EP2802644A1 - Acylhydrazones utilisées comme renforçateurs de blanchiment - Google Patents

Acylhydrazones utilisées comme renforçateurs de blanchiment

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Publication number
EP2802644A1
EP2802644A1 EP13700046.9A EP13700046A EP2802644A1 EP 2802644 A1 EP2802644 A1 EP 2802644A1 EP 13700046 A EP13700046 A EP 13700046A EP 2802644 A1 EP2802644 A1 EP 2802644A1
Authority
EP
European Patent Office
Prior art keywords
acid
alkyl
μιηοι
use according
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13700046.9A
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German (de)
English (en)
Other versions
EP2802644B1 (fr
Inventor
André HÄTZELT
Michael Dreja
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP2802644A1 publication Critical patent/EP2802644A1/fr
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to the removal of stains from food residues from textile or hard surfaces by the combination of bleaches with certain acylhydrazones.
  • Stains from food residues are among the consumer-relieving hard-to-remove spots; they often contain food additives such as thickening or stabilizing agents.
  • polysaccharide-based hydrocolloids are often found which hydrate in cold or hot water and form viscous solutions, dispersions or gels.
  • Useful polysaccharides may be of natural origin or made by modification thereof. To the natural polysaccharides count
  • Modified or semi-synthetic hydrocolloids include, for example, cellulose and starch derivatives and similar compounds, such as
  • Methoxypectins propylene glycol alginates and carboxymethyl and hydroxy guar gum.
  • a polysaccharide frequently found in food residues, guaran, is available from the seed walls of the legume Cyamopsis tetragonoloba and has a 1-4- ⁇ -D-mannopyranosyl backbone. It is used as a thickener especially in ready-made sauces and frozen foods, but also in chocolate. The accessible from carob fruit
  • Polysaccharide is also commonly used in the food industry; it also has a 1-4-.beta.-D-mannopyranosyl backbone and is likely to differ from guaran by having a lower number of D-galactosyl sidechains.
  • the generally water-soluble galactomannan accounts for the majority of stored carbohydrates, which in some cases can be up to 20% of the dry weight.
  • Galactomannan has a-galactosyl residues attached to 0-6 of mannose and may also be at least partially acetylated at 0-2 and 0-3 of the mannose residues.
  • the present invention relates to the use of a combination of a peroxidic bleaching agent with an acylhydrazone of the general formula I
  • R 2 and R 3 are independently hydrogen or an optionally substituted Ci_ 28 - alkyl, C 2 . 28 alkenyl, C 2 .
  • Heteroaryl or R2 and R3 together with the carbon atom connecting them to an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and
  • R 4 is hydrogen or a Ci_ 28 alkyl, C 2 . 28 alkenyl, C 2 . 22 alkynyl, C 3 _i 2 cycloalkyl, C 3 _i 2 - cycloalkenyl, C 7 . 9 aralkyl, C 3 . 20 -heteroalkyl, C 3 _i 2 -cycloheteroalkyl, C5-i 6 -Heteroaralkyl distr or an optionally substituted phenyl or naphthyl or heteroaryl group
  • the acylhydrazones may be in E or Z configuration; when R 2 is hydrogen, the compound of general formula (I) may be in one of its tautomeric forms or as a mixture of these.
  • R 2 is preferably hydrogen.
  • R and / or R 3 is preferably a methyl, phenyl or naphthyl group substituted with an electron withdrawing group.
  • R 4 is preferably hydrogen.
  • an electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of an alkyl group bearing N atom as optionally heteroatom-carrying heterocyclo group.
  • Preferred embodiments of the compounds according to general formula (I) include those of general formula (II),
  • R 0 is hydrogen or a C-
  • R 5 , R 6 , R 7 and R 8 independently of one another R, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-Ci_ 4 -alkyl or C 2 ⁇ -hydroxyalkyl-amino -, N-phenyl or N-naphthyl-amino, Ci_ 28 alkyl, Ci_ 28 alkoxy, phenoxy, C 2 . 28 alkenyl, C 2 . 22 alkynyl, C 3 . 12 -cycloalkyl-, C 3 . 12 cycloalkenyl, C 7 . 9 aralkyl, C 3 . 20 -heteroalkyl-, C 3 .
  • the anion A " is preferably carboxylate, such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate,
  • the compounds of general formula (I) enhance the bleaching effect of peroxidic bleaches without unacceptably damaging the substrate to be cleaned, for example the textile.
  • peroxide bleaching H 2 0 2 or in water H 2 0 2 releasing substances which include in particular alkali metal perborates, alkali metal perborates and urea; however, their use is also possible
  • peroxycarboxylic acids such as diperoxodecanedicarboxylic acid or phthalimidoperapronic acid
  • other acids or acid salts such as alkali persulfates
  • Peroxycarboxylic acid forming compound used together with an acylhydrazone of general formula I.
  • Suitable are customary bleach activators which carry O- and / or N-acyl groups for example 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), acylated phenylsulfonates and carboxylates, in particular nonanoyloxy or isononanoyloxybenzenesulfonate or benzoate, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran and also acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pen
  • the concentration of the compound of formula (I) in the aqueous washing or cleaning liquor is preferred if the concentration of the compound of formula (I) in the aqueous washing or cleaning liquor, as used for example in washing machines but also in the cleaning of carpets or
  • Preferred peroxygen concentrations (calculated as H 2 O 2 ) in the washing or cleaning liquor are in the range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and particularly preferably from 0.2 g / l to 0.5 g / l.
  • Use is preferably carried out at temperatures in the range of 10 ° C to 95 ° C, in particular 20 ° C to 40 ° C.
  • the water hardness of the water used for preparing the aqueous washing or cleaning liquor is preferably in the range from 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH.
  • the use according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
  • the uses according to the invention can be realized particularly simply by the use of a washing or cleaning agent which comprises peroxidic bleaching agent and a compound of the formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned.
  • a bleach-catalyzing complex which has a ligand with a skeleton of the formula (I) can have the corresponding ligand once or even several times, in particular twice. It can be one-or possibly two- or Pathkerning. It may also contain other neutral, anion or cationic ligands such as H 2 O, NH 3 , CH 3 OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C 2 _ 18 carboxylate, a C 1-8 -alkyl sulfate, in particular methosulfate, or a corresponding alkanesulfonate, inorganic anions, such as, for example, halide, in particular chloride, perchlorate,
  • Tetrafluoroborate hexafluorophosphate, nitrate, hydrogen sulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.
  • the agent additionally comprises a manganese, titanium, cobalt, nickel or copper salt and / or a manganese, titanium, cobalt, nickel or copper Complex without a ligand, which corresponds to a compound according to formula (I) contains.
  • the molar ratio of said transition metal or the sum of said transition metals to the compound of formula (I) is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1.
  • peroxygen compounds contained in the compositions are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and among the
  • Hydrogen peroxide-releasing inorganic salts such as perborate, percarbonate and / or persilicate, into consideration.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
  • solid peroxygen compounds If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide.
  • peroxygen compounds are present in detergents or cleaners in amounts of up to 50% by weight, more preferably from 5% to 30% by weight.
  • Detergents and cleaners which may be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, can in principle all known and customary ingredients in such agents in addition to the present invention to be used combination of peroxidic bleaching agent and compound of formula (I) contain.
  • the agents may in particular be builders, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric agents and polymer-containing actives, and other adjuvants , such as optical brighteners, foam regulators, dyes and fragrances.
  • An agent may contain conventional antimicrobial agents in addition to the ingredients previously mentioned to enhance the disinfecting effect, for example against specific germs.
  • antimicrobial additives are contained in disinfectants preferably in amounts of up to 10 wt .-%, in particular from 0, 1 wt .-% to 5 wt .-%.
  • customary bleach activators which form peroxycarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or customary bleach-activating transition metal complexes can be used.
  • the optional, especially in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example, several times acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, moreover carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulphonate, and acy
  • sugar derivatives especially pentaacetyl glucose, as well as cationic nitrile derivatives such as trimethyl ammonium acetonitrile salts.
  • the bleach activators may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the percompounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, 5 with the aid of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred.
  • Such bleach activators are preferably contained in detergents or cleaners in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • the agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having from 5 to 12 carbon atoms in the alkyl radical.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are in detergents in proportions of preferably 5 wt .-% to
  • disinfectants as well as cleaning agents for hard surfaces preferably 0, 1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants containing.
  • compositions may, in particular if they are those intended for the treatment of textiles, contain as cationic active substances with textile softening action, in particular one or more of the cationic fabric softening substances of the general formulas X, XI or XII:
  • R is -N (+) - (CH 2 ) n -CH-CH 2 (XI)
  • each group R is independently selected from C-
  • the cationic surfactants have customary anions in the charge balance necessary type and number, which can be selected in addition to, for example halides also from the anionic surfactants.
  • cationic surfactants hydroxyalkyl trialkyl ammonium compounds, in particular Ci _i 2 8 alkyl (hydroxyethyl) dimethylammoniumver- bonds, and preferably their halides, in particular chlorides, are used.
  • the agent preferably contains 0.5% by weight to 25% by weight, in particular 1% by weight to 15% by weight, of cationic surfactant.
  • a washing or cleaning agent 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, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized.
  • polycarboxylic acids in particular citric acid and sugar acids
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • 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 may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may 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. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.
  • Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Quantities near the upper limit mentioned are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 ⁇ m, and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali silicates useful as builders 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 ratio Na 2 0: Si0 2 of 1: 2 to 1: 2.8.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na 2 Si x O 2 X + iy H 2 O, 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 phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ß- and ⁇ -sodium disilicates Na 2 Si 2 0 5 y H 2 0
  • ß- and ⁇ -sodium disilicates Na 2 Si 2 0 5 y H 2 0
  • amorphous alkali silicates practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1, 9 to 2, 1, can be used.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment.
  • a granular compound of alkali metal silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, this is
  • Weight ratio of aluminosilicate to silicate in each case based on anhydrous active substances, preferably 1:10 to 10: 1 in agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Builder substances are preferably present in detergents or cleaners in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • the agent comprises a water-soluble builder block.
  • builder block it is intended to express that the agents contain no further builder substances than those which are water-soluble, ie all builder substances contained in the agent are characterized in the manner characterized
  • water-soluble is to be understood as meaning that the builder block is included in the "block", with the exception of amounts of substances which may be commercially available as impurities or stabilizing additives in small amounts in the other ingredients of the compositions the concentration, which results from the amount of the agent containing it in the usual conditions, dissolves residue.
  • at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight, of water-soluble builder block are contained in the compositions. This is preferably composed of the components
  • the water-soluble builder block contains at least 2 of the components b), c), d) and e) in amounts greater than 0 wt .-%.
  • component a in a preferred embodiment, 15% by weight to 25% by weight of alkali carbonate, which may be replaced at least proportionally by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight, bis 2.5% by weight of citric acid and / or alkali citrate.
  • the component comprises a) alkali carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 to 1: 1.
  • component b in a preferred embodiment, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.
  • phosphonic acid and / or alkali metal phosphonate in a preferred embodiment, from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate is contained.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1, 1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane -1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediaminetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1, 1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane -1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediaminetrakis (methylenephosphonic acid
  • alkali metal phosphate in particular trisodium polyphosphate, is contained.
  • Alkaliphosphat is the summary term for the alkali metal (especially sodium and
  • Potassium salts of the various phosphoric acids in which one can distinguish metaphosphoric acids (HP0 3 ) n and orthophosphoric H 3 P0 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 P0 4 exists as dihydrate (density 1, 91 like "3 , melting point 60 °) and as monohydrate (density 2.04 like " 3 ).
  • Both salts are white powders which are very slightly soluble in water and which lose the water of crystallization on heating and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and pass on Madrell's salt.
  • NaH 2 P0 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH 2 P0 4 , is a white salt of density 2.33 "3 , has a melting point of 253 ° (decomposition to form (KP0 3 ) x , potassium polyphosphate) and is slightly soluble in water Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , is a colorless, very slightly water-soluble crystalline salt which is anhydrous and contains 2 moles (density 2.066 "3 , loss of water at 95 °), 7 moles.
  • Disodium Dihydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HP0 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals which, as dodecahydrate, have a density of 1, 62, 3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20%).
  • P 2 0 5 has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P2O5) has a density of 2.536 like 3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tri-basic potassium phosphate), K 3 P0 4 , is a white, volatilized, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction for example, when Thomas slag is heated with coal and potassium sulfate. in spite of the higher price in the detergent industry, the more readily soluble and therefore highly effective potassium phosphates corresponding sodium compounds are often preferred.
  • tetra sodium diphosphate sodium pyrophosphate
  • Na 4 P 2 0 7 exists in anhydrous form (density 2.534 likes “3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° with loss of water.)
  • decahydrate density 1, 815-1, 836 like " 3 , melting point 94 ° with loss of water.
  • Na 4 P 2 0 7 is formed when disodium phosphate is heated to> 200 ° C, or when phosphoric acid is mixed with soda in a stoichiometric ratio reacted and dehydrated the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% "3 " which is soluble in water, the pH being 1%
  • the solution at 25 ° is 10.4, and condensation of the NaH 2 P0 4 or the KH 2 P0 4 results in higher molar sodium and potassium phosphates, in which cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell's salt.All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • Pentasatriumtnphosphat, Na 5 P 3 Oio sodium tripolyphosphate
  • Pentakalium triphosphate K 5 P 3 Oi 0 (potassium tripotassium) lyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P2O5, 25% K 2 0) in the trade.
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.
  • the agent is 1, 5 wt .-% to 5 wt .-% polymeric polycarboxylate, in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or
  • Contain maleic acid Contain maleic acid.
  • the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
  • enzymes which can be used in the compositions apart from the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and / or Carezyme®.
  • proteases such
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are present in detergents, cleaners and disinfectants, preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to using enzymes which are stabilized against oxidative degradation.
  • the composition contains 5% by weight to 50% by weight, in particular 8-30% by weight, of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight of builder and 0.2% to 2% by weight of enzyme selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.
  • organic solvents which can be used in the detergents and cleaners, especially if they are in liquid or pasty form, are alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4C -Ato- men, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers.
  • Such water-miscible solvents are preferably present in the compositions in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents systemic and environmentally friendly acids especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also, mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions.
  • Soil release polymers which are often referred to as "soil release” agents or because of their ability to render the treated surface, for example fiber, soot repellent, are, for example, nonionic or cationic cellulose derivatives
  • Degreasing-rich polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol
  • the preferred soil release polymers include those compounds which are formally accessible by esterification of two monomer parts.
  • first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR-) a OH, which may also be present as a polymeric diol H- (O- (CHR-) a ) b OH
  • Ph is an o-, m- or p-phen ylenrest, which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R is hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof
  • a is a number of 2 to 6 and b is a number from 1 to 300.
  • both Monomerdiolstatten -0- (CHR -) a O- and Polymerdiol- units - (0- (CHR -) a ) b O- before The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers is in the range from 250 to 100,000, in particular from 500 to 50,000.
  • the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, TrimellithTexre, Meilithklare, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • Preferred diols HO- (CHR-) a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected.
  • R is hydrogen and a is a number from 2 to 6
  • a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR -OH in which R has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be end developmentver consideration, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups.
  • the end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the Range of 1 to 50, especially 1 to 10.
  • polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10, used alone or in combination with cellulose derivatives.
  • color transfer inhibitors include polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone
  • Vinylimidazole and optionally other monomers.
  • the means for use in textile laundry may contain anti-crease agents, since textile
  • Sheet in particular of rayon, wool, cotton and mixtures thereof, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the means used.
  • the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • optical brighteners among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 2 4 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • agents can be used to prevent the tarnishing of silver objects, so-called silver corrosion inhibitors.
  • Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the Metals in one of the oxidation states II, III, IV, V or VI are present.
  • the compound according to formula (I) or the correspondingly preformed complex may be present in the form of powders or as granules, which may optionally also be coated and / or dyed and may contain conventional carrier materials and / or granulation aids. In the case of their use as granules, if desired, these may also contain further active substances, in particular bleach activator.
  • compositions with increased bulk density in particular in the range of 650 g / l to 950 g / l, is a
  • Extrusion step exhibiting method preferred.
  • Detergents, cleaners or disinfectants in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer. In a preferred embodiment of means for the particular machine cleaning of dishes, these are tablet-shaped. Examples
  • cotton substrates which had been provided with standardized soiling were, at the temperatures indicated in the table below, with a detergent containing 12.5% by weight of sodium percarbonate and 3.5% by weight of TAED (V1) otherwise equal composition (M1) to which had been added 0.2% by weight of 4- (2- (2 - ((2-hydroxyphenylmethyl) methylene) -hydrazinyl) -2-oxoethyl) -4-methyl chloride , washed under the same conditions. The treated fabric substrate was then dried and color measured. In the table below, the brightness value of the cotton gauges is given as an average of 6-fold determinations.
  • Cocoa 60 ° C 71, 2 72, 1

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Abstract

L'invention concerne des acylhydrazones. L'invention vise à améliorer les performances de nettoyage de produits détergents et nettoyants vis-à-vis des salissures dues à des résidus d'aliments contenant des polysaccharides. A cet effet, l'invention prévoit d'incorporer auxdits produits détergents et nettoyants une combinaison d'un agent de blanchiment peroxydique et de certaines acylhydrazones.
EP13700046.9A 2012-01-11 2013-01-08 Acylhydrazones utilisées comme renforçateurs de blanchiment Active EP2802644B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012200333A DE102012200333A1 (de) 2012-01-11 2012-01-11 Acylhydrazone als bleichverstärkende Wirkstoffe
PCT/EP2013/050232 WO2013104631A1 (fr) 2012-01-11 2013-01-08 Acylhydrazones utilisées comme renforçateurs de blanchiment

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EP2802644A1 true EP2802644A1 (fr) 2014-11-19
EP2802644B1 EP2802644B1 (fr) 2017-08-02

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Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8779002B2 (en) 2007-10-15 2014-07-15 Salk Institute For Biological Studies Methods for treating a variety of diseases and conditions, and compounds useful therefor
DE102013215810A1 (de) * 2013-08-09 2015-02-12 Henkel Ag & Co. Kgaa Waschmittel mit erhöhter Primärwaschkraft
DE102014209241A1 (de) * 2014-05-15 2015-11-19 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit erhöhter Bleichleistung
DE102014220663A1 (de) * 2014-10-13 2016-04-14 Henkel Ag & Co. Kgaa Farbschützende Waschmittel
DE102015205801A1 (de) 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Partikuläres Waschmittel mit Bleichekatalysator
DE102015205802A1 (de) 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit Bleichekatalysator und Riechstoffkapseln
DE102015205799A1 (de) * 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit verbesserter Fleckentfernung
DE102015209082A1 (de) * 2015-05-19 2016-11-24 Henkel Ag & Co. Kgaa Acylhydrazone als bleichverstärkende Wirkstoffe
WO2016196711A1 (fr) 2015-06-03 2016-12-08 The Procter & Gamble Company Système de fabrication de produit manufacturé
WO2016196712A1 (fr) 2015-06-03 2016-12-08 The Procter & Gamble Company Système de fabrication de produit manufacturé
US11512269B2 (en) 2015-12-15 2022-11-29 The Procter & Gamble Company Pre-moistened fibrous structures exhibiting increased capacity
WO2017106422A1 (fr) 2015-12-15 2017-06-22 The Procter & Gamble Company Structures fibreuses préhumidifiées compressibles
EP3702527B1 (fr) 2015-12-15 2021-10-27 The Procter & Gamble Company Structures fibreuses comprenant des régions présentant différentes valeurs de propriété intensives micro-ct et pentes de transition associées
EP3686343B1 (fr) 2015-12-15 2021-11-10 The Procter & Gamble Company Structures fibreuses comprenant trois regions ou plus
WO2017106412A1 (fr) 2015-12-15 2017-06-22 The Procter & Gamble Company Structures fibreuses comprenant des zones présentant différents niveaux d'additifs solides
DE102015225874A1 (de) 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Flüssige Wasch- oder Reinigungsmittel enthaltend Acylhydrazon
DE102015225881A1 (de) 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Flüssige Wasch- oder Reinigungsmittel enthaltend Acylhydrazon und Reduktionsmittel
DE102015225882A1 (de) * 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Partikuläres Mittel zur Verstärkung der Bleichwirkung
DE102015225880A1 (de) * 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Pyridingruppenhaltige Acylhydrazone
DE102016205486A1 (de) * 2016-04-04 2017-10-05 Henkel Ag & Co. Kgaa N-Methylpiperidingruppen-haltige Acylhydrazone
WO2017182295A1 (fr) * 2016-04-18 2017-10-26 Basf Se Compositions de nettoyage liquides
EP3249036A1 (fr) * 2016-05-26 2017-11-29 The Procter and Gamble Company Article de dose unitaire soluble dans l'eau à plusieurs compartiments comprenant un catalyseur de blanchiment
WO2018067488A1 (fr) * 2016-10-03 2018-04-12 The Procter & Gamble Company Composition de détergent à lessive à faible ph
RU2716130C9 (ru) * 2016-10-03 2020-05-21 Дзе Проктер Энд Гэмбл Компани Композиция моющего средства для стирки
US20180094220A1 (en) * 2016-10-03 2018-04-05 The Procter & Gamble Company Laundry detergent composition
CA3043527C (fr) 2016-12-08 2021-08-24 The Procter & Gamble Company Tampons de nettoyage pre-humidifies
WO2018106851A1 (fr) 2016-12-08 2018-06-14 The Procter & Gamble Company Structures fibreuses dotées d'une surface de contact
EP4060036A1 (fr) 2021-03-15 2022-09-21 Novozymes A/S Variantes de polypeptides
WO2022194673A1 (fr) 2021-03-15 2022-09-22 Novozymes A/S Variants de la dnase
WO2023165950A1 (fr) 2022-03-04 2023-09-07 Novozymes A/S Variants de dnase et compositions
EP4504885A1 (fr) 2022-04-08 2025-02-12 Novozymes A/S Variants et compositions d'hexosaminidase
WO2024213513A1 (fr) 2023-04-12 2024-10-17 Novozymes A/S Compositions comprenant des polypeptides ayant une activité de phosphatase alcaline
WO2026046881A1 (fr) 2024-08-26 2026-03-05 Novozymes A/S Compositions comprenant une hexosaminidase et une protéase

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
JPS5345808B2 (fr) * 1973-11-29 1978-12-09
US4412934A (en) * 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
EP0896998A1 (fr) 1997-08-14 1999-02-17 The Procter & Gamble Company Compositions détergentes pour le linge contenant une enzyme dégradant la gomme de polysaccharide
AU4690999A (en) 1998-08-13 2000-03-06 Warner-Lambert Company Diaminopyrimidines and combination therapies effective for treatment of p-glycoprotein positive cancers
US8492324B2 (en) * 2008-04-09 2013-07-23 Basf Se Use of metal hydrazide complex compounds as oxidation catalysts
CN103328455B (zh) * 2010-12-13 2016-02-24 巴斯夫欧洲公司 漂白催化剂

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2013104631A1 *

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