Classifications

• • 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
  • 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
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
• • 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
  • 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
• • 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
• • 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
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/165—Ethers
  • D06M13/17—Polyoxyalkyleneglycol ethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers
• • 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
• • 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
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• 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.
• surfactants are used, for example, for wetting solids such as fibers or hard surfaces.
• 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.
• 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.
• DE-A 19921330 describes the use of branched fatty alcohol ethoxylates having 8 to 22 carbon atoms which can be used as wool detergents.
• surfactants or surfactant mixtures which have, at least in part, better properties than those from the prior art.
• 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 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 13 C 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.
• 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.
• the short-chain component (A) 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 C 10 Guerbet alcohol mixture.
• the main components are 2-propylheptanol and 5-methyl-2-propyl-hexanol.
• the short-chain component (A) consists of at least 90%, preferably 95%, of such a mixture.
• 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.
• 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.
• 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.
• 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).
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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).
• 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.
• 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 alkanols having 1 to 12 carbon atoms, and alkanols having more than 20 carbon atoms.
• 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.
• alkoxylation products of alkanols with branching from 0 to 0.3 can arise which have a lower or higher degree of alkoxylation.
• 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.
• 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.
• 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.
• 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 C 2 -C 5 -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:
• 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.
• the present invention further relates to a method of producing a surfactant mixture according to the present invention, comprising the steps
• 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.
• soap 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, peracid
• anionic surfactants such as LAS (linear alky
• 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.
• 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 include, for example, builders, surfactants, bleaches, enzymes and further ingredients, as described below.
• 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.
• 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.
• 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.
• other components (A′) can also be present.
• 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.
• B′ organic cobuilders
• 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, for example, 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 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, ⁇ -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:
• Suitable unsaturated C 4 -C 8 -dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.
• the group (i) comprises monoethylenically unsaturated C 3 -C 8 -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 C 2 -C 22 -olefins, vinyl alkyl ethers with 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, vinyl alkyl ethers with 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) 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:
• Graft polymers of unsaturated carboxylic acids based on low molecular weight carbohydrates or hydrogenated carbohydrates are likewise suitable as (B′).
• Suitable unsaturated carboxylic acids 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.
• Suitable modifying monomers are the abovementioned monomers of groups (ii) and (iii).
• 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.
• 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.
• polyaspartic acids or cocondensates of aspartic acid with further amino acids C 4 -C 25 -mono- or -dicarboxylic acids and/or C 4 -C 25 -mono- or -diamines.
• Particular preference is given to using polyaspartic acids modified with C 6 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -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.
• (B′) ethylenediaminedisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.
• oxidized starches can be used as organic cobuilders.
• surfactant mixture according to the invention 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. C 9 -C 11 -alcohol sulfates, C 12 -C 14 -alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
• alkanesulfonates such as C 8 -C 24 -, preferably C 10 -C 18 -alkylsulfonates, and soaps, such as, for example, the Na and K salts of C 8 -C 24 -carboxylic acids.
• anionic surfactants are C 9 -C 20 linear alkylbenzenesulfonates (LAS) and C 9 -C 20 linear alkyltoluenesulfonates.
• Such anionic surfactants (C) are also C 8 -C 24 -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
• 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 C 9 -C 20 linear 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.
• nonionic surfactants D
• alkylphenol alkoxylates such as alkylphenol ethoxylates with C 6 -C 14 -alkyl chains and 5 to 30 mol of alkylene oxide units.
• 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 C 6 -C 22 -alkyl chains. Compounds of this type are obtained, for example, by acylation of reductively aminated sugars with corresponding long-chain carboxylic acid derivatives.
• 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.
• 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 C 8 -C 22 -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.
• 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.
• surfactant constituents of the surfactant mixture according to the invention should also be taken into consideration.
• 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
• 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.
• F ampholytic surfactants
• Components (E) and (F) can be present in the detergent formulation up to 25%, preferably 3-15%.
• 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).
• bleaches examples are alkali metal perborates or alkali metal carbonate perhydrates, in particular the sodium salts.
• 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.
• 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.
• 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).
• 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:
• 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.
• 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 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.
• the textile detergent formulation according to the invention can also comprise the following further customary additives in the amounts customary for this purpose:
• Suitable soil release polymers and/or graying inhibitors for detergents are, for example:
• polyesters of polyethylene oxides terminally capped at one end with di- and/or polyhydric alcohols and dicarboxylic acid are examples of polyesters of polyethylene oxides terminally capped at one end with di- and/or polyhydric alcohols and dicarboxylic acid.
• 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.
• 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.
• 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.
• 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):
• the mass ratio A:B refers here to the ratio of isodecanol to C 13 -C 15 -oxo alcohol.
• 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 —)* 12.5 100 90 100 — 14.3 100 100 — 200 14.3 200 150 — 160 Wetting 1.0 g/l, 23° C. Wetting 1.0 g/l, 23° C.
• 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] 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.
• 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.
• the emulsion stability is determined by means of the marker method, as described in DE 10247086.
• 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/m 3 is introduced.
• the emulsions obtained are mixed, and the droplet size distribution is measured by means of statistical laser scattering.
• the following tables give the d 50 , 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:
• oils used are sunflower oil (56 mm 2 /s at 25° C.) and paraffin oil (30 mm 2 /s at 25° C.).
• WFK soiled fabric 10D 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).
• 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
• 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.
• Lutensol AO7 Lutensol AO7
• without surfactant a formulation comprising Lutensol AO7 as surfactant
• Standardization was carried out linearly, with “without surfactant” being set at 0% and “Lutensol AO7” being set as 100%:
• % (Detergency) 100% ⁇ [reflectance (surfactant 1 or 2) ⁇ reflectance (“without surfactant”)]i[reflectance (“Lutensol A07”) ⁇ reflectance (“Without surfactant”)]
• 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.
• surfactant 1 is clearly superior to surfactant 2 in detergency, lack of foam, wetting rate and emulsion stability without displaying disadvantages regarding salt stability.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Health & Medical Sciences (AREA)
• Textile Engineering (AREA)
• Health & Medical Sciences (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Toxicology (AREA)
• Dentistry (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Materials Engineering (AREA)
• Detergent Compositions (AREA)
• Cosmetics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=38002640

Family Applications (3)

Family Applications After (2)

Country Status (12)

Cited By (12)

Families Citing this family (25)

Citations (20)

Family Cites Families (38)

• 2007
  • 2007-02-15 JP JP2008555758A patent/JP5210177B2/ja not_active Expired - Fee Related
  • 2007-02-15 DE DE502007002180T patent/DE502007002180D1/de active Active
  • 2007-02-15 EP EP07704591A patent/EP1988986B1/fr not_active Revoked
  • 2007-02-15 ES ES07704591T patent/ES2336379T3/es active Active
  • 2007-02-15 WO PCT/EP2007/051463 patent/WO2007096292A1/fr active Application Filing
  • 2007-02-15 KR KR1020087020604A patent/KR101057048B1/ko not_active IP Right Cessation
  • 2007-02-15 PL PL07704591T patent/PL1988986T3/pl unknown
  • 2007-02-15 AT AT07704591T patent/ATE450311T1/de active
  • 2007-02-15 BR BRPI0707852-8A patent/BRPI0707852A2/pt not_active IP Right Cessation
  • 2007-02-15 CN CN2007800063545A patent/CN101389398B/zh not_active Expired - Fee Related
  • 2007-02-15 US US12/280,114 patent/US20090023820A1/en not_active Abandoned
  • 2007-02-15 CA CA2640642A patent/CA2640642C/fr not_active Expired - Fee Related
  • 2007-02-22 US US11/677,824 patent/US7504373B2/en not_active Expired - Fee Related
  • 2007-10-31 US US11/932,420 patent/US7503333B2/en active Active

Patent Citations (21)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events