EP1321512A2 - Composition de rincage et nettoyage - Google Patents

Composition de rincage et nettoyage Download PDF

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Publication number
EP1321512A2
EP1321512A2 EP02027459A EP02027459A EP1321512A2 EP 1321512 A2 EP1321512 A2 EP 1321512A2 EP 02027459 A EP02027459 A EP 02027459A EP 02027459 A EP02027459 A EP 02027459A EP 1321512 A2 EP1321512 A2 EP 1321512A2
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EP
European Patent Office
Prior art keywords
alkyl
alcohol
acid
ether
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP02027459A
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German (de)
English (en)
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EP1321512A3 (fr
Inventor
Manfred Dr. Weuthen
Michael Elsner
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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Priority claimed from DE10162696A external-priority patent/DE10162696A1/de
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1321512A2 publication Critical patent/EP1321512A2/fr
Publication of EP1321512A3 publication Critical patent/EP1321512A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the invention relates to detergents and cleaning agents containing a combination of hydroxy mixed ether and selected anionic surfactants, optionally further nonionic surfactants, and the use such mixtures in detergents and cleaning agents.
  • Means for rinsing and cleaning hard, non-textile surfaces should mostly develop a small foam volume when used, which will decrease significantly within a few minutes.
  • Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of various types with or without the addition of builders, solubilizers (hydrotropes) or solvents. To prove the effectiveness at the beginning of the cleaning work, the consumer wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped off.
  • agents of the type mentioned are usually mixed with low-foaming nonionic surfactants.
  • liquid or solid rinse aid which can be added separately, or already in a ready-to-use form with the detergent and / or regeneration salt together ("2 in 1", “3 in 1", eg in the form of tabs and powders), ensures that the water runs off the washware as completely as possible, so that the different surfaces are residue-free and shiny at the end of the wash program.
  • Commercial rinse aids are mixtures of, for example, nonionic surfactants, solubilizers, organic acids and solvents, water and, if appropriate, preservatives and fragrances.
  • the task of the surfactants in these agents is to influence the interfacial tension of the water so that it can run off the wash ware in a thin, coherent film, so that no water drops, streaks or films remain during the subsequent drying process (so-called wetting effect).
  • surfactants in rinse aids also have to dampen the foam that arises from food residues in the dishwasher. Since the rinse aids mostly contain acids to improve the clear dry effect, the surfactants used must also be relatively insensitive to hydrolysis against acids.
  • Rinse aids are used both in the home and in commercial areas. In household dishwashers, the rinse aid is added after the pre-rinse and cleaning cycle at just under 40 ° C - 65 ° C.
  • the rinse aid must also have a foam-suppressing effect, be temperature-stable with a strong temperature gradient of 85 ° C - 35 ° C and also be sufficiently stable against alkali and active chlorine.
  • German published patent application DE 19738866 describes surfactant mixtures composed of hydroxy mixed ethers and nonionic surfactants, such as fatty alcohol polyethylene glycol / polypropylene glycol ether, optionally end-capped, which have very good foaming behavior and show excellent rinse aid effects in rinse aid. From German published patent application DT 2432757 it is known that hydroxy mixed ethers are used as foam suppressants in washing, rinsing and cleaning agents.
  • the object of the present invention was to develop detergents and cleaning agents which at the same time have good foam and cleaning behavior, in particular very good drainage behavior on plastic surfaces and high material compatibility of the surfaces to be cleaned.
  • Hydroxy mixed ether mixtures should also be provided, which can be incorporated particularly advantageously into solid formulations.
  • the problem was solved by using hydroxy mixed ethers in combination with selected anionic surfactants. This combination of hydroxy mixed ethers and selected anionic surfactants dissolves later in the cleaning liquor due to its higher melting points and takes effect at different times and in higher concentrations. This effect can be used particularly advantageously in rinse aid applications.
  • the agents according to the invention particularly impress with their colorless, clear appearance, which makes incorporation into a large number of detergents and cleaning agents possible without a complex bleaching process.
  • Hydroxy mixed ethers of the formula (I) are known from the literature and are described, for example, in German application DE 19738866 . They are produced by reacting 1,2-epoxyalkanes (R 2 CHOCH 2 ), where R 2 is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.
  • Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols of the formula R 1 -OH having 4 to 18 carbon atoms, where R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands.
  • Suitable straight-chain alcohols are butanol-1, capron, ⁇ nanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmity alcohol, heptadecanol-1, stearyl alcohol, nonadecanol 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as are obtained in the high-pressure hydrogenation of technical methyl esters based on fats and oils.
  • branched alcohols examples include so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group.
  • Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
  • the alcohols are used in the form of their alkoxylates, which are prepared in a known manner by reacting the alcohols with ethylene oxide and / or propylene oxide.
  • the alkylene units are "blocked ".
  • the detergents and cleaning agents according to the invention contain 0.01 to 25% by weight, preferably 0.025 to 20% by weight and in particular 0.1 to 15% by weight of hydroxy mixed ethers of the formula (I), calculated as active substance, based on the agent.
  • Active substance is defined as the mass of surfactants (calculated as 100% pure substance) that are contained in the detergent and cleaning agent .
  • the rinsing and cleaning agents contain anionic surfactants.
  • anionic surfactants are soaps, alkyl benzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerin ether sulfates, mono- ether sulfate sulfates , hydroxymischogether sulfate, fatty acid ether sulfate sulfates, Mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid
  • hydroxy mixed ethers with anionic surfactants are selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, Alkylbenzenesulfonates and alkanesulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates.
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (II) R 16 O-SO 3 X (VIII) in which R 16 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol as well as their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on vegetable C 12/14 fatty alcohols in the form of their sodium salts are particularly preferred.
  • ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • ether sulfates which follow the formula (III) are suitable R 17 O- (CH 2 CH 2 O) a SO 3 X (III) in which R 17 represents a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol,
  • the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
  • Alkylbenzenesulfonates preferably follow the formula (IV) , R 18 -Ph-SO 3 X (IV) in which R 18 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.
  • Alkane sulfonates are taken to mean compounds of the formula (V) .
  • R 20 and R 21 represent alkyl radicals, where R 20 and R 21 together should not have more than 50 carbon atoms.
  • the detergents and cleaning agents contain 0.1 to 20% by weight, preferably 0.25 to 15% by weight, in particular 0.4 to 10% by weight, of anionic surfactants , calculated as active substance, based on the agent.
  • the remaining 100% by weight of the detergents and cleaning agents can represent auxiliary substances and water.
  • the agents according to the invention contain further nonionic surfactants.
  • nonionic surfactants are alkyl and / or alkenyl oligoglycosides, alkoxylates of Alkanols, end-capped alkoxylates of alkanols without free OH groups, alkoxylated fatty acid lower alkyl esters, Amine oxides, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, Fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, fatty acid N-alkylglucamides, Protein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, Sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, may have a conventional, but preferably a narrow homolog distribution.
  • the further nonionic surfactants are preferably selected from the group formed by alkyl and / or Alkenyl oligoglycosides, alkoxylates of alkanols, especially fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) or fatty alcohol polypropylene glycol / polyethylene glycol ether (FAPO / EO), end group-capped Alkoxylates of alkanols without a free OH group, especially end-capped groups Fatty alcohol polyethylene glycol / polypropylene glycol ether or end-capped fatty alcohol polypropylene glycol / polyethylene glycol ether, alkoxylated fatty acid lower alkyl esters and amine oxides.
  • alkyl and / or Alkenyl oligoglycosides alkoxylates of alkanols, especially fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) or fatty alcohol polypropylene glyco
  • the detergents and cleaning agents according to the invention preferably contain alkyl and / or alkenyl oligoglycosides of the formula (VI).
  • alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the alkyl radical R 5 can be derived from primary saturated alcohols. Typical examples are butanol-1, capron, ⁇ nanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol, palmity alcohol, heptadecanol-1, stearyl alcohol, isostearecanol -1, arachidyl alcohol, heneicosanol-1, and behenyl alcohol and their technical mixtures, such as are obtained for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkenyl radical R 5 can be derived from primary unsaturated alcohols.
  • unsaturated alcohols are undecen-1-ol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, and the technical mixtures thereof, which can be obtained as described above, and their technical mixtures.
  • Alkyl or alkenyl radicals R 5 which are derived from primary alcohols having 6 to 16 carbon atoms are preferred. Particularly suitable are alkyl oligoglucosides with a chain length of C 8 -C 10 , which are obtained as a preliminary step in the separation of technical C 8 -C 18 coconut fatty alcohol by distillation and which may be contaminated with a proportion of less than 6% by weight of C12 alcohol, as well as alkyl oligoglucosides Basis of technical C 9/11 oxo alcohols.
  • the alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 14 carbon atoms.
  • Alkyl and / or alkenyl oligoglycosides of the formula (II) are preferably used, where p is a number from 1 to 3 and R5 represents an alkyl radical having 6 to 16 carbon atoms.
  • the detergents and cleaning agents according to the invention preferably contain 0.01 to 30% by weight, preferably 0.1 to 20% by weight and in particular 0.2 to 15% by weight of alkyl and / or alkenyl oligoglycosides of the formula (VI) calculated as active substance, based on the agent.
  • fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (VIII), which are optionally end-capped, R 8 O [CH 2 (CH 3 ) CHO] q (CH 2 CH 2 O) r R 9 (VIII) in which R 8 represents an alkyl and / or alkenyl radical having 8 to 22 C atoms, R 9 represents H or an alkyl radical having 1 to 8 C atoms, q represents a number from 1 to 5 and r represents a number of 0 up to 15.
  • the agents according to the invention contain fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (VII) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 1 to 10, and m represents 0 and R 7 represents hydrogen.
  • R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
  • n is a number from 1 to 10
  • m represents 0
  • R 7 represents hydrogen.
  • These are addition products of 1 to 10 moles of ethylene oxide with monofunctional alcohols.
  • the alcohols described above, such as fatty alcohols, oxo alcohols and Guerbet alcohols are suitable as alcohols. Of those alcohol ethoxylates, those are also suitable which have a narrow homolog distribution.
  • R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
  • n is a number from 2 to 7
  • m is a number of 3 to 7
  • R 7 represents hydrogen.
  • the end group-capped compounds of formula (VII) are capped with an alkyl group having 1 to 8 carbon atoms (R 7 ).
  • R 7 alkyl group having 1 to 8 carbon atoms
  • Such compounds are often referred to in the literature as mixed ethers.
  • Suitable representatives are methyl-capped compounds of the formula (VII) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, n is a number from 2 to 7, m is a number from 3 to 7 and R 7 represents a methyl group.
  • Such compounds can easily be prepared by reacting the corresponding non-end-capped fatty alcohol polyethylene glycol / polypropylene glycol ether with methyl chloride in the presence of a base.
  • Suitable representatives of alkyl-capped compounds are those of the formula (VII) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 5 to 15, m is 0 and R 7 represents an alkyl group with 4 to 8 carbon atoms.
  • the end group closure is preferably carried out with a straight-chain or branched butyl group by the corresponding fatty alcohol polyethylene glycol ether with n-butyl chloride or with tert. Butyl chloride is reacted in the presence of bases.
  • end-capped fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (VIII) may be present.
  • Such connections are described, for example, in German published patent application DE-A1- 43 23 252.
  • Particularly preferred representatives of the compounds of the formula (VIII) are those in which R 8 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, q is a number from 1 to 5, r is a number of 1 to 6 and R 9 represents hydrogen.
  • R 8 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
  • q is a number from 1 to 5
  • r is a number of 1 to 6
  • R 9 represents hydrogen.
  • These are preferably addition products of 1 to 5 mol of propylene oxide and of 1 to 6 mol of ethylene oxide with monofunctional alcohols, which have already been described as suitable in connection with the hydroxy mixed ethers.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (IX) R 10 CO- (OCH 2 CHR 11 ) w OR 12 in which R 10 CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R 11 for hydrogen or methyl, R 12 for linear or branched alkyl radicals with 1 to 4 carbon atoms and w for numbers from 1 to 20 stands.
  • Typical examples are the formal insert products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical grade and erucas.
  • the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
  • the preparation of the amine oxides of the formula (X) starts from tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide.
  • R 13 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 14 and R 15 independently of one another are R 13 or an optionally hydroxy-substituted alkyl radical with 1 to 4 carbon atoms.
  • Amine oxides of the formula (X) are preferably used, in which R 13 and R 14 are C 12/14 and C 12/18 cocoalkyl radicals and R 15 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (X) in which R 13 represents a C 12/14 or C 12/18 cocoalkyl radical and R 14 and R 15 have the meaning of a methyl or hydroxyethyl radical.
  • alkylamido amine oxides of the formula (XI) , the alkylamido radical R 23 CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from C 12/14 or C 12/18 - fatty acids with amines.
  • R 24 represents a linear or branched alkylene group with 2 to 6, preferably 2 to 4 carbon atoms and R 14 and R 15 have the meaning given in formula (X) .
  • the further nonionic surfactants can be present in the agents according to the invention in amounts of 0.1 to 15 % By weight, preferably 0.5 to 10% by weight, in particular 1 to 8% by weight, calculated as Active substance, based on the funds.
  • auxiliaries according to the invention can be used as auxiliaries, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights from 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800,000. or in particular contain butyl diglycol.
  • Abrasive materials such as quartz or wood powder or polyethylene friction bodies can also be contained. In many cases an additional bactericidal effect is desired, which is why the agents can contain cationic surfactants or biocides, for example glucoprotamine.
  • Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and its salt, and inorganic phosphonic acids.
  • peroxy bleaching agents sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 0.1 to 40% by weight.
  • the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred.
  • Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus sub-tilis, Bacillus lichenformis and Strptomyces griseus, are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.1 to 6, preferably 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the agents can contain further enzyme stabilizers .
  • enzyme stabilizers 0.5 to 1% by weight sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • foam inhibitors When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents.
  • Suitable foam inhibitors contain, for example, known organo-olysiloxanes and / or paraffins or waxes.
  • Foam regulators such as soap, fatty acids, in particular coconut fatty acid and palm kernel fatty acid, may also be included.
  • thickeners for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% by weight of maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are also particularly suitable. Examples of these are polymers available under the name Carbopol® 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.
  • Another object of the present invention is the use of hydroxy mixed ethers for rinsing and cleaning hard surfaces, preferably in the household and in the industrial and institutional fields. It is particularly suitable for use in dishwashing detergents, rinse aids, bathroom cleaners, floor cleaners, cleaners based on the clean shower concept (e.g. bathroom cleaners, which are sprayed onto walls and fittings before and after showering so that the water and soap residues run off better, and thereby Wiping is not necessary), cockpit cleaner (car, plane, ship, motorcycle), window cleaner and all-purpose cleaner.
  • Hard surfaces include ceramic surfaces, metal surfaces, painted surfaces, plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood.
  • hydroxy mixed ethers (a) and anionic surfactants (b) for rinsing and cleaning hard surfaces, in particular in automatic dishwashing detergents and / or rinse aids, which then have a particularly high level of plastic compatibility and show very good drainage behavior.
  • hydroxy mixed ethers (a) and anionic surfactants (b) in Combination with alkyl and / or alkenyl oligoglycosides in the cleaning areas listed so far.
  • the wetting properties of surfactant solutions against plastics were determined in a test based on the conditions / test parameters in a commercial dishwasher, but without the use of such.
  • plastic test specimens measuring 20 x 5 x 0.4 cm are first cleaned with 1% NaOH and then with isopropanol.
  • the test specimens pretreated in this way are then immersed in the solution to be tested and immediately removed again.
  • the evaluation is carried out visually by drawing up a ranking list or on a scale from 1 to 5.
  • 5 means that spontaneous tearing of the liquid film occurs and the wetting is completely eliminated.
  • Grade 5 is obtained when water is used.
  • the grade 1 means complete wetting of the plastic surface with an even flow of the liquid film.
  • Grade 1 is obtained when using Na-LAS (eg Maranil A 55 / COGNIS).
  • test parameters water hardness 2 ° d; salt load 700 ppm temperature 60 ° C; surfactant 0.05% AS
  • Examples V1 and V4 are comparative examples and Examples 1 to 12 are those examples according to the invention.
  • Dishwasher detergent tablets with rinse aid were first prepared from the compositions according to the invention (1 to 3; see Table 2-5) and placed in the dishwasher.
  • a Miele G 661 SC with the "Universal 50/55 ° C" cleaning program was used as the dishwasher.
  • the water hardness was about 20 ° dH.
  • the dishwasher was loaded with 20 glasses, black porcelain plates, blue PP bowls and 20 pieces of cutlery.
  • 50 g minced meat (pork: beef, 1: 1) was fried with 2 g fat and then mixed with a sauce made from 100 ml water, 1 g sauce binder and 2.5 g instant sauce powder.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP02027459A 2001-12-19 2002-12-10 Composition de rincage et nettoyage Withdrawn EP1321512A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10162696 2001-12-19
DE10162696A DE10162696A1 (de) 2001-02-01 2001-12-19 Spül- und Reinigungsmittel

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EP1321512A3 EP1321512A3 (fr) 2003-09-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009033830A1 (fr) * 2007-09-10 2009-03-19 Henkel Ag & Co. Kgaa Procédé de nettoyage
WO2013007410A1 (fr) * 2011-07-14 2013-01-17 Henkel Ag & Co. Kgaa Produits de rinçage et de lavage pour vaisselle
WO2013056863A1 (fr) * 2011-10-21 2013-04-25 Henkel Ag & Co. Kgaa Produits de rinçage et de lavage pour vaisselle

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US7485613B2 (en) * 2004-12-01 2009-02-03 Venus Laboratories, Inc. Low foaming carpet-cleaning detergent concentrate comprised of ethylene oxide adduct and without phosphates
US7459420B2 (en) * 2004-12-01 2008-12-02 Vlahakis E Van Automatic dishwashing detergent comprised of ethylene oxide adduct and without phosphates
CA3066116A1 (fr) * 2017-07-28 2019-01-31 Croda, Inc. Formulation de nettoyage comprenant un additif de solvant
CN115698239B (zh) * 2020-07-30 2024-08-27 花王株式会社 润滑剂

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DE3723873A1 (de) * 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
DE4323252C2 (de) * 1993-07-12 1995-09-14 Henkel Kgaa Klarspüler für die maschinelle Reinigung harter Oberflächen
DE19751859A1 (de) * 1997-11-22 1999-07-29 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
DE19962886A1 (de) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE19962885A1 (de) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
DE19962883A1 (de) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Waschmitteltabletten
DE19962859A1 (de) * 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Feste Waschmittel
US20030158071A1 (en) * 2000-01-28 2003-08-21 Joerg Kahre Rinsing and cleaning agents
DE10003752A1 (de) * 2000-01-28 2001-08-02 Cognis Deutschland Gmbh Spül- und Reinigungsmittel
DE10019344A1 (de) * 2000-04-18 2001-11-08 Cognis Deutschland Gmbh Wasch- und Reinigungsmittel
DE10031620A1 (de) * 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Flüssigwaschmittel
ATE276340T1 (de) * 2001-02-01 2004-10-15 Cognis Deutschland Gmbh Spül- und reinigungsmittel
DE10162696A1 (de) * 2001-02-01 2002-09-19 Cognis Deutschland Gmbh Spül- und Reinigungsmittel

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009033830A1 (fr) * 2007-09-10 2009-03-19 Henkel Ag & Co. Kgaa Procédé de nettoyage
WO2013007410A1 (fr) * 2011-07-14 2013-01-17 Henkel Ag & Co. Kgaa Produits de rinçage et de lavage pour vaisselle
WO2013056863A1 (fr) * 2011-10-21 2013-04-25 Henkel Ag & Co. Kgaa Produits de rinçage et de lavage pour vaisselle

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US20030166488A1 (en) 2003-09-04

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