EP3030642A1 - Détergent présentant une puissance de lavage primaire augmentée - Google Patents

Détergent présentant une puissance de lavage primaire augmentée

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Publication number
EP3030642A1
EP3030642A1 EP14747907.5A EP14747907A EP3030642A1 EP 3030642 A1 EP3030642 A1 EP 3030642A1 EP 14747907 A EP14747907 A EP 14747907A EP 3030642 A1 EP3030642 A1 EP 3030642A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
phenyl
alkenyl
naphthyl
heteroalkyl
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
EP14747907.5A
Other languages
German (de)
English (en)
Other versions
EP3030642B1 (fr
Inventor
André HÄTZELT
Johannes Zipfel
Arnd Kessler
Timothy O'connell
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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Priority to PL14747907T priority Critical patent/PL3030642T3/pl
Publication of EP3030642A1 publication Critical patent/EP3030642A1/fr
Application granted granted Critical
Publication of EP3030642B1 publication Critical patent/EP3030642B1/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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • 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 a combination of lipase and certain acylhydrazones for enhancing the primary detergency of laundry detergents or cleaners when washing textiles or cleaning hard surfaces against, in particular, bleach or enzyme sensitive stains, and detergents and cleaners containing such a combination.
  • the invention relates to the use of a combination of lipase with an acylhydrazone of the general formula (I),
  • R represents a CF 3 or represents a C 1-8 -alkyl, C 2-30 alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl, phenyl, naphthyl-, C7-9 aralkyl, C3-2o heteroalkyl or C3-12 cycloheteroalkyl group,
  • R 2 and R 3 independently of one another represent hydrogen or an optionally substituted C 1-28 -alkyl, C 2-30 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 cycloalkenyl, C 7- 9-aralkyl, C3-28-heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6-heteroaralkyl, phenyl, naphthyl or heteroaryl or R2 and R3 together with the carbon atom connecting them to an optionally substituted 5 -, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and R 4 is hydrogen or a d-28-alkyl, C 2-18 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3- 2o-heteroalky
  • the acylhydrazones may be in E or Z configuration; when R 2 is hydrogen, the compound of general formula (I) may be in one of its tautomeric forms or as a mixture of these.
  • R 2 is preferably hydrogen.
  • R and / or R 3 is preferably an electron-withdrawing group-substituted methyl, phenyl or naphthyl group.
  • R 4 is preferably hydrogen.
  • the electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as optionally hetero-heteroatom-carrying heteroatom group.
  • Preferred embodiments of the compounds according to general formula (I) include those of general formula (II),
  • R 0 is hydrogen or a ⁇ -28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 Cycloalkenyl, C7-9 aralkyl, C3-2o heteroalkyl, C3-i2 cycloheteroalkyl, C5-16 heteroaralkyl group 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 are each independently R, hydrogen, halogen, hydroxy, amino, optionally substituted N-mono or di-O-4-alkyl or C 2-4 hydroxyalkylamino -, N-phenyl or N-naphthyl-amino, Ci-28-alkyl, Ci-28-alkoxy, phenoxy, C2-28
  • R 5 and R 6 or R 6 and R 7 or R 7 and R 8 to form 1, 2 or 3 carbocyclic or O, NR 10 - or S-heterocyclic, optionally aromatic and / or optionally C 1-6 alkyl-substituted rings connected to each other.
  • 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 for 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
  • a lipase is an enzyme that catalyzes the hydrolysis of ester bonds in lipid substrates, especially in fats and oils. Lipases are therefore a subset of esterases. Lipases are generally versatile enzymes that accept a variety of substrates, for example, aliphatic, alicyclic, bicyclic and aromatic esters, thioesters and activated amines. Lipases act against fat residues in the laundry by catalyzing their hydrolysis (lipolysis). Lipases with broad substrate spectra are used in particular where inhomogeneous raw materials or substrate mixtures have to be reacted, for example in detergents and cleaning agents, since soiling usually consists of differently structured fats and oils.
  • the lipases known from the prior art are usually of microbial origin and are usually derived from bacteria or fungi, for example the genera Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola (Thermomyces), Trichoderma or Trichosporon. Lipases are usually produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi. Lipases preferred in the context of the present invention are derived from the fungus Humicola lanuginosa, such as, for example, the commercially available Lipases Lipolase®, Lipolase Ultra®, and in particular Lipex®.
  • the cleaning-active effects of the lipase are retained in the presence of simultaneously present acylhydrazones. Likewise, the cleaning-active effects of acylhydrazone remain in the presence of simultaneously present lipase.
  • the combined use of lipase and acylhydrazone results in a greater number of improved soilings removed than the sum of improved soilings removed using the two active ingredients individually, especially at low wash temperatures of, for example, 40 ° C and below, and even at room temperature.
  • the performance of compounds of general formula (I) may optionally be enhanced by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (III) - (IV) - (V), Cu ( l) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti (II) - (III) - (IV), and particularly 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 ligands of general formula (
  • a bleach-enhancing complex which has a ligand with a skeleton of the formula (I) may have the corresponding ligand once or more than once, 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 H2O, NH3, CH3OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C2-is carboxylate, a C18-alkyl sulfate , in particular methosulfate, or a corresponding alkanesulfonate, inorganic anions such as, for example, halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogensulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.
  • the concentration of the compound of formula (I) in aqueous liquor, as used for example in washing machines or dishwashers 0.5 ⁇ / ⁇ to 500 ⁇ / ⁇ , in particular 5 ⁇ / ⁇ to 100 ⁇ / ⁇ amounts.
  • the above-mentioned complex-forming metal ions are preferably not intentionally added, but they may be present from possible sources of such metal ions, which include, in particular, the tap water, the washing machine itself, adhesions to textiles, and stains on the fabrics.
  • metal ions inadvertently introduced with other detergent ingredients may also be considered.
  • OF PREFERRED Te peroxygen concentrations in the liquor range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and more preferably from 0.2 g / l to 0, 5 g / l.
  • the use according to the invention is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 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 21 ° dH, in particular 0 ° dH to 3 ° 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 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 use according to the invention is preferably carried out by allowing a peroxygen compound and a detergent containing an acylhydrazone of the general formula (I) and lipase to act on a contaminated textile in the course of a machine or hand washing operation.
  • the use according to the invention can be realized particularly simply by the use of a detergent containing peroxygen compound, lipase and a compound of formula (I) or a bleach catalyst obtainable from complexing with a transition metal ion thereof in the washing of textiles requiring cleaning.
  • the peroxygen compound and / or the compound of formula (I) and / or a complex obtainable therefrom and / or the lipase may also be added separately to a wash liquor which has a detergent without the particular ingredient mentioned.
  • cleaning agents for hard surfaces in the inventive use for example in the context of a dishwashing process.
  • Another object of the invention is a detergent or cleaning agent containing a peroxygen bleaching agent and a combination of lipase and a compound of formula (I).
  • Preferred embodiments also apply to the category of detergents or cleaners; in particular, the compound of formula (I) may also be present in the form of a bleach catalyst obtainable by complexation with a transition metal ion thereof from said agent.
  • Lipase is preferably contained in agents according to the invention in amounts of from 0.0005% by weight to 0.025% by weight, in particular from 0.0025% by weight to 0.01% by weight, based in each case on active protein.
  • 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 one Compound according to formula (I) corresponds contains.
  • the molar ratio of said transition metal or the sum of said transition metals to the compound according to formula (I) is preferably in the range of 0.001: 1 to 2: 1, in particular 0.01: 1 to 1: 1.
  • Agents are contained in these 0.05 wt .-% to 1 wt .-%, in particular 0, 1 wt .-% to 0.5 wt .-% of bleach-enhancing complex having a ligand according to formula (I) included.
  • Preferred transition metal is Mn.
  • organic peracids or persistent salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxo acid salts, such as alkali metal perulfates or peroxodisulfates or caroates, or diacyl peroxides or tetraacyldiperoxides, Hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing substances, such as alkali metal perborates, alkali metal peracids, alkali metal peracidates and urea perhydrate, into consideration.
  • organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxo acid salts, such as alkali metal perulfates or peroxodisulfates or caroates, or diacyl peroxides or tetraacy
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
  • solid peroxygen compounds ie an oxidase and its substrate.
  • solid peroxygen compounds 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 the compositions in amounts of up to 50% by weight, more preferably from 2% to 45% and more preferably from 5% to 20% by weight.
  • a conventional bleach activator is used together with the acyl hydrazone of the general formula (I), the general formula (II) and in particular the formula (III).
  • bleach activators are preferably present in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-%.
  • perbenzoic acid optionally substituted perhydrolysis under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, alone or in mixtures, can be used as the peroxycarboxylic acid-yielding compound.
  • Suitable bleach activators are the O- and / or N-acyl groups, in particular of the stated C atom number and / or, where appropriate bear 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, in particular nano-nanoyl or isononanoyl or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyl
  • bleach-activating compounds such as, for example, nitriles, from which perimides acids are formed under perhydrolysis conditions.
  • nitriles include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula
  • R 13 in the R represents -H, -Chta, a C 2-24 -alkyl or -alkenyl radical, a substituted C-24-alkyl or C 2- 24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH2, -CN and -N (+) -CH2-CN, an alkyl or alkenylaryl radical having a Ci-24-alkyl group, or for a substituted alkyl or alkenylaryl radical having at least one, preferably two, optionally substituted Ci -24-alkyl group (s) and optionally further substituents on the aromatic ring, 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) -CH3, -
  • the bleach activators may have been coated or granulated in known manner with coating substances, granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, granulated by means of carboxymethylcellulose 1, 5-diacetyl-2,4-dioxo-hexahydro-1, 3,5-triazine, and / or formulated in particulate form Trialkylammoniumacetonitrile 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, pyridine, 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-nonane triazacyclo- , 1, 5,9-triazacyclododecane and its substituted derivatives such as 1, 5,9-trimethyl-1, 5,9-triazacyclododecane 1, 4,8,1-tetraazacyclotetradecane and its substituted derivatives such as
  • 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 be asymmetric or two transition metal atoms -0-bridging.
  • the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands.
  • anion ligands are, 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 dinuclear 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 are ⁇ ( ⁇ ) 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) methylene] -1
  • Detergents which may be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, may in principle all known and in addition to the combination of lipase and compound according to formula (I) to be used according to the invention and optionally also the said bleach activators and catalysts such agents contain conventional ingredients.
  • the agents may in particular be builders, surface-active surfactants, water-miscible organic solvents, other 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 form-retaining polymeric agents, and other adjuvants, such as optical brighteners, foam regulators, dyes and fragrances.
  • An agent can for further enhancing the disinfecting action, for example against specific germs, additionally customary antimicrobial agents, such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bonded to organic frameworks O-acetates and O-formals, 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 their compounds, other oxidizing agents and inorganic nitrogen compounds.
  • customary antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, di
  • 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 C atoms in the alkyl radical.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in detergents in proportions of preferably 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 Hydroxyiminodisuccinate, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, especially Aminotris (methylenphosphonic acid), ethylenediaminetetrakis- (methylenephosphonic acid), lysintetra (methylenphosphoklare) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by Oxi
  • the relative average molecular weight (here and below: 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, though 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 the 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 C3-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C4-Cs-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.
  • vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with 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.
  • Very particular preference is given to polymers in which 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. Both the amounts and the weight ratios are based on the acids.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted 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.
  • 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% by weight to 25% by weight of methallylsulphonic acid or methallylsulphonate and as the third monomer 15% by weight to 40% by weight, preferably 20% to 40% by weight 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.
  • preference is given to the detergent-grade crystalline sodium aluminosilicates in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite 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 ⁇ 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 the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight.
  • the alkali metal 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 from 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.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up 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 .beta. And .delta.-sodium disilicates (Na.sub.2Si.sub.20.sub.y H.sub.2O) are preferred.
  • Also prepared from amorphous alkali metal silicates practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1, 9 to 2.1, can be used 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 of 1.9 to 3.5 are used in another embodiment.
  • a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15.
  • Suitable enzymes in the detergents are, in particular, those from the class of proteases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase and / or cellulase being 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 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 active ingredients in the compositions is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.
  • detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • diaminostilbenedisulfonic acid 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, a diethanolamino group, a methylamino group or carry 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.
  • 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% by weight and preferably in the range from 0.05% by weight to 0.5% by weight.
  • the customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein being preferably signed 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 classes of compounds 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 systemic and environmentally friendly acids especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also, mineral acids, in particular sulfuric acid or 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.
  • the preparation of solid 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.
  • V2 had a higher washing performance on 4 soiling and was the same for 86 soiling within the scope of the measuring accuracy (here and below: 6-fold determination).
  • V3 had a higher washing performance on 21 stains and was equal to 69 soiling within the scope of the measuring accuracy.
  • E1 had a higher washing performance on 27 soilings and was equal to 63 soiling within the scope of the measuring accuracy.
  • the simultaneous use of both ingredients surprisingly showed a greater number of advantages (27) than the sum of the individually used ingredients (21 +4).
  • the superiority of E1 was especially pronounced on the stains blood / milk / ink and olive oil / soot.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention vise à augmenter la puissance de lavage primaire de détergents et de produits de nettoyage contenant des composés peroxygénés. Ceci est obtenu par l'utilisation d'une combinaison de lipase avec une acylhydrazone.
EP14747907.5A 2013-08-09 2014-07-31 Détergent présentant une puissance de lavage primaire augmentée Active EP3030642B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL14747907T PL3030642T3 (pl) 2013-08-09 2014-07-31 Środek piorący o zwiększonej pierwotnej sile piorącej

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310215810 DE102013215810A1 (de) 2013-08-09 2013-08-09 Waschmittel mit erhöhter Primärwaschkraft
PCT/EP2014/066462 WO2015018728A1 (fr) 2013-08-09 2014-07-31 Détergent présentant une puissance de lavage primaire augmentée

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EP3030642A1 true EP3030642A1 (fr) 2016-06-15
EP3030642B1 EP3030642B1 (fr) 2018-09-05

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DE (1) DE102013215810A1 (fr)
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WO (1) WO2015018728A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015205802A1 (de) * 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit Bleichekatalysator und Riechstoffkapseln
DE102015205801A1 (de) * 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Partikuläres Waschmittel mit Bleichekatalysator
DE102015205799A1 (de) * 2015-03-31 2016-10-06 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit verbesserter Fleckentfernung
DE102015209082A1 (de) * 2015-05-19 2016-11-24 Henkel Ag & Co. Kgaa Acylhydrazone als bleichverstärkende Wirkstoffe
DE102015210416A1 (de) * 2015-06-08 2016-12-08 Henkel Ag & Co. Kgaa Acylhydrazone als Enzymstabilisatoren
DE102015225874A1 (de) * 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Flüssige Wasch- oder Reinigungsmittel enthaltend Acylhydrazon
CN111410864A (zh) * 2020-04-24 2020-07-14 西安理工大学 一种脂肪酶型水基油墨清洗剂及其制备方法

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Publication number Priority date Publication date Assignee Title
BRPI0814086A2 (pt) * 2007-07-23 2015-02-03 Basf Se Uso de pelo menos um complexo metálico, composição detergente, de limpeza, desifentante ou alvejante, grânulo, composto, e, complexo metálico.
MX2010010961A (es) * 2008-04-09 2010-11-05 Basf Se Uso de compuestos complejos de hidracida de metal como catalizadores de oxidacion.
BR112013014591B1 (pt) * 2010-12-13 2019-04-16 Basf Se Composição, detergente, composição de limpeza, desinfetante ou alvejante, grânulo, processo para o alvejamento de manchas ou de sujeira em materiais têxteis, e, uso de composto
DE102012200333A1 (de) * 2012-01-11 2013-07-11 Henkel Ag & Co. Kgaa Acylhydrazone als bleichverstärkende Wirkstoffe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2015018728A1 *

Also Published As

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DE102013215810A1 (de) 2015-02-12
WO2015018728A1 (fr) 2015-02-12
PL3030642T3 (pl) 2019-02-28
EP3030642B1 (fr) 2018-09-05

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