EP2895588B1 - Détergent liquide structuré à faible teneur en eau contenant des particules - Google Patents

Détergent liquide structuré à faible teneur en eau contenant des particules Download PDF

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Publication number
EP2895588B1
EP2895588B1 EP13756451.4A EP13756451A EP2895588B1 EP 2895588 B1 EP2895588 B1 EP 2895588B1 EP 13756451 A EP13756451 A EP 13756451A EP 2895588 B1 EP2895588 B1 EP 2895588B1
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EP
European Patent Office
Prior art keywords
cleaning agent
water
washing
soluble
liquid
Prior art date
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Application number
EP13756451.4A
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German (de)
English (en)
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EP2895588A1 (fr
Inventor
Frank Meier
Dirk Weinrich
Luca Bellomi
Sabine SCHÜMANN
Matthias Sunder
Thorsten Ott
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP2895588A1 publication Critical patent/EP2895588A1/fr
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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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) 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
    • C11D1/66—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
    • 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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D17/0017—Multi-phase 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • 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
    • C11D3/162—Organic compounds containing Si

Definitions

  • the invention relates to a liquid washing or cleaning agent comprising surfactant, dispersed particles and hydrophobically surface-modified silicon dioxide.
  • the invention also relates to a water-soluble packaging comprising such a liquid washing or cleaning agent.
  • Detergents and cleaning agents are now available to consumers in a wide variety of forms. In addition to powders and granules, this range also includes, for example, liquids, gels or portion packs (tablets or filled bags).
  • portion packs with liquid detergents or cleaning agents are becoming more and more popular; on the one hand, they meet the consumer's desire for simplified dosing and, on the other hand, more and more consumers are preferring liquid washing or cleaning agents.
  • liquid detergents or cleaning agents for packaging in water-soluble bags contain the lowest possible water content.
  • Liquid low-water detergent compositions which dissolve and disperse satisfactorily in water are disclosed, for example, in the international patent publication WO 02/057398 A1 described.
  • washing or cleaning agents can contain perfume capsules.
  • Stably suspending particles, such as perfume capsules, in liquids is often problematic. In particular, if the solids differ in density from the liquid, they tend to sediment or float.
  • the washing or cleaning agents contain a structuring agent.
  • Suitable structuring agents are, for example, structuring gums such as xanthan gum, guar gum, locust bean gum, gellan gum, wellan gum or carrageenan, or polyacrylate thickeners.
  • structuring agents require water in order to develop their structuring properties in a formulation. This stands in the way of structuring low-water detergents or cleaning agents, such as those used in water-soluble packaging. In addition, it is not always possible to create flow limits in systems rich in electrolytes and / or surfactants.
  • hydrophobically surface-modified pyrogenic silicon dioxide leads to structured, low-water washing or cleaning agents with dispersing properties, in which particles can be dispersed in a stable and homogeneous manner.
  • the structured washing or cleaning agents obtained are clear and transparent.
  • the surfactant is selected from the group consisting of nonionic surfactants, anionic surfactants and mixtures thereof.
  • nonionic surfactants anionic surfactants or a mixture thereof in the low-water liquid laundry detergent or cleaning agent.
  • Liquid detergents or cleaning agents which contain pyrogenic silicon dioxide surface-modified with dimethyldichlorosilane are particularly clear.
  • Liquid detergents or cleaning agents which contain pyrogenic silicon dioxide surface-modified with hexadecylsilane have a flow limit.
  • the water-soluble casing contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble casings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.
  • the liquid washing or cleaning agent necessarily contains a surfactant, particles, pyrogenic, hydrophobic surface-modified silicon dioxide and up to 15% by weight of water.
  • the liquid washing or cleaning agents contain surfactant (s), these being selected from anionic, nonionic, cationic and / or zwitterionic surfactants. Mixtures of anionic and nonionic surfactants are used according to the invention.
  • the total surfactant content of the liquid washing or cleaning agent is up to 85% by weight, is preferably below 75% by weight and particularly preferably below 70% by weight, based on the total liquid washing or cleaning agent.
  • the liquid detergent or cleaning agent contains nonionic surfactants.
  • the content of nonionic surfactant is preferably 5 to 40% by weight and more preferably 10 to 35% by weight, based in each case on the total liquid detergent or cleaning agent.
  • Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
  • a particularly preferred nonionic surfactant which can be used in the liquid washing or cleaning agent is an alkoxylated oxo alcohol.
  • Oxo alcohols are primary, partially branched, higher alcohols that are obtained in the oxo synthesis. Oxo-aldehydes or their primary aldocondensation products are converted into the corresponding oxo-alcohols by catalytic hydrogenation.
  • a C 13-15 oxo alcohol with 7 EO, a C 13-15 oxo alcohol with 8 EO or a mixture of these two oxo alcohols is preferably used as the nonionic surfactant in the liquid detergents or cleaning agents.
  • Alkoxylated fatty alcohols are particularly suitable as further nonionic surfactants. These are preferably ethoxylated, in particular primary alcohols with in particular 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol.
  • EO ethylene oxide
  • alcohol ethoxylates with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohol with 7 EO, C 12-18 alcohols with 5 EO or 7 EO and mixtures of these.
  • the stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol such as, for example, a mixture of a C 16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
  • the content of alkoxylated oxo alcohol is preferably 5 to 40% by weight and more preferably 10 to 35% by weight, based in each case on the total liquid detergent or cleaning agent.
  • the amount of further nonionic surfactants is preferably less than 5% by weight, more preferably less than 2% by weight and particularly preferably less than 1% by weight, based in each case on the total amount of liquid detergent or cleaning agent.
  • the liquid washing or cleaning agent also contains an anionic surfactant.
  • the content of anionic surfactant is preferably 5 to 50% by weight and more preferably 10 to 40% by weight, based in each case on the total liquid detergent or cleaning agent.
  • Suitable anionic surfactants include alkylbenzenesulfonic acid salts, olefin sulfonic acid salts, C 12-18 alkanesulfonic acid salts, salts of sulfuric acid monoesters with a fatty alcohol, a fatty acid soap, salts of sulfuric acid monoesters with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants.
  • alkylbenzenesulfonic acid salts, fatty acid soaps, and mixtures thereof are particularly preferred.
  • Surfactants of the sulfonate type are preferably C 9-13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is possible.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • the alk (en) yl sulfates are the salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters secondary alcohols of these chain lengths are preferred. From the point of view of washing technology, the C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates are preferred. 2,3-Alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the sulfuric acid monoesters of straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 -18 fatty alcohols with 1 to 4 EO are suitable.
  • Suitable anionic surfactants are fatty acid soaps.
  • Saturated and unsaturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, are suitable.
  • the anionic surfactants can be in the form of their sodium, potassium or magnesium or ammonium salts.
  • the anionic surfactants are preferably in the form of their sodium salts or ammonium salts.
  • Amines which can be used for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, monoethanolamine being preferred.
  • the liquid washing or cleaning agent contains an alkylbenzenesulfonic acid neutralized with monoethanolamine, in particular C 9-13 -alkylbenzenesulfonic acid, and / or a fatty acid neutralized with monoethanolamine.
  • the total amount of anionic surfactant and nonionic surfactant in the liquid washing or cleaning agent is 40 to 75% by weight and preferably 50 to 70% by weight, based on the total liquid washing or cleaning agent.
  • the detergent or cleaning agent is liquid.
  • the washing or cleaning agent can contain water, the water content being less than 15% by weight and more preferably less than 10% by weight, based in each case on the total washing or cleaning agent.
  • a liquid detergent or cleaning agent contains particles whose diameter along their greatest spatial extent is preferably 1 to 300 ⁇ m and more preferably 5 to 100 ⁇ m.
  • particles can be capsules, abrasives and also powders, granulates or compounds of compounds that are insoluble in the liquid washing or cleaning agent.
  • the particles are capsules.
  • the particles are compounds which are insoluble in the liquid washing or cleaning agent, in particular cellulose derivatives, such as, for example, carboxymethyl cellulose or hydroxyalkylmethyl celluloses, or pearlescent compounds.
  • capsule means, on the one hand, aggregates with a core-shell structure and, on the other hand, aggregates with a matrix.
  • Core-shell capsules contain at least one solid or liquid core, which is enclosed by at least one continuous shell, in particular a shell made of polymer (s).
  • the capsules can contain, for example, optical brighteners, surfactants, complexing agents, bleaching agents, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti-redeposition agents, pH adjusters, electrolytes, detergency boosters, vitamins, proteins , Foam inhibitors and UV absorbers.
  • the fillings of the capsules can be solids or liquids in the form of solutions or emulsions or suspensions.
  • the capsules can have any shape within the scope of the production process, but they are preferably approximately spherical. Their diameter along their greatest spatial extent can, depending on the components contained in their interior and the application, be between 1 ⁇ m and 100 ⁇ m, preferably between 5 and 40 ⁇ m.
  • particles which do not have a core-shell structure, but in which the active ingredient is distributed in a matrix made of a matrix-forming material. Such particles are also referred to as "speckles”.
  • the matrix formation takes place, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the prior art, as is the production of particles with these matrix-forming materials.
  • An exemplary matrix-forming material is alginate.
  • an aqueous alginate solution which also contains the active ingredient or ingredients to be included, is dripped and then hardened in a precipitation bath containing Ca 2+ ions or Al 3+ ions.
  • a precipitation bath containing Ca 2+ ions or Al 3+ ions.
  • other matrix-forming materials can be used instead of alginate.
  • the active ingredients are usually released from the capsules by destroying the shell or the matrix as a result of mechanical, thermal, chemical or enzymatic action.
  • the liquid washing or cleaning agents contain capsules in which one or more fragrances are contained.
  • the cellulose derivative is preferably selected from the group consisting of carboxymethyl cellulose (CMC), an ethersulfonic acid salt of cellulose, an acidic sulfuric acid ester salt of cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, methylhydroxyethyl cellulose, methyl carboxymethyl cellulose and a mixture of these cellulose, methyl carboxymethyl cellulose derivatives.
  • Particularly preferred cellulose derivatives include carboxymethyl cellulose, hydroxypropylmethyl cellulose, methylhydroxyethyl cellulose or mixtures of two or more of these cellulose derivatives.
  • the diameter along the greatest spatial extent of the cellulose derivatives is preferably 5 to 250 ⁇ m.
  • Suitable pearlescent compounds include, for example, mica, metal oxide coated mica, silica coated mica, bismuth oxychloride coated mica, bismuth oxychloride, glass, metal oxide coated glass, polyester glitter and / or metal glitter.
  • the diameter along the greatest spatial extent of the pearlescent compounds is preferably 5 to 25 ⁇ m.
  • a particularly preferably usable pearlescent compound is, for example, COSMI® SW-20 (ex Wunzhou Kuncai Pearlescent Pigment Co., LTD).
  • the particles can comprise abrasives such as spheres made of plastic or calcium carbonate as well as powders, granulates or compounds of compounds that are insoluble in the detergent or cleaning agent.
  • abrasives such as spheres made of plastic or calcium carbonate as well as powders, granulates or compounds of compounds that are insoluble in the detergent or cleaning agent.
  • the particles can be stably dispersed in the liquid detergents or cleaning agents.
  • Stable means that the washing or cleaning agents are stable at room temperature for a period of at least 4 weeks and preferably for at least 6 weeks without the particles in the agent creaming or sedimenting.
  • the liquid detergent or cleaning agent contains the same or different particles in amounts of 0.1 to 10% by weight, in particular 0.15 to 8% by weight and extremely preferably 0.2 to 5% by weight. -%.
  • Synthetic silicon dioxide is produced on an industrial scale in various processes. The large-scale production of synthetic silicon dioxide takes place mainly via precipitation processes starting from water glass. Silicon dioxide produced in this way is called precipitated silicas, silica gels or colloidal silicic acid, depending on the process conditions. Pyrogenic silicon dioxide is produced in an oxyhydrogen flame from liquid chlorosilanes such as silicon tetrachloride (SiCl 4 ).
  • pyrogenic, hydrophobically surface-modified silicon dioxide is particularly suitable for structuring low-water detergents or cleaning agents.
  • Particularly clear and storage-stable detergents or cleaning agents with dispersing properties are obtained if the pyrogenic silicon dioxide is hydrophobically surface-modified.
  • Particularly good and stable structuring is obtained when using hexadecylsilane or dimethyldichlorosilane surface-modified pyrogenic silicon dioxide in the liquid detergents or cleaning agents.
  • Suitable pyrogenic, hydrophobically surface-modified silicon dioxide is available, for example, under the names Aerosil® R 972, Aerosil® R 974 and Aerosil® R 816 from Evonik.
  • the amount of pyrogenic, hydrophobically surface-modified silicon dioxide in the liquid washing or cleaning agent is preferably 0.1 to 10% by weight and particularly preferably 0.2 to 2% by weight.
  • the liquid washing or cleaning agents structured with pyrogenic, hydrophobically surface-modified silicon dioxide preferably have a viscosity in the range from 200 to 2,000 mPas and more preferably in the range from 300 to 800 mPas.
  • the viscosity is determined at 20 ° C. and with a Brookfield rotary viscometer type RVT at 20 rpm.
  • liquid detergents or cleaning agents which are structured with pyrogenic silicon dioxide surface-modified with hexadecylsilane have a flow limit. This is at least 0.1 Pa and preferably at least 0.3 Pa.
  • the flow limits of the liquid detergents or cleaning agents were measured with a rotary rheometer from TA Instruments, type AR G2 at 20.degree. This is a so-called shear stress controlled rheometer.
  • a shear stress s (t) increasing with time was applied to the samples in the rheometer.
  • the shear stress can be increased from the lowest possible value (eg 2 mPa) to eg 10 Pa in the course of 10 minutes.
  • the deformation ⁇ of the sample is measured as a function of this shear stress.
  • the deformation is plotted against the shear stress in a double logarithmic plot. If the examined sample has a flow limit, one can clearly distinguish two areas in this plot. Below a certain shear stress there is a purely elastic deformation.
  • the slope of the curve ⁇ ( ⁇ ) (log-log plot) in this area is one.
  • the detergent or cleaning agent can contain other ingredients that affect the application technology and / or Further improve the aesthetic properties of the detergent or cleaning agent.
  • the detergent or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaches, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors , Anti-seizure agents, anti-crease agents, dye transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bitter agents, ironing aids, repellent and impregnating agents, skin-care agents, and anti-UV and anti-slip agents, as well as UV and anti-slip agents -Absorber.
  • the liquid detergent or cleaning agent can be filled into a water-soluble envelope and thus be part of a water-soluble packaging.
  • a water-soluble packaging also contains a water-soluble casing.
  • the water-soluble envelope is preferably formed by a water-soluble film material.
  • Such water-soluble packages can be produced by either vertical form fill sealing (VFFS) or thermoforming processes.
  • VFFS vertical form fill sealing
  • thermoforming processes thermoforming processes
  • the thermoforming process generally includes forming a first layer of a water-soluble sheet material to form bulges for receiving a composition therein, pouring the composition into the bulges, covering the bulges filled with the composition with a second layer of a water-soluble sheet material, and sealing the first and second layers with one another at least around the bulges.
  • the water-soluble envelope is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures.
  • the envelope can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, can be the same or different.
  • the water-soluble packaging comprising the liquid washing or cleaning agent and the water-soluble casing, can have one or more chambers.
  • the liquid washing or cleaning agent can be contained in one or more chambers, if present, of the water-soluble envelope.
  • the amount of liquid detergent or cleaning agent preferably corresponds to the full or half the dose that is required for a wash cycle.
  • the water-soluble casing contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Suitable water-soluble films for producing the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble envelope can additionally contain a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers may be added.
  • a preferred additional polymer are polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include vinyl alcohol as well as an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol.
  • the film material contains further additives.
  • the film material can for example contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerine, sorbitol, mannitol or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-stick agents or mixtures thereof.
  • Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable foils include foils with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the foils VF-HP from Kuraray.
  • the water-soluble packaging can be designed to be dimensionally stable or deformable.
  • the water-soluble packaging can be designed as a dimensionally stable container, for example in the form of a capsule, box, jar or container.
  • the water-soluble packaging in principle, however, it is also possible and preferred to shape the water-soluble packaging as a non-dimensionally stable container, for example as a bag.
  • the shape of such a water-soluble packaging can largely be adapted to the conditions of use. For example, a wide variety of shapes such as hoses, cushions, cylinders, bottles or disks are possible.
  • the water-soluble packaging can have one or more chambers for storing one or more agents.
  • the low-water washing or cleaning agents according to the invention and the water-soluble packaging according to the invention with the low-water washing or cleaning agent can be used for washing or cleaning textile or hard surfaces by using the low-water washing or cleaning agent according to the invention or the water-soluble packaging according to the invention with the low-water Washing or cleaning agent a washing or cleaning liquor is produced and this is brought into contact with the surface to be treated.
  • Liquid detergents or cleaning agents were produced using customary and known methods and processes. Table 1 below shows the compositions of four washing or cleaning agents E1 to E4 according to the invention and six washing or cleaning agents V1 to V6 not according to the invention. Table 1: Liquid detergents or cleaning agents E1 to E4 and V1 to V6 [all amounts are given in% by weight of active ingredient, based on the composition] ingredients E1 E2 E3 E4 V1 V2 V3 V4 V5 V6 C 10 -C 13 alkyl benzene sulfonic acid 21st 21st 21st 21st 21st 21st 21st 21st 21st 21st C 13 -C 15 oxo alcohol with 8 EO 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5
  • the four washing or cleaning agents E1 to E4 were clear and stable for 8 weeks under various climatic conditions.
  • the detergents or cleaning agents E2 and E3 had a particularly clear appearance.
  • the detergent or cleaning agent E1 had a flow limit of 0.3 Pa.
  • the detergent or cleaning agent E4 had a flow limit of 0.7 Pa.
  • each of the two washing or cleaning agents E1 and E2 0.2% by weight of perfume capsules with a particle diameter d 90 of less than 15 ⁇ m were homogeneously dispersed. 0.4% by weight of a mica and TiO 2 -containing pearlescent compound with a diameter in the range from 5 to 25 ⁇ m was dispersed in the washing or cleaning agent E3. 1.5% by weight of carboxymethyl cellulose with a particle diameter in the range from 5 to 250 ⁇ m were dispersed in the washing or cleaning agent E4.
  • the four particle-containing detergents or cleaning agents E1 to E4 were stable for 8 weeks under different climatic conditions and showed no significant creaming and / or sedimentation of the dispersed particles in each case.
  • a film of type M 8630 (ex Monosol) with a thickness of 76 ⁇ m was used to form a The bulge is drawn into a depression by means of a vacuum. The bulge was then filled with 30 ml of one of the liquid detergents or cleaning agents E1, E2, E3 or E4. After the bulges filled with the agent had been covered with a second layer of a film of the M 8630 type, the first and second layers were sealed to one another. The sealing temperature was 150 ° C. and the sealing time was 1.1 seconds.
  • water-soluble packaging with the detergent or cleaning agent E4 showed a very high graying-inhibiting cleaning performance after repeated use.

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

Claims (6)

  1. Agent de lavage ou de nettoyage liquide, comprenant
    a) 5 à 85 % en poids, par rapport à la quantité totale de l'agent de lavage ou de nettoyage, d'un tensioactif choisi dans le groupe constitué par les tensioactifs non ioniques, les tensioactifs anioniques, les tensioactifs cationiques, les tensioactifs zwitterioniques et leurs mélanges,
    b) 0,1 à 10 % en poids, par rapport à la quantité totale de l'agent de lavage ou de nettoyage, de particules,
    c) 0,1 à 10 % en poids, par rapport à la quantité totale d'agent de lavage ou de nettoyage, de dioxyde de silicium pyrogène, modifié hydrophobiquement en surface et
    d) jusqu'à 15 % en poids, par rapport à la quantité totale de l'agent de lavage ou de nettoyage, d'eau, à condition de contenir des mélanges de tensioactifs anioniques et non ioniques et sous réserve que la quantité totale de tensioactif anionique et de tensioactif non ionique soit de 40 à 75 % en poids par rapport à la quantité totale de l'agent de lavage et de nettoyage.
  2. Agent de lavage ou de nettoyage liquide selon la revendication 1, caractérisé en ce que le dioxyde de silicium pyrogène est modifié en surface à l'aide d'hexadécylsilane ou de diméthyldichlorosilane.
  3. Agent de lavage ou de nettoyage liquide selon l'une des revendications 1 ou 2, caractérisé en ce qu'il contient du dioxyde de silicium pyrogène en une quantité de 0,2 à 2 % en poids, par rapport à la quantité totale de l'agent de lavage ou de nettoyage.
  4. Agent de lavage ou de nettoyage liquide selon l'une des revendications 1 à 3, caractérisé en ce qu'il possède une viscosité comprise dans la plage entre 200 et 2000 MPa, en particulier dans la plage entre 300 et 800 MPa (20 °C, viscosimètre rotatif Brookfield type RVT à 20 tr/min).
  5. Emballage hydrosoluble contenant un agent de lavage ou de nettoyage liquide selon l'une des revendications 1 à 4 et un enrobage hydrosoluble.
  6. Emballage hydrosoluble selon la revendication 5, caractérisé en ce que l'enrobage hydrosoluble contient de l'alcool polyvinylique ou un copolymère d'alcool polyvinylique.
EP13756451.4A 2012-09-14 2013-08-29 Détergent liquide structuré à faible teneur en eau contenant des particules Active EP2895588B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012216399.9A DE102012216399A1 (de) 2012-09-14 2012-09-14 Strukturiertes, wasserarmes, flüssiges Waschmittel mit Partikeln
PCT/EP2013/067944 WO2014040865A1 (fr) 2012-09-14 2013-08-29 Détergent liquide structuré à faible teneur en eau contenant des particules

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EP2895588A1 EP2895588A1 (fr) 2015-07-22
EP2895588B1 true EP2895588B1 (fr) 2021-05-05

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US (1) US20150184115A1 (fr)
EP (1) EP2895588B1 (fr)
DE (1) DE102012216399A1 (fr)
WO (1) WO2014040865A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013200358A1 (de) * 2013-01-14 2014-07-17 Henkel Ag & Co. Kgaa Wasserarme bis wasserfreie flüssige Reinigungsmittel
DE102014225145A1 (de) * 2014-12-08 2016-06-09 Henkel Ag & Co. Kgaa Verfahren zur Herstellung flüssiger, Tensid-enthaltender Zusammensetzungen mit Fließgrenze
EP3178912A1 (fr) * 2015-12-10 2017-06-14 The Procter and Gamble Company Procédé de fabrication d'une composition de détergent à lessive liquide
PT3423558T (pt) * 2016-03-02 2019-10-15 Unilever Nv Composição detergente na forma de uma suspensão
DE102018212208A1 (de) * 2018-07-23 2020-01-23 Henkel Ag & Co. Kgaa Mehrphasiger Reinigungsmittelpouch
EP3623458A1 (fr) * 2018-09-11 2020-03-18 The Procter & Gamble Company Article de dose unitaire soluble dans l'eau

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Publication number Priority date Publication date Assignee Title
DK129804A (fr) * 1969-01-17
US5714449A (en) * 1990-02-16 1998-02-03 Unilever Patent Holdings B.V. Non-aqueous liquid cleaning products which contain modified silica
US5468418A (en) * 1990-02-26 1995-11-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition containing mixture of hydratable and non-hydratable salts
ES2090118T3 (es) * 1990-10-22 1996-10-16 Procter & Gamble Composiciones detergentes liquidas y estables que contienen blanqueador.
US5510048A (en) * 1991-05-31 1996-04-23 Colgate Palmolive Co. Nonaqueous liquid, phosphate-free, improved autoamatic dishwashing composition containing enzymes
US5643862A (en) * 1992-06-06 1997-07-01 The Procter & Gamble Company Stable foam-controlled liquid detergent compositions
US5648327A (en) * 1993-07-22 1997-07-15 The Procter & Gamble Company Stable liquid detergent compositions comprising a dispersible silicone-based suds suppressor system
WO2001000781A1 (fr) * 1999-06-25 2001-01-04 Henkel Kommanditgesellschaft Auf Aktien Emballage-portion de matiere active
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CA2325620C (fr) * 1999-11-15 2004-05-11 The Procter & Gamble Company Detergent non aqueux renfermant un agent de blanchiment formule pour limiter le chromo-transfert et la recuperation d'eau dans des machines a laver a haut rendement
GB2371307B (en) * 2001-01-19 2003-10-15 Reckitt Benckiser Nv Packaged detergent compositions
EP1352044B1 (fr) * 2001-01-19 2006-05-10 Reckitt Benckiser N.V. Ameliorations portant sur des compositions detergentes liquides
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US8648024B2 (en) * 2012-02-10 2014-02-11 Conopco, Inc. Hydrophobic silicas as squeakiness enhancers in cleansing compositions

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Publication number Publication date
US20150184115A1 (en) 2015-07-02
EP2895588A1 (fr) 2015-07-22
DE102012216399A1 (de) 2014-05-15
WO2014040865A1 (fr) 2014-03-20

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