EP1308499B1 - Surfactant mixture with hydroxy mixed ethers and polymers - Google Patents

Description

Field of invention

The invention relates to surfactant mixtures composed of hydroxy mixed ethers and polymers, optionally in Combination with ingredients commonly found in dishwashing detergents and cleaning agents, possibly with others nonionic surfactants and anionic surfactants, as well as the use of such surfactant mixtures for the production of cleaning solutions with an improved effect against re-soiling.

State of the art

Agent for rinsing and cleaning hard, non-textile surfaces in the household and commercial sector should usually develop a small volume of foam when used, which develops within significantly further reduced by a few minutes. Means of this type have long been known and in the Established market. These are essentially different aqueous surfactant solutions Type with or without the addition of builders, solubilizers (hydrotropes) or solvents. To the Proof of effectiveness at the beginning of the cleaning work is given by the consumer Foaming of the application solution desired, but the foam should collapse quickly so that Once cleaned, surfaces do not need to be wiped again. To this end, means of the aforementioned Art usually mixed with low-foaming non-ionic surfactants.

Today, machine-washed dishes in particular are subject to higher demands than those made manually washed dishes. In this way, dishes that have been completely cleaned of leftover food are not considered to be flawless rated if it is still whitish after machine dishwashing, for water hardness or other mineral salts based stains that have dried out due to lack of wetting agents Water droplets originate.

Rinse aid is therefore used to ensure that dishes are shiny and spotless. The addition of liquid or solid rinse aid, which can be added separately, or in ready-to-use form 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 completely removed from the items to be washed runs off so that the different surfaces are residue-free and at the end of the wash program are shiny.

Common rinse aids are mixtures of e.g. non-ionic 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 runs off the wash ware in a coherent film that is as thin as possible 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 aids also steam the foam caused by leftover food in the dishwasher. As the rinse aid usually contain acids to improve the clear dry effect, must be used Surfactants are also relatively insensitive to acids against hydrolysis.

Rinse aids are used both in households and in commercial areas. In household dishwashers the rinse aid is usually after the pre-wash and cleaning cycle at just under 40 ° C-65 ° C metered in. The commercial dishwashers work with only one cleaning solution, which is only is renewed by adding the rinsing solution from the previous rinsing process. So it finds there is no complete water exchange during the entire wash program. Therefore the Rinse aid also has a foam-reducing effect and is temperature-stable in the event of a strong temperature gradient of 85-35 ° C and also be sufficiently stable against alkali and active chlorine.

Furthermore, through the use of rinse aids, it should be possible to clean or rinse To equip surfaces in such a way that soiling is removed during the next cleaning process easier to remove.

German Offenlegungsschrift DE-A1 19738866 describes surfactant mixtures of mixed hydroxy ethers and nonionic surfactants, such as fatty alcohol polyethylene glycol / polypropylene glycol ether, optionally end-capped, which have very good foaming properties and show excellent rinse effects in rinse aids. From the German Offenlegungsschrift DE-OS 2432757 it is known that hydroxy mixed ethers are used as foam suppressants in detergents, dishwashing detergents and cleaning agents.

The object of the present invention was to find surfactant mixtures for the production of dishwashing detergents and cleaning agents provide that at the same time a good foaming and cleaning behavior, in particular however, it has a very good run-off behavior, thanks to an improved wetting behavior on various Surfaces, show. This creates a particularly good visual appearance on the cleaned surfaces Impression that is characterized by an increased gloss. Furthermore, a high material compatibility is especially with plastics. They should also be simplified solid Have cleaner formulations manufactured. Furthermore, the surfaces to be cleaned or rinsed should be equipped in such a way that soiling occurs 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 wettability a spotless shine is achieved on the surfaces to be cleaned. 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. This dirt can be removed without additional manual processing of the items to be washed.

Description of the invention

(a) Hydroxymischether der Formel (I), R ¹ O [CH ₂ CH(CH ₃ )O] _x [CH ₂ CH(R ² )O] _y CH ₂ CH(OH)R ³    (I) in der R¹ für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder einen Methyl-, oder Ethylrest, R³ für einen Alkylrest mit 4 bis 22 Kohlenstoffatomen, x für 0 oder 1 bis 60, y für 1 bis 80 steht und die Alkyleneinheiten sowohl in Blockform (blocked) als auch in beliebiger Reihenfolge (randomized) vorliegen können, und

(b) kationische Polymere, die Monomereinheiten der Formel (Ia) aufweisen,

in der n für eine Zahl zwischen 2 und 4, R^1a für Wasserstoff oder eine Methylgruppe steht und R^2a, R^3a und R^4a gleich oder verschieden sein können und für Wasserstoff oder eine C_1-4-Alk(en)ylgruppe stehen und X- ein Anion aus der Gruppe der Halogenidanionen oder ein Monoalkylanion der Schwefelsäurehalbester repräsentiert.

The invention relates to surfactant mixtures containing

(A) hydroxy mixed ethers of the formula (I) , R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH (R ² ) O] _y CH ₂ CH (OH) R ³ (I) in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, R ^{2 is} hydrogen or a methyl or ethyl radical, R ^{3 is} an alkyl radical having 4 to 22 carbon atoms, x is 0 or 1 to 60, y stands for 1 to 80 and the alkylene units can be present both in block form (blocked) and in any order (randomized), and

(b) cationic polymers which have monomer units of the formula (Ia) ,

in which n is a number between 2 and 4, R ^{1a is} hydrogen or a methyl group and R ^2a , R ^3a and R ^{4a can be} identical or different and are hydrogen or a C _1-4 alk (en) yl group and X- represents an anion from the group of halide anions or a monoalkyl anion of sulfuric acid half-esters.

Hydroxy mixed ethers

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 . For the purposes of the invention, preference is given to those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols of the formula R ¹ -OH, where R ^{1 is} an aliphatic, saturated, straight-chain or branched alkyl radical having 4 to 22, preferably 6 to 16, in particular 8 to 10 carbon atoms. Examples of suitable straight-chain alcohols are butanol-1, caproic alcohol, enanthal alcohol, caprylic alcohol, pelargon alcohol, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, nonadachyl alcohol, stearyl alcohol Heneicosanol-1, behenyl alcohol and their technical mixtures, such as those obtained in the high-pressure hydrogenation of technical methyl esters based on fats and oils. Examples of branched alcohols are so-called oxo alcohols, which usually have 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 previously mixing the alkoxylating reagents) with ethylene oxide and / or propylene oxide and / or butylene oxide, or by reacting in blocks with the Alkylene oxides in a certain order (blocked). Alkoxylates of alcohols obtained by reaction with 0 or 1 to 60 moles of propylene oxide (x = 0.1-60) and 1 to 80 moles (y = 1-80) of ethylene oxide, propylene oxide and / or butylene oxide (R ² = Hydrogen, methyl radical, ethyl radical) are used. Hydroxy mixed ethers, which have proven particularly suitable in the surfactant mixtures from an application point of view, follow the formula (I) in which x stands for 0 and y stands for numbers from 1 to 80, preferably from 20 to 60, in particular from 35 to 50.
In a particular embodiment, surfactant mixtures containing hydroxy mixed ethers in which x stands for 0 and y stands for numbers from 20 to 60, preferably 35 to 50, are suitable.

Particularly preferred surfactant mixtures are those which contain hydroxy mixed ethers, in which R ^{1 stands} for a linear or branched alkyl and / or alkenyl radical with 8 to 10 carbon atoms, R ³ for a linear or branched alkyl radical with 8 to 10 carbon atoms, y for numbers of 20 to 60, preferably 35 to 50. Another preferred embodiment describes hydroxy mixed ethers in which R ^{1 is a} linear alkyl radical having 4 to 22, particularly preferably 8 to 10 carbon atoms, and R ^{3 is} a linear alkyl radical having 8 to 12 carbon atoms. ^{Ethoxylated (R 2} = H) hydroxy mixed ethers (x = 0), where y stands for numbers from 2 to 40, are very particularly preferred. However, ethoxylated (R ² = H) hydroxy mixed ethers which are derived from an oxo alcohol, i.e. R ¹ is a branched alkyl radical having 8 to 16 carbon atoms and y is 40 to 60, are also preferred.

Polymers

worin n eine Zahl zwischen 2 und 4, bevorzugt 3 ist, R¹ für Wasserstoff oder eine Methylgruppe steht und R², R³ und R⁴ gleich oder verschieden sein können und für Wasserstoff oder eine C_1-4-Alk(en)ylgruppe stehen, X- ein Anion aus der Gruppe der Halogenidanionen oder ein Monoalkylanion der Schwefelsäurehalbester repräsentiert. Die Polymere enthalten die Monomereinheiten mit der Formel (la) bevorzugt in einem Anteil von 10 Mol-% bis 80 Mol-%, besonders bevorzugt von 20 Mol-% bis 60 Mol-%. Die Polymere weisen dadurch eine signifikante Soil-Release-Wirkung auf. Neben den Monomereinheiten mit der Formel (la) können als Comonomere ungesättigte Monocarbonsäuren, wie Acrylsäure, Methacrylsäure, Crotonsäure und dergleichen, Olefine, wie Ethylen, Propylen und Buten, Alkylester von ungesättigten Carbonsäuren, insbesondere Ester der Acrylsäure und Methacylsäure, deren Alkoholkomponenten Alkylgruppen von 1 bis 6 C-Atomen enthalten, wie Methylacrylat, Ethylacrylat, Methylmethacrylat, sowie deren Hydroxyderivate wie 2-Hydroxy-Ethylmethacrylat, mit ungesättigten Gruppen versehene, gegebenenfalls weiter substituierte, aromatische Verbindungen wie Styrol, Methylstyrol, Vinylstyrol und heterocyclische Verbindungen wie Vinylpyrrolidon eingesetzt werden. Als Comonomere werden bevorzugt Acrylsäure, Methacrylsäure und ihre C₁-C₆-Ester verwendet. The cationic polymers are polymers which have monomer units of the formula (la) ,

where n is a number between 2 and 4, preferably 3, R ^{1 is} hydrogen or a methyl group and R ² , R ³ and R ^{4 can be} identical or different and are 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 half-esters. The polymers contain the monomer units with the formula (Ia) preferably in a proportion of 10 mol% to 80 mol%, particularly preferably 20 mol% to 60 mol%. As a result, the polymers have a significant soil release effect. In addition to the monomer units with the formula (Ia) , 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 are 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, optionally further substituted aromatic compounds such as styrene, methyl styrene, vinyl styrene and heterocyclic compounds such as vinyl pyrrolidone which are provided with unsaturated groups. Acrylic acid, methacrylic acid and their C ₁ -C ₆ esters are preferably used as comonomers.

Also preferred are surfactant mixtures which contain polymers selected from the group which is formed by polymers or copolymers of monomers such as trialkylammonium alkyl (meth) acrylamide. The use of is particularly preferred Trimethylammonium propyl methacrylamide-sodium acrylate-ethyl acrylate polymer e.g. Polyquart Ampho 149® Cognis.

In a further embodiment, 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.

Nonionic co-surfactants

Furthermore, 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 and 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-alkyl glucamides, protein hydrolysates (especially vegetable Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution

Alkyl and / or alkenyl oligoglycosides

In a further embodiment, 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 stands} for an alkyl and / or alkenyl radical with 4 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms and p stands for numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry . As a representative of the extensive literature, reference is made to the overview article by Biermann et al. in Starch / Strength 45, 281 (1993), B. Salka in Cosm.Toil. 108, 89 (1993) and J. Kahre et al. in SÖFW-Journal No. 8, 598 (1995) . 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, caproal alcohol, enanthal alcohol, caprylic alcohol, pelargon alcohol, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol, palmityl alcohol, heptadecanol-1, iso-stearyl alcohol, stearyl 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 oxo synthesis. 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, ricinole alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidyl alcohol, eruca alcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, which can be obtained as described above, 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 of chain length C ₈ -C ₁₀ , which are obtained as first runnings in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and can be contaminated with 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.

The index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here in particular the Can assume values p = 1 to 3, the value p for a specific alkyl oligoglycoside is an analytically determined mathematical variable that usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 2.0 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 2.0 and in particular is between 1.2 and 1.7. Alkyl and / or alkenyl oligoglycosides of the formula (II) are preferably used, where p stands for numbers from 1 to 3 and R ^{5 stands} for an alkyl radical having 6 to 16 carbon atoms.

Alkoxylates of alkanols with or without end group closure

The other 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, in particular end-capped fatty alcohol polyethylene glycol / polypropylene glycol ethers or end-capped fatty alcohol polypropylene glycol / polyethylene glycol ethers, and fatty acid lower alkyl esters and amine oxides.

Fatty alcohol polyethylene glycol / polypropylene glycol ether

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 stands} for an alkyl and / or alkenyl radical with 8 to 22 carbon atoms, R ⁷ for H or an alkyl radical with 1 to 8 carbon atoms, n for a number from 1 to 40, preferably 1 to 30 , in particular 1 to 15, and m is 0 or a number from 1 to 10.

Fatty alcohol polypropylene glycol / polyethylene glycol ether

Fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV) , which are optionally end-capped, are also suitable, R ⁸ O [CH ₂ (CH ₃ ) CHO] _q (CH ₂ CH ₂ O) _r R ⁹ (IV) in which R ^{8 stands} for an alkyl and / or alkenyl radical with 8 to 22 carbon atoms, R ⁹ for H or an alkyl radical with 1 to 8 carbon atoms, q for a number from 1 to 5 and r for a number of 0 to 15 stands. The surfactant mixtures according to the invention also preferably contain fatty alcohol polyethylene glycol / polypropylene glycol ethers 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. These are adducts 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 such alcohol ethoxylates, those which have a narrow homolog distribution are also suitable.

Further suitable representatives of non-end-capped representatives 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 2 to 7, m is a number of 3 to 7 and R ^{7 represents} hydrogen. These are adducts of monofunctional alcohols of the type already described which are alkoxylated initially with 2 to 7 mol of ethylene oxide and then with 3 to 7 mol of propylene oxide. The end-capped compounds of the formula (III) are capped with an alkyl group having 1 to 8 carbon atoms (R ⁷ ). Such compounds are often referred to in the literature as mixed ethers. Suitable representatives are methyl group-capped 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 for a number from 2 to 7, m for a number from 3 to 7 and R ^{7 represents} a methyl group. Such compounds can easily be prepared by reacting the corresponding non-capped fatty alcohol polyethylene glycol / polypropylene glycol ether with methyl chloride in the presence of a base. Suitable representatives of compounds capped by alkyl groups 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 adding the corresponding fatty alcohol polyethylene glycol ether with n-butyl chloride or with tert. Butyl chloride is reacted in the presence of bases.

Instead of the compounds of the formula (III) or as a mixture with them, end-capped fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV) may optionally be present.

Such compounds are described, for example, in the German patent application DE-A1 4323252 . Particularly preferred representatives of the compounds of the formula (IV) 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 from 1 to 6 and R ^{9 represents} hydrogen. These are preferably adducts of 1 to 5 moles of propylene oxide and 1 to 6 moles of ethylene oxide with monofunctional alcohols which have already been described as suitable in connection with the hydroxy mixed ethers.

Alkoxylated fatty acid lower alkyl esters

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 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 insertion products of an average of 1 to 20 and preferably 5 to 10 mol of ethylene and / or propylene oxide into 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, petroselic acid, linoleic acid, linolenic acid, eleostearic acid, arachic acid, gadoleic acid, behenic acid and technical mixtures thereof. 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 mol of ethylene oxide in the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

Amine oxides

Compounds of the formula (VI) and / or (VII) can be used as amine oxides.

The preparation of the amine oxides of the formula (VI) starts from tertiary fatty amines which have at least one long alkyl radical and oxidizes them in the presence of hydrogen peroxide. In the case of the amine oxides of the formula (VI) which are ^{suitable for the purposes of the invention, R 13 represents} a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms, and R ¹⁴ and R ¹⁵ independently of one another represent R ¹³ or optionally one hydroxy-substituted alkyl radical with 1 to 4 carbon atoms. Preference is given to using amine oxides of the formula (VI) in which R ¹³ and R ^{14 are} C _12/14 or C _12/18 coconut alkyl radicals and R ^{15 is} a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (VI) in which R ^{13 is} a C _12/14 or C _12/18 coconut alkyl radical and R ¹⁴ and R ¹⁵ are methyl or hydroxyethyl radicals. Further suitable amine oxides are alkylamidoamine oxides of the formula (VII) , where the alkylamido ^{radical R 23} CONH is formed by the reaction of linear or branched carboxylic acids, preferably with 6 to 22, preferably with 12 to 18 carbon atoms, in particular from C _12/14 or C _{12 / 18} - Fatty acids with amines are formed. R ^{24 here 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).

Other 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-alkyl glucamides, protein hydrolysates (especially plant-based products based on wheat), Polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates are used.

Anionic co-surfactants

Typical examples of anionic co-surfactants are soaps, alkylbenzenesulfonates, secondary alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-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 sarcosinates, fatty acid taurides, N-acylamino acids such as, for example Acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. Unless the Anionic surfactants contain polyglycol ether chains, these can be conventional, preferably however, have a narrow homolog distribution. In a preferred embodiment, can the surfactant mixtures contain anionic surfactants selected from the group formed is derived from alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates

Alkyl and / or alkenyl sulfates

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 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulphates that can be used in the context of the invention are the sulphation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, petroacholeyl alcohol, petroacholeyl alcohol. Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxo synthesis. 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 with a comparable carbon chain distribution in the form of their sodium salts are particularly preferred.

Alkyl ether sulfates

Alkyl ether sulfates ("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. For the purposes of the invention, ether sulfates which follow the formula (IX) are suitable, 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 having 6 to 22 carbon atoms, a represents numbers from 1 to 10 and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of adducts of an average of 1 to 10 and in particular 2 to 5 mol of ethylene oxide with caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleidyl stearyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts. The ether sulfates can have both a conventional and a narrow homolog distribution. The use of ether sulfates based on adducts of on average 2 to 3 mol of 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 is particularly preferred.

Alkylbenzenesulfonates

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 technical mixtures thereof in the form of the sodium salts are preferably used.

Monoglyceride (ether) sulfate

in der R¹⁹CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, c, d und e in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (XI) eingesetzt, in der R¹⁹CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht.Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. They are usually prepared from triglycerides which, optionally after ethoxylation, are transesterified to give the monoglycerides and then sulfated and neutralized. It is also possible to implement the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)]. The neutralized substances can - if desired - be subjected to an ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)]. Overviews of the chemistry of 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) published. The monoglyceride (ether) sulfates to be used in the context of the invention follow the formula (XI) ,

in which R ¹⁹ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, c, d and e in total are 0 or numbers from 1 to 30, preferably 2 to 10, and X is 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 and their ethylene oxide adducts in the form of their sodium sulfonic acid or their sodium sulfonic acid adducts. Preference is given to using monoglyceride sulfates of the formula (XI) in which R ¹⁹ CO is a linear acyl radical having 8 to 18 carbon atoms.

Alkanesulfonates

Alkanesulfonates are understood as meaning compounds of the formula (XII) , R ²⁰ R ²¹ -CH-SO ₃ H (XII) in which R ²⁰ and R ²¹ stand for alkyl radicals with the proviso that R ²⁰ and R ²¹ together do not have more than 50 carbon atoms. In a preferred embodiment, non-aqueous surfactant mixtures are claimed which can optionally contain non-aqueous solubilizers. These solubilizers are described below in the section on auxiliary materials. The term “non-aqueous surfactant mixtures” is to be understood as meaning mixtures with a water content of less than or equal to 5% by weight.

cleaning supplies

Another object of the invention are means for cleaning hard surfaces, which the invention Contain surfactant mixtures of hydroxy mixed ethers and polymers according to claim 1, wherein 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 surfactants that are not 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. In a particular embodiment, 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 optionally other auxiliaries. These figures relate to% by weight (percent by weight) focus on the means.

Auxiliaries and additives

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 ethers 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 agents are cationic Surfactants or biocides, such as glucoprotamine, may contain.

Suitable builders are zeolites, sheet silicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, Citric acid and its salt, as well as inorganic phosphonic acids.

Among the compounds used as peroxy bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxycarbonate, citrate perhydrates and H ₂ O ₂ -delivering 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 theirs Mixtures in question. Particularly suitable are from bacterial strains or fungi, such as Bacillus subtilis, Enzymatic active ingredients obtained from Bacillus lichenformis and Strptomyces griseus. Preferably proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are used be used. Their proportion can be about 0.1 to 7, preferably 0.2 to 2% by weight. The enzymes can be adsorbed on carrier materials or embedded in coating substances to prevent them from becoming premature Protect decomposition.

In addition to mono- and polyfunctional alcohols and phosphonates, the agents can contain other enzyme stabilizers. For example, 0.5 to 1% by weight of 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. However, the use of 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 pyoboric acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

When used in machine cleaning processes, it can be advantageous to use the usual cleaning agents Add foam inhibitors. 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, which are 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 can be used. to 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 from 50 to 10% by weight of maleic acid. the The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the Copolymers between 2000 and 200,000, preferably between 50,000 to 120,000, based on the free acid. In particular, water-soluble polyacrylates are also suitable, for example with about 1% of a polyallyl ether of sucrose are crosslinked and which have a relative molecular weight above 1000000 have examples of this are polymers available under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably particularly preferred in amounts not exceeding 1% by weight used in amounts of 0.2 to 0.7% by weight.

The agents according to the invention for cleaning hard surfaces which are particularly preferred are Are firm at room temperature. These agents are preferably in the form of granules, powders or shaped bodies, such as tablets, bars or balls. It is particularly preferred here that the inventive Medium maximum 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 are also preferred hard surfaces, characterized in that they contain the surfactant mixtures according to the invention. Aqueous agents in the form of rinse aids for machine applications are particularly preferred Cleaning dishes.

Commercial applicability

The invention also relates to 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 action against the Resoiling of hard surfaces. The surfaces are equipped in such a way that Remove dirt more easily during the next cleaning process. The addition of polymers E.g. to rinse aid often leads to that which is otherwise strongly adhering during the next cleaning critical soiling, such as starchy soiling, can be completely removed, without manual processing (e.g. pre-rinsing) being necessary beforehand.

Rinsing and cleaning hard surfaces, in the household and in the household, is also preferred here industrial and institutional area. 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 cleaner, which is sprayed on walls and fittings before and after a shower, with it the water and soap residues run off better, and there is no need to wipe them again and before re-soiling better protection), cockpit cleaner (car, airplane, 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.

The use of the surfactant mixtures according to the invention for improvement is particularly preferred the wetting behavior in dishwashing detergents and cleaning agents, preferably on hard surfaces, in particular in machine dish washers and / or rinse aids.

It is also preferred to use surfactant mixtures according to the invention to improve the Plastic compatibility in dishwashing detergents and cleaning agents, especially in machine dishwashing detergents and / or rinse aid.

The use of hydroxy mixed ethers of the formula (I) in combination with alkyl and / or alkenyl oligoglycosides in the cleaning areas listed above is also preferred.

The surfactant mixtures according to the invention, optionally in combination, are very particularly preferred with the other surfactants already described, for the simplified production of solid detergent formulations. The hydroxy mixed ethers according to the invention can due to their higher Melting points easier in dishwashing and cleaning agent formulations, especially in solid cleaners be incorporated.

Examples Screening method for evaluating the wetting properties of surfactant solutions compared to plastic materials

The wetting properties of surfactant solutions compared to plastics have been simplified in a simplified manner Screening based on the conditions / test parameters in a commercially available dishwasher, but without the use of such, determined.

To evaluate the wetting properties, plastic test specimens measuring 20 × 5 cm are used cleaned first with 1% NaOH and then with iso-propanol. The test specimens pretreated in this way are then immersed in the solution to be tested and removed again immediately. The evaluation is done visually by setting up a ranking list or according to a grading scale from 1 to 5. 5 means that it is spontaneous The liquid film ruptures and the wetting is completely eliminated. Grade 5 will be obtained when using water. The rating 1 means complete wetting of the plastic surface with an even flow of the liquid film. Grade 1 is achieved when using Na-LAS (e.g. Maranil A 55® COGNIS).

Test parameters:

Water hardness 2 ° d Salt load 700ppm temperature 60 ° C Surfactant concentration 0.1% (active ingredient)

Test specimen:

PP (polypropylene); PE (polyethylene); PC (polycarbonate);

The test results are shown in Table 1, with V1 to V3, tests 3-6 representing comparative tests and tests 1 to 2 reflecting the examples according to the invention. Details of the active substance in% by weight V1 V2 V3 1 2 3 4th 5 6th HME 1 15.0 13.0 13.0 13.0 13.0 13.0 HME 2 15.0 13.0 Polymer 1 2.0 2.0 Polymer 2 2.0 Polymer 3 2.0 Polymer 4 2.0 Polymer 5 2.0 Cumene sulfonate 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Citric acid 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 water ad 100 PH value 1-2 Appearance at 70 ° C clear clear clear clear clear clear clear clear clear Wetting properties PP 5 4th 3 2 1 2 2 3 2 PE 5 4th 4th 2 2 3 3 3 2 Pc 5 3 3 1 1 2 2 2 2 HME 1: C8 / 10- [PO] 1- [EO] 22-C10 HME 2: C8 / 10- [EO] 40-C12 Polymer 1: trimethylammonium propyl methacrylamide-sodium acrylate-ethyl acrylate-polymer-Polyquart Ampho 149® Cognis Polymer 2: polyacrylic acid copolymer - Versicol E 11® Allied Colloids Polymer 3: terephthalic acid-ethylene glycol-polyethylene glycol-polyester-Velvetol 251 C® Rhone Poulenc Polymer 4: Polyacrylamidopropanesulfonic acid - Rheothik 80-11® Cognis Polymer 5: Protein hydrolyzate, quaternized - Gluadin WQ® Cognis

Claims (17)

1. Surfactant mixtures containing

   (a) hydroxy mixed ethers corresponding to formula (I): R ¹ O[CH ₂ CH(CH ₃ )O] _x (CH ₂ CH(R ² )O] _y CH ₂ CH(OH)R ³    (I) in which R¹ is a linear or branched alkyl and/or alkenyl group containing 4 to 22 carbon atoms, R² is hydrogen or a methyl or ethyl group, R³ is an alkyl group containing 4 to 22 carbon atoms, x = 0 or 1 to 60, y = 1 to 80 and the alkylene units may be present both in blocked form and in randomized form, and

   (b) cationic polymers which have monomer units corresponding to formula (Ia):

   

   where n is a number of 2 to 4, R^1a is hydrogen or a methyl group and R^2a, R^3a and R^4a may be the same or different and represent hydrogen or a C_1-4 alk(en)yl group, X^- is an anion from the group of halide anions or a monoalkyl anion of sulfuric acid semiester.
2. Surfactant mixtures as claimed in claim 1, characterized in that x = 0 and y = 20 to 60.
3. Surfactant mixtures as claimed in claims 1 and/or 2, characterized in that R¹ is a linear alkyl and/or alkenyl group containing 4 to 22 carbon atoms.
4. Surfactant mixtures as claimed in at least one of claims 1 to 3, characterized in that components (a) and (b) are present in a ratio by weight of 0.1:1 to 1,000:1.
5. Surfactant mixtures as claimed in at least one of claims 1 to 4, characterized in that they contain other nonionic surfactants selected from the group consisting of alkyl and/or alkenyl oligoglycosides, alkoxylates of alkanols, end-capped alkoxylates of alkanols with no 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 and mixed formals, fatty acid-N-alkyl glucamides, protein hydrolyzates (more particularly wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates.
6. Surfactant mixtures as claimed in at least one of claims 1 to 5, characterized in that they contain anionic surfactants selected from the group consisting of alkyl and/or alkenyl sulfates, alkyl ether sulfates, alkyl benzenesulfonates, monoglyceride (ether) sulfates and alkanesulfonates.
7. Surfactant mixtures as claimed in at least one of claims 1 to 6, characterized in that they are nonaqueous and optionally contain nonaqueous solvents.
8. Compositions for cleaning hard surfaces which contain the surfactant mixtures claimed in at least one of claims 1 to 7, characterized in that the compositions contain in all 0.01 to 60% by weight of surfactants and 0.01 to 10% by weight of polymers.
9. Compositions as claimed in claim 8, characterized in that the percentage content of surfactants which do not contain any hydroxy mixed ethers of formula (I) is between 0 and 85% by weight.
10. Compositions as claimed in claim 8 or 9, characterized in that they contain - based on the composition - 5 to 90% by weight builders, 0.1 to 7% by weight enzyme, 0.1 to 40% by weight bleaching agent and optionally other auxiliaries.
11. Compositions as claimed in any of claims 8 to 10, characterized in that they are solid at room temperature.
12. Compositions as claimed in claim 11, characterized in that they contain at most 10% by weight water.
13. Water-based compositions with a pH of or below 7 for cleaning hard surfaces, characterized in that they contain the surfactant mixtures claimed in any of claims 1 to 7.
14. The use of the surfactant mixtures claimed in at least one of claims 1 to 7 in laundry detergents, dishwashing detergents and cleaners.
15. The use of the surfactant mixtures claimed in at least one of claims 1 to 7 for the production of cleaning solutions with improved performance against the resoiling of hard surfaces.
16. The use of the surfactant mixtures claimed in at least one of claims 1 to 7 for improving wetting behavior in dishwashing detergents and cleaning compositions.
17. The use of the surfactant mixtures claimed in at least one of claims 1 to 7 for improving the compatibility of dishwashing detergents and cleaners with plastics.