EP0601967B1 - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

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Publication number
EP0601967B1
EP0601967B1 EP93810772A EP93810772A EP0601967B1 EP 0601967 B1 EP0601967 B1 EP 0601967B1 EP 93810772 A EP93810772 A EP 93810772A EP 93810772 A EP93810772 A EP 93810772A EP 0601967 B1 EP0601967 B1 EP 0601967B1
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EP
European Patent Office
Prior art keywords
detergent composition
hydrogen
liquid detergent
composition according
formula
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EP93810772A
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German (de)
French (fr)
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EP0601967A1 (en
Inventor
Claude Dr. Eckhardt
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • 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
    • D06L4/65—Optical bleaching or brightening with mixtures of optical 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
    • D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing

Definitions

  • the present invention relates to new, highly concentrated, aqueous and liquid detergents containing targeted disulfonated dibenzfuranylbiphenyls as optical brighteners, their preparation and their use.
  • optical brighteners in liquid detergents is known. They soak on the items to be washed during treatment and, due to their special light absorption / emission properties, lead to an elimination of the yellowish tones or an improvement in the degree of whiteness.
  • EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.
  • EP-A-394 998 e.g. Liquid detergent with a content of 25 to 65 wt.% Water known.
  • EP-A-364 027 e.g. aqueous, peracid-containing liquid detergents described, which contain optical brighteners that are stable to the peracid.
  • halogens are fluorine, chlorine and bromine, but especially chlorine.
  • C 1 -C 4 alkyl radicals come straight or branched alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, butyl and t-butyl-n into consideration as C 1 -C 4 -alkoxy come straight or branched alkoxy groups such as methoxy , Ethoxy, n-propoxy, iso-propoxy, n-butoxy and t-butoxy.
  • alkyl (or alkoxy) radicals can in turn be substituted with, for example, aryl (phenyl or naphthyl), C 1 -C 4 alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl) or t-butyl), C 1 -C 4 alkoxy (methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy or t-butoxy), OH or CN groups.
  • aryl phenyl or naphthyl
  • C 1 -C 4 alkyl methyl, ethyl, n-propyl, isopropyl, n-butyl
  • C 1 -C 4 alkoxy methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy or t-butoxy
  • OH or CN groups OH or CN groups.
  • M in the meaning of a non-chromophoric cation preferably represents alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanolammonium, mono-, di- or tripropanolammonium or tri- or tetramethylammonium.
  • alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanolammonium, mono-, di- or tripropanolammonium or tri- or tetramethylammonium.
  • Sodium, potassium and ammonium are particularly preferred.
  • Liquid detergents are known and commercially available detergents, as are described, for example, in EP-A-167 205 or US-4 507 219 or EP-A-293 040.
  • Anionic, nonionic, cationic or zwitterionic surfactants can be used as surfactants.
  • Useful surfactants are e.g. in U.S. 4,285,841, U.S. 3,929,678, U.S. 4,284,532 and GB 2,041,986.
  • the surfactants designated as preferred in EP-A-167 205 are used.
  • Nonionic surfactants are, for example, polyhydroxy fatty acid amides, as described in WO 92/06172, and alkylphenols. Furthermore, there are also alkyl polyglucosides of C 9 -C 15 -alkylene with 1-10 glucoside units such as, for example, nonylglucoside and allyl (C 12 -C 15 ) -poly (1-10) -glucoside, sorbine esters such as, for example, polyoxyethylene sorbitan monopalmitate, fatty acid ethanolamides such as, for example, coconut fatty acid diethanolamide and fatty acid ethanolamine such as tetradecylamine oxide in question.
  • alkyl polyglucosides of C 9 -C 15 -alkylene with 1-10 glucoside units such as, for example, nonylglucoside and allyl (C 12 -C 15 ) -poly (1-10) -glucoside
  • sorbine esters such as, for example, poly
  • Detergent builders or polymers include e.g. the preferably polycarboxylated compounds mentioned in U.S. 4,321,165 and U.S. 4,284,532 such as citric acid or maleic acid / acrylic acid copolymers, as well as e.g. the lignin sulfonates, formaldehyde addition products, polyethylene glycols, polyvinylpyrolidones, polyvinylimidazoles, and Al / Mg silicates.
  • the lignin sulfonates e.g. the preferably polycarboxylated compounds mentioned in U.S. 4,321,165 and U.S. 4,284,532 such as citric acid or maleic acid / acrylic acid copolymers, as well as e.g. the lignin sulfonates, formaldehyde addition products, polyethylene glycols, polyvinylpyrolidones, polyvinylimidazoles, and Al / Mg silicates.
  • Zwitterionic surfactants are e.g. Aminocarboxylic acids and alkylamine oxides.
  • Cationic surfactants are e.g. quaternary ammonium or amine compounds.
  • the formulation can contain 1 to 10% of common detergent additives such as, for example, enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, emulsifiers, thickeners, foam regulators, stabilizers, antiredeposition agents, fragrances and colorants, complexing agents or sequestering agents and solvents.
  • common detergent additives such as, for example, enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, emulsifiers, thickeners, foam regulators, stabilizers, antiredeposition agents, fragrances and colorants, complexing agents or sequestering agents and solvents.
  • salts e.g. Formates, acetates and sodium chloride can be used.
  • Targeted liquid detergents containing sulfonated dibenzofuranylbiphenyls can also be used e.g. also described in EP-A-293 040, contain up to 20% by weight of one or more bleaching agents such as phthalocyanines, peracids such as perborates or diperoxydicarboxylic acids, or peracid precursors and peracid activators or peracid catalysts.
  • bleaching agents such as phthalocyanines, peracids such as perborates or diperoxydicarboxylic acids, or peracid precursors and peracid activators or peracid catalysts.
  • the formulation is produced by mixing the components with stirring.
  • the formulation thus obtained is stable for months and does not sediment.
  • optical brighteners used is e.g. in EP-A-394 998.
  • the detergents obtained in Examples 1 and 2 are used in a concentration of 7.5 g / l for washing bleached cotton at 60 ° C. After rinsing and drying, high degrees of whiteness are achieved with negligible stain formation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)

Description

Die vorliegende Erfindung betrifft neue hochkonzentrierte, wässrige und flüssige Waschmittel enthaltend gezielt disulfonierte Dibenzfuranylbiphenyle als optische Aufheller deren Herstellung und deren Verwendung.The present invention relates to new, highly concentrated, aqueous and liquid detergents containing targeted disulfonated dibenzfuranylbiphenyls as optical brighteners, their preparation and their use.

Die Verwendung von optischen Aufhellern in flüssigen Waschmitteln ist bekannt. Sie ziehen während der Behandlung auf das Waschgut auf und führen durch ihre spezielle Lichtabsorption/Emissionseigenschaft zu einer Elimination der gelblichen Töne bzw. zu einer Verbesserung des Weissgrades.The use of optical brighteners in liquid detergents is known. They soak on the items to be washed during treatment and, due to their special light absorption / emission properties, lead to an elimination of the yellowish tones or an improvement in the degree of whiteness.

Dieser Effekt ist aber auch verantwortlich für das Auftreten von hellen Flecken wenn Textilgewebe z.B. bei einer Vorbehandlung direkt mit dem flüssigen Waschmittel in Kontakt gerät. In der EP-A-167 205 wird zur Lösung dieses Problems vorgeschlagen, monosulfonierte Stilbentriazolyl-, -triazin oder Distyrylbiphenyl-Aufheller in anionischen Flüssigwaschmitteln zu verwenden.This effect is also responsible for the appearance of light spots when textile fabrics e.g. comes into contact with the liquid detergent during pretreatment. To solve this problem, EP-A-167 205 proposes to use monosulfonated stilbene triazolyl, triazine or distyrylbiphenyl brighteners in anionic liquid detergents.

Der Trend zu immer konzentrierteren Waschmittelformulierungen stellt jedoch auch hohe Anforderungen an die Einzelkomponenten bezüglich der Einarbeitbarkeit, Löslichkeit und deren Lagerstabilität. Aus der EP-A-394 998 sind z.B. Flüssigwaschmittel mit einem Gehalt von 25 bis 65 Gew.% Wasser bekannt. In der EP-A-364 027 sind z.B. wässrige, Persäure-enthaltene Flüssigwaschmittel beschrieben, die optische Aufheller enthalten, die gegenüber der Persäure stabil sind.However, the trend towards increasingly concentrated detergent formulations also places high demands on the individual components with regard to incorporability, solubility and their storage stability. From EP-A-394 998 e.g. Liquid detergent with a content of 25 to 65 wt.% Water known. In EP-A-364 027 e.g. aqueous, peracid-containing liquid detergents described, which contain optical brighteners that are stable to the peracid.

Es wurden nun überraschenderweise gefunden, dass hochkonzentrierte, wässrige Flüssigwaschmittel, dadurch gekennzeichnet, dass sie

  • a) 0,01 bis 2 % und bevorzugt 0,002 bis 0,4 Gew.%, bezogen auf das Gewicht des Waschmittels, eines oder mehrerer disulfonierter optischer Aufheller der Formel (1)
    Figure imgb0001
     worin
       R1, R2, R3, R4 und R5 unabhängig voneinander ein Sulfonsäurerest, Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, Halogen, CN, Phenoxy oder Benzyloxy, mit der Bedingung, dass nur einer der Reste R1 bis R5 ein Sulfonsäurerest ist, bedeuten,
  • b) 6 bis 22 Gew.% und bevorzugt 8 bis 17 Gew.% Wasser, bezogen auf das Gewicht des Waschmittels, und
  • c) Tenside
enthalten, eine ausgezeichnete Lagerstabilität besitzen und nicht zur Fleckenbildung neigen.Surprisingly, it has now been found that highly concentrated, aqueous liquid detergents, characterized in that they
  • a) 0.01 to 2% and preferably 0.002 to 0.4% by weight, based on the weight of the detergent, of one or more disulfonated optical brighteners of the formula (1)
    Figure imgb0001
     wherein
    R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are a sulfonic acid residue, hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CN, phenoxy or benzyloxy, with the condition that only one of the radicals R 1 to R 5 is a sulfonic acid radical,
  • b) 6 to 22% by weight and preferably 8 to 17% by weight of water, based on the weight of the detergent, and
  • c) surfactants
contain, have an excellent storage stability and do not tend to stain.

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 oder verzweigte Alkylreste z.B. Methyl, Aethyl, n-Propyl, iso-Propyl, n-Butyl und t-Butyl in Betracht Als C1-C4-Alkoxyreste kommen unverzweigte oder verzweigte Alkoxyreste z.B. Methoxy, Aethoxy, n-Propoxy, iso-Propoxy, n-Butoxy und t-Butoxy in Betracht. Diese Alkyl- (bzw. Alkoxy-) reste können ihrerseits substituiert sein mit z.B. Aryl- (Phenyl-oder Naphthyl-), C1-C4-Alkyl-(Methyl, Aethyl, n-Propyl, iso-Propyl, n-Butyl oder t-Butyl), C1-C4-Alkoxy-(Methoxy, Aethoxy, n-Propoxy, iso-Propoxy, n-Butoxy oder t-Butoxy), OH- oder CN-Gruppen.As a C 1 -C 4 alkyl radicals come straight or branched alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, butyl and t-butyl-n into consideration as C 1 -C 4 -alkoxy come straight or branched alkoxy groups such as methoxy , Ethoxy, n-propoxy, iso-propoxy, n-butoxy and t-butoxy. These alkyl (or alkoxy) radicals can in turn be substituted with, for example, aryl (phenyl or naphthyl), C 1 -C 4 alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl) or t-butyl), C 1 -C 4 alkoxy (methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy or t-butoxy), OH or CN groups.

Bevorzugte Dibenzfuranylbiphenyle der Formel (1) sind solche
wonn

  • R1 = SO3M;
  • R2, R3, R4 und R5 unabhängig voneinander Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy. Halogen, CN, Phenoxy oder Benzyloxy, bevorzugt Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl, Methoxy, Chlor, CN, Phenoxy oder Benzyloxy, insbesondere Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl oder Chlor bedeuten; und
  • M = Wasserstoff oder ein nichtchromophores Kation; sowie Verbindungen der Formel (1) worin
  • R1 = Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, Halogen, CN, Phenoxy oder Benzyloxy;
  • R2, R3, R4 und R5 unabhängig voneinander SO3M, Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, Halogen, CN, Phenoxy oder Benzyloxy, bevorzugt SO3M, Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl, Methoxy, Chlor, CN, Phenoxy oder Benzyloxy, insbesondere SO3M, Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl oder Chlor bedeuten, mit der Bedingung, dass nur einer der Reste R2 bis R5 ein Sulfonsäurerest ist, ; und
  • M = Wasserstoff oder ein nichtchromophores Kation;
bedeuten.Preferred dibenzfuranylbiphenyls of the formula (1) are those
wonn
  • R 1 = SO 3 M;
  • R 2 , R 3 , R 4 and R 5 independently of one another hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy. Halogen, CN, phenoxy or benzyloxy, preferably hydrogen, methyl, ethyl, isopropyl, t-butyl, methoxy, chlorine, CN, phenoxy or benzyloxy, in particular hydrogen, methyl, ethyl, isopropyl, t-butyl or chlorine ; and
  • M = hydrogen or a non-chromophoric cation; as well as compounds of formula (1) wherein
  • R 1 = hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CN, phenoxy or benzyloxy;
  • R 2 , R 3 , R 4 and R 5 independently of one another SO 3 M, hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CN, phenoxy or benzyloxy, preferably SO 3 M, Is hydrogen, methyl, ethyl, isopropyl, t-butyl, methoxy, chlorine, CN, phenoxy or benzyloxy, in particular SO 3 M, is hydrogen, methyl, ethyl, isopropyl, t-butyl or chlorine, with the condition that that only one of the radicals R 2 to R 5 is a sulfonic acid radical; and
  • M = hydrogen or a non-chromophoric cation;
mean.

Besonders bevorzugt sind dabei Verbindungen der Formel (1), worin

  • R4=SO3M,
  • R1, R2, R3 und R5 unabhängig voneinander Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, Halogen, CN, Phenoxy oder Benzyloxy, bevorzugt Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl, Methoxy, Chlor, CN, Phenoxy oder Benzyloxy, insbesondere Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl oder Chlor; und
  • M = Wasserstoff oder ein nichtchromophores Kation bedeuten; sowie Verbindungen der Formel (1) worin
  • R2=SO3M
  • R1, R3, R4 und R5 unabhängig voneinander Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy, Halogen, CN, Phenoxy oder Benzyloxy, bevorzugt Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl, Methoxy, Chlor, CN, Phenoxy oder Benzyloxy, insbesondere Wasserstoff, Methyl, Aethyl, iso-Propyl, t-Butyl oder Chlor; und
  • M = Wasserstoff oder ein nichtchromophores Kation bedeuten.
Compounds of the formula (1) in which
  • R 4 = SO 3 M,
  • R 1 , R 2 , R 3 and R 5 independently of one another hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CN, phenoxy or benzyloxy, preferably hydrogen, methyl, ethyl, isopropyl, t-butyl, methoxy, chlorine, CN, phenoxy or benzyloxy, especially hydrogen, methyl, ethyl, iso-propyl, t-butyl or chlorine; and
  • M = hydrogen or a non-chromophoric cation; as well as compounds of formula (1) wherein
  • R 2 = SO 3 M
  • R 1 , R 3 , R 4 and R 5 independently of one another hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CN, phenoxy or benzyloxy, preferably hydrogen, methyl, ethyl, isopropyl, t-butyl, methoxy, chlorine, CN, phenoxy or benzyloxy, especially hydrogen, methyl, ethyl, iso-propyl, t-butyl or chlorine; and
  • M = hydrogen or a non-chromophoric cation.

M in der Bedeutung eines nichtchromophoren Kations steht vorzugsweise für Alkalimetall wie Lithium, Natrium, Kalium sowie gegebenenfalls substituiertes Ammonium wie Ammonium, Mono-, Di- oder Triethanolammonium, Mono-, Di- oder Tripropanolammonium oder Tri- oder Tetramethylammonium. Besonders bevorzugt sind hierbei Natrium, Kalium und Ammonium.M in the meaning of a non-chromophoric cation preferably represents alkali metal such as lithium, sodium, potassium and optionally substituted ammonium such as ammonium, mono-, di- or triethanolammonium, mono-, di- or tripropanolammonium or tri- or tetramethylammonium. Sodium, potassium and ammonium are particularly preferred.

Unter Flüssigwaschmitteln sind bekannte und handelsübliche Waschmittel, wie sie beispielsweise in der EP-A-167 205 oder US-4 507 219 oder EP-A-293 040 beschrieben werden, zu verstehen.Liquid detergents are known and commercially available detergents, as are described, for example, in EP-A-167 205 or US-4 507 219 or EP-A-293 040.

Als Tenside können anionische, nichtionische, kationische oder zwitterionische Tenside verwendet werden.Anionic, nonionic, cationic or zwitterionic surfactants can be used as surfactants.

Beispielsweise kann die Formulierung

  • . 0 bis 40 Gew.%, vorzugsweise 2 bis 10 Gew.% anionische Tenside,
  • . 3 bis 78 Gew.%, vorzugsweise 10 bis 60 Gew,% nichtionische Tenside,
  • . 3 bis 35 Gew.%, vorzugsweise 5 bis 25 Gew.% Ethoxylierungsprodukte,
  • . 0,5 bis 35 Gew.%, vorzugsweise 1 bis 20 Gew.% Aufbaustoffe,
  • . 0 bis 10 Gew.%, vorzugsweise 1 bis 8 Gew.% zwitterionische Tenside,
  • . 0 bis 3 Gew.%, vorzugsweise 0,7 bis 2 Gew.% kationische Tenside und
  • . 0 bis 15 Gew.%, vorzugsweise 0,2 bis 10 Gew.% Polymere
enthalten.For example, the wording
  • . 0 to 40% by weight, preferably 2 to 10% by weight, anionic surfactants,
  • . 3 to 78% by weight, preferably 10 to 60% by weight, nonionic surfactants,
  • . 3 to 35% by weight, preferably 5 to 25% by weight, of ethoxylation products,
  • . 0.5 to 35% by weight, preferably 1 to 20% by weight, of building materials,
  • . 0 to 10% by weight, preferably 1 to 8% by weight of zwitterionic surfactants,
  • . 0 to 3% by weight, preferably 0.7 to 2% by weight, of cationic surfactants and
  • . 0 to 15% by weight, preferably 0.2 to 10% by weight, of polymers
contain.

Brauchbare Tenside werden z.B. in der US-4 285 841, US-3 929 678, US-4 284 532 und GB-2 041 986 beschrieben. Insbesondere werden die in der EP-A-167 205 als bevorzugt bezeichneten Tenside eingesetzt.Useful surfactants are e.g. in U.S. 4,285,841, U.S. 3,929,678, U.S. 4,284,532 and GB 2,041,986. In particular, the surfactants designated as preferred in EP-A-167 205 are used.

Anionische Tenside sind z.B. auch

  • . Fettsäuren wie gesättigte und ungesättigte Carbonsäuren wie z.B. Öl-, Caprin-, Myristin-, Kokosnuss-, Palmkernsäure oder deren Salze;
  • . Alkylsulfate;
  • . Alkylsulfonate wie sie z.B. in der GB-A-2 141 754 genannt sind, wie Natriumpentadecylsulfonat oder Sulfobernsteinsäuredioctylether und besonders die C9-C15-Alkylbenzolsulfonate;
  • . Alkylphosphonate oder Alkylpolyphosphonate wie sie z.B. in der US-A-4 321 165 beschrieben werden.
Anionic surfactants are also, for example
  • . Fatty acids such as saturated and unsaturated carboxylic acids such as oleic, capric, myristic, coconut, palm kernel acid or their salts;
  • . Alkyl sulfates;
  • . Alkyl sulfonates as mentioned, for example, in GB-A-2 141 754, such as sodium pentadecyl sulfonate or sulfosuccinic acid dioctyl ether, and especially the C 9 -C 15 alkylbenzenesulfonates;
  • . Alkyl phosphonates or alkyl polyphosphonates such as are described, for example, in US Pat. No. 4,321,165.

Nichtionische Tenside sind z.B. Polyhydroxyfettsäureamide, wie sie in der WO 92/06172 beschrieben sind und Alkylphenole. Desweiteren kommen noch Alkylpolyglucoside von C9-C15-Alkylen mit 1-10 Glucosideinheiten wie z.B. Nonylglucosid und Allyl(C12-C15)-poly(1-10)-glucosid, Sorbinanester wie z.B. Polyoxyethylensorbitanmonopalmitat, Fettsäureethanolamide wie z.B. Kokosfettsäurediethanolamid und Fettsäureethanolaminoxide wie z.B. Tetradecylaminoxid in Frage.Nonionic surfactants are, for example, polyhydroxy fatty acid amides, as described in WO 92/06172, and alkylphenols. Furthermore, there are also alkyl polyglucosides of C 9 -C 15 -alkylene with 1-10 glucoside units such as, for example, nonylglucoside and allyl (C 12 -C 15 ) -poly (1-10) -glucoside, sorbine esters such as, for example, polyoxyethylene sorbitan monopalmitate, fatty acid ethanolamides such as, for example, coconut fatty acid diethanolamide and fatty acid ethanolamine such as tetradecylamine oxide in question.

Die Ethoxylierungsprodukte erhält man beispielesweise durch Kondensation von Ethylenoxid und/oder Propylenoxid mit einem Kohlenwasserstoff, der ein aktives Wasserstoffatom trägt, so z.B.:

  • . einem niedermolekularen, aliphatischen Polyol,
  • . einem gesättigten und/oder ungesättigten Fettalkohol mit 8 bis 22 C-Atomen,
  • . einem Alkylphenol mit 4 bis 12 C-Atomen im Alkylrest,
  • . einem Hydroxybiphenyl,
  • . einem gesättigten und/oder ungesättigten Fettamin mit 8 bis 22 C-Atomen,
  • . einer gesättigten und/oder ungesättigten Fettsäure mit 8 bis 22 C-Atomen, oder
  • . einem gesättigten und/oder ungesättigten Fettsäure-(N,N-bis-hydroxyalkyl)amid,
wobei auf 1 Mol der genannten Verbindungen vorzugsweise 3 bis 100 Mol Ethylenoxid und/oder Propylenoxid kommen. Als Beispiele seien die Alkoholethoxylate genannt. Es können aber auch Gemische dieser Umsetzungsprodukte untereinander verwendet werden. Diese Gemische erhält man durch Mischen der einzelnen Umsetzungsprodukte oder direkt durch Ethoxylierung eines Gemisches der den Umsetzungsprodukten zugrundeliegenden Verbindungen.The ethoxylation products are obtained, for example, by condensing ethylene oxide and / or propylene oxide with a hydrocarbon which carries an active hydrogen atom, for example:
  • . a low molecular weight, aliphatic polyol,
  • . a saturated and / or unsaturated fatty alcohol with 8 to 22 carbon atoms,
  • . an alkylphenol with 4 to 12 carbon atoms in the alkyl radical,
  • . a hydroxybiphenyl,
  • . a saturated and / or unsaturated fatty amine with 8 to 22 carbon atoms,
  • . a saturated and / or unsaturated fatty acid with 8 to 22 carbon atoms, or
  • . a saturated and / or unsaturated fatty acid (N, N-bis-hydroxyalkyl) amide,
preferably 1 to 3 moles of ethylene oxide and / or propylene oxide per mole of the compounds mentioned. Examples include the alcohol ethoxylates. Mixtures of these reaction products with one another can also be used. These mixtures are obtained by mixing the individual reaction products or directly by ethoxylating a mixture of the compounds on which the reaction products are based.

Als Waschmittelaufbaustoffe oder Polymere kommen z.B. die in der US-4 321 165 und US-4 284 532 erwähnten vorzugsweise polycarboxylierten Verbindungen wie zum Beispiel Zitronensäure oder Maleinsäure/Acrylsäure-Copolymere, sowie z.B. die Ligninsulfonate, Formaldehydadditionsprodukte, Polyethylenglykole, Polyvinylpyrolidone, Polyvinylimidazole, und Al/Mg-Silikate in Betracht.Detergent builders or polymers include e.g. the preferably polycarboxylated compounds mentioned in U.S. 4,321,165 and U.S. 4,284,532 such as citric acid or maleic acid / acrylic acid copolymers, as well as e.g. the lignin sulfonates, formaldehyde addition products, polyethylene glycols, polyvinylpyrolidones, polyvinylimidazoles, and Al / Mg silicates.

Zwitterionische Tenside sind z.B. Aminocarbonsäuren und Alkylaminoxide.Zwitterionic surfactants are e.g. Aminocarboxylic acids and alkylamine oxides.

Kationische Tenside sind z.B. quaternäre Ammonium oder Aminverbindungen.Cationic surfactants are e.g. quaternary ammonium or amine compounds.

Weiterhin kann die Formulierung 1 bis 10 % übliche Waschmittelzusätze wie zum Beispiel Enzyme, Enzymstabilisatoren, Antioxidantien, Konservierungs- und Desinfektionsmittel, Emulgatoren, Verdicker, Schaumregulatoren, Stabilisatoren, Antiredepositionsmittel, Duft- und Farbstoffe, Komplexbildner bzw. Sequestriermittel und Lösungsmittel enthalten.Furthermore, the formulation can contain 1 to 10% of common detergent additives such as, for example, enzymes, enzyme stabilizers, antioxidants, preservatives and disinfectants, emulsifiers, thickeners, foam regulators, stabilizers, antiredeposition agents, fragrances and colorants, complexing agents or sequestering agents and solvents.

Als Salze können z.B. Formiate, Acetate und Natriumchlorid verwendet werden.As salts, e.g. Formates, acetates and sodium chloride can be used.

Gezielt sulfonierte Dibenzofuranylbiphenyle enthaltende flüssige Waschmittel können auch, wie z.B. auch in EP-A-293 040 beschrieben, bis zu 20 Gew.% eines oder mehrerer Bleichmittel wie Phthalocyanine, Persäuren wie Perborate oder Diperoxydicarbonsäuren, oder Persäureprecursor sowie Persäureaktivatoren oder Persäurekatalysatoren enthalten.Targeted liquid detergents containing sulfonated dibenzofuranylbiphenyls can also be used e.g. also described in EP-A-293 040, contain up to 20% by weight of one or more bleaching agents such as phthalocyanines, peracids such as perborates or diperoxydicarboxylic acids, or peracid precursors and peracid activators or peracid catalysts.

Hergestellt wird die Formulierung indem man die Komponenten unter Rühren vermischt.The formulation is produced by mixing the components with stirring.

Die so erhaltene Formulierung ist über Monate stabil und sedimentiert nicht.The formulation thus obtained is stable for months and does not sediment.

Die Herstellung der verwendeten optischen Aufheller wird z.B. in der EP-A-394 998 beschrieben.The manufacture of the optical brighteners used is e.g. in EP-A-394 998.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung; Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente; der Fleckentest wird folgendermassen durchgeführt:

  • a) Aufheller/Waschmittel-Formulierung: 0,1 % (100 % Aktivsubstanz) optischer Aufheller oder Aufhellergemisch werden in einem flüssigen Waschmittel gelöst. 7,5 g dieses Aufheller enthaltenden Waschmittels (A) werden mit Wasser (10°-12° dH) bei einer Temperatur von 30°C auf 1000 ml verdünnt (Waschflotte B).
  • b) Ein 20 g Stück gebleichtes Baumwollgewebe wird auf einem Spannrahmen befestigt.
  • c) Auf eine vormarkierte, runde Fläche (5 cm Durchmesser) dieses Baumwollgewebes werden mit einer Pipette 0,6 ml der Waschmittellösung (A) gleichmässig aufgetragen, nach 30 Sekunden Einwirkzeit in die vorbereitete Waschflotte (B) gegeben und während 15 Minuten bei 60°C gewaschen. Anschliessend wird mit kaltem Wasser gespült und bei 70°C getrocknet.
  • d) Der Unterschied des Weissgrades nach Ganz zwischen der Auftragsfläche und der Umgebung ist ein Mass für das sogenannte Spotting-Verhalten (Bildung von hellen Flecken) und wird bei einfacher Textillage mit einem RFC3-Photometer von Zeiss bestimmt.
The following examples serve to illustrate the invention; Parts mean parts by weight and percentages percent by weight; The stain test is carried out as follows:
  • a) Brightener / detergent formulation: 0.1% (100% active substance) optical brightener or brightener mixture are dissolved in a liquid detergent. 7.5 g of this detergent (A) containing brightener are diluted with water (10 ° -12 ° dH) at a temperature of 30 ° C to 1000 ml (wash liquor B).
  • b) A 20 g piece of bleached cotton fabric is attached to a tenter.
  • c) 0.6 ml of the detergent solution (A) are evenly applied to a pre-marked, round surface (5 cm in diameter) of this cotton fabric, added to the prepared wash liquor (B) after 30 seconds of exposure and for 15 minutes at 60 ° C washed. It is then rinsed with cold water and dried at 70 ° C.
  • d) The difference in whiteness according to Ganz between the application area and the surroundings is a measure of the so-called spotting behavior (formation of light spots) and is determined with a simple textile layer using an RFC3 photometer from Zeiss.

Beispiel 1: Example 1 :

Bei 60°C werden die folgenden Bestandteile unter Rühren bei 60°C vermischt :

40
Teile C12-C15 Polyethoxyfettalkohol (7 EO)
15
Teile Polyethylenglykol 200
10
Teile Ethanol
5
Teile Propandiol
3,9
Teile Triacetin
5
Teile Triethanolamin
5
Teile Phosphonat
16
Teile Wasser deion.
und 0,1 Teile des optischen Aufhellers der Formel (2)
Figure imgb0002
 At 60 ° C the following ingredients are mixed with stirring at 60 ° C:
40
Parts C 12 -C 15 polyethoxy fatty alcohol (7 EO)
15
Parts of polyethylene glycol 200
10th
Parts of ethanol
5
Parts of propanediol
3.9
Share triacetin
5
Parts of triethanolamine
5
Parts of phosphonate
16
Parts of water deion.
and 0.1 part of the optical brightener of formula (2)
Figure imgb0002

Man erhält ein leicht trübes, lagerstabiles Waschmittel.A slightly cloudy, storage-stable detergent is obtained.

Beispiel 2:Example 2:

Wie Beispiel 1, mit dem Unterschied, das ein optischer Aufheller der Formel (3)

Figure imgb0003
verwendet wird.As example 1, with the difference that an optical brightener of the formula (3)
Figure imgb0003
 is used.

Beispiele 3 und 4:Examples 3 and 4:

Die in den Beispielen 1 und 2 erhaltenen Waschmittel werden in einer Konzentration von 7,5 g/l zum Waschen von gebleichter Baumwolle bei 60°C verwendet. Es werden dabei nach dem Spülen und Trocknen jeweils hohe Weissgrade bei einer vernachlässigbaren Fleckenbildung erzielt.The detergents obtained in Examples 1 and 2 are used in a concentration of 7.5 g / l for washing bleached cotton at 60 ° C. After rinsing and drying, high degrees of whiteness are achieved with negligible stain formation.

Claims (19)

  1. A highly concentrated, aqueous liquid detergent composition, comprising
    a) 0.01 to 2 %, based on the weight of the detergent composition, of one or more disulfonated fluorescent whitening agents of formula (1)
    Figure imgb0010
     wherein
    R1, R2, R3, R4 and R5 are each independently of one another a sulfonic acid radical, hydrogen, C1-C4alkyl, C1-C4alkoxy,
    halogen, CN, phenoxy or benzyloxy, with the proviso that only one of R1 to R5 is a sulfonic acid radical,
    b) 6 to 22 % by weight of water, based on the weight of the detergent composition, and
    c) surfactants, with the exception of a highly concentrated liquid detergent composition comprising
    a) about 1.5 %, based on the weight of the detergent composition, of a disulfonated fluorescent whitening agent of the formula:
    Figure imgb0011
    Figure imgb0012
    Figure imgb0013
    b) about 19 % of water, based on the weight of the detergent composition, and
    c) a nonionic surfactant obtained by condensation of 7 mol of ethylene oxide with a C15 alkanol.
  2. A liquid detergent composition according to claim 1, which comprises a fluorescent whitening agent of formula (1), wherein
    R1 = SO3M;
    M = hydrogen or a non-chromophoric cation; and
    R2, R3, R4 and R5 are each independently of one another hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, CN, phenoxy or benzyloxy.
  3. A liquid detergent composition according to claim 2, which comprises a fluorescent whitening agent of formula (1), wherein
    R1 = SO3M;
    M = is hydrogen or a non-chromophoric cation; and
    R2, R3, R4 and R5 are each independently of one another hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, chloro, CN, phenoxy or benzyloxy.
  4. A liquid detergent composition according to claim 3, which comprises a fluorescent whitening agent of formula (1), wherein
    R1 = SO3M;
    M = hydrogen or a non-chromophoric cation; and
    R2, R3, R4 and R5 are each independently of one another hydrogen, methyl, ethyl, isopropyl, tert-butyl or chloro.
  5. A liquid detergent composition according to claim 1, which comprises a fluorescent whitening agent of formula (1), wherein
    R1 = hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, CN, phenoxy or benzyloxy; R2, R3, R4 and R5 are each independently of one another SO3N, hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, CN, phenoxy or benzyloxy, with the proviso that only one of R2 to R5 is SO3M; and M = hydrogen or a non-chromophoric cation.
  6. A liquid detergent composition according to claim 1, which comprises a fluorescent whitening agent of formula (1), wherein
    R4 = SO3M
    R1, R2, R3 and R5 are each independently of one another hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, CN, phenoxy or benzyloxy; and
    M = hydrogen or a non-chromophoric cation.
  7. A liquid detergent composition according to claim 6, which comprises a fluorescent whitening agent of formula (1), wherein
    R4 = SO3M
    R1, R2, R3 and R5 are each independently of one another hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, chloro, CN, phenoxy or benzyloxy; and
    M = hydrogen or a non-chromophoric cation.
  8. A liquid detergent composition according to claim 7, which comprises a fluorescent whitening agent of formula (1), wherein
    R4 = SO3M
    R1, R2, R3 and R5 are each independently of one another hydrogen, methyl, ethyl, isopropyl, tert-butyl or chloro; and
    M = hydrogen or a non-chromophoric cation.
  9. A liquid detergent composition according to claim 1, which comprises a fluorescent whitening agent of formula (1), wherein
    R2 = SO3M;
    R1, R3, R4 and R5 are each independently of one another hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen, CN, phenoxy or benzyloxy; and
    M = hydrogen or a non-chromophoric cation.
  10. A liquid detergent composition according to claim 9, which comprises a fluorescent whitening agent of formula (1), wherein
    R2 = SO3M;
    R1, R3, R4 and R5 are each independently of one another hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, chloro, CN, phenoxy or benzyloxy; and
    M = hydrogen or a non-chromophoric cation.
  11. A liquid detergent composition according to claim 10, which comprises a fluorescent whitening agent of formula (1), wherein
    R2 = SO3M;
    R1, R3, R4 and R5 are each independently of one another hydrogen, methyl, ethyl, isopropyl, tert-butyl or chloro; and
    M = hydrogen or a non-chromophoric cation.
  12. A liquid detergent composition according to any one of claims 1 to 11, which comprises a fluorescent whitening agent of formula
    Figure imgb0014
  13. A liquid detergent composition according to any one of claims 1 to 11, which comprises a fluorescent whitening agent of formula
    Figure imgb0015
  14. A liquid detergent composition according to any one of claims 2 to 11, wherein M is sodium, potassium or ammonium.
  15. A liquid detergent composition according to any one of claims 1 to 14, which comprises 8 to 17 % by weight of water, based on the weight of the detergent composition.
  16. A liquid detergent composition according to any one of claims 1 to 15, which comprises 0.002 to 0.4 % by weight, based on the weight of the detergent composition, of one or more fluorescent whitening agents of formula (1).
  17. The use of a liquid detergent composition according to any one of claims 1 to 16 for washing and pretreating textile fabrics.
  18. The preparation of a liquid detergent composition according to any one of claims 1 to 16, which comprises mixing and homogenising fluorescent whitening agent, surfactants, auxiliaries and builders, an optional bleaching system, and water.
  19. The use of a liquid detergent composition according to any one of claims 1 to 16 for washing textile fabrics.
EP93810772A 1992-11-17 1993-11-09 Liquid detergent composition Expired - Lifetime EP0601967B1 (en)

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DE19751860C1 (en) * 1997-11-22 1999-08-19 Henkel Ecolab Gmbh & Co Ohg Washing process and preparation for its implementation
JP5396707B2 (en) * 2007-11-07 2014-01-22 ライオンハイジーン株式会社 Cleaning composition
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