EP1171568B1 - Agent detergent pour lavage manuel de la vaisselle avec microcapsules - Google Patents

Agent detergent pour lavage manuel de la vaisselle avec microcapsules Download PDF

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Publication number
EP1171568B1
EP1171568B1 EP00920698A EP00920698A EP1171568B1 EP 1171568 B1 EP1171568 B1 EP 1171568B1 EP 00920698 A EP00920698 A EP 00920698A EP 00920698 A EP00920698 A EP 00920698A EP 1171568 B1 EP1171568 B1 EP 1171568B1
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Prior art keywords
weight
composition according
microcapsules
alkyl
sodium
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EP00920698A
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German (de)
English (en)
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EP1171568A1 (fr
Inventor
Brigitte Giesen
Dagmar Zaika
Marion Wortmann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/30—Sulfonation products derived from lignin
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention relates to thickened aqueous surfactant-containing agents, in particular hand dishwashing detergents, with anionic surfactant, amphoteric surfactant, polymer and microcapsules.
  • Perfume oils, Dyes, etc. in a precisely dosable, excellent cleansing, skin-friendly, stable to temperature and storage, pourable and ecologically particularly compatible Hand dishwashing detergent, it can - by direct action of Surfactant components to the drug - rapidly to loss of efficacy (e.g., liposomes) come.
  • Another problem is the difficulty of stable incorporation of active ingredients in the rinse aid formulation (e.g., perfumes or antibacterial Active ingredients), discolorations (e.g., in plant extracts or proteins), odor problems (for example, with addition of vinegar, antibacterial agents or plant extracts) or incompatibilities between the active ingredient component and the rinsing agent.
  • An elegant method for incorporating sensitive, chemically or physically incompatible and volatile ingredients is the use of microcapsules in which these ingredients are stored stable storage and transport and from which they are used for or released mechanically, chemically, thermally or enzymatically during use become.
  • Microcapsules are finely dispersed liquid or solid coated with film-forming polymers Phases in which the polymers are produced after emulsification and coacervation or interfacial polymerization on the material to be enveloped (active ingredient) precipitate.
  • the active ingredient is shell-like enveloped by a solid membrane (microcapsule in the narrower sense) or enclosed by a matrix (microsphere or Sphere).
  • microcapsule in the summary for both variants Used meaning or possibly both terms juxtaposed.
  • the microscopic Small capsules, also called nanocapsules can be dried like powder. In this way, e.g.
  • German laid-open specification DE 2 215 441 discloses aqueous liquid dishwashing detergents containing 20 to 45% by weight of anionic and / or nonionic surfactants, 3 to 10% by weight of electrolyte and 1 to 4,000 ⁇ m diameter capsules of the carrageenan polymers , Polyvinyl alcohol or cellulose ethers, wherein the polymer and the electrolyte concentration are selected so as to ensure the stability of the capsules in the composition and the dissolution of the capsules when diluted with water.
  • Such a dishwashing detergent contains, for example, 10% by weight of capsules with a diameter of 4000 ⁇ m, 25% by weight of sodium dodecylbenzenesulfonate, 5% by weight of coconut monoethanolamide, 7% by weight of sodium sulfate, 1.5% by weight of synthetic clay or 5 %
  • capsules having a diameter of 4000 ⁇ m 20% by weight of sodium alkylbenzenesulfonate, 5% by weight of sodium C 14-16 ⁇ -olefinsulfonate, 5% by weight of lauric acid diethanolamide, 7% by weight of sodium xylenesulfonate, 3 %
  • By weight of ethanol 1% by weight of potassium chloride, 1% by weight of synthetic clay and 0.2% by weight of EDTA.
  • DE 36 15 514 A1 discloses an aqueous hand dishwashing detergent with 22% by weight of sodium ⁇ -olefinsulfonate, 6% by weight of magnesium alkylbenzenesulfonate, 2% by weight of sodium sulfate, 0.725% by weight of sodium chloride, 3% by weight .-% ethanol, 0.5 wt .-% perfume and 1.5 wt .-% fragrance-containing microcapsules of a size of 200 to 500 microns, which dissolve when diluted with water.
  • British Patent Specification No. 1,471,406 (Unilever Ltd.) relates to liquid aqueous detergents comprising at least 2% by weight of triethanolamine lauryl sulfate and a total of from 8 to 50% by weight of surfactant and from 0.5 to 2% by weight of water-soluble crosslinked polyacrylic acid having a molecular weight containing more than 1,000,000 and 0.1 to 5 wt .-% suspended phase, for example, spheroidal capsules having a diameter of 0.1 to 5 mm, and having a pH of 5.5 to 11.
  • the invention was based on the object, a precisely metered, excellent cleansing, skin-friendly, temperature and storage stable, pourable hand dishwashing detergent in which the possibly physically or chemically incompatible or sensitive ingredients in temperature, storage and transport stable, easy to handle and visually appealing form are incorporated and these only immediately before or during use.
  • the invention is a Insert the wording of claim 1.
  • the active ingredients In contrast to the ingredients related to the entire hand dishwashing detergent, the active ingredients only mean their part contained in the microcapsules.
  • the present invention is the use of the invention Means as a hand dishwashing detergent.
  • Another object of the present invention is the use of the agent according to the invention as a cleaning agent for hard surfaces.
  • the combination of anionic surfactant and amphoteric surfactant causes a particular advantageous cleaning effect and on the other hand in connection with the polymer a spatially particularly stable suspension of the microcapsules.
  • the otherwise usual Use of larger amounts of electrolyte salt to stabilize the microcapsules not required.
  • Visible microcapsules allow a particularly accurate, reproducible Dosing by counting the amount contained in the dosed amount of hand dishwashing detergent Microcapsules.
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them.
  • the oxo-alcohols or their derivatives which are obtainable, for example, by the ROELEN 's oxo synthesis, can also be used correspondingly.
  • alkaline earth metals as counterions for monovalent anions are, that means that the alkaline earth metal, of course, only in the half - to Charge balance sufficient - amount of substance as the anion is present.
  • the INCI indication means that the following - or possibly preceding - designation is a name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (CTFA) .
  • CTFA Cosmetic, Toiletry, and Fragrance Association
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service .
  • Polymers in the context of the present invention are polycarboxylates, preferably homo- and copolymers of acrylic acid, especially acrylic acid copolymers such as Acrylic acid-methacrylic acid copolymers, and polysaccharides, in particular heteropolysaccharides, as well as other common polymeric thickeners.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, Tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, e.g. propoxylated Guar, as well as their mixtures.
  • Other polysaccharide thickeners, such as starches or Cellulose derivatives may alternatively, but preferably in addition to a polysaccharide gum be used, for example, strengths of various origins and Starch derivatives, e.g.
  • Hydroxyethyl starch starch phosphate esters or starch acetates, or Carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, Hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • a preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 ⁇ 10 6 and is available, for example, from Kelco under the trade name Keltrol® , eg as a cream-colored powder Keltrol® T (transparent) or as white granules Keltrol® RD (Readily Dispersible).
  • Keltrol® eg as a cream-colored powder Keltrol® T (transparent) or as white granules Keltrol® RD (Readily Dispersible).
  • Suitable acrylic acid polymers are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene
  • carboxyvinyl polymers Such polyacrylic acids are available, inter alia, from BFGoodrich under the trade name Carbopol® , eg Carbopol® 940 (molecular weight about 4,000,000), Carbopol® 941 (molecular weight about 1,250,000) or Carbopol® 934 (molecular weight about 3,000. 000).
  • acrylic acid copolymers are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C 1-4 -alkanols (INCI acrylates copolymer), to which approx the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®
  • the anionic non-associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3);
  • crosslinked high molecular weight acrylic acid copolymers such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers
  • the content of polymer is usually between 0.01 and 8 wt .-%, preferably between 0.1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt .-%, in particular between 1 and 5% by weight and most preferably between 1.5 and 4 wt .-%, for example between 2 and 2.5 wt .-%.
  • the viscosity of the invention Means is substantially adjusted or controlled by the polymer content, wherein the required amounts may vary from polymer to polymer.
  • the surfactant composition used also plays a role in the choice of quantity.
  • hand dishwashing detergent contains a combination of at least one anionic surfactant having at least one amphoteric surfactant.
  • a special Embodiment of the invention additionally contains at least one nonionic surfactant.
  • the surfactants are usually used in amounts of from 0.2 to 60 wt .-%, preferably from 1 to 55 wt .-%, particularly preferably 3 to 50 wt .-% and most preferably 5 to 45 wt .-%.
  • the surfactant content is usually from 5 to 35% by weight, preferably from 10 to 30% by weight, in particular 14 to 25 wt .-%.
  • the surfactant content is usually 30 to 60% by weight, preferably 35 to 55 wt .-%, in particular 38 to 52 wt .-%.
  • Anionic surfactants according to the invention may be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n- alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n- alkyl ether sulfonates, ester sulfonates and
  • alkylbenzenesulfonates fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated Alcohols.
  • alkoxylated alcohols Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, within the meaning of present invention preferably with longer-chain alcohols.
  • alkoxylation is the use of mixtures of Alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Most notably Preferred for the purposes of the present invention are lower ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.
  • the anionic surfactants in particular fatty alcohol ether, in Amounts of 0.2 to 49.8 wt .-% used, particularly preferably 5 to 45 wt .-%, in particular 8 to 40 wt .-% and most preferably 10 to 36 wt .-%.
  • the agent contains as sole or preferably additional anionic surfactant, especially in combination with fatty alcohol ether sulfates, fatty alcohol sulfates, preferably between 0.5 and 15 wt .-% fatty alcohol sulfates are included.
  • amphoteric surfactants used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl substituted Amino acids, acylated amino acids or biosurfactants, of which the betaines in the frame the teachings of the invention are particularly preferred.
  • Preferred amphoteric surfactants are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),
  • R 1 is -N + (CH 3 ) 2 -CH 2 COO -
  • R 1 is -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 -
  • R 1 has the same meaning as in formula I.
  • amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula (Ia) and (Ib), most preferably the Alkylamidobetaine of the formula (Ib).
  • betaines and sulfobetaines are the following compounds designated as INCI : Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, Betaine, Canolamidopropyl Betaine, Caprylic Capramidopropyl Betaine, Camitine, Cetyl Betaine, Cocamidoethyl Betaine, Cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyethyl stearyl glycinates, dihydroxye
  • Suitable amine oxides are the following compounds designated as INCI : Almondamidopropylamine oxides, Babassuamidopropylamine oxides, Behenamine oxides, Cocamidopropyl Amine oxides, Cocamidopropylamine oxides, Cocamine oxides, Coco-Morpholine oxides, Decylamine oxides, Decyltetradecylamine oxides, Diaminopyrimidine oxides, Dihydroxyethyl C8-10 alkoxypropylamines oxides , Dihydroxyethyl C9-11 alkoxypropylamines oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel, amine oxides, hydrogenated tallowamine oxides, hydroxyethyl hydroxypropy
  • R 9 is -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 -COOM
  • R 9 is -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH 2 -COOM
  • R 9 is -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH (OH) CH 2 -SO 3 M
  • R 9 is -CO-NH- (CH 2 ) 2 -N (R 11 ) -CH 2 CH 2 O-CH 2 CH (OH) CH 2 -OPO 3 HM in which R 11 and M have the same meaning as in formula (III).
  • alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium laureth 5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodia
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa), R 13 -NH-CH 2 CH 2 COOM ' in which R 13 and M 'have the same meaning as in formula (IV).
  • alkyl substituted amino acids are the following INCI compounds: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl
  • Aminopropylglycines lauryl diethylenediaminoglycines, myristaminopropionic acid, sodium C12-15 alkoxypropyl iminodipropionate, sodium cocaminopropionate, sodium lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA-Lauraminopropionate and TEA-Myristaminopropionate.
  • Acylated amino acids are amino acids, in particular the 20 natural ⁇ -amino acids which carry on the amino nitrogen atom the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH, where R 19 is a saturated or unsaturated C 6-22- alkyl radical, preferably C 8- 18 alkyl, in particular a saturated C 10-16 alkyl radical, for example, a saturated C 12-14 alkyl radical.
  • the acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
  • acylated amino acids are the acyl derivatives summarized according to INCI under Amino Acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • amphoteric surfactants in particular Alkylamidobetaine, in quantities from 0.1 to 14.9% by weight, especially from 1 to 10% by weight, most preferably from 1.5 to 8 wt .-%, for example 2 to 7 wt .-%, used.
  • Nonionic surfactants in the context of the invention may be alkoxylates, such as polyglycol ethers, Fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped Polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also useful are ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers.
  • the alkyl polyglycosides in particular the alkyl polyglucosides.
  • Alkylpolyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, wherein, depending on the nature of the preparation, a mixture of monoalkylated, oligomeric or polymeric sugars is obtained.
  • Preferred alkyl polyglycosides are the alkyl polyglucosides, the alcohol particularly preferably being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 - to C 18 -alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, more preferably 1.1 to 1.7.
  • one or more nonionic surfactants in particular alkyl polyglycosides, in amounts of 0.1 to 14.9 wt .-%, in particular 1 to 10 wt .-% and extremely preferably 1.5 to 5 wt .-%, for example 2 to 3 wt .-% used.
  • Suitable microcapsules are all surfactant-stable capsules and capsule materials or spheres and spheroidal materials available on the market, such as Hallcrest microcapsules (capsule material: gelatin, gum arabic) from Hallcrest, Inc. (US), Coletica Thalaspheres (capsule material: marine collagen) from Coletica (FR), Lipotec Millicapseln (capsule material: alginic acid, agar-agar) from Lipotec SA (ES), Induchem Unispheres (capsule material: lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) and Unicerin C30 (capsule material: lactose, microcrystalline cellulose, hydroxypropylmethylcellulose ) of Induchem AG (CH), Kobo Glycospheres (capsule material: modified starch, fatty acid esters, phospholipids) and softspheres (capsule material: modified agar-agar) from Kobo (US) and Kuhs Probiol Nanospheres (capsule material:
  • the microcapsules can have any shape in the production-related framework, However, they are preferably ovate or ellipsoidal or approximately spherical.
  • the diameter along its largest spatial extent can vary depending on Active substance and application between 100 nm (not visually recognizable as capsule) and 10 mm.
  • the preferred diameter is in the range between 0.1 mm and 7 mm, particularly preferred are microcapsules with a diameter between 0.4 mm and 5 mm.
  • Active substances according to the invention include dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericin, Collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, Protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, plant and animal Oils such as e.g. Lecithin, soybean oil, etc., plant extracts such as e.g. Aloe vera, azulene, Witch hazel extracts, seaweed extracts, etc., allantoin, A.H.A. complexes. Active substances in the sense The invention also provides antibacterial agents, e.g.
  • Benzoic acid lactic acid, Salicylic acid, sorbic acid or mixtures thereof or their salts.
  • active ingredients For the purposes of the invention are still essential oils such.
  • color pigments or Pearlescent components are added.
  • the hand dishwashing detergent according to the invention contains in a preferred Embodiment microcapsules in which one or more representatives from the group, including dermatologically active substances, antibacterial agents, essential Oils and additives for improving the quality of the dishes and the appearance, are included.
  • the release of the active ingredient from the microcapsules can be achieved both by grinding the Microcapsules during the cleaning process as well as by breaking up with a take appropriate metering. Also conceivable is a release of the active ingredient by changing the temperature (introduction into warm rinsing water), by shifting pH, change in electrolyte content, etc.
  • the content of microcapsules is usually from 0.01 to 10% by weight, preferably from 0.1 to 5 wt .-%, in particular from 0.2 to 3 wt .-% and most preferably from 0.3 to 2 wt .-%, wherein the inventive agent exclusively similar microcapsules or else mixtures of different types of microcapsules.
  • the viscosity of the compositions according to the invention at 20 ° C. and a shear rate of 30 s -1 is between 500 and 18,000 mPa ⁇ s, preferably between 700 and 13,000 mPa ⁇ s, more preferably between 900 and 10,000 mPa ⁇ s, in particular between 1,100 and 8,000 mPa ⁇ s, most preferably between 1300 and 6500 mPa ⁇ s, for example between 1000 and 4000 mPa ⁇ s.
  • a shear rate of 30 s -1 is between 500 and 18,000 mPa ⁇ s, preferably between 700 and 13,000 mPa ⁇ s, more preferably between 900 and 10,000 mPa ⁇ s, in particular between 1,100 and 8,000 mPa ⁇ s, most preferably between 1300 and 6500 mPa ⁇ s, for example between 1000 and 4000 mPa ⁇ s.
  • the favorable viscosity is between 300 and 20,000 mPa ⁇ s, preferably between 700 and 15,000 mPa ⁇ s, particularly preferably between 1,000 and 10,000 mPa ⁇ s.
  • Values of the zero-shear viscosity ⁇ 0 which are preferred for favorable storage properties are between 100 and 5,000 Pa ⁇ s, preferably between 200 and 3,000 Pa ⁇ s.
  • the viscosity of the agents according to the invention can be adjusted by the polymer.
  • the amounts required may be different from polymer to polymer.
  • the surfactant composition used also plays a role in the choice of quantity Role like the presence of solubilizers.
  • solubilizer such as dyes and perfume oils, for example, alkanolamines, Polyols such as ethylene glycol, 1,2-propylene glycol, glycerine and others on and Polyhydric alcohols and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical serve.
  • one or more dicarboxylic acids and / or salts thereof, alone or in admixture may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as for example under the trade name Sokalan® DSC is available.
  • the use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1.3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.
  • a change in the dicarboxylic acid (salt) content can - especially in amounts above 2% by weight - contribute to a clear solution of the ingredients. Also is within certain limits an influence on the viscosity of the mixture by this Medium possible. Furthermore, this component influences the solubility of the mixture. This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30 wt .-%.
  • dicarboxylic acids and / or their salts may be used for viscosity regulation also other organic acids or their salts, such as Sodium formate, sodium acetate, sodium citrate and sodium tartrate, as well as inorganic Salts, e.g. Sodium chloride, magnesium chloride and magnesium sulfate, or salts the aforementioned anions with other alkali or alkaline earth metals individually or in Mixtures are used.
  • organic acids or their salts such as Sodium formate, sodium acetate, sodium citrate and sodium tartrate, as well as inorganic Salts, e.g. Sodium chloride, magnesium chloride and magnesium sulfate, or salts the aforementioned anions with other alkali or alkaline earth metals individually or in Mixtures are used.
  • a further advantageous component of the agents according to the invention are solvents, in particular lower alcohols, preferably ethanol, n-propanol or isopropanol, particularly preferred ethanol. They contribute to the incorporation of perfume and dye , prevent the formation of liquid-crystalline phases and contribute to the formation clear products.
  • the viscosity can be lowered by looking at the amount of solvent elevated. Too much solvent, however, causes an excessive decrease in viscosity. Therefore are inventively one or more solvents usually in amounts of 0.1 to 12 wt .-%. preferably 1 to 10 wt .-%, particularly preferably 3 to 8 wt .-%, for example 5 to 6 wt .-%, contain.
  • auxiliaries and additives customary in hand dishwashing detergents in particular UV stabilizers, perfumes, pearlescing agents ( INCI Opacifying Agents, for example glycol distearate, eg Cutina® AGS from Henkel KGaA or mixtures containing same , for example the Euperlane® from Fa Henkel KGaA), dyes, corrosion inhibitors and / or preservatives, in amounts of usually not more than 5% by weight.
  • UV stabilizers for example glycol distearate, eg Cutina® AGS from Henkel KGaA or mixtures containing same , for example the Euperlane® from Fa Henkel KGaA
  • dyes for example the Euperlane® from Fa Henkel KGaA
  • corrosion inhibitors for example the Euperlane® from Fa Henkel KGaA
  • preservatives in amounts of usually not more than 5% by weight.
  • the pH of the compositions according to the invention is - essentially because of the required hand tolerance - by means of conventional pH regulators, for example Citric acid or NaOH, in the range of 5 to 8, preferably 5.5 to 7.5, in particular 5.7 to 7 set.
  • conventional pH regulators for example Citric acid or NaOH
  • the hand dishwashing detergents according to the invention can be prepared by stirring together make the individual components in any order.
  • the order of approach is not critical to the preparation of the agent.
  • water Preferably, in this case, water, surfactants and optionally further of the above mentioned ingredients.
  • perfume and / or dye used are subsequently added to the resulting solution.
  • polymer added, optionally in the form of an aqueous solution, to the to facilitate homogeneous dissolution.
  • the pH is as previously described adjusted and finally mixed in the microcapsules.
  • compositions E1 to E16 were prepared as described above and determined their pH, their viscosity and their storage stability.
  • compositions of the compositions E1 to E16 according to the invention in% by weight and the particular properties are reproduced in Tables 1 to 3.
  • a number of agents E1 to E16 according to the invention contained traces of dye.
  • the pH of the inventive compositions E1 to E16 was adjusted to values between 5.5 and 7 with citric acid.
  • the viscosity of the compositions E1 to E16 according to the invention was determined at 20 ° C. according to Brookfield (viscometer Brookfield LV DV II +, spindle 25, rotational frequency 30 min -1 ).
  • the stability of the agents was tested by visually assessing the compositions after each 4 weeks of storage at room temperature of 20 ° C, at an elevated temperature of 40 ° C and in the cold at a temperature of 5 ° C. Irrespective of the storage temperature, none of the agents showed a visually perceptible change after 4 weeks; in particular, neither a change in the shape of the capsules nor their spatial distribution was observed on average.
  • microcapsules used were clearly visible to the naked eye from a distance of about 0.5 m.
  • the diameter of the microcapsules was 0.8 ⁇ 0.4 mm in formulation E1, 2 ⁇ 0.5 mm in formulations E2, E7, E10 and E15 and 4 ⁇ 0.5 mm in formulations E5, E8, E11 and E14 .
  • the rinsing power of the formulations according to the invention was also largely determined - with the exception of E9, E10 and E16 .
  • the determination was determined in a semi-automatic plate test apparatus using two different pure fatty soils I and II or a greasy mixed soiling in an application concentration of 4 and / or 8 g / 10 l. In this case, at a constant temperature of 40 or 45 ° C in 5 liters of water hardness 16 ° under constant conditions compared to a high-quality classical hand dishwashing detergent as a laboratory standard soiled with the test soil plate rinsed until the - formed before the experiment - foam destroyed was and the plates were not clean anymore.
  • the concentration of the agent was 4 or 8 g per liter of water.
  • the number of rinsed plates is listed in Tables 1 to 3 in percent relative to a set as 100% commercial high-performance hand dishwashing detergents as flushing power to each dirt at the concentration specified.
  • the means E3 to E7 and E15 prove by their high flushing power the superiority of hand dishwashing detergents according to the invention.

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Claims (18)

  1. Agent épaissi, aqueux, contenant un ou plusieurs agents tensioactifs, en particulier agent pour le lavage manuel de la vaisselle, qui présente, à 20°C et à un taux de cisaillement de 30 s-1 une viscosité entre 500 et 18000 mPa.s, contenant
    a) un agent tensioactif anionique,
    b) un agent tensioactif amphotère,
    c) un polymère, choisi dans le groupe constitué par les polycarboxylates, de préférence les homopolymères et les copolymères de l'acide acrylique, en particulier les copolymères de l'acide acrylique, et les polysaccharides, de préférence les hétéropolysaccharides,
    d) des microcapsules, dans lesquelles un ou plusieurs ingrédients de l'agent sont totalement ou partiellement enfermés,
    l'agent présentant un pH dans la plage de 5 à 8.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient entre 0,01 et 10% en poids de microcapsules
  3. Agent selon l'une des revendications 1 ou 2, caractérisé en ce qu'il contient des microcapsules d'un diamètre le long de son étendue spatiale la plus grande de 100 nm à 10 mm, de préférence de 0,1 mm à 7 mm.
  4. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient des microcapsules dans lesquelles sont enfermés un ou plusieurs représentants du groupe comprenant les substances dermatologiquement actives, les substances actives antibactériennes, les huiles essentielles et les additifs pour l'amélioration de l'éclat des articles lavés ainsi que de l'aspect.
  5. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient 0,01 à 8% en poids, de préférence 0,1 à 7% en poids, en particulier 0,5 à 6% en poids et de manière particulièrement préférée 1 à 5% en poids de polymère.
  6. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient un agent tensioactif anionique du groupe des sulfates aliphatiques, en particulier les sulfates d'alcool gras, les éthersulfates d'alcool gras, les dialkyléthersulfates et les sulfates de monoglycérol, des sulfonates aliphatiques, en particulier les alcanesulfonates, les oléfinesulfonates, les éthersulfonates, les n-alkyléthersulfonates, les estersulfonates et les ligninesulfonates, des alkylbenzènesulfonates, des cyanamides d'acide gras, des esters de l'acide sulfosuccinique, des iséthionates d'acide gras, des acylaminoalcanesulfonates, des sarcosinates d'acide gras, des acides éthercarboxyliques et des alkyl(éther)phosphates, de préférence les éthersulfates d'alcool gras.
  7. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient un agent tensioactif amphotère du groupe constitué par les bétaïnes, les oxydes d'amine, les alkylamidoalkylamines, les acides aminés substitués par alkyle et les acides aminés acylés, de préférence la bétaïne, en particulier la carbobétaïne.
  8. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient en outre au moins un agent tensioactif non ionique.
  9. Agent selon la revendication précédente, caractérisé en ce qu'il contient des alkylpolyglycosides, de préférence des alkylpolyglucosides.
  10. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient
    (a) 0,2 à 49,8% en poids, de préférence 5 à 45% en poids, de manière particulièrement préférée 8 à 40% en poids d'agents tensioactifs anioniques, en particulier des éthersulfates d'alcool gras,
    (b) 0,1 à 14,9% en poids, de préférence 1 à 10% en poids, d'agents tensioactifs amphotères, en particulier des alkylamidobétaïnes et
    (c) 0,1 à 14,9% en poids, de préférence 1 à 10% en poids, d'agents tensioactifs non ioniques, en particulier des alkylpolyglucosides.
  11. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient entre 0,5 et 15% en poids de sulfates d'alcool gras.
  12. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient au total 0,2 à 60% en poids, de préférence 1 à 55% en poids, de manière particulièrement préférée 3 à 50% en poids, de manière extrêmement préférée 5 à 45% en poids d'agents tensioactifs.
  13. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient un ou plusieurs solvants, en particulier des alcools de bas poids moléculaire, de préférence en des quantités entre 0,1 et 12% en poids, de manière particulièrement préférée entre 1 et 10% en poids.
  14. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient un ou plusieurs acides dicarboxyliques et/ou leurs sels, seuls ou en mélange et/ou d'autres acides organiques ou leurs sels ou des sels inorganiques.
  15. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il présente, à 20°C et à un taux de cisaillement de 30 s-1, une viscosité entre 700 et 13000 mPa.s, de manière particulièrement préférée entre 900 à 10000 mPa.s.
  16. Agent selon l'une des revendications précédentes, caractérisé en ce qu'il contient d'autres adjuvants et additifs usuels dans les agents de lavage manuel de la vaisselle, en particulier des substances abrasives, des stabilisateurs UV, des parfums, des agents conférant un éclat, des colorants, des inhibiteurs de corrosion et/ou des conservateurs.
  17. Utilisation d'un agent selon l'une des revendications précédentes, comme agent de lavage manuel de la vaisselle.
  18. Utilisation d'un agent selon l'une des revendications précédentes comme agent de nettoyage pour surfaces dures.
EP00920698A 1999-04-22 2000-04-13 Agent detergent pour lavage manuel de la vaisselle avec microcapsules Expired - Lifetime EP1171568B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19918267 1999-04-22
DE19918267A DE19918267A1 (de) 1999-04-22 1999-04-22 Handgeschirrspülmittel mit Mikrokapseln
PCT/EP2000/003305 WO2000065020A1 (fr) 1999-04-22 2000-04-13 Agent detergent pour lavage manuel de la vaisselle avec microcapsules

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EP1171568A1 EP1171568A1 (fr) 2002-01-16
EP1171568B1 true EP1171568B1 (fr) 2005-10-26

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EP (1) EP1171568B1 (fr)
AR (1) AR023555A1 (fr)
AT (1) ATE307876T1 (fr)
AU (1) AU4118000A (fr)
CA (1) CA2306376A1 (fr)
CO (1) CO5210962A1 (fr)
DE (2) DE19918267A1 (fr)
ES (1) ES2251372T3 (fr)
WO (1) WO2000065020A1 (fr)

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AU4118000A (en) 2000-11-10
WO2000065020A1 (fr) 2000-11-02
ES2251372T3 (es) 2006-05-01
DE50011454D1 (de) 2005-12-01
EP1171568A1 (fr) 2002-01-16
DE19918267A1 (de) 2000-10-26
CA2306376A1 (fr) 2000-10-22
CO5210962A1 (es) 2002-10-30
ATE307876T1 (de) 2005-11-15

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