DE10116020A1 - New polyethylene glycol hydroxy mixed ethers, used in laundry, dish-washing and other detergents, has linear or branched alkyl and/or alkenyl group, hydroxyalkyl and/or hydroxyalkenyl group and ethylene oxide units - Google Patents

Abstract

New polyethylene glycol hydroxy mixed ethers (I) have a linear or branched, 4-22C alk(en)yl group, a linear or branched, 4-24C 2-hydroxyalk(en)yl group and 40-80 ethylene oxide units. New polyethylene glycol hydroxy mixed ethers are of formula (I): R<1>O(CH2CH2O)xCH2CH(OH)R<2> (I) R<1> = linear or branched, 4-22C alkyl and/or alkenyl; R<2> = linear or branched, 2-22C alkyl and/or alkenyl; and x = 40-80. An Independent claim is also included for agents containing (I) and other usual contents for laundry, dish-washing and other detergents.

Description

Field of the Invention

The invention relates to highly ethoxylated hydroxy mixed ethers in conjunction with washing, rinsing and Detergents, and the use of such hydroxy mixed ethers as defoamers in washing, Detergents and cleaning agents.

State of the art

Means for washing and cleaning hard, non-textile surfaces used in the household and commercial sector Occasionally, a slight foam volume should develop when used, which significantly reduced within a few minutes. Means of this kind have been known for a long time and established in the market. These are essentially aqueous surfactant solutions of different types with or without the addition of builders, solubilizers (hydrotropes) or Solvents. To demonstrate effectiveness at the start of cleaning work, the consumer Although a certain amount of foam is desired in the application solution, the foam should, however, quickly increase collapse so that once cleaned surfaces do not have to be wiped down. To this end are agents of the type mentioned usually with low-foaming nonionic surfactants added.

Today more demands are placed on machine-washed dishes than on manually washed dishes. In this way, dishes that have been completely cleaned of leftovers are then used as not rated correctly if it is still whitish after machine dishwashing Water hardness or other mineral salts based stains that lack wetting agents come 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 dosage form together with the cleaning agent and / or regeneration salt ("2  in 1 "," 3 in 1 ", e.g. in the form of tabs and powders), ensures that the water is as possible completely drains from the wash ware, so that the different surfaces at the end of the Wash programs are residue-free and shiny.

Commercial rinse aids are mixtures such. B. from nonionic surfactants, solubilizers, organic acids and solvents, water and possibly preservatives and fragrances The task of the surfactants in these agents is to increase the interfacial tension of the water influence that they run off the dishes in a thin, coherent film as possible can, so that no water drops, streaks or films during the subsequent drying process remain behind (so-called network effect or network behavior).

For this reason, surfactants in rinse aids also have to contain the foam that occurs due to food residues Steam the dishwasher. Since the rinse aid mostly acids for an improvement of the clear contain dry effect, the surfactants used must also be relatively insensitive to hydrolysis against acids.

Rinse aids are used both in the home and in commercial areas. In household The rinse aid is usually washed in the dishwasher after the pre-rinse and cleaning cycle at just under 40 ° C 65 ° C metered. Commercial dishwashers work with just one cleaning fleet, the is only renewed by adding the rinse aid solution from the previous rinsing process. It there is therefore no complete water exchange during the entire washing program. Therefore the rinse aid must also have a foam-suppressing effect and be temperature-stable with a strong one Temperature gradient of a maximum of 85-35 ° C and also sufficiently stable against alkali and active chlorine his.

German published patent application DE 197 38 866 describes surfactant mixtures made from hydroxy mixed ethers and nonionic surfactants such as fatty alcohol polyethylene glycol / polypropylene glycol ether, if appropriate end group capped, described, which have a very good foaming behavior and in Rinse aids show excellent rinse aid effects.

From German published patent application DT 24 32 757 it is known that the hydroxy mixed ether is a foam damping agents can be used in detergents, dishwashing detergents and cleaning agents.

The object of the present invention was to provide washing, rinsing and cleaning agents which at the same time good foam and cleaning behavior, especially very good Drainage behavior, d. H. an improvement in the wetting behavior on plastic surfaces as well as a high  Show material compatibility, especially with plastics. In addition, simplified should be fixed Have cleaner formulations made.

The object was achieved by using selected surfactants of the hydroxy mixed ether type become.

Description of the invention

The subject of the invention are
Hydroxy mixed ether (HME) of the formula (I)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (I),

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms,
R ^{2 stands} for a linear or branched alkyl and / or alkenyl radical with 2 to 22 carbon atoms x for 40 to 80.

hydroxy mixed

Hydroxy mixed ethers are known from the literature and are described, for example, in German application DE 197 38 866 described.

They are produced by reacting 1,2-epoxyalkanes (R ² CHOCH ₂ ), where R ^{2 is} an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.

Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols of the formula R ¹ -OH having 4 to 18 carbon atoms, where R ^{1 is} an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms , stands.

Examples of suitable straight-chain alcohols are 1-butanol, Capron, Önanth, Capryl, Pelargon, Caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, nonadecanol-1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, such as those used in the high-pressure hydrogenation of technical Methyl esters based on fats and oils are obtained. Examples of branched alcohols are so-called  Oxo alcohols, which usually carry 2 to 4 methyl groups as branches and after the oxo process are produced and so-called Guerbet alcohols, which branched in the 2-position with an alkyl group are. 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 reacted by reacting the alcohols with Ethylene oxide can be produced in a known manner.

Preferred are alkoxylates of alcohols, which are reacted with 40 to 80 moles of ethylene oxide arise used.

Hydroxy mixed ethers having 40 to 60 ethylene oxide units are particularly preferred.

Preferred hydroxy mixed ethers for the purposes of the invention are those derived from ethoxylates of monohydric alcohols of the formula R ¹ -OH having 6 to 18 carbon atoms, preferably 6 to 16 and in particular 8 to 10 carbon atoms, where R ^{1 is} a linear alkyl radical and x for 40 to 60.

Hydroxy mixed ethers of the formula (I) are very particularly preferred, R1 being an alkyl radical having 8 up to 10 carbon atoms, in particular based on a native fatty alcohol, R2 for an alkyl radical 10 carbon atoms, in particular a linear alkyl radical and x stands for 40 to 60.

In a further embodiment, agents are claimed, the inventive Hydroxy mixed ethers, as well as other ingredients common in washing, rinsing and cleaning agents contain. These usual ingredients can, as described below, alkyl and / or Alkenyl oligoglycosides, other nonionic surfactants, anionic surfactants, builders, enzymes and others Auxiliaries and additives.

Alkyl and / or alkenyl oligoglycosides

In a further embodiment, the agents according to the invention contain alkyl and / or alkenyl oligoglycosides of the formula (II).

R ⁵ O- [G] _p (II),

where R ^{5 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.

They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch / Starke 45, 281 (1993), B. Salka in Cosm. Toil. 108, 89 (1993) and J. Kahre et al. in SÖFW- Journal issue 8, 598 (1995).

The alkyl and / or alkenyl oligoglycosides can differ from aldoses or ketoses with 5 or 6 Carbon atoms, preferably derived from glucose. The preferred alkyl and / or Alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.

The alkyl radical R ⁵ can be derived from primary saturated alcohols. Typical examples are butanol-1, capron, Önanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol, palmity alcohol, heptadecanol-1, stearyl alcohol, isostearyl alcohol Nonadecanol-1, arachidyl alcohol, heneicosanol-1, and behenyl alcohol and their technical mixtures, such as those 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, 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 radicals R ⁵ which are derived from primary alcohols having 6 to 16 carbon atoms are preferred.

Particularly suitable are alkyl oligoglucosides with a chain length of C ₈ -C ₁₀ , which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and which may be contaminated with a proportion of less than 6% by weight of 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 with 12 to 14 carbon atoms.

The index number p in the general formula (II) indicates the degree of oligomerization (DP), i.e. H. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in one given connection must always be an integer and in particular the values p = 1 to 3 can assume, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetical size, which usually represents a fractional number.

Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization are preferred p used from 1.1 to 2.0. From an application point of view, such 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, p being numbers from 1 to 3 and R ^{5 being} an alkyl radical having 6 to 16 carbon atoms.

In a preferred embodiment, the agents according to the invention contain 0.01 to 25% by weight, preferably 0.025 to 20% by weight and in particular 0.1 to 15% by weight of hydroxy mixed ethers of the formula (I) calculated as active substance, based on the agent.

Active substance is defined as the mass of surfactants (calculated as 100% pure substance), which in the Funds are included.

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

Nonionic surfactants

The agents according to the invention can contain further nonionic surfactants. Typical examples of nonionic surfactants are alkoxylates of alkanols, end-capped alkoxylates of Alkanols without free OH groups, alkoxylated fatty acid lower alkyl esters, amine oxides, alkylphenol poly glycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, fatty acid N-alkylglucamides, protein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates. If the nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution.  

The further nonionic surfactants are preferably selected from the group formed by Alkoxylates of alkanols, especially fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) of the formula (III) or fatty alcohol polypropylene glycol / polyethylene glycol ether (FAPO / EO) Formula (IV), end-capped alkoxylates of alkanols, especially end-group ver closed fatty alcohol polyethylene glycol / polypropylene glycol ether or end-capped fat 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 polyethylene glycol / polypropylene glycol ethers of the formula (III), which are optionally end-capped,

R ⁶ O (CH ₂ CH ₂ O) _n [CH ₂ (CH ₃ ) CHO] _m R ⁷ (III)

used, in which R ^{5 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, n 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 / polyethylene glycol ethers of the formula (IV), which are optionally end-capped,

R ⁸ O [CH ₂ (CH ₃ ) CHO] _q (CH ₂ CH ₂ O) _r R ⁹ (IV)

in which R ^{8 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 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 carbon atoms, n 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 exhibit.

Other 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 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-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 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, n is a number from 5 to 15, m is 0 and R ⁷ represents an alkyl group with 4 to 8 carbon atoms. The end group closure is preferably carried out with a straight-chain or branched butyl group by the corresponding fatty alcohol polyethylene glycol ether with n-butyl chloride or with tert. Butyl chloride is reacted in the presence of bases.

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 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 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. B. 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

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 alkylamidoamine oxides of the formula (VII), the alkylamido radical R ²³ CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular 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 agents according to the invention in amounts of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to 8% by weight, calculated as Active substance, based on the funds.

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

Anionic surfactants

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, secondary ones Alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, Sulfofatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerol ether sulfates, Hy Droxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dial kylsulfosuccinate, 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 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.  If the anionic surfactants contain polyglycol ether chains, these can be a conventional nelle, but preferably have a narrow homolog distribution.

The anionic surfactants are preferably selected from the group formed by alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and Alkanesulfonates, especially fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkanesulfonates 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 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 considered which follow the formula (IX)

R ¹⁷ O (CH ₂ CH ₂ O) _a SO ₃ X (IX)

in which R ^{17 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, a is a number from 1 to 10 and X is an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of investment products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capronal alcohol, caprylic alcohol, 2ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, and isostyl alcohol troselinyl 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. 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 ¹⁸ -Ph-SO ₃ X (X)

in which R ^{18 is} a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.

Monoglyceride (ether) sulfates

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 implement the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 05 61 825 B1, EP 05 61 999 B1 (Henkel)]. The neutralized substances can - if desired - be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 42 04 700 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. Before preferably monoglyceride sulfates of the formula (XI) are used in which R ¹⁹ CO stands for a linear acyl radical having 8 to 18 carbon atoms.

alkanesulfonates

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 agents can expediently contain 0.1 to 20% by weight, preferably 0.25 to 15% by weight, contain in particular 0.4 to 10% by weight of anionic surfactants, calculated as the active substance, based on the means. The rest, which is missing by 100% by weight, can be auxiliaries and additives as well as water represent.

The agents according to the invention can be used as usual 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 contain butyl diglycol. Abrasive materials such as Quartz or wood flour or polyethylene friction body may be included.

In many cases an additional bactericidal effect is desired, which is why the agents are cationic Surfactants or biocides, for example glucoprotamine, may contain.

Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, Nitrilotriacetic acid, citric acid and its salt, and inorganic phosphonic acids.

Among the compounds serving 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.

Enzymes come from the class of proteases, lipase, amylases, cellulases or their Mixtures in question. From bacterial strains or fungi such as Bacillus subtilis,  Bacillus lichenformis and Strptomyces griseus enzymatic active ingredients obtained. Preferably are proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes be used. Their proportion can be about 0.1 to 6, preferably 0.2 to 2% by weight. The Enzymes can be adsorbed on carriers or embedded in coating substances to counter them to protect 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 use the usual foam add 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.

For example, hardened castor oil, salts of long-chain fatty acid can be used as thickeners ren, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight %, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, as well as other polymeric compounds. 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 those made from 50 to 10% by weight of maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000 the copolymers between 2,000 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 is cross-linked and has a relative molecular weight more than 1,000,000 have examples of these are available under the name Carbopol® 940 and 941 Polymers. The crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight. particularly preferably used in amounts of 0.2 to 0.7% by weight.  

In a further embodiment there are means, in particular for automatic dishwashers preferably containing 0.1 to 15, preferably 0.5 to 12 wt .-% surfactants, the hydroxy mixed ethers of formula (I), in particular those with a degree of ethoxylation x = 40 to 60, sealed with an epoxy with a total of 12 carbon atoms (R2 = 10), generated from one native fatty alcohol with 8 to 10 carbon atoms. The agents according to the invention also contain 5 to 90, preferably 10 to 80% by weight builder, 0.1 to 6% by weight detergent enzyme, optionally 0.1 up to 40, preferably 0.5 to 30% by weight of bleaching agents and auxiliaries and additives. % By weight is based on to understand the means.

Another object of the present invention is the use of hydroxy mixed ethers Formula (I) in detergents, dishwashing detergents and cleaning agents, in particular for washing and cleaning hard ones Surfaces, preferably in the household and industrial and institutional areas. Especially suitable for use in dishwashers, rinse aids, 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 are a. Ceramic surfaces, metal surfaces, painted surfaces, Plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood.

The use of the hydroxy mixed ethers of the formula (I) according to the invention is particularly preferred to improve the wetting behavior in detergents, dishwashing detergents and cleaning agents, preferably on hard ones Surfaces, especially in machine dishwashing detergents and / or rinse aids.

Also preferred is the use of hydroxy mixed ethers of the formula (I) to improve the Plastic compatibility in detergents, dishwashing detergents and cleaning agents, especially in machine dishes Detergents and / or rinse aids.

Also preferred is the use of hydroxy mixed ethers of the formula (I) in combination with Alkyl and / or alkenyl oligoglycosides in the cleaning areas previously listed.

The hydroxy mixed ethers of the formula (I) according to the invention are very particularly preferred, optionally in combination with the other surfactants already described, to simplify Manufacture of solid cleaning formulations. The hydroxy mixed ethers according to the invention can due to their higher melting points easier in detergents, detergents and cleaning agents Formulations, especially in solid cleaners.  

Also preferred is the use of hydroxy mixed ethers of the formula (I) as defoamers in detergents, dishwashing detergents and cleaning agents, especially in machine dishwashing detergents and / or Rinse aids.

The hydroxy mixed ethers according to the invention are notable for their good foam-suppressing properties Effect, the good network effect, the high compatibility, especially with plastic and characterized by their higher melting points.

So far, hydroxy mixed ethers with a higher degree of alkoxylation have shown an improved wetting effect, however, a deterioration in the defoaming effect. In the hydroxymix according to the invention This effect does not occur in ether. Despite high network efficiency, the inventive Hydroxy mixed ether has a very good foaming behavior.

Above all, the hydroxy mixed ethers according to the invention are due to the high melting points simplified production of solid formulations. These hydroxyls also dissolve mixed ether, due to its higher melting points, later in the cleaning liquor and unfold delayed, and in higher concentration their effect. This effect can be particularly beneficial in Rinse aid applications are used. Surprisingly, the inventive ones Hydroxy mixed ethers especially because of their colorless, clear appearance that can be incorporated into a variety detergents, dishwashing detergents and cleaning agents without the need for a complex bleaching process.

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 × 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 1-5. 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. Grade 1 is at Obtain Na-LAS (e.g. Maranil A 55 / COGNIS).

In addition, at temperatures of 20 ° C and 60 ° C, the time in which the complete drainage was determined of the liquid film can be determined. These results are shown in Table 1a.

test parameters

Water hardness: 2 ° d
Salt load: 700 ppm
Temperature: 60 ° C
Surfactant concentration: 0.1%

specimen

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

The test results are shown in Table 1, with V1 to V4 comparative tests and I, II and III reproduce the examples according to the invention.  

Table 1a

With the highly ethoxylated hydroxy mixed ethers, the wetting capacity remains despite the temperature increase consistently good.

In the stress crack corrosion test, the plastic rods are briefly exposed to the product to be tested by immersion or spraying. The adhering product is not removed. After 24 hours, spraying or dipping is carried out again. In total, the plastics are exposed 5 times to the test medium. The final assessment is made visually after 14 days. Here mean:
"1" - unchanged
"2" - crack set / small crack
"3" - continuous tear
"4" break

The examples according to the invention are shown in Table 2 under I and II.  

Table 2

Stress corrosion cracking test

Table 3 shows the melting points of the hydroxy mixed ethers.

Table 3

Table 4 describes the foaming behavior of the surfactants.

To determine the foaming behavior of the surfactant mixtures, 2 eggs (approx. 100 to 110 g) were diluted in an electric mixer in a ratio of 1: 1 with water with a hardness of 16 d and stirred for 2 min. 100 g of the resulting emulsion were then filled in a double-walled measuring cylinder with a capacity of 2000 ml to 500 ml with water of 16 d and tempered to 50 ° C. With the help of a laboratory peristaltic pump, the solution was sucked from the bottom of the measuring cylinder with a glass tube. The return was carried out via a second tube, the lower end of which ended at the 2000 ml mark on the measuring cylinder. The liquid was pumped around at a rate of 4 ml / min. This pumping over creates foam. The solution was then pumped around until a foam volume of 2000 ml had been established. After the 2000 ml mark had been reached, 0.1 g of the hydroxy mixed ether according to the invention (Example III) and (in a second experiment) 0.1 g of that of a standard for rinse aid customary in the market (Example V 4) were added to this mixture. After 0.5, 1, 2, 3, 5, 10, 20 and 30 min the volume was read from the foam and the liquid. The results are summarized in Table 4:

Table 4

Claims (19)

1. Hydroxy mixed ethers according to formula (I)
R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (I),
in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms R ^{2 is} a linear or branched alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 40 to 80. 2. Hydroxy mixed ether according to claim 1, wherein x is 40 to 60. 3. Agent containing hydroxy mixed ether according to claim 1 and / or 2, and others in washing, rinsing and Cleaning agents usual ingredients. 4. Composition according to claim 3, characterized in that they contain hydroxy mixed ethers of the formula (I) in the x stands for 40 to 60. 5. Composition according to claim 3 to 4, characterized in that they contain hydroxy mixed ethers of the formula (I) in which R ^{1 is} an alkyl radical having 8 to 12 carbon atoms and R ^{2 is} an alkyl radical having 8 to 12 carbon atoms. 6. Composition according to one of claims 3 to 5, characterized in that they contain alkyl and / or alkenyl oligo glycosides of the formula (11).
R ⁵ O- [G] _p (II)
where R ^{5 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. 7. Composition according to one of claims 3 to 6, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (II) in which p represents numbers from 1 to 3 and R ⁵ for an alkyl radical having 6 to 16 carbon atoms stands. 8. Composition according to one of claims 3 to 7, characterized in that it - calculated as Active substance, based on the agent - contain 0.01 to 25 wt .-% hydroxy mixed ether of formula (I).   9. Composition according to one of claims 3 to 8, characterized in that it - calculated as Active substance, based on the agent - 0.01 to 30 wt .-% alkyl and / or alkenyl oligoglycosides Contain formula (II). 10. Agent according to one of claims 3 to 9, characterized in that it contains further nonionic Contain surfactants, preferably selected from the group formed by alkoxylates of Alkanols, end-capped alkoxylates of alkanols without free OH groups, alkoxylated Fatty acid lower alkyl esters and amine oxides. 11. Composition according to claim 10, characterized in that it is - calculated as an active substance, based on the agents - 0.1 to 15 wt .-% contain other nonionic surfactants. 12. Composition according to one of claims 3 to 11, characterized in that it is used as a further component contain anionic surfactants, preferably selected from the group formed by alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and alkane sulfonate. 13. Composition according to claim 12, characterized in that it is - calculated as an active substance, based on the agents - contain 0.1 to 20 wt .-% anionic surfactants. 14. Composition according to one of claims 3 to 13, containing

• a) 0.1 to 15 wt .-% - based on the agent - surfactants containing hydroxy mixed ethers of the formula (I)
• b) 5 to 90 wt .-% - based on the medium builder
• c) 0.1 to 6 wt .-% - based on the agent - detergent enzyme
• d) optionally 0.1 to 40% by weight, based on the composition, of bleach and
• e) other auxiliaries and additives.

15. Use of hydroxy mixed ethers according to formula (I) in claim 1, in washing, rinsing and Detergents. 16. Use of hydroxy mixed ethers according to formula (I) in claim 1, for improving the Wetting behavior, in detergents, dishwashing detergents and cleaning agents.   17. Use of hydroxy mixed ethers according to formula (I) in claim 1 to improve the Compatibility with plastics, in detergents, dishwashing detergents and cleaning agents, especially in machine dishes Detergent and / or rinse aid. 18. Use of hydroxy mixed ethers according to formula (I) in claim 1 for the simplified preparation of firm clean formulations. 19. Use of hydroxy mixed ethers according to formula (I) in claim 1, as defoamers in washing, rinsing and cleaning agents, especially in machine dishwashing detergents and / or rinse aids.