WO2011003904A1 - Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue - Google Patents

Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue Download PDF

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Publication number
WO2011003904A1
WO2011003904A1 PCT/EP2010/059634 EP2010059634W WO2011003904A1 WO 2011003904 A1 WO2011003904 A1 WO 2011003904A1 EP 2010059634 W EP2010059634 W EP 2010059634W WO 2011003904 A1 WO2011003904 A1 WO 2011003904A1
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alkanol
mixture
alkoxy groups
alkoxylation
surfactant
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PCT/EP2010/059634
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German (de)
English (en)
Inventor
Frank Rittig
Paul Klingelhoefer
Soeren Zimdahl
Frank Funke
James S. Dailey
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites

Definitions

  • 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.
  • surfactants are used, for example, for wetting solids, such as fibers or hard surfaces.
  • 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.
  • 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.
  • 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.
  • these surfactants or detergents should also have good cleaning properties.
  • (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.
  • 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.
  • 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.
  • the short-chain component (A) 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.
  • the main components are 2-propylheptanol and 5-methyl-2-propylhexanol.
  • 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
  • alkoxylation is randomly distributed or blockwise, so that the above-mentioned alkoxy groups - if they are different - occur blockwise.
  • 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.
  • 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.
  • 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.
  • an isomer mixture of 2-propylheptanol-1, 2-propyl-4-methylhexanol-1 and 2-propylmethylhexanol-1 can be used.
  • the surfactant mixture may comprise alkoxylation products, wherein alkanols form these products which do not have the above-mentioned number of carbon atoms.
  • alkanols may 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.
  • 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).
  • 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
  • alkoxylates A2 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.
  • 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.
  • 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.
  • 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.
  • ethyleneoxy units and subsequently propyleneoxy units may also be present subsequently to the alcohol radical.
  • 3- or Mehrblockalkoxyltechnik and mixed alkoxylation are possible.
  • Only ethylene oxide units A or only units B, in particular propylene oxide units are present.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the average degree of branching is 0.1 to 1 or more than 2.5 to 3.4.
  • 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).
  • 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 .-%.
  • 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.
  • 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.
  • 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.
  • 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.
  • the formulation may comprise further surfactants or hydrotropes or mixtures thereof.
  • 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.
  • 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.
  • 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:
  • 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.
  • 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), LAS (linear alky
  • 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.
  • 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.
  • 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.
  • the components (A) mentioned can be used individually or in mixtures with one another.
  • 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.
  • other components (A ') may be present.
  • 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.
  • 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, ⁇ -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:
  • Oligomaleein Acid 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,
  • 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.
  • 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;
  • 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 are also suitable as (B ').
  • 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.
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • 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- xyltechnisch 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.
  • 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.
  • 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.
  • (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.
  • (B ') are ethylenediamine disuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.
  • oxidized starches may be used as organic co-builders in addition to (B ').
  • surfactants may be used as organic co-builders in addition to (B ').
  • Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for.
  • Cg-Cn-alcohol sulfates Ci2-Ci4-alcohol sulfates, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • alkanesulfonates such as C8-C24, preferably Cio-Ci8-alkanesulfonates and soaps such as the Na and K salts of C8-C24 carboxylic acids.
  • anionic surfactants are C9-C20-linear alkylbenzenesulphonates (LAS) and -alkyltoluenesulphonates.
  • 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
  • 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.
  • LAS C9-C2o-Nnear alkylbenzenesulfonates
  • 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.
  • nonionic surfactants D 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 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.
  • 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.
  • Pluronic® propylene oxide and / or butylene oxide
  • polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-alkoxy fatty acid derivatives.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • F ampholytic surfactants
  • 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.
  • 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.
  • 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).
  • 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;
  • Acyloxybenzolsulfonklaren 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;
  • 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.
  • 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;
  • Diacyl-dioxohexahydro-1,3,5-triazines for example 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
  • 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 .-%.
  • the fiber and textile treatment agent according to the invention additionally contains 0.05 to 4 wt .-% enzymes (J).
  • J 0.05 to 4 wt .-% enzymes
  • Enzymes used in fiber and textile treatment agents are proteases, amylases, and
  • Lipases and cellulases 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 lipase is e.g. Lipolase (manufacturer: Novo Nordisk).
  • Cellulase is for example Celluzym (manufacturer: Novo Nordisk). Also the use of Celluzym (manufacturer: Novo Nordisk). Also the use of Celluzym (manufacturer: Novo Nordisk). Also the use of Celluzym (manufacturer: Novo Nordisk). Also the use of Celluzym (manufacturer: Novo Nordisk). Also the use of 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.
  • 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.
  • composition according to the invention may contain, in addition to the components mentioned, the following further customary additives in the quantities customary for this purpose:
  • 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.
  • 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.
  • 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)
  • 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
  • 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;
  • the degree of alkoxylation may be different.
  • 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 process for the preparation of a surfactant mixture according to the invention may comprise the following steps:
  • 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) CH2 ⁇ H.
  • the starting alcohols can be mixed from the individual components, resulting in the ratio according to the invention.
  • 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
  • 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.
  • 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.
  • 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.
  • 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-l2 ⁇ l-l xyl michs waive 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, Grenz inhabitassitule ⁇ thylenoxid adducts, psychologistliche Verlagsgesellschaft mbH Stuttgart 1984.
  • the alkoxylation is carried out in the presence of basic catalysts such as KOH in substance.
  • the alkoxylation can also be carried out with the concomitant use of a solvent.
  • 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.
  • 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.
  • PO propylene oxide
  • 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.
  • m is 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.
  • 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.
  • 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.
  • 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.
  • the alkyl alkoxylates are synthesized by techniques known to those skilled in the art, which lead to narrower molecular weight distributions than in base-catalyzed synthesis.
  • 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).
  • DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular sections [0029] to [0041], and the literature cited therein.
  • Zn-Co type catalysts can be used.
  • 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.
  • catalyst 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 can also be prepared by acid-catalyzed alkoxylation.
  • the acids may be Bronsted or Lewis acids.
  • 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.
  • the catalyst can be neutralized by addition of a base, for example KOH or NaOH, and filtered off as required. be rung.
  • a base for example KOH or NaOH
  • 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).
  • 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.
  • 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.
  • 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.
  • Example 1 Surfactant A (Comparative Example)
  • Surfactant B (comparative example)
  • Surfactant B and surfactant D / 1 were homogenized at about 60 ° C. and then mixed in a mass ratio of 1: 1.
  • 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.
  • 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,
  • the cotton net plate 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.
  • 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).
  • Test Solution [0.4 g of a red dye are dissolved in 11 water.
  • 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.

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Abstract

L'invention concerne un mélange de tensioactifs qui contient un constituant à chaîne courte et un constituant à chaîne longue. L'invention concerne également l'utilisation de ce mélange de tensioactifs, en particulier pour le prétraitement et le post-traitement de textiles.
PCT/EP2010/059634 2009-07-10 2010-07-06 Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue WO2011003904A1 (fr)

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US8492326B2 (en) 2010-06-28 2013-07-23 Basf Se Alkoxylates and use thereof
WO2013167438A1 (fr) 2012-05-10 2013-11-14 Basf Se Alcools alcoxylés et leur utilisation dans les formulations destinées au nettoyage de surface dure
US9062278B2 (en) 2010-02-19 2015-06-23 Basf Se Preparing ether carboxylates
US9070632B2 (en) 2010-10-07 2015-06-30 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrates having patterned or unpatterned low-k dielectric layers
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions

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US9062278B2 (en) 2010-02-19 2015-06-23 Basf Se Preparing ether carboxylates
US8492326B2 (en) 2010-06-28 2013-07-23 Basf Se Alkoxylates and use thereof
US9070632B2 (en) 2010-10-07 2015-06-30 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrates having patterned or unpatterned low-k dielectric layers
WO2013167438A1 (fr) 2012-05-10 2013-11-14 Basf Se Alcools alcoxylés et leur utilisation dans les formulations destinées au nettoyage de surface dure
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions
US11572529B2 (en) 2016-05-17 2023-02-07 Conopeo, Inc. Liquid laundry detergent compositions

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