EP1254948A1 - Gemini surfactants - Google Patents

Abstract

Geminitensides (I), i.e. polyethylene glycol bis-(2-hydroxyalk(en)yl) ether derivatives, are new. Geminitensides of formula RCH(OH)CH2-(OCH2CH2)x-OCH2CH(OH)R (I) are new. R = alkyl and/or alkenyl of 4-22C; x = 5-90. An Independent claim is included for rinsing or cleansing compositions (A) containing (I), together with other conventional components.

Description

Field of the Invention

The invention relates to gemini surfactants, optionally in conjunction with detergents and cleaning agents usual ingredients, optionally with other nonionic surfactants and anionic surfactants and the use of such gemini surfactants to improve the wetting behavior and Compatibility with plastics, for the simplified manufacture of solid cleaners and as foam-suppressing surfactant in rinse aid formulations.

State of the art

Means for rinsing and cleaning hard, non-textile surfaces, which occur in the household and commercial sector, should mostly develop a small foam volume when used, which will decrease significantly within a few minutes. Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of various types with or without the addition of builders, solubilizers (hydrotropes) or solvents. To prove the effectiveness at the beginning of the cleaning work, the consumer wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped off. For this purpose, agents of the type mentioned are usually mixed with low-foaming nonionic surfactants.
Today, more requirements are placed on machine-washed dishes than on manually washed dishes. For example, dishes that have been completely cleaned of food residues are not considered to be perfect if, after machine dishwashing, they still have whitish stains based on water hardness or other mineral salts, which, due to the lack of wetting agents, originate from dried water drops.
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 in ready-to-use form with the detergent and / or regeneration salt together ("2 in 1", "3 in 1", eg in the form of tabs and powders), ensures that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and shiny at the end of the wash program.

Common detergents and cleaning agents are mixtures of nonionic surfactants, solubilizers, organic acids and solvents, water as well as preservatives and fragrances.
The task of the surfactants in these agents is to influence the interfacial tension of the water so that it can run off the wash ware in a thin, coherent film, so that no water drops, streaks or films remain during the subsequent drying process (so-called wetting effect or wetting behavior) ).
For this reason, these surfactants also have to dampen the foam that arises from food residues in the dishwasher. Since rinse aids mostly contain acids to improve the clear dry effect, the surfactants used must also be relatively insensitive to hydrolysis against acids.
Combined products from dishwashing detergent with built-in rinse aid are being used more and more both in the household and in the commercial sector. The rinse aid was previously metered into household dishwashers and released into the rinsing chamber at just under 40 ° C - 65 ° C after the pre-rinse and cleaning cycle. The rinse aid is released from the combined dishwashing detergents (eg "2 in 1" tabs or powder) with a time delay to the detergent and is thus dosed into the rinsing chamber.

The commercial dishwashers work with only one cleaning fleet, which is only through Adding the rinsing solution from the previous rinsing process is renewed. So it takes place during no complete water exchange takes place during the entire washing program. Therefore, the flushing and Detergents also have a foam-suppressing effect, being temperature-stable with a strong one Temperature drop of 85-35 ° C and also be sufficiently stable against alkali and active chlorine.

The object of the present invention was to provide detergents and cleaning agents which at the same time have good foam and cleaning behavior, but in particular very good drainage behavior, ie an improvement in the wetting behavior on plastic surfaces and high material compatibility, in particular with plastics. In addition, it should be easier to prepare solid detergent formulations.
The problem was solved by using selected surfactants of the gemini surfactant type.

Description of the invention

The invention relates to gemini surfactants of the formula (I), R-CHOH-CH 2 [OCH 2 CH 2 ] XO-CH 2 -CHOH-R in which pure linear or branched alkyl and / or alkenyl radical having 4 to 22, preferably 8 to 18, in particular 8 to 12 carbon atoms and x is 5 to 90, preferably 10 to 45 and in particular 12 to 35.

gemini

Gemini surfactants are generally prepared by reacting 1,2-epoxyalkanes (CH ₂ CHO-R), where R is a linear or branched, saturated or unsaturated alkyl and / or alkenyl radical, with polyols.

Here, polyol is the collective name for polyhydric alcohols or polyalkylene glycols, i.e. H. as an organic compound containing at least two hydroxyl groups in the mole. The polyalkylene glycols also include reaction products of polyhydric alcohols To understand alkoxylation reagents such as ethylene oxide and propylene oxide.

For the purposes of the invention, polyethylene glycol HO- [OCH ₂ CH ₂ ] x-OH is used as the polyol.
Gemini surfactants of the formula (I) are particularly preferred, where x is from 10 to 45, preferably from 12 to 35.
Gemini surfactants of the formula (I) are very particularly preferred, where R is a linear or branched alkyl radical having 8 to 12 carbon atoms.

Gemini surfactants of the formula (I) are further preferred, where R is a linear alkyl radical with 8 to 12 carbon atoms, especially with 10 carbon atoms.

In a further embodiment, gemini surfactants of the formula (I) are preferred, which thereby are characterized in that they are at least 80% by weight, preferably 85 to 100% by weight, in particular Contain 95 to 100 wt.% Gemini surfactants, in which all free hydroxyl groups of Polyethylene glycols are sealed with 1,2-epoxyalkane units.

Furthermore, in a further embodiment, detergents and cleaning agents are claimed which contain the gemini surfactants according to the invention and further ingredients customary in detergents and cleaning agents.
As described below, these customary ingredients can be alkyl and / or alkenyl oligoglycosides, other nonionic surfactants, anionic surfactants, builders, enzymes and other auxiliaries and additives.
Rinsing and cleaning agents which contain gemini surfactants of the formula (I) in which x is from 5 to 90, preferably from 10 to 45, in particular from 12 to 35 and R for a linear or branched alkyl and / or alkenyl radical are very particularly preferred 4 to 22 carbon atoms.

Alkyl and / or alkenyl oligoglycosides

In a further embodiment, the rinsing and cleaning agents according to the invention contain alkyl and / or alkenyl oligoglycosides of the formula (II). R 1 O- [G] P where R ^{1 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.

They can be obtained according to the relevant procedures in preparative organic chemistry.
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 oligo glucosides .
The alkyl radical R ¹ can be derived from primary saturated alcohols . Typical examples are butanol-1, capron, Önanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol , palmity alcohol , heptadecanol-1, stearyl alcohol, isostearecanol alcohol -1, arachidyl alcohol, heneicosanol-1, and behenyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
The alkenyl radical R ¹ 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 their technical mixtures, which can be obtained as described above, and their technical mixtures.

Alkyl or alkenyl radical R ¹ 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 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 ¹ 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 that Can assume values p = 1 to 3, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which 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, preference is given to those 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 ^{1 represents} an alkyl radical having 6 to 16 carbon atoms.

In a preferred embodiment , the washing-up and cleaning agents according to the invention contain 0.01 to 25% by weight, preferably 0.025 to 20% by weight and in particular 0.1 to 15% by weight of gemini surfactants of the formula (I), calculated as active substance, based on the Medium.
Active substance is defined here as the mass of surfactant (calculated as 100% pure substance) contained in the agent.

In a further embodiment , the washing-up and cleaning agents according to the invention contain 0.01 to 30% by weight, preferably 0.1 to 20% by weight and in particular 0.2 to 15% by weight of alkyl and / or alkenyl oligoglycosides of the formula (II) calculated as Active substance, based on the funds.

Nonionic surfactants

The detergents and cleaning agents according to the invention can contain further nonionic surfactants. Typical examples of non-ionic surfactants are 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 triglycerol ethers, fatty glucide amides, mixed glycidyl amides, mixed glycidyl amides, mixed glycidyl amides, mixed glycidyl amides, mixed glycidyl amides, and mixed acid amides vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
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.

Fatty alcohol polyethylene glycol / polypropylene

In a preferred embodiment, fatty alcohol poly ethylene glycol / poly propylene glycol ether of the formula (III), which are optionally end group-capped, R 6 O (CH 2 CH 2 O) n1 [CH 2 (CH 3 ) CHO] m R 7 used, in which R ^{6 is} an alkyl and / or alkenyl radical having 8 to 22 C atoms, R ^{7 is} H or an alkyl radical having 1 to 8 C atoms, n1 is 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

Also suitable are fatty alcohol polypropylene glycol / poly ethylene glycol ethers of the formula (IV), which are optionally end-capped, R 8th O [CH 2 (CH 3 ) CHO] q (CH 2 CH 2 O) r R 9 in which R ^{8 is} an alkyl and / or alkenyl radical with 8 to 22 C atoms, R ⁹ for H or an alkyl radical with 1 to 8 C atoms, q for a number from 1 to 5 and r for a number of 0 to 15.

According to a preferred embodiment , the rinsing and cleaning agents according to the invention 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 C atoms, n1 is a number from 1 to 10 , and m represents 0 and 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 such alcohol ethoxylates, those are also suitable which have a narrow homolog distribution.
Further suitable representatives of non-end-capped representatives are those of the formula (III) in which R ⁶ for an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n1 for a number from 2 to 7, m for a number of 3 to 7 and R ^{7 represents} hydrogen. These are addition products of monofunctional alcohols alkoxylated first with 2 to 7 mol of ethylene oxide and then with 3 to 7 mol of propylene oxide of the type already described.

The end group-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, n1 is a number from 2 to 7, m is a number from 3 to 7 and R ^{7 represents} a methyl group. Such compounds can easily be prepared by reacting the corresponding non-end-capped fatty alcohol polyethylene glycol / polypropylene glycol ether with methyl chloride in the presence of a base.

Suitable representatives of alkyl-capped compounds are those of the formula (III) in which R ^{6 is} an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n1 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.

Instead of the compounds of the formula (III) or in a mixture with them, end-capped fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV) may be present. Such connections are described, for example, in German published patent application DE-A1- 43 23 252. Particularly preferred representatives of the compounds of the formula (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 of 1 to 6 and R ^{9 represents} hydrogen. These are preferably addition products of 1 to 5 mol of propylene oxide and of 1 to 6 mol of ethylene oxide with monofunctional alcohols, which have already been described as suitable in connection with the gemini surfactants.

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 in which R ¹⁰ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{11 is} hydrogen or methyl, R ^{12 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands. Typical examples are the formal insert products of an average of 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 mixtures 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.

amine oxides

Bei der Herstellung der Aminoxide der Formel (VI) geht man von tertiären Fettaminen aus, die mindestens einen langen Alkylrest aufweisen, und oxidiert sie in Gegenwart von Wasserstoffperoxid. Bei den im Sinne der Erfindung in Betracht kommenden Aminoxiden der Formel (VI), steht R¹³ für einen linearen oder verzweigten Alkylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, sowie R¹⁴ und R¹⁵ unabhängig voneinander für R¹³ oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen. Vorzugsweise werden Aminoxide der Formel (VI) eingesetzt, in der R¹³ und R¹⁴ für C_12/14- bzw. C_12/18-Kokosalkylreste stehen und R¹⁵ einen Methyl- oder einen Hydroxyethylrest bedeutet. Ebenfalls bevorzugt sind Aminoxide der Formel (VI), in denen R¹³ für einen C_12/14- bzw. C_12/18- Kokosalkylrest steht und R¹⁴ und R¹⁵ die Bedeutung eines Methyl- oder Hydroxyethylrestes haben.
Weitere geeignete Aminoxide sind Alkylamido-aminoxide der Formel (VII), wobei der Alkylamido-Rest R²³CONH durch die Reaktion von linearen oder verzweigten Carbonsäuren, vorzugsweise mit 6 bis 22, bevorzugt mit 12 bis 18 Kohlenstoffatomen, insbesondere aus C_12/14- bzw. C_12/18- Fettsäuren mit Aminen entsteht. Dabei stellt R²⁴ eine linerare oder verzweigte Alkylengruppe dar mit 2 bis 6, vorzugsweise 2 bis 4 Kohlenstoffatomen und R¹⁴ und R¹⁵ haben die in Formel (VI) angegebene Bedeutung. Compounds of the formula (VI) and / or 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 is oxidized 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 are R ¹³ or, if appropriate hydroxy-substituted alkyl radical having 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. Also preferred are 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.
Further suitable amine oxides are alkylamido -amine 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 from C _12/14 or C _12/18 - fatty acids with amines. 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) .

The further nonionic surfactants can be present in the detergents and cleaning agents according to the invention in amounts of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to 8% by weight, calculated as the active substance, based on the means.

According to the present invention, the rinsing and cleaning agents according to the invention can contain anionic surfactants .

Anionic surfactants

Typical examples of anionic surfactants are soaps, alkylbenzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerin ether sulfates, mono ether sulfate sulfate, hydroxymischogether sulfate, fatty acid ether sulfate sulfates, Mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyllactylate, alkyl acylate glate fatty acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids, acylolate glucosate fatty acids and acylolate glucosate fatty acid based on, (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

The anionic surfactants are preferably selected from the group consisting of 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 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.
Typical examples of 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 and their technical mixtures, which are obtained from 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.

alkyl ether

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 are suitable which follow the formula (IX) R 17 O- (CH 2 CH 2 O) a SO 3 X 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 caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, aryl alcohol 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, ole alcohol 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. 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

Alkylbenzenesulfonates preferably follow the formula (X), R 16 Ph-SO 3 X in which R ^{18 represents} a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph a phenyl radical and X 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.

Monoalycerid (ether) sulfates

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. The usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)]. If desired, 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.

alkanesulfonates

R²⁰ und R²¹ stehen für Alkylreste, wobei R²⁰ und R²¹ zusammen nicht mehr als 50 Kohlenstoffatome haben sollen.Alkane sulfonates are taken to mean compounds of the formula (XII).

R ²⁰ and R ²¹ represent alkyl radicals, where R ²⁰ and R ²¹ together should not have more than 50 carbon atoms.

The washing-up and cleaning agents can expediently contain 0.01 to 20% by weight, preferably 0.25 to 15% by weight, in particular 0.4 to 10% by weight, of anionic surfactants , calculated as the active substance, based on the agent. The rest, which is missing by 100% by weight, can be auxiliary substances and additives as well as water.

Auxiliaries and additives

The rinsing and cleaning agents according to the invention can be used as customary ingredients or auxiliaries and additives, 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.
Abrasive materials such as quartz or wood flour or polyethylene friction bodies can also be contained.
In many cases an additional bactericidal effect is desired, which is why the detergents and cleaning agents can contain cationic surfactants or biocides, for example glucoprotamine.
Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and its salt, and inorganic phosphonic acids.

Among the compounds used as peroxy bleaching agents , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H ₂ O ₂ -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 0.1 to 40% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. The use of sodium percarbonate in conjunction with alkyl and / or alkenyl oligoglycosides is also preferred.

Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.1 to 6, preferably 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition.

In addition to mono- and polyfunctional alcohols and phosphonates, the agents can contain further 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. 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 pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors contain, for example, known organoolysiloxanes and / or paraffins or waxes. Foam regulators, such as soap, fatty acids, in particular coconut fatty acid and palm kernel fatty acid, may also be included.

Examples of thickeners which can be used are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% by weight of maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.

In a further embodiment, detergents and cleaning agents, preferably for automatic dishwashers, are preferred which contain 0.1 to 15, preferably 0.5 to 12% by weight of surfactants which contain gemini surfactants of the formula (I), in particular those based on Polyethylene glycol, where x is 10 to 45, R is a linear alkyl radical with 8 to 12 carbon atoms.
In addition, the agents according to the invention contain 5 to 90, preferably 10 to 80 wt.% Builders, 0.1 to 6 wt.% Detergent enzyme, optionally 0.1 to 40, preferably 0.5 to 30 wt.% Bleaches and auxiliaries and additives , % By weight is to be understood in relation to the average.

Powdery or tablet-shaped dishwashing detergents are very particularly preferred, which can also have a rinse aid function at the same time. The are particularly preferred "2 in 1" and "3 in 1" recipes for automatic dishwashing described at the beginning.

Another object of the present invention is the use of gemini surfactants Formula (I) for rinsing and cleaning hard surfaces, preferably in the household and industrial and institutional area.

The use in dishwashers, bathroom cleaners, floor cleaners, Cleaner according to the clean shower concept (e.g. bathroom cleaner, before and after showering is sprayed onto walls and fittings so that the water and soap residues run off better, and wiping is not necessary), cockpit cleaner (car, plane, ship, motorcycle), window cleaner and all-purpose cleaner. Hard surfaces include Ceramic surfaces, metal surfaces, painted surfaces, Plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood.

The use of the gemini surfactants of the formula (I) according to the invention is particularly preferred for Improvement of the wetting behavior in detergents and cleaning agents, preferably on hard ones Surfaces, especially in machine dishwashers, that contain rinse aid.

Preference is furthermore given to the use of gemini surfactants of the formula (I) for improving the Plastic compatibility in detergents and cleaning agents, especially in machine dishwashers, that contain rinse aid.

Preference is furthermore given to the use of gemini surfactants of the formula (I) in combination with alkyl and / or Alkenyl oligoglycosides in the cleaning areas listed so far.

The gemini surfactants of the formula (I) according to the invention, if appropriate, are very particularly preferred in combination with the other surfactants already described, for the simplified production of solid detergent formulations. The gemini surfactants according to the invention can because of their higher Melting points easier in detergent and cleaning agent formulations, especially in solid cleaners be incorporated.

Also preferred is the use of gemini surfactants according to formula (I) as a foam-suppressant Surfactant in detergents and cleaning agents.

In contrast to the previously known hydroxy mixed ethers, the inventive ones are distinguished Gemini surfactants, in addition to their foam-suppressing effect and high tolerance, in particular compared to plastic, due to their higher melting points. This makes them particularly suitable for simplified production of solid formulations. The gemini surfactants also dissolve, due to their higher melting points, later in the cleaning liquor and unfold with a time delay, and in higher concentration their effect. This effect can be particularly advantageous in machine Dishwashing detergents with built-in rinse aid can be used.

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

The wetting properties of surfactant solutions against plastics were combined in one Simplified screening based on the conditions / test parameters in a commercially available Dishwasher, but without the use of such.

Plastic test specimens measuring 20 x 5 cm are used to evaluate the wetting properties 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 takes place visually by compiling 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 removed. grade 5 is obtained when using water. The grade 1 means complete wetting of the Plastic surface with a smooth flow of the liquid film.

Test parameters:

water hardness 2 ° d salt load 700 ppm temperature 60 ° C surfactant 0.1%

Test specimens:

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

The test results are shown in Table 1, V1 to V2 comparative tests and I, II and III representing the examples according to the invention. Wetting properties on plastics Composition in% active substance V1 V2 I II III 2-hydroxydodecyl ether-PEG 600-2-hydroxydodecyl ether - - - - 0.1 2-hydroxydodecyl ether-PEG 1000-2-hydroxydodecyl ether - - - 0.1 - 2-hydroxydodecyl ether-PEG 1500-2-hydroxydodecyl ether - - 0.1 - Poly Tergent SLF-18B-45 * - 0.1 - Water, 2 ° d / 700ppm NaCI 100 99.9 99.9 99.9 99.9 Wetting properties on plastics Temperature: 60 ° C / plastic "PP" 5 4 2 1 3 Temperature: 60 ° C / plastic "PE" 5 3 2 1 4 Temperature: 60 ° C / plastic "PC" 5 4 2 1 3

Table 2 shows the melting points of the gemini surfactants. Melting points / areas ° C 2-hydroxydodecyl ether-PEG 600-2-hydroxydodecyl ether 27 2-hydroxydodecyl ether-PEG 1000-2-hydroxydodecyl ether 36 2-hydroxydodecyl ether-PEG 1500-2-hydroxydodecyl ether 43 C 12/14 FA 5EO + 4PO liquid at room temperature Poly Tergent SLF-18B-45 27-32

Gemini surfactants with melting points above 35 ° C. are used to formulate combination products made from dishwashing detergent and rinse aid ("2 in 1". "3 in 1"). Sample recipes for machine dishwashing detergents 1 2 3 Active substance in% 2-hydroxydodecyl ether-PEG 600-2-hydroxydodecyl ether 14 2-hydroxydodecyl ether-PEG 1000-2-hydroxydodecyl ether 14 2-hydroxydodecyl ether-PEG 1500-2-hydroxydodecyl ether 14 Sodium tripolyphosphate 45 45 45 Sodium perborate 12 12 12 soda 15 15 15 Water glass 2.0 10 10 10 Enzymes (protease, amylase) 2 2 2 Other ingredients ad 100

Claims (20)

Gemini surfactants according to formula (I) R-CHOH-CH 2 - [OCH 2 CH 2 ] X -O-CH 2 -CHOH-R in which R is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms and x is 5 to 90. Gemini surfactants of formula (I) according to claim 1, wherein x is 10 to 45, preferably 12 to 35. Gemini surfactants of the formula (I) according to Claim 1 and / or 2, where R is a linear or is a branched alkyl radical having 8 to 12 carbon atoms. Gemini surfactants of the formula (I) according to one of Claims 1 to 3, where R is a linear alkyl radical has 8 to 12 carbon atoms Gemini surfactants of the formula (I) according to one of Claims 1 to 4, characterized in that they contain at least 80% by weight of gemini surfactants in which all the free hydroxyl groups of the polyethylene glycol are sealed with 1,2-epoxyalkanes. Rinsing and cleaning agents containing gemini surfactants of the formula (I) according to Claims 1 to 5, and other ingredients common in detergents and cleaning agents. Detergent and cleaning agent according to claim 6, characterized in that they contain gemini surfactants of the formula (I) in which x is 5 to 90, preferably 10 to 45, in particular 12 to 35, R for a linear or branched alkyl and / or Alkenyl radical having 4 to 22 carbon atoms. Detergent and cleaning agent according to one of claims 6 to 7, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (II). R 1 O- [G] p where R ^{1 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. Dishwashing and cleaning agent according to one of claims 6 to 8, characterized in that they contain calculated as active substance, based on the agent, 0.01 to 25% by weight of gemini surfactants of the formula (I). Detergent and cleaning agent according to one of claims 6 to 9, characterized in that they contain, calculated as active substance, based on the agent, 0.01 to 30% by weight of alkyl and / or alkenyl oligoglycosides of the formula (II). Dishwashing and cleaning agent according to one of claims 6 to 10, characterized in that they contain further nonionic surfactants , preferably selected from the group consisting of alkoxylates of alkanols, end-capped alkoxylates of alkanols, alkoxylated fatty acid lower alkyl esters and amine oxides. Dishwashing and cleaning agents according to claim 11, characterized in that - calculated as active substance, based on the agent - contain 0.1 to 15% by weight of further nonionic surfactants . Dishwashing and cleaning agent according to one of claims 6 to 12, characterized in that they contain anionic surfactants as a further component, preferably selected from the group formed by alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, monoglycerol ether) sulfates and alkanesulfonates , Detergent and cleaning agent according to claim 13, characterized in that - calculated as active substance, based on the agent - contain 0.01 to 20% by weight of anionic surfactants . Detergent and cleaning agent according to one of claims 6 to 14, containing a. 0.1 to 15% by weight, based on the medium surfactants, which contain gemini surfactants of the formula (I) b. 5 to 90% by weight based on the medium builders c. 0.1 to 6% by weight, based on the detergent enzyme d. optionally 0.1 to 40% by weight based on the medium bleach and e. other auxiliaries and additives. Use of gemini surfactants according to formula (I) in claim 1 for rinsing and cleaning hard surfaces. Use of gemini surfactants according to formula (I) in claim 1 to improve the Wetting behavior, in detergents and cleaning agents. Use of gemini surfactants according to formula (I) in claim 1 to improve the Compatibility with plastics, in detergents and cleaning agents, especially in machine dishwashers, that contain rinse aid. Use of gemini surfactants according to formula (I) in claim 1 for simplified production of solid detergent formulations. Use of gemini surfactants according to formula (I) in claim 1 as a foam-suppressing surfactant in detergents and cleaning agents.