EP3095847B1 - Produit de lavage et de nettoyage a hygiene amelioree - Google Patents

Produit de lavage et de nettoyage a hygiene amelioree Download PDF

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Publication number
EP3095847B1
EP3095847B1 EP16168842.9A EP16168842A EP3095847B1 EP 3095847 B1 EP3095847 B1 EP 3095847B1 EP 16168842 A EP16168842 A EP 16168842A EP 3095847 B1 EP3095847 B1 EP 3095847B1
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EP
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Prior art keywords
alkyl
general formula
acylhydrazone
acid
phenyl
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EP16168842.9A
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German (de)
English (en)
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EP3095847A1 (fr
Inventor
André HÄTZELT
Mirko Weide
Thorsten Bastigkeit
Michael Dreja
Christian Kastner
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL16168842T priority Critical patent/PL3095847T3/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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • 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

Definitions

  • the present invention relates to the improvement of the antimicrobial efficacy of detergents and cleaners by the combination of bleaches with certain acylhydrazones.
  • Microorganisms such as bacteria, fungi and viruses can colonize household and textile surfaces; Bacteria and fungi can also multiply on such surfaces. This can result in hygiene risks, but also lead to unaesthetic microbial deposits, so-called biofilms, as well as to unpleasant odors.
  • microorganisms are often insufficiently killed in the washing process or at least removed from the textile. This can lead to the spread of germs from one textile to another during the washing process, especially when this is a bleach-free detergent used.
  • the invention relates to the use of a combination of peroxygen bleaching agent with an acylhydrazone of the general formula (I),
  • R 1 is a CF 3 or a C 1-28 -alkyl, C 2-28 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl- , Phenyl, naphthyl, C 7-9 -aralkyl, C 3-20 -heteroalkyl or C 3-12 -cycloheteroalkyl, R 2 and R 3 independently of one another represent hydrogen or an optionally substituted 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 3-28 heteroalkyl, C 3 -12- Cycloheteroalkyl-, C 5-16 -Heteroaralkyl-, phenyl-, naphthyl- or heteroaryl group or R 2 and R 3 together with the carbon atom connecting them
  • 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 an electron-withdrawing group-substituted methyl, phenyl or naphthyl group.
  • R 4 is preferably hydrogen.
  • an electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as heterocycloalkyl optionally carrying further heteroatoms.
  • Preferred embodiments of the compounds according to general formula (I) include those of general formula (II),
  • R 1 is a C 1-4 alkyl group having a substituent selected from
  • 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 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl, and A - represents the anion of an organic or inorganic acid;
  • R 2 and R 4 represent the Have the meaning given in formula (I) and 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 or N-naphthylamino, C 1-28 alkyl, C 1-28 alkoxy, phenoxy, C 2-28 alkenyl, C 2-22 Alky
  • 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
  • the compounds of the general formula (I) enhance the disinfecting effect of peroxygen compounds without unacceptably damaging the textile to be cleaned by the use of the combination essential to the invention, especially at low levels Wash temperatures of below 60 ° C, such as 30 ° C, and even at room temperature.
  • peroxygen compounds H 2 O 2 or in water H 2 O 2 releasing substances which include in particular alkali metal perborates, alkali metal percarbonate and urea;
  • peroxycarboxylic acids such as diperoxodecanedicarboxylic acid or phthalimidopercaproic acid, other peroxoacids or peroxosauric salts such as alkali persulfates or peroxodisulfates or caroates, or diacyl peroxides or tetraacyldiperoxides.
  • the performance of compounds of the general formula (I) or the general formula (II) may optionally be limited 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 more preferably those selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III);
  • the acylhydrazone can also be used in the form of complex compounds of said metal central atoms with
  • a disinfection-enhancing complex which has a ligand with a skeleton of the formula (I) or formula (II) may have the corresponding ligand once or even several times, in particular twice. It may be one or possibly two or more nuclear. 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.
  • Another object of the invention is a method for removing Gram-negative bacteria from textile or hard surfaces by contacting the surface with an aqueous preparation comprising an acylhydrazone of the general formula (II) and a persoxy-containing bleaching agent.
  • the concentration of the compound of the formula (I) or formula (II) in the aqueous washing or cleaning liquor used, for example, in washing machines or dishwashers is 0.5 ⁇ 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 and / or copper ions in the aqueous liquor is preferably in the range from 0.05 ⁇ mol / l to 500 ⁇ mol / l, in particular from 1 ⁇ mol / l to 100 ⁇ mol / l.
  • Preferred peroxygen concentrations (calculated as H 2 O 2 ) in the aqueous 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 and the inventive method are preferably carried out at temperatures in the range of 10 ° C to 95 ° C, in particular 20 ° C to 40 ° C and particularly preferably at temperatures below 30 ° C.
  • the water hardness of the water used for preparing the aqueous liquor is preferably in the range from 0 ° dH to 27 ° dH, in particular 0 ° dH to 21 ° dH.
  • the water hardness is preferably in the range of 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH, which can be achieved for example by the use of conventional builder materials or water softeners.
  • the use according to the invention and the method according to the invention are preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
  • the use according to the invention is preferably carried out in such a way that a washing or cleaning agent containing a peroxygen compound and an acylhydrazone of the general formula (I) or the general formula (II), in the context of a machine or carried out by hand washing or cleaning operation a contaminated textile or a contaminated hard surface is allowed to act.
  • the use according to the invention and the process according to the invention can be realized particularly simply by the use of a washing or cleaning agent which contains the peroxygen compound and a compound of the formula (I) or of the formula (II) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned become.
  • the peroxygen compound and / or the compound of formula (I) or (II) and / or a complex obtainable therefrom may also be added separately to an aqueous liquor having an agent without the particular ingredient mentioned.
  • 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.
  • Preferred transition metal is Mn.
  • 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 3% by weight to 10% by weight of hydrogen peroxide.
  • peroxygen compounds are present in amounts of from 1% to 20%, and more preferably from 7% to 15%, by weight in detergents or cleaners.
  • a conventional bleach activator is used together with the acylhydrazone of the general formula (I) and in particular the general formula (II).
  • bleach activators are preferably present in amounts of from 0.01% by weight to 10% by weight, in particular from 1% by weight to 3% by weight, in each case based on the total agent. Preference is given to using peroxycarboxylic acid-forming compound and acylhydrazone in molar ratios in the range from 4: 1 to 100: 1, in particular from 25: 1 to 50: 1, under perhydrolysis conditions.
  • peroxycarboxylic acid-supplying compound in particular compounds which under perhydrolysis conditions optionally substituted perbenzoic acid and / or aliphatic peroxycarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms be used alone or in mixtures.
  • Suitable are bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benz
  • a peroxycarboxylic acid or a peroxycarboxylic acid perhydrolysis-forming compound is used together with the acylhydrazone of the general formula (I) or (II), and the peroxygen-compound-containing agent is a peroxycarboxylic acid or a combination of hydrogen peroxide-releasing compound Perhydrolysis conditions peroxycarboxylic acid forming compound.
  • the composition contains at least 1% by weight, in particular at least 1.5% by weight, of peroxycarboxylic acid-forming compound under perhydrolysis conditions.
  • bleach-activating compounds such as, for example, nitriles, from which perimides acids are formed under perhydrolysis conditions, may be present.
  • R 11 is -H, -CH 3 , a C 2-24 -alkyl or alkenyl radical, a substituted C 1-24 -alkyl or C 2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN and -N (+) -CH 2 -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C 1-24 -alkyl group (s) and optionally further substituents on the aromatic ring, R 12 and R 13 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH)
  • the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose.
  • Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred.
  • customary bleach-activating transition metal complexes are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Suitable ligands in such 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 , Triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane and its substituted derivatives such as 1,4,7-trimethyl-1,4,7-triazacyclononane, 1.5 , 9-triazacyclododecane and its substituted derivatives such as 1,5,9-trimethyl-1,5,9-triazacyclododecane 1,4,8,11-tetraazacyclotetradecane and its substituted derivatives such as 5,5,7,12,12,14- Hexamethyl-1,4,8,11-tetraazacyclotetrade
  • the inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, 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 chelated to a transition metal, or it may bridge two transition metal atoms asymmetrically or ⁇ 1 -O-bridge.
  • the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands.
  • anion ligands for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, 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. In particular, such ligands can also act bridging, so that polynuclear complexes arise.
  • both metal atoms in the complex need not be the same.
  • the use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention.
  • anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate.
  • transition metal complex compounds that can be used are Mn (IV) 2 ( ⁇ -O) 3 (1,4,7-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) m
  • Detergents or cleaning agents which may be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, can be used in addition to the combination of peroxygen compound and compound to be used according to the invention according to formula (I) and the said bleach activators and catalysts in principle all known and customary in such agents ingredients.
  • 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 be used to further enhance the disinfecting effect, for example against specific germs, in addition conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O.
  • conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O.
  • benzamidines isothiazolines, phthalimide derivatives, pyridine derivatives, amines, quaternary ammonium compounds, guanidines, amphoteric compounds, quinolines, benzimidazoles, IPBC, dithiocarbamates, metals and metal compounds such as silver and silver salts, halogens such as chlorine, iodine and theirs Compounds, other oxidizing agents and inorganic nitrogen compounds.
  • Such antimicrobial additives are preferably present in amounts of up to 10 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%, each based on the total agent included; in a preferred embodiment, however, they are free of such additional disinfecting agents.
  • the agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 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 ones 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 sulfo fatty acid esters, which in the sulfonation of Fatty acid methyl or ethyl esters arise.
  • Such surfactants are present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight,
  • a detergent 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 glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), Ethylenediaminetetrakis (methylenephosphonic acid), Lysintetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by
  • the relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic 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.
  • 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 maleate 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 derived from benzene or benzene derivatives , 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.
  • terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol.
  • 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 hydrous, agents.
  • 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.
  • the detergent-grade crystalline sodium aluminosilicates particularly 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 above 30 microns and preferably consist of at least 80 wt .-% of particles having a size less than 10 microns.
  • Their calcium binding capacity is generally 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 the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight.
  • the alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline.
  • 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 of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates 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 in the 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 1.9 to 3.5 are used in a further embodiment.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • Suitable enzymes in the detergents are, in particular, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or or cellulase is particularly preferred.
  • the proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%.
  • the enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.
  • 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 graying inhibitors and / or soil-release agents in the compositions is generally not more than 2 wt .-%, and is preferably 0.5 wt .-% to 1.5 wt .-%.
  • detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • 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.
  • mixtures of brighteners can be used.
  • brighteners of the 1,3-diaryl-2-pyrazolines type for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable.
  • the content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, and preferably in the range of 0.05 wt .-% to 0.5 wt .-%.
  • the customary foam regulators which can be used in detergents 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 having 12 to 22 carbon atoms.
  • the proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.
  • the agents may contain water as a solvent.
  • organic solvents which can be used in the compositions, in particular 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 compound classes ethers.
  • Such water-miscible solvents are present in the compositions in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% 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 alkali metal 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 .-%, included.
  • compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, thermally-sensitive ingredients optionally being added separately later.
  • compositions 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.
  • compositions are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and bleach-activating agents Active ingredients are expected to be produced.
  • a process comprising an extrusion step is preferred.
  • a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

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Claims (11)

  1. Utilisation d'une combinaison constituée d'un agent de blanchiment contenant du peroxygène comportant une acylhydrazone de formule générale (I),
    Figure imgb0012
     dans laquelle R1 représente CF3 ou un groupe alkyle C1-28, alcényle C2-28, alcynyle C2-22, cycloalkyle C3-12, cycloalcényle C3-12, phényle, naphtyle, aralkyle C7-9, hétéroalkyle C3-20 ou cyclohétéroalkyle C3-12, R2 et R3 représentent indépendamment un atome d'hydrogène ou un groupe alkyle C1-28, alcényle C2-28, alcynyleC2-22, cycloalkyle C3-12, cycloalcényle C3-12, aralkyle C7-9, hétéroalkyle C3-28, cyclohétéroalkyle C3-12, hétéroaralkyle C5-16, phényle, naphtyle ou hétéroaryle éventuellement substitué, ou R2 et R3 conjointement avec l'atome de carbone qui le relie représentent un cycle à 5, 6, 7, 8 ou 9 chaînons éventuellement substitué, lequel cycle peut éventuellement contenir des hétéroatomes, et R4 représente un atome d'hydrogène ou un groupe alkyle C1-28, alcényle C2-28, cycloalkyle C3-12, cycloalcényle C3-12, aralkyle C7-9, hétéroalkyle C3-20, cyclohétéroalkyle C3-12, hétéroaralkyle C5-16 ou un groupe phényle ou naphtyle ou hétéroaryle éventuellement substitué, pour améliorer l'efficacité antimicrobienne des détergents et des produits de nettoyage contre des bactéries gram-négatives.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'on fait agir un détergent ou un produit de nettoyage contenant un composé peroxygéné et une acylhydrazone de formule générale (I) sur un textile souillé ou une surface dure souillée au cours d'une opération de lavage ou de nettoyage effectuée mécaniquement ou manuellement.
  3. Procédé d'élimination de bactéries gram-négatives des surfaces textiles ou dures par mise en contact de la surface avec une préparation aqueuse comprenant une acylhydrazone de formule générale (I) et un agent de blanchiment contenant du peroxygène.
  4. Utilisation selon la revendication 1 ou 2 ou procédé selon la revendication 3, caractérisé(e) en ce que l'acylhydrazone de formule générale (I) est utilisée en présence de H2O2 ou de substances libérant du H2O2 dans l'eau.
  5. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que l'acylhydrazone de formule générale (I) est utilisée en présence d'ions manganèse, titane, cobalt, nickel ou cuivre.
  6. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que un acide peroxocarboxylique ou un composé formant un acide peroxocarboxylique dans des conditions de perhydrolyse est utilisé conjointement avec l'acylhydrazone de formule générale (I).
  7. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que la concentration du composé selon la formule (I) dans la liqueur aqueuse est comprise entre 0,5 et 500 µmol/l, en particulier entre 5 et 100 µmol/l.
  8. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que la concentration en peroxygène (calculée en H2O2) dans la liqueur est comprise entre 0,001 et 10 g/l, en particulier entre 0,1 et 1 g/l, et de préférence entre 0,2 et 0,5 g/l.
  9. Utilisation d'une combinaison constituée d'un agent de blanchiment contenant du peroxygène comportant une acylhydrazone de formule générale (II),
    Figure imgb0013
     dans laquelle R1 représente un groupe akyle C1-4 contenant un substituant
    Figure imgb0014
     dans lequel R10 est un atome d'hydrogène ou un groupe alkyle C1-28, alcényle C2-28, alcynyle C2-22, cycloalkyle C3-12, cycloalcényle C3-12, aralkyle C7-9, hétéroalkyle C3-20, cyclohétéroalkyle C3-12, hétéroaralkyle C5-16 et A' représente l'anion d'un acide organique ou inorganique, R2 et R4 sont définis comme définis dans la formule (I) selon la revendication 1, et R5, R6, R7 et R8 représentent indépendamment R1, un atome d'hydrogène, un atome d'halogène, un groupe hydroxy, amino, un groupe N-mono ou dialkyle C1-4 ou hydroxyalkylamino C2-4, N-phényle ou N-naphtylamino, alkyle C1-28, alcoxy C1-28, phénoxy, alcényle C2-28, alcynyle C2-22, cycloalkyle C3-12, cycloalcényle C3-12, aralkyle C7-9, hétéroalkyle C3-20, cyclohétéroalkyle C3-12, hétéroaralkyle C5-16, phényle ou naphtyle éventuellement substitué, les substituants étant choisis dans les groupes alkyle C1-4, alcoxy C1-4, hydroxy, sulfo, sulfato, halogène, cyano, nitro, carboxy, phényle, phénoxy, naphtoxy, amino, N-mono ou dialkyle C1-4 ou hydroxyalkylamino C2-4, N-phényl ou N-naphthylamino, ou R5 et R6 ou R6 et R7 ou R7 et R8 sont réunis ensemble pour former 1, 2 ou 3 cycles carbocycliques ou O, NR10 ou S-hétérocycliques éventuellement aromatiques et/ou éventuellement substitués par alkyle C1-6, pour améliorer l'efficacité antimicrobienne des détergents ou des produits de nettoyage contre des bactéries gram-négatives.
  10. Procédé d'élimination de bactéries gram-négatives des surfaces textiles ou dures par mise en contact de la surface avec une préparation aqueuse comprenant une acylhydrazone de formule générale (II) et un agent de blanchiment contenant du peroxygène.
  11. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que l'acylhydrazone est utilisée sous la forme de composés complexes d'atomes centraux de manganèse, de titane, de cobalt, de nickel ou de cuivre comportant des ligands de formule générale (I), en particulier de formule générale (II).
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US5179127A (en) * 1990-05-24 1993-01-12 Rohm And Haas Company Halopropargyl acyl compound, compositions, microbicidal uses and processes of preparation
MX2010010961A (es) 2008-04-09 2010-11-05 Basf Se Uso de compuestos complejos de hidracida de metal como catalizadores de oxidacion.
WO2012080088A1 (fr) 2010-12-13 2012-06-21 Basf Se Catalyseurs de blanchiment
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