US20090023820A1

US20090023820A1 - Surfactant mixture containing short-chain and also long-chain components

Info

Publication number: US20090023820A1
Application number: US12/280,114
Authority: US
Inventors: James S. Dailey; Ernst Lippert; Sridhar G. Iyer; Ulrich Steinbrenner; Christoffer Kieburg; Jurgen Tropsch; Richard Baur; Soeren Zimdahl
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-02-22
Filing date: 2007-02-15
Publication date: 2009-01-22
Also published as: JP5210177B2; EP1988986B1; ATE450311T1; DE502007002180D1; WO2007096292A1; CA2640642C; CA2640642A1; CN101389398B; EP1988986A1; US7504373B2; US7503333B2; ES2336379T3; US20070225189A1; PL1988986T3; CN101389398A; KR101057048B1; KR20080087178A; JP2009527611A; US20080103083A1; BRPI0707852A2

Abstract

The present invention relates to a surfactant mixture comprising

(A) a short-chain component comprising the alkoxylation product of alkanols, where the alkanols have 8 to 12 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have an average degree of branching of at least 1; and
(B) a long-chain component comprising the alkoxylation product of alkanols where the alkanols have 13 to 20 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have an average degree of branching of from 0.0 to 0.3;
and phosphate esters, sulfate esters and ether carboxylates thereof.

In addition, the present invention relates to a formulation comprising such surfactant mixtures, and to the use of these, for example for the cleaning of hard surfaces.

Description

The present invention relates to a surfactant mixture, to formulations comprising such surfactant mixtures, to methods of producing the surfactant mixtures, and to their use.
Surfactants are amphiphilic interface-active compounds which comprise a hydrophobic molecular moiety and also a hydrophilic molecular moiety and, in addition, can have charged or uncharged groups. Surfactants are orientedly adsorbed at interfaces and thereby reduce the interfacial tension so that these can form, in solution, association colloids above the critical micelle-formation concentration, meaning that substances which are per se water-insoluble in aqueous solutions are solubilized.
On account of these properties, surfactants are used, for example, for wetting solids such as fibers or hard surfaces. Here, surfactants are often used in combinations with one another and with further auxiliaries. Typical fields of application are detergents and cleaners for textiles and leather, as formulation of paints and coatings and, for example, in the recovery of petroleum.
Interesting surfactants are in particular those which represent alkoxylation products of alcohols. Here, it has been shown that it is particularly favorable to provide such compounds in various mixtures.
JP-A 2004/091686 describes the mixture of surfactants, where an alkoxylated branched aliphatic alcohol having 8 to 11 carbon atoms is mixed with a further aliphatic alcohol having 12 to 20 carbon atoms, which is likewise alkoxylated.
JP-A 2003/336092 likewise describes polyalkoxylene alkyl ethers which have to satisfy certain conditions.
JP-A 2004/035755 describes a nonionic surface-active composition which has alkyleneoxy adducts of an aliphatic alcohol with a HLB value of from 6 to 14.5, and of an aliphatic alcohol with a HLB value of from 11 to 16.
WO-A 94/11330 describes alkoxylates of 2-propylheptanol and their use for cleaning textile materials.
The same alkoxylates are described in WO-A 94/11331 for degreasing hard surfaces.
Finally, DE-A 19921330 describes the use of branched fatty alcohol ethoxylates having 8 to 22 carbon atoms which can be used as wool detergents.
Despite numerous surfactants which are described in the prior art, there continues to be a need for surfactants or surfactant mixtures which have, at least in part, better properties than those from the prior art. Such properties refer in particular to their wetting behavior, salt tolerance, foam formation, low tendency to form gels, their washing performance and their emulsion stability.
An object of the present invention is therefore to provide a surfactant mixture which, at least in relation to one of the properties listed above, has behavior which is superior to surfactants of the prior art.
The object is achieved by a surfactant mixture comprising

(A) a short-chain component comprising the alkoxylation product of alkanols, where the alkanols have 8 to 12 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have an average degree of branching of at least 1; and
(B) a long-chain component comprising the alkoxylation product of alkanols where the alkanols have 13 to 20 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have an average degree of branching of from 0.0 to 0.3.

The degree of branching of the alkanols (of the alkanol mixture) here is defined as follows:
The degree of branching of an alcohol arises from the branches of the carbon backbone. For each alcohol molecule, it is defined as the number of carbon atoms which are bonded to three further carbon atoms, plus two times the number of carbon atoms which are bonded to four further carbon atoms. The average degree of branching of an alcohol mixture arises from the sum of all degrees of branching of the individual molecules divided by the number of individual molecules. The degree of branching is determined, for example, by means of NMR methods. This can be carried out through analysis of the carbon backbone with suitable coupling methods (COSY, DEPT, INADEQUATE), followed by a quantification via ¹³C NMR with relaxation reagents. However, other NMR methods or GC-MS methods are also possible.
The average number of alkoxy groups arises from the sum of all alkoxy groups of the individual molecules divided by the number of individual molecules.
Mainly, it has been found that a surfactant mixture, as described in more detail above, of short-chain and long-chain component can have particularly good properties, particularly with regard to the abovementioned properties.
The surfactant mixture according to the present invention comprises a short-chain component (A) which has the alkoxylation product of branched alkanols, where the alkanols have 8 to 12 carbon atoms. More preferably, the alkanols have 9 to 11 carbon atoms, it being particularly preferred if the alkanols have 10 carbon atoms.
The short-chain component (A) of the surfactant mixture according to the invention can also comprise only one such alkanol, but typically a mixture of such alkanols.
If two or more alkanols are used for the short-chain component (A) if the alkanol has 10 carbon atoms, it is preferred that this mixture is a C₁₀Guerbet alcohol mixture. Here, the main components are 2-propylheptanol and 5-methyl-2-propyl-hexanol. Preferably, the short-chain component (A) consists of at least 90%, preferably 95%, of such a mixture.
In addition, it is preferred that the short-chain component comprises no isodecanol.
The degree of alkoxylation of the alkanol(s) for the short-chain component (A) according to the present invention assumes, on average, values from 3 to 30 alkoxy groups per alkanol.
The alkoxy groups may be ethoxy, propoxy, butoxy and pentoxy groups. It is possible for the alkoxylation to take place in random distribution or blockwise, meaning that correspondingly blockwise groups chosen from ethoxy, propoxy, butoxy and pentoxy groups can arise.
However, it is preferred that the alkoxylation product for the short-chain component (A) has a fraction of ethoxy groups relative to the total number of alkoxy groups which is at least 0.5 for the particular alkoxylation product. More preferably, this is at least 0.75 and it is especially preferred if the alkoxylation product comprises exclusively ethoxy groups as alkoxy groups.
It is preferred if the alkanol mixture of the short-chain component (A) has an average degree of branching of from 1.0 to 2.0. More preferably, the alkanol mixture of the short-chain component (A) has an average degree of branching in the range from 1 to 1.5.
Besides alkoxylation products of branched alkanols which form the short-chain component of the surfactant mixture, it is likewise possible that alkoxylation products of unsaturated aliphatic alcohols are present, where these can have the same number of carbon atoms as the alkanols for the short-chain component (A). However, it is preferred if this group of compounds has a weight fraction, based on the total weight of the surfactant mixture, below 10% by weight, preferably less than 5% by weight.
In addition, the surfactant mixture can have alkoxylation products, where alkanols form these products which do not have the number of carbon atoms stated above. 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% by weight, preferably of less than 5% by weight, based on the total weight of the surfactant mixture.
Moreover, alkoxylation products of branched alkanols can arise which have a lower or higher degree of alkoxylation. Mention is to be made here in particular of a degree of alkoxylation of 1, 2, and 31 and more alkoxy groups. 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. Less than 10% by weight are more preferred, in particular less than 5% by weight.
In addition, the surfactant mixture of the present invention comprises a long-chain component (B) which has the alkoxylation product of alkanols which have an average degree of branching of from 0.0 to 0.3 and at least 13 to 20 carbon atoms. Preferably, the alkanol mixture of the long-chain component (B) has 16 to 20 carbon atoms and in particular 16 to 18 carbon atoms.
The long-chain component (B) can also be the alkoxylation product of a single alkanol, although this typically has two or more such alkanols.
If mixtures are used, C_12-14-coconut fatty alcohols, native alcohols or alkanols obtained from the Ziegler-ALFOL process, for example, are conceivable. Tallow fatty alcohol can likewise be used. This tallow fatty alcohol can be produced, for example, from cotton oil, linseed oil, corn oil, olive oil, peanut oil, rapeseed oil, rice bran oil, dyer's safflower oil, soybean oil, sunflower oil or beef fat, pork fat, poultry fat, fish fat. Preferably, the long-chain component (B) consists of at least 90% by weight, preferably of at least 95% by weight, of such a mixture.
The average degree of alkoxylation of the alkanol mixture for the long-chain component (B) according to the present invention assumes values from 3 to 30 alkoxy groups per alkanol.
The alkoxy groups can be ethoxy, propoxy, butoxy and pentoxy groups. It is possible for the alkoxylation to take place in random distribution or blockwise, meaning that correspondingly blockwise groups chosen from ethoxy, propoxy, butoxy and pentoxy groups can arise.
However, it is preferred that the alkoxylation product for the long-chain component (B) has a fraction of ethoxy groups relative to the total number of alkoxy groups which is at least 0.5 for the particular alkoxylation product. More preferably, this is at least 0.75 and it is particularly preferred if the alkoxylation product comprises exclusively ethoxy groups as alkoxy groups.
The alkanol mixture of the long-chain component (B) has an average degree of branching of from 0.0 to 0.3.
Besides alkoxylation products of such alkanols which form the long-chain component (B) of the surfactant mixture, it is likewise possible that alkoxylation products of unsaturated aliphatic alcohols are present, where these can have 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, below 30% by weight, preferably less than 15% by weight. More preferably, the fraction is less than 10% by weight, in particular less than 5% by weight.
In addition, the surfactant mixture can have alkoxylation products, where alkanols form these products which do not have the number of carbon atoms stated above. In particular, these are alkanols having 1 to 12 carbon atoms, and alkanols having more than 20 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.
Moreover, alkoxylation products of alkanols with branching from 0 to 0.3 can arise which have a lower or higher degree of alkoxylation. Here, mention is to be made in particular of a degree of alkoxylation of 1, 2, and 31 and more alkoxy groups. 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 fraction is below 10% by weight, in particular below 5% by weight.
Preferably, the ratio of the weight fraction of the short-chain component (A) in the surfactant mixture to the weight fraction of the long-chain component (B) in the surfactant mixture is a value range from 99:1 to 1:99. More preferably, this range is 97:3 to 30:70, in addition more preferably 95:5 to 50:50 and especially preferably 90:10 to 70:30.
The respective fraction of components (A) and (B) based on the total fraction of the surfactant mixture is preferably in each case at least 50% by weight, more preferably at least 60% by weight, further more preferably at least 75% by weight, in addition more preferably 90% by weight, based on the total weight of the surfactant mixture.
Preferably, the HLB value according to Griffin is in the range from 10 to 15 for the surfactant mixture according to the present invention.
The surfactant mixture of the present invention comprises components (A) and (B) which each comprise at least one alkoxylation product of alcohols. The surfactant mixture according to the invention can also still comprise residues of the unreacted alcohols. However, it is preferred if their fraction is less than 15% by weight, particularly preferably less than 10% by weight, based on the total weight of the surfactant mixture.
The alkoxylation products can be used as they are, or their phosphates, sulfate esters or ether carboxylates (carbonates) are used. These can be neutral or in the form of a salt. Suitable counterions are alkali metal and alkaline earth metal cations or ammonium ions, and also alkyl- and alkanolammonium ions.
The present invention further relates to a formulation comprising a surfactant mixture according to the invention.
The formulation can, for example, comprise 0.01 to 90% by weight of water. Moreover or alternatively, the formulation can have further surfactants or hydrotropes or mixtures thereof. For example, mention may be made here of alcohol alkoxylates of the formula P(O-R-Ao_n)_m-H, where P is a saturated, unsaturated or aromatic carbon backbone to which m alcohol functions are joined which have in turn been etherified with, on average, in each case n alkylene oxide units. n here has a value from 1 to 4 and m a value from 1 to 10. R is an alkylene group having 1 to 10 carbon atoms, Ao is a C₂-C₅-alkylene oxide. Examples thereof are methylethylene glycols, butylethylene glycols, pentylethylene glycols, hexylethylene glycols, butylpropylene glycols, trimethylolpropane ethoxylates, glycerol ethoxylates, pentaerythritol ethoxylates, ethoxylates and propoxylates of bisphenol A.
The present invention further relates to a method of producing a surfactant mixture, comprising the steps:

(a) alkoxylation of an alkanol mixture, where the mixture has 8 to 12 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanol mixture has an average degree of branching of at least 1, preferably 1.0 to 2, more preferably 1.0 to 1.5;
(b) alkoxylation of an alkanol mixture, where the alkanol mixture has 13 to 20 hydrocarbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxylation groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanol mixture has an average degree of branching of from 0.0 to 0.3; and
(c) mixing the alkoxylation products obtained in step (a) and (b).

Besides the method described above for producing a surfactant mixture, the corresponding alkanols for the short-chain component (A) and long-chain component (B) can also be mixed before the alkoxylation and then the mixture can subsequently be subjected to an alkoxylation.
Consequently, the present invention further relates to a method of producing a surfactant mixture according to the present invention, comprising the steps

(a) mixing a first alkanol mixture which has 8 to 12 carbon atoms and an average degree of branching of at least 1 with at least one second alkanol mixture which has 13 to 20 carbon atoms and an average degree of branching of from 0.0 to 0.3; and
(b) alkoxylation of the mixture of the first and second mixture from step (a), where the number of alkoxy groups per alkanol group in the alkoxylation product assumes an average value of from 3 to 30 and the alkoxy group is chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups.

The surfactant mixtures or formulations according to the invention can be used, for example, as surfactant formulations for cleaning hard surfaces. Suitable surfactant formulations for which the surfactant mixtures according to the invention can be provided as additives are described, for example, in Formulating Detergents and Personal Care Products by Louis Ho Tan Tai, AOCS Press, 2000.
As further components, they comprise, for example, soap, anionic surfactants, such as LAS (linear alkyl benzenesulfonate) or paraffinsulfonates or FAS (fatty alcohol sulfate) or FAES (fatty alcohol ethersulfate), acid, such as phosphoric acid, amidosulfonic 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-methylglycine-N,N-diacetic acid), phosphonates, polymers, such as polyacrylates, copolymers maleic acid-acrylic acid, alkali donors, such as hydroxides, silicates, carbonates, perfume oils, oxidizing agents, 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 Sch6nfeldt, Grenzflächenaktive Ethylenoxyaddukte [Interface-active ethyleneoxy adducts]. These also discuss formulations for the other specified uses in principle. These may be household cleaners, such as all-purpose cleaners, dishwashing detergents for manual and automatic dishwashing, metal degreasing, industrial applications, such as cleaners for the food industry, bottlewashing, etc. They may also be printing roll and printing plate cleaners in the printing industry. Suitable further ingredients are known to the person skilled in the art.
Uses of a surfactant mixture according to the invention or of a formulation according to the invention are:

- Humectants, in particular for the printing industry.
- Cosmetic, pharmaceutical and crop protection formulations. Suitable crop protection formulations are described, for example, in EP-A 0 050 228. Further ingredients customary for crop protection compositions may be present.
- Paints, coating compositions, dyes, pigment preparations and adhesives in the coatings and polymer film industry.
- Leather-degreasing compositions.
- Formulations for the textile industry, such as leveling agents or formulations for yarn cleaning.
- Fiber processing and auxiliaries for the paper and pulp industry.
- Metal processing, such as metal finishing and electroplating sector.
- Food industry.
- Water treatment and production of drinking water.
- Fermentation.
- Mineral processing and dust control.
- Building auxiliaries.
- Emulsion polymerization and preparation of dispersions.
- Coolants and lubricants.

Such formulations usually comprise ingredients such as surfactants, builders, fragrances and dyes, complexing agents, polymers and other ingredients. Typical formulations are described, for example in WO 01/32820. Further ingredients suitable for various 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 U.S. Pat. No. 5,340,495 and in Schönfeldt, see above, for example.
In general, the compositions according to the invention can be used in all areas where the effect of interface-active substances is necessary.
The present invention therefore also relates to detergents, cleaners, wetting agents, coatings, adhesives, leather-degreasing compositions, humectants or textile-treatment compositions or cosmetic, pharmaceutical or crop protection formulations comprising a composition according to the invention or a composition prepared by a method according to the invention. The products here preferably comprise 0.1 to 80% by weight of the compositions.
The customary constituents of the detergents according to the invention, in particular textile detergents, include, for example, builders, surfactants, bleaches, enzymes and further ingredients, as described below.

Builders

Inorganic builders (A′) suitable for combination with the surfactants according to the invention are primarily crystalline or amorphous alumosilicates with ion-exchanging properties, such as, 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 for 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, U.S. 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 sheet silicates, e.g. SKS-6 (manufacturer: Hoechst). The silicates can 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, for example, sodium metasilicate, which has a polymeric structure, or Britesil® H20 (manufacturer: Akzo) can likewise be used.
Suitable inorganic builder substances based on carbonate are carbonates and hydrogencarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferably, Na, Li and Mg carbonates or hydrogencarbonates, in particular sodium carbonate and/or sodium hydrogencarbonate, are used.
Customary phosphates as inorganic builders are polyphosphates, such as, for example, pentasodium triphosphate.
The specified components (A′) can be used individually or in mixtures with one another. Of particular interest as inorganic builder component is a mixture of alumosilicates and carbonates, in particular of zeolites, primarily zeolite A, and alkali metal carbonates, primarily sodium carbonate, in the weight ratio 98:2 to 20:80, in particular from 85:15 to 40:60. Besides this mixture, other components (A′) can also be present.
In a preferred embodiment, the textile detergent formulation according to the invention comprises 0.1 to 20% by weight, in particular 1 to 12% by weight, of organic cobuilders (B′) in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, or phosphonic acids or salts thereof, in particular Na or K salts.
Suitable low molecular weight carboxylic acids or phosphonic acids for (B′) are, for example:
C₄-C₂₀-di-, -tri- and -tetracarboxylic acids, such as, for example, succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids with C₂-C₁₆-alkyl or -alkenyl radicals;
C₄-C₂₀-hydroxycarboxylic acids, such as, for example, malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
aminopolycarboxylic acids, such as, for example, nitrilotriacetic acid, β-alanine-diacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserine-diacetic acid, methylglycinediacetic acid and alkylethylenediamine triacetates;
salts of phosphonic acids, such as, for example, hydroxyethanediphosphonic acid.
Suitable oligomeric or polymeric carboxylic acids for (B′) are, for example:
oligomaleic acids, as are described, for example, in EP-A 451 508 and EP-A 396 303;
co- and terpolymers of unsaturated C₄-C₈-dicarboxylic acids, where the comonomers may be copolymerized monoethylenically unsaturated monomers
from the group (i) in amounts of up to 95% by weight,
from the group (ii) in amounts of up to 60% by weight and
from the group (iii) in amounts of up to 20% by weight.
Suitable unsaturated C₄-C₈-dicarboxylic acids here are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.
The group (i) comprises monoethylenically unsaturated C₃-C₈-monocarboxylic acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.
Group (ii) comprises monoethylenically unsaturated C₂-C₂₂-olefins, vinyl alkyl ethers with C₁-C₈-alkyl groups, styrene, vinyl esters of C₁-C₈-carboxylic acids, (meth)acrylamide and vinylpyrrolidone. From group (ii), preference is given to using C₂-C₆-olefins, vinyl alkyl ethers with C₁-C₄-alkyl groups, vinyl acetate and vinyl propionate.
Group (iii) comprises (meth)acrylic esters of C₁-C₈-alcohols, (meth)acrylonitrile, (meth)acrylamides of C₁-C₈-amines, N-vinylformamide and vinylimidazole.
If the polymers of group (ii) comprise vinyl esters in copolymerized form, these may also be present in partially or completely hydrolyzed form to give vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from U.S. Pat. No. 3,887,806 and DE-A 43 13 909.
Suitable copolymers of dicarboxylic acids for (B′) are preferably:
copolymers of maleic acid and acrylic acid in the weight ratio 100:90 to 95:5, particularly preferably those in the weight ratio 30:70 to 90:10 with molar masses from 100 000 to 150 000;
terpolymers of maleic acid, acrylic acid and a vinyl ester of a C₁-C₃-carboxylic acid in the weight ratio 10 (maleic acid):90 (acrylic acid+vinyl ester) to 95 (maleic acid):10 (acrylic acid +vinyl ester), where the weight ratio of acrylic acid to the vinyl ester can vary in the range from 30:70 to 70:30;
copolymers of maleic acid with C₂-C₈-olefins in the molar ratio 40:60 to 80:20, where copolymers of maleic acid with ethylene, propylene or isobutene in the molar ratio 50:50 are particularly preferred.
Graft polymers of unsaturated carboxylic acids based on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. U.S. Pat. No. 5,227,446, DE-A 44 15 623 and DE-A 43 13 909, are likewise suitable as (B′).
Suitable unsaturated carboxylic acids here are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, and mixtures of acrylic acid and maleic acid, which are grafted on in amounts of from 40 to 95% by weight, based on the component to be grafted.
For the modification, additionally up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers are present in copolymerized form. Suitable modifying monomers are the abovementioned monomers of groups (ii) and (iii).
Suitable graft bases are degraded polysaccharides, such as, for example, acidically or enzymatically degraded starches, inulins or cellulose, protein hydrolysates and reduced (hydrogenated or reductively aminated) degraded polysaccharides, such as, for example, mannitol, sorbitol, aminosorbitol and N-alkylglucamine, and also polyalkylene glycols with molar masses up to M_w=5000, such as, for example, polyethylene glycols, ethylene oxide/propylene oxide or ethylene oxide/butylene oxide or ethylene oxide/propylene oxide/butylene oxide block copolymers and alkoxylated mono- or polyhydric C₁-C₂₂-alcohols, cf. U.S. Pat. No. 5,756,456.
From this group, preference is given to using grafted degraded or degraded reduced starches and grafted polyethylene oxides, where 20 to 80% by weight of monomers, based on the graft component, are used in the graft polymerization. For the grafting, a mixture of maleic acid and acrylic acid in the weight ratio from 90:10 to 10:90 is preferably used.
Polyglyoxylic acids suitable as (B′) are described, for example, in EP-B 001 004, U.S. Pat. No. 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the polyglyoxylic acids can have various structures.
Polyamidocarboxylic acids and modified polyamidocarboxylic acids suitable as (B′) are known, for example, from EP-A 454 126, EP-B 511 037, WO-A 94/01486 and EP-A 581 452.
As (B′), use is made in particular also of polyaspartic acids or cocondensates of aspartic acid with further amino acids, C₄-C₂₅-mono- or -dicarboxylic acids and/or C₄-C₂₅-mono- or -diamines. Particular preference is given to using polyaspartic acids modified with C₆-C₂₂-mono- or -dicarboxylic acids or with C₆-C₂₂-mono- or -diamines produced in phosphorus-containing acids.
Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds suitable as (B′) are known, for example, from WO-A 93/22362 and WO-A 92/16493. Such condensates comprising carboxyl groups usually have molecular masses up to 10 000, preferably up to 5000.
Further suitable as (B′) are ethylenediaminedisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.
Furthermore, in addition to (B′), oxidized starches can be used as organic cobuilders.

Surfactants

Besides the surfactant mixture according to the invention, further surfactants can be used.
Suitable inorganic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms, e.g. C₉-C₁₁-alcohol sulfates, C₁₂-C₁₄-alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
Further suitable anionic surfactants are alkanesulfonates, such as C₈-C₂₄-, preferably C₁₀-C₁₈-alkylsulfonates, and soaps, such as, for example, the Na and K salts of C₈-C₂₄-carboxylic acids.
Further suitable anionic surfactants are C₉-C₂₀linear alkylbenzenesulfonates (LAS) and C₉-C₂₀linear alkyltoluenesulfonates.
Further suitable anionic surfactants (C) are also C₈-C₂₄-olefinsulfonates and -disulfonates, which can also constitute mixtures of alkene- and hydroxyalkane-sulfonates or -disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glyceryl sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffinsulfonates having about 20 to about 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkylsuccinic acids, alkenylsuccinic acids or half-esters or half-amides thereof, alkylsulfo-succinic acids or amides thereof, mono- and diesters of sulfosuccinic acids, acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates, and hydroxyalkyl sarcosinates.
The anionic surfactants are preferably added to the detergent 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, for example, hydroxyethylammonium, di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts.
Component (C) is present in the textile detergent formulation according to the invention preferably in an amount of from 3 to 30% by weight, in particular 5 to 20% by weight. If C₉-C₂₀linear alkylbenzenesulfonates (LAS) are used, these are usually used in an amount up to 25% by weight, in particular up to 20% by weight. It is possible to use only one class of anionic surfactants on its own, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, although it is also possible to use mixtures from different classes, e.g. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates. Within the individual classes of anionic surfactants, mixtures of different species can also be used.
A further class of suitable surfactants to be mentioned 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 comprise mostly 1 to 20, preferably 1.1 to 5, glucoside units. Another class of nonionic surfactants are N-alkylglucamides with C₆-C₂₂-alkyl chains. Compounds of this type are obtained, for example, by acylation of reductively aminated sugars with corresponding long-chain carboxylic acid derivatives.
Further suitable as nonionic surfactants (D) are also 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-aryloxy-polyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular terminally capped, and also fatty acid alkanolamide alkoxylates.
Component (D) is present in the textile detergent formulation according to the invention preferably in an amount of from 1 to 20% by weight, in particular 3 to 12% by weight. It is possible to use only one class of nonionic surfactants on its own, in particular only alkoxylated C₈-C₂₂-alcohols, but it is also possible to use mixtures from different classes. Within the individual classes of nonionic surfactants, mixtures of different species can also be used.
Since the balance between the specified types of surfactant is of importance for the effectiveness of the detergent formulation according to the invention, anionic surfactants (C) and nonionic surfactants (D) are preferably in the weight ratio from 95:5 to 20:80, in particular from 80:20 to 50:50. Here, the surfactant constituents of the surfactant mixture according to the invention should also be taken into consideration.
Furthermore, cationic surfactants (E) can also be present in the detergents according to the invention.
Suitable cationic surfactants are, for example, interface-active compounds comprising ammonium groups, such as, for example, alkyldimethylammonium halides and compounds of the general formula
RR′R″R′″N⁺X⁻
in which the radical R to R′″ are alkyl, aryl radicals, alkylalkoxy, arylalkoxy, hydroxyalkyl(alkoxy), hydroxyaryl(alkoxy) groups and X is a suitable anion.
The detergents according to the invention can, if appropriate, also comprise ampholytic surfactants (F), such as, for example, aliphatic derivatives of secondary or tertiary amines which comprise an anionic group in one of the side chains, alkyldimethylamine oxides or alkyl- or alkoxymethylamine oxides.
Components (E) and (F) can be present in the detergent formulation up to 25%, preferably 3-15%.

Bleaches

In a further preferred embodiment, the textile detergent formulation according to the invention additionally comprises 0.5 to 30% by weight, in particular 5 to 27% by weight, especially 10 to 23% by weight, of bleaches (G). Examples are alkali metal perborates or alkali metal carbonate perhydrates, in particular the sodium salts.
One example of an organic peracid which can be used is peracetic acid, which is preferably used during commercial textile washing or commercial cleaning.
Bleach or textile detergent compositions to be used advantageously comprise C_1-12-percarboxylic acids, C_8-16-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 dodecanemono-peracids, decane- and dodecanediperacid, 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 comprise acrylic acid basic building blocks in which a peroxy function is present. The percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali metal or alkaline earth metal salts. These bleaches (G) are used, if appropriate, in combination with 0 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8% by weight, of bleach activators (H). In the case of color detergents, the bleach (G) (if present) is usually used without bleach activator (H), otherwise bleach activators (H) are also usually present.
Suitable bleach activators (H) are:

- polyacylated sugars, e.g. pentaacetylglucose;
- acyloxybenzenesulfonic acids and alkali metal and alkaline earth metal salts thereof, e.g. sodium p-isononanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate;
- N,N-diacetylated and N,N,N′,N′-tetraacylated amines, e.g. N,N,N′,N′-tetra-acetylmethylenediamine 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-sulfonylcarboxamides, e.g. N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide;
- N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. monoacetylmaleic acid hydrazide;
- O,N,N-trisubstituted hydroxylamines, e.g. O-benzoyl-N,N-succinylhydroxyl-amine, O-acetyl-N,N-succinylhydroxylamine or O,N,N-triacetylhydroxyl-amine;
- N,N′-diacylsulfurylamides, e.g. N,N′-dimethyl-N,N′-diacetylsulfurylamide or N,N′-diethyl-N,N′-dipropionylsulfurylamide;
- triacyl cyanurates, e.g. triacetyl cyanurate or tribenzoyl cyanurate;
- carboxylic anhydrides, e.g. benzoic acid anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
- 1,3-diacyl-4,5-diacyloxyimidazolines, e.g. 1,3-diacetyl-4,5-diacetoxy-imidazoline;
- tetraacetylglycoluril and tetrapropionylglycoluril;
- diacylated 2,5-diketopiperazines, e.g. 1,4-diacetyl-2,5-diketopiperazine;
- acylation products of propylenediurea and 2,2-dimethylpropylenediurea, e.g. tetraacetylpropylenediurea;
- α-acyloxypolyacylmalonamides, e.g. α-acetoxy-N,N′-diacetylmalonamide;
- diacyldioxohexahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine;
- benz(4H)-1,3-oxazin-4-ones with alkyl radicals, e.g. methyl, or aromatic radicals, e.g. phenyl, in the 2 position.

The described bleaching system of bleaches and bleach activators can, if appropriate, also comprise bleach catalysts. Suitable bleach catalyst are, for example, quaternized imines and sulfonimines, which are described, for example, in U.S. 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. In the case of their use in the detergent formulations, such compounds are incorporated at most in amounts up to 1.5% by weight, in particular up to 0.5% by weight.
Besides the described bleaching system of bleaches, bleach activators and, if appropriate, bleach catalysts, the use of systems with enzymatic peroxide release or of photoactivated bleach systems is also conceivable for the textile detergent formulation according to the invention.

Enzymes

In a further preferred embodiment, the textile detergent formulation according to the invention additionally comprises 0.05 to 4% by weight of enzymes (J). Enzymes preferably used in detergents are proteases, amylases, lipases and cellulases. Of the enzymes, preferably amounts of 0.1-1.5% by weight, particularly preferably 0.2 to 1.0% by weight, of the formulated enzyme are added. Suitable proteases are, for example, savinase and esperase (manufacturer: Novo Nordisk). A suitable lipase is, for example, lipolase (manufacturer: Novo Nordisk). A suitable cellulase is, for example, celluzym (manufacturer: Novo Nordisk). The use of peroxidases for activating the bleaching system is also possible. It is possible to use individual enzymes or a combination of different enzymes. If appropriate, the textile detergent formulation according to the invention can also comprise enzyme stabilizers, e.g. calcium propionate, sodium formate or boric acids or salts thereof, and/or oxidation inhibitors.

Further Ingredients

Besides the specified main components (A) to (J), the textile detergent formulation according to the invention can also comprise the following further customary additives in the amounts customary for this purpose:

- Graying inhibitors and soil release polymers

Suitable soil release polymers and/or graying inhibitors for detergents are, for example:
polyesters of polyethylene oxides with ethylene glycol and/or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
polyesters of polyethylene oxides terminally capped at one end with di- and/or polyhydric alcohols and dicarboxylic acid.
Such polyesters are known, for example from U.S. Pat. No. 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 U.S. Pat. No. 5,142,020.
Further suitable soil release polymers are amphiphilic graft polymers or copolymers of vinyl esters and/or acrylic esters onto polyalkylene oxides (cf. U.S. Pat. No. 4,746,456, U.S. Pat. No. 4,846,995, DE-A 37 11 299, U.S. Pat. No. 4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat. No. 4,849,126) or modified celluloses, such as, for example, methyl-cellulose, hydroxypropylcellulose or carboxymethylcellulose.

- color transfer inhibitors, for example homopolymers and copolymers of vinylpyrrolidone, of vinylimidazole, of vinyloxazolidone or of 4-vinylpyridine N-oxide having molar masses of from 15 000 to 100 000, and crosslinked finely divided polymers based on these monomers;
- nonsurfactant-like foam suppressants or foam inhibitors, for example organopolysiloxanes and mixtures thereof with microfine, if appropriate silanized, silica, and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica;
- complexing agents (also in the function of organic cobuilders);
- optical brighteners;
- polyethylene glycols; polypropylene glycols
- perfumes or fragrances;
- fillers;
- inorganic extenders, e.g. sodium sulfate,
- formulation auxiliaries;
- solubility improvers;
- opacifiers and pearlizing agents;
- dyes;
- corrosion inhibitors;
- peroxide stabilizers;
- electrolytes.

The detergent formulation according to the invention is preferably solid, i.e. is usually in powder or granule form or in the form of an extrudate or tablet.
The powder- or granule-formed detergents according to the invention can comprise up to 60% by weight of inorganic extenders. Sodium sulfate is usually used for this purpose. Preferably, however, the detergents according to the invention have a low content of extenders and comprise only up to 20% by weight, particularly preferably only up to 8% by weight, of extenders, particularly in the case of compact or ultracompact detergents. The solid detergents according to the invention can have various bulk densities in the range from 300 to 1300 g/l, in particular from 550 to 1200 g/l. Modern compact detergents generally have high bulk densities and exhibit a granule structure. The methods customary in the art can be used for the desired compaction of the detergents.
The detergent formulation according to the invention can be produced by customary methods and, if appropriate, be formulated.
Typical compositions of compact standard detergents and color detergents are given below (the percentages refer, in the text below and also in the examples, to the weight; the data in brackets in the case of compositions (a) and (b) are preferred ranges):

(a) Composition of Compact Standard Detergent (Powder or Granule Form)

1-60% (8-30%) of a surfactant mixture according to the invention and, if appropriate, at least one anionic surfactant (C) in combination with a nonionic surfactant (D)
5-50% (10-45%) of at least one inorganic builder (A)
0.1-20% (0.5-15%) of at least one organic cobuilder (B)
5-30% (10-25%) of an inorganic bleach (G)
0.1-15% (1-8%) of a bleach activator (H)
0-1% (at most 0.5%) of a bleach catalyst
0.05-5% (0.1-2.5%) of a color transfer inhibitor
0.3-1.5% of a soil release polymer
0.1-4% (0.2-2%) enzyme or enzyme mixture (J)

Further customary additives:
Sodium sulfate, complexing agent, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers

(b) Composition of Color Detergent (Powder or Granule Form)

3-50% (8-30%) of a surfactant mixture according to the invention and, if appropriate, at least one anionic surfactant (C) in combination with a nonionic surfactant (D)
10-60% (20-55%) of at least one inorganic builder (A)
0-15% (0-5%) of an inorganic bleach (G)
0.05-5% (0.2-2.5%) of a color transfer inhibitor
0.1-20% (1-8%) of at least one organic cobuilder (B)
0.2-2% enzyme or enzyme mixture (J)
0.2-1.5% soil release polymer

Further customary additives:
Sodium sulfate, complexing agent, phosphonates, optical brighteners, perfume oils, foam suppressants, graying inhibitors, bleach stabilizers.
The invention is illustrated in more detail by reference to the examples below.

EXAMPLES

Example 1 “Surfactant 1”

A mixture of 2-propylheptanol and 5-methyl-2-propylhexanol, which is sold as technical-grade 2-propylheptanol (2-PH) by BASF, as short-chain component (A) (average degree of branching of 1.15) and tallow fatty alcohol (C₁₆-C₁₈-alcohol) as long-chain component (B) (average degree of branching of approximately 0) are mixed in various mass ratios (A:B=2-PH: C₁₆-C₁₈-alcohol) and then ethoxylated by means of KOH catalysis, with various HLB values according to Griffin (20 times the mass fraction of ethylene oxide in the product) being established.

Comparative Example 2 (=“Surfactant 2”)

A mixture of isodecanol (Exxal 10N, Exxon) (average degree of branching of 2.2) and C₁₃-C₁₅-oxo alcohol (average degree of branching of 0.6) (C₁₃-C₁₅alcohol, BASF) is reacted analogously to example 1 with ethylene oxide to give “surfactant 2”. The mass ratio A:B refers here to the ratio of isodecanol to C₁₃-C₁₅-oxo alcohol.

Tests

1) Wetting of Cotton According to EN 1772

The tables below show the wetting times (according to EN 1772, 2 g/l soda) of the surfactant mixture according to the invention (“surfactant 1”) and of the reference mixture (“surfactant 2”)


Surfactant 1	Surfactant 2
Wetting 0.5 g/l, 23° C.	Wetting 0.5 g/l, 23° C.

A:B

[g:g]

A:B

[g:g]

HLB	1:0	9:1	8:2	7:3	HLB	1:0	9:1	8:2	7:3

11.6	60	40	40	60	11.6	70	70	70	80
12.5	60	60	60	—)*	12.5	100	90	100	—
14.3	100	100	—	200	14.3	200	150	—	160

Wetting 1.0 g/l, 23° C.

Ratio

HLB	1:0	9:1	8:2	7:3	HLB	1:0	9:1	8:2	7:3

11.6	10	10	10	20	11.6	20	20	20	30
12.5	10	20	20	—	12.5	25	25	30	—
14.3	20	20	—	60	14.3	70	70	—	80

Wetting 2.0 g/l, 23° C.

Ratio

HLB	1:0	9:1	8:2	7:3	HLB	1:0	9:1	8:2	7:3

11.6	10	5	5	5	11.6	5	5	5	5
12.5	5	5	5	—	12.5	5	5	5	—
14.3	5	10	—	20	14.3	15	15	—	30

*not measured.
Summary:
It is clear to see that the wetting power of surfactant 1 is better than that of surfactant 2, particularly at higher dilutions.

2) Stability Against Lyotropic Salts (Example NaOH)

2% surfactant mixture is mixed with aqueous NaOH solutions (0%, 1%, 2%, 3% etc.), and after storage for 24 h at 23° C., it is tested whether the mixture is stable (clear or cloudy) or whether phase separation or creaming has taken place. The highest concentration of NaOH at which the formulation appears still optically one-phase (clear or cloudy) after 24 h at 23° C. is given.


	Surfactant 1		Surfactant 2
	% NaOH, 23° C.		% NaOH, 23° C.

A:B [g:g]

HLB	9:1	8:2	7:3	HLB	9:1	8:2	7:3

11.0	—)*	2	—	11.0	—	2	—
11.6	3	—	5	11.6	—	—	—
12.5	—	3	—	12.5	—	3	—
14.0	—	5	—	14.0	—	5	—
14.3	5	—	5	14.3	—	—	—

*not measured.
Summary:
Surfactant 1 and surfactant 2 behave similarly.

3) Formation of Gel Phases with Water

Surfactant 1 is combined with water and homogenized well. The mixture is then left to rest for 24 h at 23° C. Then, a Brookfield rheometer (spindle 2-7, 60 rpm, 23° C.) is used to determine the viscosity of the mixture.


Concen-	A:B = 9:1,	A:B = 9:1	A:B = 7:3	A:B = 7:3
tration (%)	HLB = 11.6	HLB = 14.3	HLB = 11.6	HLB = 14.3

90	70	120	90	200
80	80	140	120	210
70	140	150	5400	240
60	7100	180	7000	4700
50	35 000	190	520	>100 000
40	300	140	130	210
30	260	50	110	40
20	260	20	100	10
10	70	10	20	5

4) Determination of the Emulsion Stability

The emulsion stability is determined by means of the marker method, as described in DE 10247086. In two 600 ml beakers, 1% by weight of surfactant is mixed with 69% by weight of water and then 30% by weight of oil—dyed yellow or blue—are added. Then, using a propeller stirrer for 15 minutes, an input of about 10 kW/m³is introduced. The emulsions obtained are mixed, and the droplet size distribution is measured by means of statistical laser scattering. The following tables give the d₅₀, the median of the droplets.
The emulsions are then stored at 23° C. At periodic intervals, the emulsions are shaken, a sample is taken and the fraction of green drops, formed by coalescence, is determined by means of microscopy and electronic image analysis. The measured green fractions are then plotted against the storage time and fitted by the following function by the least squares method:
Green(t)=100% $ (1-exp(-a$t)).
The stability constant S is finally obtained from S=-log(a $ month).
The oils used are sunflower oil (56 mm²/s at 25° C.) and paraffin oil (30 mm²/s at 25° C.).


A:B [g:g]	HLB	d 50	S

Surfactant 1

Paraffin oil

9:1	11.6	40	0.3
9:1	14.3	54	0.8
7:3	11.6	52	1.0
7:3	14.3	56	0.9

Sunflower oil

9:1	11.6	99	1.2
9:1	14.3	68	1.2
7:3	11.6	75	1.4
7:3	14.3	71	1.1

Surfactant 2

Paraffin oil

8:2	11	171	−0.1
8:2	12.5	188	0.7
8:2	14	101	1.1

Sunflower oil

8:2	11	71	−0.1
8:2	12.5	74	−0.7
8:2	14	99	−0.1

Summary:
In the case of paraffin oil, significantly smaller emulsion droplets are found with surfactant 1 compared to surfactant 2 for approximately identical emulsion stability. In the case of sunflower oil, a drastically improved emulsion stability is found with surfactant 1 compared to surfactant 2.

5) Determination of the Detergency During High-Temperature Cotton Washing

About 10 g of WFK soiled fabric 10D are rolled up and placed into a small laundry basket for a washing machine Ahiba Texomat. 200 ml of a wash liquor of softened water and 1 g/l of the respective surfactant are poured into the glass container and brought to 60° C. in the dyeing and washing apparatus. The device is started and heated from 60° C. to 95° C. in 15 min, at 95° C., the temperature is held for 15 min. The soiled fabric is then removed, and rinsed twice hot and once cold. The fabric is squeezed, dried and mangled while hot. The degree of whiteness on the soiled side of the fabric is assessed in Berger units on a suitable spectrometer (Datacolor-spectrometer Spectraflash 500).


	Concentration

A:B = 9:1,	A:B = 9:1,	A:B = 7:3	A:B = 7:3
HLB = 11.6	HLB = 14.3	HLB = 11.6	HLB = 14.3

Degree of	54	57	57	58
whiteness
according
to Berger

6) Determination of the Detergency Analogous to Household Washing

The washing experiments were carried out under the following conditions:


Washing conditions	Primary wash

Device	Launder-o-meter from Atlas, Chicago USA
Wash liquor	250 ml
Wash time	30 min at stated temperature (including heating
	time)
Detergent dosing	5 g/l
Water hardness	3 mmol/l Ca:Mg 4:1
Liquor ratio	1:12.5

Test fabric from wfk Testgewebe GmbH, Brüggen, Germany


	wfk 10 D	Skin grease/pigment on cotton
	wfk 20 D	Skin grease/pigment on 65% polyester/35% cotton
	wfk 10 PF	Plant grease/pigment on cotton

Detergent Formulation


	Zeolite A	30%
	Sodium carbonate	12%
	Sodium silicate	3%
	Tylose CR 1500 p	1.2%
	Sodium perborate monohydrate	14.4%
	Tetraacetylethylenediamine	4%
	Acrylic acid/maleic acid copolymer (MW 70 000)	5%
	Soap	0.5%
	Sodium sulfate	4%
	Water	20.9%
	Surfactant	5%

After rinsing, spinning was carried out and the fabric was hung up to dry individually. The fabric was measured using an Elrepho 2000 from Data Color, Heidenheim, 6 measurement points per item of fabric. The reflectance value was determined at 460 nm. Large values for the reflectance here indicate good soil release and high primary detergency.
The washed test fabrics are measured using a photometer from Data Color (Elrepho 2000). The table below gives the reflectance value (R at 460 nm) in percent. The higher the reflectance value, the better the primary detergency.
For each run, a formulation comprising Lutensol AO7 as surfactant (“Lutensol AO7”), and a formulation in which the surfactant was replaced by water (“without surfactant”) were also washed as control experiments. These experiments serve to standardize the washing results. Standardization was carried out linearly, with “without surfactant” being set at 0% and “Lutensol AO7” being set as 100%:

Calculation Formula:

% (Detergency)=100%·[reflectance (surfactant 1 or 2)−reflectance (“without surfactant”)]i[reflectance (“Lutensol A07”)−reflectance (“Without surfactant”)]


	Standardized: “without” = 0%
	“Lutensol AO7” = 100%

		Reflectance	% Detergency
	A:B	WFK	WFK	Mean

	HLB	[g/g]	10 D	20 D	10 PF	10 D	20 D	10 PF	value

Surfactant 1

Washing at 25° C.

without surfactant			51.6	44.1	42.7
Lutensol AO7			57.0	58.1	48.7
Surfactant 1	10.5	9:1	59.0	51.4	47.2	136%	52%	75%	88%
Surfactant 1	11.0	9:1	56.7	50.7	46.0	93%	47%	55%	65%
Surfactant 1	11.6	9:1	56.1	49.7	45.0	83%	40%	38%	54%
Surfactant 1	12.5	9:1	56.0	51.0	44.1	81%	49%	23%	51%
Surfactant 1	14.3	9:1	55.3	47.8	43.8	68%	26%	19%	38%
Surfactant 1	10.5	7:3	60.3	53.3	48.8	160%	66%	102%	109%
Surfactant 1	11.0	7:3	56.4	51.2	48.5	89%	51%	97%	79%
Surfactant 1	11.6	7:3	52.9	50.1	45.9	24%	43%	53%	40%
Surfactant 1	13.0	7:3	59.4	52.7	45.5	144%	61%	47%	84%
Surfactant 1	14.3	7:3	51.9	48.0	43.5	7%	28%	14%	16%

Washing at 40° C.

without surfactant			52.5	45.8	44.8
Lutensol AO7			61.7	65.7	54.3
Surfactant 1	10.5	9:1	62.0	53.0	52.5	103%	36%	81%	73%
Surfactant 1	11.0	9:1	59.7	52.3	51.0	78%	32%	65%	59%
Surfactant 1	11.6	9:1	59.7	51.8	48.5	78%	30%	39%	49%
Surfactant 1	12.5	9:1	62.8	50.7	53.6	111%	24%	93%	76%
Surfactant 1	14.3	9:1	58.7	47.4	43.5	68%	8%	−13%	21%
Surfactant 1	10.5	7:3	61.5	57.4	53.3	97%	58%	89%	82%
Surfactant 1	11.0	7:3	61.1	57.4	51.5	93%	58%	71%	74%
Surfactant 1	11.6	7:3	60.5	56.1	46.2	87%	51%	15%	51%
Surfactant 1	13.0	7:3	62.7	54.9	51.6	111%	46%	72%	76%
Surfactant 1	14.3	7:3	57.5	49.7	44.1	54%	19%	−7%	22%

Washing at 60° C.

without surfactant			55.0	46.3	47.8
Lutensol AO7			67.0	71.7	59.3
Surfactant 1	10.5	9:1	64.0	51.7	55.3	75%	21%	65%	54%
Surfactant 1	11.0	9:1	68.2	52.4	55.3	110%	24%	65%	66%
Surfactant 1	11.6	9:1	65.6	56.1	52.5	88%	39%	41%	56%
Surfactant 1	12.5	9:1	64.0	55.4	55.4	76%	36%	66%	59%
Surfactant 1	14.3	9:1	59.6	55.3	49.8	38%	35%	17%	30%
Surfactant 1	10.5	7:3	68.2	54.3	56.2	110%	31%	73%	71%
Surfactant 1	11.0	7:3	67.0	61.0	55.7	100%	58%	69%	76%
Surfactant 1	11.6	7:3	64.0	68.2	51.9	75%	86%	35%	66%
Surfactant 1	13.0	7:3	66.9	62.2	59.4	99%	63%	101%	88%
Surfactant 1	14.3	7:3	57.0	57.3	53.5	17%	43%	50%	37%

Surfactant 2

Washing at 25° C.

without surfactant			54.2	43.4	42.7
Lutensol AO7			62.8	59.3	47.6
Surfactant 2	11.0	9:1	59.8	50.2	44.2	66%	42%	31%	46%
Surfactant 2	12.5	9:1	58.2	47.7	44.0	47%	27%	27%	34%
Surfactant 2	11.0	7:3	59.2	56.5	47.4	58%	82%	96%	79%
Surfactant 2	13.0	7:3	61.9	50.9	47.1	90%	47%	90%	76%

Washing at 40° C.

without surfactant			55.2	43.0	44.9
Lutensol AO7			63.7	68.9	56.9
Surfactant 2	11.0	9:1	60.2	52.9	51.6	59%	38%	56%	51%
Surfactant 2	12.5	9:1	62.2	52.7	49.1	82%	37%	35%	52%
Surfactant 2	11.0	7:3	60.4	63.7	53.3	62%	80%	70%	71%
Surfactant 2	13.0	7:3	61.7	61.7	50.7	77%	72%	49%	66%

Washing at 60° C.

without surfactant			57.8	42.9	45.5
Lutensol AO7			67.0	73.1	63.1
Surfactant 2	11.0	9:1	65.9	55.7	53.4	87%	42%	45%	58%
Surfactant 2	12.5	9:1	66.3	62.1	53.2	92%	63%	44%	66%
Surfactant 2	11.0	7:3	64.3	62.1	54.2	71%	64%	49%	61%
Surfactant 2	13.0	7:3	62.4	65.9	55.1	50%	76%	55%	60%

Summary:
On average, surfactant 1 achieves an approximately 11% point better detergency
than surfactant 2 over all 3 fabrics and over all 3 washing temperatures.

7) Whipped Foam Test

A whipped foam test was carried out according to EN 12728 (2 g/l, 40° C.). The results are summarized in the table below.


		Surfactant 1	Surfactant 2
A:B [g:g]	HLB	Foam in ml	Foam in ml

9:1	11.6	140	250
9:1	12.5	270	220
9:1	14.3	400	390
8:2	11.6	200	260
8:2	12.5	280	290
7:3	11.6	170	220
7:3	14.3	340	390

Summary:
Surfactant 1 is a weaker foamer than surfactant 2.

Overall, surfactant 1 is clearly superior to surfactant 2 in detergency, lack of foam, wetting rate and emulsion stability without displaying disadvantages regarding salt stability.

Claims

1. A surfactant mixture comprising

(A) a short-chain component comprising the alkoxylation product of alkanols, where the alkanols have 8 to 12 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have an average degree of branching of at least 1; and

(B) a long-chain component comprising the alkoxylation product of alkanols where the alkanols have 13 to 20 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have an average degree of branching of from 0.0 to 0.3;

and phosphate, sulfate esters and ether carboxylates thereof.

2. The surfactant mixture according to claim 1, wherein for the short-chain component (A) and/or the long-chain component (B), the fraction of ethoxy groups relative to the total number of alkoxy groups for the particular alkoxylation product is at least 0.5.

3. The surfactant mixture according to one of claims 1 to 2, wherein the at least one alkanol of the long-chain component (B) has 16 to 20 carbon atoms.

4. The surfactant mixture according to one of claims 1 to 3, wherein the at least one alkanol of the short-chain component (A) has an average degree of branching of from 1.0 to 2.0.

5. The surfactant mixture according to one of claims 1 to 4, wherein the ratio of the weight fraction of the short-chain component (A) in the surfactant mixture to the weight fraction of the long-chain component (B) in the surfactant mixture assumes a value in the range from 99:1 to 1:99.

6. The surfactant mixture according to one of claims 1 to 5, which has a HLB value according to Griffin in the range from 10 to 15.

7. A formulation comprising a surfactant mixture according to one of claims 1 to 6.

8. A method of producing a surfactant mixture according to one of claims 1 to 6, comprising the steps:

(a) alkoxylation of an alkanol mixture, where the alkanol mixture has 8 to 12 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanol mixture has an average degree of branching of at least 1;

(b) alkoxylation of an alkanol mixture, where the alkanol mixture has 13 to 20 carbon atoms and the average number of alkoxy groups per alkanol group in the alkoxylation product assumes a value from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups and the alkanol mixture has an average degree of branching of from 0.0 to 0.3; and

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

9. A method of producing a surfactant mixture according to one of claims 1 to 6, comprising the steps

(a) mixing a first alkanol mixture which has 8 to 12 carbon atoms and an average degree of branching of at least 1 with at least one second alkanol mixture which has 13 to 20 carbon atoms and an average degree of branching of from 0.0 to 0.3; and

(b) alkoxylation of the mixture of the first and second mixture, where the number of alkoxy groups per alkanol group in the alkoxylation product assumes an average value of from 3 to 30 and the alkoxy groups are chosen from the group consisting of ethoxy, propoxy, butoxy and pentoxy groups.

10. The use of a surfactant mixture according to one of claims 1 to 6 or of a formulation according to claim 7 as emulsifier, foam regulator, wetting agent, in particular for hard surfaces, humectant.

11. The use according to claim 10 in detergents, for the cleaning of hard surfaces, in cosmetic, pharmaceutical and crop protection formulations, paints, coating compositions, adhesives, leather-degreasing compositions, for the textile industry, fiber processing, metal processing, food industry, water treatment, paper industry, fermentation or mineral processing and in emulsion polymerizations.