EP1309669B1 - Doses d'agent de lavage, de rin age ou de nettoyage a formulation liquide mecaniquement stables - Google Patents

Doses d'agent de lavage, de rin age ou de nettoyage a formulation liquide mecaniquement stables

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Publication number
EP1309669B1
EP1309669B1 EP01974141A EP01974141A EP1309669B1 EP 1309669 B1 EP1309669 B1 EP 1309669B1 EP 01974141 A EP01974141 A EP 01974141A EP 01974141 A EP01974141 A EP 01974141A EP 1309669 B1 EP1309669 B1 EP 1309669B1
Authority
EP
European Patent Office
Prior art keywords
washing
water
cleaning
detergent
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP01974141A
Other languages
German (de)
English (en)
Other versions
EP1309669A2 (fr
Inventor
Hans-Jürgen Riebe
Rainer Geberzahn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1309669A2 publication Critical patent/EP1309669A2/fr
Application granted granted Critical
Publication of EP1309669B1 publication Critical patent/EP1309669B1/fr
Anticipated expiration legal-status Critical
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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
    • 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

Definitions

  • the present invention relates to mechanically stable, liquid formulated detergent, detergent or detergent portions.
  • the present invention relates to detergent, detergent or detergent portions in the form of formulations that are liquid in the production and filling and whose viscosity increases over time, resulting in that encapsulated formulations due to their thixotropic or pseudoplastic behavior are mechanically stable.
  • thickening agents examples include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose and cellulose ethers, hydroxyethyl cellulose, hydroxypropyl cellulose and the like, gum ethers, polyacryl - u.
  • the use of these thickening agents for increasing the viscosity in a wide variety of liquids has long been State of the art.
  • the use of polymers in liquid detergents has long been known.
  • Liquid detergents having viscosities of between 500 and 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European Patent Application EP-A 691 399 (Colgate). These agents contain 10 to 45% by weight of surfactant (s), at least one builder, and 0.01 to 5% by weight of a mercapto-end-capped, intermediate molecular weight polymer of between 1,500 and 50,000 gmol -1 .
  • boron compounds in aqueous liquid detergents are described in EP-A 381 262 (Unilever).
  • the liquid detergents described contain the boron compounds and a polyol as enzyme stabilization system for a mixture of proteolytic and lipolytic enzymes, preferred stabilizer systems consisting of a sorbitol / borax mixture.
  • a polyol as enzyme stabilization system for a mixture of proteolytic and lipolytic enzymes
  • preferred stabilizer systems consisting of a sorbitol / borax mixture.
  • Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in EP-A 724 013 (Colgate). This effect is achieved by the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, wherein the concentrate has a viscosity of less than 2,500 mPas and when diluted with water loses its micellar structure in favor of the formation of a lamellar phase.
  • WO96 / 01305 (Unilever) describes an aqueous cleaning and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion having particle sizes of 10 to 100 nm.
  • the composition contains 20 to 70 wt .-% water, 15 to 40 wt .-% of a surfactant system containing at least one nonionic surfactant from the group of alkoxylated alcohols and not more than 20 wt .-% anion, cation, ampho- or contains zwitterionic surfactants, 5 to 30 wt .-% of solvent and 5 to 20 wt .-% water-insoluble oil.
  • EP 1 314 654 A, EP 1 120 459 A and WO 0 206 431 A disclose detergents; Detergent or detergent portions with liquid based formulation.
  • Aqueous, highly viscous liquid detergents in bulk form with surfactants and other customary ingredients of detergents and cleaners and a thickening system of polyurethanes or modified polyacrylates, a boron compound and one or more complexing agents, in particular low molecular weight hydroxycarboxylic acids, are described in the document WO 99/28430.
  • Portioned detergents, dishwashing detergents or detergents with thixotropic or pseudoplastic flow behavior of the wash-active, dishwashing or cleaning-active components contained therein can not be gathered from this prior art.
  • Aqueous, highly viscous liquid detergents in bulk form with surfactants and other customary ingredients of detergents and cleaners and a thickening system of a polymeric thickener or swelling agent, a boron compound and one or more complexing agents, in particular low molecular weight hydroxycarboxylic acids, are described in WO 99/27051 , Portioned detergents, dishwashing detergents or detergents with thixotropic or pseudoplastic flow behavior of the wash-active, dishwashing or cleaning-active components contained therein can not be gathered from this prior art.
  • WO 96/10072 and WO 96/10073 describe surfactant formulations for treating highly soiled laundry in the form of a stable suspension of a solid, substantially insoluble particulate material of an inorganic peroxide bleach and an anionic surfactant in one aqueous liquid phase of a fatty alcohol ethoxylate as a non-ionic surfactant and an anhydrous organic solvent of low polarity, and a method for producing such a surfactant preparation by mixing the solid components in a vigorously agitated mixture of the liquid components.
  • the preparations should have a viscosity of 300 to 5,000 cps (Brookfield, # 5 spindle at 50 rpm), without providing information on non-Newtonian behavior of the preparations.
  • EP-A-0 738 778 discloses non-aqueous liquid detergent compositions in the form of stable suspensions of solid particles of bleaches, bleach activators, alkalis, builders and anionic surfactants in non-aqueous mixtures of anionic (alkali metal or alkanolamine) surfactants.
  • WO 97/00938 (Procter & Gamble) describes non-aqueous liquid detergent formulations in the form of stable dispersions of bleach (eg peroxy bleach) and optionally bleach activator and organic builders in non-aqueous mixtures of alkali metal salts of alkylbenzenesulfonates, Fatty alcohol ethoxylates and non-polar organic solvents.
  • bleach eg peroxy bleach
  • organic builders in non-aqueous mixtures of alkali metal salts of alkylbenzenesulfonates, Fatty alcohol ethoxylates and non-polar organic solvents.
  • the preparations should have a viscosity of 300 to 5,000 cps (Brookfield, # 5 spindle at 50 rpm), without providing information on non-Newtonian behavior of the preparations.
  • WO 97/00936 and WO 97/00937 describe non-aqueous ( ⁇ 5 wt .-% water) surfactant preparations in the form of liquids, gels or pastes, the anionic and / or nonionic surfactants , nonaqueous organic diluents (eg, fatty alcohol alkoxylates or nonpolar organic solvents) and clay soilings removing polymers (e.g., alkoxylated cationic diamines or polyamines (WO 97/00936) and bleaching agents and salts of divalent metals as bleach activators (WO 97/00937)).
  • nonaqueous organic diluents eg, fatty alcohol alkoxylates or nonpolar organic solvents
  • clay soilings removing polymers e.g., alkoxylated cationic diamines or polyamines (WO 97/00936) and bleaching agents and salts of divalent metals as bleach activators (WO 97/0093
  • WO 98/00507 to WO 98/00512 and WO 98/00514 to WO 98/00517 describe various non-aqueous ( ⁇ 5% by weight water) liquid detergents in which solid components (bleaching agents, bleaches Precursors, bleach activators, enzymes) are dispersed or suspended in anhydrous mixtures containing at least one surfactant and non-aqueous diluent or solvent.
  • solid components bleaches Precursors, bleach activators, enzymes
  • the viscosity behavior of such preparations is not addressed in any of the cited documents.
  • Preparations of the abovementioned type were usually given to the consumer in containers containing large quantities of liquid such as, for example, plastic bottles.
  • the dosage was then as needed (degree of contamination of the washing, rinsing or cleaning, amount of washing, rinsing or cleaning) or experience in each individual case with suitable devices for measuring amounts of liquid.
  • such formulations can be incorporated into water-soluble gelatin capsules or foil pouches and thus can be added to the laundry, rinsing or cleaning stock as a pre-dosed detergent, rinse or detergent portion.
  • detergent, dishwashing or cleaning agent portions based on liquid formulations of washing-active, dishwashing or cleaning-active components, the formulations having a high viscosity.
  • particularly advantageous detergent, detergent or cleaning agent portions result in cases in which the liquid formulations during processing, for example during manufacture from their detergent-active, rinse-active or detergent-active components, during stirring, during pumping and during filling of the the detergent, detergent or detergent portions provided sheaths (capsules, balls, bags) have a low, after release of the mechanical action, however, have a high viscosity.
  • a thixotropic or pseudoplastic - in any case non-Newtonian - behavior of the liquid formulations of washing-active, dishwashing or cleaning-active components unexpectedly leads to detergent, detergent or cleaner portions with significantly improved performance properties.
  • the invention therefore relates to a detergent, dishwashing or cleaning agent portion comprising a completely or partially water-soluble casing with a thickness of 1 to 300 .mu.m in capsule form, which is a liquid-based formulation with non-Newtonian flow behavior at least one washing active, rinse or completely encloses cleaning active material, with a compression resistance of 10 to 10 5 N at 23 ° C.
  • the invention relates to a detergent, detergent or cleaning agent portion comprising a completely or partially water-soluble coating with a thickness of 1 to 300 ⁇ m in spherical form, which completely surrounds a liquid-based formulation with non-Newtonian flow behavior of at least one washing-active, rinsing-active or cleaning-active material, with a compression resistance of 10 to 10 5 N at 23 ° C.
  • the invention relates to a detergent, detergent or cleaning agent portion comprising a wholly or partially water-soluble envelope having a thickness of 1 to 300 .mu.m in the form of a bag containing a liquid-based formulation with non-Newtonian flow behavior at least one wash-active, rinse-active or cleaning-active material completely surrounds, with a compression resistance of 10 to 10 5 N at 23 ° C.
  • the invention also relates to a washing method, a rinsing method and a cleaning method using the detergent, detergent or detergent portions described in more detail below.
  • the term "detergent, dishwashing or cleaning agent portion” is understood to mean a quantity of a detergent, dishwashing agent or cleaning agent which is sufficient for a washing, rinsing or cleaning process taking place in an aqueous phase.
  • This can be, for example, a machine washing, rinsing or cleaning process, as is carried out with commercially available washing machines or dishwashers or cleaning machines.
  • this term also refers to a hand washing cycle (performed, for example, in a hand basin or in a bowl) or a dishwashing process carried out by means of a cleaning liquor in a vessel, such as a bucket, or another process of washing, rinsing or cleaning Understood.
  • the detergent, detergent or cleaner portions are preferably used in automatic washing, rinsing or cleaning operations.
  • detergent partial portion or “detergent partial portion” or “detergent partial portion” is understood to mean a portion of a detergent, dishwashing or cleaning agent portion which is in one of other detergents, dishwashing detergents and detergents. or detergent sub-portions of separate phase is in spatial association with other detergent, rinse or detergent portions of the same detergent, rinse or detergent portion and is prepared by appropriate means so as to be separate from other detergents, dishwashing or cleaning agents Portions of the same detergent, detergent or detergent portion may be added to the liquor and optionally dissolved or suspended in it.
  • a detergent, detergent or detergent partial portion may contain the same ingredients as another detergent, detergent or detergent portion of the same detergent, detergent or detergent portion;
  • two detergent, detergent or detergent partial portions of the same detergent, detergent or cleaner portion preferably contain different ingredients, in particular different detergent-active, rinse-active or detergent-active preparations.
  • detergent or cleaner portions contain measured amounts of at least one washing-active, rinsing-active or cleaning-active preparation, usually measured amounts of several washing-active, rinse-active or cleaning-active preparations. It is possible that the portions only Wash-active, rinse-active or cleaning-active preparations of a particular composition. According to the invention, however, it is preferred that several, usually at least two, washing active, rinse active or cleaning active preparations of different composition in the detergent, detergent or detergent portions are included.
  • the composition may be (qualitatively) different with regard to the concentration of the individual components of the washing-active, rinsing-active or cleaning-active preparation (quantitatively) and / or with regard to the nature of the individual components of the washing-active, rinsing-active or cleaning-active preparation. It is particularly preferred that the components are adapted in terms of nature and concentration to the tasks that have to meet the detergent, detergent or detergent partial portions in the washing, rinsing or cleaning process.
  • wash-active preparation or "rinse-active preparation” or “cleansing-active preparation” is understood as meaning preparations, materials or components of all conceivable ones understood with a washing, rinsing or cleaning process relevant substances. These are primarily the actual detergents, dishwashing detergents or cleaning agents with their individual components explained in the further course of the description.
  • active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers (for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.
  • active ingredients such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, specialty polymers (for example, those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the term being limited to these substance groups.
  • wash-active preparations materials, components
  • dishwashing preparations materials, components
  • cleaning-active preparations materials, components
  • constituents of such "wash-active preparations (materials, components)", “dishwashing preparations (materials, components)” or “cleaning-active preparations (materials, components)” may also be washing auxiliaries, rinse aids and cleaning aids, examples of which are optical brighteners, UV protective substances
  • Soil repellents, ie polymers which counteract re-soiling of fibers or hard surfaces, as well as silver protectants are also considered laundry-active or dishwashing active preparations.
  • the detergent, rinse or detergent portion of the invention comprises a wholly or partially water-soluble wrapper.
  • the shape of the envelope according to the invention is not limited to specific forms. Basically, all Archimedean and Platonic bodies, ie three-dimensional shaped bodies, come into question as forms of envelopment. Examples of the shape of the wrapper are capsules, cubes, spheres, ovoid moldings, cuboids, cones, rods or bags. Also hollow body with one or more compartments, as described in the co-pending patent application no. DE 100 33 827.5 entitled "compartment hollow body", are suitable as a sheath for the washing active, rinse or cleaning active materials.
  • Suitable materials for the completely or partially water-soluble coating are in principle all materials in question, which under the given conditions of a washing process, rinsing or cleaning process (temperature, pH, concentration of detergent components) in aqueous phase can completely or partially dissolve.
  • the polymer materials may particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, in particular modified starches, and mixtures (polymer blends, composites, co-extrudates, etc.) of the materials mentioned To belong.
  • Particularly preferred are gelatin and polyvinyl alcohols and the two materials mentioned in each case in combination with starch or modified starch.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n in small quantities also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 -] contain. Since the corresponding monomer (vinyl alcohol) is not stable in free form, polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. By these technical methods, PVAL are also available which contain a predetermined residual amount of acetate groups.
  • PVAL eg Mowiol® grades from Hoechst
  • PVAL polyvinyl acetates with a residual content of acetyl groups, for example, about 1 to 2 or 11 to 13 mol%.
  • the water solubility of PVAL can be reduced by aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available under the name "SOLUBLON®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
  • PVP Polyvinylpyrrolidones
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides PEOX for short, are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2 ] n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
  • detergent, detergent and cleaner portions whose packaging consists of at least partially water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000). There are still few Amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Preferred casings of at least partially water-soluble film consist of a polymer having a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol.
  • the water-soluble film forming the coating has a thickness of from 1 to 300 .mu.m, preferably from 2 to 200 .mu.m, particularly preferably from 5 to 150 .mu.m and in particular from 10 to 100 .mu.m.
  • these water-soluble films can be produced by various production methods. Blow molding, calendering and casting processes should be mentioned here in principle.
  • the films are blown starting from a melt with air through a mandrel to a hose.
  • the calendering process which is likewise one of the preferred production processes
  • the raw materials plasticized by suitable additives are atomized to form the films.
  • an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film.
  • this film is additionally powdered before or during the removal.
  • organic and / or inorganic salts are also suitable.
  • these are salts which can be formed into a coating, for example by crystallization, compression, compression or other suitable processes, and which dissolve under the conditions of the washing, rinsing or cleaning process in sufficient time in water or aqueous liquor.
  • those salts are used which can also assume further functions in a washing, rinsing or cleaning process.
  • the essential advantage of this embodiment is that the sheath within a practically relevant short time - as a non-limiting example can be a few seconds to 5 min - under exactly defined conditions in the wash liquor, wash liquor or cleaning liquor at least partially dissolves and thus accordingly meets the requirements of the wrapped contents, ie the wash-active, rinse-active or cleaning-active material or several materials in the fleet.
  • the water-soluble coating comprises regions which are less soluble or not water-soluble or only water-soluble at relatively high temperatures and regions which are readily soluble in water or soluble in water at low temperature.
  • the coating does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility.
  • areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand.
  • an envelope provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the casing.
  • wrapping systems in the form of multi-chamber bags or in the form of nested hollow bodies (eg balls: "onion system") can also be provided.
  • controlled release systems of the detergent-active, rinse-active or cleaning-active ingredients can be produced.
  • the less readily water-soluble areas or areas which are not water-soluble or areas of the enclosure which are only water-soluble at higher temperatures are areas of a material which is essentially chemically that of the readily water-soluble areas or at lower temperature water-soluble areas, but has a higher layer thickness and / or a modified degree of polymerization of the same polymer and / or has a higher degree of crosslinking the same polymer structure and / or a higher degree of acetalization (PVAL) and / or a content of water-insoluble salt components and / or has a content of a water-insoluble polymer.
  • PVAL acetalization
  • a further embodiment of the invention which is likewise preferred on account of the advantageous properties, provides detergent, detergent or cleaning agent portions in which the completely or partially water-soluble coating contains one or more washing-active, rinse-active or cleaning-active components, in particular those components which are incorporated in US Pat Detergents, detergents or cleaning agents are present in small quantities.
  • Suitable components include, for example, bleaches or at least portions thereof, bleach activators, enzymes, dyes, fragrances, optical brighteners and / or soil repellents, but also other components of the detergent, dishwashing or cleaning agent portions.
  • the completely or partially water-soluble coating of the detergent, detergent or cleaner portions according to the invention completely surrounds a liquid-based formulation of at least one wash-active, rinse-active or cleaning-active material.
  • liquid-based is understood to mean that the formulation of a wash-active, rinse-active or cleaning-active material or several wash-active, rinse-active or cleaning-active materials, at least during production, is a formulation prepared on the basis of liquid components will be explained in detail below, even if this formulation contains in a larger amount of solid components (suspended or dispersed) and / or increases in viscosity after preparation in the absence of shear, for example by at least 10%, preferably by at least 50%, more preferably by at least 100%, so that it can no longer be called "liquid” in the narrower sense.
  • Liquid-based formulations of detergent, rinse or detergent portions according to the invention completely surrounded by the wraps can be either low-water formulations or substantially anhydrous formulations.
  • Low-water formulations comprise water as an essential component in an amount of, for example, ⁇ 15% by weight, based on the weight of all components of the formulation.
  • non-aqueous or essentially anhydrous formulations comprise water only in small amounts, preferably in amounts of ⁇ 5% by weight, more preferably in amounts of from 1 to 3% by weight, based in each case on the weight of all components of the formulation, non-aqueous or substantially anhydrous formulations being particularly preferred.
  • the formulations contain surfactant (s) using anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, the proportion of nonionic surfactants should be greater than the proportion of anionic surfactants.
  • the total surfactant content of the detergent, dishwashing or cleaning agent portions is preferably above 30% by weight, based on the total liquid detergent.
  • 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 can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols containing 3 EO, 4 EO or 7 EO, C 9-11 alcohols 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 12-14 -alcohol with 3 EO and C 12-18 -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 include 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.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon 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 any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example, in Japanese Patent Application JP 58/217598, or which are preferably prepared according to the method described in International Patent Application WO 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.
  • polyhydroxy fatty acid amides of the formula I, in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z 1 ] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups ,
  • 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 II, R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and 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, with C 1-4 alkyl or phenyl radicals being preferred, and [Z 2 ] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.
  • [Z 2 ] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, 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 according to the teaching of international application WO 95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of preferred formulations of nonionic surfactants is 5 to 95 wt .-%, preferably 10 to 60 wt .-% and in particular 15 to 50 wt .-%, each based on the total agent.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation 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 having 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 monoesters of C 12 -C 18 fatty alcohols, for example 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, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • EO ethylene oxide
  • 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 as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (description see above).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • 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 of natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine, monoisopropanolamine or triisopropanolamine.
  • the anionic surfactants are preferably present in the form of their ammonium salts, in particular their ammonium salts with at least one long-chain alkyl radical or alkanolamine radical on the ammonium nitrogen.
  • the content of preferred detergent, detergent or cleaner portions of anionic surfactants is 5 to 95 wt .-%, preferably 10 to 60 wt .-% and in particular 15 to 50 wt .-%, each based on the total portion.
  • the detergent, rinse or detergent portions of the present invention may contain other ingredients that further the performance and / or aesthetics of the composition improve.
  • preferred detergent, rinse or cleaning agent portions in addition to the surfactant (s) comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, Fragrances, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellents and impregnating agents, swelling agents and Slip Resistant and UV absorber.
  • Suitable builders which may be present in the detergent, dishwashing or cleaning agent portions according to the invention 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 O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y 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-A 0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .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 delayed dissolution are and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima 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, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.
  • Especially preferred are densified / 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.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of 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 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated Isotridecanoles.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • 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 can be incorporated into the detergent portions.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • bleach catalysts can also be incorporated into the wash-active preparations for the portions according to the invention.
  • These substances are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or -carbonylkomplexe.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Suitable enzymes for use in detergent, detergent or cleaner portions are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned.
  • the hydrolases contribute, for example, in the laundry for the removal of stains such as proteinaceous, fat or starchy stains and graying.
  • cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • Bacillus subtilis Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • 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 enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest for the detergent, detergent or cleaner portions of the invention.
  • lipolytic enzymes are the known cutinases. Peroxidases 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 ⁇ -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 targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulating substances to protect them from premature decomposition, or may also be embedded in the water-soluble encapsulants of the present invention.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%.
  • Non-aqueous solvents which can be used in the detergent, detergent or cleaner portions according to the invention are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, 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, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether, N-
  • pH adjusting agents 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.
  • the amount of these adjusting agents does not exceed 2% by weight of the total formulation.
  • detergent or cleaner portions can be colored with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the formulation and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • Suitable foam inhibitors which can be used in the detergent, dishwashing or cleaning agent portions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to carrier materials.
  • Suitable anti-redeposition 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 known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred among the compounds mentioned are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners can be added to the detergent portions according to the invention in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure yellow with the yellowed or yellowed wash White results.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions.
  • Grayness inhibitors based on optionally modified polyacrylates and their copolymers are also suitable according to the invention.
  • detergent, detergent or cleaner portions of the invention may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.
  • 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) dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textiles or as additives to laundry detergents, with the additional benefit of providing a softening effect.
  • silicone derivatives can be used in the detergent portions according to the invention. These additionally improve the rinsing behavior of the portions according to the invention by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely 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 are in the range between 100 and 100,000 mPas at 25 ° C., it being possible to use the silicones in amounts of between 0.2 and 5% by weight, based on the total agent.
  • the agents according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Links, which have these desired properties are, for example, the active by non-radioactive deactivation compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Also suitable are 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 body's own urocanic acid.
  • Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or of nitrilotriacetic acid (NTA) or of their derivatives or derivatives and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which are in preferred detergent, detergent or detergent portions in amounts of 0.01 to 1.5 wt .-%, preferably 0.02 to 1 wt .-% and in particular of 0 , 03 to 0.5 wt .-% are included.
  • These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-
  • the low-water formulation comprises a thickening system.
  • a thickening system This may consist of one or may consist of several component (s).
  • a component is a polymeric thickener.
  • These high molecular weight substances which are also called swelling agents and absorb liquids, swell up and finally pass into viscous true or colloidal solutions, originate from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.
  • Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
  • Modified natural products come mainly from the group of modified starches and celluloses, examples include carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and core flour ethers.
  • Thickeners from the mentioned classes of substances are commercially widely available and are described, for example, under the trade names Acusol® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral® GT -282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer-11 (dicarboxylic acid copolymer, Schöner GmbH), Deuteron®-XG (anionic heteropolysaccharide based on ⁇ -D-glucose, D-manose, D-glucuronic acid, more beautiful GmbH), Deuteron®-XN (nonionic polysaccharide, Schöner GmbH), Dicrylan®-Verdicker-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA®-81 and EMA® -91 (ethylene oxide).
  • Acusol® -820 methacryl
  • Preferred low-water formulations contain as a component of the thickening system 0.01 to 4% by weight, preferably 0.1 to 3% by weight and in particular 0.4 to 1.5% by weight, of a polysaccharide.
  • a preferred polymeric polysaccharide thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions, and a molecular weight from 2 to 15 million g / mole.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) 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 can be described by the following formula:
  • Preferred aqueous formulations of the detergent, detergent or cleaner portions contain as component a) of the thickening system, in each case based on the total agent, 0.01 to 4 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.4 to 1.5% by weight, xanthan.
  • the second component of the thickening system is a boron compound, which is used in amounts of 0.5 to 7 wt .-%.
  • boron compounds useful in the present invention are boric acid, boric oxide, alkali metal borates such as ammonium, sodium and potassium ortho-, meta- and pyroborates, borax in its various stages of hydration and polyborates such as alkali metal pentaborates.
  • Organic boron compounds such as esters of boric acid can also be used.
  • Preferred liquid detergent portions contain from 0.0001 to 5 wt .-%, preferably 0.001 to 4 wt .-% and in particular 0.01 to 3 wt .-% of a boron compound.
  • the detergent, dishwashing or cleaning agent portions according to the invention may contain from 0 to 20% by weight of a complexing agent.
  • a complexing agent is understood to mean low molecular weight hydroxycarboxylic acids, such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof.
  • liquid detergent portions contain as component c) of the thickening system citric acid or sodium citrate, wherein liquid detergent portions are preferred, the 1.0 to 15.0 wt .-%, preferably 2.0 to 10.0 wt .-% and in particular 2.0 to 7.0 wt .-%, sodium citrate.
  • the first component of the thickening system is a polyurethane or a modified polyacrylate, which is used in amounts of 0.2 to 5 wt .-%, based on the total portion.
  • Polyurethanes are prepared by polyaddition from dihydric and higher alcohols and isocyanates and are described by the general formula III: in which R 3 is a low molecular weight or polymeric diol radical, R 4 is an aliphatic or aromatic group and n is a natural number.
  • R 3 is preferably a linear or branched C 2-12 -alk (en) yl group, but may also be a radical of a higher-valent alcohol, whereby crosslinked polyurethanes are formed, which differ from the formula III given above in that the Rest R 3 more -O-CO-NH groups are bonded.
  • TDI 2,4- or 2,6-toluene diisocyanate
  • MDI C 6 H 4 -CH 2 -C 6 H 4
  • HMDI, R 4 (CH 2 ) 6 ].
  • polyurethane-based thickeners are known, for example, under the names Acrysol® PM 12 V (3-5% modified starch mixture and 14-16% PUR resin in water, Rohm & Haas), Borchigel® L75-N (nonionic polyurethane Dispersion, 50% in water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco® DSX-1514 (PUR dispersion, 40% in water / Butyltriglycol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / digyl ether, Rohm & Haas) and Rilanit® VPW-3116 (PUR dispersion, 43% in water, Henkel).
  • Preferred detergent, detergent or cleaning agent portions contain 0.01 to 4 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.5 to 1.5 wt .-% of a polyurethane.
  • modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula IV: in the R 5 is H or a branched or unbranched C 1 - to C 4 -alk (en) yl radical, X is NR 7 or O, R 6 is an optionally alkoxylated branched or unbranched, possibly substituted C 8 - to C 22 - Alk (en) yl radical, R 7 is H or R 6 and n is a natural number.
  • such modified polyacrylates are esters or amides of acrylic acid or of an ⁇ -substituted acrylic acid.
  • polyacrylamides NR 5
  • Preferred alkoxylation levels are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.
  • the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation.
  • Formula IV only gives formulas for idealized homopolymers. Can be used in the frame However, the present invention also copolymers in which the proportion of monomer units satisfying the formula IV, at least 30 wt .-% is. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO - groups.
  • modified polyacrylates are polyacrylate-polymethacrylate copolymers which satisfy the formula IVa in which R 6 is a preferably unbranched, saturated or unsaturated C 8 - to C 22 -alk (en) yl radical, R 8 and R 9 independently of one another are H or CH 3 , the degree of polymerization n is a natural number and the degree of alkoxylation a natural number is between 2 and 30, preferably between 10 and 20.
  • Products of the formula Iva are commercially available, for example, under the name Acusol® 820 (Rohm & Haas) in the form of 30% strength by weight dispersions in water.
  • R 6 is a stearyl radical
  • R 8 is a hydrogen atom
  • R 9 is H or CH 3
  • the degree of ethoxylation a is 20.
  • Preferred detergent, detergent or cleaner portions contain, based on the total agent, 0.01 to 4 wt .-%, preferably 0.1 to 3 wt .-% and in particular 0.5 to 2.0 wt. % of a modified polyacrylate of formula IV.
  • this low-water or anhydrous formulation preferably comprises one or more anionic surfactants (e) and / or one or more nonionic surfactants to adjust their rheological parameters ( e) comprehensive material.
  • the anionic surfactant (s) is / are selected from the group of the sulfonates and sulfates and mixtures thereof and / or the nonionic surfactant (s) selected from the group of alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and their mixtures.
  • washing-active, rinsing-active or cleaning-active materials which are contained in the detergent, dishwashing or cleaning agent portions according to the invention can in a preferred embodiment as anionic surfactants, optionally in the presence of further anionic and / or not ionic surfactants which use isopropanolammonium ether sulphates according to the article "U.
  • polymers with thickening effect are used in low-water or substantially anhydrous systems, which can also be used as associative thickener.
  • These may be, for example (but not limited to) acrylate based polymers, e.g. T. may have relatively high molecular masses in the range of> 1,000,000 g / mol. They are used in amounts of from 0.01 to 10% by weight, for example in amounts of from 0.5 to 4% by weight, in the wash-active, rinse-active or cleaning-active formulations.
  • Suitable products are, for example, the products marketed by Rohm & Haas under the name Acusol R , which are predominantly polyacrylates with different alkylation or crosslinking or hydrophobically modified nonionic polyols, or the products marketed by BF Goodrich under the name Carbopol R , which Polyacrylates or copolymers of acrylic acid and alkylated (preferably C 5 - to C 10 -alkylated) acrylic acids, or the products marketed by BF Goodrich under the name Pemulen R , the high molecular weight acrylic acid copolymers of the type Acry-lat / C 10 - to C 30 -alkyl acrylate crosspolymer are.
  • polyacrylate or polyurethane thickeners can also be used in anhydrous or essentially anhydrous systems which offer the possibility of adjusting the viscosity via a different mechanism of action (ie not associative) in the presence of small amounts of water.
  • detergent, detergent or cleaner portions in which the liquid-based formulations exhibit non-Newtonian flow behavior preferably exhibit thixotropic or pseudoplastic flow behavior.
  • the liquid-based formulations have a low viscosity during production, for example a viscosity in the range of 10 to 50 mPa ⁇ s, and the liquid-based formulations have a higher viscosity during storage, etc., for example in the range of 10 to 100,000 mPa ⁇ s, preferably 100 to 20,000 mPa ⁇ s, more preferably a viscosity in the range of 200 to 10,000 mPa ⁇ s.
  • the viscosity may be lower than in systems in which solid components (which are visually noticeable in a cloudiness) are present; The latter usually become thicker during storage ("setting") and may even become pasty.
  • Detergent, detergent or cleaning agent portions according to the present invention which are present for example in capsule form, in spherical form or in the form of bags, have a high mechanical stability (depending on the particular shape), which results in that the portions much less likely to burst or burst.
  • the mechanical stability can be measured according to per se known (and described in more detail in the examples) method as compression resistance. This is generally defined as the resistance that the molded article opposes to a stamping pressure applied to it (under standardized conditions) and, as stated above, is dependent on the shape of the portion, but also on the strength of its ingredients, on temperature and optionally of further parameters.
  • Detergent, detergent or detergent portions in capsule form according to the invention have a compression resistance of from 10 to 10 5 at 23 ° C.
  • Spherical detergent, rinse or detergent portions in accordance with the invention have a crush resistance of 10 to 10 5 N at 23 ° C and more preferably from 10 2 to 10 4 N at 23 ° C.
  • Detergent, detergent or detergent portions in the form of sachets according to the invention have an upset resistance of from 10 to 10 5 N at 23 ° C and even more preferably from 10 2 to 10 4 N at 23 ° C.
  • the liquid-based formulations of at least one wash-active, rinse-active or cleaning-active material contained in the wraps of the detergent, rinse or detergent portion may be clear solutions of one or more wash-active, rinse-active or cleaning-active component (s) or microemulsions.
  • the liquid-based formulations may contain one or more solids suspended or dispersed, in particular when low-water or substantially anhydrous formulations are used. This is an advantage over the prior art because water-sensitive components of washing-active, rinse-active or cleaning-active materials can be stably and evenly distributed in the liquid phase and problems with activity reduction do not occur.
  • the process for the preparation of detergent, detergent or detergent portions is subject to no restrictions in principle. It is usually carried out by simply mixing the ingredients in stirred tanks, optionally present water, non-aqueous solvents and liquid surfactant (s) are suitably presented and the other ingredients are added in portions. Separate heating in the preparation is not required, if desired, the temperature of the mixture should not exceed 80 ° C.
  • the liquid mixture prepared according to step (c) can be introduced into the coating only with a time lag and closed with the liquid-based formulation.
  • the particular shear force applied to the liquid-based formulation of at least one detergent-active, rinse-active or cleaning-active material to incorporate the remaining (particularly solid) components into this formulation can be> 0 , 01 min -1 , preferably in the range of 0.1 to 50,000 min -1 , more preferably in the range of 5 to 20,000 min -1 , even more preferably in the range of 30 to 10,000 min -1 .
  • the portions according to the present invention can also be used in other areas. So they are, for example, as a cleaner for toilet cisterns for optionally continuous delivery of a cleaning and disinfecting agent to the toilet flushing water or as a cleaner for piping, etc. conceivable.
  • such cleaners may also include gas (e) releasing systems (eg, an acid such as citric acid with a carbonate such as sodium carbonate).
  • the strength of detergent, detergent or detergent portions according to the invention was determined by the following standardized method:
  • the determination was carried out with a universal testing machine from Zwick Type 1425.
  • At least 10 samples of each variety were tested. As a rule, the samples were tested immediately after conditioning. At the request of the client, however, a previous storage under different climatic conditions can take place.
  • the samples were conditioned for at least 24 hours prior to each test.
  • the test was carried out in a normal atmosphere at 23 ° C / 50% rel. Humidity.
  • test samples were always tested in a plastic bag as splash protection.
  • the thickness of the material of this bag should be at least 100 ⁇ m.
  • the film bag was placed in the splash guard bag centered on the lower base plate. This was placed vertically below the upper baseplate.
  • the printing press was set at a compression speed of 10 mm / min. set. Afterwards the test procedure was started. The force [N] exerted on the bag at bursting moment was printed on the connected printer.
  • Bag burst strength is given in N.
  • the tensile stress is given in N / cm 2 .
  • a conventional free-flowing detergent formulation was filled into a gelatine ball of the Swisscaps company equivalent to Examples 1 to 7 above.
  • the recipe is given in Table 2 below. Viscosity was also determined by Brookfield. ⁇ b> Table 2 ⁇ / b> Marlox MO 124 33 Marlinat 242 / 90M 40 Edenor K12-18 5 Monoethanolamine 6 Polyethylene glycol 400 14 hydroxyethane 1 Perfume 1 Viscosity in mPa ⁇ s 20 rpm 258 Compression resistance at 23 ° C (in N) 69.4

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Claims (22)

  1. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, comprenant une enveloppe complètement ou partiellement soluble dans l'eau, possédant une épaisseur de 1 à 300 µm sous la forme d'une capsule, qui entoure complètement une formulation à base liquide manifestant un comportement d'écoulement de type non newtonien, d'au moins une matière possédant une activité de lavage, de rinçage ou de nettoyage, possédant une résistance à l'écrasement de 10 à 105 N à 23 °C.
  2. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, comprenant une enveloppe complètement ou partiellement soluble dans l'eau, possédant une épaisseur de 1 à 300 µm sous la forme d'une sphère, qui entoure complètement une formulation à base liquide manifestant un comportement d'écoulement de type non newtonien, d'au moins une matière possédant une activité de lavage, de rinçage ou de nettoyage, possédant une résistance à l'écrasement de 10 à 105 N à 23 °C.
  3. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, comprenant une enveloppe complètement ou partiellement soluble dans l'eau, possédant une épaisseur de 1 à 300 µm sous la forme d'une poche, qui entoure complètement une formulation à base liquide manifestant un comportement d'écoulement de type non newtonien, d'au moins une matière possédant une activité de lavage, de rinçage ou de nettoyage, possédant une résistance à l'écrasement de 10 à 105 N à 23°C.
  4. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 3, dans laquelle la valeur de la résistance à l'écrasement s'élève de 102 à 104 N, et de manière encore plus préférée de 200 à 5.000 N, chaque fois mesurée à 23 °C.
  5. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 4, comprenant une enveloppe complètement ou partiellement soluble dans l'eau constituée d'une matière choisie parmi le groupe comprenant de l'alcool polyvinylique (le cas échéant partiellement acétalisé), de la polyvinylpyrrolidone, de l'oxyde de polyéthylène, de la gélatine, de la cellulose et ses dérivés, de l'amidon et ses dérivés, ses mélanges et ses composites, des sels inorganiques et des mélanges des matières mentionnées.
  6. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 5, comprenant une enveloppe complètement soluble dans l'eau choisie parmi le groupe comprenant une capsule constituée de gélatine, de préférence de gélatine molle, une poche constituée d'alcool polyvinylique (le cas échéant partiellement acétalisé), une sphère constituée d'alcool polyvinylique (le cas échéant partiellement acétalisé) ou de gélatine, de préférence de gélatine molle, ou encore d'un sel inorganique ou d'un mélange de sels inorganiques.
  7. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon la revendication 5 ou 6, dans laquelle l'enveloppe soluble dans l'eau comprend des zones moins aisément solubles dans l'eau ou pas du tout solubles dans l'eau ou manifestant une solubilité dans l'eau seulement à température élevée et des zones aisément solubles dans l'eau ou manifestant une solubilité dans l'eau à basse température.
  8. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon la revendication 7, dans laquelle les zones de l'enveloppe moins aisément solubles dans l'eau ou pas du tout solubles dans l'eau ou manifestant une solubilité dans l'eau seulement à température supérieure représentent des zones constituées d'une matière qui correspond, du point de vue chimique, essentiellement à celle des zones aisément solubles dans l'eau ou manifestant une solubilité dans l'eau à une température inférieure, mais qui présente une épaisseur de couche supérieure et/ou qui présente un degré de polymérisation modifié et/ou qui présente un degré de réticulation supérieur et/ou qui présente un degré d'acétalisation supérieur et/ou qui présente une teneur en composants salins insolubles dans l'eau et/ou qui présente une teneur en polymères insolubles dans l'eau.
  9. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 8, dans laquelle l'enveloppe complètement ou partiellement soluble dans l'eau contient, à l'état incorporé, un ou plusieurs composants possédant une activité de lavage, de rinçage ou de nettoyage, en particulier des composants qui ne sont ajoutés que dans des quantités minimes dans des agents de lavage, dans des agents de rinçage ou dans des agents de nettoyage.
  10. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 9, dans laquelle la formulation à base liquide d'au moins une matière possédant une activité de lavage, de rinçage ou de nettoyage, est une formulation pauvre en eau.
  11. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 10, dans laquelle la formulation pauvre en eau comprend un système épaississant.
  12. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon la revendication 11, dans laquelle la formulation pauvre en eau comprend, à titre de système épaississant, un épaississant polymère et le cas échéant des composants supplémentaires pour favoriser l'épaississement.
  13. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 9, dans laquelle la formulation à base liquide d'au moins une matière possédant une activité de lavage, de rinçage ou de nettoyage est une formulation non aqueuse, de préférence essentiellement anhydre, de préférence est une formulation comprenant de l'eau à concurrence de moins de 5 % en poids, de manière plus préférée est une formulation comprenant de l'eau à concurrence de 1 à 3 % en poids, de manière de loin préférée est une formulation anhydre.
  14. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 9 et 13, dans laquelle la formulation non aqueuse, respectivement essentiellement anhydre est une formulation contenant un ou plusieurs agents tensioactifs anioniques et/ou un ou plusieurs agents tensioactifs non ioniques.
  15. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 9, 13 et 14, dans laquelle le(s) agent(s) anionique(s) est (sont) choisi(s) parmi le groupe comprenant des sulfonates et des sulfates ainsi que leurs mélanges, et/ou dans laquelle le(s) agent(s) tensioactif(s) non ionique(s) est (sont) choisi(s) parmi le groupe comprenant des alcools alcoxylés, des esters alkyliques d'acides gras alcoxylés, des alkylglycosides et leurs mélanges.
  16. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 15, dans laquelle les formulations à base liquide manifestent un comportement d'écoulement thixotrope ou pseudoplastique.
  17. Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage, selon l'une quelconque des revendications 1 à 16, dans laquelle les formulations à base liquide présentent, lors de la préparation, une faible viscosité et manifestent, par la suite, une augmentation de la viscosité d'au moins 10 %, de préférence d'au moins 50 %, de manière plus préférée d'au moins 100 %.
  18. Procédé pour la préparation d'une portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage qui comprend une enveloppe complètement ou partiellement soluble dans l'eau sous la forme d'une capsule, sous la forme d'une sphère ou sous la forme d'une poche, ladite enveloppe entourant, quant à elle, complètement une formulation à base liquide d'au moins une matière possédant une activité de lavage, de rinçage ou de nettoyage, comprenant les étapes:
    (a) déposer au préalable au moins un composant liquide de la formulation à base liquide d'au moins une matière possédant une activité de lavage, de rinçage ou de nettoyage et mettre ledit composant liquide en mouvement en lui appliquant une vitesse de cisaillement déterminée ;
    (b) le cas échéant, ajouter un ou plusieurs composants liquides supplémentaires à la formulation à base liquide ;
    (c) dans la phase liquide ainsi préparée, le cas échéant incorporer un ou plusieurs composants solides de la formulation à base liquide et ajouter, le cas échéant, par la suite un ou plusieurs composants supplémentaires solides et/ou liquides et maintenir en l'occurrence une vitesse de cisaillement déterminée ; et
    (d) le cas échéant, introduire le mélange liquide préparé conformément à l'étape (c) directement dans l'enveloppe et refermer cette dernière autour de la formulation à base liquide.
  19. Procédé selon la revendication 18, dans lequel on introduit dans l'enveloppe le mélange liquide préparé conformément à l'étape (c) seulement après un certain retard et on ferme l'enveloppe autour de la formulation à base liquide.
  20. Procédé de lavage, en particulier procédé pour le lavage mécanique dans un lave-linge disponible dans le commerce, comprenant les étapes:
    (a) introduire une portion d'agent de lavage selon l'une quelconque des revendications 1 à 17 dans le lave-linge, en particulier dans le distributeur de détergent ou dans le tambour de lavage ;
    (b) par addition d'eau, établir un contact entre la portion d'agent de lavage et le bain de lavage ;
    (c) régler les conditions de lavage désirées ; et
    (d) lors de la mise en place des conditions désirées, libérer dans le bain de lavage la/les matière(s) présentant une activité de lavage de la portion d'agent de lavage et amener le bain de lavage en contact avec le linge à laver.
  21. Procédé de rinçage, en particulier procédé pour le rinçage mécanique dans un lave-vaisselle disponible dans le commerce, comprenant les étapes:
    (a) introduire une portion d'agent de rinçage selon l'une quelconque des revendications 1 à 17 dans le lave-vaisselle, en particulier dans le distributeur de détergent ou dans le compartiment à vaisselle ;
    (b) par addition d'eau, établir un contact entre la portion d'agent de rinçage et le bain de rinçage ;
    (c) régler les conditions désirées de rinçage ; et
    (d) lors de la mise en place de ces conditions, libérer dans le bain de rinçage la/les matière(s) possédant une activité de rinçage de la portion d'agent de rinçage et amener le bain de rinçage en contact avec la vaisselle à rincer.
  22. Procédé de nettoyage, comprenant les étapes consistant à :
    (a) introduire une portion d'agent de nettoyage selon l'une quelconque des revendications 1 à 17 dans le bain de nettoyage ;
    (b) régler les conditions de nettoyage désirées ; et
    (c) lors de la mise en place de ces conditions, libérer dans le bain de nettoyage la/les matière(s) possédant une activité de nettoyage de l'agent de nettoyage et amener le bain de nettoyage en contact avec la matière à nettoyer.
EP01974141A 2000-08-17 2001-08-08 Doses d'agent de lavage, de rin age ou de nettoyage a formulation liquide mecaniquement stables Revoked EP1309669B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10040724A DE10040724A1 (de) 2000-08-17 2000-08-17 Mechanisch stabile, flüssig formulierte Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen
DE10040724 2000-08-17
PCT/EP2001/009173 WO2002014460A2 (fr) 2000-08-17 2001-08-08 Doses d'agent de lavage, de rinçage ou de nettoyage a formulation liquide mecaniquement stables

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EP1309669A2 EP1309669A2 (fr) 2003-05-14
EP1309669B1 true EP1309669B1 (fr) 2006-10-04

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US (1) US20040063598A1 (fr)
EP (1) EP1309669B1 (fr)
AT (1) ATE341611T1 (fr)
AU (1) AU2001293743A1 (fr)
DE (2) DE10040724A1 (fr)
ES (1) ES2272543T3 (fr)
WO (1) WO2002014460A2 (fr)

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WO2002006431A2 (fr) * 2000-07-14 2002-01-24 Henkel Kommanditgesellschaft Auf Aktien Corps creux a compartiment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2828368B1 (fr) 2012-03-19 2018-06-06 Henkel AG & Co. KGaA Composition détergente liquide ayant une puissance de nettoyage augmentée

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DE50111157D1 (de) 2006-11-16
EP1309669A2 (fr) 2003-05-14
AU2001293743A1 (en) 2002-02-25
DE10040724A1 (de) 2002-03-07
WO2002014460A3 (fr) 2002-05-10
ES2272543T3 (es) 2007-05-01
US20040063598A1 (en) 2004-04-01
WO2002014460A2 (fr) 2002-02-21
ATE341611T1 (de) 2006-10-15

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