EP1308499A1 - Melangé tensioactif avec hydroxy-ethers mixtes et polyméres - Google Patents

Melangé tensioactif avec hydroxy-ethers mixtes et polyméres Download PDF

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Publication number
EP1308499A1
EP1308499A1 EP02023859A EP02023859A EP1308499A1 EP 1308499 A1 EP1308499 A1 EP 1308499A1 EP 02023859 A EP02023859 A EP 02023859A EP 02023859 A EP02023859 A EP 02023859A EP 1308499 A1 EP1308499 A1 EP 1308499A1
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alkyl
surfactant mixtures
alcohol
mixtures according
polymers
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German (de)
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EP1308499B1 (fr
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Ditmar Kischkel
Manfred Dr. Weuthen
Michael Elsner
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust

Definitions

  • the invention relates to surfactant mixtures of hydroxy mixed ethers and polymers, optionally in Combination with ingredients common in detergents and cleaning agents, if necessary with additional ones nonionic surfactants and anionic surfactants, and the use of such surfactant mixtures for the production of cleaning solutions with improved effectiveness against re-soiling.
  • Rinse aid is therefore used to ensure that dishes are clear and spotless.
  • the addition of liquid or solid rinse aid, which can be added separately, or already ready to use Dosage form together with the cleaning agent and / or regeneration salt ("2 in 1", “3 in 1", e.g. in the form of tabs and powders) ensures that the water is as complete as possible expires so that the different surfaces are residue-free at the end of the wash program are shiny.
  • rinse aids are mixtures e.g. from nonionic surfactants, solubilizers, organic acids and solvents, water and possibly preservatives and fragrances.
  • the task of the surfactants in these agents is to increase the interfacial tension of the water influence that it should run off the dishes in a thin, coherent film can, so that no water drops, streaks or films remain during the subsequent drying process (so-called network effect or network behavior). That is why surfactants must be used in rinse aid also dampen the foam from food residues in the dishwasher. Because the rinse aid mostly contain acids to improve the clear dry effect, the used must Surfactants are also relatively insensitive to hydrolysis against acids.
  • Rinse aids are used both in the home and in commercial areas.
  • the rinse aid is usually after the pre-rinse and cleaning cycle at almost 40 ° C-65 ° C added.
  • the commercial dishwashers work with only one cleaning fleet, which only is renewed by adding the rinse aid solution from the previous rinsing process. So it takes place There is no complete water exchange during the entire washing program. Therefore, the Rinse aid also has a foam-suppressing effect, being temperature-stable when there is a steep temperature gradient of 85-35 ° C and also be sufficiently stable against alkali and active chlorine.
  • rinse aids to clean or rinse them Equip surfaces in such a way that they become dirty during the next cleaning process easier to remove.
  • German Offenlegungsschrift DE-A1 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 aids. From German Offenlegungsschrift DE-OS 2432757 it is known that hydroxy mixed ethers can be used as foam suppressants in washing, rinsing and cleaning agents.
  • the object of the present invention was to provide surfactant mixtures for the production of detergents and cleaning agents To provide, at the same time, good foam and cleaning behavior, in particular however, a very good drainage behavior, due to an improved wetting behavior on different Surfaces, show. This creates a particularly good visual on the cleaned surfaces Impression that is characterized by an increased gloss. Furthermore, a high material compatibility, especially with plastics. In addition, simplified should be fixed Have cleaner formulations made. Furthermore, the surfaces to be cleaned or rinsed be equipped in such a way that dirt is present during the next cleaning process easier to remove.
  • the object could be achieved by the combination of hydroxy mixed ethers according to the invention and polymers in the mixing ratio according to the invention. Due to the very good wetting ability a spotless shine of the surfaces to be cleaned is achieved. The addition of polymers to rinse aid leads to the otherwise strongly adhering and often critical soiling during the next cleaning such as. starchy soiling, can be completely removed. These stains can be removed without additional manual processing of the wash ware.
  • Hydroxy mixed ethers of the formula (I) are usually prepared by reacting 1,2-epoxyalkanes (R 3 CHOCH 2 ), where R 3 is an alkyl and / or alkenyl radical having 4 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, where R 1 for an aliphatic, saturated, straight-chain or branched alkyl radical having 4 to 22, preferably 6 to 16, in particular 8 is up to 10 carbon atoms.
  • Suitable straight-chain alcohols are butanol-1, caprone alcohol, enanthal alcohol, caprylic alcohol, pelargonium alcohol, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmity alcohol, heptadecanol-1, aradachyl alcohol, stearyl alcohol Heneicosanol-1, behenyl alcohol and their technical mixtures, as they occur 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 by reacting the alcohols in any order (randomized, with statistical distribution by mixing the alkoxylation reagents beforehand) with ethylene oxide and / or propylene oxide and / or butylene oxide, or by blockwise conversion with the Alkylene oxides in a certain order (blocked).
  • Hydroxy mixed ethers which have proven to be particularly suitable from an application point of view in the surfactant mixtures, follow the formula (I) in which x is 0 and y is a number from 1 to 80, preferably from 20 to 60, in particular from 35 to 50.
  • those surfactant mixtures are suitable which contain hydroxy mixed ethers in which x is 0 and y is a number from 20 to 60, preferably 35 to 50.
  • R 1 is a linear alkyl radical having 4 to 22, particularly preferably 8 to 10, carbon atoms
  • R 3 is a linear alkyl radical having 8 to 12 carbon atoms.
  • R 1 is a branched alkyl radical having 8 to 16 carbon atoms and y is 40 to 60.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone-vinylimidazole polymers, such as, for example, Luviquat®® products (BASF) of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiamethylene-triaminophenylaminodiaminophenyl
  • Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, non-crosslinked acrylamide acrylamide and polyacrylamide acrylamide / polyacrylamide acrylamide / polyacrylamide acrylamide / non-crosslinked acrylamide and polyamides with non-crosslinked acrylamide and polyamides , Octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone
  • the surfactant mixtures contain cationic polymers which have monomer units of the formula (Ia) wherein n is a number between 2 and 4, preferably 3, R 1 represents hydrogen or a methyl group and R 2 , R 3 and R 4 can be the same or different and represents hydrogen or a C 1-4 alk (en) yl group stand, X- represents an anion from the group of halide anions or a monoalkyl anion of sulfuric acid semiesters.
  • the polymers preferably contain the monomer units of the formula (Ia) in a proportion of 10 mol% to 80 mol%, particularly preferably 20 mol% to 60 mol%.
  • the polymers have a significant soil release effect.
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like
  • olefins such as ethylene, propylene and butene
  • alkyl esters of unsaturated carboxylic acids in particular esters of acrylic acid and methacrylic acid
  • the alcohol components of which have alkyl groups of 1 contain up to 6 carbon atoms, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and their hydroxy derivatives, such as 2-hydroxyethyl methacrylate, with unsaturated groups, optionally further substituted aromatic compounds such as styrene, methyl styrene, vinyl st
  • surfactant mixtures which contain polymers which are selected from the group which is formed from polymers or copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide, dialkyldiallyldiammonium salts, polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, guar, cellulose and starch derivatives, Polyadducts of ethylene oxide with ammonium groups, polyesters and polyamides with quaternary Side groups.
  • polyacrylic acid copolymers e.g. Versicol E11® or Glascol E11® (Allied Colloids), polyacrylamidopropanesulfonic acid e.g.
  • Rheothik 80-11® (Cognis), trimethylammonium propyl methacrylamide sodium acrylate ethyl acrylate polymer e.g. Polyquart® Ampho 149® Cognis. Also preferred are quaternized protein hydrolyzates e.g. Gluadin WQ ® (Cognis).
  • soil-repellant polymers is also preferred.
  • the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is particularly in the range of 750 to 5000, i.e. the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • Draw the polymers are characterized by an average molecular weight of about 5000 to 200,000 and can be one Block, but preferably have a random structure.
  • Preferred polymers are those with molar ratios Ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers that link Polyethylene glycol units with a molecular weight of 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples for commercially available polymers, the products are Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • the surfactant mixtures according to the invention contain the components (a) and (b) in a weight ratio of 0.1: 1 to 1000: 1, preferably 1: 1 to 100: 1, in particular preferably 5: 1 to 20: 1.
  • the surfactant mixtures according to the invention can contain nonionic co-surfactants which are selected from the group formed by 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 forms, fatty acid N-alkyl glucamides, protein hydrolyzates (especially vegetable Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates.
  • the nonionic surfactants contain polyglycol ether chains, they can be a conventional, but preferably have a narrow homolog distribution
  • the surfactant mixtures according to the invention contain alkyl and / or alkenyl oligoglycosides of the formula (II) , R 5 O- [G] p (II) in which R 5 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.
  • R 5 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10.
  • the 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, caprone alcohol, enanthal alcohol, capryll alcohol, pelargon alcohol, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol, palmity alcohol, heptadecanol-1, stearyl alcohol, isostearyl alcohol, isostyl alcohol , Heneicosanol-1, and behenyl alcohol and their technical mixtures, such as those obtained 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. Typical examples of 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.
  • alkyl oligoglucosides of chain length 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 C 12 alcohol, as well as alkyl oligoglucosides based on 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 whose degree of oligomerization is less than 2.0 and in particular between 1.2 and 1.7.
  • Alkyl and / or alkenyl oligoglycosides of the formula (II) are preferably used, where p represents numbers from 1 to 3 and R 5 represents an alkyl radical having 6 to 16 carbon atoms.
  • the further nonionic surfactants are preferably selected from the group formed by alkoxylates of alkanols, in particular fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) of the formula (III) or fatty alcohol polypropylene glycol / polyethylene glycol ether (FAPO / EO) of the formula (IV) , end-capped Alkoxylates of alkanols, especially end-capped fatty alcohol polyethylene glycol / polypropylene glycol ether or end-capped fatty alcohol polypropylene glycol / polyethylene glycol ether, and fatty acid lower alkyl esters and amine oxides.
  • alkoxylates of alkanols in particular fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) of the formula (III) or fatty alcohol polypropylene glycol / polyethylene glycol ether (FAPO / EO) of the formula (IV)
  • Fatty alcohol polyethylene glycol / polypropylene glycol ethers of the formula (III) which are optionally end-capped, are preferred, R 6 O (CH 2 CH 2 O) n [CH 2 (CH 3 ) CHO] m R 7 (III) used, in which R 6 represents an alkyl and / or alkenyl radical having 8 to 22 C atoms, R 7 represents H or an alkyl radical having 1 to 8 C atoms, n for a number from 1 to 40, preferably 1 to 30 , in particular 1 to 15, and m represents 0 or a number from 1 to 10.
  • fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV) which are optionally end-capped, R 8 O [CH 2 (CH 3 ) CHO] q (CH 2 CH 2 O) r R 9 (IV) 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 surfactant mixtures according to the invention furthermore preferably contain fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (III) 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 is 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 is 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.
  • 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.
  • Suitable representatives are methyl group-locked compounds of the formula (III) 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 2 to 7, m is a number from 3 to 7 and R 7 represents a methyl group.
  • 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 from 3 to 7
  • 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 (III) 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 (IV) may be present.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R 10 CO- (OCH 2 CHR 11 ) w OR 12 (V) 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. Conversion 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 (VI) 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, if appropriate hydroxy-substituted alkyl radical with 1 to 4 carbon atoms.
  • Amine oxides of the formula (VI) 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.
  • Amine oxides of the formula (VI) 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 are likewise preferred.
  • alkylamidoamine oxides of the formula (VII) , 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 C 12/14 or C 12 / 18 - Fatty acids with amines are formed.
  • R 24 represents a linear or branched alkylene group having 2 to 6, preferably 2 to 4 carbon atoms and R 14 and R 15 have the meaning given in formula (VI) .
  • nonionic surfactants that can be used are 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 are used.
  • anionic co-surfactants are soaps, alkylbenzenesulfonates, secondary alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, Alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, Monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, Fatty acid isethionates, fatty acid sarcosinate
  • the Containing anionic surfactants polyglycol ether chains, these can be conventional, preferably however, have a narrow homolog distribution.
  • the surfactant mixtures contain anionic surfactants selected from the group formed is of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, monoglyceride (ether) sulfates and alkane sulfonates, especially 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 (VIII) 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 C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution 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 sulfur dioxide
  • CSA chlorosulfonic acid
  • ether sulfates are suitable which follow the formula (IX) R 17 O- (CH 2 CH 2 O) a SO 3 X (IX) 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 (X) , R 18 -Ph-SO 3 X (X) 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.
  • Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their production is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized.
  • suitable sulfating agents preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
  • the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)].
  • Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67 , 8 (1990) .
  • the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (XI) , in which R 19 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, c, d and e in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal.
  • Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide.
  • Monoglyceride sulfates of the formula (XI) are preferably used, in which R 19 CO stands for a linear acyl radical having 8 to 18 carbon atoms.
  • Alkane sulfonates are taken to mean compounds of the formula (XII) R 20 R 21 -CH-SO 3 H (XII) in which R 20 and R 21 represent alkyl radicals with the proviso that R 20 and R 21 together have no more than 50 carbon atoms.
  • non-aqueous surfactant mixtures are claimed, which may optionally contain non-aqueous solubilizers. These solubilizers are described below in the chapter on auxiliary substances.
  • non-aqueous surfactant mixtures is understood to mean mixtures with a water content of less than or equal to 5% by weight.
  • Another object of the invention are agents for cleaning hard surfaces that the invention Contain surfactant mixtures of Hydroxymischethem and polymers, the agents contain a total of 0.01 to 60% by weight, preferably 0.1 to 15, preferably 0.5 to 12% by weight of surfactants and 0.01 to 10% by weight, preferably 0.1 to 8% by weight, preferably 0.2 to 7% by weight, of polymers. It is particularly preferred here that the proportion of the surfactants that do not contain hydroxy mixed ethers of the formula (I) are between 0 to 85% by weight, preferably 1 to 50% by weight, in particular 10 to 30% by weight lies.
  • these agents contain 5 to 90% by weight, preferably 10 to 80% by weight builder, 0.1 to 7% by weight enzyme, 0.1 to 40% by weight, preferably 0.5 to 30% by weight Bleaching agents and possibly other auxiliary substances.
  • these figures are in% by weight (percent by weight) on the agent.
  • the agents 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 of 400,000 to 800,000, or in particular butyl diglycol. In many cases an additional bactericidal effect is desired, which is why the agent is cationic Surfactants or biocides, for example glucoprotamine, may contain.
  • 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
  • Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, Citric acid and its salt, as well as inorganic phosphonic acids.
  • 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.
  • Enzymes come from the class of proteases, lipase, amylases, cellulases or their Mixtures in question. From bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus enzymatic substances obtained. Preferably are proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes be used. Their proportion can be about 0.1 to 7, preferably 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in enveloping substances to protect them against premature To protect decomposition.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use 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.
  • Suitable foam inhibitors contain, for example, known organo-olysiloxanes and / or paraffins or waxes. It can also contain foam regulators, such as soap, fatty acids, especially coconut fatty acid and palm kernel fatty acid.
  • 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, as well as other polymeric compounds.
  • polymeric polycarboxylates for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers acrylic acid with maleic acid, preferably from 50 to 10% by weight of maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of Copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
  • water-soluble polyacrylates are also suitable, for example with approximately 1% of a polyallyl ether of sucrose are cross-linked and have a relative molecular weight above 1000000 own examples of these are polymers available under the name Carbopol® 940 and 941.
  • the cross-linked polyacrylates are preferably particularly preferred in amounts not exceeding 1% by weight used in amounts of 0.2 to 0.7 wt .-%.
  • the agents according to the invention for cleaning hard surfaces which are particularly preferred Room temperature are fixed. These agents are preferably in the form of granules, powders or moldings, such as tablets, bars or balls. It is particularly preferred here that the inventive Average at most 10% by weight, in particular 1 to 5% by weight and very particularly preferably 2 to 4% by weight Contain water.
  • aqueous agents with a pH of less than or equal to 7 for cleaning hard surfaces characterized in that they contain the surfactant mixtures according to the invention.
  • Aqueous agents in the form of rinse aids for the machine are particularly preferred Cleaning dishes.
  • Another object of the invention is the use of the surfactant mixtures according to the invention in detergents, dishwashing detergents and cleaning agents.
  • the use of the invention is also claimed Surfactant mixtures for the production of cleaning solutions with improved activity against the Re-soiling of hard surfaces.
  • the surfaces are equipped in such a way that the dirt can be removed more easily during the next cleaning process.
  • the addition of polymers e.g. to rinse aid often leads to the otherwise strongly adhering to the next cleaning critical soiling, e.g. starchy soiling, can be completely removed, without manual processing (e.g. pre-rinsing) being necessary beforehand.
  • Hard surfaces include Ceramic surfaces, metal surfaces, painted surfaces, plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood.
  • surfactant mixtures according to the invention is particularly preferred for improvement the wetting behavior in detergents and cleaning agents, preferably on hard surfaces, in particular in machine dishwashers and / or rinse aids.
  • surfactant mixtures according to the invention for improving the Plastic compatibility in detergents and cleaning agents, especially in machine dishwashers and / or rinse aid.
  • the surfactant mixtures according to the invention are very particularly preferred, optionally in combination with the other surfactants already described, for the simplified production of solid cleaning formulations.
  • the hydroxy mixed ethers according to the invention can because of their higher Melting points easier in detergent and cleaning agent formulations, especially in solid cleaners be incorporated.
  • plastic test specimens measuring 20 x 5 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 (e.g. Maranil A 55® COGNIS).
  • Test parameters water hardness 2 ° d salt load 700 ppm temperature 60 ° C surfactant 0.1% (active substance)
  • PP polypropylene
  • PE polyethylene
  • PC polycarbonate

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EP02023859A 2001-11-02 2002-10-24 Melangé tensioactif avec hydroxy-ethers mixtes et polyméres Expired - Lifetime EP1308499B1 (fr)

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DE10153768A DE10153768A1 (de) 2001-11-02 2001-11-02 Hydroxymischether mit Polymeren
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Cited By (3)

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WO2005100523A1 (fr) * 2004-04-16 2005-10-27 Henkel Kommanditgesellschaft Auf Aktien Nettoyant hydrophylisant pour surfaces dures
WO2007009555A1 (fr) * 2005-07-21 2007-01-25 Henkel Kommanditgesellschaft Auf Aktien Produits de nettoyage et d'entretien presentant une emulsibilite amelioree
WO2013164492A1 (fr) * 2012-07-13 2013-11-07 Basf Se Utilisation de tensioactifs alcoxylés non ioniques comme additifs dans des compositions de nettoyage aqueuses pour membrane

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EP1201816A1 (fr) * 2000-10-27 2002-05-02 The Procter & Gamble Company Traitement de vêtements pour résistance contre les faux plis
DE10153768A1 (de) * 2001-11-02 2003-05-15 Cognis Deutschland Gmbh Hydroxymischether mit Polymeren
DE10163856A1 (de) * 2001-12-22 2003-07-10 Cognis Deutschland Gmbh Hydroxymischether und Polymere in Form von festen Mitteln als Vorcompound für Wasch-, Spül- und Reinigungsmittel
DE102005060431A1 (de) * 2005-12-15 2007-06-21 Henkel Kgaa Maschinelles Geschirrspülmittel
US8852353B2 (en) * 2008-12-10 2014-10-07 Michael Oberlander Solid dishmachine detergent not requiring a separate rinse additive
EP2336280A1 (fr) * 2009-12-05 2011-06-22 Cognis IP Management GmbH Utilisation d'alkyl (oligo)glycosides ramifiés dans des produits de nettoyage
BR112022026756A2 (pt) * 2020-07-02 2023-01-24 Basf Se Composto, processo para preparar composto de fórmula geral e para limpar louça em uma máquina de lavar louça automática, uso de um composto ou de uma combinação de pelo menos dois compostos, e, composição de limpeza

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DE19962885A1 (de) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
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WO2007009555A1 (fr) * 2005-07-21 2007-01-25 Henkel Kommanditgesellschaft Auf Aktien Produits de nettoyage et d'entretien presentant une emulsibilite amelioree
WO2013164492A1 (fr) * 2012-07-13 2013-11-07 Basf Se Utilisation de tensioactifs alcoxylés non ioniques comme additifs dans des compositions de nettoyage aqueuses pour membrane
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DE10153768A1 (de) 2003-05-15
DE50204068D1 (de) 2005-10-06

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