EP1171568A1 - Agent detergent pour lavage manuel de la vaisselle avec microcapsules - Google Patents

Agent detergent pour lavage manuel de la vaisselle avec microcapsules

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Publication number
EP1171568A1
EP1171568A1 EP00920698A EP00920698A EP1171568A1 EP 1171568 A1 EP1171568 A1 EP 1171568A1 EP 00920698 A EP00920698 A EP 00920698A EP 00920698 A EP00920698 A EP 00920698A EP 1171568 A1 EP1171568 A1 EP 1171568A1
Authority
EP
European Patent Office
Prior art keywords
weight
agent according
microcapsules
alkyl
agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00920698A
Other languages
German (de)
English (en)
Other versions
EP1171568B1 (fr
Inventor
Brigitte Giesen
Dagmar Zaika
Marion Wortmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication of EP1171568A1 publication Critical patent/EP1171568A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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.
  • Another problem is the difficulty with the stable incorporation of active ingredients into the detergent formulation (e.g. with perfumes or antibacterial agents), discoloration (e.g. with plant extracts or proteins), odor problems (e.g. with the addition of vinegar, antibacterial agents or plant extracts) or incompatibilities between the active ingredient and the detergent.
  • active ingredients e.g. with perfumes or antibacterial agents
  • discoloration e.g. with plant extracts or proteins
  • odor problems e.g. with the addition of vinegar, antibacterial agents or plant extracts
  • incompatibilities between the active ingredient and the detergent.
  • An elegant method for incorporating sensitive, chemically or physically incompatible and volatile ingredients is the use of microcapsules, in which these ingredients are enclosed during storage and transportation and from which they are released mechanically, chemically, thermally or enzymatically for use.
  • Microcapsules are finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers precipitate on the material (active ingredient) to be encased after emulsification and coacervation or interfacial polymerization.
  • the active ingredient is enclosed in a shell-like membrane (microcapsule in the narrower sense) or enclosed in a matrix (microsphere or sphere).
  • microcapsule is used in a summarizing sense for both variants, or if necessary both terms are placed side by side.
  • the micro Skopically small capsules, also called nanocapsules, can be dried like powder.
  • microencapsulation is used, for example, for perfume powders, which are easier and longer effective to use as microcapsules.
  • aqueous liquid dishwashing detergents with 20 to 45% by weight of anionic and / or nonionic surfactants, 3 to 10% by weight of electrolyte and capsules with a diameter of 1 to 4000 ⁇ m are made from the Polymer Carrageenan, polyvinyl alcohol or cellulose ether known, the polymer and the electrolyte concentration are selected so that the stability of the capsules in the agent and the dissolution of the capsules are guaranteed when diluted with water.
  • Such a dishwashing detergent contains, for example, 10% by weight capsules with a diameter of 4000 ⁇ m, 25% by weight of sodium dodecylbenzenesulfonate, 5% by weight of coco monoethanolamide, 7% by weight of sodium sulfate, 1.5% by weight of synthetic clay or 5% by weight capsules with a diameter of 4000 ⁇ m, 20% by weight sodium alkylbenzenesulfonate, 5% by weight sodium C 14-16- ⁇ -olefin sulfonate, 5% by weight lauric acid diethanolamide, 7% by weight % Sodium xylene sulfonate, 3% by weight ethanol, 1% by weight potassium chloride,
  • fragrance-containing microcapsules with a size of 200 to 500 ⁇ m, which can be found in the Dilute with water.
  • British Patent 1,471,406 (Unilever Ltd.) relates to liquid aqueous detergents containing at least 2% by weight of triethanolamine lauryl sulfate and a total of 8 to 50% by weight of surfactant and 0.5 to 2% by weight of water-soluble crosslinked polyacrylic acid with a molecular weight of more than 1,000,000 and 0.1 to 5% by weight of suspended phase, for example spheroidal capsules with a diameter of 0.1 to 5 mm, and have a pH of 5.5 to 11.
  • the invention was based on the object of providing a precisely meterable, excellently cleaning, skin-compatible, temperature and storage stable, pourable hand dishwashing liquid in which the possibly physically or chemically incompatible or sensitive ingredients in temperature, storage and transport stable, easy to handle and are integrated in a visually appealing form and only release them immediately before or during use.
  • the invention relates to a thickened aqueous surfactant-containing agent, in particular hand dishwashing agent, containing anionic surfactant, amphoteric surfactant, polymer and microcapsules, in which one or more ingredients of the agent are wholly or partly enclosed.
  • the active ingredients only mean the part contained in the microcapsules.
  • the present invention also relates to the use of the agent according to the invention as a hand dishwashing agent.
  • the detergents are just as good at cleaning other hard surfaces made of glass, ceramic, plastic or metal in the home and business. Accordingly, the present invention further relates to the use of the agent according to the invention as a cleaning agent for hard surfaces.
  • anionic surfactant and amphoteric surfactant brings about a particularly advantageous cleaning action and on the other hand, in conjunction with the polymer, a spatially particularly stable suspension of the microcapsules.
  • the otherwise usual use of large amounts of electrolyte salt to stabilize the microcapsules is therefore not necessary.
  • Visible microcapsules allow particularly precise, reproducible dosing by counting the microcapsules contained in the metered amount of hand dishwashing liquid.
  • fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives, preferably having 6 to 22 carbon atoms.
  • the former are preferred for ecological reasons, in particular because of their vegetable basis than based on renewable raw materials, without but to limit the teaching of the invention to them.
  • the oxo alcohols or their derivatives obtainable, for example, according to ROELE ⁇ / oxo synthesis can also be used accordingly.
  • alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is naturally only present in half the amount of the substance - sufficient to balance the charge - like the anion.
  • INCI means that the following - or possibly preceding - name is a name according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA).
  • CTFA Cosmetic, Toiletry, and Fragrance Association
  • CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service.
  • polymers are polycarboxylates, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers, such as acrylic acid-methacrylic acid copolymers, and polysaccharides, in particular heteropolysaccharides, and other customary polymeric thickeners.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenan and their salts, guar, guaran, tragacant, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar and their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, can alternatively, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, e.g.
  • 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 KeltroP, for example as cream-colored powder KeltroP T (transparent) or as white granulate Keltrof ' RD (f? ily dispersible).
  • KeltroP for example as cream-colored powder KeltroP T (transparent) or as white granulate Keltrof ' RD (f? ily dispersible).
  • Suitable acrylic acid polymers are, for example, high molecular weight homopolymers of acrylic acid (INCI carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyl vinyl polymers.
  • polyacrylic acids are obtainable inter alia from Fa. BFGoodrich under the tradename Carbopof ®, for example CarbopoP 940 (molecular weight approximately 4,000,000), Carbopof 941 (molecular weight approximately 1,250,000) or CarbopoP 934 (molecular weight approximately 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 esters ⁇ INCI acrylates copolymer), preferably formed with C 1-4 alkanols which about 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 available, for example from Messrs.
  • Rohm & Haas under the trade names Aculyn ® and AcusoP are, for example, the anionic non-associative polymers> 4c -.
  • the polymer content is usually between 0.01 and 8% by weight, preferably between 0.1 and 7% by weight, particularly preferably between 0.5 and 6% by weight, 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 agents according to the invention is adjusted or controlled essentially via the polymer content, the amounts required can vary from polymer to polymer.
  • the surfactant composition used also plays a role in the choice of quantity.
  • the hand dishwashing detergent according to the invention contains a combination of at least one anionic surfactant with at least one amphoteric surfactant.
  • at least one nonionic surfactant is additionally contained.
  • the surfactants are usually used in amounts of 0.2 to 60% by weight, preferably 1 to 55% by weight, particularly preferably 3 to 50% by weight and extremely preferably 5 to 45% by weight.
  • the surfactant content is usually 5 to 35% by weight, preferably 10 to 30% by weight, in particular 14 to 25 % By weight.
  • the surfactant content is usually 30 to 60% by weight, preferably 35 to 55% by weight, in particular 38 up to 52% by weight.
  • Anionic surfactants according to the invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, /. Alkyl ether sulfonates, ester sulfonates and lignin sulfonates.
  • Alkylbenzenesulfonates fatty acid cyanamides, sulfobemosuccinates, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid aurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
  • the fatty alcohol ether sulfates are particularly preferred in the context of the present invention.
  • Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • alkoxylated alcohols generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention preferably with longer-chain alcohols.
  • a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions.
  • a further embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Low-ethoxylated fatty alcohols are very particularly preferred for the purposes of the present invention. Get 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 sulfates, are preferably used in amounts of 0.2 to 49.8% by weight, particularly preferably 5 to 45% by weight, in particular 8 to 40% by weight and extremely preferably 10 to 36% by weight .-%.
  • the agent contains, as the sole or preferably additional anionic surfactant, in particular in combination with fatty alcohol ether sulfates, fatty alcohol sulfates, preferably between 0.5 and 15% by weight of fatty alcohol sulfates.
  • amphoteric surfactants which can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which betaines are particularly preferred in the context of the teaching according to the invention.
  • Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula I,
  • R 1 is a saturated or unsaturated Ce ⁇ alkyl radical, preferably C 8 . 18 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical,
  • n is a number from 1 to 10, preferably 2 to 5, in particular 3, x 0 or 1, preferably 1,
  • R 2 , R 3 independently of one another are a C 1-4 -alkyl radical, optionally hydroxy-substituted, such as, for example, a hydroxyethyl radical, but in particular a methyl radical, m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and Y COO, SO 3 , OPO (OR 5 ) O or P (O) (OR 5 ) O, where R 5 is a hydrogen atom
  • alkyl and alkyl amido betaines, betaines of formula I with a carboxylate group are also called carbobetaines.
  • Preferred amphoteric surfactants are the alkyl betaines of the formula (Ia), the alkyl amido betaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),
  • 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 alkylamidobetaines of the formula (Ib).
  • betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, Babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, capryl / capramidopropyl betaines, beta-amine, beta-amine, betaine , Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Co-Co-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycina- te, Dihydroxyethyl Stearyl Glycinate, Dihydroxyeth
  • the amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • alkylamine oxides in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Preferred amine oxides satisfy formula II
  • R 6 a saturated or unsaturated Ce - ⁇ - alkyl radical, preferably C 8 . 18 -alkyl radical, in particular a saturated C 10 . 16 -alkyl radical, for example a saturated C 12-14 -alkyl radical, which in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH 2 ) z - is bonded to the nitrogen atom N, where z for a number from 1 to 10, preferably 2 to 5, in particular 3, R 7 , R 8, independently of one another, is a d- 4 -alkyl radical, optionally hydroxy-substituted, such as, for example, a hydroxyethyl radical , in particular a methyl radical.
  • Suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidium Oxide Oxide Alkoxypropylamine oxides, dihydroxyethyl C9-11 alkoxypropylamine oxides, dihydroxyethyl C12-15 alkoxypropylamine oxides, dihydroxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamine oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel amine oxides, hydrogenated hydroxylethyl hydroxyl oxides Alkoxypropylamine Oxide, Isostearamidopropyl
  • alkylamidoalkylamines are amphoteric surfactants of the formula (III)
  • R 9 a saturated or unsaturated Ce - ⁇ - alkyl radical, preferably C 8 . 18 alkyl radical, in particular a saturated C 10- ⁇ 6 alkyl radical, for example a saturated C 12-14 alkyl radical,
  • R 10 is a hydrogen atom H or a C 1-4 alkyl radical, preferably H, i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
  • R 11 is a hydrogen atom H or CH 2 COOM (to M su), j is a number from 1 to 4, preferably 1 or 2, in particular 1, k is a number from 0 to 4, preferably 0 or 1,
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine.
  • alkylamidoalkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA- Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate.
  • Disodium Capryloamphodiacetate Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 pionate Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipro-, Disodium PPG-2-lsodeceth-7 Carboxyamphodiacetate, Disodium Stearoam - phodiacetate, proamphohydroxypropylsulfonate Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium
  • Preferred alkyl-substituted amino acids according to the invention are monoalkyl-substituted amino acids according to formula (IV),
  • R 13 a saturated or unsaturated Ce - ⁇ - alkyl radical, preferably C 8 . 18 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12 . 14 -alkyl radical
  • R 14 is a hydrogen atom H or a C M -alkyl radical, preferably H
  • u is a number from 0 to 4, preferably 0 or 1, in particular 1
  • M ' is a hydrogen, an alkali metal detail, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine,
  • R 15 is a saturated or unsaturated Ce ⁇ alkyl radical, preferably C 8 . 18 -alkyl radical, in particular a saturated C 10 . 16 alkyl radical, for example a saturated C 12-14 alkyl radical, v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine, where M" may have the same or two different meanings in the two carboxy groups, e.g. Can be hydrogen and sodium or twice sodium is
  • R 16 a saturated or unsaturated C, 5 . 22 alkyl radical, preferably C 8-18 alkyl radical, in particular a saturated C 1 (M6 alkyl radical, for example a saturated C 12.
  • R 17 is a hydrogen atom or a C 1-4 alkyl radical, optionally hydroxy - or amine-substituted, for example a methyl, ethyl, hydroxyethyl or amine propyl radical
  • R 18 is the radical of one of the 20 natural ⁇ -amino acids H 2 NCH (R 18 ) COOH
  • M '" is a hydrogen, an alkali metal Alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa)
  • alkyl-substituted amino acids are the following compounds named according to INCI: aminopropyl lauryl glutamine, cocaminobutyric acid, cocaminopropionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium lauhminodipropionate, disodium stodipionionate, disodium stodipionate, disodium stodipionate, disodium stodipionate, disodium stodipinionate, disodium stodipinionate, disodium stodipinionate, disodium stodipinionate, disodium stodipinionate, disodium stodipinionidate, disodium stodipropionate, disodium stodipodioninate Diethylenedia
  • Acylated amino acids are amino acids, in particular the 20 natural ⁇ -amino acids, which carry 19 COOH at the amino nitrogen is the acyl radical R 19 CO of a saturated or unsaturated fatty acid R, where R 19 is a saturated or unsaturated C 6-22.
  • the acylated amino acids can also be used as 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 alkylamido betaines, are preferably used in amounts of 0.1 to 14.9% by weight, in particular 1 to 10% by weight, extremely preferably 1.5 to 8% by weight, for example 2 to 7 % By weight.
  • Nonionic surfactants in the context of the invention can 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. Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers can also be used.
  • An important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glycotene surfactants, such as alkyl polyglycosides and fatty acid glucamides.
  • alkyl polyglycosides are particularly preferred, in particular the alkyl polyglucosides.
  • Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols using the relevant methods of preparative organic chemistry, depending on the type of preparation, a mixture of monoalkylated, oomeric or polymeric sugars is preferred.
  • Preferred alkyl polyglycosides are the alkyl poly- glucosides, the alcohol being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 -C 18 -alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, in particular 1 being particularly preferred , 1 to 3, most preferably 1.1 to 1.7
  • One or more nonionic surfactants are preferably used in amounts of 0.1 to 14.9% by weight, in particular 1 to 10% by weight and extremely preferably 1.5 to 5% by weight, for example 2 to 3% by weight. % used
  • the hand dishwashing detergent contains
  • anionic surfactants in particular fatty alcohol ether sulfates,
  • microcapsules that can be used are all the surfactant-stable capsules and capsule materials or spheres and spherical materials available on the market, such as Hallcrest Microcapsules (capsule material gelatin, gum arabic) from Hallcrest, Ine (US), Coletica Thalaspheres (capsule material from Maritime Collica) (FR), Lipotec milk capsules (capsule material alginic acid, agar-agar) from Lipotec SA (ES), Induchem Unispheres (capsule material lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose) and Unicenn C30 (capsule material lactose, microcrystalline cellulose (hydroxypropylmethyl cellulose), derypropylmethyl cellulose CH), Kobo Glycospheres (capsule material modified starch, fatty acid esters, phospholipids) and Softspheres (capsule material modified agar agar) from Kobo (US) as well as Kuhs Probiol Nanospheres (capsule material phospholipids
  • the diameter along its greatest spatial extent can be between 100 nm (not visually recognizable as a capsule) and 10 mm.
  • the preferred diameter is in the range between 0.1 mm and 7 mm, microcapsules with a diameter between 0.4 mm and 5 mm are particularly preferred.
  • Active substances in the sense of the invention include dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate -Fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as Lecithin, soybean oil, etc., plant extracts such as e.g. Aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, A.H.A. complexes. Active substances in the sense of the invention are also antibacterial active substances, such as e.g.
  • Benzoic acid lactic acid, salicylic acid, sorbic acid or mixtures thereof or their salts.
  • active ingredients within the meaning of the invention are essential oils such as. B. perfumes, limes, geraniol, nerol as well as additives to improve the wash load gloss, e.g. Understand vinegar. Colorants, color pigments or pearlescent components are added to improve the appearance.
  • the hand dishwashing detergent according to the invention contains microcapsules in which one or more representatives from the group comprising dermatologically active substances, antibacterial active substances, essential oils and additives for improving the wash load gloss and the appearance are included.
  • the active ingredient can be released from the microcapsules both by grinding the microcapsules during the cleaning process and by breaking them open using a suitable metering device. It is also conceivable to release the active ingredient by changing the temperature (introducing it into warm soapy water), by shifting the pH value, changing the electrolyte content, etc.
  • the content of microcapsules is usually from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.2 to 3% by weight and extremely preferably from 0.3 to 2% by weight, wherein the agent according to the invention can contain only identical microcapsules or else mixtures of different types of microcapsules.
  • the viscosity which is favorable for the agents according to the invention is at 20 ° C. and a shear rate of 10 s -1 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, or at 20 ° C and a shear rate of 30 s ' 1 between 500 and 18,000 mPa-s, preferably between 700 and 13,000 mPa-s, particularly preferably between 900 and 10,000 mPa-s, in particular between 1,100 and 8,000 mPa-s, extremely preferably between 1,300 and 6,500 mPa-s, for example between 1,000 and 4,000 mPa-s.
  • Preferred zero shear viscosity values ⁇ 0 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 can vary from polymer to polymer.
  • the surfactant composition used also plays a role in the choice of quantity, as does the presence of solubilizers.
  • solubilizers for example for dyes and perfume oils, for example alkanolamines, polyols such as ethylene glycol, 1, 2-propylene glycol, glycerol and other mono- and polyhydric alcohols and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical can be used.
  • alkanolamines polyols such as ethylene glycol, 1, 2-propylene glycol, glycerol and other mono- and polyhydric alcohols and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical can be used.
  • one or more dicarboxylic acids and / or their salts can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, such as those sold under the trade name Sokalan ® DSC is available.
  • the use here is advantageous in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1, 3 to 6% by weight and particularly preferably 2 to 4% by weight.
  • dicarboxylic acids and / or their salts instead of or in addition to the dicarboxylic acids and / or their salts, other organic acids or their salts, such as, for example, sodium formate, sodium acetate, sodium citrate and sodium tartrate, and inorganic salts, such as e.g. Sodium chloride, magnesium chloride and magnesium sulfate, or also salts of the aforementioned anions with other alkali or alkaline earth metals can be used individually or in mixtures.
  • organic acids or their salts such as, for example, sodium formate, sodium acetate, sodium citrate and sodium tartrate
  • inorganic salts such as e.g. Sodium chloride, magnesium chloride and magnesium sulfate, or also salts of the aforementioned anions with other alkali or alkaline earth metals can be used individually or in mixtures.
  • solvents in particular lower alcohols, preferably ethanol, n-propanol or / ' so-propanol, particularly preferred ethanol. They contribute to the incorporation of perfume and dye, prevent the formation of liquid-crystalline phases and play a part in the formation of clear products.
  • the viscosity can be reduced by increasing the amount of solvent. However, too much solvent causes the viscosity to drop too much. Therefore, according to the invention, one or more solvents are usually present in amounts of 0.1 to 12% by weight, preferably 1 to 10% by weight, particularly preferably 3 to 8% by weight, for example 5 to 6% by weight .
  • a further improved cleaning performance, especially in the case of burnt-on dirt, is obtained when using abrasives, preferably water-soluble abrasives, in particular alkali metal bicarbonate, alkali metal sulfate.
  • auxiliaries and additives customary in hand dishwashing detergents in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents; for example glycol distearate, for example Cutina 1 ' AG S from Henkel KGaA, or be, usually no longer contain the Euperlane ® from. Henkel KGaA), dyes, corrosion inhibitors and / or preservatives in amounts of 5 wt .-% as mixtures comprising, for example.
  • the pH of the agents according to the invention can be adjusted by means of customary pH regulators, for example citric acid or NaOH, a range from 5 to 8, preferably 5.5 to 7.5, in particular 5, essentially due to the required hand compatibility. 7 to 7 is preferred.
  • customary pH regulators for example citric acid or NaOH
  • the hand dishwashing detergents according to the invention can be produced by stirring the individual components together in any order.
  • the order of preparation is not decisive for the preparation of the agent.
  • Agents E1 to E16 according to the invention were prepared as described above and their pH, viscosity and storage stability were determined.
  • compositions of the agents E1 to E16 according to the invention in% by weight and the specific properties are shown in Tables 1 to 3.
  • a number of the agents E1 to E16 according to the invention contained traces of dye.
  • the pH of the agents E1 to E16 according to the invention was adjusted to between 5.5 and 7 with citric acid.
  • the viscosity of the agents E1 to E16 according to the invention was determined at 20.degree. C. according to Brookfield (viscometer ⁇ roo // e / o'V DV // +; spindle 25; rotational frequency 30 min "1 ).
  • the stability of the agents was checked by visually assessing the agents after four weeks' storage at room temperature of 20 ° C, at an elevated temperature of 40 ° C or in the cold at a temperature of 5 ° C. None of the agents showed - regardless of the storage temperature - a visually perceptible change after 4 weeks, in particular, neither a change in the shape of the capsules nor in their spatial distribution was observed on average.
  • Microcapsule ⁇ Lipotec Type III 0.5 - - - - - - -
  • Microcapsule (Lipotec Type II ML 210) - 0.5 - - - - - -
  • Microcapsule ⁇ Lipotec Type I ML 051) 0.5 - - 0.2 - - 0.8
  • microcapsules used were clearly visible to the naked eye from a distance of approximately 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 performance of the recipes according to the invention was also largely determined - apart from E9, E10 and E16. The determination was determined in a semi-automatic plate test apparatus using two different pure grease stains I and II or a greasy mixed stain in an application concentration of 4 and / or 8 g / 10 l. The plates were soiled with the test dirt at a constant temperature of 40 or 45 ° C in 5 l of water with a hardness of 16 ° under constant conditions compared to a high-quality classic hand dishwashing liquid as a laboratory standard until the foam - which had formed before the start of the test - was destroyed was and the plates were no longer clean. The concentration of the agent was 4 or 8 g per liter of water. The number of dishes washed is shown in Tables 1 to 3 as a percentage in relation to a commercially available high-performance hand dishwashing detergent used as washing performance on the respective dirt at the concentration specified.
  • agents E3 to E7 and E15 demonstrate the superiority of inventive hand dishwashing detergents due to their high washing performance.

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne un agent détergent pour lavage manuel de la vaisselle et a pour but de fournir un agent de ce type qui soit fluide, stable à la température et au stockage, tolérant pour la peau, dosable avec précision, de propriétés nettoyantes remarquables, dans lequel les constituants physiquement ou chimiquement incompatibles ou sensibles sont incorporés sous une forme stable à la température, au stockage et au transport, facilement manipulable et appropriée optiquement, et sont libérés immédiatement avant l'utilisation ou pendant l'utilisation. Ce but est atteint grâce à l'invention, laquelle a pour objet un agent aqueux, épaississant, tensio-actif, renfermant des tensio-actifs anioniques, des tensio-actifs amphotères, des polymères, ainsi que des microcapsules dans lesquelles un ou plusieurs constituants de détergent lave-vaisselle sont inclus totalement ou partiellement.
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

Publications (2)

Publication Number Publication Date
EP1171568A1 true EP1171568A1 (fr) 2002-01-16
EP1171568B1 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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DE102007017654A1 (de) 2007-04-12 2008-10-16 Henkel Ag & Co. Kgaa Bis(hydroxychinolin)-Metallkomplexe als Bleichkatalysatoren
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Publication number Publication date
EP1171568B1 (fr) 2005-10-26
AR023555A1 (es) 2002-09-04
AU4118000A (en) 2000-11-10
WO2000065020A1 (fr) 2000-11-02
ES2251372T3 (es) 2006-05-01
DE50011454D1 (de) 2005-12-01
DE19918267A1 (de) 2000-10-26
CA2306376A1 (fr) 2000-10-22
CO5210962A1 (es) 2002-10-30
ATE307876T1 (de) 2005-11-15

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