EP2802644B1 - Acylhydrazones utilisées comme renforçateurs de blanchiment - Google Patents

Acylhydrazones utilisées comme renforçateurs de blanchiment Download PDF

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EP2802644B1
EP2802644B1 EP13700046.9A EP13700046A EP2802644B1 EP 2802644 B1 EP2802644 B1 EP 2802644B1 EP 13700046 A EP13700046 A EP 13700046A EP 2802644 B1 EP2802644 B1 EP 2802644B1
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acid
alkyl
use according
μmol
weight
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EP2802644A1 (fr
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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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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 one of the consumer-reluctant hard-to-remove stains; 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.
  • the natural polysaccharides include algal extracts, plant extracts, hydrocolloids from seeds or roots, and hydrocolloids obtainable by microbial fermentation.
  • Modified or semi-synthetic hydrocolloids include, for example, cellulose and starch derivatives and similar compounds such as methoxy-pectins, propylene glycol alginates and carboxymethyl and hydroxypropyl guar gum.
  • a commonly found food residue polysaccharide, guaran is available from the seed walls of 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 polysaccharide obtainable from locust bean fruits is also frequently used in the food industry; it also has a 1-4- ⁇ -D-mannopyranosyl backbone and is likely to differ from guaran by having a lower number of D-galactosyl side chains.
  • 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 ⁇ -galactosyl residues attached to O-6 of mannose and may also be at least partially acetylated to O-2 and O-3 of the mannose residues.
  • 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 1 and / or R 3 is preferably a methyl, phenyl or naphthyl group substituted with an electron withdrawing group.
  • R 4 is preferably hydrogen.
  • the electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as optionally hetero-heteroatom-carrying heteroatom group.
  • R 1 is a C 1-4 alkyl group having a substituent in which R 10 represents hydrogen or a C 1-28 -alkyl, C 2-28 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl-, C 7-9 aralkyl, C 3-20 hieteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl, and A - is the anion of an organic or inorganic acid;
  • R 2 and R 4 are as defined
  • R 5 , R 6 , R 7 and R 8 independently of one another are R 1 , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-C 1-4 -alkyl or C 2-4 -hydroxyalkylamino, N-phenyl
  • the anion A - is preferably carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, bicarbonate or Carbonate, wherein in polyvalent anions, the charge balance can be achieved by the presence of additional cations such as sodium or ammonium ions.
  • carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphat
  • H 2 O 2 or water-H 2 O 2 releasing substances are preferably used as peroxidic bleaching agents, which include, in particular, alkali metal perborates, alkali metal perborates and urea perhydrate; However, it is also possible to use them in combination with peroxycarboxylic acids such as diperoxodecanedicarboxylic acid or phthalimidopercaproic acid, with other acids or acidic salts such as alkali persulfates or peroxodisulfates or caroates, or with diacyl peroxides or tetraacyldiperoxides.
  • peroxidic bleaching agents include, in particular, alkali metal perborates, alkali metal perborates and urea perhydrate;
  • peroxycarboxylic acids such as diperoxodecanedicarboxylic acid or phthalimidopercaproic acid
  • other acids or acidic salts such as alkali persulfates or peroxodisulfates or car
  • the performance of compounds of general formula (I) may optionally be controlled by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (III) - (IV) - (V), Cu ( I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti (II) - (III) - (IV) and particularly preferably selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III) Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III) are further enhanced; If desired, it is also possible to use complex compounds of the abovementioned metal central atoms with ligands of the general formula (I
  • a peroxycarboxylic acid forming compound in particular in the presence of H 2 O 2 releasing peroxygen compounds, is used together with an acylhydrazone of the general formula I under perhydrolysis conditions.
  • 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, especially nonanoyloxy or isononanoyloxybenzenesulfonate or benzoate, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, especially pentaace
  • the concentration of the compound of the formula (I) in the aqueous washing or cleaning liquor, such as in washing machines but also in the cleaning of carpets or upholstery materials or when cleaning hard surfaces such as tiles, tiles or harness, that can also be carried out using conventional dishwashers is used is 0.5 .mu.mol / l to 500 .mu.mol / l, in particular 5 .mu.mol / l to 100 .mu.mol / l.
  • the concentration of manganese, titanium, cobalt, nickel or copper ions in the aqueous washing or cleaning liquor is preferably in the range from 0.1 ⁇ mol / l to 500 ⁇ mol / l, in particular 1 ⁇ mol / l to 100 ⁇ mol / l.
  • 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.
  • the use according to the invention is preferably carried out at temperatures in the range from 10 ° C.
  • the water hardness of the water used for the preparation of the aqueous washing or cleaning solution 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 1-18 alkyl sulfate, especially methosulfate, or a corresponding alkanesulfonate, inorganic anions such as halide, especially chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, 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 under the washing conditions 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. 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.
  • 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 in such agents ingredients except the inventively to be used combination of peroxidic bleaching agent and compound of formula (I) contain.
  • the agents may include, in particular, builders, surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle reducing polymeric agents, and formulating polymeric 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, furthermore carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulphonate, and
  • the bleach activators may have been coated or granulated in a known manner with coating substances to avoid interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having mean particle sizes of 0.01 mm to 0.8 mm, granulated 1.5- 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.
  • N-alkyl-amines vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, and of alkylphenols having 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 present in detergents in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while 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.
  • 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.
  • the cationic surfactants used are hydroxyalkyl trialkylammonium compounds, in particular C 12-18 -alkyl (hydroxyethyl) dimethylammonium compounds, and preferably their halides, in particular chlorides.
  • 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 methylglycinediacetic 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 may also contain polymerized small amounts of polyme
  • 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. used.
  • detergent grade crystalline sodium aluminosilicates especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity is usually 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 metal 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 may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, the so-called module, 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. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 O 5 .yH 2 O) are preferred.
  • amorphous alkali metal silicates practically anhydrous crystalline alkali metal silicates of the abovementioned 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 1.9 to 3.5 are used in a further preferred embodiment.
  • a granular compound of alkali metal silicate and alkali metal carbonate is used, as it is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • 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 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 Contain 2.5 wt .-% 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 wt .-% to 5 wt .-% alkali silicate with a modulus in the range of 1.8 to 2.5 are included.
  • 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'-ethylenediamine tetrakis (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
  • 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 (HPO 3 ) n and orthophosphoric H 3 PO 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 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and pass on Madrell's salt.
  • NaH 2 PO 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 potassium, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° (decomposition to form (KPO 3 ) x , potassium polyphosphate) and is slightly soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 is a colorless, very slightly water-soluble crystalline salt.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -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 tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering 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 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates.
  • Pentapotassium triphosphate K 5 P 3 O 10 (potassium tripolyphosphate) comes for example in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) 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: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • 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 contains 1.5% to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • homopolymers of acrylic acid particularly preferred are 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 -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether.
  • 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 can system and environmentally acceptable acids, 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, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably contained in the compositions not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Soil release polymers are, for example, nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil release 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.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • 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 of 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, Trimellitic acid, mellitic acid, 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.
  • the preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • R 11 is hydrogen and a is a number from 2 to 6
  • R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 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.
  • 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 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 from 1 to 50, especially from 1 to 10.
  • suitable for use in laundry detergents of textiles color transfer inhibitors include polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
  • the means for use in textile laundry may contain anti-wrinkling agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • anti-wrinkling agents 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 compositions.
  • the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of 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 24 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 preferably bound to 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 having an increased bulk density in particular in the range from 650 g / l to 950 g / l
  • a process comprising an extrusion step is 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.
  • cotton substrates which had been provided with standardized soiling were, at the temperatures indicated in the table below, with a detergent (V1) containing 12.5% by weight of sodium percarbonate and 3.5% by weight of TAED 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.
  • Table 1 Bleaching performance [remission values in%] soiling; temperature V1 M1 Chocolate milk / carbon black; 30 ° C 59.3 62.7 Cocoa; 60 ° C 71.2 72.1 Porridge; 60 ° C 76.9 78.3 Drinking chocolate; 40 ° C 61.3 62.4 Chocolate cream; 30 ° C 77.6 78.4 "Mole”; 30 ° C 72.1 74.2

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Claims (10)

  1. Utilisation d'une combinaison d'un agent de blanchiment au peroxyde avec une acylhydrazone de la formule I,
    Figure imgb0013
    dans laquelle R1 représente un groupement CF3 ou un groupement alkyle en C1 à C28, alcényle en C2 à C28, alcynyle en C2 à C22, cycloalkyle en C3 à C12, cycloalcényle en C3 à C12, phényle, naphtyle, aralkyle en C7 à C9, hétéroalkyle en C3 à C20 ou cyclohétéroalkyle en C3 à C12,
    R2 et R3 représentent indépendamment un hydrogène ou un groupement alkyle en C1 à C28, alcényle en C2 à C28, alcynyle en C2 à C22, cycloalkyle en C3 à C12, cycloalcényle en C3 à C12, aralkyle en C7 à C9, hétéroalkyle en C3 à C28 ou cyclohétéroalkyle en C3 à C12, hétéroaralkyle en C5 à C16, phényle, naphthyle ou hétéroaryle éventuellement substitué ou R2 et R3 représentent, conjointement avec le carbone auquel ils sont liés, un cycle éventuellement substitué à 5, 6, 7, 8 ou 9 chaînons, qui peut contenir éventuellement des hétéroatomes, et
    R4 représente un hydrogène ou un groupement en C1 à C28, alcényle en C2 à C28, alcynyle en C2 à C22, cycloalkyle en C3 à C12, cycloalcényle en C3 à C12, aralkyle en C7 à C9, hétéroalkyle en C3 à C20, cyclohétéroalkyle en C3 à C20, hétéroaralkyle en C5 à C16 ou un groupe phényle éventuellement substitué ou un groupement phényle, naphtyle ou hétéroaryle,
    pour améliorer le pouvoir d'élimination de salissures d'agents de lavage ou de nettoyage concernant des salissures qui proviennent de résidus alimentaires contenant des polysaccharides.
  2. Utilisation selon la revendication 1, caractérisée en ce que le pouvoir d'élimination de salissures d'agents de lavage ou de nettoyage concerne des salissures qui sont constituées de chocolat ou qui comportent une proportion de chocolat.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'acylhydrazone de la formule générale I est utilisée en présence de H2O2 ou de substances libérant du H2O2 dans l'eau.
  4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que l'acylhydrazone de la formule générale I est utilisée en présence d'ions manganèse, titane, cobalt, nickel ou cuivre.
  5. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce que l'on utilise un composé, formant un acide peroxycarboxylique dans des conditions de perhydrolyse, conjointement avec une acylhydrazone de la formule générale I.
  6. Utilisation selon l'une des revendications 1 à 5, caractérisée en ce que la concentration du composé selon la formule (I) dans le bain de lavage ou de nettoyage aqueux est dans la gamme de 0,5 µmol/l à 500 µmol/l, en particulier de 5 µmol/l à 100 µmol/l.
  7. Utilisation selon l'une des revendications 4 à 6, caractérisée en ce que la concentration des ions manganèse, titane, cobalt, nickel ou cuivre dans le bain de lavage ou de nettoyage aqueux est dans la gamme de 0,1 µmol/l à 500 µmol/l, en particulier de 1 µmol/l à 100 µmol/l.
  8. Utilisation selon l'une des revendications 5 à 7, caractérisée en ce que la concentration du peroxyde d'hydrogène (calculée en tant que H2O2) dans le bain de lavage ou de nettoyage dans la gamme de 0,001 g/l à 10 g/l, en particulier de 0,1 g/l à 1 g/l et de manière particulièrement préférée de 0,2 g/l à 0,5 g/l.
  9. Utilisation selon l'une des revendications 1 à 8, caractérisé en ce qu'elle est mis en oeuvre à des températures dans la gamme de 10°C à 95°C, en particulier de 20°C à 40°C.
  10. Utilisation selon l'une des revendications 1 à 9, caractérisée en ce que l'acylhydrazone correspondant à la formule générale II,
    Figure imgb0014
     dans laquelle R1 représente un groupement alkyle en C1 à C4 qui porte un substituant
    Figure imgb0015
     dans lequel R10 est un hydrogène ou un groupement alkyle en C1 à C28, alcényle en C2 à C28, alcynyle en C2 à C22, cycloalkyle en C3 à C12, cycloalcényle en C3 à C12, aralkyle en C7 à C9, hétéroalkyle en C3 à C20 ou cyclohétéroalkyle en C3 à C12, hétéroaralkyle en C5 à C16, et A- représente l'anion d'un acide organique ou minéral,
    R2 et R4 sont les significations indiqués pour la formule (I) et
    R5, R6, R7 et R8 représentent indépendamment R1, un hydrogène, un halogène, un groupement hydroxy, amino, N-mono- ou di-alkyle en C1 à C4, ou hydroxyalkyl en C2 à C4 éventuellement substitué, amino, N-phényle ou N-naphtyl-amino, alkyle en C1 à C28, alcoxy en C1 à C28, phénoxy, alcényle en C2 à C28, alcynyle en C2 à C22, cycloalkyle en C3 à C12, cycloalcényle en C3 à C12, aralkyle en C7 à C9, hétéroalkyle en C3 à C20, cyclohétéroalkyle en C3 à C12, hétéroaralkyle en C5 à C16, phényle ou naphtyle, les substituants étant choisis parmi les groupements alkyle en C1 à C4, alcoxy en C1 à C4, hydroxy, sulfo, sulfato, halogéno, cyano, nitro, carboxy, phényle, phénoxy, naphtoxy, amino, N-mono- ou di-alkyle en C1 à C4, hydroxyalkyl-amino en C2 à C4, N-phényle ou N-naphtyl-amino, ou
    R5 et R6 ou R6 et R7 ou R7 et R8 étant reliés entre eux pour former 1, 2 ou 3 noyaux carbocycliques ou noyaux O-, NR10- ou S-hétérocycliques, éventuellement aromatiques et/ou éventuellement à substitution alkyle en C1 à C6.
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