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EP2504419B1 - Agent de lavage ou de nettoyage comprenant un complexe de métaux de transition activateur de blanchiment, produit in situ - Google Patents

Agent de lavage ou de nettoyage comprenant un complexe de métaux de transition activateur de blanchiment, produit in situ Download PDF

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Publication number
EP2504419B1
EP2504419B1 EP10784491.2A EP10784491A EP2504419B1 EP 2504419 B1 EP2504419 B1 EP 2504419B1 EP 10784491 A EP10784491 A EP 10784491A EP 2504419 B1 EP2504419 B1 EP 2504419B1
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EP
European Patent Office
Prior art keywords
formula
acid
cleaning
washing
weight
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EP10784491.2A
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German (de)
English (en)
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EP2504419A1 (fr
Inventor
André HÄTZELT
Anette Nordskog
Siglinde Erpenbach
Jörg SUNDERMEYER
Felix GÄRTNER
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL10784491T priority Critical patent/PL2504419T3/pl
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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
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to the use of certain iminodiols which are capable of complexing with transition metal ions, or a suitably pre-formed transition metal complex for enhancing the cleaning performance of detergents against soils, as well as detergents and cleaners containing the iminodiol or complex.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators which are able to provide peroxycarboxylic acids under the abovementioned perhydrolysis conditions and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example reactive Esters, polyacylated alkylenediamines, in particular N, N, N ', N'-tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides, in particular, phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyl
  • transition metal compounds for increasing the oxidation power of peroxygen compounds or atmospheric oxygen in detergents and cleaners has also been proposed on various occasions.
  • the transition metal compounds proposed for this purpose include, for example, manganese, iron, cobalt, ruthenium or molybdenum-salene complexes, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, cobalt, Ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, and manganese complexes with polyazacycloalkane ligands, such as TACN.
  • Detergents containing bleach catalysts are made WO 2005/116179 and DE102007017654 known.
  • An object of the invention is accordingly the use of a bleach catalyst in the form of a complex of Fe, Mo, Mn and / or W, in particular Fe and / or Mn, with a ligand having a skeleton of the formula (I), for enhancing the cleaning performance of detergents or cleaners, in particular with respect to bleachable and / or protein-containing stains, wherein the skeleton of the formula (I) can also be bridged and mono- or polysubstituted.
  • the preparation of the metal-ligand complex can generally be carried out in a simple manner by mixing a metal salt of the corresponding metal with the corresponding ligand in an aqueous environment. By setting a suitable redox potential, the formation of a desired oxidation state can be promoted.
  • the substituents which may be bonded to the basic structure of the formula (I) may in particular be selected from alkyl, in particular C 1-22 -alkyl, preferably C 1-18 -alkyl, trifluoromethyl, cycloalkyl, in particular C 3-8 -cycloalkyl , Cycloalkylalkyl, in particular C 3-8 -cycloalkyl-C 1-12 -alkyl, alkenyl, in particular C 2-18 -alkenyl, alkynyl, in particular C 2-18 -alkynyl, heteroalkyl, heterocycloalkyl, alkoxy, in particular C 1-18 - alkoxy, alkylsulfanyl, especially C 1-18 alkylsulfanyl, alkyl-sulfinyl, in particular C 1-18 alkylsulfinyl, alkylsulfonyl, in particular C 1-18 alkylsulfonyl, alkanoyl, especially C 1
  • substituted or bridged derivatives of the skeleton of the general formula (I) correspond to the formulas (II) or (III), wherein R 1 and R 2 in formula (II) independently represent hydrogen, a phenyl group, a benzyl group or a C 1-20 alkyl group, and preferably R 1 and R 2 are each a phenyl group.
  • the inventively intended success also occurs when one does not use the said complex, but only the corresponding ligand with a skeleton according to formula (I) and the fleet used contains at least one called transition metal ion, wherein the oxidation state of said metals because of usually in the aqueous liquor usually rapidly adjusting redox equilibrium among the different oxidation states is not essential.
  • Another object of the invention is therefore the use of a compound having a skeleton according to formula (I), for enhancing the cleaning performance of detergents and cleaners, especially bleachable and / or protein-containing stains, in aqueous, in particular surfactant-containing liquor, the Fe, Mo, Mn and / or W ions, in particular Fe and / or Mn Ions, contains.
  • Further objects of the invention are a process for washing textiles and a process for cleaning hard surfaces, in particular for machine dishwashing, using a compound having a skeleton according to formula (I) or a bleach catalyst in the form of a complex of Fe, Mo, Mn and / or W, in particular Fe and / or Mn, with a ligand having a skeleton of the formula (I).
  • the concentration of the compound with a skeleton of the formula (I) in the aqueous washing or cleaning liquor is 0.5 ⁇ mol / l to 1500 ⁇ mol / l, in particular 1 ⁇ mol / l to 300 ⁇ mol / l.
  • the concentration of Fe, Mo, Mn and / or W, in particular Fe and / or Mn, 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 up 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 inventive use and the inventive method 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 and the method 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 or the processes according to the invention can be realized particularly simply by the use of a washing or cleaning agent which comprises a compound having a skeleton of the formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion.
  • a washing or cleaning agent which comprises a compound having a skeleton of the formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion.
  • Detergents for cleaning textiles and agents for cleaning hard surfaces, in particular dishwashing detergents, and among these preferably those for machine use, which have a compound with a skeleton of the formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned in addition to conventional ones compatible ingredients, in particular a surfactant are therefore further objects of the invention.
  • the use of the invention or the inventive method can also in the presence of persoxy-containing bleach or an inventive agent may additionally contain pers oxygen-containing bleach.
  • 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 contains a Fe, Mo, Mn and / or W salt and / or an Fe, Mo, Mn and / or or W complex without a ligand corresponding to a compound having a skeleton of the formula (I).
  • 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.
  • compositions according to the invention 0.05 to 1% by weight, in particular 0.1 to 0.5% by weight, of bleach-catalyzing complex comprising a ligand of the formula I) included.
  • Preferred transition metals in the context of the use according to the invention, the process according to the invention and the agent according to the invention are Fe and Mn, in particular Mn.
  • Particularly suitable peroxygen compounds in the compositions are organic peracids or persalts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and / or persilicate.
  • 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 up to 50 wt .-%, in particular from 5 wt .-% to 30 wt .-%, present in detergents or cleaners according to the invention.
  • compositions according to the invention which can be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, may contain, in principle, all known ingredients customary in such agents apart from the ligand or bleach catalyst to be used according to the invention.
  • the agents according to the invention may in particular be builder substances, 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-formulating agents, and further adjuvants, such as optical brighteners, foam regulators, additional peroxygen activators, dyes and fragrances.
  • An agent according to the invention can contain conventional antimicrobial active ingredients in addition to the ingredients mentioned above in order to enhance the disinfecting action, for example against special germs.
  • antimicrobial additives are contained in the disinfectants according to the invention 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 includes the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfuryl amides and cyanurates, in addition to carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-phenolsulfonat, and acylated
  • 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.
  • compositions of the invention 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 the cleaning or washing agents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the disinfectant according to the invention as well as inventive cleaning agent preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants.
  • 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.
  • An agent according to the invention preferably contains 0.5% by weight to 25% by weight, in particular 1% by weight to 15% by weight, of cationic surfactant.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, 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-diene 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
  • 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 paste-form or liquid, in particular water-containing, agents according to the invention.
  • 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 which according to the data of German patent specification DE 24 12 837 can be determined, 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 in the compositions according to the invention 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.
  • compositions according to the invention can be prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions.
  • 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 from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as 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 especially 1: 1 to 2: 1.
  • Builder substances are preferably present in the detergents or cleaners according to the invention 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 components b), c), d) and e) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate.
  • inventive compositions are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, 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 of the composition according to the invention, 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.
  • agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate.
  • 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 metal salts, such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic 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.
  • alkali metal salts such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, amino-tris (methylenephosphonic acid ), N, N
  • alkali metal phosphate in particular trisodium polyphosphate, are 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.
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • 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.
  • Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), 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 are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also 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 can be used according to the invention.
  • agents according to the invention contain from 1.5% by weight 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 preferably present in the detergents, cleaners and disinfectants according to the invention in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to stabilizing enzymes which are stabilized against oxidative degradation become.
  • the agent 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.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers.
  • Such water-miscible solvents are in the inventive Detergents preferably not more than 30 wt .-%, in particular from 6 wt .-% to 20 wt .-%, present.
  • the compositions according to the invention can contain system- and environmentally compatible 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 not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions according to the invention.
  • 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, especially 12 to 140.
  • the molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000
  • the acid underlying the remainder 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.
  • acids having at least two carboxyl groups be included in the soil release-capable polyester.
  • 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, in particular from 1 to 10.
  • Polyvinylpyrrolidones, polyvinylimidazoles, polyvinylpyrrolidones, polyvinylpyrrolidones which are suitable for use in laundry detergents according to the invention are especially polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
  • the inventive compositions for use in the textile laundry may contain anti-crease 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-crease 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.
  • 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 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 silanated silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica 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.
  • 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 having a skeleton of the 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 auxiliaries. In the case of their use as granules, if desired, these may also contain further active substances, in particular bleach activator.
  • compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, with peroxygen compound and bleach activator combination optionally being added later.
  • a process comprising an extrusion step is preferred.
  • Detergents, cleaners or disinfectants according to the invention 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.
  • 2-Bromoanisole (97.0 g, 0.52 mol, 1.0 eq) was dissolved in 150 ml of pentane. With vigorous stirring and cooling with an ice bath, 325 ml of a 1.6 M solution of n-butyllithium in hexane (0.52 mol, 1.0 eq) were slowly added dropwise. A white suspension forms, which was stirred for a further 3 h at 0 ° C., then for 9 h at room temperature. The white solid was filtered off and washed with pentane (4x30 ml). After drying in vacuo, 2-lithioanisole was isolated as a fine white powder.
  • reaction mixture was added to ice and then extracted with diethyl ether (3x 40 ml).
  • the combined organic phases (yellow) were dried over MgSO 4 and the solvent removed on a rotary evaporator.
  • the manganese dioxide was filtered off and the solvent was removed on a rotary evaporator.
  • the product was dried in vacuo.
  • KO t Bu (18.6 g, 0.17 mol, 5.5 eq) was dissolved in 10 ml of DMF and cooled to 0 ° C. Then, solid diethylaminoethanethiol hydrochloride (12.8 g, 0.08 mol, 2.5 eq) was added in several portions. After 15 minutes, the reaction mixture was warmed to room temperature. A solution of 8-methoxy-2- (2-methoxyphenyl) quinoline (8.0 g, 0.03 mol, 1.0 eq) in 20 ml of DMF was slowly added dropwise. The brown reaction mixture was refluxed for 1.5 h, with color change observed after rotorgear.
  • the on Room temperature cooled Grignard solution was added to a pre-cooled to 0 ° C solution of the nickel catalyst [Ni (dppe) Cl 2 ] (1.8 g, 3.8 mol%) and 2-chloropyridine (10.0 g, 88.1 mmol, 1 , 0 eq) in 90 ml of THF.
  • the deep red reaction solution was stirred for 10 min at 0 ° C and then for 17 h at RT.
  • the aqueous phase was washed with DCM (4x20 ml) and then neutralized with concentrated KOH solution.
  • the product was extracted with DCM (4x 50 ml).
  • the combined organic extraction phases were dried over MgSO 4 and the solvent removed on a rotary evaporator.
  • IR spectroscopy (KBr) ⁇ / cm -1 : 2966 (w), 2836 (w), 2229 (w), 1602 (m), 1583 (s), 1494 (m), 1463 (m), 1494 (m ), 1258 (s), 1170 (w), 1128 (w), 1023 (m), 812 (w), 753 (s).
  • the reaction was quenched by the addition of 2N aqueous HCl and the pH of the solution was adjusted to pH 7 with aqueous NaHCO 3 solution.
  • the aqueous phase was extracted with ethyl acetate (4x 20 ml) and after drying the combined organic phases over MgSO 4, the solvent is removed under reduced pressure.
  • the brown residue was dissolved in chloroform and hexane added until turbidity occurred.
  • the after storage at 4 ° C overnight Forming crystalline precipitate was filtered off, washed with hexane and dried in vacuo.
  • cotton substrates provided with standardized tea soiling (T) or standardized blueberry juice soiling (S) were treated for 30 minutes at 20 ° C, 30 ° C or 40 ° C in the respective solutions.
  • the treated fabric substrate was rinsed under running water and then dried and color measured.
  • the brightness value of the cotton measuring pieces is indicated (5-fold determinations, the mean values are indicated).
  • Table 1 Bleaching performance in surfactant-containing H 2 O 2 A B C D TAED 20 ° C, T 51.5 51.5 54.6 56.0 50.8 20 ° C, p 37.7 37.9 37.1 37.6 nb 30 ° C, T 54.3 54.8 57.4 57.6 51.5 30 ° C, p 41.1 41.2 41.8 42.3 nb 40 ° C, T 60.8 61.6 60.4 59.2 55.9 40 ° C, p 45.6 45.3 45.7 46.5 nb nb: not determined V1 + A V1 + B V1 + C V1 + D V2 20 ° C, T 49.6 50.3 52.2 52.8 50.2 20 ° C, p 53.9 54.2 52.9 54.7 nb 30 ° C, T 53.1 53.5 54.7 54.4 53.3 30 ° C, p 56.6 56.1 57.9 59.2 nb 40 ° C, T 57.7 57.5 56.8 58.5 55.9 40 °

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Claims (10)

  1. Agent de nettoyage ou de lavage, caractérisé en ce qu'il contient un composé ayant une structure de la formule (I),
    Figure imgb0031
     en plus d'ingrédients usuels compatibles avec celui-ci, la structure de la formule (I) pouvant également être pontée et monosubstituée ou polysubstituée.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient en plus un sel de Mo, Mn et/ou W et/ou un complexe de Mo, Mn et/ou W sans ligand correspondant au composé ayant une structure de la formule (I).
  3. Agent selon la revendication 1 ou 2, caractérisé en ce qu'il contient 0,001% à 2% en poids, notamment 0,01 % à 1 % en poids, du composé ayant une structure de la formule (I) et/ou en ce que le rapport molaire des métaux de transition au composé ayant une structure de la formule (I) est de préférence dans la gamme de 0,001:1 à 2:1, notamment de 0,01:1 à 1:1.
  4. Agent de nettoyage ou de lavage, caractérisé en ce qu'il contient un catalyseur de blanchiment, accessible à partir d'un composé ayant une structure de la formule (I)
    Figure imgb0032
     par complexation avec du Fe, Mo, Mn et/ou W, en plus d'ingrédients habituels compatibles avec ledit catalyseur, la structure de la formule (I) pouvant également être pontée et monosubstituée ou polysubstituée.
  5. Agent selon l'une des revendications 1 à 4, caractérisé en ce qu'il contient en plus jusqu'à 50% en poids, notamment 5% en poids à 30% en poids, d'un composé peroxygéné, le composé peroxygéné étant de préférence choisi dans le groupe comprenant le peroxyde d'hydrogène, le perborate alcalin, le percarbonate alcalin et leurs mélanges.
  6. Utilisation d'un composé ayant une structure de la formule (I) ou d'un catalyseur de blanchiment sous la forme d'un complexe du Fe, Mo, Mn et/ou W avec un ligand ayant une structure de la formule (I),
    Figure imgb0033
     pour renforcer le pouvoir nettoyant des agents de nettoyage et de lavage dans un bain aqueux, comportant notamment des tensioactifs, qui contient des ions Fe, Mo, Mn et/ou W, la structure de la formule (I) pouvant également être pontée et monosubstituée ou polysubstituée et l'agent de nettoyage ou de lavage contenant de préférence un composé peroxygéné.
  7. Procédé de lavage de textiles ou de nettoyage de surfaces dures, notamment de nettoyage mécanique de la vaisselle, par utilisation d'un composé ayant une structure de la formule (I)
    Figure imgb0034
     ou d'un catalyseur de blanchiment sous la forme d'un complexe du Fe, Mo, Mn et/ou W avec un ligand ayant une structure de la formule (I), la structure de la formule (I) pouvant également être pontée et monosubstituée ou polysubstituée.
  8. Procédé selon la revendication 7, caractérisé en ce que l'on utilise un bain de nettoyage ou de lavage aqueux dans lequel la concentration en Fe, Mo, Mn et/ou W est dans la gamme de 0,1 µmol/l à 500 µmol/L, notamment de 1 µmol/l à 100 µmol/l.
  9. Agent selon la revendication 4 ou 5, utilisation selon la revendication 6 ou procédé selon la revendication 7 ou 8, caractérisé en ce que le complexe à catalyseur de blanchiment, qui comprend un ligand ayant une structure de la formule (I), contient d'autres ligands neutres, anioniques ou cationiques, notamment H2O, NH3, CH3OH, l'acétylacétone, la terpyridine, des anions organiques tels que le citrate, l'oxalate, le tartrate, le formiate, un carboxylate en C2-18, un sulfate d'alkyle en C1-18, notamment le méthosulfate ou un sulfonate d'alcane correspondant, des anions minéraux tels qu'un halogénure, notamment un chlorure, un perchlorate un tétrafluoroborate, un hexafluorophosphate, un nitrate, un sulfate d'hydrogène, un hydroxyde ou un hydroperoxyde, ou des ligands de pontage tels que des diamines d'alkylène.
  10. Agent selon la revendication 4 ou 5 ou 9, utilisation selon la revendication 6 ou 9 ou procédé selon l'une des revendications 7 à 9, caractérisé en ce que le composé ayant une structure de la formule (I) correspond à la formule générale (II), dans laquelle R1 et R2 représente indépendamment un hydrogène, un groupe phényle, un groupe benzyle ou un groupe alkyle en C1-20, ou à la formule générale (III).
    Figure imgb0035
    Figure imgb0036
EP10784491.2A 2009-11-24 2010-11-22 Agent de lavage ou de nettoyage comprenant un complexe de métaux de transition activateur de blanchiment, produit in situ Not-in-force EP2504419B1 (fr)

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DE102009047037A DE102009047037A1 (de) 2009-11-24 2009-11-24 Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex
PCT/EP2010/067894 WO2011064158A1 (fr) 2009-11-24 2010-11-22 Agent de lavage ou de nettoyage comprenant un complexe de métaux de transition activateur de blanchiment, produit in situ

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MX342855B (es) * 2011-08-15 2016-10-13 Procter & Gamble Composiciones detergentes que contienen compuestos de piridinol-n-oxido.
US20130111675A1 (en) 2011-11-03 2013-05-09 Ecolab Usa Inc. Sustainable laundry sour compositions with iron control
WO2017078636A1 (fr) 2015-11-04 2017-05-11 Hayat Kimya Sanayi Anonim Sirketi Compositions comprenant des complexes métalliques à base d'acide humique oxydé
CN113999107A (zh) * 2021-11-02 2022-02-01 杜心赟 一种高效制备3-烷基-2-羟基苯甲酸的方法

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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
EP1747259A1 (fr) * 2004-05-17 2007-01-31 Henkel Kommanditgesellschaft auf Aktien Agent de lavage comprenant un complexe de metal de transition qui renforce le blanchiment et est produit eventuellement in situ
DE102007017654A1 (de) * 2007-04-12 2008-10-16 Henkel Ag & Co. Kgaa Bis(hydroxychinolin)-Metallkomplexe als Bleichkatalysatoren

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US20120264668A1 (en) 2012-10-18
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