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
  • C11D1/02—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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/043—Liquid or thixotropic (gel) compositions

Definitions

• the invention relates to a combination of nonionic surfactant with anionic surfactant, which can be produced at least partly on the basis of renewable raw materials and which has superior washing performance on oily soiling.
• the invention also relates to detergents or cleaning agents which contain this combination of surfactants.
• surfactants to reduce the surface tension of water, to form dispersions and to provide solubility has long been well known in the field of detergents and cleaning agents. Although many surfactants are made wholly or partly based on renewable raw materials, some powerful and widely used representatives are still based on petrochemicals. In addition, there is a constant desire to provide surfactants with outstanding performance properties in order to be able to achieve high performance even with low surfactant use.
• the object of the present invention is to provide surfactants which have advantageous application properties and can be produced as far as possible on the basis of renewable raw materials.
• the surfactants should be kind to the skin and also able to be formulated together with other surfactants, so that they are particularly suitable for use in detergents and cleaning agents.
• Rhamnolipids are compounds in which a mono- or dirhamnose unit is glycosidically linked to the hydroxyl group of a ⁇ -hydroxyl fatty acid, it being possible for the fatty acid to be esterified with a hydroxyl group of another hydroxyl-containing fatty acid molecule. They are obtained by fermentation of bacteria of the genus Pseudomonas, in particular Pseudomonas aeruginosa, preferably when they grow on hydrophobic substrates such as n-alkanes or vegetable oils. Because of their surface-active behavior and their origin, rhamnolipids belong to the so-called biosurfactants. For example, 3-(hydroxydecanoyloxy)decanoic acid dirhamnoside has the formula
• detergents which contain 1 to 60% by weight of a surfactant which forms a micellar phase at pH 7.0 and 25° C. in a 1% by weight aqueous solution and a surfactant which forms a lamellar phase at pH 7.0 and 25° C. in a 1% by weight aqueous solution Contain phase-forming surfactant, where rhamnolipid can be both the micellar phase and the lamellar phase-forming surfactant.
• the European patent specification EP 1 445 302 B1 relates to detergents containing at least one glycolipid biosurfactant and at least one non-glycolipid surfactant, which are in a micellar phase.
• compositions containing from 0.001% to 99.99% by weight of anionic and/or nonionic surfactant and from 0.001% to 99.99% by weight of glycolipid, the glycolipids including, for example, sophorolipids, rhamnolipids, glucose lipids, trehalose lipids and cellobiose lipids.
• the European patent application EP 2 787 065 A1 discloses mono- and dirhamnolipid-containing fabric detergents in which the weight ratio of dirhamnolipid to monorhamnolipid is greater than 51:49.
• Rhamnolipid mixtures are known which contain 51% to 95% by weight of a specific dirhamnolipid and 0.5% to 9% by weight of a specific monorhamnolipid, in which the weight ratio of dirhamnolipid to monorhamnolipid is greater than 91: 9 is.
• Detergents or cleaning agents containing rhamnolipid and N-containing polymer are from the international patent application WO 2016/096478 A1 known.
• the present invention relates to a surfactant combination of an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) or its salt, CH3(CH2)m(-OR)n-OH (Ia) in which R is a linear or branched alkyl group having 2 to 4 carbon atoms, in particular 2 carbon atoms, m is a number from 9 to 15, x and y are independently numbers from 0 to 12, z is one number from 1 to 4, where the sum x + y + z is in the range from 10 to 16, n is a number from 1 to 5, o is 2, 1 or 0, p is 0 or 1, and R 1 and R 2 independently of one another are identical or different organic radicals having 2 to 24, in particular 5 to 13, carbon atoms.
• the salts of the compounds of the general formula (II) in question here are preferably those in which the carboxyl H atom is replaced by an alkali metal cation or the grouping N + R 3 R 4 R 5 R 6 in which R 3 , R 4 , R 5 and R 6 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms, is replaced, that is, the carboxylic acid group is present as a carboxylate anion.
• Surfactants of the general formula (Ib) are less preferred than the surfactants of the general formula (Ia) since they can only be obtained from a renewable raw material base with comparatively great effort.
• Preferred surfactants of the general formula (Ia) are those in which m is a number in the range from 11 to 15 and/or n is a number in the range from 2 to 4.
• Surfactants of the general formula (Ia) or (Ib) can be prepared in a known manner by alkoxylation of alcohols CH 3 (CH 2 ) m -OH or produce, with the use of alcohol mixtures, the indices m, x, y and z here and in the compounds of general formula (Ia) or (Ib) can also be non-integers.
• Ethylene oxide is preferably used in the alkoxylation. Since homologous mixtures are generally formed during the alkoxylation of the alcohols, the average degree of alkoxylation n in the compounds of the general formula (Ia) or (Ib) can also not be an integer.
• the alcohol CH 3 (CH 2 ) m -OH is preferably a fatty alcohol and thus also comes from a renewable raw material base.
• the particularly preferred surfactants of the general formula (Ia) include the linear C 12 alcohol with 3 ethylene oxide groups and the linear C 14 alcohol with 4 ethylene oxide groups, as well as the technical alkoxylates, which are obtained by reacting 1 molar equivalent of linear C 12 alcohol or linear C 14 -alcohol with 2, 3 or 4 molar equivalents of ethylene oxide are formed.
• the weight ratio of alkyl polyglycol ether to rhamnolipid is preferably in the range from 50:50 to 99:1 , in particular from 70:30 to 95:5 and particularly preferably from 80:20 to 90:10. If the surfactant combinations contain mixtures of compounds of the general formula (Ia) and the general formula (Ib), those of the general formula (Ia) are preferably present in larger proportions by weight than those of the general formula (Ib).
• surfactant combinations according to the invention are ideal as an ingredient in detergents and cleaning agents, cosmetics such as shampoos, toothpastes, and for other areas of application in which anionic surfactants have usually been used to date, such as in the food industry, geosciences, tertiary oil production, plastics technology , metalworking, photography, paper recycling, tool cleaning and firefighting.
• the surfactant combination essential to the invention develops its advantageous effect even at low temperatures, it or a composition containing it is preferably used in processes for washing laundry or cleaning hard surfaces that are carried out at temperatures of up to 30.degree.
• a washing or cleaning agent according to the invention preferably contains 5% by weight to 70% by weight, in particular 10% by weight to 50% by weight and particularly preferably 12% by weight to 40% by weight of the surfactant combination defined above .
• the washing or cleaning agent can contain other ingredients which further improve the performance and/or aesthetic properties of the agent.
• the agent preferably additionally contains one or more substances from the group of nonionic surfactants, anionic surfactants, builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes , foam inhibitors, anti-redeposition agents, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial active ingredients, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobic and impregnating agents, skin care active ingredients, swelling and Non-slip agents, softening components and UV absorbers.
• a washing or cleaning agent according to the invention can contain up to 30% by weight of further surfactants in addition to the surfactant combination essential to the invention, with the surfactants additionally present preferably being obtainable from renewable raw materials.
• the surfactants additionally present preferably being obtainable from renewable raw materials.
• no further surfactant is present in addition to the surfactant combination that is essential to the invention.
• the agent according to the invention can contain additional nonionic surfactants.
• Suitable nonionic surfactants include alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkyl phenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.
• alkyl glycosides of the general formula R 7 O(G) q can also be used as further nonionic surfactants, in which R 7 is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 C- corresponds to atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of oligomerization q which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably q is from 1.2 to 1.4.
• nonionic surfactants which are used either as the sole additional nonionic surfactant or in combination with other additional nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type can also be used.
• suitable surfactants are polyhydroxy fatty acid amides of the formula in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C 1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can be converted to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide catalyst.
• a composition according to the invention preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
• the water-soluble organic builder substances include polycarboxylic acids, especially citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, especially glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, especially aminotris(methylenephosphonic acid), Ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in
• the relative average molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g/mol and 200,000 g/mol, that of the copolymers between 2,000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g /mol, based on the free acid.
• a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000.
• Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
• Terpolymers which contain two unsaturated acids and/or their salts as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.
• the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth)acrylic acid.
• the second acidic monomer or its salt can be a derivative of a C 4 -C 8 -dicarboxylic acid, maleic acid being particularly preferred.
• the third monomeric unit is formed by vinyl alcohol and/or preferably an esterified vinyl alcohol.
• vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol.
• Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight, of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and/or vinyl acetate.
• the weight ratio of (meth)acrylic acid or (meth)acrylate to maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1 and in particular 2:1 and 2 .5:1.
• the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which has an alkyl radical in the 2-position, preferably a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted.
• Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight, of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight.
• % preferably 15% to 25% by weight of methallyl sulphonic acid or methallyl sulphonate and as a third monomer 15% to 40% by weight, preferably 20% to 40% by weight of a carbohydrate.
• This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred.
• the use of the third monomer presumably incorporates predetermined breaking points into the polymer, which are responsible for the good biodegradability of the polymer.
• These terpolymers generally have a relative average molecular weight of between 1000 g/mol and 200,000 g/mol, preferably between 200 g/mol and 50,000 g/mol.
• copolymers are those which have acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers.
• the organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid compositions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
• Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in pasty or liquid, in particular aqueous, compositions.
• Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
• crystalline or amorphous, water-dispersible alkali metal aluminosilicates in amounts of not more than 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts from 5% by weight to 15% by weight, are used as water-insoluble inorganic builder materials. -% used.
• the detergent grade crystalline sodium aluminosilicates particularly zeolite A, zeolite P, and zeolite MAP and optionally zeolite X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
• suitable aluminosilicates do not have any particles with a particle size of more than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m.
• Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
• water-soluble inorganic builder materials can be present.
• polyphosphates such as sodium triphosphate
• these include in particular the water-soluble crystalline and/or amorphous alkali metal silicate builders.
• Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight.
• the alkali metal silicates which can be used as builder materials preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1:1.1 to 1:12, and can be present in amorphous or crystalline form.
• Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na 2 O:SiO 2 ratio of 1:2 to 1:2.8.
• Crystalline phyllosilicates of the general formula Na 2 Si x O 2x+1 y H 2 O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
• Preferred crystalline layered silicates are those in which x has the value 2 or 3 in the general formula mentioned.
• both ⁇ - and ⁇ -sodium disilicates are preferred.
• Practically anhydrous crystalline alkali metal silicates of the above general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali metal silicates can also be used in the compositions.
• a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda.
• Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment.
• a granular compound of alkali metal silicate and alkali metal carbonate is used, as is commercially available, for example, under the name Nabion® 15.
• Suitable peroxidic bleaching agents are, in particular, organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid and diperdodecanedioic acid, and salts thereof, such as magnesium monoperoxyphthalate, diacyl peroxides, Hydrogen peroxide and inorganic salts releasing hydrogen peroxide under the conditions of use, such as alkali metal perborate, alkali metal percarbonate and/or alkali metal persilicate, and hydrogen peroxide inclusion compounds, such as H 2 O 2 -urea adducts, and mixtures of these.
• organic peracids or peracidic salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid and diperdodecanedioic acid, and salts thereof, such as magnesium monoperoxyphthalate, diacyl peroxides, Hydrogen peroxide and
• Hydrogen peroxide can also be generated with the help of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. Alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide is particularly preferably used.
• a detergent that can be used within the scope of the invention contains peroxidic bleaching agents in amounts of preferably up to 60% by weight, in particular from 5% by weight to 50% by weight and particularly preferably from 15% by weight to 30% by weight.
• Peroxidic bleaching agent particles preferably have a particle size in the range from 10 ⁇ m to 5000 ⁇ m, in particular from 50 ⁇ m to 1000 ⁇ m and/or a density from 0.85 g/cm 3 to 4.9 g/cm 3 , in particular from 0 91 g/cm 3 to 2.7 g/cm 3 .
• compounds which under perhydrolysis conditions produce substituted perbenzoic acid and/or aliphatic peroxocarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms can be used alone or in mixtures as the bleach-activating compound which produces peroxocarboxylic acid under perhydrolysis conditions.
• Bleach activators which carry O- and/or N-acyl groups, in particular the number of carbon atoms mentioned, and/or optionally substituted benzoyl groups are suitable.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyloxybenzene sulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBA), their formal carbonic acid ester derivatives such as 4-(2-decanoyloxyethoxycarbonyl
• bleach-activating compounds such as nitriles, from which perimidic acids form under perhydrolysis conditions, may be present.
• nitriles include, in particular, aminoacetonitrile derivatives with a quaternized nitrogen atom according to the formula in which R 1 is -H, -CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 1-24 -alkyl or C 2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN and -N (+) -CH 2 -CN, an alkyl or alkenylaryl radical having a C 1-24 alkyl group, or a substituted alkyl or alkenylaryl radical having at least one, preferably two, optionally substituted C 1-24 -alkyl group(s) and optionally
• Bleach activators which form peroxocarboxylic acids or perimidic acids under perhydrolysis conditions are preferably present in detergents according to the invention in amounts of up to 25% by weight, in particular 0.1% by weight to 10% by weight.
• Bleach activator particles preferably have a particle size in the range from 10 ⁇ m to 5000 ⁇ m, in particular from 50 ⁇ m to 1000 ⁇ m and/or a density from 0.85 g/cm 3 to 4.9 g/cm 3 , in particular 0.91 g/cm 3 to 2.7 g/cm 3 .
• transition metal complexes in addition to or instead of the bleach activators mentioned is possible.
• These are preferably chosen from complexes of cobalt, iron, copper, titanium, vanadium, manganese and ruthenium.
• Both inorganic and organic compounds are suitable as ligands in such transition metal complexes, including, in addition to carboxylates, in particular compounds with primary, secondary and/or tertiary amine and/or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , triazole, 2,2'-bispyridylamine, tris(2-pyridylmethyl)amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl -1,5,9-triazacyclododecane, (bis-((1-methylimidazol-2-yl)-methyl))
• the inorganic neutral ligands include, in particular, ammonia and water. If not all of the coordination sites of the central transition metal atom are occupied by neutral ligands, the complex contains other, preferably anionic and, among these, in particular, monodentate or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2 ) - group, ie a nitro ligand or a nitrite ligand.
• the (NO 2 ) - group can also be chelated to a transition metal or it can bridge two transition metal atoms asymmetrically or ⁇ 1-O.
• the transition metal complexes can also carry other, generally simpler, ligands, in particular monovalent or polyvalent anion ligands.
• ligands for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate are suitable.
• the anion ligands should ensure the charge balance between the transition metal central atom and the ligand system.
• the presence of oxo ligands, peroxo ligands and imino ligands is also possible.
• such ligands can also have a bridging effect, so that polynuclear complexes are formed.
• both metal atoms in the complex do not have to be the same. It is also possible to use binuclear complexes in which the two central transition metal atoms have different oxidation numbers. If anion ligands are missing or the presence of anion ligands does not lead to charge equalization in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention.
• anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate.
• transition metal complex compounds that can be used are [N,N'-bis[(2-hydroxy-5-vinylphenyl)methylene]-1,2-diaminocyclohexane]manganese(III) chloride, [N,N' -Bis[(2-hydroxy-5-nitrophenyl)methylene]-1,2-diaminocyclohexane]manganese(III) acetate, [N,N'-Bis[(2-hydroxyphenyl)methylene]- 1,2-phenylenediamine] manganese (III) acetate, [N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-Bis[(2-hydroxyphenyl)methylene]-1,2-diaminoethane] manganese(III) chloride, [N,N'-Bis[(2-hydroxy-5-sulfonatophenyl)
• Enzymes that can be used in the agents are those from the class of proteases, amylases, lipases, cutinases, pullulases, hemicellulases, cellulases, oxidases, laccases and peroxidases, and mixtures thereof.
• fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus.
• the enzymes can be adsorbed on carriers and/or embedded in coating substances in order to protect them against premature inactivation.
• the detergents or cleaning agents according to the invention preferably contain them in amounts of up to 5% by weight, in particular from 0.002% by weight to 4% by weight.
• the agent according to the invention contains protease, it preferably has a proteolytic activity in the range from about 100 PU/g to about 10,000 PU/g, in particular 300 PU/g to 8000 PU/g. If several enzymes are to be used in the agent according to the invention, this can be carried out by incorporating the two or more separate enzymes or enzymes prepared separately in a known manner, or by two or more enzymes prepared together in a granulate.
• the agents according to the invention can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali metal hydroxides.
• acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali metal hydroxides.
• Such pH regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
• Graying inhibitors have the task of keeping the dirt detached from the textile fibers suspended in the liquor.
• Water-soluble colloids usually of an organic nature, are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose.
• starch derivatives other than those mentioned above can be used, for example aldehyde starches.
• Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used, for example in amounts of 0.1 to 5% by weight, based on the detergent.
• the agents can contain a customary color transfer inhibitor, which is then preferably present in amounts of up to 2% by weight, in particular 0.1% by weight to 1% by weight, which in a preferred embodiment is selected from the polymers of vinylpyrrolidone , vinylimidazole, vinylpyridine-N-oxide or the copolymers of these.
• enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance that supplies hydrogen peroxide in water.
• a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, it also being possible to additionally use the above-mentioned polymeric dye transfer inhibitor active substances.
• Polyvinylpyrrolidone preferably has an average molar mass in the range from 10,000 g/mol to 60,000 g/mol, in particular in the range from 25,000 g/mol to 50,000 g/mol.
• copolymers those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5:1 to 1:1 with an average molar mass in the range from 5000 g/mol to 50,000 g/mol, in particular 10,000 g/mol to 20,000 g/mol, are preferred .
• the detergents are free from such additional color transfer inhibitors.
• Detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
• Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds that instead of morpholino - carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl, or4- (4-chlorostyryl)-4'-(2-sulfostyryl)diphenyls. Mixtures of the aforementioned optical brighteners can also be used.
• foam inhibitors are soaps of natural or synthetic origin which have a high proportion of C 18 -C 24 fatty acids.
• suitable non-surfactant foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanated silica, and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also used with advantage, for example those made of silicones, paraffins or waxes.
• the foam inhibitors, in particular silicone- and/or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
• the agent according to the invention is in particulate form and, in addition to the surfactant essential to the invention, contains builders, in particular in an amount in the range from 1% by weight to 60% by weight.
• an agent according to the invention is liquid and contains up to 90% by weight, in particular 10% by weight to 85% by weight, preferably 25% by weight to 75% by weight, and particularly preferably 35 65% by weight of water, water-miscible solvent or a mixture of water and water-miscible solvent.
• Water-miscible solvents include, for example, monohydric alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols and triols having 2 to 4 carbon atoms, in particular ethylene glycol, propylene glycol and glycerol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned.
• Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 2% by weight to 20% by weight.
• the agent according to the invention is present in portions, ready for single dosing, in a chamber formed from water-soluble material; the agent then preferably contains less than 15% by weight, in particular in the range from 1% by weight to 12% by weight, of water.
• a portion is an independent dosing unit with at least one chamber containing the product to be dosed.
• a chamber is a space delimited by walls (e.g. by a foil), which can also exist without the material to be dosed (possibly with a change in its shape).
• a surface coating or a layer of a surface coating is therefore not a wall according to the present invention.
• the walls of the chamber are made of a water-soluble material.
• the water solubility of the material can be determined using a square film of said material (film: 22 ⁇ 22 mm with a thickness of 76 ⁇ m) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol.
• Said framed film is immersed in 800 ml of distilled water at a temperature of 20 °C in a 1 liter beaker with a circular bottom (Schott, Mainz, 1000 ml beaker, low shape) so that the surface of the clamped film is at right angles to the bottom surface of the beaker, the top edge of the frame is 1 cm below the water surface and the bottom edge of the frame is oriented parallel to the bottom surface of the beaker such that the bottom edge of the frame runs along the radius of the bottom surface of the beaker and the center of the bottom edge of the frame located above the center of the radius of the bottom of the beaker.
• the material dissolves within 600 seconds with stirring (stirring speed, magnetic stirrer 300 rpm, stirring rod: 5 cm long) in such a way that individual solid particles are no longer visible to the naked eye.
• the walls of the chambers and thus the water-soluble envelopes of the detergents according to the invention are preferably formed by a water-soluble film material.
• Such water soluble packages can be made either by vertical form fill sealing processes or by thermoforming processes.
• the thermoforming process generally includes forming a first sheet of water-soluble film material to form recesses for receiving a composition therein, filling the composition into the recesses, covering the composition-filled recesses with a second sheet of water-soluble film material, and sealing the first and second layers together at least around the bulges.
• the water-soluble film material is preferably selected from polymers or polymer blends.
• the cover can be formed from one or from two or more layers of water-soluble film material.
• the water-soluble film materials of the first layer and the further layers, if any, can be the same or different.
• the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer; it particularly preferably consists of polyvinyl alcohol or polyvinyl alcohol copolymer.
• Water-soluble films for producing the water-soluble casing are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
• Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.
• Polymers selected from the group comprising polymers containing acrylic acid, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid and/or mixtures of the above polymers can also be added to a film material suitable for producing the water-soluble covering. It is also possible to copolymerize monomers on which such polymers are based, individually or in mixtures of two or more, with vinyl acetate.
• preferred polyvinyl alcohol copolymers include an ethylenically unsaturated carboxylic acid, its salt or its ester.
• Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof; among the esters, C 1-4 alkyl esters or hydroxyalkyl esters are preferred.
• preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, ethylenically unsaturated dicarboxylic acids as further monomers. Examples of suitable dicarboxylic acids are itaconic acid, maleic acid, fumaric acid and mixtures thereof, itaconic acid being particularly preferred.
• Suitable water-soluble films for use in the overwraps of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
• Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL films from Aicello Chemical Europe GmbH or Kuraray VF-HP films.
• the detergent or cleaning agent portion comprising the detergent or cleaning agent and the water-soluble envelope, can have one or more chambers.
• the water-soluble casings with a chamber can have an essentially dimensionally stable configuration in the form of a sphere, an ellipsoid of revolution, a cube, a parallelepiped or a cushion with a circular, elliptical, square or rectangular basic shape.
• the agent can be contained in one or more compartments, if any, of the water-soluble coating.
• the water-soluble envelope has two chambers.
• both compartments may each contain a solid part composition or each contain a liquid part composition, or the first compartment may contain a liquid part composition and the second compartment may contain a solid part composition.
• the proportions of the agents contained in the different compartments of a water-soluble envelope with two or more compartments can have the same composition.
• the agents in a water-soluble envelope with at least two chambers preferably have partial compositions which differ in at least one ingredient and/or in the content of at least one ingredient.
• a part-composition of such agents according to the invention has an enzyme and/or bleach activator and a further part-composition present separately from this has peroxidic bleaching agent, in which case the first-mentioned part-composition has in particular no peroxidic bleach and the second-mentioned part-composition has in particular no enzyme and no bleach activator.
• portion-by-portion packaging in a water-soluble envelope the user is able to use one or, if desired, several, preferably one, of the portions in the washing machine or dishwasher, in particular in the dispenser compartment of a washing machine, or in a container for carrying out a manual washing or cleaning process.
• Portion packs of this type meet the consumer's desire for simplified dosing.
• the coating material dissolves so that the ingredients are released and can develop their effect in the liquor.
• a water-coated portion preferably weighs 10 g to 35 g, in particular 12 g to 28 g and particularly preferably 12 g to 15 g, with 0.3 g to 2.5 g, in particular 0 .7 g to 1.2 g are eliminated.
• solid agents according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, with enzymes and any other heat-sensitive ingredients such as bleaching agents optionally being added separately later.
• a process having an extrusion step is preferred.
• Liquid or pasty agents according to the invention in the form of solutions containing water and conventional solvents are generally produced by simply mixing the ingredients, which can be added to an automatic mixer as such or as a solution.
• the washing performance of surfactant combinations according to the invention was determined in comparison with conventional surfactant mixtures in a miniaturized washing device.
• aqueous solutions of 1 g/l each of the mixtures given in Table 1 below (which had the weight ratio of the individual surfactants given in brackets) were used at 30° C. to wash cotton test fabrics with standardized oily soiling and the Y value determined after drying.
• the values also given in Table 1 were obtained.
• a clear superiority of the surfactant mixtures E1 and E2 according to the invention is observed in comparison to other surfactant systems (V1 and V2) customary in commercial detergents consisting of linear alkyl benzene sulfonate, C 12/14 ether sulfate and a nonionic surfactant C 12/18 -7EO.
• 65 E1: rhamnolipid + C12 fatty alcohol-3EO (25:75) 67.5
• E2 rhamnolipid + C14 fatty alcohol 4EO (12:88) 68.2

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• 2021
  • 2021-12-20 DE DE102021214680.5A patent/DE102021214680A1/de not_active Withdrawn
• 2022
  • 2022-12-05 EP EP22211350.8A patent/EP4198112A1/fr active Pending

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