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WO2003004593A1 - Produit de nettoyage a plusieurs phases - Google Patents

Produit de nettoyage a plusieurs phases Download PDF

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Publication number
WO2003004593A1
WO2003004593A1 PCT/EP2002/006889 EP0206889W WO03004593A1 WO 2003004593 A1 WO2003004593 A1 WO 2003004593A1 EP 0206889 W EP0206889 W EP 0206889W WO 03004593 A1 WO03004593 A1 WO 03004593A1
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WO
WIPO (PCT)
Prior art keywords
detergent
cleaning
hand dishwashing
alkyl
water
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.)
Ceased
Application number
PCT/EP2002/006889
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German (de)
English (en)
Inventor
Elke Scholl
Birgit GLÜSEN
Michael Dreja
Wolfgang Von Rybinski
Georg Meine
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO2003004593A1 publication Critical patent/WO2003004593A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to detergent-containing detergents, in particular hand dishwashing detergents.
  • Conventional cleaning agents or hand dishwashing detergents are usually formulated as low-viscosity to viscous aqueous liquids. These practically exclusively single-phase formulated liquid cleaning or hand dishwashing detergents enable the user to easily produce the desired washing liquor or cleaning solution, which is also referred to as the application liquor, by diluting the cleaning or washing-up liquid concentrate without the user having to use the concentrated form of the agent comes into direct skin contact. Such skin contact is undesirable since the agents in concentrated form often have an irritating effect on the skin which the user perceives as unpleasant.
  • Conventional single-phase hand dishwashing detergents and also cleaning agents usually contain water as the main constituent, in which the fat-dissolving and foam-active surfactants are dissolved.
  • a serious disadvantage of conventional hand dishwashing detergents is that after the hand dishwashing detergent concentrate has been diluted with water, the user inevitably has a certain surfactant mixture or detergent component mixture in a certain concentration range, depending on the dishwashing detergent used. The resulting wash liquor is then used for manual cleaning of the entire wash ware.
  • a specific hand dishwashing detergent composition or surfactant concentration which is matched to the respective wash ware, has or would have significantly better cleaning properties.
  • the hand dishwashing detergent Since, for economic and ecological reasons, the user does not use a specifically designed hand dishwashing detergent for each special wash ware, the hand dishwashing detergent must inevitably contain all the components necessary for cleaning the respective wash ware. This has the consequence, for example, that when cleaning glass, which is usually carried out at the beginning of the washing process, with a universally applicable hand dishwashing detergent there is basically a strong foaming and a high fat-dissolving power, although, as stated above, this is undesirable or unnecessary ,
  • any care products for the wash ware for example care components for glass and ceramic surfaces
  • the wash liquor right from the start, namely with the addition of the hand dishwashing liquid.
  • the care components were only added after the glasses had been cleaned.
  • All previously known hand dishwashing detergents are not matched to the cleaning of the different items to be washed, which usually takes place in chronological phases or in steps, but rather represents a compromise in terms of Cleaning of, for example, glass, dishes with grease soiling, cutlery, etc. This applies both to the conventional single-phase and two-phase hand dishwashing detergents and, for example, to the previously described solid detergents and cleaning agents.
  • cleaning agents such as floor cleaners.
  • the user receives an appropriate cleaning solution or application liquor with a specific surfactant mixture or detergent component composition.
  • the resulting cleaning solution thus contains, in addition to the dirt-dissolving substances, also appropriate care components which, for example, give the cleaned floor a glossy effect, provide the cleaned floor with a protective layer or are intended to prevent the cleaned surface from being soiled again quickly.
  • all detergent components ie dirt-dissolving substances and care components, are forcibly applied to the surface to be cleaned when the agent is used. For understandable reasons, a gradual application of dirt-dissolving substances and care components would be advantageous, especially for heavily soiled surfaces, and would lead to a better cleaning result.
  • DE 198 54 267 relates to a coated active substance for manual cleaning agents for hard surfaces, such as hand dishwashing liquid.
  • the casing preferably consists of a material which contains at least one natural or synthetic polymer or a mixture thereof and which dissolves in water at about 35 ° C. within about 10 to 50 seconds, preferably about 20 to 40 seconds.
  • the detergents or dishwashing detergents based on coated active substances according to DE 198 54 267 are distinguished by improved storage stability, but do not have a formulation which is coordinated with the chronological course of a cleaning process and therefore have the disadvantages described above.
  • WO 94/14941 relates to aqueous neutral or slightly alkaline, automatic dishwashing detergents which are free from anionic and cationic surfactants.
  • the Machine dishwashing detergents can be enclosed in water-soluble or water-dispersible containers, which consist, for example, of gelatin.
  • the automatic dishwashing detergents described in WO 94/14941 which may include enclosed or encapsulated detergent components, are unsuitable as hand dishwashing detergents.
  • the gelatin coating of the active ingredients described in the documents only serves to stabilize the components and to allow simple dosing.
  • EP-A-9261754 relates to a foam bath in the form of a mixture of amine salts and long-chain alkyl ether sulfates and 25 to 35% by weight of liquid polyethylene glycols, encapsulated in an elastic gelatin capsule.
  • EP-A-0533 239 relates to aqueous liquid detergent compositions which comprise enzymes and encapsulated bleach particles.
  • the cleaning agents are particularly suitable for use as automatic dishwashing agents.
  • the encapsulation of individual components, namely the bleaching agents, also serves to improve the shelf life or stability here, since interactions between the enzyme and the bleaching particles are to be avoided.
  • the solution to the problems lies in the provision of a surfactant-containing detergent, in particular hand dishwashing detergent, the detergent being single-phase or multi-phase and wherein at least one phase has moldings which are suitable for releasing at least one detergent or detergent component when diluted with water with a time delay.
  • Delayed for the purposes of the present invention means that the shaped bodies dissolve when diluted with water at a specific point in time or during a specific period of time.
  • the terms “detergent component” and “detergent component” also include auxiliaries and additives, such as, for example, perfume or dyes, in addition to cleaning-active substances.
  • the detergents or hand dishwashing detergents according to the invention are generally dissolved in water at a temperature of up to 50 ° C. and the resulting application liquor is then used, for example, for manual cleaning of hard surfaces and / or soft surfaces, in particular glasses, eating utensils and cookware etc. used.
  • the term "manual cleaning" in the sense of the present invention naturally also includes a cleaning process which is carried out with the aid of mechanical aids, such as a brush, sponge or the like.
  • the cleaning agent or hand dishwashing agent formulated according to the invention overcomes the disadvantages of the agents described in the prior art and enables an application liquor composition which is coordinated and optimized for the individual cleaning phases and rinsing phases.
  • the cleaning agent in particular rinsing agent, has at least one, preferably liquid phase, which dissolves essentially without any time delay when diluted with water.
  • this immediately soluble phase contains the detergent or detergent components that are particularly suitable for the rinse effect on glass, since glasses or glass objects are first cleaned in a conventional manual rinsing process.
  • the liquid phase particularly preferably contains detergent components selected from the group comprising nonionic surfactants, in particular end-capped C ⁇ -C 22 alkyl alcohol polyglycol ethers, secondary alkane sulfonates, linear alkyl benzene sulfonates and alkyl polyglucosides.
  • nonionic surfactants in particular end-capped C ⁇ -C 22 alkyl alcohol polyglycol ethers, secondary alkane sulfonates, linear alkyl benzene sulfonates and alkyl polyglucosides.
  • the liquid phase of the cleaning agent according to the invention contains between 5 and 45% by weight of surfactants, based on the liquid phase, preferably selected from the group comprising nonionic surfactants, anionic surfactants, betaines, amine oxides and cationic surfactants, the proportion of cationic surfactants is preferably less than 5% by weight.
  • the cleaning agent or hand dishwashing detergent according to the invention contains molded articles which contain the cleaning agents or detergents contained in the molded articles. Release detergent components with a time delay when diluted with water.
  • the aforementioned “encapsulated” components are not released into water immediately after the addition of the agent, that is to say after the cleaning solution or rinsing liquor has been prepared, but only after a certain period of time.
  • the shaped bodies are diluted with water at a temperature of about 40 ° C.
  • a period of up to 10 min preferably within a period of 0.5 to 9 min, more preferably within 1 to 8 min, particularly preferably within 3 to 8 min at ⁇ 70% , preferably to ⁇ 80%, particularly preferably to> 90% and particularly preferably to 99 to 100% dissolved.
  • the user has one for the second cleaning phase or Rinsing phase, which consists, for example, in the cleaning of plates and pots soiled with grease, etc., a detergent composition optimized for this specific cleaning process is available.
  • the time-delayed dissolution process of the shaped bodies can be controlled using various mechanisms for releasing the active substances.
  • the cleaning or rinsing agent components contained in the molded body for example surfactant components with strong fat-dissolving power, foam-forming components, etc., are preferably provided with suitable casing, coating and / or matrix materials.
  • the coating or encapsulation while receiving, for example, capsule-like shaped bodies allows a particularly precise and precisely controllable release of the aforementioned components.
  • the dissolving of the shaped bodies can take place, for example, in a time-controlled manner, in a pH-controlled manner, in a temperature-controlled manner or also in an electrolyte-controlled manner when diluted.
  • a thickener is added to the liquid phase, so that a stabilization and uniform distribution of the shaped bodies, which particularly preferably have a spherical or capsule-like shape, is ensured in the aforementioned liquid phase.
  • thickener is added to the liquid phase, so that the moldings “float” in the aforementioned liquid or gel-like phase. This ensures that the user actually produces the cleaning and The necessary proportions of detergent or rinsing agent components are added in the correct ratio
  • a uniform distribution of the shaped bodies or a targeted addition can also be achieved by shaking vigorously immediately before preparing the cleaning solution or rinsing liquor.
  • the moldings are particularly preferably present in the liquid phase at from 0.1 to 30% by weight, preferably from 0.2 to 10% by weight and particularly preferably from 0.5 to 3% by weight, based on the liquid phase ,
  • the detergent in particular hand dishwashing detergent, contains moldings with the same or different detergent or dishwashing component composition, the components from the group comprising silver detergents, corrosion protection agents, hand or skin care agents, special care agents, preferably care agents for ceramics and / or glass, agents for removing special soiling, fat-dissolving substances or mixtures thereof are selected.
  • Particularly preferred cleaning or rinsing agent components include betaines, fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkanesulfonates, linear alkylbenzenesulfonates, alkyl alcohol polyglycol ethers, alkyl polygucosides, fatty acid alkanolamides, amine oxides and mixtures thereof.
  • “Fat-dissolving substances” in the sense of the present invention include, in addition to the aforementioned substances, also hydrophobic components.
  • Suitable hydrophobic components include, for example, dialkyl ethers with identical or different C 4 - to Cu-alkyl radicals, in particular linear dioctyl ethers; hydrocarbons with a boiling range from 100 to 300 ° C. especially 140 to 280 ° C, especially aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, especially limonene and the pine oil extracted from pine roots and stumps and also mixtures of these hydrophobic components.
  • Suitable cleaning and rinsing agent components are, for example, under the trade names Hostapur® SAS 60 (secondary alkane sulfonate from Clariant), Texapon® SPN 70 (fatty alcohol ether sulfate from Henkel KGaA, Düsseldorf), Empinin® KS8 (fatty alcohol ether sulfate from Albright & Wilson GmbH, Frankfurt), Ceraminox ® (amine oxide from Clariant), Sulfopon® 101 (C12-C14 lauryl sulfate from Henkel KGaA, Düsseldorf), Dehyton® (various betaines from Henkel KGaA, Düsseldorf).
  • Hostapur® SAS 60 secondary alkane sulfonate from Clariant
  • Texapon® SPN 70 fatty alcohol ether sulfate from Henkel KGaA, Düsseldorf
  • Empinin® KS8 fatty alcohol ether sulfate from Albright & Wilson GmbH, Frankfurt
  • Ceraminox ® amine
  • substances selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used as silver protection agents.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • Other cleaning or rinsing agent components are gloss drying additives, cleaning enhancers, antimicrobial agents or disinfectants, antistatic agents, preservatives (eg glutaraldehyde), bleaching systems and dyes, and opacifiers or skin protection agents, as described in EP-A-522 556.
  • the detergent in particular dishwashing detergent, comprises: a) shaped articles with a first detergent component composition comprising at least one component selected from the group consisting of silver detergents, corrosion inhibitors, hand and skin care agents, special care agents, preferably care agents for ceramics and / or glass, and / or means for removing special soiling; and b) moldings with a second detergent component composition comprising at least one fat-dissolving substance, preferably selected from the group consisting of betaines, fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates, linear alkylbenzenesulfonates, alkyl alcohol polyglycol ethers, alkyl polyglucosides, fatty acid alkanolamides, amine oxides and / or hydrophobic components Shaped body a) contained first detergent component composition when the detergent is diluted with water, preferably before the second detergent component composition contained in shaped body b) is released.
  • a first detergent component composition compris
  • molded bodies a) and b) differ from one another externally, for example in color.
  • the release mechanism The components contained in molded body a) or b) can be based on the various possible parameters mentioned above. If a suitable shell or matrix material is used, the dissolution of the respective shaped bodies can be controlled almost at any time, pH-controlled, temperature-controlled or even electrolyte strength-controlled.
  • the first cleaning or rinsing agent component composition contained in molded body a) is released upon dilution in water before the second cleaning or rinsing agent component composition contained in molded body b), i. H. that the materials or the release mechanism are selected so that the composition in the cleaning solution or rinsing liquor is matched or optimized to the respective cleaning or rinsing phase.
  • the molded body b) preferably contains components which are particularly suitable for removing heavily greasy soiling, for example on plates.
  • the cleaning agent according to the invention in particular hand dishwashing liquid, in a preferred embodiment comprises a liquid phase and moldings with the same or different composition.
  • the shaped bodies can in principle have any shape, with shapes which can be produced economically and economically being preferred. These include, for example, all shapes which are rotationally symmetrical with respect to at least one axis, for example the spherical shape, elliptical shapes or cylindrical shapes, a capsule in the form of a cylinder closed at both ends being preferred.
  • the matrix, coating and / or coating materials of the shaped bodies are selected such that they dissolve only slowly in water and the incorporated filler components are only incorporated into the application or at a specific point in time or during a specific period of time. Dispense wash liquor.
  • the coating, coating and / or matrix material suitable according to the invention is preferably water-soluble, or at least water-dispersible, that is to say that the material at least partially dissolves after being introduced into water or at least a dispersion is formed, so that the covering, coating and / or matrix becomes permeable at a predetermined point in time or after a certain period of time and an exchange of substances between the water surrounding the shaped body and the enclosed cleaning agents or detergent components is made possible.
  • Suitable coating, matrix and / or coating materials include polymers and / or copolymers which are suitable for the dissolution mechanism provided in each case.
  • Suitable materials include alginic acid, alginates, pectins, guar flour, starch, dextrins, gelatin, organic modified natural substances, in particular carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and the like, polysaccharides, organic fully synthetic substances, in particular polyacrylic and polymethacrylic compounds, Vinyl polymers, in particular polyvinyl alcohols, polycarboxylic acids, polyethers, polyimines, polyamides, polyelectrolytes and, in principle, water-soluble or water-disintegrating polymers.
  • the material from which the covering is made can contain additives which influence the elasticity and water solubility.
  • Suitable plasticizers are, for example, glycol, sorbitol and glycerin.
  • a time-controlled release of detergent components can be achieved, for example, by changing the pH of the cleaning solution or rinsing liquor. If you consider, for example, the process of manually cleaning dishes, the initial pH value of the washing liquor changes during the washing process. If one assumes that in the first rinsing phase, namely when cleaning the glasses, the object to be rinsed is first cleaned in the washing liquor and then rinsed with fresh water, the pH will drop due to the dilution with pH-neutral water -Values in the washing liquor. The resulting pH value depends on the volume and the detergent component concentration in the washing liquor and on the amount of fresh water added. This pH value change in the rinsing liquor can be used to control the dissolution process of the shaped bodies in a targeted manner. This effect or such a change in pH value is of course also the case with the dilution of cleaning and washing-up liquid concentrates and with diluted ones Observe cleaning agents and can also be used to control the dissolution process of the moldings.
  • wrapping, matrix and / or coating materials which experience a change in the physicochemical properties when the pH of the application liquor changes. It is particularly preferred that such substances have an increased solubility in water and / or a decrease in the diffusion density when the pH changes.
  • These substances include basic substances, in particular basic polymers and / or copolymers.
  • the principle of pH-dependent water solubility is usually based on protonation or deprotonation of functional side groups of the polymers.
  • Such polymers with pH-dependent solubility are also known, inter alia, from the pharmaceutical industry, for example in connection with enteric coatings on tablets.
  • pH-sensitive coating, matrix and / or coating materials are (co) polymers which preferably have amino groups or aminoalkyl groups.
  • Suitable comonomers are, for example, acrylates, methacrylates, maleinates or derivatives of these compounds.
  • Polymaleimide copolymers, polyacrylamides, polyvinylpyrrolidone copolymers and / or polyurethanes are also suitable.
  • the shaped bodies are dissolved under electrolyte control and / or the detergent components contained therein are released due to a change in the electrolyte concentration.
  • the cleaning or rinsing agent components are released from the shaped bodies in a temperature-controlled manner.
  • the moldings are produced, for example, from a melt dispersion or emulsion containing the detergent components, the melt suspension or emulsion essentially consisting of a coating substance which has a melting point above 30 ° C.
  • the in the melt suspension Components or emulsion to be incorporated can be at the processing temperature both in solid and in liquid form.
  • the coating substances which on the one hand relate to the melting or solidification behavior, but on the other hand also relate to the material properties of the coating in the solidified area at ambient temperature. Since the coating should only release the cleaning or rinsing agent components contained therein in the application liquor and not under thermal stress during transport or storage, the coating substances preferably have a melting point above 30 ° C.
  • waxes are understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 30 ° C. without decomposition and are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.
  • the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
  • vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or
  • the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated requirements with regard to the softening point can also be used as covering materials. Suitable synthetic compounds have been found for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll 66 ® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used.
  • Tegin ® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances.
  • Shellac for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as a coating material according to the invention.
  • wax alcohols are also included in the waxes in the context of the present invention, for example.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as a constituent of the casing, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • suitable coating substances for the temperature-controlled release of the cleaning or rinsing agent components include polyethylene glycols, polyvinylpyrrolidones, polyethers, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and / or hydroxyethyl propyl cellulose.
  • Another object of the present invention is the use of the cleaning agent according to the invention for cleaning hard surfaces and / or soft surfaces, preferably as an all-purpose cleaner, bathroom cleaner, floor cleaner, car cleaner, glass cleaner, furniture care agent, furniture cleaner, Facade cleaner, detergent and / or the like and particularly preferably for cleaning dishes.
  • the present invention relates to a method for cleaning a hard and / or soft surface with an aqueous cleaning liquor, which is characterized in that the cleaning liquor is produced by dissolving or dispersing the cleaning agent according to the invention in water.
  • the detergent and dishwashing detergent components of the detergent or hand dishwashing detergent according to the present invention include the following substances or groups of substances:
  • the active cleaning phases according to the invention can contain anionic, nonionic, amphoteric or cationic surfactants or surfactant mixtures from one, several or all of these classes of surfactants as surfactant components.
  • the detergents in particular hand dishwashing detergents, contain surfactants, distributed over the various phases, in amounts, based on the overall formulation, of 5 to 55% by weight, preferably 10 to 30% by weight.
  • Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates as well as aliphatic and aromatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates, lignin sulfonates, lignin sulfonates.
  • Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isothionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half esters of the C 2 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10- C 2 o-oxo alcohols and the half esters of secondary alcohols (secondary alkyl sulfates) of these chain lengths are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the agent according to the invention as (hand) dishwashing detergent, the C 2 -C 6 alkyl sulfates and C 2 -C 15 alkyl sulfates and C 4 -Ci 5 alkyl sulfates are preferred.
  • Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company at available under the name DAN ® , e.g. B. the products mentioned in US Pat. Nos.
  • the fatty alcohol ether sulfates are particularly preferred in the context of the present invention.
  • Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • Suitable alkoxylated alcohols are obtained by reacting ethylene oxide with longer-chain alcohols, for example with straight-chain or branched alcohols with chain lengths of C to C 2 ⁇ such as 2-methyl-branched C 9 to Cn fatty alcohols.
  • a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Mixtures of ethylene oxide and propylene oxide can also be used in the ethoxylation reaction.
  • Low-ethoxylated fatty alcohols 0.5 to 4 mol EO, preferably 1 to 2 mol EO) are very particularly preferred in the sense of the present invention.
  • alkane in particular the secondary alkane sulfonates of unbranched paraffinic hydrocarbons, in particular C- ⁇ 2 _i 8 -alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, be won.
  • a preferred secondary alkane sulfonates is as Hostapur SAS ® 60, sold by Clariant secondary Ci-Na 3 -i 7 alkane.
  • Suitable surfactants of the sulfonate type are alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, of the kind obtained, for example, from C 2 - 8 mono-olefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
  • Alkylbenzene sulfonates in the context of the teaching according to the invention are alkylbenzenesulfonates having a linear or branched, saturated or unsaturated C 6-22 alkyl, preferably C 8-18 alkyl, especially C 9 _i 4 alkyl, most preferably C ⁇ o- 13 alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, and also as ammonium salts or mono-, di- or trialkanolammonium salts, preferably mono-, di- or triethanol and / or -isopropanolammonium salts, especially mono-, di- or
  • Triethanolammonium salts but also used as alkylbenzenesulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or trialkanolamine.
  • esters of 2-sulfo fatty acids e.g. the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • the anionic surfactants are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and, in the case of the sulfonates, also in the form of the acid, for example dodecylbenzenesulfonic acid, C ⁇ 0 -C ⁇ 3 alkylbenzene and / or C ⁇ 0 -C ⁇ 4 alkylbenzene used.
  • the cleaning agents according to the invention can also contain soaps, ie alkali metal or ammonium salts of saturated or unsaturated C6-C22 fatty acids.
  • Nonionic surfactants in the context of the invention can be alkoxylates, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end group-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters as well as alkyl polyglycosides or nitrogenous surfactants.
  • alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end group-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters as well as alkyl polyglycosides or nitrogenous surfactants.
  • Non-ionic surfactants which can preferably be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl -, 2-butyl or 2-methyl-2-butyl
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
  • End group-capped fatty alcohol polyglycol ethers which are sold under the trade name Dehypon® by Henkel KGaA, Düsseldorf, are particularly preferably used in the context of the present invention.
  • C 6 -C 22 alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be represented by the formula
  • R 1 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18, in particular 10 to 16, carbon atoms, p for 0 or numbers from 1 to 3 and e for numbers from 1 to 20.
  • the C 6 -C 22 alkyl alcohol polyglycol ethers can be added to alkyl alcohols, preferably to oxo alcohols, by addition of propylene oxide and / or ethylene oxide branched chain primary alcohols obtainable by oxosynthesis or to fatty alcohols.
  • Typical examples are polyglycol ethers in which R 1 is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7.
  • At least one alkyl alcohol polyglycol ether with a linear alkyl radical R 1 is combined with at least one alkyl alcohol polyglycol ether with a branched alkyl radical R 1 , for example C 2 -C 6 fatty alcohol + 5.5-EO and isodecanol + 6-EO. It is further preferred here that the linear alkyl radical comprises more carbon atoms than the branched alkyl radical.
  • Fatty alcohol + 3 EO, and mixtures thereof - C ⁇ -fatty alcohol + 1.2PO + 8.4EO, C 8- ⁇ o-fatty alcohol + 5EO, C ⁇ 2- i4 fatty alcohol + 6 EO C 12 and 14 are particularly preferred.
  • Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula R 2 0 [G] x , in which R 2 is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] is a glycosidically linked sugar radical and x is are a number from 1 to 10.
  • APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry.
  • the index number x in the abovementioned general formula indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • the value x for a certain alkyl glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number.
  • Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6.
  • Xylose, but especially glucose, is preferably used as the glycosidic sugar.
  • the alkyl or alkenyl radical R 2 can be derived from primary alcohols having 8 to 22, preferably 8 to 14, carbon atoms.
  • Typical examples are capronic alcohol, capryial alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from RoELEN's oxosynthesis.
  • the alkyl or alkenyl radical R 2 is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.
  • Suitable nitrogen-containing nonionic surfactants are, for example, amine oxides, polyhydroxy fatty acid amides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10.
  • Ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred.
  • the particularly suitable compounds include the lauric acid, myristic acid and palmitic acid monoethanolamides.
  • the amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Preferred amine oxides satisfy the formula R 1 R 2 R 3 N + -0 ⁇ , in which R 1 is a saturated or unsaturated C 6-22 alkyl radical, preferably Cs-is-alkyl radical, in particular a saturated C ⁇ o- 16 alkyl radical, for example a saturated C 2 _i 4 alkyl radical which in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -0- (CH 2 ) z - is bonded to the nitrogen atom N, where z in each case represents a number from 1 to 10, preferably 2 to 5, in particular 3, and R 2 and R 3 independently of one another are an optional
  • Suitable amine oxides are the following compounds named in accordance with INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimethyl Oxide Oxide, Dioxopoxymethyl Oxide Oxide, Diaminopyrimethyl Oxide Oxide, Diaminopyrimethyl Oxide Oxide, , Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallow
  • Preferred amine oxide (s) are, for example, cocamine oxides (N-cocoalkyl-N, N-dimethylamine oxide), dihydroxyethyl tallowamine oxides (N-tallow alkyl-N, N-dihydroxyethylamine oxide) and / or cocamidopropylamine oxides (cocoamidopropylamine oxide), in particular Cocamidopropylamine oxides.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula R 1 I
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 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.
  • Suitable amphoteric surfactants are, for example, betaines.
  • Suitable betaines are the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R A ) (R B ) (R c ) N + CH 2 COO " , in which R A is one optionally interrupted by heteroatoms or heteroatom groups, alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R B and R c are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 1 -C 8 -alkyl-dimethylcarboxy-methylbetaines and Cn-C ⁇ 7- alkylamidopropyldimethylcarboxymethylbetaines, and betaines according to formula A,
  • R 1 is a saturated or unsaturated C 6-22 alkyl radical, C 8-18 alkyl group, preferably, in particular a saturated C ⁇ 0-16 alkyl radical, for example a saturated C 2 -i 4 alkyl radical,
  • n is a number from 1 to 10, preferably 2 to 5, in particular 3, x 0 or 1, preferably 1,
  • R ", R '" independently of one another are a C 4 alkyl radical, optionally hydroxy-substituted, such as, for example, a hydroxyethyl radical, but in particular a methyl radical, m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and
  • Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamido betaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4, R'-N + (CH 3 ) 2 -CH 2 COO- (A1) R 1 -CO- NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO- (A2)
  • amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula A1 and A2, most preferably the alkylamidobetaines of the formula A2.
  • betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, Babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, capryl / capramidopropyl betaine, betaine, carnitine, cocaine , Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glyc
  • a preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine).
  • Particularly preferred amphoteric surfactants are caprylic / capramidopropyl betaine (GAB), which is available, for example, from Th. Goldschmidt AG or Henkel KGaA under the trade names Tegotens® B 810, Tegobetain® F50 or Dehyton®.
  • alkylamidoalkylamines are amphoteric surfactants of the formula B
  • C 8-18 alkyl radical in particular a saturated C 0-16 alkyl radical, for example a saturated C ⁇ - alkyl radical
  • R i is a hydrogen atom H or CH 2 COOM (to M su)
  • j is a number from 1 to 4, preferably 1 or 2, in particular
  • R 12 is a C ⁇ - alkyl group or M (see below), and M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine , for example protonated mono-, di- or
  • Triethanolamine is.
  • alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropyl- sulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-lsodeceth-7 Carboxyamph
  • Cocoamphohydroxypropylsulfonate Sodium Cocoamphopropionate, Sodium Comamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoampho- propionate, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropyl- sulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoampho-hydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphoprop
  • Alkyl-substituted amino acids preferred according to the invention are monoalkyl-substituted amino acids according to formula C,
  • Cs- 18 alkyl radical in particular a saturated C ⁇ 0-16 alkyl radical, for example a saturated Ci 2 -i 4 alkyl radical
  • R x is a hydrogen atom H or a C ⁇ - 4 alkyl radical, preferably H
  • u is a number from 0 to 4 , preferably 0 or 1, in particular 1
  • M ' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or
  • Triethanolamine is,
  • R x ⁇ is a saturated or unsaturated C 6-22 -alkyl radical, preferably C ⁇ -is-alkyl radical, in particular a saturated C ⁇ o- 16 -alkyl radical, for example a saturated Ci 2 - 14 -alkyl radical
  • v is a number from 1 to 5, preferably 2 or 3, in particular 2
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups can have the same or two different meanings, for example hydrogen and sodium or twice sodium is
  • Cs-is-alkyl radical in particular a saturated C ⁇ o- 16 alkyl radical, for example a saturated C ⁇ -u-alkyl radical
  • R xl is a hydrogen atom or a optionally substituted by hydroxy or amine, for example a methyl, ethyl, hydroxyethyl or
  • R x ⁇ v the rest of one of the 20 natural ⁇ -amino acids H 2 NCH (R xlv ) COOH, and M '"a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or
  • Triethanolamine is.
  • alkyl-substituted amino acids are the aminopropionates according to formula C1,
  • alkyl-substituted amino acids are the following compounds named according to INCI: aminopropyl lauryl glutamine, cocaminobutyric acid, cocaminopropionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium laurododropropionate, disodium stiminaminodipionate, disodium steariminodiphenate Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminopropionate.
  • Acylated amino acids are amino acids, especially the 20 natural ⁇ -amino acids, which contain the acyl residue R xv CO of a saturated or unsaturated fatty acid R COOH wear xv, where R xv a saturated or unsaturated C 6-22 alkyl, preferably Cs-is-alkyl radical, particularly a saturated Cio-i ⁇ alkyl group, for example a saturated C ⁇ - alkyl.
  • the acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
  • acylated amino acids are the acyl derivatives summarized according to INCI under amino acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R i ⁇ ) (R iv ) (R v ) (R vi ) N + X " , in which R ⁇ i to R vi represent four identical or different types, in particular two long and two short-chain, alkyl radicals and X "represent an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • the cleaning agents according to the invention contain one or more hydrophobic components.
  • the hydrophobic components above all improve the cleaning effect against hydrophobic contaminants such as greasy dirt.
  • Suitable hydrophobic components are, for example, dialkyl ethers with the same or different C 4 -C 6 -alkyl radicals, in particular linear dioctyl ether; Hydrocarbons with a boiling range of 100 to 300 ° C, especially 140 to 280 ° C, for. B.
  • hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures.
  • the cleaning agents according to the invention can contain one or more builders.
  • Suitable builders are, for example, alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium citrate, gluconate and nitrilotriacetate, as well as sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium hydroxide Amines, especially mono- and triethanolamine, or mixtures thereof.
  • compositions contain builders in amounts, based on the composition, of 0 to 30% by weight, preferably 0.1 to 20% by weight, in particular 1 to 15% by weight, extremely preferably 2 to 10% by weight ,
  • a preferred builder is citrate from the group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium citrates, preferably mono-, di- or triethanolammonium citrates, or mixtures thereof, in particular sodium citrate, extremely preferably potassium citrate.
  • a particularly preferred alkaline builder is potassium hydroxide.
  • the builder is also to act as a pH-stabilizing buffer, alkali metal and alkaline earth metal carbonates and bicarbonates, e.g. Soda, preferred.
  • the cleaning agents according to the invention optionally contain at least one antimicrobial active ingredient, preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, Carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen acetals and formals, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial quinoline compounds, amphoteric compounds 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and other halogens or halogen compounds as well as peroxides or perox
  • guanidines including the biguanidines and polyguanidines are, for example, 1,6-bis- (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1,6-di- (N ⁇ , N ⁇ , -phenyldiguanido-N 5 , N 5 l ) -hexane-tetrahydochloride, 1, 6-di- (Ni.Ni'-phenyl-Ni.Ni-methyldiguanido-Ns.Ns'J-hexane-dihydrochloride, 1,6-di- (N- ⁇ , N ⁇ '-chlorophenyldiguanido-N 5 , N 5 ') -hexane-dihydrochloride, 1,6-di- (N ⁇ , N ⁇ '-2,6-dichlorophenyldiguanido-N 5 , N 5 ') -hexane-
  • antimicrobial agents see also International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature, publisher: The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street , NW, Suite 300, Washington, DC 20036, USA): Alcohol, Benzalkonium Chloride, Benzethonium Chloride, Camellia Sinensis Leaf Extract, Candida Bombicola / Glucose / Methyl, Rapeseedate Ferment, Hydrogen Peroxide, Methylbenzethonium Chloride, Phenol, Pinus Pinaster Bark Extract, Pinus Tabulaeformis Bark Extract, Poloxamer 188, PVP-lodine, Rosmarinus Officinalis (Rosemary), Leaf Extract and Vitis Vinifera (Grape) Seed Extract.
  • CTFA Cosmetic, Toiletry, and Fragrance Association
  • the agent according to the invention particularly preferably contains at least one quaternary ammonium compound (QAV) with an antimicobial action according to the general formula (R i ⁇ ) (R iv ) (R v ) (R vi ) N + X " in which R i ⁇ to R vi are identical or different C 1 -C 22 -alkyl radicals, C 7 -C 28 -aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound , represent and X "are halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QAV are by reacting tertiary amines with alkylating agents, such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as. B. methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • the alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (mp-dichlorobenzyldimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6 ), Benzoxonium chloride (Benzyl dodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide
  • benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1, 1, 3 , 3-tetramethylbutyl) phenoxy] ethoxy] ethyl] - benzylammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides such as di- ⁇ -decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethyl- ammonium bromide (CAS No.
  • QAV benzalkonium chlorides with Cs-Cis-alkyl radicals, in particular C 12 -Ci 4 -Akly! -Benzyl-dimethylammonium chloride.
  • Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) - hexaminiumchlorid as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
  • the content of antimicrobial active ingredient, in particular surface-active quaternary compound, according to the invention is between 0 to 10% by weight, preferably 0.2 to 5% by weight, in particular 0.5 to 3% by weight, particularly preferably 1 to 2% by weight .-%, for example 1.5 wt .-%.
  • the liquid phase used according to the invention can contain one or more thickeners, preferably in an amount of 0.01 to 5% by weight, in particular 0.05 to 2.5% by weight, particularly preferably 0.1 to 1 % By weight.
  • Suitable thickeners are organic natural thickeners, such as agar agar, carrageenan, tragacanth, arabic gum, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin or Casein, organic modified natural substances such as carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, gum flour, organic fully synthetic thickeners such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines or polyamides, and inorganic Thickeners such as polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas.
  • organic natural thickeners such as agar agar, carrageenan, tragacanth, arabic gum, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, ge
  • the polyacrylic and polymethacrylic compounds 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 (/ ⁇ / C / name according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer), also known as carboxyvinyl polymers.
  • CFA Cosmetic, Toiletry, and Fragrance Association
  • Such polyacrylic acids are available from BFGoodrich, among others, under the trade name CarbopoP, for example CarbopoP 940 (molecular weight approx. 4,000,000), CarbopoP 941 (molecular weight approx.
  • acrylic acid copolymers (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C 4 -alkanols, to which, for example, the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, from Rohm & Haas under the trade names Aculyn ® and Acusot ® are available, for example the anionic non-associative polymers Aculyn ® 33 (crosslinked), AcusoP 810 and AcusoP 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic acid, butyl acrylate and their simple esters (INCI acrylates copolymer), preferably formed with C 4
  • Preferred thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures.
  • polysaccharide gums for example gum arabic, agar, alginates, carrageenans and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives can be used alternatively, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • a particularly preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 * 10 6 and is available, for example, from Kelco under the trade name KeltroP, for example as a cream-colored powder KeltroP T (Transparent) or as white granulate KeltroP RD (Readily Dispersable).
  • KeltroP for example as a cream-colored powder KeltroP T (Transparent) or as white granulate KeltroP RD (Readily Dispersable).
  • the agents according to the invention can contain further auxiliaries and additives as are customary in such agents.
  • auxiliaries and additives include in particular perfume and fragrances, polymers, soil release agents, solvents, such as Ethanol, isopropanol and glycol ether, solubilizers, hydrotropes such as e.g. Cumene sulfonate, octyl sulfate, butyl glucoside and butyl glycol, cleaning enhancers, disinfectants, antistatic agents, preservatives, bleaching systems, enzymes and dyes as well as opacifiers or skin protection agents, as described in EP-A-522 556.
  • Preferred auxiliaries and additives are perfume and fragrances and dyes.
  • the cleaning or hand dishwashing detergents according to the invention in particular the moldings, can be produced in a manner known per se.
  • the firm Phases or moldings can be obtained, for example, by coating in the immersion, fog or spray process.
  • a capsule phase according to the invention that is to say a shaped body which contains suitable detergent components, by means of the so-called dropletization process, which is described, for example, in DE 2215441 Unilever.
  • a clear, colorless hand dishwashing liquid was formulated with blue capsules.
  • Capsules consisting of an aqueous solution of 40% C12-14 ether sulfate Na salt, 10% cocamidopropyl betaine, 10% C12-14 sulfate Na salt, 17% ethylene glycol and 0.1% base blue dye were encapsulated in polyvinyl alcohol gel, made from a solution of 10% polyvinyl alcohol (PVAI from Erkol), 0.0005% boric acid, balance water, using an extruder with a concentric outlet opening. The solution was dripped in the form of droplets in a collecting bath consisting of an aqueous solution of 0.5% NaOH and 20% Na 2 S0 4 .
  • the capsule phase was added in a concentration of 5 - 30% in the basic rinsing solution. It was stable when stored. When it was diluted to the application concentration at a temperature of 40 ° C., it dissolved within 10 minutes and released the enclosed surfactant. The resulting diluted basic rinsing solution gently cleaned glasses. The blue capsules loosened sets off with a time delay and releases a surfactant mixture for the powerful cleaning of greasy, contaminated dishes.
  • a clear hand dishwashing detergent was formulated with blue and green capsules.
  • Capsules consisting of an aqueous solution of 40% C12-14 ether sulfate Na salt, 10% cocamidopropyl betaine, 10% C12-14 sulfate Na salt, 17% ethylene glycol and 0.1% base blue dye were encapsulated in polyvinyl alcohol gel, made from a solution of 10% polyvinyl alcohol (PVAI from Erkol), 0.0005% boric acid, balance water, using an extruder with a concentric outlet opening. The solution was dripped in the form of droplets into a collecting bath consisting of an aqueous solution of 0.5% NaOH and 20% Na 2 SO 4 .
  • PVAI polyvinyl alcohol
  • Capsules were produced, consisting of a core of 10 parts of TiO 2 powder and 6 parts of thiourea dispersed in 84 parts of liquid paraffin with the addition of 0.1% base green dye and a capsule wall made of carrageenan gum.
  • the encapsulation was carried out using an aqueous solution of 1% Satiagel (K-carrageenan), 2% Aubygel (i-carrageenan), 0.25% Tragon (locust bean gum) and 2% glycerol and an extruder with a concentric outlet at 70 ° C ,
  • the solution was dripped in the form of droplets into a collecting bath consisting of a solution of 5% KCI, 20% water and 75% alcohol.
  • Both capsule phases were added in a concentration of 2.5 - 15% to the basic rinsing solution. It is stable when stored. The entire formulation was added to the water when dosing. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules loosened. The released thiourea was particularly effective in cleaning silver cutlery stains. After another 5-10 minutes, the blue capsule phase dissolved and released the surfactant mixture, which effectively cleaned dishes contaminated with fat.
  • a clear hand dishwashing detergent was formulated with blue and green capsules.
  • the formulation corresponded to that described in Example 2. However, instead of the silver cleaner, the green phase contained aminopolysiloxane as a care component for glass and ceramics.
  • the agent When dosing, the agent was placed in water. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules came off. The released active ingredient is particularly suitable for the care of glass and ceramic surfaces. After another 5-10 minutes, the blue capsule phase dissolved and released a surfactant mixture for the powerful cleaning of greasy, contaminated dishes.
  • a clear hand dishwashing detergent was formulated with blue and green capsules.
  • the formulation corresponded to that described in Example 2. However, instead of the silver cleaner, the green phase contained jojoba oil as a skin care component.
  • the formulation When dosing, the formulation was placed in water. The immediately rinsed basic rinsing solution cleaned the glasses very gently, after about 5 minutes the green capsules loosened. The released active ingredient is particularly suitable for skin care. After another 5-10 minutes, the blue capsule phase dissolved and released a surfactant mixture for the powerful cleaning of dishes contaminated with fat.
  • a clear hand dishwashing detergent was formulated with blue capsules.
  • the basic rinse solution corresponded to that described in Example 1.
  • Example 2 The same basic rinsing solution as in Example 1 was used.
  • Capsules were prepared by containing an aqueous emulsion containing 0.8% alginate, 1% polyvinyl alcohol, 40% C12-14 ether sulfate Na salt, 10% cocamido propyl betaine and 0.1% base blue dye in an aqueous precipitation bath 5% calcium chloride and 10% sodium sulfate dripped. The capsules obtained were filtered off, washed and added to the basic rinsing solution.
  • composition of further basic rinse solutions A to E (external liquid phase) suitable according to the invention is shown in Table 1 below.
  • Table 1 The composition of further basic rinse solutions A to E (external liquid phase) suitable according to the invention is shown in Table 1 below.
  • a clear hand dishwashing detergent was formulated with blue capsules.
  • the basic rinse solution corresponded to that described in Example 1.
  • Example 2 The same basic rinsing solution as in Example 1 was used.
  • Capsules were prepared by dropping an aqueous emulsion containing 0.8% alginate, 1% polyvinyl alcohol, 25% limonene oil and 0.1% base blue dye into an aqueous precipitation bath containing 5% calcium chloride and 10% sodium sulfate. The capsules obtained were filtered off, washed and added to the basic rinsing solution.
  • a clear hand dishwashing liquid was formulated with blue capsules.
  • the basic rinse solution corresponded to that described in Example 1.
  • Example 2 The same basic rinsing solution as in Example 1 was used.
  • Capsules were prepared by using an aqueous emulsion containing 0.8%
  • the capsules obtained were filtered off, washed and added to the basic rinsing solution.
  • the capsules which dissolve on dilution, released fragrances and skin care substances.

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Abstract

La présente invention concerne un produit de nettoyage à une ou plusieurs phases contenant des tensioactifs, en particulier un produit pour le lavage de la vaisselle à la main, au moins une phase comprenant des corps formés conçus pour libérer de façon différée au moins un composant du produit de nettoyage en se diluant dans l'eau. Ce produit de nettoyage comprend des corps formés qui libèrent de façon différée en se diluant dans l'eau les composants de nettoyage ou de lavage qu'ils contiennent. Selon l'invention, les composants "encapsulés" précités ne sont pas libérés immédiatement après la diffusion du produit dans l'eau, soit après la formation de la solution de nettoyage ou de l'eau de lavage, mais seulement après un certain temps. De cette façon, l'utilisateur dispose, à l'issue de la première phase de nettoyage ou de lavage, par exemple le nettoyage de verres, d'une composition de produit de nettoyage pour la deuxième phase de nettoyage ou de lavage, par exemple le nettoyage d'assiettes ou de plats relativement gras, cette composition étant optimisée pour cette opération de nettoyage spécifique.
PCT/EP2002/006889 2001-06-30 2002-06-21 Produit de nettoyage a plusieurs phases Ceased WO2003004593A1 (fr)

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DE10131722A DE10131722A1 (de) 2001-06-30 2001-06-30 Mehrphasen-Reinigungsmittel
DE10131722.0 2001-06-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003054125A1 (fr) * 2001-12-20 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Agent de nettoyage a microcapsules

Citations (7)

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Publication number Priority date Publication date Assignee Title
US3708429A (en) * 1970-03-06 1973-01-02 Lever Brothers Ltd Cleaning compositions
DE19817964A1 (de) * 1998-04-22 1999-10-28 Henkel Kgaa Umhüllte Reinigungsmittelkomponente
WO2000006688A1 (fr) * 1998-07-29 2000-02-10 Reckitt Benckiser N.V. Composition s'utilisant dans un lave-vaisselle
WO2000046337A1 (fr) * 1999-02-02 2000-08-10 Quest International B.V. Composition detergente
DE19918265A1 (de) * 1999-04-22 2000-10-26 Henkel Kgaa Abrasivstoffhaltiges Reinigungsmittel mit Mikrokapseln
DE19932144A1 (de) * 1999-07-09 2001-01-11 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel
US6242405B1 (en) * 1995-12-29 2001-06-05 Novo Nordisk A/S Enzyme-containing particles and liquid detergent concentrate

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Publication number Priority date Publication date Assignee Title
GB1390503A (en) * 1971-03-30 1975-04-16 Unilever Ltd Liquid detergent compositions
DE19721708A1 (de) * 1997-05-23 1998-11-26 Henkel Kgaa Verkapseltes Reinigungsmittel

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3708429A (en) * 1970-03-06 1973-01-02 Lever Brothers Ltd Cleaning compositions
US6242405B1 (en) * 1995-12-29 2001-06-05 Novo Nordisk A/S Enzyme-containing particles and liquid detergent concentrate
DE19817964A1 (de) * 1998-04-22 1999-10-28 Henkel Kgaa Umhüllte Reinigungsmittelkomponente
WO2000006688A1 (fr) * 1998-07-29 2000-02-10 Reckitt Benckiser N.V. Composition s'utilisant dans un lave-vaisselle
WO2000046337A1 (fr) * 1999-02-02 2000-08-10 Quest International B.V. Composition detergente
DE19918265A1 (de) * 1999-04-22 2000-10-26 Henkel Kgaa Abrasivstoffhaltiges Reinigungsmittel mit Mikrokapseln
DE19932144A1 (de) * 1999-07-09 2001-01-11 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003054125A1 (fr) * 2001-12-20 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Agent de nettoyage a microcapsules

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