EP1904613B1 - Produits de nettoyage et d'entretien presentant une emulsibilite amelioree - Google Patents

Produits de nettoyage et d'entretien presentant une emulsibilite amelioree Download PDF

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Publication number
EP1904613B1
EP1904613B1 EP06754551A EP06754551A EP1904613B1 EP 1904613 B1 EP1904613 B1 EP 1904613B1 EP 06754551 A EP06754551 A EP 06754551A EP 06754551 A EP06754551 A EP 06754551A EP 1904613 B1 EP1904613 B1 EP 1904613B1
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EP
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Prior art keywords
acid
mol
preferentially
fatty alcohol
agent according
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EP06754551A
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German (de)
English (en)
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EP1904613A1 (fr
Inventor
Arnd Kessler
Claudia Schattling
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to a cleaning or care agent, in particular a hard surface cleaner, which has a higher emulsifying ability for fats and oils compared to known agents, the use of this agent for cleaning and maintenance of hard surfaces such as the interior of washing machines and dishwashers and a method for cleaning and care of washing machines or dishwashers.
  • a cleaning or care agent in particular a hard surface cleaner, which has a higher emulsifying ability for fats and oils compared to known agents, the use of this agent for cleaning and maintenance of hard surfaces such as the interior of washing machines and dishwashers and a method for cleaning and care of washing machines or dishwashers.
  • Cleaning or care products usually contain surfactants and have a wide range of uses and depending on a very different composition. After the pH, alkaline, neutral and acid cleaning or care products, according to the offer form liquid and solid cleaning or care products are distinguished. Especially for liquid cleaning or care products, the consumer expects that he can use the agents both in the undiluted and in the dilute aqueous state and in each case receives a satisfactory cleaning or care result.
  • the surfactants and / or alkali carriers which can be replaced by acids depending on the application, optionally also solvents such as glycol ethers and lower alcohols.
  • the formulations also contain builders, depending on the type, also bleaching agents, enzymes, as well as perfume oils and dyes. The cleaning success depends to a large extent on the - also geographically very different - type of soil and the properties of the surfaces to be cleaned.
  • cleaning or care products are used as general-purpose or special agents (car care products, oven cleaners, descaling agents, window cleaners, stain removers, floor care products, glass ceramic hob cleaners, stoves, leather care products, metal cleaners, furniture care products, pipe cleaners, sanitary cleaners, abrasives, carpet care products or toilet cleaners) assembled.
  • Technical cleaning or care products are mainly used in the beverage, food, cosmetic and pharmaceutical industries, but also in the metal industry for metal degreasing.
  • the product group also includes cleaning or care products for car washes, tank truck and aircraft cleaning or care products.
  • the group of cleaning or care products includes, for example, the dishwashing detergents and agents for cleaning or care of washing machine or dishwasher interior.
  • EP 1 308 499 discloses a surfactant blend with hydroxy mixed ethers and polymers.
  • cleaning agent sprays for removing lime deposits on bathroom tiles or for degreasing metal objects such as extractor hoods.
  • Means that provide good cleaning or care results without significant mechanical treatment offer in addition to the convenience for the user also the ability to clean surfaces whose mechanical treatment with the means is not or only to a small extent possible.
  • mechanically poorly cleaned surfaces are corners and angled surfaces, the inner surface of pipes and funnels, sharp-edged or intertwined surfaces, meshes, hose connections, but also surfaces which, due to their nature, must not be subjected to mechanical stress.
  • appliances such as washing machines or dishwashers, coffee machines or kettles are incomplete from the inside and only with great effort by mechanical action, for example, by a rag or a brush to clean, so that even for these applications cleaning or care products that perform well without significant mechanical treatment, are desired.
  • the effect of the cleaning or care products should be so great that not only the large surfaces the inside of the machine, which are exposed to the direct and intense operating pressure of the cleaning fleet and thus experience quite a mechanical load, but also angled areas, hose connections, door seals and all low-flow zones are optimally cleaned and / or maintained in these machines.
  • the object of the present invention was to provide a cleaning or care agent which overcomes the above-mentioned problems.
  • this agent should have an increased emulsifying ability for fats and oils and thus improved performance in the area of fat removal.
  • Cleaning or care compositions according to the invention which comprise a combination of the two nonionic surfactants A and B and a thickening agent, show otherwise cleansed or care-containing preparations which instead of the nonionic surfactant A are used and / or the nonionic surfactant B nonionic surfactant (s) of other compound class (s) or only a nonionic surfactant of the above structure and a thickener or two different nonionic surfactants of the above structure, but containing no thickener, a significantly increased emulsifying for Fats and oils.
  • the cleaning or care agent according to the invention is preferably used in the treatment of hard surfaces and is particularly suitable for the cleaning or care of washing machines or dishwashers, especially for dishwashers.
  • an increase in the emulsifying capacity is surprisingly achieved by the combination of a thickening agent with two different nonionic surfactants of the above structure.
  • Particularly good performance in the area of grease removal is achieved when using such cleaning or care agents in which the surfactant system at least one nonionic surfactant A having an average molecular weight between 200 and 1200 g / mol, preferably between 300 and 1100 g / mol, particularly preferred between 400 and 1000 g / mol and in particular between 500 and 900 g / mol and at least one further nonionic surfactant B having an average molecular weight between 1000 and 2500 g / mol, preferably between 1100 and 2400 g / mol, preferably between 1200 and 2300 g / mol, particularly preferably between 1300 and 2200 and in particular between 1400 and 2100 g / mol.
  • the surfactant system may consist of two surfactants with different chemical structure, but with comparable average molecular weight.
  • the average molar masses of the nonionic surfactants A and B preferably deviate from one another by at least 20 g / mol.
  • the difference between the average molar masses of the two nonionic surfactants A and B is preferably at least 100, preferably at least 200, preferably at least 300, preferably at least 400, more preferably at least 500, very preferably at least 600 and in particular at least 700 g / mol.
  • the sum of the proportions by weight of the two nonionic surfactants A and B, in particular of all nonionic surfactants present in the composition, is preferably less than 10% by weight, particularly preferably less than 8% by weight, very particularly preferably less than 6% by weight in inventive compositions .-%, more preferably less than 4 wt .-% and in particular less than 3 wt .-%.
  • the weight ratio between surfactant A and surfactant B is preferably between 10: 1 and 1: 1, preferably between 8.5: 1 and 1, 25: 1, more preferably between 7: 1 and 1.5: 1, preferably between 5.5: 1 and 1.75: 1 and in particular between 4: 1 and 2: 1.
  • the surfactant B is from 0.1 to 1.7 wt .-%, preferably 0.2 to 1.4 wt .-%, particularly preferably 0.3 to 1.1 wt .-% and in particular to 0 , 4 to 0.8% by weight in the composition.
  • the proportion of the surfactant A in the composition according to the invention is preferably 0.6 to 5 wt .-%, preferably 0.8 to 4 wt .-%, particularly preferably 1.0 to 3 wt .-% and in particular 1.2 to 2 wt .-%.
  • nonionic surfactants within the scope of the invention are nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s.
  • nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
  • the agent according to the invention contains a nonionic surfactant B having a melting point above 25 ° C., preferably above 30 ° C., more preferably above 35 ° C. and especially above 4.0 ° C., and additionally a nonionic surfactant A having a melting point below 25 ° C, preferably below 22.5 ° C, more preferably below 20 ° C and especially below 17.5 ° C.
  • nonionic surfactants which can be represented by the formula R 1 O- [CH 2 CH (R 2 ) O ] x -R 3 are suitable for combination with the thickener.
  • nonionic surfactants A and B are alcohol alkoxylates, in particular fatty alcohol alkoxylates.
  • Both mixed alkoxylated fatty alcohol alkoxylates and fatty alcohol alkoxylates in which the radical R 2 is not varied may be present in the compositions according to the invention.
  • Fettalkoholalkoxylate be by alkoxylation, ie reaction with ethylene oxide, propylene oxide or butylene oxide, etc., but preferably ethoxylation and / or propoxylation of primary long-chain fatty or oxo alcohols in the presence of basic or acidic catalysts at temperatures of 120-200 ° C and pressures of 1-10 bar received.
  • a polyglycol ether mixture of varying degrees alkoxylated homologues whose Distribution may vary depending on the catalyst and the amount of alkoxide between a Gauss and a non-selective Schulz-Flory curve.
  • additive products of from 1 to 40 mol, preferably from 5 to 30 mol, of ethylene oxide and / or propylene oxide onto monofunctional alcohols are preferably used in the cleansing or care compositions according to the invention.
  • monofunctional alcohols the so-called fatty alcohols such as caproic, caprylic, lauryl, myristyl, cetyl and stearyl alcohols and their technical mixtures are suitable.
  • monofunctional, branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group.
  • Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol or 2-octyldodecanol.
  • the suitable alcohols also coconut, palm, tallow and oleyl alcohol are mentioned.
  • Preferably usable alkyl ethoxylates are the addition products of 2 to 15, preferably 2 to 10 moles of ethylene oxide (EO) and / or propylene oxide (PO) to fatty alcohols having 4 to 22, preferably 12 to 18 and in particular 12 to 14 carbon atoms in the alkyl radical.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable surfactants are, for example, C 12-14 fatty alcohols having 1 to 10 EO, preferably C 12-14 fatty alcohols having 2, 3 4, 6 or 7 EO, C 12-18 fatty alcohols having 1 to 10 EO, preferably C 12-18 fatty alcohols with 2, 3, 4, 5, 8 or 9 EO, C 12-14 fatty alcohols having 1 to 8 EO and 1 to 8 PO, preferably C 12-14 fatty alcohols with 4 EO and 5 PO, with 6 EO and 4 PO, with 2 EO and 4 PO or with 5 EO and 4 PO, C 12-18 fatty alcohols having 1 to 8 EO and 1 to 8 PO, preferably C 12-18 fatty alcohols with 2 EO and 4 PO and the adducts of isodecanol or C 9 -11 (oxo) alcohol with 2.5 or 3, 5, 6, 7, 8, 10 or 11 EO.
  • ethoxylated nonionic surfactants selected from C 6-20 monohydroxyalkanols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles, preferably more than 20 moles and especially more than 25 moles of ethylene oxide per mole of alcohol were used.
  • a particularly preferred nonionic surfactant is of a straight chain or branched, preferably a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), with preference for one.
  • the narrow range ethoxylates are particularly preferred.
  • each R 2 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • x for the nonionic surfactant B has a value between 14 and 60, preferably between 18 and 52, more preferably between 22 and 46 and most preferably between 26 and 38.
  • the radical R 2 can vary, so that both ethoxy, and propoxy and / or buthoxy units are contained in the nonionic surfactant.
  • the nonionic surfactant B contains only ethylene oxide, propylene oxide or butylene oxide units.
  • the surfactant B contains only ethylene oxide units.
  • the value for x with less than 20, preferably less than 15 and in particular less than 10 is preferably smaller than in the surfactant A.
  • the variation of the radical R 2 can be excluded, so that the nonionic surfactant A only Contains ethylene oxide, only propylene oxide or only butylene oxide units.
  • the surfactant A contains different radicals R 2 .
  • Preferred nonionic surfactant A in the context of the invention are adducts of from 1 to 10 mol, preferably from 2 to 7 mol and in particular from 4 to 5 Mole of ethylene oxide and 1 to 10 moles of propylene oxide, preferably 2 to 6 moles and especially 3 to 4 moles of propylene oxide to higher molecular weight fatty alcohols into consideration.
  • the hydrocarbon radical of the surfactant A contains preferably 8 to 18, preferably 10 to 16 and in particular 12 to 14 carbon atoms.
  • a composition according to the invention contains a C 12 -C 14 -alkyl alcohol alkoxylate which comprises both ethoxy and propoxy units, and a C 16 -C 18 -alkyl alcohol ethoxylate.
  • nonionic surfactants are the so-called mixed ethers, which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols, which are subsequently reacted with alkyl groups in the presence of bases and end-capped.
  • Particularly suitable mixed ethers in the context of the present invention are those which have been prepared by end-capping with a C 1 -C 8 -alkyl halide, in particular with a C 1 -C 4 -alkyl halide.
  • Particular preference is given to n-butyl and methyl, in particular n-butyl, end-capped mixed ethers.
  • Typical examples of a mixed ether based on a C 12/18 or C 12/14 - alcohol residue to which 5 to 10 moles of ethylene oxide have been attached are C 12-18 fatty alcohols with 3, 4, 5 or 10 EO (in each case n-butyl end-capped), C 12-14 fatty alcohols with 9 or 10 EO (each n-butyl end-capped).
  • Hydroxymix ethers of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15, are particularly preferred.
  • hydroxy mixed ethers are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , are hydrocarbon radicals for R 2, R 3 H or R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms for R 1 or (K 30 - 1 - - j) is a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for a value between 1 and 12, preferably between 1 and 5.
  • R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 are hydrocarbon radicals for R 2, R 3 H
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 can be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and, for example, a large number (EO) groups combined with a small number (PO). Includes groups, or vice versa.
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particular preference is given to hydroxy mixed ethers in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred hydroxy mixed ethers in the context of the present invention.
  • hydroxy mixed ethers having EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded to each other before one block from the other groups follows.
  • hydroxy mixed ethers of the general formula R 1 O [CH 2 CH 2 O] w [CH 2 CH (R 2 ) O] x [CH 2 CH 2 O] y [CH 2 CH (R 3 ) O] z H in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical, each R 2 or R 3 group is independently selected from -CH 3 , - CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • the preferred hydroxy mixed ethers of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If natural sources are used, the radical R 1 has an even number of carbon atoms and is unbranched, as a rule, the linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow fatty alcohol or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • hydroxy mixed ethers are preferred in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred hydroxy mixed ether in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • Hydroxy mixed ethers are summarize, particularly preferably having a C 9-15 alkyl group having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • hydroxy mixed ethers of the general formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 which in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 28 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH 2 CH (OH) - and in which x is between 1 and 90, preferably 40 and 80 and especially between 40 and 40 and 60 stands.
  • R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1
  • the corresponding end-capped hydroxy mixed ethers of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R 2 CH (O) CH 2 with an ethoxylated alcohol of the formula R 1 O [CH 2 CH 2 O] x-1 CH 2 CH 2 OH ,
  • Hydroxymix ethers of the general formula R 1 O [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 in which R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 . but preferably represents -CH 3 , and x and y independently of one another are values between 1 and 32, are preferred according to the invention, wherein hydroxy mixed ethers with values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred ,
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned hydroxy mixed ethers represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • alkoxy block polymers which are preferably composed of alternating ethylene oxide, propylene oxide and / or butylene oxide units.
  • alkoxy block polymers of the formulas HO- (EO) x (PO) y (EO) z -H, HO- (PO) x (EO) y (PO) z -H, HO- (EO) x (PO) y ( PO) z -H, HO- (EO) x (EO) y (PO) z -H, HO- (EO) x (BO) y (EO) z -H, HO- (BO) x (EO) y (BO) z -H, HO- (BO) x (EO) y (BO) z -H, HO- (EO) x (BO) y (BO) z -H, HO- (EO) x (BO) y (BO) z -H, HO- (EO) x (BO)
  • the block polymers preferably have molecular weights between 100 and 15,000 g / mol, in particular 900 to 4000 g / mol.
  • Suitable block polymers are, for example, the Pluronic® types (BASF) Pluronic® PE 3100 and PE 4300.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight.
  • -% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • compositions of the invention are thickeners.
  • thickeners also called thickeners
  • the field of application of thickeners is generally to increase the viscosity of liquids.
  • the effect of the thickener is based on various effects such as swelling, gelation, association of micelles, solvation, formation of network structures and / or hydrogen bonds and their interaction.
  • the molecular structure and relative molecular weight of the hydrocolloids determine the degree of thickening.
  • the compositions according to the invention contain inorganic thickeners such as silica, clays, phyllosilicates, preferably smectites, in particular montmorillonite or hectorite; low molecular weight organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or polyamides.
  • inorganic thickeners such as silica, clays, phyllosilicates, preferably smectites, in particular montmorillonite or hectorite
  • low molecular weight organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or polyamides.
  • Polyvinyl alcohols, polyacrylic and polymethacrylic acids and their salts, polyacrylamides, polyvinylpyrrolidone, polyethylene glycols, styrene-maleic anhydride copolymers and salts thereof are used in particular from the large group of organic fully synthetic thickeners. Particular preference is given to the copo
  • Preferred thickening agents come from the groups of organic natural thickening agents such as starch, gelatin and casein and the modified natural substances, in particular the polysaccharides.
  • Important representatives of the latter group are (hydroxy) ethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose, succinoglycan, xanthan gum, guar gum, locust bean gum, tragacanth, as well as derivatives and mixtures of these thickeners.
  • the thickener contained in the agents of the invention is selected from polysaccharides, preferably from cellulose compounds, xanthan gum and guar gum, and from acrylate thickeners, urethane thickeners and clays.
  • xanthan gum and derivatives thereof are available under the names Keltrol® RD (CP Kelco), Kelzan® S (CP Kelco), Kelzan® T (CP Kelco), Rhodopol® T (Rhodia) and Rhodigel® X747 (Rhone Poulenc).
  • the xanthan gum content makes at least 20 wt .-%, preferably at least 40 wt .-%, preferably at least 60 wt .-%, particularly preferably at least 80 wt .-% and in particular at least 90 wt .-%, especially 99 wt .-% of the total thickener contained in the agent.
  • washing or cleaning agent 0.05 to 1 wt .-%, preferably 0.1 to 0.9 wt .-%, particularly preferably 0.15 to 0.8 wt.%, Preferably 0.2 to 0, 7 wt .-%, preferably 0.25 to 0.6 wt .-%, very particularly preferably 0.3 to 0.5 wt .-% and in particular 0.3 to 0.4 wt .-% thickener.
  • the weight ratio of surfactant A to thickener is preferably between 50: 1 and 1:10. This ratio is preferably between 22: 1 and 1: 2, preferably between 18: 1 and 1: 1.5, more preferably between 14: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1, and in particular between 6: 1 and 2: 1.
  • the weight ratio between surfactant B and thickener is preferably between 40: 1 and 1:30. This ratio is preferably between 10: 1 and 1: 8, preferably between 7.5: 1 and 1: 6, particularly preferably between 5: 1 and 1: 4 and in particular between 2.5: 1 and 1: 2.
  • a 1 wt .-% solution in water (20 ° C) has a pH of less than 5.5, preferably less than 5.0, more preferably less than 4.5, most preferably less than 4.0 and in particular less than 3 , 5 on.
  • the undiluted liquid composition preferably has a pH of less than 6, preferably less than 5, more preferably less than 4, more preferably less than 3 and in particular less than 2.5.
  • the agent preferably contains an organic or inorganic acid.
  • the washing or cleaning agent at least 10 wt .-%, preferably at least 13 wt .-%, more preferably at least 16 wt .-%, most preferably at least 19 wt .-% and in particular at least 22 wt .-%, based on the total agent, of an inorganic or organic acid.
  • Suitable acids are organic mono- or polybasic, optionally substituted by hydroxyl groups, optionally unsaturated carboxylic acids having 2 to 6 carbon atoms in the molecule.
  • the acid has a dissociation constant less than 10 -6 .
  • Preferred aliphatic acids are formic acid, acetic acid. Adipic, succinic, tartaric, malic, glutaric, sorbic, maleic, malonic, lactic, glycolic, propionic, oxalic and especially citric acid.
  • Salicylic acid or benzoic acid is preferably used from the group of aromatic carboxylic acids.
  • lactobionic acid and gluconic acid are lactobionic acid and gluconic acid.
  • Preferred inorganic acids are boric acid, sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid. Also suitable is cyanuric acid.
  • the inventive agents may simultaneously contain one, two, three, four, five or up to 12 different organic and / or inorganic acids (acid mixtures).
  • the cleaning or care agents contain less than 5, preferably less than 4, more preferably less than 3 and in particular only one acid.
  • the proportion by weight of one of the acids, preferably of citric acid, in the agent is preferably at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, more preferably at least 80 wt .-%, more preferably at least 90 wt .-% and in particular at least 95 wt .-%, based on the acids contained.
  • acids in the sense of the present invention are the builders. Also, anionic surfactants as well as the anionic surfactants present in an agent in protonated form due to a low pH, ie the anionic surfactant acids, are not acids in the sense of the present invention.
  • the proportion of the acid, based on the acid / salt pair is preferably at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 40% by weight. %, preferably at least 55 wt .-%, preferably at least 60 wt .-% and in particular at least 85 wt .-%.
  • inventive cleaning or care agents additionally contain at least one surfactant from the group of anionic, cationic and amphoteric surfactants.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably 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 the sulfonation obtained.
  • 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 are synthetic, petrochemical. Basis produced straight-chain alkyl radical containing an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable Anionteriside.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. They are used in the cleaning or care products due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
  • alkylsulfosuccinic acid which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with 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: Sulfosuccinates, whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are 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 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 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.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the inventive agent preferably contains at least one surfactant selected from the group consisting of alkylphenoxybenzenedisulfonates, linear or branched alkylbenzenesulfonates, linear or branched alkylnaphthalene sulfonates, alkylsulfonates, olefinsulfonates, paraffin sulfonates, alkylarylsulfonates, soaps, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates or monoglycerol sulfates.
  • surfactant selected from the group consisting of alkylphenoxybenzenedisulfonates, linear or branched alkylbenzenesulfonates, linear or branched alkylnaphthalene sulfonates, alkylsulfonates, olefinsulfonates, paraffin sulfonates, al
  • the agent comprises an alkylbenzenesulfonate, preferably an alkylbenzenesulfonate having an alkyl chain length of C 2 -C 20 , in particular cumene sulfonate.
  • the agent preferably contains an anionic surfactant which has hydrotropic properties.
  • anionic surfactant (s) preferably anionic surfactant (s) with hydrotropic properties
  • their content is preferably between 2 and 10% by weight, preferably between 3 and 9% by weight. , most preferably between less than 4 and 8 wt .-% and in particular between 5 and 7 wt .-%.
  • Automatic dishwashing detergents which contain only hydrotropic properties from the group of anionic surfactants are particularly preferred.
  • Betaines and / or amine oxides in the compositions according to the invention are preferably less than 10% by weight, preferably less than 8% by weight, more preferably less than 6% by weight, more preferably less than 4% by weight, completely more preferably less than 2% by weight, and especially not at all.
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1 wt .-%. Agents which do not contain cationic and / or amphoteric surfactants are particularly preferred.
  • the inventive agent may be in solid form such as powders, pellets, tablets, capsules, pearls, as well as in liquid form. If the agent is solid at room temperature, it is preferably completely or partially flowable / liquid at temperatures below 90 ° C., preferably below 80 ° C., preferably below 70 ° C., more preferably below 60 ° C. and in particular below 55 ° C.
  • liquid thus refers to any state that is characterized at 20 ° C by a fluid (flowable) state of matter.
  • the agent is in the liquid state and has a viscosity above 50 mPas, preferably between 100 and 700 mPas, preferably between 200 and 600 mPas and in particular between 300 and 500 mPas.
  • Suitable carriers of liquid agents are water, nonaqueous solvents and mixtures of these.
  • Suitable organic carriers are alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers ), Ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (Nitrobenzene), halogenated hydrocarbons (dichlorome
  • Such a solvent mixture is, for example, benzine, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 80% by weight and in particular above 90% by weight, in each case based on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.
  • water, alcohol or an alcohol / water mixture preferably a water / alcohol mixture
  • a polyhydric alcohol and in particular glycerol is preferably used.
  • a water / glycerol mixture serves as a carrier.
  • the ratio between alcohol and water in the carrier is preferably between 10: 1 and 1: 100, preferably between 1: 1 and 1:90, particularly preferably between 1: 5 and 1:80, very particularly preferably between 1:10 and 1: 60 and especially between 1:15 and 1:40.
  • composition according to the invention may contain abrasive, undissolved and / or dispersed constituents, be cloudy or translucent or clear.
  • agents according to the invention described above preferably comprise further cleaning-active and / or care-active substances, preferably from the group of builders, polymers, bleaches, bleach activators, enzymes. Corrosion inhibitors, disintegrants, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and where there are no ecological prejudices against their use - even the phosphates.
  • alkali carriers examples include alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates ,. Alkali metal sesquicarbonates, the said alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is particularly preferred.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, those of polycarboxylic acids being those Carboxylic acids are understood to carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives .
  • copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • the agents according to the invention preferably contain methylglycinediacetic acid (MGDA), ethylenediaminetetraacetic acid (EDTA) and / or nitrilotriacetic acid (NTA), their salts and mixtures of the acids and / or salts.
  • MGDA methylglycinediacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • nonionic surfactants In addition to the nonionic surfactants already mentioned, it is possible to use further nonionic surfactants known to the person skilled in the art. However, the proportion of additionally used nonionic surfactants is preferably below 10% by weight, more preferably below 8% by weight, preferably below 6% by weight, more preferably below 4% by weight and in particular below 2% by weight. , With particular preference, no nonionic surfactants which can not be represented by the formula R 1 O- (CH 2 CH (R 2 ) O] x -R 3 are used.
  • Suitable nonionic surfactants which can be used in addition to the nonionic surfactants described above are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 C 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.
  • the agents according to the invention preferably contain less than 2.5% by weight, preferably less than 1.5% by weight, more preferably less than 0.5% by weight and in particular no amine oxide.
  • polyhydroxy fatty acid amides of the formula wherein R 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] 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 are customary can 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.
  • nonionic polymers In addition to nonionic polymers, it is also possible to use cationic, anionic and amphoteric polymers.
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • Particularly preferred amphoteric polymers are from the group of the Methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 (R 2 ) C C (R 3 ) COOH in which R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy 3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid.
  • Styrenesulfonic acid vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those which contain from 20 to 85% by weight of monomer from group i). From 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii).
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the bleaching agents are a cleaning substance used with particular preference.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2- yielding peracidic salts or peracids, such as perbenzoates.
  • Bleach activators are used in laundry detergents or cleaners, for example, to achieve an improved bleaching effect when cleaned at temperatures of 60 ° C and below.
  • As 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.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2, 5-dihydrofuran, n-methyl-morpholinium
  • bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.
  • bleach catalysts can also be used.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti-V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are preferably used.
  • Enzymes can be used to increase the cleaning performance of the agents according to the invention. These include in particular proteases, amylases, lipases. Hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof.
  • the composition contains 0.6 to 5.0 wt .-%, preferably 0.8 to 4 wt .-% of a C 12 -C 18 alkyl alcohol alkoxylate, preferably a C 12 -C 14 alkyl alcohol alkoxylate having an average molecular weight of about 500 - 900 g / mol, 0.1 to 1.7 wt .-%, preferably 0.2 to 1.4% by weight of a C 12 -C 18 -alkyl alcohol alkoxylate, preferably a C 16 -C 18 -alkyl alcohol alkoxylate having an average molar mass of 1400-2100 g / mol, 0.05 to 1% by weight, preferably 0, 1 to 0.9 wt .-% of a thickener, preferably a thickener from the group of polysaccharides and in particular xanthan gum and at least 10 wt .-%, preferably at least 13 wt .-% of an inorganic
  • an agent which comprises from 0.6% to 5.0%, preferably from 0.8% to 4%, by weight of a C 12 -C 18 alkyl alcohol, preferably a C 12 -C 14 alkyl alcohol, both is ethoxylated and propoxylated and preferably contains 2 to 7 moles, in particular 4 to 5 moles of ethylene oxide and 2 to 7 moles of propylene oxide, in particular 3 to 4 moles of propylene oxide, 0.1 to 1.7 wt .-%, preferably 0.2 to 1.4 wt .-% of a C 12 -C 18 alkyl alcohol alkoxylate, preferably a C 16 -C 18 -Alkytalkoholalkoxylats containing no propylene oxide units and at least 15, preferably at least 25 ethylene oxide units, 0.05 to 1 wt .-%, preferably 0.1 to 0.9 wt .-% of a thickener, preferably a thickener from the group of polysaccharides and in
  • compositions of further preferred agents according to the invention are given in the table below.
  • the abbreviation M means average molecular weight.
  • the proportion of citric acid, based on the acid mixture is at least 50% by weight, preferably at least 80% by weight.
  • the ratio of water to glycerol is between 1: 1 and 1:90, preferably between 1:10 and 1:60.
  • the agent additionally contains a surfactant having hydrotropic properties, preferably cumene sulfonate, basic components such as alkali metal caustic solutions and / or perfume. The stated percentages by weight are based on the total agent.
  • Cleaning or care eyes which consist of water, the agent of the invention and fatty.
  • Contaminants have been prepared, due to the increased emulsifying capacity of the composition, separate much later than corresponding alkalis obtained using known means of the prior art, preferably no longer into multiple phases, i. in an aqueous and / or organic phase, on.
  • a quantification of the emulsifying ability of the agents is possible by means of standardized phase separation tests. Suitable shake and pump simulation tests are described in detail in the examples.
  • a liquor containing the inventive agent, a standardized oily component and water in fixed amounts in a pump simulation test within 1 minute shows a phase separation of less than 15%, preferably less than 10%, more preferably less than 5%. , more preferably less than 2.5%, more preferably less than 1.0% and especially less than 0.2%, or less than 40%, preferably less than 30%, more preferably within 5 minutes less than 20%, more preferably less than 10%, more preferably less than 5%, and most preferably less than 2.5%.
  • Another object of the present invention is the use of the agent according to the invention for cleaning and care of hard surfaces, preferably of washing machines or dishwashers, in particular of dishwashers.
  • Third object of the present invention is a method for cleaning and care of a washing machine or dishwasher, preferably a dishwasher, in which the inventive agent is introduced into the unloaded machine and then the washing or cleaning program is started.
  • the agent is preferably introduced into the cutlery basket or directly into one of the baskets or the machine interior (interior floor).
  • the compositions according to the invention are used either by introduction into the dosing drawer or into the washing drum.
  • the consumer can apply the agent directly from a supply bottle or a storage package to the surface to be cleaned. At least for cleaning and / or Care of washing machines or dishwashers, however, it is preferred that the consumer brings the agent in a prefabricated dosage unit, such as a tablet a pouch with a solid or liquid filling or a small bottle in the machine without the risk of skin contact with the agent exposed to become.
  • a prefabricated dosage unit such as a tablet a pouch with a solid or liquid filling or a small bottle in the machine without the risk of skin contact with the agent exposed to become.
  • This dosing unit preferably comprises 100 to 400 ml, preferably 200 to 300 ml or 100 to 400 g, preferably 200 to 300 g.
  • the average amount can vary by simultaneously using 2, 3, 4, 5 or 6 dosing units.
  • the inventive agent is released at the beginning of the consumer started washing or cleaning program of the washing machine or dishwasher in the machine interior.
  • This can be achieved by completely or partially dissolving or dispersing the packaging or by melting individual or all packaging parts at temperatures of preferably less than 60 ° C., more preferably less than 50 ° C. and in particular less than 40 ° C.
  • the consumer for example, to remove the closure part from a dosing unit such as a bottle filled with a solidified melt, a wax or a gel, and then introduce the dosing unit with the opening downwards into the interior of the machine.
  • a dosing unit such as a bottle filled with a solidified melt, a wax or a gel
  • the viscosity of the agent is reduced by the warm wash liquor and thus allows a rapid release of the liquid agent by flowing out of the package.
  • At least 80% by weight, preferably at least 90% by weight and in particular at least 95% by weight of the agent used in a package are preferred within 15, preferably within 12, preferably within 9, more preferably within 6 and in particular released within 5 minutes after reaching the maximum liquor temperature in the washing machine or dishwasher interior.
  • the agent has such a low viscosity that it flows out immediately after removal of the closure with a suitable inclination of the container and thus is available during the entire cleaning or care process.
  • the maximum liquor temperature is preferably greater than 30 ° C, preferably greater than 35 ° C. more preferably greater than 40 ° C, preferably greater than 45 ° C, most preferably greater than 50 ° C and in particular 60 ° C to 70 ° C.
  • Phase separation takes place and it settles on the cylinder bottom an aqueous. Phase off. The volume of this newly forming phase is measured in milliliters as a function of time. Phase separation after Recipe 1 Recipe 2 Recipe 3 Recipe 4 1 minute 0 mL 12 mL 2 mL 20 mL 5 minutes 3 mL 35 mL 10 mL 50 mL
  • This test is used to simulate the short-term energy input through a circulation pump in a household dishwasher.
  • the energy for making the emulsion is introduced into the system at 800 rpm using a four-blade 30 mm diameter stirrer (IKA RW 20).
  • IKA RW 20 dilute 10 mL of the product with 40 mL of distilled water, place in a beaker and add 50 mL of olive oil (Bertolli Extra Vergine).
  • the stirrer is switched on for 30 seconds.
  • the sample is transferred to a 100 mL graduated cylinder.
  • a phase separation takes place in which settles an aqueous phase at the bottom of the cylinder.
  • the volume of this newly forming phase is measured in milliliters as a function of time.
  • Phase separation after Recipe 1 Recipe 2 Recipe 3 Recipe 4 1 minute 0 mL 10 mL 1 mL 12 mL 5 minutes 2 mL 31 mL 5 mL 40 mL
  • formulation 1 shows the best emulsion stability and thus the agent used the highest emulsifying ability.
  • formulation 2 or without surfactant system coagulate very quickly.
  • the incorporation of the thickener causes a significant improvement in the emulsion stability (Comparison of Recipes 1 and 2).
  • surfactant B improves the stability of the emulsion again (Comparison of Formulas .1 and 3). Only the combination of surfactant A, surfactant B and the thickener leads to the best performance.
  • a system without surfactants only with thickening agent separates in the fastest time and thus has the lowest emulsifying capacity (formula 4).

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Claims (23)

  1. Agent de nettoyage et d'entretien, comprenant
    - un système tensio-actif comprenant au moins deux tensio-actifs non ioniques A et B, qui présentent des structures chimiques différentes l'une de l'autre, pourtant les deux peuvent être représentées par la structure

            R1O-[CH2CH(R2)O]x-R3

    dans laquelle
    R1 et R3 représentent indépendamment l'un de l'autre, H ou un résidu hydrocarboné aliphatique ou aromatique, saturé ou insaturé, linéaire ou ramifié, ayant de 1 à 30 atomes de carbone, dans lequel jusqu'à 6 fonctions hydroxy et/ou jusqu'à 3 fonctions éther peuvent être contenues, au moins l'un des radicaux R1 et R3 ne représentant pas H,
    R2 représente H ou un résidu méthyle, éthyle, n-propyle, isopropyle, n-butyle, 2-butyle, ou 2-méthyl-butyle, chaque R2 pour x ≥ 2 pouvant être différent et
    x représente des valeurs supérieures à 1 ;
    ainsi que
    - un épaississant,
    dans lequel une solution à 1 % en poids de l'agent dans de l'eau (20°C) présente une valeur de pH inférieure à 6.
  2. Agent selon la revendication 1, caractérisé en ce que le système tensio-actif comprend au moins un tensio-actif A non ionique ayant une masse molaire moyenne comprise entre 200 et 1 200 g/mol, de préférence entre 300 et 1 100 g/mol, de manière particulièrement préférée entre 400 et 1 000 g/mol, et en particulier entre 500 et 900 g/mol, et au moins un tensio-actif B supplémentaire non ionique ayant une masse molaire moyenne comprise entre 1 000 et 2 500 g/mol, de préférence comprise entre 1 100 et 2 400 g/mol, préférentiellement comprise entre 1 200 et 2 300 g/mol, de manière particulièrement préférée comprise entre 1 300 et 2 200, et en particulier comprise entre 1 400 et 2 100 g/mol.
  3. Agent selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que la différence des masses molaires moyennes des deux tensio-actifs A et B non ioniques est d'au moins 100, préférentiellement d'au moins 200, de préférence d'au moins 300, encore de préférence d'au moins 400, de manière particulièrement préférée d'au moins 500, de manière tout particulièrement préférée d'au moins 600, et en particulier d'au moins 700 g/mol.
  4. Agent selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le rapport pondéral entre le tensio-actif A et le tensio-actif B est compris entre 10:1 et 1:1, préférentiellement entre 8,5:1 et 1,25:1, de manière particulièrement préférée entre 7:1 et 1,5:1, de manière encore préférée entre 5,1:1 et 1,75:1, et en particulier entre 4:1 et 2:1.
  5. Agent selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le tensio-actif B est contenu à raison de 0,1 à 1,7% en poids, de préférence de 0,2 à 1,4% en poids, de manière particulièrement préférée de 0,3 à 1,1 % en poids, et en particulier de 0,4 à 0,8% en poids dans l'agent.
  6. Agent selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le tensio-actif A est contenu à raison de 0,6 à 5% en poids, de préférence de 0,8 à 4% en poids, de manière particulièrement préférée de 1,3 à 3% en poids, et en particulier de 1,2 à 2% en poids dans l'agent.
  7. Agent selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les tensio-actifs A et B non ioniques présentent la structure suivante

            R1O-[CH2CH(R2)O]x-H

    dans laquelle
    R1 représente un résidu hydrocarboné aliphatique linéaire ou ramifié ayant de 4 à 20 atomes de carbone, préférentiellement ayant de 12 à 20 atomes de carbone, et en particulier ayant de 12 à 18 atomes de carbone,
    R2 représente H ou un résidu méthyle, éthyle, n-propyle, isopropyle, n-butyle, 2-butyle, ou 2-méthyl-butyle en particulier un résidu éthyle ou propyle, chaque R2 pour x ≥ 2 pouvant être différent et
    x représente des valeurs supérieures à 1.
  8. Agent selon la revendication 7, caractérisé en ce que le système tensio-actif contient un alcoxylate d'alcool alkylique en C12 à C14, lequel comprend aussi bien des motifs éthoxy que des motifs propoxy et contient un éthoxylate d'alcool alkylique en C16 à C18.
  9. Agent selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'épaississant est choisi parmi les polysaccharides, de préférence parmi les composés cellulosiques, la gomme xanthane et la gomme de guar, et parmi les épaississants à base d'acrylate, les épaississants à base d'uréthane, et les argiles.
  10. Agent selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il contient au moins 10% en poids, de préférence au moins 13% en poids, de manière particulièrement préférée au moins 16% en poids, de manière tout particulièrement préférée au moins 19% en poids, et en particulier au moins 22% en poids d'un acide inorganique ou organique.
  11. Agent selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'acide organique ou inorganique est choisi parmi les acides :
    l'acide formique, l'acide acétique, l'acide adipique, l'acide succinique, l'acide tartrique, l'acide malique, l'acide glutarique, l'acide sorbique, l'acide maléique, l'acide malonique, l'acide lactique, l'acide glycolique, l'acide propionique, l'acide oxalique, l'acide citrique, l'acide salicylique, l'acide benzoïque, l'acide lactobionique, l'acide gluconique, l'acide borique, l'acide sulfaminique, l'acide phosphorique, l'acide sulfurique, l'acide chlorhydrique, l'acide nitrique, l'acide cyanurique, ou des mélanges de ces acides.
  12. Agent selon la revendication 11, caractérisé en ce que deux ou plusieurs acides sont présents dans l'agent et que la proportion pondérale d'acide citrique dans ce mélange de deux ou plusieurs acides, constitue au moins 50% en poids, préférentiellement au moins 60% en poids, de préférence au moins 70% en poids, de manière particulièrement préférée au moins 80% en poids, de manière encore préférée au moins 90% en poids, et en particulier au moins 95% en poids, par rapport aux acides contenus.
  13. Agent selon l'une quelconque des revendications 1 à 12, caractérisé en ce que l'agent contient en outre au moins un tensio-actif issu du groupe des tensio-actifs anioniques, cationiques et amphotères.
  14. Agent selon la revendication 13, caractérisé en ce qu'il contient un tensio-actif anionique qui présente des propriétés hydrotropes.
  15. Agent selon la revendication 13 ou 14, caractérisé en ce que l' agent contient au moins un tensio-actif issu du groupe formé par les alkylphénoxybenzène-disulfonates, les alkylbenzène-sulfonates linéaires ou ramifiés, les alkylnaphtalène-sulfonates linéaires ou ramifiés, les alkylsulfonates, les sulfonates d'oléfine, les sulfonates de paraffine, les alkylarylsulfonates, les savons, les alkylsulfates, les alkyléthersulfates, les alkylamidoéthersulfates, les alkylarylpolyéthersulfates, les sulfates de monoglycérol, de préférence les alkylbenzène-sulfonates.
  16. Agent selon l'une quelconque des revendications 1 à 15, caractérisé en ce que de l'eau, un alcool ou un mélange alcool/eau, de préférence un mélange eau/alcool, et en particulier un mélange eau/glycérol, sont mis en oeuvre en tant que véhicule.
  17. Agent selon la revendication 16, caractérisé en ce que la proportion entre l'alcool et l'eau dans le véhicule est comprise entre 10:1 et 1:100, de préférence comprise entre 1:1 et 1:90, de manière particulièrement préférée entre 1:5 et 1:80, de manière tout particulièrement préférée entre 1:10 et 1:60 et en particulier entre 1:15 et 1:40.
  18. Agent selon l'une quelconque des revendications 1 à 17, caractérisé en ce que l'agent présente une viscosité supérieure à 50 mPa.s, préférentiellement comprise entre 100 et 700 mPa.s, de préférence entre 200 et 600 mPa.s et en particulier entre 300 et 500 mPa.s.
  19. Agent selon l'une quelconque des revendications 1 à 18, caractérisé en ce que l'agent présente dans un test de simulation de pompage en l'espace d'une minute, une séparation de phase inférieure à 15%, de préférence inférieure à 10%, de manière particulièrement préférée inférieure à 5%, de manière tout particulièrement préférée inférieure à 2,5%, de manière encore préférée inférieure à 1,0%, et en particulier inférieure à 0,2%, ou en l'espace de 5 minutes, inférieure à 40%, de préférence inférieure à 30%, de manière particulièrement préférée inférieure à 20%, de manière tout particulièrement préférée inférieure à 10%, de manière encore préférée inférieur à 5% et en particulier inférieure à 2,5%.
  20. Agent selon l'une quelconque des revendications 1 à 19, caractérisé en ce qu'il contient de 0,6 à 5,0% en poids, préférentiellement de 0,8 à 4% en poids, d'un alcoxylate d'alcool alkylique en C12 à C18, préférentiellement d'un alcoxylate d'alcool alkylique en C12 à C14, ayant une masse molaire moyenne de 500 à 900 g/mol, de 0,1 à 1,7 % en poids, préférentiellement de 0,2 à 1,4% en poids d'un alcoxylate d'alcool alkylique en C12 à C18, de préférence un alcoxylate d'alcool alkylique C16 à C18 ayant une masse molaire moyenne de 1 400 à 2 100 g/mol, de 0,05 à 1% en poids, préférentiellement de 0,1 à 0,9% en poids d'un épaississant, de préférence un épaississant issu du groupe formé par les polysaccharides, en particulier la gomme xanthane, et au moins 10% en poids, préférentiellement au moins 13% en poids d'un acide inorganique ou organique, préférentiellement l'acide citrique, ainsi que de préférence en sus 2 à 10% en poids de cumène-sulfonate.
  21. Agent selon l'une quelconque des revendications 1 à 20, caractérisé en ce qu'il contient de 0,6 à 5,0% en poids, préférentiellement de 0,8 à 4% en poids, d'un alcool alkylique en C12 à C18, préférentiellement d'un alcool alkylique en C12 à C14, qui est aussi bien éthoxylé que propoxylé et contient de préférence 2 à 7 moles, en particulier 4 à 5 moles d'oxyde d'éthylène et 2 à 7 moles d'oxyde de propylène, en particulier 3 à 4 moles d'oxyde de propylène, contient 0,1 à 1,7% en poids, préférentiellement 0,2 à 1,4% en poids d'un alcoxylate d'alcool alkylique en C12 à C18, préférentiellement d'un alcoxylate d'alcool alkylique en C16 à C8, qui ne contient pas de motif oxyde de propylène, et contient au moins 15, préférentiellement au moins 25, motifs oxyde d'éthylène, 0,05 à 1% en poids, préférentiellement 0,1 à 0,9% en poids d'un épaississant, préférentiellement un épaississant issu du groupe formé par les polysaccharides et en particulier la gomme xanthane, au moins 10% en poids, préférentiellement au moins 13% en poids d'un acide inorganique ou organique, de préférence l'acide citrique, ainsi que de préférence le glycérol.
  22. Utilisation de l'agent selon l'une quelconque des revendications 1 à 21, pour le nettoyage et l'entretien de surfaces dures, de préférence de machines à laver ou lave-vaisselle, en particulier de lave-vaisselle.
  23. Procédé pour le nettoyage et l'entretien d'une machine à laver ou d'un lave-vaisselle, de préférence d'un lave-vaisselle, caractérisé en ce que l'on introduit l'agent selon l'une quelconque des revendications 1 à 21 dans la machine non chargée et que l'on démarre ensuite le programme de lavage ou de nettoyage.
EP06754551A 2005-07-21 2006-06-24 Produits de nettoyage et d'entretien presentant une emulsibilite amelioree Revoked EP1904613B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06754551T PL1904613T3 (pl) 2005-07-21 2006-06-24 Środek czyszczący i pielęgnacyjny o polepszonej emulgowalności

Applications Claiming Priority (2)

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DE102005034752A DE102005034752A1 (de) 2005-07-21 2005-07-21 Reinigungs- und Pflegemittel mit verbesserter Emulgierfähigkeit
PCT/EP2006/006111 WO2007009555A1 (fr) 2005-07-21 2006-06-24 Produits de nettoyage et d'entretien presentant une emulsibilite amelioree

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EP1904613A1 EP1904613A1 (fr) 2008-04-02
EP1904613B1 true EP1904613B1 (fr) 2009-12-23

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EP (1) EP1904613B1 (fr)
AT (1) ATE452956T1 (fr)
DE (2) DE102005034752A1 (fr)
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WO (1) WO2007009555A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009029637A1 (de) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
EP2333040B2 (fr) 2009-12-10 2019-11-13 The Procter & Gamble Company Composition de détergent
EP2333042B1 (fr) * 2009-12-10 2015-07-01 The Procter and Gamble Company Utilisation de détergent
ES2581934T3 (es) 2009-12-10 2016-09-08 The Procter & Gamble Company Método para medir la capacidad de eliminación de suciedad de un producto limpiador
DE102019220454A1 (de) * 2019-12-20 2021-06-24 Henkel Ag & Co. Kgaa Verfahren zur Reinigung und Pflege einer automatischen Geschirrspülmaschine

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3002789A1 (de) 1980-01-26 1981-07-30 Henkel KGaA, 4000 Düsseldorf Fluessiges reinigung- und pflegemittel
EP0256148A1 (fr) 1986-08-12 1988-02-24 Joh. A. Benckiser GmbH Détergent liquide, granulé ou sous forme de poudre, spécialement pour machines à laver la vaisselle
DE3815291A1 (de) * 1988-05-05 1989-11-23 Basf Ag Waessrige saure reinigerformulierungen
DE4233696A1 (de) 1992-10-07 1994-04-14 Henkel Kgaa Maschinenpflegestift
EP0629691B1 (fr) * 1993-06-09 1998-10-21 The Procter & Gamble Company Emulsions aqueuses stables d'agents tensioactifs non-ioniques
EP0598973A1 (fr) * 1992-11-26 1994-06-01 The Procter & Gamble Company Composition de nettoyage liquide pour tous usages
PT629690E (pt) * 1993-06-09 2000-04-28 Procter & Gamble Emulsoes aquosas estaveis de agentes tensioactivos nao ionicos
MX192030B (es) * 1994-05-17 1999-05-14 Johnson & Son Inc S C Composicion de desmanchado previo para lavanderia con espesante polimerico asociativo.
MX9704500A (es) * 1994-12-16 1997-10-31 Procter & Gamble Limpiadores para superficies duras que comprenden alcoholes de guerbet altamente etoxilados.
DE19523117A1 (de) * 1995-06-26 1997-01-02 Henkel Ecolab Gmbh & Co Ohg Wäßriges saures Reinigungsmittel
US5707952A (en) * 1996-04-24 1998-01-13 Colgate-Palmolive Company Thickened acid composition
GB9619682D0 (en) * 1996-09-20 1996-11-06 Unilever Plc Improvements relating to antimicrobial cleaning compositions
DE10003752A1 (de) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh Spül- und Reinigungsmittel
DE10003809A1 (de) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh Klarspülmittel
GB0002229D0 (en) * 2000-02-01 2000-03-22 Reckitt & Colman Inc Improvements in or relating to organic compositions
DE50200978D1 (de) * 2001-02-01 2004-10-21 Cognis Deutschland Gmbh Spül- und Reinigungsmittel
DE10153768A1 (de) * 2001-11-02 2003-05-15 Cognis Deutschland Gmbh Hydroxymischether mit Polymeren
DE102004015392A1 (de) * 2004-03-26 2005-10-20 Henkel Kgaa Maschinelles Geschirrspülmittel

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PL1904613T3 (pl) 2010-06-30
DE502006005735D1 (de) 2010-02-04
EP1904613A1 (fr) 2008-04-02
ATE452956T1 (de) 2010-01-15
DE102005034752A1 (de) 2007-01-25
WO2007009555A1 (fr) 2007-01-25

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