WO2001055289A1 - Detergents with a bleaching effect - Google Patents

Abstract

The invention relates to detergents with a bleaching effect. Said detergents contain hydroxymixethers, alkyl and/or alkenyl oligoglycosides and bleaching agents, as well as optionally, non-ionic tensides and anionic tensides. The invention also relates to the use of mixtures of this type in detergent products.

Description

"Bleaching detergents and cleaning agents"

Field of the Invention

The invention relates to bleaching detergents and cleaning agents containing hydroxy mixed ethers; Alkyl and / or alkenyl oligoglycosides and bleaches, optionally further nonionic surfactants and anionic surfactants, and the use of such mixtures in detergents and cleaning agents.

State of the art

Patent law WO 98/11 186 (Procter & Gamble) describes surfactant mixtures with hydroxy mixed ethers for the production of automatic dishwashing detergents. These mixtures can additionally contain bleaching agents such as Contain chlorine bleach or peroxides to help remove dirt through the bleaching effect. A further property right of Procter & Gamble, WO 98/11187 describes, in addition to the hydroxy mixed ethers and bleaching agents, further nonionic surfactants, such as fatty alcohol polyethylene glycol / polypropylene glycol ether and fatty alcohol polypropylene glycol / polyethylene glycol ether for the production of automatic dishwashing detergents.

From German published patent application DT 2432757 it is known that hydroxy mixed ethers can be used as foam suppressants in washing, rinsing and cleaning agents.

The object of the present invention was to develop bleaching detergents and cleaning agents which at the same time show good foam and cleaning behavior, in particular a very good wettability of plastics and high material compatibility of the surfaces to be cleaned. It was important to increase the stability of the bleach in both strong alkaline and strong acid surfactant mixtures. Description of the invention

The invention relates to bleaching detergents and cleaning agents

a. Hydroxy mixed ethers of the formula (I)

R 0 [CH2CHR 0] χ [CH ₂ CHR30] yCH ₂ CH (OH) R4 (I) in the R ¹ for alkyl and / or alkenyl radical with 4 to 22 carbon atoms

R ^{2 represents} hydrogen or a methyl or ethyl radical

R ^{3 represents} hydrogen or a methyl or ethyl radical

R ⁴ for an alkyl radical with 2 to 22 carbon atoms x for 0 or 1 to 30, y for 0 or 1 to 30, where x + y> = 1,

b. Alkyl and / or alkenyl oligoglycosides of the formula (II)

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

c. Bleach.

hydroxy mixed

Hydroxy mixed ethers of the formula (I) are known from the literature and are described, for example, in German application DE 19738866. They are prepared by reacting 1,2-epoxyalkanes (R ⁴ CHOCH2), where R ^{4 is} an aliphatic saturated, straight-chain or branched alkyl radical having 2 to 22, in particular 6 to 16 carbon atoms, with alcohols which have been alkoxylated. 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 having 4 to 18 carbon atoms, where R ^{1 is} for a aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms.

Examples of suitable straight-chain alcohols are butanol-1, capron, Önanth, capryl, pelargon, caprinal alcohol, undecanol-1, auryl 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, as they occur in the high-pressure hydrogenation of technical methyl esters based on fats and oils. Examples of such branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.

The alcohols are used in the form of their alkoxylates, which are prepared in a known manner by reacting the alcohols in any order with ethylene oxide, propylene oxide and / or butylene oxide.

In a preferred embodiment, alkoxylates of alcohols which are formed by reaction with 10 to 50 mol of ethylene oxide are used, where R ² and R ^{3 are} hydrogen and x + y = 1-50. A further embodiment describes both alkoxylates which are formed by reacting alcohol with 1 to 10 mol of propylene oxide (R ² = methyl, x = 1-10) and 10 to 30 mol of ethylene oxide (R ³ = hydrogen, y = 10-30), and also by reaction with 10 to 30 moles of ethylene oxide (R ² = hydrogen, x = 10-30) and 1 to 10 moles of propylene oxide (R ³ = methyl, y = 1-10).

Hydroxy mixed ethers of the formula (I) are particularly suitable, where R ^{2 is} a methyl radical and R ^{3 is} hydrogen, which is advantageously carried out by reacting alcohol with 1 to 3 mol of propylene oxide (x = 1-3) and then with 10 to 25 mol Ethylene oxide (y = 10-25) have been produced.

Alkyl and / or alkenyl oligoglycosides

The rinsing and cleaning agents according to the invention absolutely contain alkyl and / or alkenyl oligoglycosides of the formula (II). 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 /force 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 be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.

The alkyl radical R ⁵ can be derived from primary saturated alcohols. Typical examples are butanol-1, capron, Önanth, capryl, pelargonal, 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 are obtained for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.

The alkenyl radical R ⁵ can also 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.

Those whose alkyl or alkenyl radical R ⁵ are derived from primary alcohols having 6 to 16 carbon atoms are preferred.

Particularly suitable are alkyl oligoglucosides with a chain length of Cβ-Cio, which are obtained as a preliminary step in the separation of technical Cβ-Ciβ-coconut fatty alcohol by distillation and which may be contaminated with a proportion of less than 6% by weight of Ci2-alcohol, as well as alkyl oligoglucosides based on technical Cg / oxoalcohols.

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), i.e. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While p must always be an integer in a given compound and in particular can assume the values p = 1 to 3 here, the value p for a certain alkyl oligoglycoside is one analytically determined arithmetic size, 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, such alkyl and / or Alkenyl oligoglycosides are preferred, the degree of oligomerization of which is less than 2.0 and in particular between 1.2 and 1.7.

bleach

The rinsing and cleaning agents according to the invention also contain bleaching agents. Bleaches which are selected from the group formed by peroxide compounds, alkali metal hypochlorites, in particular hydrogen peroxide and sodium hypochlorite, are preferred.

Typical bleaching agents are peroxide compounds. This means substances that contain an O-0 group, such as perborates, percarbonates, percarboxylic acids and persulfates. Substances that release hydrogen peroxide, but especially hydrogen peroxide itself, are also suitable bleaching agents. These compounds can contain any amount of water of crystallization, sodium perborate with mono- or tetrahydrate is preferred.

Mixtures of hydrogen peroxide and hydrogen peroxide-releasing compounds can also be used.

Other typical bleaching agents are alkali metal hypochlorites. This includes lithium-potassium and especially sodium hypochlorite.

In a preferred embodiment, the detergents and cleaning agents according to the invention contain 0.01 to 25% by weight, preferably 0.05 to 15% by weight and in particular 0.1 to 10% by weight, of hydroxy mixed ethers of the formula (I) calculated as Active substance, based on the funds. For the purposes of the invention, active substance means pure substance.

In a further embodiment, the rinsing 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 agent.

The detergents and cleaning agents preferably contain 0.1 to 30% by weight of bleach, preferably hydrogen peroxide and sodium hypochlorite. Hydrogen peroxide preferably in amounts of 1 to 15% by weight, preferably 5 to 12% by weight and in particular 6 to 10% by weight. Sodium hypochlorite will preferably used in amounts of 0.1 to 30% by weight, preferably 0.5 to 20% by weight and in particular 1 to 10% by weight. The calculation is made as an active substance, based on the funds.

Nonionic surfactants

The agents according to the invention can contain further nonionic surfactants. Typical examples of other nonionic surfactants are alkoxylates of alkanols, end-capped alkoxylates of alkanols without free OH groups, alkoxylated fatty acid lower alkyl esters, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, fatty acid amides, mixed ether amides, and vegetable formulas (mixed ether amides), in particular (vegetable formulas) Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. 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.

Fettalkoholpolvethylenglykol / polypropylenglvkolether

In a preferred embodiment, fatty alcohol polyethylene glycol / polypropylene glycol ethers of the formula (III), which are optionally end-capped,

R60 (CH ₂ CH ₂ 0) n [CH2 (CH3) CHO] m R ⁷ (III)

contain, in which R ^{6 represents} an alkyl and / or alkenyl radical having 8 to 22 C atoms, R ^{7 represents} H or an alkyl radical having 1 to 8 C atoms, n represents 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 0 [CH ₂ (CH3) CHO] _q (CH2CH ₂ 0) 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 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 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.

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. Further 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 ⁰ CO- (OCH ₂ CHRii) WOR ¹² (V)

in which R ¹⁰ CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ¹¹ for hydrogen or methyl, R ¹² for linear or branched alkyl radicals with 1 to 4 carbon atoms and w for numbers from 1 to 20 stands. Typical examples are the formal insert products of 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 and mixtures thereof. The products are usually prepared by inserting the alkoxides into the carbonyl ester bond in the presence of special catalysts, such as eg caicinated hydrotaicit. 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.

IR ¹³ -N-> 0 (VI)

(VII)

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 ^{4 are} C12 / 14 or C12 / 18 coconut alkyl radicals and R ^{15 is} a methyl or a hydroxyethyl radical. Amine oxides of the formula (VI) in which R ^{13 represents} a C12 / 14 or C12 / 18 cocoalkyl radical and R ¹⁴ and R ^{15 have} the meaning of a methyl or hydroxyethyl radical are also preferred. Further suitable amine oxides are alkylamido-amine oxides of the formula (VII), the alkylamido radical R ²³ C0NH 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 Cwu or C12 / 18- fatty acids with amines. R ^{24 represents} a linear or branched alkenyl group with 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 used 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 rinsing and cleaning agents can contain anionic surfactants. Anionic surfactants

Typical examples of anionic surfactants are soaps, alkyl benzene 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 sulfates, hydroxymischogether sulfates, fatty acid ether sulfate 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-acyl amino acids such as, for example, acyl lactate acids, especially acyl lactate fatty acids, acyl glucosate fats, acyl glucosate fatty acids, acyl glucosate fatty acids, acyl glucosate fatty acids, acyl glucosate fatty acids, acyl glucosate fatty acids, acyl glucosate fatty acids, acyl glucosate fatty acids, acyl glucosate fats, acyl glucosate fatty acids, acyl glucosate fats, acyl glucosate fats, acyl glucosate fatty acids, acyl glucosate fats, acyl glucosate fats and acyl glucosate fats, acyl glucate fats, acyl glucate fats, acyl glucate fats, acyl glucate fettings, acyl glucosate fats, acyl glucate fats and acyl glucosate fats, in particular and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

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 and linear alkyl benzene sulfonates, are preferably contained as anionic surfactants.

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 0-S0 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, petroselachcohol, 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 n Sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on Ci6 / ßβ-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 SO3 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)

Ri 0- (CH ₂ CH2θ) aS0 ₃ X (IX)

in which R ^{17 represents} a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 mol ethylene oxide onto capronalcohol, caprylic alcohol, 2ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol, isostyl alcohol Petselinyl 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 C12 / 14 or C12 / 18 coconut oil alcohol fractions in the form of their sodium and / or magnesium salts.

alkylbenzenesulfonates

Alkylbenzenesulfonates preferably follow the formula (X),

R ¹⁸ -Ph-S0 ₃ X (X) in which R ^{18 represents} a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph represents a phenyl radical and X represents 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.

Monoqlycerid (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 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 A. K. Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and F. U. 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),

I

CH-0 (CH ₂ CH ₂ 0) _d H (XI)

I

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 form of sulfuric acid with sulfuric acid trioxide. In front- 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

Alkane sulfonates can be divided into primary and secondary alkane sulfonates. This means compounds of the form (XII),

^ -CH-R »(XU)

SO3H

where in primary alkanesulfonates R ^{20 is} hydrogen and R ^{21 is} an alkyl radical with no more than 50 carbons. The secondary alkanesulfonates are preferred.

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 expediently contain 0.1 to 20% by weight, preferably 0.5 to 15% by weight, in particular 1 to 10% by weight, of anionic surfactants, calculated as active substance, based on the agents. The rest of the detergents and cleaning agents, which are missing by 100% by weight, can represent auxiliary substances and water.

The detergents and cleaning agents can be present both as aqueous solutions and in solid form or as a gel. It is particularly preferred that they are in the form of aqueous solutions. The pH of the detergents and cleaning agents in the form of aqueous solutions is in the range from 1 to 6.5, preferably between 2 to 5, for use as an acidic, bleaching cleaner. Acidic, bleaching cleaners are those which are adjusted to a pH <= 6.5 by adding inorganic and organic acids, in particular amidosulfonic acids, citric acid, malic acid and acetic acid and their salts, such as trisodium citrate. In order to act as an alkaline, bleaching cleaner, the dishwashing detergents and cleaning agents according to the invention are adjusted to a pH between 7 and 14, preferably between 10 and 13.5, by adding alkali metal hydroxide, ammonia or organic bases such as triethanolamine. Potassium hydroxide and in particular sodium hydroxide are suitable as alkali metal hydroxides, which are preferably used in amounts of 0.5 to 3% by weight.

The agents according to the invention can contain, for example, complexing agents such as phosphonic acid derivatives, preferably hydroxyethane-1,1-diphosphonic acid, as auxiliaries. Farther foam regulators, such as, for example, fatty acids and their salts, according to the formula (XIII) can be present

fatty acid salts

R CO-OM (XIII)

where R ²² CO is an acyl radical having 12 to 22 carbon atoms and M is an alkali metal. Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their mixtures they occur during the pressure splitting of technical fats and oils. Salts of technical coconut, palm kernel or tallow fatty acids are preferably used. Since the formulations according to the invention are also strongly alkaline, the fatty acids which are neutralized in situ when they are introduced into the mixture can also be used instead of the salts. The fatty acid salts are preferably used in amounts of 1.5 to 2% by weight.

The agents according to the invention can be used as further auxiliaries, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights of 600 to 1,500,000, preferably with a molecular weight of 400,000 to 800,000 , or in particular contain butyl diglycol. It can also contain builders, abrasives, such as quartz or wood flour or polyethylene rubbers, and bleach activators, such as TAED.

Auxiliaries and additives which the preparations may further contain include, for example, further active chlorine-stable fragrances, optical brighteners, dyes and pigments in a total amount of from 0.01 to 0.5% by weight, based on the composition.

The fragrances known to be active chlorine-resistant include, for example, monocyclic and bicyclic monoterpene alcohols and their esters with acetic or propionic acid (for example isoborneal, dihydroterpene oil, isobornyl acetate, dihydroterpenyl acetate). The optical brighteners can be, for example, the potassium salt of 4,4'-bis (1, 2,3-triazolyl) - (2 -) - stilbin-2,2-sulfonic acid, which is sold under the Phorwite® BHC brand 766 is distributed. Possible color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow® BG 300 (Sandoz). The sequestering agent may furthermore contain electrolyte salts in amounts of 0.1 to 2 and preferably 0.5 to 1% by weight, which may be polyacrylates, carbonates, silicates, phosphates, amine oxide phosphonic acids and lignin sulfonates and mixtures thereof.

Another object of the present invention is the use of hydroxy mixed ethers in combination with alkyl and / or alkenyl oligoglycosides and bleaching agents in bleaching detergents and cleaning agents, preferably for the household and the industrial and institutional sectors. These formulations are particularly suitable for bathroom cleaners, sanitary cleaners, toilet cleaners, floor cleaners, abrasives and all-purpose cleaners.

Examples

¹ HME: hydroxy mixed ether

² APG: alkyl and / or alkenyl oligoglycosides

³ Soap solution made from 21% fatty acid C12-98 and 12% potassium hydroxide solution (50%) and water ad 100

Claims

claims 1. containing bleaching detergents and cleaning agents, a. Hydroxy mixed ethers of the formula (I) R ¹ 0 [CH ₂ CHR ² 0] χ [CH2CHR ³ 0] yCH ₂ CH (OH) R ⁴ (I) in the R ¹ for alkyl and / or alkenyl radical with 4 to 22 carbon atoms R ^{2 represents} hydrogen or a methyl or ethyl radical R ^{3 represents} hydrogen or a methyl or ethyl radical R ^{4 is} an alkyl radical with 2 to 22 carbon atoms x is 0 or 1 to 30, y is 0 or 1 to 30, where x + y> = 1, b. Alkyl and / or alkenyl oligoglycosides of the formula (II) RO- [G] p (II) in which R ^{5 is an} alkyl and / or alkenyl radical having 4 to 22 carbon atoms G is a sugar radical having 5 or 6 carbon atoms p is a number from 1 to 10, c. Bleach. 2. Dishwashing and cleaning agent according to claim 1, characterized in that they contain hydroxy mixed ethers of the formula (I) in which R ^{2 is} a methyl radical, R ^{3 is} hydrogen. 3. Dishwashing and cleaning agent according to one of claims 1 and / or 2, characterized in that they contain hydroxy mixed ethers of the formula (I), where x is from 1 to 3 and y is from 10 to 25. 4. Detergent and cleaning agent according to one of claims 1 to 3, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (II) in which p represents numbers from 1 to 3. 5. Dishwashing and cleaning agent according to one of claims 1 to 4, characterized in that they contain bleaching agents selected from the group formed by peroxide compounds and alkali metal hypochlorites, in particular hydrogen peroxide and sodium hypochlorite. 6. Detergent and cleaning agent according to claim 1, characterized in that they contain - calculated as active substance, based on the agent - 0.01 to 25 wt .-% hydroxy mixed ether of formula (I). 7. detergent and cleaning agent according to claim 1, characterized in that they contain - calculated as active substance, based on the agent - 0.01 to 30 wt .-% alkyl and / or alkenyl oligoglycosides of the formula (II). 8. Dishwashing and cleaning agent according to claim 1, characterized in that they contain - calculated as pure substance, based on the agent - 0.1 to 30 wt .-% bleach 9. detergent and cleaning agent according to one of claims 1 to 8, characterized in that they contain further nonionic 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. 10. Dishwashing and cleaning agent according to claim 9, characterized in that they contain 0.1 to 15% by weight of other nonionic surfactants, calculated as the active substance, based on the agent. 11. Detergent and cleaning agent according to one of claims 1 to 10, 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, alkyl benzene sulfonates, monoglyceride ( ether) sulfates and secondary alkanesulfonates. 12. Detergent and cleaning agent according to claim 11, characterized in that they contain - calculated as active substance, based on the agent - 0.1 to 20 wt .-% anionic surfactants. 13. Detergent and cleaning agent according to claim 1, characterized in that they are in the form of aqueous solutions. 14. Detergent and cleaning agent according to claim 13, characterized in that the pH is between 1 to 6.5. 15. Detergent and cleaning agent according to claim 13, characterized in that the pH is between 7 and 14. 16. Use of hydroxy mixed ethers in combination with alkyl and / or alkenyl oligoglycosides and bleaches in bleaching detergents and cleaning agents.