WO2006034758A1 - Wasch- und reinigungsmittel mit immobilisierten aktiven inhaltsstoffen - Google Patents
Wasch- und reinigungsmittel mit immobilisierten aktiven inhaltsstoffen Download PDFInfo
- Publication number
- WO2006034758A1 WO2006034758A1 PCT/EP2005/009155 EP2005009155W WO2006034758A1 WO 2006034758 A1 WO2006034758 A1 WO 2006034758A1 EP 2005009155 W EP2005009155 W EP 2005009155W WO 2006034758 A1 WO2006034758 A1 WO 2006034758A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cleaning agent
- active ingredient
- aqueous liquid
- capsule
- agent according
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
-
- 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
- C11D17/0039—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
Definitions
- the invention relates to an aqueous liquid washing and cleaning agent containing surfactant (s) and other conventional ingredients of detergents and cleaners.
- the invention also relates to processes for the preparation of an aqueous liquid washing and cleaning agent and to its use.
- liquid detergents and cleaning agents which, even after storage and transport, optimally exert their effect at the time of application. This means that the ingredients of the liquid washing and cleaning agent have previously neither been ab ⁇ set off, decomposed or volatilized.
- Costly and correspondingly expensive packaging can for example prevent the loss of volatile components.
- Chemically incompatible components can be stored separately from the remaining components of the liquid detergent and cleaning agent and then added to the application.
- the use of opaque packaging prevents the decomposition of photosensitive components, but also has the disadvantage that the consumer can not see the appearance and quantity of the liquid detergent and cleaning agent.
- a concept for the incorporation of sensitive, chemically or physically incompatible as well as volatile ingredients is the use of capsules in which these ingredients arehim ⁇ closed.
- capsules two types are distinguished. On the one hand, there are capsules with a core-shell structure in which the ingredient is surrounded by a wall or barrier. On the other hand, there are capsules in which the ingredient is distributed in a matrix of a matrix-forming material. Such capsules are also referred to as "speckies".
- EP 0 266 796 A1 describes a water-soluble microcapsule containing enzymes which can be stably suspended in a concentrated aqueous, surfactant-containing solution and which dissolves on dilution with water.
- the water-soluble microcapsule has a coating of polyvinyl alcohol.
- GB 1 390 503 A discloses aqueous liquid detergents containing capsules that are insoluble in the liquid detergent but release their entrapped contents as soon as the ionic strength decreases when diluted with water.
- the capsule preferably has a water-soluble coating of cellulose ether, polyacrylate, polyvinyl alcohol or polyethylene oxide.
- GB 1 461 775 A also describes aqueous liquid detergents containing capsules which dissolve on dilution with water.
- the capsules contain either hardened carrageenan or a modified pectin and a water-dispersible pigment.
- WO 97/14780 describes encapsulated bleaches which contain a coating of a polymerized material ge.
- the gelled polymer material is preferably an alginate.
- WO 97/24178 describes particles having a polymeric matrix containing enzymes or other detergent-active agents, the matrix being formed from a copolymer.
- the matrix swells on contact with wash water and thus allows the release of the active ingredients.
- the particles additionally comprise a sheath of a polymeric material.
- EP 1 149 149 A1 discloses a detergent composition comprising a matrix-encapsulated active ingredient.
- the matrix of the capsules contains a hydrated anionic gum and the encapsulated active ingredient is preferably a perfume.
- a disadvantage of such a capsule is that the active ingredient must be sufficiently large, ie have a high molecular weight, so that the active ingredient does not diffuse out of the capsule into the surrounding detergent and cleaner composition (so-called bleeding out).
- small molecules can get into the cleaning liquid and there cause unwanted discoloration, agglomeration, odor problems and destruction of active washing substances or self-destructed.
- This object is achieved by an aqueous liquid washing and cleaning agent containing surfactant (s) and other conventional ingredients of detergents and cleaners, wherein the agent contains at least one capsule, the capsule comprises an active ingredient in a matrix and the active Ingredient is immobilized by attachment to a substrate.
- the size and also the molecular weight of the active ingredient is increased and thus bleeding or diffusing out of the active ingredient from the capsule into the surrounding washing and cleaning agent composition is prevented or significantly minimized.
- the substrate is specific to the active ingredient.
- an active ingredient is targeted and effectively immobilized.
- the active ingredient is selected from the group of enzymes and metal cations.
- Metal cations are small molecules that can diffuse out of the capsules very quickly and then trigger unwanted reactions in the surrounding detergent and cleaning agent composition. But enzymes can also easily get out of the capsules into the surrounding detergent and cleaner composition. There, the enzymes can be destroyed, for example, by existing bleaching agents and are then available during the actual washing process no longer or significantly reduced Konzen ⁇ tration available. This has a negative effect on the washing and cleaning performance.
- the enzyme form an enzyme-substrate complex with the substrate.
- Enzyme-substrate complexes are particularly stable and form very specific. By forming such an enzyme-substrate complex, it is possible to effectively and effectively immobilize a specific enzyme as an active ingredient in a capsule.
- the enzyme is selected from the group of cellulases, proteases, amylases, and lipases.
- these enzymes provide an indispensable contribution to the washing and cleaning performance.
- Cellulases for example, degrade carbohydrate-containing impurities, while the proteases have the ability to degrade proteinaceous impurities or the lipases have fat-splitting activity.
- the amylases show activity in the breakdown of starch, glycogen and / or dextrin. The immobilization and thus stabilization of one or more sensitive enzymes in capsules is therefore particularly advantageous.
- a particularly preferred embodiment of the invention provides that the enzyme is a cellulase and the substrate is cellulose.
- the cellulase is a particularly important enzyme in detergents and cleaning agents, as it makes an important contribution to the secondary washing performance in addition to the degradation of carbohydrate-containing impurities, since it has an anti-redeposition effect as well as a smoothing and color-refreshing effect on textiles.
- the substrate cellulose is specific for the Celululasen and thus causes an effective immobilization and stabilization of the cellulases used in detergents and cleaners.
- the capsule additionally contains at least one hollow microspheres.
- Hollow microspheres have a diameter of 2 to 500 .mu.m, in particular of 5 to 20 .mu.m, and a specific gravity of less than 1 g-cm '3 .
- the density of the capsules can be adjusted to the density of the surrounding detergent composition to prevent unwanted settling or floating (creaming) of the capsules.
- the matrix is selected from a material selected from the group comprising carrageenan, alginate and gellan gum.
- These materials can be crosslinked particularly well with cations to crosslinked insoluble gels.
- spherical capsules containing a matrix can be prepared in a simple manner.
- the capsule additionally contains a filler.
- a filler is preferably selected from the group of silicic acids and aluminum silicates.
- the matrix is reinforced and thus obtain particularly robust capsules.
- the fillers, in particular the silicas, in the actual washing process improve the solubility of the capsules.
- the washing and cleaning agent contains dispersed capsules whose diameter along their largest spatial extent is 0.01 to 10,000 microns.
- a process for producing an aqueous liquid washing and cleaning agent containing surfactant (s) and other conventional ingredients of detergents and cleaners, and at least one capsule wherein the capsule comprises an active ingredient in a matrix is also disclosed in which the active ingredient is bound to a substrate.
- the invention also claims the use of a washing and cleaning agent according to the invention for cleaning textile fabrics.
- washing and cleaning agents according to the invention are described in detail below, inter alia, by way of examples.
- the washing and cleaning agents according to the invention contain as a compelling component at least one capsule comprising an active ingredient in a matrix, the active ingredient being immobilized by attachment to a substrate.
- the matrix of the capsule may comprise, for example, carrageenan, alginate or gellan gum. These materials can be crosslinked to insoluble gels using mono- or polyvalent cations.
- Alginate is a naturally occurring salt of alginic acid and is found in all brown algae (Phaeophycea) as a cell wall component.
- Alginates are acidic, carboxy-containing polysaccharides having a relative molecular weight M R of about 200,000, consisting of D-mannuronic acid and L-guluronic acid in different ratios, which are linked to 1, 4-glycosidic bonds.
- the sodium, potassium, ammonium and magnesium alginates are water-soluble.
- the viscosity of alginate solutions depends, inter alia, on the molar mass and on the counterion. For example, calcium alginates form thermo-reversible gels at certain proportions.
- Sodium alginates give very viscous solutions with water and can be cross-linked by interaction with di- or trivalent metal ions such as Ca 2+ .
- Ingredients, which are also contained in the aqueous sodium alginate solution, are thus enclosed in an alginate matrix.
- Carrageenan is an extract of the red algae (Chondrus c ⁇ spus and Gigartina stellata) that belong to the Floridae. In the presence of K + ions or Ca 2+ ions, carrageenan cross-links.
- Gellan Gum is an unbranched, heterologous, heterologous microbial saccharide with a tetrasaccharide repeat unit consisting of the monomers glucose, glucuronic acid, and rhamnose, wherein approximately each repeat unit is esterified with an L-glycerate and every other repeat unit is esterified with an acetate.
- Gellan gum cross-links in the presence of K + ions, nations, Ca 2+ ions or Mg 2+ ions. Of the materials mentioned for the matrix, alginate is preferred.
- the capsules may include, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and / or fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents Substances, graying inhibitors, antiredeposition agents, pH adjusters, electrolytes, foam inhibitors, UV absorbers, cationic surfactants, vitamins, proteins, preservatives, washing power boosters and / or pearlescers, provided that these bind to a substrate.
- the amount of active ingredient in the aqueous alginate solution is preferably between 0.01 and 40 wt .-%, more preferably between 0.05 and 20 wt .-%, particularly preferably between 0.1 and 5 wt .-% and more preferably between 0.5 and 1.5% by weight.
- Suitable substrates are all compounds which enter into any kind of binding with an active ingredient, without substantially changing the original properties of the active ingredient.
- the compounds used as substrate preferably have a high molecular weight. It is particularly preferred that the substrate is specific to the active ingredient.
- an enzyme as the active ingredient it may be preferable to form an enzyme-substrate complex.
- cellulose can be used as a substrate.
- a encapsulated tease a protein is suitably used as a substrate.
- a lipase is to be present as an active ingredient in a capsule, it can be bound, for example, to a long-chain triglyceride as substrate.
- the substrate may comprise one or long chain ligands.
- the amount of substrate in the aqueous alginate solution is preferably between 0.01 and 10 wt .-%, more preferably between 0.2 and 5 wt .-%, particularly preferably between 1 and 2 wt .-%.
- the capsules may additionally contain hollow microspheres.
- Hollow microspheres are particles microns with a diameter of 2 to 500, micrometers in particular from 5 to 20, and a spezi ⁇ fish weighing less than 1 g-cm "3. Conveniently, the hollow microspheres round and smooth.
- the hollow microspheres may be prepared from inorganic material such as water glass, aluminum silicate, borosilicate glass, soda lime glass or a ceramic or of organic polymers such as, for example, homopolymers or copolymers of styrene, acrylonitrile and vinylidene chloride ® (ex Akzo Nobel), Scotchlite® (ex 3M), Dualite® (es Sovereign Specialty Chemicals), Sphericel® (ex Potters Industries), Zeeospheres® (ex 3M), Q-Cel® (ex PQ Corporation) or Extendospheres® (ex PQ Corporation)
- suitable hollow microspheres are available under the product name E-Spheres from OMEGA MINERALS E-Spheres are white, ceramic hollow microspheres which are offered in different particle sizes, particle size distributions, bulk densities and bulk volume. Many of the hollow microspheres mentioned are chemically inert and are dispersed in the wash liquor after destruction of the capsule and then removed with it.
- the density of the capsules can be varied or adjusted by incorporating hollow microspheres.
- the amount of hollow microspheres in a capsule depends on the desired density of the capsule. However, it is preferred that the amount of hollow microcoils in the aqueous alginate solution is preferably between 0 and 10% by weight, more preferably between 1 and 5% by weight and particularly preferably between 2 and 4% by weight. % is.
- the capsules furthermore may also contain fillers, such as preferably silicic acids or aluminum silicates, in particular zeolites.
- fillers such as preferably silicic acids or aluminum silicates, in particular zeolites.
- Silicas which are suitable as fillers are commercially available under the names Aerosil® or Sipemat® (both ex Degussa).
- Other suitable fillers are aluminum silicates and in particular zeolites.
- Ein ⁇ can be set zeolite A, zeolite P, zeolite X or mixtures thereof.
- Suitable zeolites include, for example, commercial products such as Wessalith® (ex Degussa), zeolite MAP® (ex Crosfield) or VEGOBOND AX® (ex SASOL).
- the amount of filler in the aqueous alginate solution is preferably between 0 and 20 wt .-%, more preferably between 1 and 10 wt .-% and particularly preferably between 2 and 10 wt .-%.
- the fillers on the one hand give the capsules a robust structure and thus have a positive effect on the stability of the capsules.
- the fillers in particular the silicic acids, can improve the solubility of the capsules in the actual washing process.
- the capsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent, depending on the components contained in their interior and the application between 0.01 microns (not visually recognizable as a capsule) and 10,000 microns. Preferred are visible microcapsules with a diameter in the range of 100 microns to 7,000 microns, in particular from 400 microns to 5,000 microns.
- the capsule may be colored.
- the capsule may contain one or more coloring agents such as a pigment or a dye. It may also be preferred that the capsule contains a preservative.
- an aqueous alginate solution which also contains the active ingredient to be enclosed or the active ingredient to be included and the substrate and optionally other components such as filler (s), hollow microspheres, preservatives and coloring agents is preferably dripped and then hardened in a precipitation bath containing Ca 2+ ions. It is very particularly preferred that first the active ingredient (s) and the respective substrate are brought into contact with each other before the aqueous alginate solution is prepared, so that it is ensured that the active ingredient is bound to the substrate.
- the preparation of the alginate capsules can be done for example by means of a Vetropfungsanlange the company Rieter Automatik GmbH.
- the dripping of the aqueous alginate solution takes place, which includes the active ingredient to be enclosed and the substrate and optionally Filler (s), hollow microspheres, preservative agent! and coloring agents, by imposing a vibration generated by means of an oscillating membrane.
- the droplet break is due to the increased shear when swinging back the membrane.
- the dropping itself can take place, for example, through a single nozzle or through a nozzle plate with 10 to 500, preferably 50 to 100 openings.
- the nozzles preferably have openings with a diameter in the range of 0.2 to 2, preferably 0.3 to 0.8 mm.
- the dripping can be carried out in a precipitation bath, which is designed as a stirred tank or boiler.
- a precipitation bath which is designed as a stirred tank or boiler.
- capsules and the enclosed active ingredient can be destroyed again during the stirring, since the stirring process by introducing energy also leads to an undesirable increase in temperature.
- the precipitation bath is designed as a kind of flow channel.
- the dripping takes place in a gleich ⁇ shaped flow that promotes the drops so quickly from the dripping zone that they are not hit by subsequent drops and can stick together. As long as the capsules are not fully cured, they will float up; As they harden, they sediment.
- dropping methods may be used which differ by different droplet forming technologies.
- plants of the company Gouda, the company Cavis or the company GeniaLab be called.
- the amount of alginate in the aqueous alginate solution is preferably between 0.01 and 10 wt .-%, more preferably between 0.1 and 5 wt .-% and in particular preferably between 1 and 3 wt .-%.
- sodium alginate is used.
- the alginate-based capsules subsequently to be washed with water and then washed in an aqueous solution with a complexing agent, such as dequest, for free Ca 2+ ions, which undesired interactions with ingredients of the liquid wash - And detergent, for example, the fatty acid soaps, ein ⁇ go, wash out. Subsequently, the alginate-based capsules are again washed with water to remove excess complexing agent.
- a complexing agent such as dequest
- the capsules can be dried before use in a detergent and cleaning agent, but they are preferably used moist.
- the release of the active ingredient from the capsules is usually during the application of the agents containing them by destruction of the matrix due to mechanical, thermal, chemical or enzymatic action.
- the liquid detergents and cleaners contain identical or different capsules in amounts of from 0.01 to 10% by weight, in particular from 0.2 to 8% by weight and very preferably 0.5 to 5% by weight.
- the liquid detergents and cleaners contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
- the total surfactant content of the liquid washing and cleaning agent is preferably below 40% by weight and more preferably below 35% by weight, based on the total liquid detergent and cleaning agent.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably methyl-branched in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 -alcohols with 3 EO, 4 EO or 7 EO, C 9-11 -alcohol with 7 EO, C 13 . 15- alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12- - U -AlkOhOl with 3 EO and C 12- - I8 - Alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
- block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
- alkylglycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched aliphatic radical, in particular methyl-branched in the 2-position, having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
- nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in the international patent application WO-A-90/13533.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
- surfactants are polyhydroxy fatty acid amides of the formula (2),
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (3),
- R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 Carbon atoms
- R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred
- [Z] is a linear polyhydroxyalkyl radical whose Alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably wise ethoxylated or propoxylated derivatives of this radical.
- [Z] is preferably obtained by reductive amination of a sugar, for example, glucoses, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar for example, glucoses, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, according to the teaching of international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- the content of nonionic surfactants is the liquid detergents and cleaners preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15% by weight, each based on the total agent.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- Suitable surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, such as are obtained, for example, from C 12-18 -monoolefins with terminal or internal double groups Bonding obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
- alkanesulfonates from C 2 - 1 8-alkanes, for example, obtained by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
- esters of .alpha.-sulfo fatty acids for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as used in the Preparation can be obtained by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric acid half esters of 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 of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- sulfuric acid monoesters of the straight-chain or branched C 7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or Ci 2 - 18 - Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and ins ⁇ particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8- 8 i - fatty alcohol radicals or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols which are themselves nonionic surfactants (description see below).
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Particularly preferred anionic surfactants are soaps. Suitable are 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 from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
- the anionic surfactants including the soaps may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the content of preferred liquid detergents and cleaners to anionic surfactants be ⁇ 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, in each case based on the total agent.
- the viscosity of the liquid detergent and cleaning agent can be by conventional Standardmetho ⁇ the (for example, Brookfield viscometer LVT-II at 20 U / min and 20 0 C, spindle 3) sen gemes ⁇ and is preferably in the range of 500 to 5000 mPas.
- Preferred agents have viscosities of from 700 to 4000 mPas, with values between 1000 and 3000 mPas being particularly preferred.
- the liquid detergents and cleaning agents may contain further ingredients which further improve the performance and / or aesthetic properties of the liquid detergent and cleaning agent.
- preferred agents additionally contain the capsules and to the surfactant (s) one or more substances from the group of builders, bleach, bleach activators, enzymes, electrolyte, nonaqueous solvents, pH adjusters, fragrances, Perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-caking agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellents and impregnating agents , Swelling and anti-slip agents and UV absorbers.
- Suitable builders which may be present in the liquid detergents and cleaners are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x ⁇ 2 ⁇ + i H 2 O, where M is sodium or hydrogen, x is a number from 1 to 9 and 4 is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline sheet silicates are described, for example, in European Patent Application EP-AO 164 514.
- Preferred crystalline layered silicates of the formula given are those in which IVI is sodium and x is 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 1 YH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Lender ⁇ delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation, which have a width of several degrees of the diffraction angle. However, it may very well lead to particularly good builder properties if the silicate particles give washed-out or even sharp diffraction peaks in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and, in particular, up to a maximum of 20 nm being preferred.
- Such so-called X-ray namorphic silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are particularly preferred.
- Commercially available and preferably usable in the context of the present invention is, for example, a co-crystallizate of zeolite X and zeolite A. (about 80 wt .-% zeolite X), which is sold by SASOL under the brand name VEGOBOND AX ® and by the formula
- zeolite can be used as a spray-dried powder or else as an undried, stabilized suspension which is still moist from its preparation.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 2 -C 18 fatty alcohols having 2 to 5 Ethylenoxidgru ppen, C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular from 20 to 22% by weight, of bound water.
- phosphates as builder substances, if such an application should not be avoided for ecological reasons.
- Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and, in particular, tripolyphosphates.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- bleach activators in the detergent and cleaning agent incorporated were ⁇ the.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Ge are suitable substances which carry O- and / or N-acyl groups of said carbon atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2, 5-diacetoxy-2, 5-dihydrofuran.
- TAED tetraacetylethylened
- bleach catalysts can also be incorporated into the liquid detergents and cleaners.
- These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and also Co, Fe, Cu and Ru ammine complexes are bleach catalysts usable.
- the liquid detergent and cleaning agent preferably contains a thickener.
- the thickening agent can be, for example, a polyacrylate thickener, xanthan gum, gellan gum, guar gum, alginate, carrageenan, carboxymethylcellulose, bentonites, wellan gum, joan kernel flour, agar-agar, tragacanth, gum arabic, pectins, polyoses, starch, dex ⁇ trine, gelatin and casein include.
- modified natural substances such as modified starches and celluloses, examples which may be mentioned here include carboxymethylcellulose and other cellulose ethers, hydroxyethyl and -propylcellulose and core flour ethers, can be used as thickening agents.
- the polyacrylic and polymethacrylic thickeners include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the "International Dictionary of Cosmetic Ingingients” of "The Cosmetic,” Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers.
- Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from BF Goodrich under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight about 250,000) or Carbopol 934 (molecular weight about 3,000,000).
- copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer) which are preferably formed with C 1-4 -alkanols, to which approx the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 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 Acusoi® and from Degussa (Goldschrnidt) under the trade name Tego® Polymer, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusoi 810, Acusoi 820, Acusoi 823 and Acusoi 830 (CAS 25852-37- 3); (ii)
- xanthan gum a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons.
- Xanthan gum is formed from a chain of ⁇ -1,4-linked glucose (cellose) with side chains.
- the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
- Xanthan gum can be described by the following formula (1):
- Xanthan gum Basic unit of xanthan gum Xanthan gum is available, for example, from Kelco under the trade name Keltrol® and Kelzan® or also from Rhodia under the trade name Rhodopol®.
- Preferred aqueous liquid detergents and cleaners contain from 0.01 to 1% by weight and preferably from 0.1 to 0.5% by weight of thickener, based on the total composition.
- the aqueous liquid detergents and cleaners may contain enzymes in encapsulated form and / or directly in the detergent composition.
- Suitable enzymes are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydro- lases and mixtures of the enzymes mentioned. All of these hydrolases in the laundry contribute to the removal of stains such as protein-, grease- or starch-containing stains and graying.
- cellulases and other glycosyl hydrolases can contribute to color retention and to increasing the softness of the textile by removing pilling and microfibrils.
- Oxireductases can also be used for bleaching or inhibiting color transfer.
- Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.
- Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.
- subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Wirk ⁇ the enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
- lipolytic enzymes are the known cutinases. Peroxides or oxidases have also proved suitable in some cases.
- Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
- As cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by means of targeted mixtures of the cellulases.
- the enzymes may be adsorbed to carriers to protect against premature degradation.
- the proportion of enzymes, enzyme mixtures or enzyme granules directly in the Detergent composition may be, for example, about 0.1 to 5 wt%, preferably 0.12 to about 2.5 wt%.
- electrolytes from the group of inorganic salts a wide number of Aggregates can be used.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production technology perspective, the use of NaCl or MgCl 2 in the compositions is preferred.
- the proportion of electrolytes in the agents is usually 0.5 to 5 wt .-%.
- Non-aqueous solvents which can be used in the liquid detergents and cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water.
- the solvents are selected from ethenyl, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or Butoxytrigly- kol, 1-butoxyethoxy-2 propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl
- pH adjusters In order to bring the pH of the liquid detergents and cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Normally, the amount of these adjusting agents does not exceed 7% by weight of the total formulation.
- Suitable dyestuffs whose selection does not cause any difficulty to the skilled person have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to textile fibers in order not to dye them.
- Suitable foam inhibitors which can be used in the liquid detergents and cleaners are, for example, soaps, paraffins or silicone oils which, if appropriate, can be applied to support materials.
- Suitable antiredeposition agents which are also referred to as "soil repellents" are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on nonionic cellulose ethers and the polymers known from the prior art of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these sulfonated derivatives of phthalic and terephthalic acid polymers.
- Optical brighteners can be added to the liquid detergents and cleaning agents in order to eliminate graying and yellowing of the treated textile fabrics
- These fabrics are absorbed by the fibers and cause brightening and simulated bleaching action by converting the invisible ultraviolet radiation into visible longer wavelength light, wherein the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and gives the whiteness of the bruised or yellowed wash pure white .
- Suitable compounds are derived, for example, from the substance classes of FIG.
- optical brighteners 4'-diamino-2,2'-stilbenedisulfonic (flavone acids), 4.4 * -Distyryl-biphenylene, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-di- arylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole Systems and heterocycles-substituted pyrene derivatives
- the optical brighteners are usually used in amounts of between 0.03 and 0.3 wt .-%, based on the finished agent, ein ⁇ set.
- Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatin, salts of ether sulphonic acids or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose.
- soluble starch preparations and other than the abovementioned starch products can be used, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful.
- cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcellulose methylcarboxymethylcellulose and mixtures thereof in amounts of 0.1 to 5 wt .-%, based on the means used.
- compositions may contain synthetic crease inhibitors.
- the liquid detergents and cleaning agents may contain antimicrobial agents.
- antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, with the compounds according to the invention also being based entirely on these compounds can be waived.
- the agents may contain antioxidants.
- This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocachines and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
- Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
- External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
- External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873,214 and GB 839,407.
- the lauryl (or stearyl) dimethyl benzyl ammonium chlorides disclosed herein are useful as antistatics for textile Flat fabric or as an additive to detergents, wherein additionally a softening effect is achieved.
- silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are fully or partially fluorinated.
- Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
- the viscosities of the preferred silicones at 25 0 C in the range between 100 and 100,000 mPas, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total composition can be used.
- the liquid detergents and cleaners may also contain UV absorbers, which are applied to the treated textile fabrics and improve the light resistance of the fibers.
- UV absorbers are, for example, the compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position which are active by radiationless deactivation.
- substituted benzotriazoles phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
- a preferred class of complexing agents are the phosphonates which are present in preferred liquid detergents and cleaners in amounts of from 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight and in particular 0.03 to 1, 5 wt .-% are included.
- These preferred compounds include, in particular, organophosphonates, such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylene triamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
- organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylene triamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phospho
- the resulting aqueous liquid detergents and cleaners are preferably clear, ie they have no sediment and are particularly preferably transparent or at least translucent.
- the detergents and cleaning agents according to the invention can be used for cleaning textile surface fabrics.
- gellan gum is first placed in water and at 80 0 C allowed to swell. Subsequently, a small amount of a salt solution, preferably with tri- or divalent metal cations, such as Al 3+ or Ca 2+ , is added. In the next step, the acidic components such as the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc., and the nonionic surfactants are added. Subsequently, a base such as NaOH, KOH, triethanolamine or monoethanolamine is added followed by the fatty acid, if any.
- a salt solution preferably with tri- or divalent metal cations, such as Al 3+ or Ca 2+
- the remaining ingredients and the solvents of the aqueous liquid washing and cleaning agent and, if present, the polyacrylate thickener are added to the mixture and the pH is adjusted to about 8.5.
- the particles to be dispersed can be added and distributed homogeneously in the aqueous liquid washing and cleaning agent by stirring and / or mixing.
- liquid detergents and cleaners without gellan gum by conventional methods and methods in which, for example, the ingredients are simply mixed in stirred tanks, water, non-aqueous solvent and surfactant (s) are conveniently presented and the other ingredients are added in portions , Separate heating in the production is not necessary if it is desired, should the temperature of the mixture did not exceed 8O 0 C.
- the capsules can be stably dispersed in the aqueous liquid washing and cleaning agent, for example by dispersion.
- Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting.
- the respective alginate solutions had the compositions given in Table 1 (in% by weight).
- Aerosil 200 3 3 3 - - -
- the resulting capsules K1 to K 6 were washed several times with water and a complexing agent, such as Dequest®.
- capsules K1 and K2 were then stored for 2 weeks at room temperature in water auf ⁇ . Subsequent enzyme analysis of capsules K1 and K2 and the surrounding solution gave the following values:
- the capsules according to the invention can be stably dispersed in aqueous liquid detergents and cleaners of very different compositions.
- Stable means that the agent at room temperature and at 4O 0 C for a period of at least 4 weeks and preferably are stable for at least 6 weeks without creaming or sedimenting means.
- Table 2 shows washing and cleaning agents E1 to E4 according to the invention.
- the washing and cleaning agents E1 to E4 obtained had a viscosity of around 1,000 mPas.
- the pH of the liquid detergents and cleaners was 8.5.
- Capsules K7 were prepared with alginate as matrix material in a hardening bath (composition as in Example 1) by means of a Rieter drip system or vetropft.
- the alginate solution had the composition given in Table 3 (in% by weight).
- the resulting capsules K7 were washed several times with water and a complexing agent such as Dequest®.
- capsules K7 were then stored for 4 weeks at room temperature in water or in liquid detergent E3. Subsequent enzyme analysis of capsules K7 and the surrounding solution gave the following values:
- capsules with the compositions according to Table 3 were, however, prepared analogously without corn starch and stored in water at room temperature. After a short storage time, there was just as much enzyme in the storage solution as in the capsule itself.
Landscapes
- 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)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES05782788.3T ES2393788T5 (es) | 2004-09-29 | 2005-08-25 | Detergentes y productos de limpieza con ingredientes activos inmovilizados |
PL05782788T PL1794277T5 (pl) | 2004-09-29 | 2005-08-25 | Środki piorące i czyszczące z unieruchomionymi składnikami aktywnymi |
JP2007533889A JP2008514768A (ja) | 2004-09-29 | 2005-08-25 | 固定化活性成分を含む洗剤および洗浄剤 |
US11/664,139 US20070256251A1 (en) | 2004-09-29 | 2005-08-25 | Washing and Cleaning Products Comprising Immobilized Active Ingredients |
EP05782788.3A EP1794277B2 (de) | 2004-09-29 | 2005-08-25 | Wasch- und reinigungsmittel mit immobilisierten aktiven inhaltsstoffen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004047097A DE102004047097A1 (de) | 2004-09-29 | 2004-09-29 | Wasch- und Reinigungsmittel mit immobilisierten aktiven Inhaltsstoffen |
DE102004047097.9 | 2004-09-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006034758A1 true WO2006034758A1 (de) | 2006-04-06 |
Family
ID=35428134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/009155 WO2006034758A1 (de) | 2004-09-29 | 2005-08-25 | Wasch- und reinigungsmittel mit immobilisierten aktiven inhaltsstoffen |
Country Status (7)
Country | Link |
---|---|
US (1) | US20070256251A1 (de) |
EP (1) | EP1794277B2 (de) |
JP (1) | JP2008514768A (de) |
DE (1) | DE102004047097A1 (de) |
ES (1) | ES2393788T5 (de) |
PL (1) | PL1794277T5 (de) |
WO (1) | WO2006034758A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007017070A1 (de) * | 2005-08-10 | 2007-02-15 | Henkel Kommanditgesellschaft Auf Aktien | Wasch- und reinigungsmittel mit gut löslichen kapseln |
WO2007134977A1 (de) | 2006-05-19 | 2007-11-29 | Henkel Ag & Co. Kgaa | Verkapselte bleichmittelteilchen |
EP3085763A1 (de) | 2015-04-24 | 2016-10-26 | Henkel AG & Co. KGaA | Verfahren zur herstellung von kapseln mit einer polymeren matrix |
EP1794277B2 (de) † | 2004-09-29 | 2018-03-21 | Henkel AG & Co. KGaA | Wasch- und reinigungsmittel mit immobilisierten aktiven inhaltsstoffen |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090209447A1 (en) * | 2008-02-15 | 2009-08-20 | Michelle Meek | Cleaning compositions |
JP5378140B2 (ja) * | 2009-10-07 | 2013-12-25 | 花王株式会社 | 液体洗浄剤組成物の製造方法 |
GB201212098D0 (en) * | 2012-07-06 | 2012-08-22 | Xeros Ltd | New cleaning material |
WO2014200657A1 (en) | 2013-06-13 | 2014-12-18 | Danisco Us Inc. | Alpha-amylase from streptomyces xiamenensis |
WO2014200658A1 (en) | 2013-06-13 | 2014-12-18 | Danisco Us Inc. | Alpha-amylase from promicromonospora vindobonensis |
WO2014200656A1 (en) | 2013-06-13 | 2014-12-18 | Danisco Us Inc. | Alpha-amylase from streptomyces umbrinus |
EP3011020A1 (de) | 2013-06-17 | 2016-04-27 | Danisco US Inc. | Alpha-amylase aus einem mitglied der bacillaceae-familie |
US20160186102A1 (en) | 2013-10-03 | 2016-06-30 | Danisco Us Inc. | Alpha-amylases from exiguobacterium, and methods of use, thereof |
WO2015050723A1 (en) | 2013-10-03 | 2015-04-09 | Danisco Us Inc. | Alpha-amylases from exiguobacterium, and methods of use, thereof |
GB201319782D0 (en) | 2013-11-08 | 2013-12-25 | Xeros Ltd | Cleaning method and apparatus |
WO2015077126A1 (en) | 2013-11-20 | 2015-05-28 | Danisco Us Inc. | Variant alpha-amylases having reduced susceptibility to protease cleavage, and methods of use, thereof |
DE102015120866A1 (de) | 2015-12-01 | 2017-06-01 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Verfahren zur Herstellung von feuerfesten Kompositpartikeln und von Speiserelementen für die Gießereiindustrie, entsprechende Speiserelemente und Verwendungen |
WO2017173190A2 (en) | 2016-04-01 | 2017-10-05 | Danisco Us Inc. | Alpha-amylases, compositions & methods |
WO2017173324A2 (en) | 2016-04-01 | 2017-10-05 | Danisco Us Inc. | Alpha-amylases, compositions & methods |
CN113677786A (zh) * | 2019-05-08 | 2021-11-19 | 伊英克公司 | 包含封装的酶的液体洗涤剂组合物 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1390503A (en) | 1971-03-30 | 1975-04-16 | Unilever Ltd | Liquid detergent compositions |
GB1461775A (en) | 1973-04-27 | 1977-01-19 | Unilever Ltd | Detergent composition |
WO1997014780A1 (en) | 1995-10-16 | 1997-04-24 | Unilever N.V. | Encapsulated bleach particles |
WO1997024178A1 (en) | 1995-12-29 | 1997-07-10 | Allied Colloids Limited | Polymeric particulate materials and compositions containing them |
US6225372B1 (en) | 1995-12-29 | 2001-05-01 | Ciba Speciality Chemicals Water Treatments, Limited | Particles having a polymeric shell and their production |
US6242405B1 (en) | 1995-12-29 | 2001-06-05 | Novo Nordisk A/S | Enzyme-containing particles and liquid detergent concentrate |
EP1149149A1 (de) | 1999-02-02 | 2001-10-31 | Quest International B.V. | Reinigungsmittelzusammensetzung |
DE10205872A1 (de) | 2001-02-16 | 2003-03-27 | Rainer Pommersheim | Mikrokapsel insbesondere zur Immobilisierung von organischen oder anorganischen Feststoffen, Flüssigkeiten und/oder Gasen |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT362038B (de) * | 1978-09-18 | 1981-04-27 | Henkel Kgaa | Mittel zur stabilisierung von enzymen |
JP2598674B2 (ja) † | 1988-05-06 | 1997-04-09 | 昭和電工株式会社 | 酵素含有水溶性マイクロカプセルの製造法 |
US5073292A (en) * | 1990-06-07 | 1991-12-17 | Lever Brothers Company, Division Of Conopco, Inc. | Heavy duty liquid detergent compositions containing enzymes stabilized by quaternary nitrogen substituted proteins |
US5385959A (en) * | 1992-04-29 | 1995-01-31 | Lever Brothers Company, Division Of Conopco, Inc. | Capsule which comprises a component subject to degradation and a composite polymer |
EP0672102B1 (de) * | 1992-04-29 | 1996-06-19 | Unilever Plc | Kapsel mit einer zur zersetzung neigenden komponente sowie einem verbundpolymer |
US5385958A (en) † | 1993-03-05 | 1995-01-31 | Dymax Corporation | Activator formulation and composition utilizing same |
EP0835302A1 (de) † | 1995-06-28 | 1998-04-15 | Novo Nordisk A/S | Cellulase mit verringerter mobilität |
SE505545C2 (sv) † | 1995-12-27 | 1997-09-15 | Lindab Ab | Element för anslutning till en långsträckt ränna samt sätt att framställa detta element |
JPH11502256A (ja) * | 1995-12-29 | 1999-02-23 | ザ、プロクター、エンド、ギャンブル、カンパニー | 固定化酵素を含有する洗剤組成物 |
US5846927A (en) † | 1996-04-08 | 1998-12-08 | Lever Brothers Company, Division Of Conopco, Inc. | Matrix or core shell enzyme capsule compositions comprising defined density modifying solids surrounded by defined core structurant material |
AUPO009797A0 (en) † | 1997-10-30 | 1997-11-20 | Coms21 Ltd | Population monitoring |
DE19804656A1 (de) * | 1998-02-06 | 1999-08-12 | Henkel Kgaa | Cellulasehaltiges Waschmittel |
ES2247749T3 (es) * | 1999-07-02 | 2006-03-01 | Cognis Ip Management Gmbh | Microcapsulas iii. |
ATE326520T1 (de) * | 1999-09-24 | 2006-06-15 | Novozymes As | Teilchen für flüssige zubereitungen |
US6673763B1 (en) * | 1999-09-24 | 2004-01-06 | Novozymes A/S | Particles for liquid compositions |
DE19956382A1 (de) * | 1999-11-24 | 2001-05-31 | Henkel Kgaa | Verfahren zur Herstellung von mikroverkapselten Enzymen |
DE10019936A1 (de) * | 1999-12-04 | 2001-10-25 | Henkel Kgaa | Wasch- und Reinigungsmittel |
WO2001074980A2 (en) † | 2000-04-03 | 2001-10-11 | Novozymes A/S | Enzyme tablets for cleaning improvement |
US20030045446A1 (en) * | 2001-02-12 | 2003-03-06 | Dihora Jiten Odhavji | Delivery system having encapsulated porous carrier loaded with additives |
GB2374082A (en) * | 2001-04-04 | 2002-10-09 | Procter & Gamble | Particles for a detergent product |
DE10138753B4 (de) † | 2001-08-07 | 2017-07-20 | Henkel Ag & Co. Kgaa | Wasch- und Reinigungsmittel mit Hybrid-Alpha-Amylasen |
DE102004047097A1 (de) † | 2004-09-29 | 2006-04-06 | Henkel Kgaa | Wasch- und Reinigungsmittel mit immobilisierten aktiven Inhaltsstoffen |
DE102005038070A1 (de) * | 2005-08-10 | 2007-03-15 | Henkel Kgaa | Wasch- und Reinigungsmittel mit gut löslichen Kapseln |
-
2004
- 2004-09-29 DE DE102004047097A patent/DE102004047097A1/de not_active Ceased
-
2005
- 2005-08-25 PL PL05782788T patent/PL1794277T5/pl unknown
- 2005-08-25 US US11/664,139 patent/US20070256251A1/en not_active Abandoned
- 2005-08-25 EP EP05782788.3A patent/EP1794277B2/de active Active
- 2005-08-25 WO PCT/EP2005/009155 patent/WO2006034758A1/de active Application Filing
- 2005-08-25 ES ES05782788.3T patent/ES2393788T5/es active Active
- 2005-08-25 JP JP2007533889A patent/JP2008514768A/ja active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1390503A (en) | 1971-03-30 | 1975-04-16 | Unilever Ltd | Liquid detergent compositions |
GB1461775A (en) | 1973-04-27 | 1977-01-19 | Unilever Ltd | Detergent composition |
WO1997014780A1 (en) | 1995-10-16 | 1997-04-24 | Unilever N.V. | Encapsulated bleach particles |
WO1997024178A1 (en) | 1995-12-29 | 1997-07-10 | Allied Colloids Limited | Polymeric particulate materials and compositions containing them |
US6225372B1 (en) | 1995-12-29 | 2001-05-01 | Ciba Speciality Chemicals Water Treatments, Limited | Particles having a polymeric shell and their production |
US6242405B1 (en) | 1995-12-29 | 2001-06-05 | Novo Nordisk A/S | Enzyme-containing particles and liquid detergent concentrate |
EP1149149A1 (de) | 1999-02-02 | 2001-10-31 | Quest International B.V. | Reinigungsmittelzusammensetzung |
DE10205872A1 (de) | 2001-02-16 | 2003-03-27 | Rainer Pommersheim | Mikrokapsel insbesondere zur Immobilisierung von organischen oder anorganischen Feststoffen, Flüssigkeiten und/oder Gasen |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1794277B2 (de) † | 2004-09-29 | 2018-03-21 | Henkel AG & Co. KGaA | Wasch- und reinigungsmittel mit immobilisierten aktiven inhaltsstoffen |
WO2007017070A1 (de) * | 2005-08-10 | 2007-02-15 | Henkel Kommanditgesellschaft Auf Aktien | Wasch- und reinigungsmittel mit gut löslichen kapseln |
US7638476B2 (en) | 2005-08-10 | 2009-12-29 | Henkel Ag & Co. Kgaa | Washing and cleaning agents comprising readily soluble capsules |
WO2007134977A1 (de) | 2006-05-19 | 2007-11-29 | Henkel Ag & Co. Kgaa | Verkapselte bleichmittelteilchen |
US7897557B2 (en) | 2006-05-19 | 2011-03-01 | Henkel Ag & Co. Kgaa | Encapsulated bleaching agent particles |
EP3085763A1 (de) | 2015-04-24 | 2016-10-26 | Henkel AG & Co. KGaA | Verfahren zur herstellung von kapseln mit einer polymeren matrix |
DE102015207534A1 (de) | 2015-04-24 | 2016-10-27 | Henkel Ag & Co. Kgaa | Verfahren zur Herstellung von Kapseln mit einer polymeren Matrix |
Also Published As
Publication number | Publication date |
---|---|
PL1794277T5 (pl) | 2018-09-28 |
EP1794277B2 (de) | 2018-03-21 |
EP1794277B1 (de) | 2012-10-03 |
DE102004047097A1 (de) | 2006-04-06 |
JP2008514768A (ja) | 2008-05-08 |
ES2393788T5 (es) | 2018-05-09 |
ES2393788T3 (es) | 2012-12-28 |
US20070256251A1 (en) | 2007-11-08 |
EP1794277A1 (de) | 2007-06-13 |
PL1794277T3 (pl) | 2013-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1794277B2 (de) | Wasch- und reinigungsmittel mit immobilisierten aktiven inhaltsstoffen | |
EP1924679B1 (de) | Wasch- und reinigungsmittel mit gut löslichen kapseln | |
EP1781766B1 (de) | Klares wasch- und reinigungsmittel mit fliessgrenze | |
EP1863895B1 (de) | Klares wasch- oder reinigungsmittel mit fliessgrenze | |
EP2021449B1 (de) | Verkapselte bleichmittelteilchen | |
EP1309669B1 (de) | Mechanisch stabile, flüssig formulierte waschmittel-, spülmittel- oder reinigungsmittel-portionen | |
EP2956534B1 (de) | Vergrauungsinhibierende waschmittel | |
EP1989282B1 (de) | Vergrauungsinhibierendes flüssigwaschmittel | |
EP1838829B1 (de) | Antiadhesive polymer zur verhinderung der adhesion von mikroorganismen an textilien und zur verhinderung von weschegeruch | |
EP1034242B1 (de) | Stabile höherviskose flüssigwaschmittel | |
DE19752163A1 (de) | Niedrigkonzentrierte höherviskose Flüssigwaschmittel | |
DE102008047233A1 (de) | Feste, Textil-pflegende Zusammensetzung mit einem Polysaccharid | |
EP2113025B1 (de) | Verfahren zur herstellung teilchenförmiger bleichmittelzusammensetzungen | |
DE102019007303A1 (de) | Vergrauungsinhilbierende Waschmittel | |
WO2021078554A1 (de) | Vergrauungsinhibierende waschmittel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005782788 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007533889 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11664139 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2005782788 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11664139 Country of ref document: US |