des Zinksalzes der Ricinolsäure unter Zusatz von Wasser in einem Mischaggregat innig vermischt, wobei sich vorzugsweise ein Granulat ausbildet, das erhaltene Gemisch mit ggf. erhitzter Luft zu einem rieselfähigen Produkt trocknet, das man ggf. in der Wirbelschicht mit einer Lösung des Säuregruppen enthaltenden Polymerbestandteils durch Aufsprühen versetzt und ggf. erneut mit ggf. erhitzter Luft trocknet.9. A process for the preparation of a detergent additive according to any one of claims 1 to 8, characterized in that a mixture of the water-soluble polymer component based on N-vinylpyrrolidone and the cationic compound and optionally the zinc salt of ricinoleic acid with the addition of water intimately in a mixing unit mixed, wherein preferably a granulate forms, the mixture obtained with optionally heated air dries to a free-flowing product, which is optionally mixed in the fluidized bed with a solution of the polymer component containing acid groups by spraying and optionally dried again with optionally heated air . 10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man als Mischaggregat einem Wirbelschicht-Mischer oder vorzugsweise einen Mischgranulator verwendet.10. The method according to claim 9, characterized in that a fluidized bed mixer or preferably a mixing granulator is used as the mixing unit. 11. Verfahren nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, daß man das im Waschmittelzusatz enthaltene Wasser nach dem Mischen im Mischaggregat und/oder nach dem ggf. er folgten Aufsprühen der Lösung des Säurengruppen enthaltenden Polymerbestandteils durch Einblasen von ggf. bis auf 80 ° C erhitzter Luft bis auf einen Restwassergehalt von maximal 15 Gew.-% entfernt.11. The method according to any one of claims 9 or 10, characterized in that the water contained in the detergent additive after mixing in the mixing unit and / or after optionally spraying it on the solution of the acid group-containing polymer component by blowing in, possibly up to 80 ° C of heated air removed to a residual water content of maximum 15 wt .-%. 12. Waschmittel, gekennzeichnet durch einen Zusatz nach einem der Ansprüche 1 bis 8, vorzugsweise in Mengen von 0,5 bis 10, insbesondere in Mengen von 1 bis 5 Gew.-%.12. Detergent, characterized by an additive according to one of claims 1 to 8, preferably in amounts of 0.5 to 10, in particular in amounts of 1 to 5% by weight.
EP19890101618 1988-02-06 1989-01-31 Detergent additive Withdrawn EP0327927A3 (en)

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TR28338A (en) * 1992-07-15 1996-04-25 Procter & Gamble Compositions containing surfactant, which inhibit dye transfer.
US5604197A (en) * 1993-07-22 1997-02-18 The Procter & Gamble Company Softening through the wash compositions
US5633225A (en) * 1992-07-15 1997-05-27 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
EP0779358A2 (en) 1995-12-16 1997-06-18 Unilever Plc Detergent composition
EP0800570A1 (en) * 1994-12-29 1997-10-15 The Procter & Gamble Company Laundry detergent composition comprising substantially water-insoluble polymeric dye transfer inhibiting agent
US5710118A (en) * 1993-07-23 1998-01-20 The Procter & Gamble Company Detergent compostions inhibiting dye transfer comprising copolymers of n-vinylimidazole and n-vinylpyrrolidone
US5710119A (en) * 1993-07-23 1998-01-20 The Procter & Gamble Company Detergent compositions inhibiting dye transfer comprising copolymers of N-vinylimidazole and N-vinylpyrrolidone
WO1998028397A1 (en) * 1996-12-20 1998-07-02 The Procter & Gamble Company A process for making a free-flowing particulate dye transfer inhibiting detergent admix
US5776878A (en) * 1994-01-13 1998-07-07 The Procter & Gamble Company Liquid detergent compositions containing brighteners and polymers for preventing fabric spotting
CN1040656C (en) * 1992-07-15 1998-11-11 普罗格特-甘布尔公司 Surfactant-containing dye transfer inhibiting compositions
US6121223A (en) * 1997-04-30 2000-09-19 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition comprising dye transfer inhibiting polymer and water soluble sunscreen
US6191098B1 (en) 1999-04-28 2001-02-20 National Starch And Chemical Investment Holding Corporation Polyvinylpyridinium derivatives as anti-dye transfer agents
US6228783B1 (en) 1998-12-31 2001-05-08 National Starch And Chemical Investment Holding Corporation Laundry article which attracts soil and dyes
EP0668902B2 (en) † 1992-11-16 2001-06-13 The Procter & Gamble Company Fabric softening compositions with dye transfer inhibitors for improved fabric appearance
US6306815B1 (en) 1999-09-10 2001-10-23 National Starch And Chemical Investment Holding Corporation Quaternary polyvinylpyrridinium derivatives as anti-dye transfer agents
US6528047B2 (en) 2001-04-18 2003-03-04 Goldschmidt Chemical Corporation Odor absorption and deodorization
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
US7125835B2 (en) 2002-10-10 2006-10-24 International Flavors & Fragrances Inc Encapsulated fragrance chemicals
USRE39450E1 (en) * 1999-04-28 2006-12-26 National Starch And Chemical Investment Holding Co Polyvinylpyrridinium derivatives as anti-dye transfer agents
EP1935483A2 (en) 2006-12-15 2008-06-25 International Flavors & Fragrances, Inc. Encapsulated active material containing nanoscaled material
US7585824B2 (en) 2002-10-10 2009-09-08 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
EP2545988A2 (en) 2005-12-15 2013-01-16 International Flavors & Fragrances, Inc. Encapsulated active material with reduced formaldehyde potential
EP3210666A1 (en) 2005-12-15 2017-08-30 International Flavors & Fragrances Inc. Process for preparing a high stability microcapsule product and method for using same
CN110684144A (en) * 2019-10-28 2020-01-14 浙江理工大学上虞工业技术研究院有限公司 Preparation method of anti-staining soaping agent

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EP0538228A1 (en) * 1991-10-14 1993-04-21 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
TR26870A (en) * 1991-10-14 1994-08-22 Procter & Gamble Detergent compositions to prevent dye transfer during washing
EP0587550A1 (en) * 1992-07-15 1994-03-16 The Procter & Gamble Company Surfactant containing dye transfer inhibiting compositions
CN1040656C (en) * 1992-07-15 1998-11-11 普罗格特-甘布尔公司 Surfactant-containing dye transfer inhibiting compositions
WO1994002580A1 (en) * 1992-07-15 1994-02-03 The Procter & Gamble Company Surfactant-containing dye transfer inhibiting compositions
WO1994002581A1 (en) * 1992-07-15 1994-02-03 The Procter & Gamble Company Dye transfer inhibiting compositions comprising bleaching agents
WO1994002576A1 (en) * 1992-07-15 1994-02-03 The Procter & Gamble Company Built dye transfer inhibiting compositions
WO1994002579A1 (en) * 1992-07-15 1994-02-03 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
TR28338A (en) * 1992-07-15 1996-04-25 Procter & Gamble Compositions containing surfactant, which inhibit dye transfer.
EP0587549A1 (en) * 1992-07-15 1994-03-16 The Procter & Gamble Company Dye transfer inhibiting compositions comprising bleaching agents
US5478489A (en) * 1992-07-15 1995-12-26 The Procter & Gamble Company Dye transfer inhibiting compositions comprising bleaching agents and a polyamine N-oxide polymer
TR28340A (en) * 1992-07-15 1996-05-02 Procter & Gamble Paint transfer preventive compositions containing bleaching agents.
EP0581752A1 (en) * 1992-07-15 1994-02-02 The Procter & Gamble Company Built dye transfer inhibiting compositions
EP0579295A1 (en) * 1992-07-15 1994-01-19 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
US5633225A (en) * 1992-07-15 1997-05-27 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
WO1994003567A2 (en) * 1992-08-03 1994-02-17 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrrolidone
CN1039028C (en) * 1992-08-03 1998-07-08 普罗格特-甘布尔公司 Particulate laundry detergent compositions with polyvinyl pyrrolidone
WO1994003567A3 (en) * 1992-08-03 1994-06-23 Procter & Gamble Particulate laundry detergent compositions with polyvinyl pyrrolidone
EP0584736A1 (en) * 1992-08-25 1994-03-02 Hoechst Aktiengesellschaft Use of polyvinyl alcohols as detergent additive
EP0668902B2 (en) † 1992-11-16 2001-06-13 The Procter & Gamble Company Fabric softening compositions with dye transfer inhibitors for improved fabric appearance
WO1994013775A1 (en) * 1992-12-16 1994-06-23 Henkel Kommanditgesellschaft Auf Aktien Method of producing washing agents in powder form
EP0692947A4 (en) * 1993-04-09 1996-03-13 Procter & Gamble Machine dishwashing method employing a metallo catalyst and enzymatic source of hydrogen peroxide
EP0692947A1 (en) * 1993-04-09 1996-01-24 The Procter & Gamble Company Machine dishwashing method employing a metallo catalyst and enzymatic source of hydrogen peroxide
WO1995003387A1 (en) * 1993-07-22 1995-02-02 The Procter & Gamble Company Softening through the wash compositions
US5604197A (en) * 1993-07-22 1997-02-18 The Procter & Gamble Company Softening through the wash compositions
US5710118A (en) * 1993-07-23 1998-01-20 The Procter & Gamble Company Detergent compostions inhibiting dye transfer comprising copolymers of n-vinylimidazole and n-vinylpyrrolidone
US5710119A (en) * 1993-07-23 1998-01-20 The Procter & Gamble Company Detergent compositions inhibiting dye transfer comprising copolymers of N-vinylimidazole and N-vinylpyrrolidone
WO1995003382A1 (en) * 1993-07-23 1995-02-02 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
WO1995003388A1 (en) * 1993-07-23 1995-02-02 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
US5451341A (en) * 1993-09-10 1995-09-19 The Procter & Gamble Company Soil release polymer in detergent compositions containing dye transfer inhibiting agents to improve cleaning performance
US5776878A (en) * 1994-01-13 1998-07-07 The Procter & Gamble Company Liquid detergent compositions containing brighteners and polymers for preventing fabric spotting
WO1995028462A1 (en) * 1994-04-14 1995-10-26 The Procter & Gamble Company Detergent compositions comprising dye transfer inhibitors, and process for making them
WO1995033026A1 (en) * 1994-06-01 1995-12-07 The Procter & Gamble Company Dye transfer inhibiting compositions containing oleoyl sarcosinate
WO1996010621A1 (en) * 1994-09-30 1996-04-11 The Procter & Gamble Company Dye transfer inhibiting compositions containing betaines
EP0800570A1 (en) * 1994-12-29 1997-10-15 The Procter & Gamble Company Laundry detergent composition comprising substantially water-insoluble polymeric dye transfer inhibiting agent
EP0800570A4 (en) * 1994-12-29 1998-01-28 Procter & Gamble Laundry detergent composition comprising substantially water-insoluble polymeric dye transfer inhibiting agent
US5872093A (en) * 1995-12-16 1999-02-16 Lever Brothers Company, Division Of Conopco, Inc. Detergent compostion
EP0779358A2 (en) 1995-12-16 1997-06-18 Unilever Plc Detergent composition
US6133224A (en) * 1996-12-20 2000-10-17 The Procter & Gamble Company Process for making a free-flowing particulate dye transfer inhibiting detergent admix
WO1998028397A1 (en) * 1996-12-20 1998-07-02 The Procter & Gamble Company A process for making a free-flowing particulate dye transfer inhibiting detergent admix
US6121223A (en) * 1997-04-30 2000-09-19 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition comprising dye transfer inhibiting polymer and water soluble sunscreen
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
US6228783B1 (en) 1998-12-31 2001-05-08 National Starch And Chemical Investment Holding Corporation Laundry article which attracts soil and dyes
US6191098B1 (en) 1999-04-28 2001-02-20 National Starch And Chemical Investment Holding Corporation Polyvinylpyridinium derivatives as anti-dye transfer agents
USRE39450E1 (en) * 1999-04-28 2006-12-26 National Starch And Chemical Investment Holding Co Polyvinylpyrridinium derivatives as anti-dye transfer agents
US6306815B1 (en) 1999-09-10 2001-10-23 National Starch And Chemical Investment Holding Corporation Quaternary polyvinylpyrridinium derivatives as anti-dye transfer agents
US6528047B2 (en) 2001-04-18 2003-03-04 Goldschmidt Chemical Corporation Odor absorption and deodorization
US7125835B2 (en) 2002-10-10 2006-10-24 International Flavors & Fragrances Inc Encapsulated fragrance chemicals
US7196049B2 (en) 2002-10-10 2007-03-27 International Flavors & Fragrances, Inc Encapsulated fragrance chemicals
US7585824B2 (en) 2002-10-10 2009-09-08 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
EP2545988A2 (en) 2005-12-15 2013-01-16 International Flavors & Fragrances, Inc. Encapsulated active material with reduced formaldehyde potential
EP3210666A1 (en) 2005-12-15 2017-08-30 International Flavors & Fragrances Inc. Process for preparing a high stability microcapsule product and method for using same
EP1935483A2 (en) 2006-12-15 2008-06-25 International Flavors & Fragrances, Inc. Encapsulated active material containing nanoscaled material
CN110684144A (en) * 2019-10-28 2020-01-14 浙江理工大学上虞工业技术研究院有限公司 Preparation method of anti-staining soaping agent

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DK48989D0 (en) 1989-02-02
DK48989A (en) 1989-08-07
EP0327927A3 (en) 1990-09-19

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