EP2663625B1 - Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage - Google Patents

Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage Download PDF

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EP2663625B1
EP2663625B1 EP12700080.0A EP12700080A EP2663625B1 EP 2663625 B1 EP2663625 B1 EP 2663625B1 EP 12700080 A EP12700080 A EP 12700080A EP 2663625 B1 EP2663625 B1 EP 2663625B1
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Prior art keywords
acid
weight
washing
alkyl
dishwashing
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German (de)
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EP2663625A1 (fr
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Sophie Maitro-Vogel
Jürgen Tropsch
Wolfgang Spiegler
Roman Benedikt Raether
Christian Bittner
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BASF SE
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BASF SE
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/755—Sulfoxides
    • 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
    • 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
    • C11D1/008—Polymeric surface-active agents
    • 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
    • C11D1/74—Carboxylates or sulfonates esters 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets

Definitions

  • the present invention relates to the use of (oxidized) thioethers of alcohol alkoxylates in detergents and cleaners, especially in dishwashing detergents, and detergents and cleaners, especially dishwashing detergents containing (oxidized) thioethers of alcohol alkoxylates.
  • These (oxidized) thioethers are suitable in particular as surfactants with rinse aid function (rinse aid surfactants).
  • "Oxidized” refers to the sulfur atom in the thioether, which may be in oxidized form as the sulfoxide (SO) or sulfonyl (SO 2 ).
  • Surfactants are substances that can lower the interfacial tension.
  • surfactants have a characteristic structure and have at least one hydrophilic and at least one hydrophobic functional group. If both parts of the molecule are in equilibrium, the substance will accumulate and align at an interface, i. hydrophilic groups, for example, in an aqueous phase and the hydrophobic groups in the direction of other solid, liquid or gaseous phases.
  • Another special feature of surfactants is the formation of higher aggregates, the so-called micelles.
  • the surfactant molecules arrange in such a way that the polar groups form, for example, a spherical shell. This causes matter such as soil particles to be solubilized in an aqueous solution to form micelles. Therefore, surfactants are particularly suitable for cleaning surfaces and as an additive in detergents.
  • Surfactants having a hydrophobic and a hydrophilic block are widely used. However, their tendency to foaming makes them for many applications not or only partially usable. For applications where strong foaming is not desired, nonionic surfactants have therefore been developed which have a second hydrophobic block, which limits the foam volume.
  • the second hydrophobic block can be derived, for example, from a fatty alcohol.
  • dishwashing detergents which contain such a surfactant, in particular dishwashing detergents for dishwashers, often results in residues remaining on the dishes cleaned therewith (so-called "spotting” in the case of the formation of punctiform linings or "filming") Trap of film-like coverings).
  • the second hydrophobic block may alternatively be derived from a fatty acid.
  • dishwashing detergents which contain such surfactants, the problem of deposit formation is no longer so great;
  • these surfactants are susceptible to hydrolysis due to the ester group, which greatly limits their usefulness in alkaline formulations and at higher temperatures, especially during prolonged washing operations.
  • Thioethers of alcohol alkoxylates and their oxidized form are basically known; eg from the US 3,627,845 , This document describes the use of such compounds as biologically active agents, for example as fungicides, acaricides and anthelmintics, and as surface active agents in agrochemical formulations and coating compositions. A use as a detergent or cleaning agent is not mentioned.
  • DE-A-4406441 describes end-capped sulfur-containing fatty alcohol polyglycol ethers which carry a C 1 -C 4 -alkyl group on the sulfur atom. These are used as surfactants, especially in all-purpose cleaners and dishwashing detergents.
  • the object of the present invention was to provide compounds which do not have the disadvantages of the surfactants of the prior art.
  • the compounds should have no or no strong foaming tendency; they should leave less residue, especially spotting residue, on dishes washed therewith, and they should not or at least be less susceptible to hydrolysis than the fatty acid ester-based surfactants.
  • the compounds should have the highest possible melting point, so that they can also be formulated in solid detergents and cleaners.
  • the invention relates to detergents or cleaners which are dishwashing detergents containing at least one compound of the formula I as defined above.
  • C 1 -C 5 -alkyl is a linear or branched alkyl radical having 1 to 5 carbon atoms. Examples of these are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and position isomers thereof.
  • C 6 -C 18 -alkyl represents a linear or branched alkyl radical having 6 to 18 carbon atoms. Examples thereof are hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and positional isomers thereof.
  • C 8 -C 24 -alkyl represents a linear or branched alkyl radical having 8 to 24 carbon atoms. Examples of these are octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl and positional isomers thereof.
  • Branched C 8 -C 24 alkyl are the positional isomers of octyl, such as 2-ethylhexyl, the positional isomers of n-nonyl, the positional isomers of n-decyl, such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-nonyl Dodecyl, the positional isomers of n-tridecyl, the positional isomers of n-tetradecyl, the positional isomers of n-pentadecyl, the positional isomers of n-hexadecyl, the positional isomers of n-heptadecyl, the positional isomers of n-octadecyl, the positional isomers of n-nonadecyl , the positional isomers of n-eicosy
  • C 10 -C 14 -alkyl represents a linear or branched alkyl radical having 10 to 14 carbon atoms. Examples of these are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl and positional isomers thereof.
  • Branched C 10 -C 14 alkyl are the positional isomers of n-decyl such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the positional isomers of n-tridecyl and the positional isomers of n-tetradecyl.
  • C 10 -C 15 -alkyl represents a linear or branched alkyl radical having 10 to 15 carbon atoms. Examples of these are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and positional isomers thereof.
  • Branched C 10 -C 15 alkyl are the positional isomers of n-decyl such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the positional isomers of n-tridecyl, the positional isomers of n-tetradecyl and the Positional isomers of n-pentadecyl.
  • C 8 -C 15 -alkyl represents a linear or branched alkyl radical having 8 to 15 carbon atoms. Examples thereof are the radicals mentioned above for C 10 -C 15 -alkyl, as well as octyl, 2-ethylhexyl, nonyl and positional isomers thereof.
  • Branched C 8 -C 15 alkyl are the positional isomers of octyl, such as 2-ethylhexyl, the positional isomers of n-nonyl, the positional isomers of n-decyl, such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-nonyl Dodecyl, the positional isomers of n-tridecyl, the positional isomers of n-tetradecyl, and the positional isomers of n-pentadecyl.
  • C 12 alkyl represents dodecyl and its positional isomers.
  • the compounds I used according to the invention may be chemically pure substances or mixtures of different compounds I. In general, it will be due to their manufacturing process and the starting materials used therein, which may be technical products or product mixtures, mixtures of different compounds I, for example, in the meaning of the variables R, R ', l, m, n and / or x differ.
  • R is preferably C 8 -C 15 -alkyl, more preferably C 10 -C 15 -alkyl and especially C 10 -C 14 -alkyl.
  • the alkyl radical R is branched.
  • R are 2-propylheptyl, tridecyl and its positional isomers such as isotridecyl (ie branched tridecyl radicals and mixtures thereof), n-dodecyl (lauryl), n-tetradecyl (myristyl) and mixtures thereof.
  • R ' is C 10 -C 14 -alkyl and in particular C 12 -alkyl (dodecyl); especially for n-dodecyl.
  • R 1 and R 2 independently of one another preferably represent methyl.
  • m is a number from 25 to 50, preferably from 25 to 45 and in particular from 25 to 40.
  • I and n independently of one another preferably represent a number from 0 to 5 and particularly preferably 0, 1, 2 or 3. In particular, I and n represent 0.
  • the ethyleneoxy repeating units (-CH 2 -CH 2 -O-) and the repeating units (-CH 2 -CH (R 1 ) -O- and / or or (-CH 2 -CH (R 2 ) -O-) are arranged randomly or in blocks, preferably they are arranged in blocks, ie all repeating units I optionally present -CH 2 -CH (R 1 ) -O- form a block followed by the ethyleneoxy block (-CH 2 -CH 2 -O-) m, followed by all n optionally repeating units -CH 2 -CH (R 2 ) -O- join as a block.
  • x is preferably 0 or 1.
  • the compounds I are characterized by a relatively high melting point.
  • the melting point is at least 35 ° C, e.g. 35 to 50 ° C, preferably 35 to 47 ° C and especially 35 to 45 ° C; more preferably at least 38 ° C, e.g. 38 to 50 ° C, preferably 38 to 47 ° C and especially 38 to 45 ° C; and especially at least 40 ° C, e.g. 40 to 50 ° C, preferably 40 to 47 ° C and especially 40 to 45 ° C.
  • the reaction with the epoxides is preferably carried out in anhydrous medium under base catalysis.
  • the reaction preferably takes place under an inert gas atmosphere, such as nitrogen or argon.
  • Suitable bases include, for example, inorganic bases such as alkali metal hydroxides, e.g. Lithium, sodium or potassium hydroxide, alkaline earth metal hydroxides, e.g. Magnesium or calcium hydroxide, alkali metal carbonates, e.g. Lithium, sodium or potassium carbonate, or alkaline earth metal carbonates, e.g. Magnesium or calcium carbonate.
  • alkali metal hydroxides e.g. Lithium, sodium or potassium hydroxide
  • alkaline earth metal hydroxides e.g. Magnesium or calcium hydroxide
  • alkali metal carbonates e.g. Lithium, sodium or potassium carbonate
  • alkaline earth metal carbonates e.g. Magnesium or calcium carbonate.
  • the reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 150 ° C.
  • the reaction is preferably carried out under elevated pressure, e.g. at 1.1 to 10 bar or 1.2 to 5 bar, which is built up by the inert gas and / or the epoxide (in particular ethylene oxide).
  • a pre-pressure with inert gas usually nitrogen, is built up prior to introduction of the epoxide.
  • This pre-pressure is preferably in the range from 1.1 to 5 bar, more preferably from 1.2 to 3 bar and in particular from 1.2 to 2 bar.
  • the addition of the epoxide (in particular ethylene oxide) then usually leads to a further pressure increase.
  • the pressure during the actual reaction is in the range of preferably 1.2 to 10 bar, more preferably from 2 to 8 bar.
  • the resulting product mixture can be neutralized if desired.
  • the condensation with the mercaptoethanol is preferably carried out under acidic catalysis.
  • Suitable acids are, for example, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid and acid ion exchangers.
  • the water of reaction formed is preferably removed, for example by azeotropic distillation or stripping with an inert gas. If the water of reaction is to be removed by azeotropic distillation, the condensation is advantageously carried out in a solvent which forms a minimum azeotrope with water, such as toluene or the xylenes. After the reaction, the resulting product mixture can be neutralized if desired.
  • the compounds I can be used according to the invention in the form of the solution obtained in their preparation. Preferably, however, they are isolated by conventional methods and, if desired, purified.
  • the compounds I are used in dishwashing detergents. With particular preference, they are used in machine dishwashing detergents. Dishwashing agents, in particular machine dishwashing detergents, with rinse aid function are preferred among these.
  • the detergents and cleaners containing the compounds I are preferably solid at room temperature (20 ° C.).
  • the solid detergents and cleaning agents may be powdered or tablet-shaped products ("tabs").
  • they are tablet-shaped products ("tabs"), i. to tablet-shaped dishwashing detergent, in particular to tablet-shaped machine dishwashing detergent.
  • “5 in 1” products also typically contain a glass preservative and a rinse aid reinforcing agent.
  • "7 in 1” products also contain a stainless steel luster agent and an encrusting agent.
  • the compounds I are used in tablet-form multifunctional machine dishwashing detergents, where they completely or partially replace the usual rinse aid.
  • the compounds I have both an effect as a surfactant and as a rinse aid. Therefore, the invention also relates to the use of the compounds I as a surfactant and / or as a rinse aid. In particular, the invention relates to the use of the compounds I as a surfactant with a clear rinse effect or as a rinse aid surfactant.
  • the compounds I used according to the invention are distinguished, in particular, by an outstanding deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine. They act both against inorganic and against organic deposits inhibiting.
  • the inorganic coverings are, in particular, calcium and magnesium phosphate, carbonate, silicate and / or phosphonate, which are formed from the calcium and magnesium salts contained in the water and the builders contained in customary dishwashing detergents.
  • the organic coverings are in particular dirt constituents from the wash liquor, such as, for example, Protein, starch and fat deposits.
  • the compounds I used according to the invention are also effective against so-called carry-over coverings, which originate from the residual water quantity in the bottom of the dishwasher and u. a. Dishwashing residues and possibly also residual dirt from the previous wash cycle of the dishwasher included.
  • Another object of the invention are detergents or cleaners, which are dishwashing detergents containing at least one compound of formula I.
  • suitable washing or cleaning agents reference is made to the above statements.
  • the washing and cleaning agents are dishwashing detergents, of which machine dishwashing detergents are preferred.
  • dishwashing detergents in particular machine dishwashing detergents, with a rinse aid function.
  • the washing and cleaning agent according to the invention is preferably solid at room temperature (20 ° C.).
  • suitable and preferred solid detergents and cleaning agents reference is made to the above statements.
  • the washing and cleaning agents according to the invention are tablet-shaped multifunctional machine dishwashing detergents.
  • the compounds I in the final rinse be included; however, they are preferably present as a solid in the tablet-shaped dishwashing detergent.
  • the percentages by weight relate to the total weight of the dishwashing detergent.
  • the dishwashing agent according to the invention particularly preferably comprises at least one enzyme.
  • the percentages by weight relate to the total weight of the dishwashing detergent.
  • the dishwashing composition according to the invention additionally comprises at least one bleaching agent.
  • the percentages by weight relate to the total weight of the dishwashing detergent.
  • Builders sometimes referred to as sequestrants, builders, chelating agents, chelants, or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitation. They help to break up dirt, disperse dirt particles, help to loosen dirt and sometimes have their own washing effect. In addition, when they are solid and used in powdered formulations, they hold the powder free-flowing.
  • Suitable builders can be both organic and inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g. Hydroxyalkylphosphonklaren, phosphonates, aminopolycarboxylic acids and their salts and polymeric compounds containing carboxylic acid groups and their salts.
  • Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as zeolites.
  • zeolites Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially reactive with other cations such as Li, K, Ca, Mg or ammonium is exchanged.
  • Suitable zeolites are for example in the US-A-4604224 described.
  • Crystalline silicates suitable as builders are, for example, disilicates or sheet silicates, for example 5-Na 2 Si 2 O 5 or B-Na 2 Si 2 O 5 (SKS 6 or SKS 7).
  • the silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates.
  • Amorphous silicates such as sodium metasilicate having a polymeric structure or amorphous disilicate (Britesil® H 20 manufactured by Akzo) are also useful. Preferred among these is sodium disilicate.
  • Suitable inorganic builders based on carbonate are carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate.
  • Typical phosphates used as inorganic builders are alkali metal orthophosphates and / or polyphosphates, e.g. Pentasodium.
  • Suitable organic builders are C 4 -C 30 -di-, -tri- and -tetracarboxylic acids, for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids with C 2 -C 20 -alkyl or -alkenyl radicals ,
  • Suitable organic builders are furthermore hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C 4 -C 20 -hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid. Preferred among these are citric acid and its salts.
  • Suitable organic builders are furthermore phosphonic acids, such as, for example, hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof.
  • phosphonic acids such as, for example, hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof.
  • phosphonic acids include, for example, phosphonobutanetricarboxylic acid, aminotris-methylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediamine tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholino-methanediphosphonic acid, 1-hydroxy-C 1 - to C 10 -alkyl-1,1-diphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid. Preference is given here to 1-hydroxyethane-1,1-diphosphonic acid and salts thereof.
  • Suitable organic builders are also aminopolycarboxylic acids such as nitrilotriacetic acid (NTA), nitrilo monoacetic dipropionic acid, nitrilotripropionic acid, ⁇ -alaninediacetic acid ( ⁇ -ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N- (alkyl) ethylenediaminetriacetic acid, N- (hydroxyalkyl) ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediamine disuccinic acid, serinediacetic acid, isoserinediacetic acid, L-aspartic diacetic acid, L-glutamic diacetic acid, methyl
  • Suitable organic builders are also polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. These preferably have a number average molecular weight in the range from 800 to 70,000 g / mol, particularly preferably from 900 to 50,000 g / mol, in particular from 1,000 to 20,000 g / mol, especially from 1,000 to 10,000 g / mol.
  • the term acrylic acid homopolymer also encompasses polymers in which the carboxylic acid groups are partially or completely neutralized. These include acrylic acid homopolymers in which the carboxylic acid groups are present partially or completely in the form of alkali metal salts or ammonium salts. Preference is given to acrylic acid homopolymers in which the carboxylic acid groups are protonated or in which the carboxylic acid groups are present partially or completely in the form of sodium salts.
  • Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as used, for example, in US Pat EP-A 451 508 and EP-A 396 303 are described.
  • Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C 4 -C 8 -dicarboxylic acids, comonomers being monoethylenically unsaturated monomers from group (i) given below in amounts of up to 95% by weight, from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight.
  • suitable unsaturated C 4 -C 8 -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.
  • the group (i) comprises monoethylenically unsaturated C 3 -C 8 monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid.
  • acrylic acid and methacrylic acid are used.
  • Group (ii) comprises monoethylenically unsaturated C 2 -C 22 -olefins, vinylalkyl ethers having C 1 -C 8 -alkyl groups, styrene, vinyl esters of C 1 -C 8 -carboxylic acids, (meth) acrylamide and vinylpyrrolidone.
  • group (ii) preference is given to C 2 -C 6 -olefins, vinylalkyl ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate used. If the polymers of group (ii) contain copolymerized vinyl esters, these may also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are for example US-A 3887806 such as DE-A 4313909 known.
  • Group (iii) comprises (meth) acrylic esters of C 1 -C 8 -alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 -amines, N-vinylformamide and N-vinylimidazole.
  • Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of monoethylenically unsaturated C 3 -C 8 -monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially of acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, such as copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, more preferably those in the weight ratio 30:70 to 90:10 with molecular weights of 1000 to 150,000; Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C 1 -C 3 carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), wherein the weight ratio of acrylic acid to the vinyl ester in the range of 30:70 to 70:30 may vary; Copolymers of maleic acid with C 2 -C
  • Suitable polymeric compounds containing carboxylic acid groups are furthermore copolymers of from 50 to 98% by weight of ethylenically unsaturated weak carboxylic acids with from 2 to 50% by weight of ethylenically unsaturated sulfonic acids, as described, for example, in US Pat EP-A-0877002 are described.
  • Suitable weak ethylenically unsaturated carboxylic acids are, in particular, C 3 -C 6 -monocarboxylic acids, such as acrylic acid and methacrylic acid.
  • Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamindo-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2- propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and salts of these acids.
  • the copolymers may further contain copolymerized 0 to 30 wt .-% of ethylenically unsaturated C 4 -C 8 dicarboxylic acids, such as maleic acid, and 0 to 30 wt .-% of at least one monomer which is copolymerizable with the aforementioned monomers.
  • the latter are, for example, C 1 -C 4 -alkyl esters of (meth) acrylic acid, C 1 -C 4 -hydroxyalkyl esters of (meth) acrylic acid, acrylamide, alkyl-substituted acrylamide, N, N-dialkyl-substituted acrylamide, vinylphosphonic acid , Vinyl acetate, allyl alcohols, sulfonated allyl alcohols, styrene and other vinyl aromatics, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole or N-vinylpyridine.
  • the weight average molecular weight of these copolymers is in the range of 3,000 to 50,000.
  • copolymers having about 77% by weight of at least one ethylenically unsaturated C 3 -C 6 monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid.
  • Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates are also suitable.
  • suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.
  • acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.
  • For modification, in addition up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers may be present in copolymerized form.
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • polyethylene glycols ethylene oxide / Propylenoxid
  • Ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyhydric C 1 -C 22 -alcohols (cf. US-A-5756456 ).
  • polyglyoxylic acids as used, for example, in EP-B-001004 .
  • US-A-5399286 US-A-5399286 .
  • DE-A-4106355 and EP-A-656 914 are described.
  • the end groups of the polyglyoxylic acids can have different structures.
  • polyamidocarboxylic acids and modified polyamidocarboxylic acids are suitable; These are for example off EP-A-454126 .
  • Polyaspartic acids or co-condensates of aspartic acid with further amino acids, C 4 -C 25 -mono- or -dicarboxylic acids and / or C 4 -C 25 -mono- or -diynes can also be used as polymeric compounds containing carboxylic acid groups. Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C 6 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines.
  • polyacrylic acids are also preferred in partially or completely neutralized form.
  • organic builders are iminodisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, alkyl polyaminocarboxylates, aminopolyalkylene phosphonates, polyglutamates, hydrophobically modified citric acid such as e.g. Agaricinic acid, poly (alpha) -hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylenediamine triacetate, and alkylamides of ethylenediaminetetraacetic acid such as EDTA tallowamide.
  • oxidized starches can also be used as organic builders.
  • component b a mixture of different builders is used as component b).
  • the mixture of different builders preferably comprises at least two of the following constituents: at least one carbonate (eg sodium carbonate), at least one silicate (eg sodium disilkat), at least one polymeric carboxylic acid group-containing compound or at least one polymeric carboxylic acid group-containing compound in which the carboxylic acid groups are partially or completely neutralized (for example, polyacrylic acid), at least one (poly) hydroxycarboxylic acid or a salt thereof (eg citric acid or a citrate), at least one aminopolycarboxylic acid or a salt thereof (eg methylglycinediacetic acid or a salt thereof, eg a sodium salt thereof), at least one phosphonic acid (eg.
  • at least one carbonate eg sodium carbonate
  • at least one silicate eg sodium disilkat
  • polymeric carboxylic acid group-containing compound or at least one polymeric carboxylic acid group-containing compound in which the carboxylic acid groups are partially or completely neutralized for example, polyacrylic acid
  • the mixture particularly preferably contains at least one carbonate, at least one silicate and at least one polymeric (partially) neutralized carboxylic acid group-containing compound and optionally at least one of the following: at least one (poly) hydroxycarboxylic acid or a salt thereof, at least one phosphonic acid, at least one phosphate.
  • the mixture contains at least one carbonate, at least one silicate, at least one polymeric optionally (partially) neutralized carboxylic acid group-containing compound, at least one (poly) hydroxycarboxylic acid or a salt thereof and at least one phosphonic acid, and optionally at least one phosphate.
  • the percentages by weight are based on the total weight of the builder.
  • the enzymes are preferably selected from hydrolases such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the aforementioned enzymes. All of these hydrolases contribute to the soil dissolution and removal of proteinaceous, fatty or starchy contaminants. For bleaching also Oxireduktasen can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • Suitable hydrolases are e.g. ⁇ -glucosidases (EC number 3.2.1.20), proteases (Ovozyme® (ex Novozymes), EC number 3.2.1.20), amylases [Purastar® (ex Genencor), Termamyl® (ex Novozymes), Stainzyme® (ex Novozymes ), Duramyl® (from Novozymes)], mannanases [Purabrite® (from Genencor), Mannastar® (from Genencor), Mannaway® (from Novozymes)] and cellulases [Carezyme® (from Novozymes), Celluzyme® (from Novozymes), Endolase, Puradax® (from Genencor)].
  • Suitable amylases include in particular ⁇ -amylases (EC number 3.2.1.1), iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • Suitable lipases are esterases, such as Lipex and Lipolase.
  • Examples of lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • the dishwashing agent according to the invention preferably contains at least one protease and / or amylase.
  • protease and / or amylase-containing mixtures are particularly preferred.
  • Preferred proteases in the aforementioned mixtures are subtilisin-type proteases (Savinase, etc .: EC number 3.4.21.62).
  • the enzymes may be adsorbed to carriers to protect against premature degradation.
  • the washing and cleaning agent of the invention may further comprise enzyme stabilizers, e.g. Calcium propionate, sodium formate or boric acids or their salts, and / or oxidation inhibitors included.
  • enzyme stabilizers e.g. Calcium propionate, sodium formate or boric acids or their salts, and / or oxidation inhibitors included.
  • the bleaching agents d) are preferably bleaching systems which, in addition to bleaching agents, optionally also contain bleach activators, bleach catalysts and / or bleach stabilizers.
  • Suitable bleaching agents are, for example, percarboxylic acids, e.g. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or terephthalic acid, salts of percarboxylic acids, e.g. Sodium percarbonate, adducts of hydrogen peroxide with inorganic salts, e.g. Sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide to organic compounds, e.g. Urea perhydrate, or of inorganic peroxy salts, e.g. Alkali metal persulfates, or peroxodisulfates.
  • percarboxylic acids e.g. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or terephthalic acid
  • Suitable bleach activators are, for example, polyacylated sugars, for example pentaacetylglucose; Acyloxybenzolsulfonklaren and their alkali and Erdalkaiimetallsalze, for example, sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzene sulfonate; N, N-diacylated and N, N, N ', N'-tetraacylated amines, eg N, N, N', N'-tetraacetylmethylenediamine and -ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl -ptoluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin; N-alkyl-N-sulfonylcarbonamide
  • a bleaching system of bleaches and bleach activators may optionally also contain bleach catalysts.
  • Suitable bleach catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US Pat US-A 5,360,569 and EP-A 453 003 are described.
  • Particularly effective bleach catalysts are manganese complexes which are described, for example, in US Pat WO-A 94/21777 are described.
  • Such compounds in the case of their use in the washing and cleaning agents at most in amounts of up to 1.5 wt .-%, in particular up to 0.5 wt .-%, in the case of very active manganese complexes in amounts up to 0.1 wt. -%, incorporated.
  • the use of systems with enzymatic peroxide release or of photoactivated bleach systems is also possible for the detergents and cleaners according to the invention.
  • Surfactants from group e) other than component a) may be cationic, anionic, zwitterionic or nonionic.
  • Suitable nonionic surfactants are, for example, alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 20, preferably 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably 2- Position may be methyl branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO, 4 EO or 7 EO, C 9 -C 11 -alcohol with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO ,
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • alcohol ethoxylates which have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO or 30 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • R a O (G) y (1) in which R a is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a glycoside unit having 5 or 6 C atoms, preferably glucose , stands.
  • the degree of oligomerization y, the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, y is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters such as, for example in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (3) wherein R e is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R f is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms and R g is a linear, branched or is a cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, with C 1 -C 4 alkyl or phenyl groups being preferred, and [Z] 1 being a linear polyhydroxyalkyl group whose alkyl chain is substituted with at least two hydroxyl groups , or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] 1 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be prepared, for example, according to WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
  • Suitable anionic surfactants are, for example, those of the sulfonate type and sulfates.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C 12 -C 18 -monoolefins having terminal or internal double bonds by sulfonation gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • 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, for example, according to the U.S. Patents 3,234,258 or 5,075,041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants.
  • the sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • alkylsulfosuccinic acid which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable anionic surfactants are also soaps.
  • Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants 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.
  • Cationic surfactants are, for example, ammonium salts, such as C 8 -C 16 -dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.
  • Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, for example C 6 -C 18 -alkylbetaines or C 6 -C 15 -alkylsulfobetaines or amine oxides, such as alkyldimethylamine oxides.
  • Solvents contained in component e) are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, they are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol,
  • foam inhibitors or defoamers of component e) are soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable bases of component e) are, in particular, the carbonates mentioned above in the builders.
  • the washing and cleaning agents according to the invention are gel-like, ie the washing and cleaning agents are preferably gelatinous dishwashing agents, of which gel-type machine dishwashing detergents are particularly preferred.
  • these are gelatinous dishwashing detergents, preferably machine dishwashing detergents, with a rinse aid function.
  • Gel-like detergents and cleaners are understood as meaning fluid agents which have a viscosity at room temperature (20 ° C.) which is higher than that of water, but which are still sufficiently fluid that they can be metered without problems using customary dosing aids.
  • the gel-type detergents and cleaners according to the invention preferably have a viscosity of from 0.5 to 100, particularly preferably from 0.5 to 50 and in particular from 1 to 30, Pa.s at 20 ° C.
  • the percentages by weight relate to the total weight of the dishwashing detergent.
  • the amounts by weight of a) to e3) add up to 100 wt .-%.
  • the dishwashing agent according to the invention particularly preferably comprises at least one enzyme.
  • the percentages by weight relate to the total weight of the dishwashing detergent.
  • the amounts by weight of a) to e3) add up to 100 wt .-%.
  • the percentages by weight relate to the total weight of the dishwashing detergent.
  • the amounts by weight of a) to e3) add up to 100 wt .-%.
  • the thickeners serve to impart the desired viscosity to the dishwashing agent according to the invention.
  • any known thickeners are suitable, provided they do not exert a negative influence on the effect of the dishwashing detergent.
  • Suitable thickeners may be both of natural origin and of synthetic nature.
  • thickeners of natural origin examples include xanthan gum, locust bean gum, guar gum, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose and the like.
  • Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, e.g. Phyllosilicates, as well as the silicates mentioned in the builders.
  • Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partially) crosslinked homopolymers of acrylic acid, for example with an allyl ether of sucrose or pentaerythritol or homopolymers of acrylic acid (Carbomer) crosslinked with propylene, for example the Carbopol® grades from BF Goodridge (eg Carbopol ® 676, 940, 941, 934 and the like.) Or the Polygel® brands of 3V Sigma (eg Polygel® DA), copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and a (meth) acrylate derived from long-chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (eg Acusol® 820 or 1206A), copolymers of two
  • C 1 -C 4 -alkyl esters for example copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate t, for example the Aculyn® and Acusol® brands from Rohm & Haas (eg Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers, for example with an allyl ether of sucrose or pentaerythritol crosslinked copolymers C 10 -C 30 -alkyl acrylates having one or more comonomers selected from acrylic acid, methacrylic acid and their C 1 -C 4 -alkyl esters (eg Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas) ,
  • Examples of synthetic thickeners are further reaction products of maleic acid polymers with ethoxylated long-chain alcohols, e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; Polyethylene glycols, polyamides, polyimines and polycarboxylic acids.
  • ethoxylated long-chain alcohols e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP
  • Polyethylene glycols, polyamides, polyimines and polycarboxylic acids e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP.
  • Preferred thickeners are xanthans and the abovementioned polyacrylic and polymethacrylic compounds.
  • the compounds I used according to the invention are distinguished by a high melting point in comparison to conventional surfactants of the prior art, which allows their use in solid detergents and cleaners. They have no or no strong foaming tendency, they have a good deposit-inhibiting action on dishes washed therewith, in particular with regard to spotting, and they are not hydrolysis-labile.
  • the alcohol to be alkoxylated (isotridecanol, 2-propylheptanol or C 12 / C 14 -alcohol, 1.0 eq) is mixed with an aqueous KOH solution which contains 50% by weight of KOH , The amount of KOH is 0.2 wt .-% of the product to be produced.
  • the mixture is dehydrated at 100 ° C and 20 mbar for 2 h. Then it is rinsed three times with N 2 , a pre-pressure of about 1.3 bar N 2 is set and the temperature is raised to 120 ° C.
  • the ethylene oxide (n mol eq.) is metered in so that the temperature remains between 125 and 135 ° C.
  • the mixture is then stirred for 5 h at 125 ° C, rinsed with N 2 , cooled to 70 ° C and the reactor emptied.
  • the crude product is degassed on a rotary evaporator for 2 h at 100 ° C ( ⁇ 20 mbar vacuum).
  • This basic crude product can be deionized with commercially available Mg silicates, which are then filtered off. Alternatively, the neutralization can also be carried out with the aid of acetic acid.
  • the bright product is characterized by means of a 1 H NMR spectrum in CDCl 3 and a gel permeation chromatography and an OH number determination and determines the yield (> 98%).
  • A is a comparative polymer.
  • the foam volume was determined indirectly by measuring the foaming over the speed of the spray arm of the dishwasher.
  • 10 ml of stirred chicken egg, 19 g of a basic dishwashing detergent (48 parts of sodium metasilicate x 5H 2 O, 45 parts of sodium triphosphate, 5 parts of sodium carbonate) and 1 g of the surfactant (AF) in the dishwasher (Miele Disinfector G 7735 CD MCU; MCU version S04.01).
  • the number of revolutions of the spray arm was then measured.
  • the foam level is high, the spray arm is slowed down, at low levels it can work at the highest possible speed (about 125 rpm).
  • the top speed of the dishwasher is usually about 125 rpm when there is no foam.
  • the maximum speed in the dishwasher was set artificially in the present experiment (by drilling the spray arm, position of the nozzles) to obtain a wider range, which can distinguish products better.
  • the rotational speed was measured at 40, 50 and 60 ° C.
  • the following table lists rotor speeds in rpm at different temperatures. temperature A B C D e F 40 [° C] 119 99 128 122 84 89 50 [° C] 121 111 131 122 106 90 60 [° C] 122 117 122 122 117 101
  • Ovozyme® and Stainzyme® are trademarks of Novozymes
  • Sokalan® and Trilon® are trademarks of BASF SE
  • Britesil® is a trademark of PQ Corp.
  • Cublen® is a trademark of Zschimmer & Schwarz Mohsdorf GmbH & Co KG.
  • Grading spotting A B C D e F knife 1 5 2 2 5 2 drinking glass 1 2 1 2 1 1 Melaminteller 1 3 2 2 2 3 total 3 10 5 6 8th 6 Rating filming

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Claims (16)

  1. Utilisation de composés de formule I

            R-O-[-CH2CH(R1)-O]-l-[-CH2CH2-O-]-m-[-CH2CH(R2)-O-]-n-CH2CH2-S(O)x-R'     (I)

    dans laquelle
    R représente alkyle en C8-C24 ;
    R' représente alkyle en C10-C14 ;
    R1 et R2 représentent indépendamment l'un de l'autre et indépendamment de leurs occurrences respectives alkyle en C1-C5 ;
    m représente un nombre de 25 à 50 ;
    l et n représentent indépendamment l'un de l'autre un nombre de 0 à 15 ; et
    x représente 0, 1 ou 2 ;
    dans des détergents, les détergents étant choisis parmi les agents de lavage de la vaisselle.
  2. Utilisation selon la revendication 1, dans laquelle les détergents sont choisis parmi les agents de lavage de la vaisselle en machine.
  3. Utilisation selon l'une quelconque des revendications 1 ou 2, dans laquelle les détergents sont choisis parmi les agents de lavage de la vaisselle ayant une fonction de rinçage.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle les composés I sont utilisés en tant que tensioactifs.
  5. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle les composés I sont utilisés en tant que tensioactifs de rinçage.
  6. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle R représente alkyle en C10-C15.
  7. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle R1 et R2 représentent indépendamment l'un de l'autre et indépendamment de leurs occurrences respectives méthyle.
  8. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle l et n représentent 0.
  9. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle x représente 0 ou 1.
  10. Détergent, qui est un agent de lavage de la vaisselle, contenant au moins un composé de formule I selon la définition dans l'une quelconque des revendications 1 et 6 à 9.
  11. Détergent selon la revendication 10, qui est un agent de lavage de la vaisselle en machine.
  12. Détergent selon la revendication 10 ou 11, qui est un agent de lavage de la vaisselle ayant une fonction de rinçage.
  13. Détergent selon l'une quelconque des revendications 10 à 12, qui est solide à température ambiante.
  14. Détergent selon l'une quelconque des revendications 11 à 13, comprenant les constituants suivants :
    a) au moins un composé de formule I : de 0,1 à 20 % en poids ;
    b) au moins un adjuvant : de 5 à 80 % en poids ;
    c) éventuellement au moins une enzyme : de 0 à 8 % en poids ;
    d) éventuellement au moins un agent blanchissant : de 0 à 30 % en poids ; et
    e) éventuellement au moins un autre additif, qui est choisi parmi les tensioactifs différents de a), les bases, les inhibiteurs de corrosion, les antimousses, les colorants, les parfums, les charges, les adjuvants de pastillage, les agents de désintégration, les épaississants, les solubilisants, les solvants organiques et l'eau : de 0 à 50 % en poids ;
    par rapport au poids total du détergent.
  15. Détergent selon l'une quelconque des revendications 10 à 12 et 14, qui est sous forme de gel à température ambiante.
  16. Détergent selon la revendication 15, comprenant les constituants suivants :
    a) au moins un composé de formule I : de 0,1 à 20 % en poids ;
    b) au moins un adjuvant : de 5 à 80 % en poids ;
    c) éventuellement au moins une enzyme : de 0 à 8 % en poids ;
    d) éventuellement au moins un agent blanchissant : de 0 à 30 % en poids ;
    e1) de l'eau : de 10 à 90 % en poids ;
    e2) au moins un épaississant : de 0,1 à 8 % en poids ; et
    e3) éventuellement au moins un autre additif, qui est choisi parmi les tensioactifs différents de a), les bases, les inhibiteurs de corrosion, les antimousses, les colorants, les parfums, les charges, les solubilisants et les solvants organiques : de 0 à 25 % en poids ;
    par rapport au poids total du détergent.
EP12700080.0A 2011-01-13 2012-01-12 Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage Not-in-force EP2663625B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12700080.0A EP2663625B1 (fr) 2011-01-13 2012-01-12 Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11150875 2011-01-13
PCT/EP2012/050421 WO2012095481A1 (fr) 2011-01-13 2012-01-12 Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage
EP12700080.0A EP2663625B1 (fr) 2011-01-13 2012-01-12 Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage

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EP2663625A1 EP2663625A1 (fr) 2013-11-20
EP2663625B1 true EP2663625B1 (fr) 2018-06-27

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EP (1) EP2663625B1 (fr)
JP (1) JP5931920B2 (fr)
KR (1) KR101891479B1 (fr)
CN (1) CN103314094B (fr)
BR (1) BR112013017438A2 (fr)
CA (1) CA2822855A1 (fr)
ES (1) ES2686304T3 (fr)
MX (1) MX2013007891A (fr)
RU (1) RU2597014C2 (fr)
WO (1) WO2012095481A1 (fr)

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EP3475404A1 (fr) 2016-06-23 2019-05-01 Novozymes A/S Utilisation d'enzymes, composition et procédé d'élimination de salissures
US10584306B2 (en) 2017-08-11 2020-03-10 Board Of Regents Of The University Of Oklahoma Surfactant microemulsions

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Publication number Publication date
RU2013137510A (ru) 2015-02-20
CN103314094B (zh) 2016-05-25
BR112013017438A2 (pt) 2016-09-27
JP2014502665A (ja) 2014-02-03
RU2597014C2 (ru) 2016-09-10
MX2013007891A (es) 2013-08-27
KR101891479B1 (ko) 2018-08-24
ES2686304T3 (es) 2018-10-17
WO2012095481A1 (fr) 2012-07-19
EP2663625A1 (fr) 2013-11-20
KR20140040085A (ko) 2014-04-02
JP5931920B2 (ja) 2016-06-08
CA2822855A1 (fr) 2012-07-19
CN103314094A (zh) 2013-09-18

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