EP2714877A1 - Systèmes activateurs pour composés peroxygénés - Google Patents

Systèmes activateurs pour composés peroxygénés

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Publication number
EP2714877A1
EP2714877A1 EP12722337.8A EP12722337A EP2714877A1 EP 2714877 A1 EP2714877 A1 EP 2714877A1 EP 12722337 A EP12722337 A EP 12722337A EP 2714877 A1 EP2714877 A1 EP 2714877A1
Authority
EP
European Patent Office
Prior art keywords
acid
iii
compound
lewis acid
peroxycarboxylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12722337.8A
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German (de)
English (en)
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EP2714877B1 (fr
Inventor
André HÄTZELT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL12722337T priority Critical patent/PL2714877T3/pl
Publication of EP2714877A1 publication Critical patent/EP2714877A1/fr
Application granted granted Critical
Publication of EP2714877B1 publication Critical patent/EP2714877B1/fr
Active legal-status Critical Current
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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
    • C11D3/39—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 systems of Lewis acid and Peroxocarbonklare redesignnder under perhydrolysis conditions for the activation of peroxygen compounds, in particular for bleaching of Farbanschmutzungen in the washing of textiles, and detergents, cleaners and disinfectants containing such systems.
  • 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 0 2 or alkali perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by the addition of so-called bleach activators, which are capable of being among those mentioned
  • Washing process is available, for example by suitable wrapping measures.
  • the present invention has the object of improving the oxidation and bleaching performance of inorganic peroxygen compounds by accelerating the formation of peroxycarboxylic acid from peroxycarboxylic acid-containing bleach activator and peroxygen bleach,
  • the invention relates to the use of a system of Lewis acid and under Perhy- drolyse waive peroxocarbonklare redesignnder substance as an activator for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfecting solutions.
  • Another object of the invention is the use of Lewis acid to accelerate the Peroxocarbonchureoeuvre particular inorganic peroxygen compound and Peroxocarbonchure redesignnder under perhydrolysis conditions, especially when washing textiles or when cleaning hard surfaces, and in particular in aqueous systems.
  • Another object is a process for the preparation of peroxycarboxylic acid, especially in aqueous solution, in particular inorganic peroxygen compound and peroxocarbonklare redesignnder under perhydrolysis conditions, which is characterized in that one uses Lewis acid.
  • the mole ratio of peroxycarboxylic acid to the compound to Lewis acid is preferably 100: 1 to 1:50, more preferably 10: 1 to 1: 5, and most preferably 2: 1 to 1: 4.
  • the system of Lewis acid and perhydrolysis peroxocarboxylic acid-yielding compound is preferably used for bleaching paint stains during the washing of textiles, especially in aqueous, surfactant-containing liquor.
  • bleaching of color stains is to be understood in its broadest sense and includes both the bleaching of dirt present on the textile, the bleaching of debris located in the wash liquor, and the deoxidation of the wash liquor in the wash liquor Textile dyes that detach under the washing conditions of textiles before they can be applied to different colored textiles.
  • Another preferred embodiment of the invention is the use of the Lewis acid system and the peroxycarboxylic acid perhydrolysis compound in cleaning solutions for hard surfaces, especially for dishes, for bleaching stained soils, for example tea.
  • bleaching is understood as meaning both the bleaching of dirt on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the dishwashing liquor.
  • detergents, cleaners and disinfectants which contain the abovementioned system of Lewis acid and peroxycarboxylic acid-yielding compound under perhydrolysis conditions.
  • the system of Lewis acid and under perhydrolysis Peroxocarbonchure- leaching compound in the sense of an activator can be used wherever it depends on a particular increase in the oxidation effect of the peroxygen compounds at low temperatures, for example the bleaching of textiles or hair, in the oxidation of organic or inorganic intermediates and in the disinfection.
  • Lewis acids are electrophilic electron pair acceptors, so they can attach electron pairs. They have at least one unoccupied orbital in their valence electron shell.
  • Lewis acids are preferably selected from bismuth (III) salts, indium (III) salts, and samarium (III) salts and mixtures thereof, among which
  • Bismuth (III) oxinitrate, indium (III) sulfate and samarium (III) nitrate and mixtures of these are particularly preferred.
  • peroxycarboxylic acid-releasing compound As under perhydrolysis conditions peroxycarboxylic acid-releasing compound can be any organic compound.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoyl-succinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or Isononanoyl- or Lauroyloxybenzol- sulfonate (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and
  • acylated sugar derivatives in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.
  • PAG pentaacetylglucose
  • PAG pentaacetylfruktose
  • tetraacetylxylose tetraacetylxylose
  • octaacetyllactose acetylated
  • acetylated optionally N-alkylated glucamine and gluconolactone
  • lactams for example N-benzoylcaprolactam.
  • the use of the present invention is to provide conditions under which the peroxygen compound and the bleach-enhancing system of Lewis acid and peroxycarboxylic acid-yielding compound can react with each other under perhydrolysis conditions, with the aim of obtaining more strongly oxidizing secondary products.
  • Such conditions are especially present when the reactants meet in aqueous solution.
  • This can be done by separately adding the peroxygen compound and the bleach-enhancing system to an optionally detergent or cleaner-containing solution.
  • the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent which contains the said bleaching-intensifying system and optionally a peroxidic oxidizing agent.
  • the peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a peroxygen-free agent is used.
  • the conditions can be varied widely.
  • the amounts of peroxygen compounds are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm of active oxygen are present.
  • An inventive washing, cleaning or disinfecting agent preferably contains 0.01 wt .-% to 10 wt .-%, in particular 1 wt .-% to 3 wt .-% under perhydrolysis conditions peroxocarboxylic acid-liederder compound in addition to conventional, with the peroxygen compound and the inventively used system compatible ingredients.
  • the system or its individual components used in accordance with the invention may or may, as well as the peroxygen compound, if desired, be adsorbed to carriers in a manner known in principle and / or embedded in enveloping substances.
  • wrapping can be achieved in addition to a generally improved storage stability, that the peroxycarboxylic acid formation takes place accelerated according to the invention, but uses the formation or acceleration only after release from the wrapping material, so that other washing or
  • Detergent ingredients such as enzymes
  • the detergents, cleaners and disinfectants according to the invention which may be present as particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may contain, in principle, all known ingredients customary in such agents besides the bleach-enhancing system used according to the invention.
  • the detergents and cleaners according to the invention may in particular be builders, surface-active surfactants, organic and / or inorganic peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, dye transfer inhibitors, foam regulators, additional peroxygen Activators and dyes and fragrances included.
  • a disinfectant according to the invention may contain conventional antimicrobial active ingredients in addition to the previously mentioned ingredients to enhance the disinfecting action against special germs.
  • antimicrobial additives are preferably not more than 10% by weight, particularly preferably from 0.1% by weight to 5% by weight, in the disinfectants according to the invention.
  • Suitable peroxygen compounds 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 inorganic salts releasing hydrogen peroxide under the conditions of purification, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide inclusion compounds, such as H. 2 0 2 -Harnstoffaddukte, into consideration.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
  • 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.
  • the peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of these containing agents, which may in principle contain all conventional detergents, cleaners or disinfectant ingredients.
  • Particular preference is given to alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions containing 3% by weight to
  • a washing or cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 25% by weight, in particular from 1% by weight to 20% by weight and more preferably from 7% by weight to 15% by weight. % present, while in disinfectants according to the invention preferably from 0.5 wt .-% to 40 wt .-%, in particular from 5 wt .-% to 20 wt .-%, of peroxygen compounds are included.
  • the compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols having in each case 12 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having from 5 to 12 carbon atoms in the alkyl radical ,
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are in the detergents or detergents according to the invention in
  • 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 -diphosphonic acid, polymers
  • Hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable May contain copolymerized substances without carboxylic acid functionality.
  • the relative average molecular weight (here and below: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably benzene or benzene derivatives derives, is substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight.
  • % preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a
  • Carbohydrate This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose.
  • the use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a relative average molecular weight between 1,000 and 200,000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000. Further preferred copolymers are those which are used as monomers acrolein and
  • Acrylic acid / acrylic acid salts or vinyl acetate Acrylic acid / acrylic acid salts or vinyl acetate.
  • Builders can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 weight percent aqueous solutions are used. 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, polyphosphates, preferably sodium triphosphate.
  • water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used.
  • Detergent grade sodium aluminosilicates in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. 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 ⁇ m, and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
  • Their calcium binding inhibitor is usually in the range of 100 to 200 mg CaO per gram.
  • water-soluble inorganic builder materials may be included.
  • polyphosphates such as sodium triphosphate
  • these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders.
  • Such water-soluble inorganic builder materials are preferably present in agents according to the invention in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight.
  • the alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to Si0 2 below 0.95, in particular from 1: 1, 1 to 1: 12 and may be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 0: Si0 2 of 1: 2 to 1: 2.8.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na 2 Si x O 2 X + iy H 2 O, in which x, the so-called modulus, is a number from 1 to 9 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline Phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • 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.
  • Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further embodiment of compositions according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as it is known, for example
  • Nabion® 15 is commercially available.
  • Machine dishwashing detergents according to the invention are preferably of low alkalinity and contain the customary alkali carriers such as, for example, alkali metal silicates, alkali metal carbonates and / or alkali hydrogencarbonates.
  • Alkali silicates may be present in amounts of up to 30% by weight, based on the total agent.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with.
  • the alkali carrier system preferably used in the inventive compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is present in an amount of up to 60 wt .-%, preferably 10 wt .-% to 40 wt .-% , Depending on which pH is ultimately desired, the ratio of carbonate used and bicarbonate used varies, but usually an excess of sodium bicarbonate is used, so that the weight ratio of bicarbonate to carbonate is generally from 1: 1 to 15: 1.
  • dishwashing compositions according to the invention, 20 wt.% To 40 wt.% Of water-soluble organic builders, in particular alkali citrate, 5 wt.% To 15 wt.% Alkali carbonate and 20 wt 40 wt .-% Alkalidisilikat included.
  • bleach-activating compounds such as nitriles, from which perimic acids are formed may be present.
  • nitriles include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula R 2 -N (+) - (CR 4 R 5) -CN X w R 3 in which R is -H, -CH 3, a C 2 -24 alkyl or alkenyl group, a substituted 4-alkyl CI_ 2 - or C 2 .
  • 24-alkenyl radical having at least one substituent from the group -Cl, -Br,
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 - CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, - CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, - CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , - (CH 2 CH 2 -O) n H with n
  • Cumene sulfonate the C9.15-Alkylbenzolsulfonat.en, the CI_ 20 alkyl sulfates, the C 8 - methyl ester 22 -carboxylic acid, sulfate, hydrogen sulfate, and their mixtures, can be used.
  • Oxygen-carrying sulfonimines and / or acylhydrazones can also be used.
  • the presence of bleach-catalyzing transition metal complexes is also possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Suitable ligands in the transition metal complexes are both inorganic and organic compounds, which in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , amine 2,2 '-Bispyridyl- triazole, tris (2-pyridylmethyl) amine, 1, 4,7-triazacyclononane, 1, 4,7-trimethyl-1, 4,7-triazacyclononane, 1, 5.9 Trimethyl-1, 5,9-triazacyclododecane, (bis ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N ' - (bis (1-methylimidazole) 2-yl) -methyl) -ethylenediamine, N-bis (2-benzimidazolylmethyl)
  • the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands.
  • these include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2 ) " group, that is, a nitro ligand or a nitrito ligand
  • the (NO 2 ) " group may also be attached to a transition metal be chelate-bound or asymmetric or VO-bridged to two transition metal atoms.
  • the transition metal complexes to be used in the activator system according to the invention may also contain further, generally simpler ligands, in particular mono- or polyvalent anion ligands.
  • ligands for example, nitrate, actetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate.
  • the anion ligands should provide charge balance between the transition metal central atom and the ligand system.
  • the presence of oxo ligands, peroxo ligands and imino ligands is also possible.
  • such ligands can also act bridging, so that polynuclear complexes arise.
  • anionic counterions are present in the transition metal complex compounds to be used according to the invention, which neutralize the cationic transition metal complex.
  • anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, benzoate or citrate.
  • transition metal complex compounds are , 4,7-trimethyl-1, 4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [(2-hydroxy-5-vinylphenyl) -methylene] -1, 2-diaminocyclohexane] -manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1,2-diaminocyclohexane] manganese (III) acetate, [N, N'-bis [ (2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] - manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-diamin
  • Suitable enzymes in the compositions according to the invention are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or cellulase particularly preferred is.
  • the proportion is preferably 0.2 wt .-% to 1, 5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%.
  • the enzymes can be adsorbed on carriers in the usual way and / or in
  • Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose.
  • cellulose ethers such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose.
  • sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used.
  • Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • the proportion of grayness inhibitors and / or soil-release active ingredients in compositions according to the invention is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.
  • optical brightener for particular textiles made of cellulose fibers (for example, cotton), for example, derivatives of Diaminostilbendisulfonklare or their
  • alkali metal salts For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used.
  • polyamide fibers are particularly well brighteners of the type of 1, 3-diaryl-2-pyrazolines, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds.
  • the content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%.
  • the agent is free of such agents.
  • the usual foam regulators which can be used in the compositions according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic.
  • the polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof.
  • Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each have 12 to 22 carbon atoms.
  • foam regulators can preferably 0.2 wt .-% to 2 wt .-% amount.
  • 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 present in compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.
  • 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 alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contained in the inventive compositions.
  • 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, wherein peroxygen compound and bleach catalyst are optionally added separately later.
  • compositions according to the invention in the form of solutions containing aqueous or other conventional solvents are produced particularly advantageously by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • compositions according to the invention are preferably in the form of pulverulent, granular or tablet-shaped preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable material
  • compositions and admixing the more sensitive components which in particular enzymes, bleach and the bleach-activating system can be expected, can be produced.
  • inventive 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.
  • the procedure is preferably such that all components are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric presses or
  • Rotary presses pressed with pressing pressures in the range of 200 10 5 Pa to 1 500 10 5 Pa. you thus obtains without difficulty fracture-resistant, yet sufficiently rapidly soluble under application conditions tablets with flexural strength of usually over 150 N.
  • a tablet produced in a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm up to 40 mm.
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be effected by using the builder components with at least a proportion of liquid mixture components in a first process substep while increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other constituents of the agent, including the bleach-activating system, combined with the thus obtained premix.

Abstract

L'invention vise à améliorer l'action d'oxydation et de blanchiment de composés peroxygénés à des températures basses. L'invention se caractérise à cet effet par l'utilisation d'un système d'acide de Lewis et d'un composé délivrant de l'acide peroxocaboxylique dans des conditions de perhydrolyse.
EP12722337.8A 2011-05-24 2012-05-16 Systèmes activateurs pour composés peroxygénés Active EP2714877B1 (fr)

Priority Applications (1)

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PL12722337T PL2714877T3 (pl) 2011-05-24 2012-05-16 Układy aktywatorów dla związków nadtlenowych

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011076417A DE102011076417A1 (de) 2011-05-24 2011-05-24 Aktivatorsysteme für Persauerstoffverbindungen
PCT/EP2012/059085 WO2012159944A1 (fr) 2011-05-24 2012-05-16 Systèmes activateurs pour composés peroxygénés

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EP2714877A1 true EP2714877A1 (fr) 2014-04-09
EP2714877B1 EP2714877B1 (fr) 2017-07-05

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EP (1) EP2714877B1 (fr)
DE (1) DE102011076417A1 (fr)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10358622B2 (en) 2012-09-13 2019-07-23 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US10433547B2 (en) 2014-12-18 2019-10-08 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
DE102014209241A1 (de) * 2014-05-15 2015-11-19 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit erhöhter Bleichleistung
US9845290B2 (en) 2014-12-18 2017-12-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US10172351B2 (en) 2015-09-04 2019-01-08 Ecolab Usa Inc. Performic acid on-site generator and formulator
US10285401B2 (en) 2015-09-10 2019-05-14 Ecolab Usa Inc. Self indicating antimicrobial chemistry
EP3724310A4 (fr) 2017-12-15 2021-07-21 Rhodia Operations Composition contenant un complexe métallique de lanthanide
CN112312769A (zh) 2018-06-15 2021-02-02 埃科莱布美国股份有限公司 用于乳头治疗的现场产生的过甲酸组合物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2297096A (en) * 1995-01-20 1996-07-24 Procter & Gamble Bleaching composition.
US6416687B1 (en) * 1996-08-21 2002-07-09 The Procter & Gamble Company Bleaching compositions
FR2792500B1 (fr) * 1999-04-23 2004-05-21 Internat Redox Dev Composition aqueuse, notamment sous forme de gel, a base de ho2f , acides et ions metalliques, procede de preparation notamment quand lesdits ions sont ag2+ et utilisation dans le domaine de la desinfection et/ou du traitement de surface
GB2402132B (en) * 2003-05-28 2005-10-19 Reckitt Benckiser Nv Dishwasher anti-corrosion composition
DE102009017724A1 (de) * 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10358622B2 (en) 2012-09-13 2019-07-23 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
US10433547B2 (en) 2014-12-18 2019-10-08 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate

Also Published As

Publication number Publication date
WO2012159944A1 (fr) 2012-11-29
EP2714877B1 (fr) 2017-07-05
DE102011076417A1 (de) 2012-11-29
PL2714877T3 (pl) 2017-12-29

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