WO2012095481A1 - 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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WO2012095481A1
WO2012095481A1 PCT/EP2012/050421 EP2012050421W WO2012095481A1 WO 2012095481 A1 WO2012095481 A1 WO 2012095481A1 EP 2012050421 W EP2012050421 W EP 2012050421W WO 2012095481 A1 WO2012095481 A1 WO 2012095481A1
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weight
acid
washing
detergents
cleaning agent
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PCT/EP2012/050421
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German (de)
English (en)
Inventor
Sophie Maitro-Vogel
Jürgen Tropsch
Wolfgang Spiegler
Roman Benedikt Raether
Christian Bittner
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Basf Se
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Priority to EP12700080.0A priority Critical patent/EP2663625B1/fr
Priority to BR112013017438A priority patent/BR112013017438A2/pt
Priority to JP2013548840A priority patent/JP5931920B2/ja
Priority to KR1020137018367A priority patent/KR101891479B1/ko
Priority to RU2013137510/04A priority patent/RU2597014C2/ru
Priority to CA2822855A priority patent/CA2822855A1/fr
Priority to MX2013007891A priority patent/MX2013007891A/es
Priority to ES12700080.0T priority patent/ES2686304T3/es
Priority to CN201280005218.5A priority patent/CN103314094B/zh
Publication of WO2012095481A1 publication Critical patent/WO2012095481A1/fr

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    • 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 (SO2).
  • 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 substances such as dirt particles in an aqueous solution to become soluble 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, frequently results in residues remaining on the dishes cleaned therewith (so-called "spotting” in the case of the formation of punctiform linings or "filming") "in the case 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;
  • ester group these surfactants are sensitive to hydrolysis, which severely restricts their usability in alkaline formulations and at relatively high temperatures, in particular during prolonged washing operations.
  • Thioethers of alcohol alkoxylates and their oxidized form are basically known; e.g. from US 3,627,845.
  • This document describes the use of such compounds as biologically active agents, e.g. as fungicides, acaricides and anthelmintics, and as surface active agents in agrochemical formulations and coating agents.
  • a use as a detergent or cleaning agent is not mentioned.
  • 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.
  • R is C 8 -C 2 4 alkyl
  • R ' is C 6 -C 18 -alkyl
  • m is a number from 10 to 100;
  • I and n independently represent a number from 0 to 15;
  • C 1 -C 8 -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 ⁇ -Cis-alkyl represents a linear or branched alkyl radical having 6 to 18 carbon atoms.
  • Cs-C24-alkyl is 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 Cs-C24 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-dodecyl, the position 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-eicosyl, the positional
  • Cio-Ci4-alkyl is 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 1 -C 4 -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.
  • Cio-C 15 -alkyl is 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 cio-cis-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.
  • Cs-Cis-alkyl is a linear or branched alkyl radical having 8 to 15 carbon atoms. Examples thereof are the radicals mentioned above for C 1 -C 6 -alkyl and also octyl, 2-ethylhexyl, nonyl and positional isomers thereof.
  • Branched Cs-Cis-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-dodecyl, the positional isomers of n-tridecyl, the positional isomers of n-tetradecyl, and the positional isomers of n-pentadecyl.
  • Ci2-alkyl stands for dodecyl and its position isomers.
  • the compounds I used according to the invention may be chemically pure substances or mixtures of different compounds I.
  • mixtures of different compounds I which can be understood, for example, to be the variables R, R ', I, m, n and /. or x differ.
  • R is preferably Cs-Cis-alkyl, particularly preferably Cio-Cis-alkyl and especially Cio-C-alkyl.
  • the alkyl radical R is branched.
  • R are 2-propylheptyl, tridecyl and des- positional isomers such as isotridecyl (ie branched tridecyl radicals and mixtures thereof), n-dodecyl (lauryl), n-tetradecyl (myristyl) and mixtures thereof.
  • R ' is preferably C 1 -C 4 -alkyl and in particular C 1 -C 2 -alkyl (dodecyl); espe- cially for n-dodecyl.
  • R 1 and R 2 independently of one another preferably represent methyl.
  • m is preferably from 20 to 50, more preferably from 25 to 50, more preferably from 25 to 45, and most preferably 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. If at least one of the indices I or n does not stand for 0, the Ethylenoxy repeat units (-CH2-CH2-O-) and the repeating units (-CH 2 -CH (R 1 ) -O- and / or (-CH 2 -CH (R 2 ) -O-) randomly or in blocks Preferably, they are arranged in blocks, ie all optional repeating units -CH 2 -CH (R 1 ) -O- form a block which is followed by the ethyleneoxy block (-CH 2 -CH 2 -O-) m connect all optionally repeating units -CH 2 -CH (R 2 ) -O- as a block, x preferably stands for 0 or 1.
  • the compounds I are distinguished by a relatively high melting point, preferably the melting point is at least 35 ° C., eg 35 to 50 ° C, preferably 35 to 47 ° C and especially 35 to 45 ° C, particularly preferably at least 38 ° C, eg 38 to 50 ° C, preferably 38 to 47 ° C and especially 38 to 45 ° C; and in particular at least 40 ° C, for example 40 to 50 ° C, preferably 40 to 47 ° C and in particular 40 to 45 ° C.
  • the melting point is at least 35 ° C., eg 35 to 50 ° C, preferably 35 to 47 ° C and especially 35 to 45 ° C, particularly preferably at least 38 ° C, eg 38 to 50 ° C, preferably 38 to 47 ° C and especially 38 to 45 ° C; and in particular at least 40 ° C, for example 40 to 50 ° C, preferably 40 to 47 ° C and in particular 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. Magnesia 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. Magnesia 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 form is in the range of 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 generally leads to a further pressure increase.
  • the pressure during the actual reaction is in the range of preferably from 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 formed reaction water is removed, e.g. 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.
  • conventional oxidizing agents such as hydrogen peroxide, brown oxide. stone, a permanganate, m-chloroperbenzoic acid or a perchlorate.
  • 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 of the formula I can in principle be used in all common detergents and cleaners.
  • detergents are understood to mean those agents which are used for cleaning flexible materials with high absorbency, e.g. of materials having a textile character, while cleaning agents in the context of the present invention are understood to mean those agents which are suitable for cleaning closed-surface materials, i. with a surface which has no or only a few and small pores and consequently has no or only a low absorbency.
  • Examples of flexible materials with high absorbency are those which contain or consist of natural, synthetic or semisynthetic fiber materials and which therefore generally have at least in part a textile character.
  • the fibrous or fibrous materials may in principle be in any form found in use or in manufacture and processing.
  • fibers may be present randomly in the form of flake or debris, ordered in the form of threads, yarns, threads, or in the form of fabrics such as nonwovens, loden fabrics or felt, fabrics, knitted fabrics in all conceivable weave types.
  • the fibers may be raw fibers or fibers at any stage of processing. Examples are natural protein or cellulose fibers, such as wool, silk, cotton, sisal, hemp or coconut fibers, or synthetic fibers, such as polyester, polyamide or polyacrylonitrile fibers.
  • Examples of materials that have little or no pores and little or no absorbency are metal, glass, enamel or ceramic.
  • Typical objects from these materials are, for example, metal sinks, cutlery, glass and porcelain dishes, bathtubs, sinks, tiles, cured synthetic resins, such as decorative melamine resin surfaces on kitchen furniture or painted metal surfaces such as refrigerators and car bodies, printed circuit boards.
  • detergents containing the compounds I include dishwashing detergents such as hand dishwashing detergents or dishwasher detergents, metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high-pressure cleaners, neutral cleaners, alkaline cleaners, acid cleaners, spray degreasers, dairy cleaners, large kitchen cleaners, apparatus cleaners in the industry, in particular the chemical industry, cleaner for car wash and also household all-purpose cleaner.
  • dishwashing detergents such as hand dishwashing detergents or dishwasher detergents, metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high-pressure cleaners, neutral cleaners, alkaline cleaners, acid cleaners, spray degreasers, dairy cleaners, large kitchen cleaners, apparatus cleaners in the industry, in particular the chemical industry, cleaner for car wash and also household all-purpose cleaner.
  • the compounds I are preferably 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 tabular products ("tabs").
  • they are tablet-shaped products ("tabs”).
  • Particularly preferred are tablet-shaped dishwashing detergents, in particular tablet-shaped dishwasher detergents.
  • the compounds I are used in tablet-form multifunctional machine dishwashing detergents, where they completely or partially replace the customary rinse aids. 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.
  • 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 conventional dishwashing detergents.
  • the organic coverings are, in particular, dirt components from the wash liquor, such as, for example, protein, starch and fat deposits.
  • the compounds I used according to the invention are also active in relation to so-called carry-over coverings, which originate from the residual water quantity in the bottom of the dishwasher and which contain, inter alia, dishwasher residues and possibly also dirt residues from the previous wash cycle of the dishwasher.
  • Another object of the invention are detergents or cleaning agents 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 preferably dishwashing agents, 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 washing 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. In these compounds I may be contained in the final rinse; however, they are preferably present as a solid in the tablet-shaped dishwashing detergent.
  • the dishwashing agent according to the invention preferably comprises the following constituents:
  • At least one builder also referred to as sequestering agent, builder, complexing agent, chelator, chelating agent or softening agent
  • surfactants other than a bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tableting aids, disintegrating agents, thickeners, solubilizers, organic solvents and water.
  • At least one builder from 5 to 80% by weight
  • At least one bleaching agent from 0 to 30% by weight;
  • At least one further additive from 0 to 50% by weight.
  • the weight percentages relate to the total weight of the dishwashing detergent.
  • the dishwashing agent according to the invention particularly preferably comprises at least one enzyme.
  • the abovementioned constituents are particularly preferably contained in the following proportions in the dishwashing composition according to the invention: a) at least one compound of the formula I: from 0.1 to 10% by weight;
  • At least one builder from 20 to 80% by weight
  • At least one bleaching agent from 0 to 30% by weight;
  • the percentages by weight relate to the total weight of the dishwashing detergent.
  • the dishwashing agent of the invention further comprises at least one bleaching agent.
  • the abovementioned constituents are present in the following proportions in the dishwashing composition according to the invention: a) at least one compound of the formula I: from 0.1 to 10% by weight;
  • At least one builder from 20 to 80% by weight
  • At least one bleaching agent from 5 to 25% by weight
  • At least one further additive from 0 to 50% by weight.
  • 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 keep 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, for example hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and their salts, and polymers containing carboxylic acid groups and salts thereof.
  • Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as zeolites.
  • 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 exchanged with other cations such as Li, K, Ca, Mg or ammonium.
  • Suitable zeolites are described, for example, in US Pat. 4604224.
  • Crystalline silicates suitable as builders are, for example, silicates 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, for example, sodium metasilicate, which has a polymeric structure, or amorphous disilicate (Britesil® H 20 manufacturer: Akzo) can also be used. 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, such as e.g. Pentasodium.
  • Suitable organic builders are, for example, C 4 -C 30 -di-, -tri- and -tetracarboxylic acids, such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentane-tetracarboxylic acid and alkyl- and alkenylsuccinic acids with C 2 -C 2 0-alkyl- or alkenyl- residues.
  • C 4 -C 30 -di-, -tri- and -tetracarboxylic acids such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentane-tetracarboxylic acid and alkyl- and alkenylsuccinic acids with C 2 -C 2 0-alkyl- or alkenyl- residues.
  • Suitable organic builders are furthermore hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C 4 -C 20 -hydroxycarboxylic acids, such as, for example, acetic 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 also phosphonic acids, e.g. Hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof. These include e.g. Phosphonobutanetricarboxylic acid, aminotris-methylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediamine tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholino-methanediphosphonic acid, 1-hydroxy-C 1 -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.
  • phosphonic acids e.g. Hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof.
  • Suitable organic builders are, furthermore, aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrile monooligigipropionic acid, nitrilotripropionic acid, Alaninediacetic acid (.beta.-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,
  • 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 described, for example, in EP-A 451 508 and EP-A 396 303.
  • 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.
  • the group (i) comprises monoethylenically unsaturated C3-Cs monocarboxylic acids such as, for example, 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 using C 2 -C 6 -olefins, vinylalkyl ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate. If the polymers of group (ii) contain vinyl esters in copolymerized form, these may also be partially or completely converted into vinyl alcohol Structural units are hydrolyzed. Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 4313909.
  • Group (iii) comprises (meth) acrylic esters of C 1 -C 8-alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 -amine, N-vinylformamide and N-vinylimidazole.
  • Suitable polymeric carboxylic acid group-containing compounds are also homopolymers of the monoethylenically unsaturated Cs-Cs monocarboxylic acids, such as e.g. Acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, e.g.
  • 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 EP-A-0877002.
  • 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-methacrylic acid amido-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 C4-C8 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
  • the weight The 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 C3-C6 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 abovementioned monomers of groups (ii) and (iii).
  • Ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyhydric Ci-C 22 -alcohols see US-A-5756456.
  • polyglyoxylic acids as described, for example, in EP-B-001004, US Pat. No. 5,399,286, DE-A-4106355 and EP-A-656914.
  • the end groups of the polyglyoxylic acids can have different structures.
  • polyamidocarboxylic acids and modified polyamidocarboxylic acids are suitable; these are known, for example, from EP-A-454126, EP-B-51 1037, WO-A94 / 01486 and EP-A-581452.
  • polyaspartic acids or co-condensates of aspartic acid with other amino acids, C4-C25 mono- or dicarboxylic acids and / or C4-C25 mono- or - diamines can 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 1 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines. Among the polymeric compounds containing carboxylic acid groups, polyacrylic acids are also preferred in partially or completely neutralized form.
  • organic builders iminodisuccinic acid, oxydibasic acid, aminopolycarboxylates, alkylpolyaminocarboxylates, 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. Furthermore, 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 ( eg 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 1-hydroxyethane 1 - (1, 1-diphosphonic acid); H EDP), at least one phosphate.
  • at least one carbonate eg sodium carbonate
  • at least one silicate eg sodium disilkat
  • 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 ingredients are preferably contained in the following amounts:
  • 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 abovementioned 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 enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.
  • 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), Cellucome® (from Novozymes ), Endolase, Puradax® (from Genencor)].
  • Suitable amylases include in particular ⁇ -amylases (EC number 3.2.1.1), iso-amylases, pululanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • Suitable lipases are esterases, such as Lipex and Lipolase.
  • Examples of lipolytic enzymes are the known cutinases.
  • the dishwashing agent according to the invention preferably contains at least one protease and / or amylase.
  • the dishwashing composition according to the invention preferably contains an enzyme mixture.
  • enzyme mixtures which contain or consist of the following enzymes are preferred:
  • Amylase, cellulase and lipase or lipolytic enzymes
  • Protease protease
  • lipase or lipolytic enzymes
  • cellulase cellulase
  • protease and / or amylase-containing mixtures are particularly preferred.
  • Preferred proteases in the aforementioned mixtures are subtilisin-type proteases (Savinase, etc .; EC No. 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.
  • 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; Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, for example, sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; - ⁇ , ⁇ -diacylated and ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacylated amines, for example ⁇ , ⁇ , ⁇ ', ⁇ '- tetraacetylmethylenediamine and ethylenediamine (TAED), ⁇ , ⁇ -diacetylaniline, N, N-diacetyl -ptoluidine or 1, 3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin; N-alkyl-N-
  • 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. No. 5,360,569 and EP-A 453,003.
  • Particularly effective bleach catalysts are manganese complexes, which are described, for example, in WO-A 94/21777.
  • Such compounds in the case of their use in detergents and cleaners, 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.
  • 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 having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for
  • ethoxylated alcohols include, for example, C 12 -Ci4-alcohols with 3 EO, 4 EO or 7 EO, Cn-alcohol with 7 EO, C13-Cis alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 2 -C 8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci2-Ci4 alcohol containing 3 EO and Ci2-cis-alcohol containing 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Also suitable are alcohol ethoxylates which have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • fatty alcohols with more than 12 EO 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.
  • nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are obtainable by simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.
  • nonionic surfactants and alkyl glycosides of the general formula (1) are also possible.
  • R a O (G) y (1) are used, wherein R a is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G for a glycoside unit with 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization y which determines the distribution ment 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 as described, for example, in Japanese Patent Application JP 58/217598 or preferably prepared according to the process described in International Patent Application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula (2),
  • R c is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [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 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 Ra is a linear, branched or cyclic Alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C 4 -alkyl or phenyl radicals, and [Z] 1 being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [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 converted, for example, according to WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.
  • Suitable anionic surfactants are, for example, those of the sulfonate type and sulfates.
  • surfactants of the sulfonate type preferably C9-C13 alkylbenzenesulfonates, Olefinsulfonate, i. Mixtures of alkene and Hydroxyalkansul- fonates and disulfonates, as obtained for example from Ci2-Ci8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • alkanesulfonates which are obtained from C 12 -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.
  • 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 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred.
  • 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. From a washing-technical point of view, preference is given to the C 12 -C 16 -alkyl sulfates and C 12 -C 20 -alkyl sulfates and also C -C -alkyl sulfates. Also, 2,3-alkyl sulfates, which are prepared, for example, according to US Pat. Nos.
  • the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-C2i alcohols, such as 2-methyl-branched Cg-Cn alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci 2 -Ci 8 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 Ce-Cie 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 Al k (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 including the soaps may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di-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 Cs-C16-dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.
  • Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines such as e.g. C ⁇ -Cis-alkylbetaines or C ⁇ -Cis-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. They are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butane diol, glycerol, diglycol, propyl or butyl diglycol, 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, i-but
  • 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.
  • the gel-type detergents and cleaners are preferably gelatinous dishwashing agents, of which gel-type machine dishwashing detergents are particularly preferred. In particular, 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-like 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.
  • gelatinous dishwashing detergent according to the invention preferably comprises the following constituents:
  • At least one builder also referred to as sequestering agent, builder, complexing agent, chelator, chelating agent or softening agent
  • e3) optionally at least one further additive, which is preferably selected from surfactants other than a), bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, solubilizers and organic solvents.
  • surfactants other than a bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, solubilizers and organic solvents.
  • constituents are preferably present in the following proportions in the gel dishwashing detergent according to the invention: a) at least one compound of the formula I: from 0.1 to 20% by weight;
  • At least one builder from 5 to 80% by weight
  • At least one bleaching agent from 0 to 30% by weight;
  • e2) at least one thickener: from 0.1 to 8% by weight;
  • e3) at least one further additive: from 0 to 25% by weight.
  • 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 abovementioned constituents are particularly preferably contained in the following proportions in the gel dishwashing detergent according to the invention: a) at least one compound of the formula I: from 0.1 to 10% by weight;
  • At least one builder from 5 to 60% by weight
  • At least one bleaching agent from 0 to 30% by weight;
  • e2) at least one thickener: from 0.1 to 6% by weight;
  • e3) at least one further additive: from 0 to 25% by weight.
  • 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 abovementioned constituents are present in the following proportions in the gel dishwashing detergent according to the invention: at least one compound of the formula I: from 0.1 to 10% by weight;
  • At least one builder from 5 to 40% by weight;
  • At least one enzyme from 0.1 to 6% by weight;
  • At least one bleaching agent from 0 to 25% by weight
  • At least one thickener from 0.3 to 5% by weight
  • At least one further additive from 0 to 25% by weight.
  • 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 carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose 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.
  • 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 crosslinked with propylene
  • Acrylic acid e.g. the Carbopo D grades from BF Goodridge (eg Carbopol® 676, 940, 941, 934 and the like) or the Polyge D grades from 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 Acuso D brands from Rohm & Haas (eg Acusol® 820 or 1206A), copolymers of two or more monomers , which are selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters, eg Copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl me
  • Aculyn® and Acuso D brands from Rohm & Haas eg Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830
  • crosslinked high molecular weight acrylic acid copolymers for example with an allyl ether of sucrose or pentaerythritol cross-linked copolymers of C 1 -C 30 -alkyl acrylates having one or more monomers 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-1 19 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-1 19 from ISP
  • Polyethylene glycols, polyamides, polyimines and polycarboxylic acids e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-1 19 from ISP.
  • 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 susceptible to hydrolysis.
  • the alcohol to be alkoxylated is treated with an aqueous KOH solution which contains 50% by weight of KOH. added.
  • 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.
  • N2 a pre-pressure of about 1.3 bar N2 is set and the temperature is raised to 120.degree.
  • 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 N2, 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 the yield is determined (> 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 base dishwashing detergent (48 parts of sodium metasilicate x 5H2O, 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; 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 dishwashing machine was set artificially in this experiment (by drilling on the spray arm, position of the nozzles) in order to obtain a wider range which makes products more distinguishable.
  • the rotational speed was measured at 40, 50 and 60 ° C.
  • the following table lists rotor speeds in rpm at different temperatures.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne l'utilisation de thioéthers (oxydés) d'alcoxylates d'alcools dans des détergents et produits de nettoyage, en particulier dans des détergents pour vaisselle, et des détergents et produits de nettoyage, en particulier des détergents pour vaisselle, qui contiennent des thioéthers (oxydés) d'alcoxylates d'alcools. Ces thioéthers (oxydés) conviennent en particulier comme tensioactifs à fonction de rinçage (tensioactif de rinçage). Le terme "oxydé" se rapporte ici à l'atome de soufre dans le thioéther, qui peut se trouver, sous forme oxydée, sous forme de sulfoxyde (SO) ou de sulfonyle (SO2).
PCT/EP2012/050421 2011-01-13 2012-01-12 Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage WO2012095481A1 (fr)

Priority Applications (9)

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
BR112013017438A BR112013017438A2 (pt) 2011-01-13 2012-01-12 uso de compostos, e, composição para limpeza ou lavagem
JP2013548840A JP5931920B2 (ja) 2011-01-13 2012-01-12 洗剤及び清浄剤における、アルコールアルコキシレートの場合によって酸化されたチオエーテルの使用
KR1020137018367A KR101891479B1 (ko) 2011-01-13 2012-01-12 세제 및 세정제에서의 알코올 알콕실레이트의 임의로 산화된 티오에테르의 용도
RU2013137510/04A RU2597014C2 (ru) 2011-01-13 2012-01-12 Применение, при необходимости, окисленных простых тиоэфиров алкоксилатов спирта в моющих и чистящих средствах
CA2822855A CA2822855A1 (fr) 2011-01-13 2012-01-12 Utilisation de thioethers eventuellement oxydes d'alcoxylates d'alcools dans des detergents et produits de nettoyage
MX2013007891A MX2013007891A (es) 2011-01-13 2012-01-12 Uso de tioeteres opcionalmente oxidados de alcoxilatos de alcohol en detergentes y agentes de limpieza.
ES12700080.0T ES2686304T3 (es) 2011-01-13 2012-01-12 Uso de tioéteres de alcoholalcoxilatos dado el caso oxidados en detergentes y agentes de limpieza
CN201280005218.5A CN103314094B (zh) 2011-01-13 2012-01-12 醇烷氧基化物的任选氧化的硫醚在洗涤剂和清洗剂中的用途

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EP11150875 2011-01-13
EP11150875.0 2011-01-13

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CA (1) CA2822855A1 (fr)
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US9184057B2 (en) 2011-03-18 2015-11-10 Basf Se Method for manufacturing integrated circuit devices, optical devices, micromachines and mechanical precision devices having patterned material layers with line-space dimensions of 50 nm and less
EP3087054A4 (fr) * 2013-12-27 2017-10-25 Novus International Inc. Tensioactifs ethoxylés
WO2017220422A1 (fr) 2016-06-23 2017-12-28 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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CN115821276A (zh) * 2022-07-07 2023-03-21 中山市浩科化工科技有限公司 一种新能源金属用的强力清洗剂及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9184057B2 (en) 2011-03-18 2015-11-10 Basf Se Method for manufacturing integrated circuit devices, optical devices, micromachines and mechanical precision devices having patterned material layers with line-space dimensions of 50 nm and less
EP3087054A4 (fr) * 2013-12-27 2017-10-25 Novus International Inc. Tensioactifs ethoxylés
WO2017220422A1 (fr) 2016-06-23 2017-12-28 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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CA2822855A1 (fr) 2012-07-19
MX2013007891A (es) 2013-08-27
RU2013137510A (ru) 2015-02-20
RU2597014C2 (ru) 2016-09-10
BR112013017438A2 (pt) 2016-09-27
CN103314094B (zh) 2016-05-25
KR101891479B1 (ko) 2018-08-24
ES2686304T3 (es) 2018-10-17
CN103314094A (zh) 2013-09-18
EP2663625B1 (fr) 2018-06-27
EP2663625A1 (fr) 2013-11-20
JP2014502665A (ja) 2014-02-03
JP5931920B2 (ja) 2016-06-08
KR20140040085A (ko) 2014-04-02

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