EP0724621A1

EP0724621A1 - Detergent mixtures

Info

Publication number: EP0724621A1
Application number: EP94926148A
Authority: EP
Inventors: Bernd Fabry; Ingo Wegener
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-08-13
Filing date: 1994-08-04
Publication date: 1996-08-07
Also published as: DE4327327A1; WO1995005441A1

Abstract

New detergent mixtures contain (a) mixed ethers having the formula (I), in which R1 stands for a strictly linear residue with 8 to 10 carbon atoms, R2 stands for an alkyl residue with 1 to 4 carbon atoms or for a benzyl residue, m equals numbers from 0.5 to 2 and n equals numbers from 6 to 9; and (b) at least one additional non-ionic surfactant selected in the group formed by fatty alcohol polyethyleneglycol ethers with limited homologue distribution, fatty alcohol polypropyleneglycol/polyethyleneglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alkyl and/or alkenyl oligoglycosides, fatty acid N-alkylpolyhydroxyalkyl amides, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates, phosphoric acid esters or amine oxides. These mixtures are suitable for preparing numerous non-foaming or foam-inhibited surface active agents, such as detergents for dishwashers, clear rinsing agents, bottle cleaning agents, dispersing agents, universal detergents, flotation collectors, etc.

Description

Detergent mixtures

Field of the Invention

The invention relates to new detergent mixtures containing special mixed ethers and selected nonionic surfactants and the use of these mixtures for the production of numerous surface-active agents.

State of the art

The presence of foam is extremely undesirable for a large number of technical processes. So it happens z. B. both in the mechanical cleaning of beer or milk bottles and the spray cleaning of automotive sheets not only on the cleaning or degreasing effect of the surface-active agents used, the avoidance of foam, which can severely affect the system functions, is of equal importance . This is all the more true since in many cases highly active, but also highly foaming anionic surfactants are used.

The problem of foam regulation has, of course, been known for a long time and, accordingly, from the prior art Known a variety of more or less convincing solutions, which can be divided into two groups:

One is a process involving the addition of defoamers, many of which are paraffinic hydrocarbons or silicone compounds. For the applications described, however, this is undesirable in most cases. The second group of processes involves the use of surface-active agents which are themselves low-foaming and, if appropriate, additionally have defoaming properties. As a rule, these are nonionic surfactants or systems similar to surfactants, such as, for example, fatty alcohol propylene glycol ethers or block polymers of ethylene and propylene glycol, which, however, do not have sufficient biodegradability.

End group-capped fatty alcohol polyglycol ethers, so-called “mixed ethers”, which have been established by R. Piorr in Fat.Sei.Technol., Have established themselves as particularly effective low-foam surfactants. 89, 106 (1987).

The use of mixed ethers as low-foaming agents is also extensively described in the patent literature. For example, from EP-A 0 124 815 (Henkel) mixed ethers with 8 to 18 carbon atoms in the fatty alkyl and 7 to 12 ethylene oxide units in the polyether chain are known as foam-suppressing additives to low-foam cleaning agents. For the same purpose, EP-B 0 303 928 (Henkel) octyl and / or mixed decyl ethers with 3 to 4 ethylene oxide units.

Mixed foams with 6 to 12 carbon atoms in the fatty alkyl radical and EO / PO / EO blocks in the polyether chain are proposed in EP-A 0 180 081 (BASF) for foam suppression in the processing of foods and in fermentation processes. According to the teaching of EP-B 0 324 340 (Henkel), mixed ethers having 6 to 28 carbon atoms in the fatty alkyl radical and 2 to 10 ethylene oxide units in the polyether chain can also be used for this purpose.

Finally, EP-A 0 420 802 (Ciba-Geigy) proposes wetting agents for textile pretreatment which contain fatty alcohol polyglycol ethers which are open-chain and / or end-capped. Suitable feedstocks are disclosed which have a fatty alkyl radical of at least 8, preferably 9 to 14 carbon atoms and 2 to 24, preferably 4 to 8 alkylene oxide units in the polyether chain; they can be open-chain or end-capped with a C ₁ -C ₈ alkyl group, a cycloaliphatic radical with at least 5 carbon atoms and a phenyl-lower alkyl or styryl radical. According to the only embodiment, only the use of an open-chain adduct of 15 moles of alkylene oxide with a C ₉ -C ₁₁ oxo alcohol is disclosed.

A large number of mixed ether types can be prepared by varying the fatty alcohol component, the alkylene oxide groups, the degree of alkoxylation and the type of end group closure. The selection of the mentioned fonts, which none Claiming completeness accordingly shows that a large number of mixed ethers are used for the large number of application areas.

However, there is an urgent need on the market to standardize the mixed ether types. Specifically, mixed ethers or formulations containing mixed ethers are required, which can advantageously be used in areas as diverse as machine bottle cleaning, dispersing of dyes or machine dishwashing. The object of the invention is therefore to be seen in providing a solution to the problems described.

Description of the invention

The invention relates to detergent mixtures comprising a) mixed ethers of the formula (I),

in which R ^ is a strictly linear alkyl radical having 8 to 10 carbon atoms, R ^{2 is} an alkyl radical having 1 to 4 carbon atoms or a benzyl radical, m is a number from 0.5 to 2 and n is a number from 6 to 9, and b ) at least one other nonionic surfactant selected from the group consisting of fatty alcohol polyethylene glycol ethers having a narrowed homolog distribution Fettalkoholpolypropylenglycol / polyethylene glycol ethers, fatty acid polyglycol esters, Fettsäureamidpolyglycolethern, Fettaminpolyglycolethern, alkoxylated triglycerides, alkyl and / or alkenyl oligoglycosides, fatty acid N-alkylpolyhydroxyalkylamides, polyol fatty, Zuckerestern, sorbitan esters, polysorbates, Phosphorsäureestern and amine oxides.

It has surprisingly been found that combinations of a very special type of mixed ether and selected nonionic surfactants have particularly advantageous foam, wetting, rinsing, cleaning and dispersing properties and are readily biodegradable. The detergent mixtures according to the invention are therefore suitable for use in very different areas of application in which they are active over a wide temperature range.

The present examples and comparative examples show that even a slight modification of the length of the fatty alkyl chain or the degree of ethoxylation causes a significant deterioration in the wetting and foaming power of the mixed ethers both as individual surfactants and in the mixture with nonionic surfactants, while an increase in the propylene glycol content or the introduction branches in the fatty alkyl radical drastically deteriorate the biodegradability of the products and their foam-suppressing effect. Mixed ether

Mixed ethers are known substances that can be obtained by the relevant methods of preparative organic chemistry. They are usually produced using the WILLIAMSON ether synthesis method, in which fatty alcohol polyglycol ethers are condensed with alkyl halides in the presence of strong bases. Methods for their preparation are for example from the publications DE-OS 28 00 710 (Kuraray) and DE-Cl 37 44 525 (Henkel).

Typical examples of mixed ethers which can be considered as component a) of the detergent mixtures according to the invention are methyl, ethyl, butyl or benzyl end group capped adducts of 0.5 to 2 mol of propylene oxide and 6 to 9 mol of ethylene oxide with octanol and / or decanol. From an application point of view, preference is given to mixed ethers of the formula (I) in which R ¹ for an octyl radical, R ⁴ for an n-butyl radical, m for numbers from 1.2 to 1.7 and n for numbers from 6 to 8 and in particular 7 stand up to 8, ideal. In terms of low foam, wetting capacity and biodegradability, a mixed ether is to be emphasized, which is accessible by the addition of first 1.2 moles of propylene oxide and then 6 or 7 moles of ethylene oxide to octanol and subsequent end group sealing with butyl chloride.

In this context, the term “strictly linear” is to be understood such that the content of branched species in the fatty alkyl radical must not exceed 0.5% by weight. This makes it clear that mixed ethers based on oxo alcohols, their The proportion of branched homologues is usually in the range from 5 to 25% by weight, for which wetting agents according to the invention are not suitable.

NRE fatty alcohol polypropylene glycol ether

Examples of suitable second nonionic surfactant components are fatty alcohol polyethylene glycol ethers with a narrow homolog distribution, which follow the formula (II)

R ³ O- (CH ₂ CH ₂ O) _x H (II) in which R ^{3 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and x represents numbers from 1 to 12.

The term "narrow homolog distribution" or "NRE" (= narrow range ethoxylates) is to be understood as meaning products which, for example, from J.Am. Oil.Chem.Soc. 63, 691 (1986) are known and, compared to conventional nonionic surfactants, have a significantly narrower distribution of the degrees of ethoxylation in the mixture of the polyglycol ethers, which is close to a Gaussian distribution. The fatty alcohol polyethylene glycol ethers which can be used as component b) for the purposes of the invention are preferably substances which are prepared by ethoxylation of the corresponding fatty alcohols in the presence of calcined or hydrophobized layer compounds, in particular hydrotalcite. Relevant descriptions of the procedures can be found e.g. B. in the two German patent applications DE-Al 38 43 713 and DE-Al 40 10 606 (Henkel). Typical examples are addition products of 1 to 10, preferably 2 to 7, moles of ethylene oxide onto fatty alcohols with 8 to 18, preferably 12 to 14 carbon atoms, such as, for example, C _12/14 coconut fatty alcohol-2,5EO-NRE (Arlypon ^(R) F, Henkel KGaA, Düsseldorf / FRG) or C _12/14 coconut _fatty alcohol-3,6-EO-NRE (Dehydol ^(R) LS-3-NRE).

Fatty alcohol polypropylene polyethylene glycol ether

A further nonionic class of surfactants are fatty alcohol polypropylene polyethylene glycol ethers of the formula (III)

in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, y stands for numbers from 1 to 3 and z stands for numbers from 1 to 5.

These are selected fatty alcohol polyglycol ethers, which can be produced by the addition of a small amount of propylene oxide and subsequent ethoxylation. With regard to the application properties and thus the usability, the order of these measures - first PO, then EO attachment - is just as important as the amount of PO and EO units. Typical examples are polyglycol ethers of the formula (III) in which R ^{4 is} an alkyl radical having 8 to 18, preferably 12 to 18 carbon atoms, y is 1 and z is a number from 2 to 5 (dehydol ^(R) LS-12, LS -14, LS-15, Henkel KGaA, Düsseldorf / FRG).

Alkyl and / or alkenyl oligoglycosides

Another class of nonionic surfactants which can be used particularly advantageously as component b) are alkyl and / or alkenyl oligoglycosides of the formula (IV)

R ⁵ -O- [G] _p (IV) in which R ^{5 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10.

Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature, reference is made here to the publications EP-Al-0 301 298 and WO 90/3977.

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 index number p in the general formula (IV) indicates the degree of oligomerization (DP degree), 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 can assume the values p = 1 to 6 in particular, 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 3.0 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 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ^ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl 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. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3).

The alkyl or alkenyl radical R ⁵ can also differ from primary alcohols with 12 to 22, preferably 12 to 14 Derive carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Fatty acid N-alkyl polyhydroxyalkylamides

Another preferred class of surfactants which can make up component b) are fatty acid N-alkylpolyhydroxyalkylamides of the formula (V)

in which R ⁶ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ⁷ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.

The fatty acid N-alkyl polyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent aylation with a fatty acid, a fatty acid alkyl ester or one Fatty acid chloride can be obtained. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO 92/06984.

The fatty acid amides are preferably derived from reducing sugars, for example maltose, palatinose and in particular from glucose. The preferred fatty acid amides are therefore fatty acid N-alkylglucamides as represented by the formula (VI):

The fatty acid N-alkylpolyhydroxyfatty acid amides used are preferably fatty acid N-alkylglucamides of the formula (VI) in which R ^{7 is} hydrogen or an amine group and R ⁶ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (VI) which are obtained by reductive amination of glucose with methylamine and subsequent aylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative are particularly preferred. The other nonionic surfactants in question are also known substances, which are described, for example, in J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts, surfactants and mineral oil additives", Thieme Verlag, Stuttgart, 1978, pp. 123-217. They are preferably compounds having 6 to 22, in particular 12 to 18, carbon atoms in the fat residue and 1 to 10, in particular 2 to 7, alkylene oxide units in the hydrophilic chain.

The detergent mixtures according to the invention can contain components a) and b) in a weight ratio of 10: 1 to 1:10, preferably 4: 1 to 1: 4, and particularly preferably 2: 1 to 1: 2. This information is based on anhydrous components. Accordingly, the detergent mixtures can be anhydrous, but they can also contain water in amounts of 10 to 90, preferably 15 to 50% by weight, based on the mixture as a whole, and can thus be marketed as concentrates, pastes or dilute solutions.

Industrial applicability

The detergent mixtures according to the invention are foam-free or low-foam and can further reduce the foam in low-foam formulations. They have excellent wetting, rinsing, cleaning and dispersing properties and are easily biodegradable. Another object of the invention therefore relates to their use for the production of surface-active agents, for example agents for machine bottle cleaning, agents for tacuh or spray cleaning of body panels, agents for foam regulation in the sugar industry, machine dishwashing detergents, rinse aids, all-purpose cleaners, dispersants for dyes and flotation aids, in which they can be contained in amounts of 1 to 90, preferably 2 to 50 and in particular 2 to 15% by weight, based on the composition.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples I. Testing of wetting and foaming capacity and degradability

1.1. Network assets

The wetting capacity was determined according to the immersion wetting method with 1 g active substance / l, 20 ° C. in water of 16 ° d. For details of the method, see Tens.Surf.Det. 27, 243 (1990). The network time t _{n was determined} in s.

1.2. Foaming power

The foaming power was determined using the whipped foam method with 1 g of active substance / 1, 20 ° C. in water at 16 ° d. For details of the method, see Tens.Surf. Det. 27, 243 (1990). The base foam (t = 0) and the foam disintegration after 5 min in ml were determined.

1.3. Biodegradability

Biodegradability was investigated using the closed bottle test method. The degradation rate BOD / COD was determined after 30 days against the standard

C _{12/18 fatty} alcohol-10-EO-butyl ether (100%). For details see Fette, Seifen, Anstrichmitt., 87, 421 (1985).

The results are summarized in Tab. 1. The properties of the detergent mixtures according to the invention are summarized in Table 2. For this purpose, water-free products were mixed in a weight ratio of 1: 1 and the wetting capacity and the foaming behavior were investigated using the methods described above. The mixed ether AI and the nonionic surfactants B1 to B4 are according to the invention, the mixed ether X1 and the nonionic surfactant C1 are used for comparison.

Surfactants used

A1: Octanol-1,2PO, 7EO-butyl ether

B1: C _12/14 coconut fatty alcohol 2,5EO-NRE

Arlypon ^(R) F

B2: C _12/14 coconut fatty alcohol-lPO-4EO

Dehydol ^(R) LS14,

B3: C _12/14 coconut oil alcohol oligoglucoside (DP = 1.3)

Plantaren ^(R) APG-600 CS-UP

B4: C _12/14 coconut fatty acid N-methylglucamide

X1: octanol-1, 2PO-5EO-butyl ether

C1: C _12/14 coconut fatty alcohol-2EO (conventional)

Dehydol ^(R) -LS 2

All branded products are commercial products from Henkel KGaA, Düsseldorf / FRG.

The foam-suppressing effect of the detergent mixtures was determined using the free-fall cycle method. The foam development of 1 g / 1 resolin red alone and with the addition of 1 g / 1 detergent mixture was investigated. The test mixtures were heated from T = 20 to 54 ° C within t = 30 min. The results are summarized in Tab. 3.

Rinse aid

Recipe I (according to the invention)

5.5% by weight octanol-1,2PO, 6EO-butyl ether

12.0 wt% C _12/14 coconut fatty alcohol-1PO, 4EO 12.0 wt% isopropyl alcohol

7.0% by weight of citric acid

0.5% by weight fragrance

Water ad 100% by weight

Recipe II (according to the invention)

4.5% by weight octanol-1,2PO, 6EO-butyl ether

2.0% by weight of C _12/14 coconut alkyl oligoglucoside 11.0% by weight of C _12/14 coconut fatty alcohol 1PO, 4EO 15.0% by weight of isopropyl alcohol

7.0% by weight of citric acid

0.5% by weight fragrance

Water ad 100% by weight

Recipe III (for comparison)

5.5% by weight octanol-1,2PO, 5EO-butyl ether 12.0% by weight C _12/14 coconut fatty alcohol-1PO, 4EO 12.0% by weight isopropyl alcohol

7.0% by weight of citric acid

0.5% by weight fragrance

Water ad 100% by weight To assess the rinse aid, the tests were carried out in the Bauknecht GSF 1162 dishwasher with softened water. The 65 ° C normal program was selected for this. 40 ml of Somat ^(R) cleaner (Henkel) were dosed into the cleaning cycle. The amount of rinse aid - formulations I to III - was 3 ml and was dosed by hand at 50 ° C in the rinse aid cycle. The salt load in the water was between 600 and 700 mg / 1. 3 rinse cycles were carried out for each rinse aid formulation. The following dishes were used to assess the drying and the rinse aid effect: o "Neckar-Becher" glasses (Schott-Zwiesel), 6 pieces o "Brasilia" stainless steel knife (WMF), 3 pieces o white Prozellan dinner plates (Fa. Arzberg), 3 pieces o red plastic plate "Valon dinner plate"

(Fa. Haßmann), 3 pieces

2.1. Drying

The dishwasher door was fully opened 15 minutes after the end of the washing program. After 5 minutes the drying was determined by counting the remaining drops on the dishes listed below. Rating: 0 points = more than 5 drops

1 point = 5 drops

2 points = 4 drops

3 points = 3 drops

4 points = 2 drops

5 points = 1 drop

6 points = 0 drops (optimal drying)

2.2. Rinse aid effect

After the drying had been assessed, the dishes were placed outside the dishwasher for 30 minutes to cool and then visually checked under lighting in a black box. The dried residual drops, streaks, deposits, cloudy films etc. remaining on the dishes and cutlery were assessed.

0 points = poor rinse aid effect

6 points = optimal rinse aid effect

The results are summarized in Tab. 4:

III. Dispersibility for dyes

The dispersibility of the detergent mixtures according to the invention was determined on the basis of the filtration of various dye dispersions through a paper filter (AATCC test). Here, a dispersion is sucked through two paper filters by means of vacuum and the amount and distribution of the filter residue on the dried filter paper are visually determined against a scale. At the same time, the filtration time is also measured. The test provides information about the state of the dispersion with regard to the fineness of the particles. For details, see an overview in Melliand Textilber. 10. 755 (1988).

Mixture IV (according to the invention)

50% by weight octyl-1,2PO, 6EO-butyl ether

50% by weight of C _12/14 cocoalkyl oligoglucoside

Mixture V (according to the invention)

50% by weight octyl-1,2PO, 6EO-butyl ether

50% by weight of C _12/14 coconut fatty acid N-methylglucamide

Mixture VI (for comparison)

50% by weight octyl-1,2PO, 5EO-butyl ether

50% by weight of C _12/14 cocoalkyl oligoglucoside 1.5 g - based on solids content - of the dispersant (mixtures IV to VI) were dissolved in 500 ml of deionized water at 80 ° C. and adjusted to pH 5 with acetic acid. With stirring, 0.3 g of dye (palanil scarlet RR) was added to the solution. The liquor was heated to 120 ° C. at a rate of 3 ° C./min and held at this temperature for 30 minutes. The mixture was then allowed to cool to 80 ° C. and filtered through a layer of two round filter papers (MN 640 d above, blue tape 589.3 below). The filtration time and the homogeneity of the dye flow and the residue on the upper filter paper were assessed:

I homogeneous, no specks

II homogeneous, few specks

III little homogeneous, some specks

IV inhomogeneous

The results are summarized in Table 5.

IV. Examples of recipes

4.1. Automatic dishwashing detergents a) Octyl-1,2PO, 6EO-butyl ether ...... 8.0% by weight C _12/14 coconut oil alcohol-3.5EO-NRE 4.0% by weight

Citric acid trisodium salt .... 3.0% by weight

Acrylic / maleic acid copolymer .... 4.0% by weight

Triethanolamine .................. 4.0% by weight

Polymeric glucose acrylic acid ester. 2.0% by weight

Nitrilotriacetate trisodium salt. 1.0% by weight

Preservatives ............ 0.5% by weight

Fragrances and dyes ............ 0.5% by weight b) Acrylic / maleic acid copolymer .... 15.0% by weight trisodium salt of citric acid .... 15 , 0% by weight

Sodium carbonate ................. 10.0% by weight

Sodium bicarbonate ......... 10.0 G.e.w .-%

Octyl-1,2PO, 6EO-butyl ether ...... 2.0% by weight of C _12/14 coconut fatty alcohol-lPO-3EO. 2.0% by weight

Bleach activator ................. 1.0% by weight

Enzymes .......................... 1.0% by weight

Fragrances and dyes ............ 1.0% by weight ad 100% by weight water

4.2. Rinse aid a) C _12/14 fatty alcohol-1PO, 4EO ...... 10.0% by weight

Octyl-1,2PO, 6EO-butyl ether ...... 5.5% by weight

Isopropyl alcohol ................ 12.0 G.e.w ..-%

Citric acid ................... 7.0% by weight

Fragrances ...................... 0.5% by weight ad 100% by weight water b) C _12/14 fatty alcohol-1PO, 4EO. ..... 7.0% by weight of C _12/14 fatty acid N-methylglucamide 5.0% by weight

Octyl-1,2P0,6EO-butyl ether ...... 4.5% by weight

Isopropyl alcohol ................ 12.0% by weight

Citric acid ................... 3.0% by weight

Fragrances ...................... 0.5% by weight ad 100% by weight water

4.3. Dispersing agent for dyes a) C _12/14 coconut fatty alcohol-2.5EO-NRE 50.0% by weight octyl-1,2PO, 6EO-butyl ether ...... 50.0% by weight b) C _{12 / 14} cocoalkyl oligoglucoside .. 30.0 wt.% Octyl-1,2PO, 7EO-butyl ether ...... 70.0 wt.% C) C _12/14 coco alkyl oligoglucoside .. 15.0 wt. -%

Octyl-1,2PO, 7EO-butyl ether ...... 70.0% by weight C _12/18 coconut _fatty alcohol-30 EO ... 15.0% by weight 4.4. Metal cleaning agents

Sodium metasilicate. . . . . . . . . . ... 40% by weight

Sodium . . . . . . . . . . . . . . . . 10% by weight

Sodium tripolyphosphate. . . . . .... 10% by weight

Octyl-1,2PO, 6EO-butyl ether. , , , , , 2% by weight of C _12/14 cocoalkyl glucoside. , , , , , , 2 wt .-% ad 100 wt .-% water

4.5. All-purpose cleaner

Octyl-1,2PO, 6EO-butyl ether. , , , , , 3 wt% C _12/14 fatty alcohol-1PO, 4EO. , , , , , 2% by weight

Octyl sulfate sodium salt. . . . . .... 3% by weight

Oleic acid sodium salt. . . . . .... . . . 2% by weight

Isopropyl alcohol. . . . . . . . . . . . . . . . 4% by weight to 100% by weight of water

4.6. Flotation collector for non-sulfidic ores a) Octyl-1,2PO, 6EO-butyl ether. , , , , , 25% by weight C _12/14 fatty alcohol-1PO, 4EO. , , , , , 25% by weight

Oleic acid sodium salt. , , , , .... , , , 50% by weight b) octyl-1,2PO, 6EO-butyl ether. , , , , , 25% by weight of C _12/14 cocoalkyl oligoglucoside. 25% by weight

Dioctylsulfosuccinate ... . . . . . . . . . 50% by weight

Claims

claims

1. Detergent mixtures containing a) mixed ethers of the formula (I),

in which R ^{1 is} a strictly linear alkyl radical having 8 to 10 carbon atoms, R ^{2 is} an alkyl radical having 1 to 4 carbon atoms or a benzyl radical, m is a number from 0.5 to 2 and n is a number from 6 to 9, and b ) at least one further nonionic surfactant chosen from the group formed by Fettalkoholpolyethylengylcolethern with a narrow homolog distribution, Fettalkoholpolypropylenglycol-polyethylene glycol ethers, oligoglycosides fatty acid polyglycol esters, Fettsäureamidpolyglycolethern, Fettaminpolyglycolethern, alkoxylated triglycerides, alkyl and / or fatty acid N-alkyl polyhydroxyalkyl amides, polyol fatty acid esters, Zuckerestern , Sorbitan esters, polysorbates, phosphoric acid esters and amine oxides.

2. Detergent mixtures according to claim 1, characterized in that they contain as component a) mixed ethers of the formula (I) in which Rl is an n-octyl radical, R4 is a n-butyl radical, m stands for numbers from 1.2 to 1.7 and n stands for numbers from 6 to 8.

3. Detergent mixtures according to claims 1 and 2, characterized in that they contain as component b) fatty alcohol polyethylene glycol ethers with a narrowed homolog distribution, which follow the formula (II),

R ³ O- (CH ₂ CH ₂ O) _x H (II) in which R3 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and x is a number from 1 to 12.

4. Detergent mixtures according to claims 1 and 2, characterized in that they contain as component b) fatty alcohol polypropylene glycol polyethylene glycol ether of the formula (III),

in which R4 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, y stands for numbers from 1 to 3 and z stands for numbers from 1 to 5.

5. Detergent mixtures according to claims 1 and 2, characterized in that they contain as component b) alkyl and / or alkenyl oligoglycosides of the formula (IV). R ⁵ -O- [G] _P (IV) in which R ^{5 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10.

6. Detergent mixtures according to claims 1 and 2, characterized in that they contain as component b) fatty acid N-alkyl polyhydroxyalkylamides of the formula (V),

7. Detergent mixtures according to claims 1 to 6, characterized in that they contain components a) and b) in a weight ratio of 10: 1 to 1:10.

8. Detergent mixtures according to claims 1 to 7, characterized in that they contain water in amounts of 10 to 90 wt .-% - based on the total mixture.

9. Use of detergent mixtures according to claims 1 to 8 for the production of surface-active agents.