WO2011003904A1

WO2011003904A1 - Surfactant mixture having short- and long-chained components

Info

Publication number: WO2011003904A1
Application number: PCT/EP2010/059634
Authority: WO
Inventors: Frank Rittig; Paul Klingelhoefer; Soeren Zimdahl; Frank Funke; James S. Dailey
Original assignee: Basf Se
Priority date: 2009-07-10
Filing date: 2010-07-06
Publication date: 2011-01-13

Abstract

The present invention relates to a surfactant mixtures, containing a short-chained and a long-chained component, and to the use of said surfactant mixture, in particular for the pre- and post-treatment of textiles.

Description

Surfactant mixture with short and long-chain components

The present invention relates to a surfactant mixture, formulations such surfactant containing mixtures, processes for the preparation of the surfactant mixtures and their use. Surfactants are amphiphilic surface-active compounds which contain a hydrophobic and a hydrophilic part of the molecule and may also have charged or uncharged groups. Surfactants are adsorbed to interfacial surfaces and thereby reduce the interfacial tension so that they can form association colloids in solution above the critical micelle formation concentration so that water-insoluble substances are solubilized in aqueous solutions.

Because of these properties, surfactants are used, for example, for wetting solids, such as fibers or hard surfaces. Here, surfactants are often used in combination with each other and with other excipients. Typical fields of application include detergents and cleaners for textiles and leather, as a formulation of paints and coatings and, for example, in the extraction of crude oil.

Interesting surfactants are, in particular, those which are alkoxylation products of alcohols. It has been shown that it is particularly favorable to provide such compounds in different mixtures. In particular mixtures of long and short-chain surfactants are suitable here.

Such mixtures are described, for example, in WO-A 2007/096292, US-A 2008/103083, DE-A 102 18 752, JP-A 2003/336092 and JP-A 2004/035755.

Furthermore, it is important that surfactants, in addition to their good surfactant properties, are also readily biodegradable.

Biodegradable surfactants or detergents are described, for example, in WO-A 98/23566. For the use of such surfactants or detergents in the treatment of fibers and fabrics made of natural and synthetic materials, these should also have good cleaning properties. For example, it is important for the post-cleaning of cotton / polyamide blends or polyester / polyamide blends that the surfactants or detergents have good removal properties of silicone oils.

It is therefore an object of the present invention to provide surfactants or detergents which have a corresponding property profile, i. on the one hand have a good biodegradability and on the other hand are well suited for the removal of silicone oils.

This object has surprisingly been achieved by containing a surfactant mixture

(A) a short-chain component containing the alkoxylation product of alkanols, wherein the alkanols have 9 to 11, preferably 10 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value of 1 to 20, the alkoxy groups C2-4- Alkoxy groups and the alkanols have a mean degree of branching in the range of 0.9 to 2.5; and

(B) a long-chain component containing the alkoxylation of alkanols, wherein the alkanols have 12 to 18 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation takes a value of 1 to 20, the alkoxy groups represent C2-4 alkoxy groups and the Alkanols have a mean degree of branching from 0 to 3.5; or their phosphate, sulfate esters and ether carboxylates.

This means that both the short-chain and the long-chain component can have the alkoxylation products as such or alternatively or additionally their phosphate, sulfate esters and ether carboxylates.

The degree of branching of the alkanols (the alkanol mixture) is defined as follows:

The degree of branching of an alcohol results from the branches of the carbon skeleton. It is defined for each alcohol molecule as the number of carbon atoms attached to three other carbon atoms plus twice the number of carbon atoms Carbon atoms bonded to four further carbon atoms. The average degree of branching of an alcohol mixture results from the sum of all branching degrees of the individual molecules divided by the number of individual molecules. The degree of branching is determined, for example, by NMR methods. This can be done by analysis of the C-skeleton with suitable coupling methods (COZY, DEPT, INADEQUATE), followed by quantitation via ¹³ C NMR with relaxation reagents. However, other NMR methods or GC-MS methods are possible.

The average number of alkoxy groups results from the sum of all alkoxy groups of the individual molecules divided by the number of individual molecules.

A surfactant mixture is preferred when the alkoxy groups are independently selected from the group consisting of ethoxy and propoxy groups, and it is particularly preferred when the alkoxy group is an ethoxy group.

A surfactant mixture in which the proportion of ethoxy groups to the total number of alkoxy groups for the respective alkoxylation product is at least 0.5 for the short-chain component (A) and / or the long-chain component (B) is particularly preferred.

The surfactant mixture according to the present invention contains a short-chain component (A) comprising the alkoxylation product of branched alkanols, wherein the alkanols have 8 to 12 carbon atoms. More preferably, the alkano-1e has from 9 to 11 carbon atoms, especially preferred when the alkanols have 10 carbon atoms.

The short-chain component (A) of the surfactant mixture according to the invention may also contain only one such alkanol, but typically a mixture of such alkanols.

When several alkanols are used for the short-chain component (A), in the case where the alkanol has 10 carbon atoms, it is preferable that this mixture is a Cio-Guerbet alcohol mixture. Here, the main components are 2-propylheptanol and 5-methyl-2-propylhexanol. Preferably, the short-chain component (A) consists of at least 90%, preferably 95%, of such a mixed and especially preferred from at least 90%, preferably 95% 2-propylheptanol

It is possible that the alkoxylation is randomly distributed or blockwise, so that the above-mentioned alkoxy groups - if they are different - occur blockwise.

However, it is preferred that the alkoxylation product for the short-chain component (A) has a proportion of ethoxy groups to the total number of alkoxy groups, which is at least 0.5 for the respective alkoxylation product. More preferably, this is at least 0.75, and is particularly preferred when the alkoxylation product contains only ethoxy groups as alkoxy groups.

It is preferred if the alkanol mixture of the short-chain component (A) has a mean degree of branching of 0 to 2.5. The alkanol mixture of the short-chain component (A) preferably has an average degree of branching in the range from 0.9 to 1.5, particularly preferably 1.

In the surfactant mixture according to the invention, the short-chain component (A) preferably contains 2-propylheptanol. A mixture of 2-propylheptanol-1 and 2-propyl-4-methylhexanol-1 can also be used for the short-chain component (A), it being particularly preferred if the ratio of 2-propylheptanol-1: 2-propyl 4-methylhexanol-1 is about 70:30. Likewise, an isomer mixture of 2-propylheptanol-1, 2-propyl-4-methylhexanol-1 and 2-propylmethylhexanol-1 can be used.

Furthermore, the surfactant mixture may comprise alkoxylation products, wherein alkanols form these products which do not have the above-mentioned number of carbon atoms. These are in particular alkanols having 1 to 7 carbon atoms and alkanols having more than 12 carbon atoms. However, it is preferred if this group of compounds has a weight fraction of at most 10 wt .-%, preferably less than 5 wt .-%, based on the total weight of the surfactant mixture. Particularly preferred alkoxylate products for the short-chain component (A) are alkoxylates of the general formula (I).

C ₅ HiiCH (C ₃ H 7) CH ₂ O (A) n (B) _m H (I) with the meaning

A ethyleneoxy B C3-4-alkyleneoxy, that is propyleneoxy, butyleneoxy or mixtures thereof, preferably propyleneoxy, where groups A and B can be randomly distributed, alternating or in the form of two or more blocks in any order, n number from 0 to 30, m Number from 0 to 20 n + m at least 0.1 and at most 30 where

70 to 99 wt .-% alkoxylates A1, in which CsHn has the meaning n-CsHn, and

1 to 30 wt .-% alkoxylates A2, in which C ₅ Hn has the meaning C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ , present in the mixture.

In the general formula (I), n is preferably a number in the range of 0.1 to 30, especially 3 to 12. m is preferably a number in the range of 0 to 8, especially 1 to 8, particularly preferably 1 to 5. B is preferably propyleneoxy and / or butyleneoxy. In the alkoxylates according to the invention, propyleneoxy units and subsequently ethyleneoxy units can subsequently be present on the alcohol radical. The corresponding alkoxy radicals are preferably present in block form. n and m denote an average value, which is the average for the alkoxylates. Therefore, n and m can also differ from integer values. In the alkoxylation of alkanols, a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to some extent by using different alkoxylation catalysts. In the alkoxylate mixtures according to the invention, ethyleneoxy units and subsequently propyleneoxy units may also be present subsequently to the alcohol radical. Furthermore, there may be statistical mixtures of ethylene oxide units and propylene oxide units. Also 3- or Mehrblockalkoxylierung and mixed alkoxylation are possible. It is also possible that only ethylene oxide units A or only units B, in particular propylene oxide units, are present. By selecting suitable amounts of groups A and B, the property spectrum of the alkoxylate mixtures according to the invention can be adapted depending on the practical requirements. Particularly preferred is first reacted with propylene oxide, butylene oxide or mixtures thereof and then with ethylene oxide. However, it is likewise possible for the reaction to take place with ethylene oxide alone.

Particularly preferred in the general formula (I) B is propyleneoxy. n is then more preferably a number from 1 to 20; m is more preferably a number from 1 to 8. A surfactant mixture in which the at least one alkanol of the long-chain component (B) has 12 to 18 carbon atoms is particularly preferred.

Thus, the surfactant mixture of the present invention comprises a long-chain component (B) comprising the alkoxylation product of alkanols having a mean degree of branching of at most 3.5 and at least 12 to 18 carbon atoms. Preferably, the alkanol mixture of the long-chain component (B) has from 12 to 16 carbon atoms, e.g. 14 carbon atoms.

The long-chain component (B) may also be the alkoxylation product of a single alkanol, but typically has several such alcohols. The average degree of alkoxylation of the alkanol mixture for the long-chain component (B) according to the present invention assumes values of 0.1 to 30 alkoxy groups per alkanol. Preferably, the value is in the range of from 1 to 30 alkoxy groups, more preferably from 3 to 30, more preferably from 3 to 20, more preferably from 4 to 15, and most preferably from 5 to 10.

However, it is preferred that the alkoxylation product for the long-chain component (B) has a proportion of ethoxy groups to the total number of alkoxy groups, which is at least 0.5 for the respective alkoxylation product. More preferably, this is at least 0.75, and is particularly preferred when the alkoxylation product contains only ethoxy groups as alkoxy groups.

The alkanol mixture of the long-chain component (B) has an average degree of branching from 0 to a maximum of 3.5. There are various preferred embodiments: Preferably, the average degree of branching is 0.1 to 1 or more than 2.5 to 3.4.

In addition to alkoxylation products of such alkanols which form the long-chain component (B) of the surfactant mixture, it is likewise possible for alkoxylation products of unsaturated aliphatic alcohols to be present, these having the same number of carbon atoms as the alkanols for the long-chain component (B). However, it is preferred if this group of compounds has a weight fraction based on the total weight of the surfactant mixture of less than 30% by weight, preferably less than 15% by weight. More preferably, the proportion is less than 10 wt .-%, in particular less than 5 wt .-%.

Furthermore, the surfactant mixture may comprise alkoxylation products, wherein alkanols form these products which do not have the above-mentioned number of carbon atoms. These are in particular alkanols having 1 to 12 carbon atoms and alkanols having more than 18 carbon atoms. However, it is preferred if this group of compounds has a weight fraction of at most 10% by weight, preferably at most 5% by weight, based on the total weight of the surfactant mixture. In addition, alkoxylation products of alkanols having a maximum of 3.5 branching may occur, which are not alkoxylated or have a higher degree of alkoxylation exhibit. A degree of alkoxylation of 31 and more alkoxy groups should be mentioned in particular. It is preferred if this group of compounds has less than 30% by weight, preferably less than 15% by weight, based on the total weight of the surfactant mixture. More preferably, the proportion is less than 10% by weight, in particular less than 5% by weight.

A surfactant mixture as described above in which the ratio of the molar fraction of the short-chain component (A) in the surfactant mixture to the molar fraction of the long-chain component (B) in the surfactant mixture assumes a value in the range from 99: 1 to 1:99 represents one further preferred subject of the present invention.

The surfactant mixture of the present invention contains components (A) and (B) each containing at least one alkoxylation product of alcohols. The surfactant mixture according to the invention may also contain residues of the unreacted alcohols. However, it is preferred if their proportion is below 15% by weight, more preferably below 10% by weight, based on the total weight of the surfactant mixture.

A surfactant mixture in which the short-chain component (A) and the long-chain component (B) differ in their alkoxyl groups is preferable.

The alkoxylation products can be used as such, or their phosphates, sulfate esters or Ethercarboxylate (carbonates) are used. These may be neutral or present as a salt. Suitable counterions are alkali metal and alkaline earth metal cations or ammonium ions and also alkyl and alkanolammonium ions.

A formulation comprising a surfactant mixture according to the invention represents a further embodiment of the invention. Preferably, the ratio of the mass fraction of the short-chain component (A) in the surfactant mixture or in the formulation to the mass fraction of the long-chain component (B) in the surfactant mixture or in the formulation in FIG Range of from 99: 1 to 1:99. More preferably, this range is 95: 5 to 25: 75, more preferably 90:10 to 50:50, even more preferably 80:20 to 50:50, and especially in the range from 70:30 to 50:50. Preferably, the proportion is greater than 1: 1. The added amount of components (A) and (B) relative to the total amount of the surfactant mixture in a formulation is preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 75% by weight. , more preferably 90 wt .-%, based on the total weight of the surfactant mixture.

The formulation may contain, for example, 0.01 to 90% by weight of water. In addition or alternatively, the formulation may comprise further surfactants or hydrotropes or mixtures thereof. For example, alcohol alkoxylates of the formula P (OR-Ao _n ) _m -H may be mentioned here, where P is a saturated, unsaturated or aromatic carbon skeleton to which m alcohol functions are linked, which in turn were etherified with an average of n alkylene oxide units , n has a value of 1 to 4 and m has a value of 1 to 10. R is an alkylene group having 1 to 10 C atoms, Ao is a C ₂ -C 5 alkylene oxide. Examples thereof are methylethylene glycols, butyl ethylene glycols, pentyl ethylene glycols, hexyl ethylene glycols, butyl propylene glycols, trimethylolpropane ethoxylates, glycerol ethoxylates, pentaerythritol ethoxylates, ethoxylates and propoxylates of bisphenol A.

In addition to the components (A) and (B), the surfactant mixture or the formulation according to the invention may contain other surfactants which differ from the components (A) and (B) or contain further chemical compounds. Here, for example, called polyalkylene glycols, which are optionally formed or added in the preparation of the mixture or the formulation. Exemplary polyalkylene glycols are polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol (PBG), and combinations thereof. Particularly preferred are polyethylene glycols. These may have a number average molecular weight of up to 12,000 g / mol. The polyalkylene glycols may have, for example, a number average molecular weight of 200 to 12,000, 200 to 3000, 300 to 2000, 400 to 2000, 300 to 1000, 400 to 1000, 400 to 800, 600 to 800 or about 700 g / mol. An exemplary chemical structure of polyethylene glycol having a number average molecular weight of about 700 g / mol is:

HIGH ₂ (CH ₂ OCH ₂ ) χCH ₂ OH, where x is a natural number from 9 to 22. Based on the total weight of the mixture, the proportion of polyalkylene glycols is preferably from 1 to 20, more preferably from 4 to 14,% by weight.

The surfactant mixtures or formulations according to the invention can be used, for example, as surfactant formulations for cleaning hard surfaces. Suitable surfactant formulations which can be additized with the surfactant mixtures according to the invention are described, for example, in Formulating Detergents and Personal Care Products by Louis Ho Tan Tai, AOCS Press, 2000. They contain, for example as further components soap, anionic surfactants such as LAS (linear alkylbenzenesulfonate) or paraffin sulfonates or FAS (fatty alcohol sulfate) or FAES (fatty alcohol ether sulfate), acid such as phosphoric acid, sulfamic acid, citric acid, lactic acid, acetic acid, other organic and inorganic acids, solvents such as ethylene glycol , Isopropanol, complexing agents such as EDTA (N, N, N ', N'-ethylenediaminetetraacetic acid), NTA (N, N, N-nitrilotriacetic acid), MGDA (2-methyl-glycine-N, N-diacetic acid), GLDA (glutamic acid diacetate) , ASDA (aspartic acid diacrylate), IDS (iminodisuccinate), HEIDA (hydroxyethyl imine diacetate), EDDS (ethylenediamine disuccinate), phosphonates, polymers such as polyacrylates, copolymers of maleic-acrylic acid, alkali donors such as hydroxides, silicates, carbonates, perfume oils, oxidants such as Perborates, peracids or trichloroisocyanuric acid, Na or K dichloroisocyanurates, enzymes; See also Milton J. Rosen, Manilal Dahanayake, Industrial Utilization of Surfactants, AOCS Press, 2000, and Nikolaus Schonfeldt, Ethyleneoxyadhesive Surfaces. Here are also formulations for the other applications mentioned dealt with in principle. It can be household cleaners such as all-purpose cleaners, dishwashing detergents for manual and automatic dishwashing, metal degreasing, industrial applications such as detergents for the food industry, bottle washing, etc. It may also be printing roll and printing plate cleaning agents in the printing industry. Suitable further ingredients are known to the person skilled in the art.

The usual constituents of the formulations according to the invention include, when it comes to fiber and textile treatment agents, for example, builders, surfactants, bleaching agents, enzymes and other ingredients, as described below. Builder Suitable inorganic builders (A ') for combination with the surfactants according to the invention are, above all, crystalline or amorphous aluminosilicates with ion-exchanging properties, in particular zeolites. Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially exchanged with other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in EP-A 0 038 591, EP-A 0 021 491, EP-A 0 087 035, US Pat. No. 4,604,224, GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384,070 and WO-A 94/24251. Suitable crystalline silicates (A) are, for example, disilicates or layered silicates, for. B. SKS-6 (manufacturer: Hoechst). The silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates.

Amorphous silicates such as sodium metasilicate, which comprises a polymeric structure, or Britesil ^® H20 (manufactured by Akzo) are also useful.

Suitable inorganic builders based on carbonate are carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate.

Usual phosphates as inorganic builders are polyphosphates such. B. pentasodium triphosphate.

The components (A) mentioned can be used individually or in mixtures with one another. Of particular interest as an inorganic builder component is a mixture of aluminosilicates and carbonates, in particular of zeolites, especially zeolite A, and alkali metal carbonates, especially sodium carbonate, in a weight ratio of 98: 2 to 20:80, in particular of 85: 15 to 40: 60. In addition to this mixture, other components (A ') may be present.

In a preferred embodiment, the laundry detergent according to the invention contains

Formulation 0.1 to 20 wt .-%. in particular from 1 to 12% by weight of organic cobuilders (B ') in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular in particular polycarboxylic acids, or phosphonic acids or their salts, especially Na or K salts.

Suitable low molecular weight carboxylic acids or phosphonic acids for (B ') are, for example:

C 4 -C 20 di-, tri- and tetracarboxylic acids such as e.g. Succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids with C 2 -C 16 -alkyl or -alkenyl radicals;

C 4 -C 20 hydroxycarboxylic acids, e.g. Malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;

Aminopolycarboxylic acids such as e.g. Nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, methylglycinediacetic acid and alkylethylenediamine triacetate;

Salts of phosphonic acids, e.g. Hydroxyethane. Suitable oligomeric or polymeric carboxylic acids for (B ') are, for example:

Oligomaleeinsäuren, as described for example in EP-A 451 508 and EP-A 396 303; Copolymers and terpolymers of unsaturated C 4 -C 8 -dicarboxylic acids, comonomers being monoethylenically unsaturated monomers from group (i) in amounts of up to 95% by weight,

from the group (ii) in amounts of up to 60 wt .-% and

from the group (iii) may be copolymerized in amounts of up to 20 wt .-%.

Examples of suitable unsaturated C 4 -C 8 -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid. The group (i) comprises monoethylenically unsaturated Cs-Cs monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Preferably, from group (i), acrylic acid and methacrylic acid are used. Group (ii) comprises monoethylenically unsaturated C 2 -C 22 -olefins, vinylalkyl ethers having C 1 -C 8 -alkyl groups, styrene, vinyl esters of C 1 -C 8 -carboxylic acids, (meth) acrylamide and vinylpyrrolidone. From group (ii), preference is given to using C 2 -C 6 -olefins, vinylalkyl ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate. Group (iii) comprises (meth) acrylic esters of C 1 -C 8 -alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 -amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) contain copolymerized vinyl esters, these may also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 43 13 909.

Copolymers of dicarboxylic acids are preferably suitable for (B '): copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of from 30:70 to 90:10 with molecular weights of from 100,000 to 150,000;

Terpolymers of maleic acid, acrylic acid and a vinyl ester of a Ci-C3 carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), wherein the weight ratio of acrylic acid to vinyl ester in the range of 30: 70 to 70: 30 may vary;

Copolymers of maleic acid with C2-Cs olefins in the molar ratio 40:60 to 80:20, with copolymers of maleic acid with ethylene, propylene or isobutene in the molar ratio 50:50 are particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US Pat. No. 5,227,446, DE-A 44 15 623 and DE-A 43 13 909 are also suitable as (B '). Examples of suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid in amounts of from 40 to 95% by weight, based on the component to be grafted to be grafted on.

For modification, in addition up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers may be present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).

As a graft base, degraded polysaccharides such as e.g. acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolysates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as e.g. Mannitol, sorbitol, aminosorbitol and N-alkylglucamine, as well as polyalkylene glycols having molar masses of up to Mw = 5,000, such as Polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alko- xylierte mono- or polyhydric Ci-C22-alcohols, see. US Pat. No. 5,756,456.

Grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization. For grafting, a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used. Polyglyoxylic acids suitable as (B ') are described, for example, in EP-B 001 004, US Pat. No. 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the polyglyoxylic acids may have different structures.

Examples of suitable polyamidocarboxylic acids and modified polyamidocarboxylic acids as (B ') are known from EP-A 454 126, EP-B 511 037, WO-A 94/01486 and EP-A 581 452.

As (B ') is used in particular also polyaspartic acids or cocondensates of

Aspartic acid with further amino acids, C4-C25 mono- or dicarboxylic acids and / or C4-C25 mono- or diamines. Particularly preferred are in phosphorus-containing acids prepared, modified with C6-C22 mono- or dicarboxylic acids or with C6-C22 mono- or - diamines modified polyaspartic acids.

Suitable (B ') condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds are e.g. known from WO-A 93/22362 and WO-A 92/16493. Such condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.

Also suitable as (B ') are ethylenediamine disuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.

Furthermore, oxidized starches may be used as organic co-builders in addition to (B '). surfactants

In addition to the surfactant mixture according to the invention, it is possible to use further surfactants. Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for. As Cg-Cn-alcohol sulfates, Ci2-Ci4-alcohol sulfates, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are alkanesulfonates such as C8-C24, preferably Cio-Ci8-alkanesulfonates and soaps such as the Na and K salts of C8-C24 carboxylic acids.

Further suitable anionic surfactants are C9-C20-linear alkylbenzenesulphonates (LAS) and -alkyltoluenesulphonates.

Also suitable as anionic surfactants (C) are C8-C24-olefinsulfonates and disulphonates, which may also be mixtures of alkene and hydroxyalkanesulfonates or -disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, Pa - raffinic sulfonates containing from about 20 to about 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyltau- rate, acylmethyl taurates, alkylsuccinic acids, alkenylsuccinic acids or their half-esters or hemiamides, alkylsulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids, acylsarcosinates, sulfated alkylpolyglucosides, alkylpolyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferably added to the fiber and textile treatment agent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

The component (C) is present in the fiber and textile treatment agent according to the invention preferably in an amount of 3 to 30 wt .-%, in particular 5 to 20 wt .-% before. If C9-C2o-Nnear alkylbenzenesulfonates (LAS) are also used, they are usually used in an amount of up to 25% by weight, in particular up to 20% by weight. Only one class of anionic surfactants can be used alone, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use mixtures of different classes, eg. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates. Within the individual classes of anionic surfactants it is also possible to use mixtures of different species.

Another class of suitable surfactants are nonionic surfactants D, in particular alkylphenol alkoxylates such as alkylphenol ethoxylates with C6-C14-alkyl chains and 5 to 30 mol of alkylene oxide units. Another class of nonionic surfactants are alkyl polyglucosides or hydroxyalkyl polyglucosides having 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1, 1 to 5 glucoside units. Another class of nonionic surfactants are N-alkylglucamides with C6-C22 alkyl chains. Such compounds are obtained, for example, by acylation of reducingly-terminated sugars with corresponding long-chain carboxylic acid derivatives.

Also suitable as nonionic surfactants (D) are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic®) and Tetronic®) brands from BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-alkoxy fatty acid derivatives. Aryloxy-polyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end-capped, and fatty acid alkanolamide alkoxylates. The component (D) is present in the fiber and textile treatment agent according to the invention preferably in an amount of 1 to 20 wt .-%, in particular 3 to 12 wt .-% before. Only one class of nonionic surfactants alone can be used, in particular only alkoxylated C8-C22 alcohols, but it is also possible to use mixtures of different classes. Within the individual classes of nonionic surfactants, mixtures of different species can also be used.

Since the balance between the surfactant types mentioned is of importance for the effectiveness of the fiber and textile treatment agents according to the invention, anionic surfactants (C) and nonionic surfactants (D) are preferably in the weight ratio of 95: 5 to 20:80, in particular from 80:20 to 50:50. The surfactant constituents of the surfactant mixture according to the invention should also be taken into account. Furthermore, cationic surfactants (E) can also be present in the fiber and textile treatment agents according to the invention.

Suitable cationic surfactants are, for example, ammonium-containing surface-active compounds, such as e.g. Alkyldimethylammoniumhalogenide and compounds of the general formula

RR ¹ R ¹¹ FTN ⁺ x- in which the radicals R to R '"are alkyl, aryl radicals, alkylalkoxy, arylalkoxy, hydroxyalkyl (alkoxy), hydroxyaryl (alkoxy) groups and X is a suitable anion ,

Optionally, the fiber and textile treatment agents of the invention may also contain ampholytic surfactants (F), such as e.g. aliphatic derivatives of secondary or tertiary amines which contain an anionic group in one of the side chains, alkyldimethylamine oxides or alkyl or alkoxymethylamine oxides.

Components (E) and (F) may contain up to 25%, preferably 3-15% in the fiber and textile treatment agent. bleach In a further preferred embodiment, the fiber and textile treatment agent according to the invention additionally contains 0.5 to 30 wt .-%, in particular 5 to 27 wt .-%, especially 10 to 23 wt .-% bleaching agent (G). Examples are alkali metal perborates or alkali metal perhydrate, in particular the sodium salts.

An example of a useful organic peracid is peracetic acid, which is preferably used in commercial laundry or commercial cleaning. Advantageously usable fiber and textile treatment agents contain C-12-percarboxylic acids, C8-16 -dipercarboxylic acids, imidopercaproic acids, or aryldipercaproic acids. Preferred examples of acids which can be used are peracetic acid, linear or branched octane, nonane, decane or dodecane monoperacids, decane and dodecanedioic acid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid and terephthaloyldipercaproic acid. It is likewise possible to use polymeric peracids, for example those which contain acrylic acid structural units in which a peroxy function is present. The percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts. These bleaching agents (G) are optionally used in combination with 0 to 15 wt .-%, preferably 0.1 to 15 wt .-%, in particular 0.5 to 8 wt .-% bleach activators (H). In the case of color detergents, the bleaching agent (G) (if present) is generally used without bleach activator (H), otherwise bleach activators (H) are usually present. Suitable bleach activators (H) are: polyacylated sugars, eg. For example, pentaacetylglucose;

Acyloxybenzolsulfonsäuren and their alkali and alkaline earth metal salts, eg. Sodium p-isononanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate;

N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. N, N, N ', N'-tetraacetylmethylenediamine and ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1, 3-diacylated hydantoins such as 1,3-diacetyl -5,5-dimethylhydantoin; N-alkyl-N-sulfonyl-carboxamides, eg. N-methyl-N-mesyl-acetamide or N-methyl-N-mesylbenzamide;

N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. Monoacetylmaleic acid hydrazide;

O, N, N-trisubstituted hydroxylamines, for example O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, -succinyl-hydroxylamine or O, N, N-triacetylhydroxylamine; - N, N'-Diacyl-sulfurylamides, z. B. N, N'-dimethyl-N, N'-diacetylsulfurylamid or N ₁ N'-diethyl-N, N'-dipropionyl-sulfurylamide;

Triacylcyanurates, e.g. Triacetyl cyanurate or tribenzoyl cyanurate; - Carboxylic anhydrides, eg. Benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;

1, 3-Diacyl-4,5-diacyloxy-imidazolines, eg. B. 1,3-diacetyl-4,5-diacetoxyimidazoline; Tetraacetylglycoluril and tetrapropionylglycoluril; diacylated 2,5-diketopiperazines, e.g. 1,4-diacetyl-2,5-diketopiperazine;

Acylation products of propylene diurea and 2,2-dimethylpropylenediurea, e.g. tetraacetylpropylenediurea; α-acyloxy-polyacyl malonamides, e.g. For example, α-acetoxy-N, N'-diacetylmalonamide;

Diacyl-dioxohexahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;

Benz (4H) 1, 3-oxazin-4-ones with alkyl radicals, eg. As methyl, or aromatic radicals such as phenyl, in the 2-position. The bleach system of bleaches and bleach activators described may optionally also contain bleach catalysts. Suitable bleach catalysts are included for example quaternized imines and sulfonimines, which are described, for example, in US Pat. No. 5,360,569 and EP-A 0 453 003. Particularly effective bleach catalysts are manganese complexes which are described, for example, in WO-A 94/21777. Such compounds are incorporated in the case of their use in detergent formulations at most in amounts of up to 1, 5 wt .-%, in particular up to 0.5 wt .-%.

In addition to the described bleaching system comprising bleaches, bleach activators and optionally bleach catalysts, the use of systems with enzymatic peroxide release or of photoactivated bleach systems is also conceivable for the fiber and textile treatment agent according to the invention.

enzymes

In a further preferred embodiment, the fiber and textile treatment agent according to the invention additionally contains 0.05 to 4 wt .-% enzymes (J). Preferably in

Enzymes used in fiber and textile treatment agents are proteases, amylases,

Lipases and cellulases. Of the enzymes are preferably amounts of 0.1 - 1, 5

Wt .-%, in particular preferably 0.2 to 1, 0 wt .-%, added to the formulated enzyme. Suitable proteases are, for. Savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is e.g. Lipolase (manufacturer: Novo Nordisk). A suitable

Cellulase is for example Celluzym (manufacturer: Novo Nordisk). Also the use of

Peroxidases to activate the bleaching system is possible. You can use individual enzymes or a combination of different enzymes. Optionally, the textile detergent formulation according to the invention can still enzyme stabilizers, for. As calcium propionate, N atri formate iat or boric acids or their salts, and / or oxidation inhibitors.

Other Ingredients The formulation according to the invention may contain, in addition to the components mentioned, the following further customary additives in the quantities customary for this purpose:

Grayness Inhibitors and Soil Release Polymers Suitable soil release polymers and / or grayness inhibitors for fiber and textile treatment agents include: Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids; Polyesters of unilaterally end-capped polyethylene oxides with dihydric and / or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from US-A 3,557,039, GB-A 1 154 730, EP-A 0 185 427, EP-A 0 241 984, EP-A 0 241 985, EP-A 0 272 033 and US-A 5,142,020.

Further suitable soil-release polymers are amphiphilic graft copolymers or copolymers of terephthalic acid, vinyl and / or acrylic esters on polyalkylene oxides (cf., US-A 4,746,456, US-A 4,846,995, DE-A 37 11 299, US-A 4,904,408, US Pat -A 4,846,994 and US-A 4,849,126)

Furthermore, anti-redeposition agents such as modified celluloses, e.g. As methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose present.

Fluorocarbon products are also preferably used for the textile pre-treatment and post-treatment.

Another object of the present invention is a process for preparing a surfactant mixture according to the invention, comprising the steps

(a) alkoxylation of an alkanol or of an alkanol mixture, wherein the alkanol or the alkanol mixture has from 9 to 11, preferably 10 carbon atoms, the average number of alkoxy groups per alkanol group in the alkoxylation product is from 1 to 20, the alkoxy groups C2-4- Represent alkoxy groups and the alkanol mixture has a mean degree of branching from 0 to 2.5. The alkanol mixture of the short-chain component (A) preferably has an average degree of branching in the range from 0.9 to 1.5, particularly preferably 1;

(b) alkoxylation of an alkanol mixture in which the alkanol mixture has 12 to 18 carbon atoms, the average number of alkoxy groups per alkanol group in the alkoxylation product is 1 to 20, the alkoxy groups are C 2-4 alkoxy groups and the alkanol mixture has a mean degree of branching 0 to 3.5, preferably from 0.9 to 2.5, such as 2; and (c) mixing the alkoxylation products obtained in steps (a) and (b).

It will be apparent to those skilled in the art that the degree of alkoxylation may be different. In addition to the above-described process for producing a surfactant mixture, the corresponding alkanols for the short-chain component (A) and long-chain component (B) may also be mixed prior to the alkoxylation and then subjected to alkoxylation. Accordingly, a process for the preparation of a surfactant mixture according to the invention, comprising the steps

(a) mixing a first alcohol or alcohol mixture having from 9 to 11, preferably 10 carbon atoms and a mean degree of branching from 0 to 2.5, the alkanol mixture of the short-chain component (A) preferably having an average degree of branching in the range from 0.9 to 1, 5 and more preferably of 1, with at least one second alkanol mixture having 12 to 18 carbon atoms and an average degree of branching from 0 to 3.5, preferably from 0.9 to 2.5, such as 2 has; and

(b) alkoxylating the mixture of first alkanol or alkanol mixture and second alkanol mixture, the number of alkoxy groups per alkanol group in the alkoxylation product assuming an average value of from 1 to 20, and the alkoxy groups being C 2-4 alkoxy groups,

a further subject of the present invention. Furthermore, a process for the preparation of a surfactant mixture according to the invention may comprise the following steps:

(a) alkoxylating a first alkanol mixture wherein the number of alkoxy groups per alkanol group in the alkoxylation product has an average value of 0.1 to 30 and the alkoxy groups are C2-4 alkoxy groups;

(b) adding the second alkanol mixture; (c) alkoxylating the mixture of (b), wherein the number of alkoxy groups per alkanol group in the alkoxylation product has an average value of 0.1 to 30 and the alkoxy groups represent C2-4 alkoxy groups, the first alkanol mixture being 9 to 11, preferably 10 carbon atoms and an average degree of branching of 0.5 to 2.5, preferably 0.9 to 1, 5 and particularly preferably 1 and the second alkanol mixture 12 to 18 carbon atoms and an average degree of branching from 0 to a maximum of 3.5, preferably 0 , 1 to 1 or more than 2.5 to 3.4 or first and second mixture are reversed.

The order of addition of the alkanol mixtures can thus be chosen arbitrarily.

The alkoxylate mixtures of the invention are obtained by alkoxylation of the underlying alcohols C5HnCH (C3H7) CH2θH. The starting alcohols can be mixed from the individual components, resulting in the ratio according to the invention.

In the general formula (I), the group CsHn may be n-CsHn, C ₂ H ₅ CH (CH ₃ ) CH ₂ or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ . The alkoxylates are mixtures in which

70 to 99 wt .-%, preferably 85 to 96 wt .-% alkoxylates A1 are present, in which C5H11 has the meaning n-CsHn, and

1 to 30 wt .-%, preferably 4 to 15 wt .-% alkoxylates A2, in which C5H11 has the meaning C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ has ,

The radical C ₃ H ₇ preferably has the meaning nC ₃ H ₇ .

The alkoxylation is preferably catalyzed by strong bases which are expediently added in the form of an alkali metal alkoxide, alkali metal hydroxide or alkaline earth metal hydroxide, generally in an amount of from 0.1 to 1% by weight, based on the amount of the alkanol R ² -OH (See G. Gee et al., J.Chem.Soc. (1961), 1345; B. Wojtech, Makromol. Chem. 66, (1966), 180). Acid catalysis of the addition reaction is also possible. In addition to Bronsted acids are also Lewis acids such as AICI ₃ or BF ₃ dietherate, BF ₃ , BF ₃ x H ₃ PO ₄ , SbCl ₄ x 2 H ₂ O, Hydrotalcite (See PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963).) Also suitable as a catalyst are double metal cyanide (DMC) compounds In principle, all compounds known to the person skilled in the art can be used.

Suitable catalyst DMC compounds are u. a. in WO-A 03/091192.

The DMC compounds can be used as a powder, paste or suspension or be shaped into a shaped body, introduced into moldings, foams or the like, or applied to shaped bodies, foams or the like.

The catalyst concentration used for the alkoxylation, based on the final amount skeleton, is typically less than 2000 ppm (ie mg catalyst per kg product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, more preferably less than 25 ppm.

The addition reaction is carried out at temperatures of 90 to 240 ⁰ C, preferably from 120 to 180 ⁰ C, in a closed vessel. The alkylene oxide or the mixture of different alkylene oxides is mixed with the mixture of alkanol mixture according to the invention and alkali under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature. If desired, the alkylene oxide can be diluted with up to about 30 to 60% with an inert gas. This provides additional security against explosive polyaddition of the alkylene oxide.

If an alkylene oxide mixture is used, polyether chains are formed in which the various alkylene oxide units are virtually randomly distributed. Variations in the distribution of the building blocks along the polyether chain arise due to different reaction rates of the components and can also be achieved arbitrarily borrowed by continuous supply of an alkylene oxide mixture of program-controlled composition. If the various alkylene oxides are added brought to the reaction, we obtain polyether chains with block-like distribution of alkylene oxide units.

The length of the polyether chains varies randomly within the reaction product by an average value, the stoichiometric value resulting essentially from the addition amount.

Preferred alkoxylate mixtures of the general formula (I) can be obtained according to the invention by reacting alcohols of the general formula C5HiiCH (C3H ₇₎ CI-l2θl-l xylierungsbedingungen first with propylene oxide and then with ethylene oxide to alcohol or with ethylene oxide only. Suitable alkoxylation conditions are described above and in Nikolaus Schonfeldt, Grenzflächenaktive Äthylenoxid adducts, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart 1984. In general, the alkoxylation is carried out in the presence of basic catalysts such as KOH in substance. However, the alkoxylation can also be carried out with the concomitant use of a solvent. To prepare these alkoxylate mixtures according to the invention, the alcohols are first reacted with a suitable amount of propylene oxide and then with a suitable amount of ethylene oxide or only with ethylene oxide. In this case, a polymerization of the alkylene oxide is set in motion, which inevitably leads to a statistical distribution of homologues whose mean value is given here with n and m.

The alkoxylate mixtures according to the invention for the short-chain component (A) only require a propylene oxide (PO) block of very short length bonded directly to the alcohol in order to lower the residual alcohol content. This is particularly advantageous because the biodegradability of the product decreases as the PO block lengthens. Such alkoxylate mixtures thus allow maximum degrees of freedom in the choice of the length of the PO block, the length being limited downwards by the increasing residual alcohol content and upwards by the deterioration of the biological degradability. This is particularly advantageous if only a short ethylene oxide block follows the PO block.

Therefore, it is further preferred in the context of the present invention for m to be an integer or fractional number with 0 <m <5, for example 0 <m <2, preferably 0 <m <1.5, particularly preferably 0 <m <1.2 , in particular 0 <m <1. Alkyl alkoxylates (BA) of the general formula (II) are particularly preferred here.

R ¹ O- (CH ₂ CH (R ² ) O) _m (CH ₂ CH ₂ O) n H (II). The alkyl alkoxylates (BA) comprise m alkoxy groups of the general formula - CH ² CH (R ² ) O- and n ethoxy groups -CH ² CH ² O-. The formula of the alkoxy group is expressly to include units of the formula -CH (R ² ) CH ² O-, ie the inverse incorporation of the alkoxy group into the surfactant, it also being possible for both arrangements to be represented in a surfactant molecule. R ² is selected so that the underlying alkoxy group represents a C 3-10 -alkoxy group, wherein a surfactant molecule can also have several different radicals R ² . R ² is preferably a methyl, ethyl, and / or n-propyl group, and particularly preferably a methyl group, ie the alkoxy group is a propoxy group.

The numbers n and m relate in a known manner to the average value of the alkoxy or ethoxy groups present in the surfactant, the mean value of course not having to be a natural number, but also being an arbitrary rational number.

The numbers n and m have the meaning given for formula (I). In the mixture, however, the values n and m for short and long-chain components need not be equal. The arrangement of the alkoxy groups and ethoxy groups in the surfactant (II), if both types of groups are present, may be random or alternating, or there may be a block structure. It is preferably a block structure in which the alkoxy and ethoxy groups are actually arranged in the order of R ¹ O - alkoxy block - ethoxy block-H.

The alkyl alkoxylates (BA) can be prepared in a manner known in principle by alkoxylation of the alcohol R ¹ -OH. The carrying out of alkoxylations is known in principle to the person skilled in the art. It is also known to the person skilled in the art that the molecular weight distribution of the alkoxylates can be influenced by the reaction conditions, in particular the choice of the catalyst. The alkyl alkoxylates (BA) can be prepared, for example, by base-catalyzed alkoxylation. For this purpose, the alcohol R ¹ -OH can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal such as sodium methylate. By reduced pressure (eg <100 mbar) and / or increasing the temperature (30 to 150 ⁰ C) can still be withdrawn in the mixture existing water. The alcohol is then present as the corresponding alkoxide. It is then inertized with inert gas (eg nitrogen) and the or the alkylene oxide (s) at temperatures of 60 to 180 ⁰ C up to a pressure of max. 10 bar added gradually. At the end of the reaction, the catalyst can be neutralized by addition of acid (eg acetic acid or phosphoric acid) and can be filtered off if necessary. Alkyl alkoxylates prepared by KOH catalysis generally have a relatively broad molecular weight distribution.

In a preferred embodiment of the invention, the alkyl alkoxylates (BA) are synthesized by techniques known to those skilled in the art, which lead to narrower molecular weight distributions than in base-catalyzed synthesis. For this purpose, for example, double hydroxide clays as described in DE 43 25 237 A1 can be used as the catalyst. The alkoxylation can be carried out particularly preferably using double metal cyanide catalysts (DMC catalysts). Suitable DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular sections [0029] to [0041], and the literature cited therein. For example, Zn-Co type catalysts can be used. To carry out the reaction, alcohol R ¹ -OH can be added to the catalyst, the mixture is dehydrated as described above and reacted with the alkylene oxides as described. Usually, not more than 250 ppm of catalyst are used with respect to the mixture, and the catalyst may remain in the product due to this small amount. Surfactants of the invention prepared by means of DMC catalysis are distinguished by the fact that they result in a better lowering of the interfacial tension in the water-petroleum system than products prepared by means of KOH catalysis.

Alkylalkoxylates (BA) can also be prepared by acid-catalyzed alkoxylation. The acids may be Bronsted or Lewis acids. To carry out the reaction, alcohol R ¹ -OH can be added to the catalyst, the mixture can be dehydrated as described above and reacted with the alkylene oxides as described. At the end of the reaction, the catalyst can be neutralized by addition of a base, for example KOH or NaOH, and filtered off as required. be rung. With the choice of the catalyst, the structure of the hydrophilic group X can be influenced. While in basic catalysis the alkoxy units are incorporated into the alkyl alkoxylate predominantly in the orientation shown in formula (Ia), in acidic catalysis the units are incorporated into larger portions in the orientation (Ib).

The use of a surfactant mixture according to the invention or of a formulation according to the invention as emulsifier, foam regulator, wetting agent, in particular for hard surfaces and humectants constitutes a further subject of the present invention.

Other ingredients suitable for different applications are described in EP-A 0 620 270, WO 95/27034, EP-A 0 681 865, EP-A 0 616 026, EP-A 0 616 028, DE-A 42 37 178 and US 5,340,495 and in Schonfeldt, so described by way of example.

The use in detergents, for cleaning hard surfaces, in cosmetic, pharmaceutical and crop protection formulations, paints, coating compositions, adhesives, leather degreasing agents, for the textile industry, fiber processing, metal processing, food industry, water treatment, paper industry, fermentation or mineral processing and in emulsion polymerizations is preferred. Use of a surfactant mixture as described above or a formulation as described above for the pretreatment and / or after-treatment of fabrics or fabrics selected from the group consisting of: wool, cotton, polyamide, polyester, polyurethane-polyethylene glycol copolymers (eg Lycra® ) Polylactic acid, linen and mixtures of these.

The present invention is further illustrated by the following examples:

Example 1 : Surfactant A (Comparative Example)

1 mole of nonylphenol was ethoxylated by KOH catalysis with 9 moles of ethylene oxide (EO) to give a distribution of the degrees of ethoxylation. Example 2:

Surfactant B (comparative example)

300 g of a C12,14-alcohol mixture of C8 <0,3 wt .-%, C10 <1, 0 wt .-%, C12> 65,0 wt .-%, C14 21, 0 to 28,0 wt .-% , C16 4.0 to 8.0 wt .-%, C18 <0.5 wt .-%, for example, Radianol C12-C16 1726 Fa. Oleone were charged with 2.6 g of KOH (45 wt .-% in Water) and dehydrated together at 80 ⁰ C and reduced pressure (about 20 mbar). Then 594 g of ethylene oxide were metered in at 150 ^° C. and reacted at this temperature. The end of the reaction was determined by the pressure drop. After rinsing with inert gas and cooling to room temperature, the catalyst was neutralized by the addition of 1.25 g of concentrated acetic acid.

Example 3:

Surfactant C (Comparative Example)

316 g of a mixture of 2-propylheptanol (2-PH) and 5-methyl-2-propylhexanol sold by BASF as technical 2-propylheptanol (t2-PH) were mixed with 2.6 g of KOH (45% by weight). in water) and dewatered together at 80 ⁰ C and reduced pressure (about 20 mbar). Then at 120 208.8 g propylene oxide were metered in up to 130 ⁰ C and reacted at this temperature. The end of the reaction was determined via the pressure drop. Subsequently, 580.8 g of ethylene oxide were metered in and reacted at this temperature. After rinsing with inert gas and cooling to room temperature, the catalyst was neutralized by adding 1.25 g of concentrated acetic acid.

Example 4:

Surfactant D / 1

316 g of a mixture of 2-propylheptanol (2-PH) and 5-methyl-2-propylhexanol sold as t2-PH by BASF were initially charged with 2.6 g of KOH (45% by weight in water) and combined Dehydrated at 80 ⁰ C and reduced pressure (about 20 mbar). Then at 120 to 130 ⁰ C 139.2 g of propylene oxide were metered in and reacted at this temperature. The end of the reaction was determined by the pressure drop. Subsequently, 396 g of ethylene oxide were metered in and reacted at this temperature. After rinsing with inert gas and cooling to room temperature, the catalyst was neutralized by the addition of 1.25 g of concentrated acetic acid.

Example 5:

Surfactant D

Surfactant B and surfactant D / 1 were homogenized at about 60 ^° C. and then mixed in a mass ratio of 1: 1.

Example 6:

Surfactant E

see US2008 / 0103083

1260 g of a mixture of 2-propylheptanol (2-PH) and 5-methyl-2-propylhexanol, sold as t2-PH by BASF, 5040 g of a C12,14 alcohol mixture of C8 <0.3 wt.%, C10 <1, 0 wt .-%, C12> 65.0 wt .-%, C14 21, 0-28,0 wt .-%, C16 4.0 to 8.0 wt .-%, C18 <0.5 wt %, for example Radianol C12-C16 1726 from Oleon, were mixed with 61 g of potassium hydroxide-water mixture (45% by weight of KOH). The mixture is heated to 85 ⁰ C, and stirred for 1 h at this temperature. Subsequently, a temperature of 1 10 ⁰ C and a pressure of 90 psig was set. Thereafter, 8130 g of ethylene oxide are added at a feed rate of 1100 to 1200 g / h, while the temperature was raised to 145 ⁰ C. Both alcohol ethoxylate and polyethylene glycol were formed. After completion of the reaction, the reaction vessel was cooled to 80 ⁰ C and the surfactants were neutralized with glacial acetic acid. Example 7:

Surfactant F

161, 76 g of a mixture of 2-propylheptanol (2-PH) and 5-methyl-2-propylhexanol, which is sold as t2-PH by BASF, and 242.64 g of a C12,14 alcohol mixture of C8 <0.3 wt %, C10 <1, 0% by weight, C12> 65.0% by weight, C14 21, 0 to 28.0% by weight, C16 4.0 to 8.0% by weight, C18 <0.5 wt .-%, were charged with 2.6 g of KOH (45 wt .-% in water) and dewatered together at 80 ⁰ C and reduced pressure (about 20 mbar). Then at 150 ⁰ C 387.6 g ethylene oxide were metered in and reacted at this temperature. The end of the reaction was determined by the pressure drop. After rinsing with inert gas and cooling to room temperature, the catalyst was neutralized by the addition of 1.25 g of concentrated acetic acid. Example 8:

Surfactant G

65.42 g of a mixture of 2-propylheptanol (2-PH) and 5-methyl-2-propylhexanol sold as t2-PH by BASF and 261.68 g of a C12, 16 alcohol (eg Radianol C12 -C16 1726 Fa. Oleon) are charged with 2.6 g of KOH (45 wt .-% in water) and dehydrated together at 80 ⁰ C and reduced pressure (about 20 mbar). Then at 150 ⁰ C 449.3 g ethylene oxide were metered in and reacted at this temperature. The end of the reaction was determined by the pressure drop. After rinsing with inert gas and cooling to room temperature, the catalyst was neutralized by the addition of 1.25 g of concentrated acetic acid.

Example 9:

Surfactant H, see US2008 / 0103083

400 g of a mixture of 2-propylheptanol (2-PH) and 5-methyl-2-propylhexanol sold as t2-PH by BASF, 1600 g of a C12, 14 alcohol mixture of C8 <0.3 wt.%, C10 <1, 0 wt .-%, C12> 65.0 wt .-%, C14 21, 0 to 28.0 wt .-%, C16 4.0 to 8.0 wt .-%, C18 <0.5 % By weight, for example Radianol C12-C16 1726 from Oleon, were mixed with 22 g of potassium hydroxide-water mixture (45% by weight of KOH). The mixture was heated to 85 ⁰ C, and stirred for 1 h at this temperature. Subsequently, a temperature of 110 ⁰ C and a pressure of 90 psig was divided. Thereafter, 3753 g of ethylene oxide were added at a feed rate of 1100 to 1200 g / h while the temperature was raised to 145 ⁰ C. Both alcohol ethoxylate and polyethylene glycol were formed. After completion of the reaction, the reaction vessel was cooled to 80 ⁰ C and the surfactants were neutralized with glacial acetic acid.

Example 10:

readings

Surfactant BW wetting foam oil removal oil removal knit

(Def. S.u.) Gravexoil 921 from ting oil ES 22

Shell

Unit S ml Note Note

A compare 51 200 3 8

B see 88 285 1 5

C see 48 545 8 9

D 74 385 1 2

E 70 305 1 1 F 90 25 2 2

G 82 350 1 2

H 88 220 1 2

For the evaluation, the data for the wetting power and the foam performance were based on the reference (surfactant A) (value of surfactant A divided by the value of surfactant B, C,

..., K) and compared with surfactant A, B or C.

z. B. Realtive value for surfactant B = wetting time of surfactant A / wetting time of surfactant B

Concerning foam behavior, it had to be considered that the value of 0 ml is possible. Therefore, here the sum of the reference (surfactant A) + 100 ml divided by the sum of 100 + surfactant (A to K) was divided:

z. B. relative value for surfactant B = (100 + surfactant A) / (100 + surfactant B)

Relative values

Surfactant BW Net foam oil removal oil removal average

Gravexoil 921 Knitting oil ES

from Shell 22

A compare 1 1, 00 1, 00 1, 00 1, 00

B compare 0.58 0.78 3.00 1, 60 1, 49

C compare 1, 06 0.47 0.38 0.89 0.70

D 0.69 0.62 3.00 4.00 2.08

E 0.73 0.74 3.00 8.00 3.12

F 0.57 2.4 1, 50 4.00 2.12

G 0.62 0.67 3.00 4.00 2.07

H 0.58 0.94 3.00 4.00 2.13

Conclusion: the considered surfactant mixtures are much better suited for the considered applications.

Definition / description of the measurement conditions.

Nets of cotton (BW)

The tables show network times according to EN 1772 (August 2000),

After adding the respective amount of surfactant (1 g / l), the cotton net plate is taken with the immersion clamp, immersed in the test solution (VE - water + approx. 2 g soda / l) and the immersion clamp is opened, whereby the stopwatch is started. Measured is the Time from the moment of immersion to when the net begins to sink. From the results of at least 10 individual measurements at the same concentration, the mean value is calculated. Measurements in which the plate is stuck by tilting must be repeated.

Foaming behavior according to EN 12728

Instruments: graduated cylinder (1000 ml), perforated discs - foam stamp (perforated disc diameter: approx. 5.5 cm)

A solution of 1 g / l surfactant in 10 ° d water (heated to 40 ⁰ C) is prepared and filled 200 ml of it in the measuring cylinder. The foam is generated by blowing the foam stamp 30 times (a 1 sec.). An additional 30 seconds after shingling, the foam volume is measured (ml).

Evaluation:

ml foam = [total volume (foam + solution)] - 200 ml (sample solution)

oil removal

Execution:

On 10 g (length approx. 30 cm) of knitwear, one drop of the oil to be tested is applied with a pipette and left to work overnight.

Removal of the oil by washing test:

Fleet ratio: 1:20

Formulation: 1, 0 g / L of the detergent to be tested

1, 0 g / L soda (2 ml 10% solution), wash at 98 ⁰ C x 30 min

4 rinses at different temperatures. The samples are spun and dried

Rating:

1. Test Solution [0.4 g of a red dye are dissolved in 11 water.

2. 2.0 g knitwear (with oil stain)

3. Implementation: (In Lab-o-mat) • Add 8 ml of the test solution to a 250 ml beaker and make up to 80 ml of water.

• The temperature is brought to 60 ⁰ C and maintained during the dyeing process

• The knitted fabric to be tested is added and stirred for 10 minutes.

• The knitted fabric is rinsed cold for 10 min and dried for 3 min at 150 ⁰ C

Assessment: The lower the former oil stain is stained, the better the emulsifying ability of the detergent Grade 1 (completely removed) to 10 (no distance).

The examples show that the surfactant mixtures according to the invention have markedly improved foam behavior, wettability and oil release properties. The combination of these properties is not achievable with the previously known surfactant mixtures. That the effects at a temperature of 70 ⁰ C are particularly pronounced, is particularly advantageous because fibers and textiles in this temperature range, ie in the range of 60 to 80 ⁰ C of a pre- or post-treatment are subjected.

Claims

claims

1. containing surfactant mixture

(A) a short-chain component containing the alkoxylation product of alkanols, wherein the alkanols have 9 to 11 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation takes a value of 1 to 20, the alkoxy groups represent C 2-4 alkoxy and the alkanols one having a mean degree of branching in the range of 0 to 2.5; and

(B) a long-chain component containing the alkoxylation of alkanols, wherein the alkanols have 12 to 18 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation takes a value of 1 to 20, the alkoxy groups represent C 2-4 alkoxy groups and the alkanols having a mean degree of branching of 0 to 3.5; or their phosphate, sulfate esters and ether carboxylates.

2. A surfactant mixture according to claim 1, characterized in that the alkoxy groups are independently selected from the group consisting of ethoxy and propoxy group.

3. Surfactant mixture according to one of claims 1 or 2, characterized in that for the short-chain component (A) and / or the long-chain component (B), the proportion of ethoxy groups to the total number of alkoxy groups for the respective alkoxylation at least 0.5.

4. A surfactant mixture according to any one of claims 1 to 3, characterized in that the at least one alkanol of the long-chain component (B) has 12 to 18 carbon atoms.

5. A surfactant mixture according to claim 4, characterized in that the at least one alkanol of the long-chain component (B) has 12 to 16 carbon atoms.

6. A surfactant mixture according to any one of claims 1 to 5, characterized in that the ratio of the molar fraction of the short-chain component (A) in the surfactant mixture to the molar fraction of the long-chain component (B) in the surfactant mixture has a value in the range of 99: 1 to 1 : 99 accepts.

7. Formulation containing a surfactant mixture according to one of claims 1 to 6.

8. A process for preparing a surfactant mixture according to any one of claims 1 to 6, comprising the steps

(a) alkoxylation of an alkanol or of an alkanol mixture in which the alkanol or the alkanol mixture has 9 to 1 1 carbon atoms, the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value of 1 to 20, the alkoxy groups C2-4-

Alkoxy groups and the alkanol mixture has a mean degree of branching in the range of 0.9 to 1, 1;

(b) alkoxylation of an alkanol mixture wherein the alkanol mixture has from 12 to 18 carbon atoms, the average number of alkoxy groups per

Alkanolgruppe in the alkoxylation takes on a value of 1 to 20, the alkoxy groups represent C2-4 alkoxy groups and the alkanol mixture has an average degree of branching from 0 to 3.5; and

(c) mixing the alkoxylation products obtained in steps (a) and (b).

9. A process for the preparation of a surfactant mixture according to any one of claims 1 to 6, comprising the steps

(a) mixing a first alcohol or alcohol mixture having 9 to 11 carbon atoms and an average degree of branching in the range of 0.9 to 1.1 with at least one second alkanol mixture having 12 to 18 carbon atoms and a mean degree of branching of 0 to 3 5; and (b) alkoxylating the mixture of first alkanol or alkanol mixture and second alkanol mixture, wherein the number of alkoxy groups per alkanol group in the alkoxylation product assumes an average value of 1 to 20 and the alkoxy groups represent C 2-4 alkoxy groups.

10. Use of a surfactant mixture according to any one of claims 1 to 6 or a formulation according to claim 7 as an emulsifier, foam regulators, wetting agents, in particular for hard surfaces, humectants.

1 1. Use according to claim 10 in detergents, for cleaning hard surfaces, in cosmetic, pharmaceutical and crop protection formulations, paints, coatings, adhesives, leather degreasing agents, for the textile industry, fiber processing, metal processing, food industry, water treatment, paper industry, fermentation or mineral processing and in emulsion polymerizations ,

12. Use of a surfactant mixture according to any one of claims 1 to 6 or a formulation according to claim 7 for the pre- and / or post-treatment of

Fibers, fabrics and fabrics selected from the group consisting of: wool, cotton, polyamide, polyester, polyurethane-polyethylene glycol copolymer, polylactic acid, linen and mixtures thereof.