EP1000136A1 - Produit detergent contenant de la glucanase et destine aux surfaces dures - Google Patents

Produit detergent contenant de la glucanase et destine aux surfaces dures

Info

Publication number
EP1000136A1
EP1000136A1 EP98943758A EP98943758A EP1000136A1 EP 1000136 A1 EP1000136 A1 EP 1000136A1 EP 98943758 A EP98943758 A EP 98943758A EP 98943758 A EP98943758 A EP 98943758A EP 1000136 A1 EP1000136 A1 EP 1000136A1
Authority
EP
European Patent Office
Prior art keywords
weight
glucanase
cleaning
dishes
hard surfaces
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
EP98943758A
Other languages
German (de)
English (en)
Other versions
EP1000136B1 (fr
Inventor
Karl-Heinz Maurer
Christian Nitsch
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
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1000136A1 publication Critical patent/EP1000136A1/fr
Application granted granted Critical
Publication of EP1000136B1 publication Critical patent/EP1000136B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

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
    • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase

Definitions

  • the present invention relates to agents for cleaning hard surfaces, in particular dishes, which contain ⁇ -glucanase to increase their cleaning performance.
  • Enzymes in particular proteases, lipases and amylases, are used extensively in washing, auxiliary washing and cleaning agents. They are primarily used to remove protein, fat and starch stains.
  • polysaccharide soiling is that naturally occurring polysaccharides, such as those found in foods, do not normally consist exclusively of starch, but also contain other or otherwise linked saccharides. While ⁇ -amylases intended for use in dishwashing detergents are generally well suited to hydrolyzing the starch content of polysaccharide stains into water-soluble oligosaccharides, their dirt removal ability may be perceived as being in need of improvement if stains from other polysaccharides are involved or make up larger parts of the polysaccharide stains. For example, cereals such as oatmeal, muesli, cornflakes or wholegrain dough have higher or lower levels of glucans and lichenans, which lead to dishes that have come into contact with these foods that are difficult to remove.
  • the aim of the applicant was to remedy this situation and to develop a means for cleaning hard surfaces, such as, for example, particularly for machine washing of dishes, which has improved cleaning performance compared to polysaccharide stains.
  • ⁇ -glucanases which can be used according to the invention can be obtained from microorganisms, for example Achromobacter lunatus, Athrobacter luteus, Aspergillus aculeatus, Aspergillus niger, Bacillus subtilis, Bacillus amyloliquefaciens, Disporotrichum dimorphosporum, Humicola insolens, Penicillium trichemicusi, penicillium emersonii or Penicilliumusillumumusillusumumusillus A commercially available product is offered, for example, under the name Cereflo® (manufacturer: Novo Nordisk A / S).
  • the preferred ⁇ -glucanases include an enzyme obtainable from Bacillus alkalophilus (DSM 9956), which is the subject of the unpublished German patent application DE 197 32 751.
  • ⁇ -glucanase is preferably incorporated into agents according to the invention in amounts such that they have glucanolytic activities in the range from 0.05 U / g to 2 U / g, in particular from 0.06 U / g to 0.5 U / g.
  • the determination of glucanolytic activity is based on modifications by M. Lever in Anal. Biochem. 47 (1972), 273-279 and Anal. Biochem. iü (1977), 21-27 described method. A 0.5% by weight solution of ⁇ -glucan in 50 mM glycine buffer (pH 9.0) is used for this.
  • ⁇ -glucanase for removing polysaccharide stains on hard surfaces, in particular dishes
  • a method for removing polysaccharide stains from hard surfaces, in particular dishes by using ⁇ -glucanase.
  • the ⁇ -glucanase alone or as a component of a pretreatment agent, can be applied to dishes contaminated with polysaccharide stains in the sense of a pretreatment step before the rinsing process.
  • the ⁇ -glucanase is preferably used as a constituent of an aqueous cleaning solution which can additionally contain the usual ingredients of detergent or dishwashing liquors.
  • Glucanolytic activities in the range from 0.1 U / 1 to 6 U / 1, in particular from 0.15 U / 1 to 1.5 U / 1, are preferred in the aqueous cleaning solution.
  • the glucanolytic activities mentioned need not be maintained over the entire rinsing cycle in order to achieve the desired cleaning result, as long as it is ensured that at least for a short time, for example about 1 to 20 minutes, in particular 5 to 15 minutes, a glucanolytic activity occurs in the range mentioned.
  • An agent according to the invention in particular has an amylolytic activity in the range from about 0.5 U / g to about 3 U / g, in particular from about 1 U / g to about 2 U / g.
  • the amylase activity is determined analogously to the standardized method described above for the glucanase activity, using soluble starch instead of glucan.
  • the cleaning agents according to the invention which can be present as granules, powdered or tablet-shaped solids, as other shaped bodies, as homogeneous solutions or suspensions, can, in addition to the ⁇ -glucanase used according to the invention, in principle contain all known ingredients which are customary in such agents.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, bleaching agents based on organic and / or in particular inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators and / or further auxiliaries, such as silver corrosion inhibitors, Foam regulators and dyes and fragrances included.
  • a cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof.
  • Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.
  • Suitable water-soluble builder components in cleaning agents according to the invention are in principle all builders usually used in agents for the automatic cleaning of dishes, for example alkali metal phosphates, which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples include trisodium phosphate, tetrasodium diphosphate,
  • other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin of the polycarboxylate type, which act in particular in hard water regions as co-builders.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids are suitable.
  • polymers of native origin that can be used as co-builders include, for example, oxidized starch, as known, for example, from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • the preferred organic builder components include the salts of citric acid, especially sodium citrate.
  • Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the co-builder salts mentioned can also be present.
  • a machine cleaning agent for dishes according to the invention contains the usual alkali carriers such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 40% by weight, based on the total agent. However, the use of the highly alkaline metasilicates as alkali carriers is preferably avoided entirely.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 50% by weight, preferably 5 wt .-% to 40 wt .-%, is included. Depending on which pH value is ultimately desired, the ratio of carbonate and bicarbonate used can vary.
  • agents according to the invention 20% by weight to 60% by weight of water-soluble organic builders, in particular alkali citrate, 3% by weight to 20% by weight of alkali carbonate and 5% by weight to 40% by weight of alkali disilicate contain.
  • Suitable peroxygen compounds are in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate.
  • Hydrogen peroxide can also be generated using an enzymatic system, i.e. 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 coated in a manner known in principle.
  • Alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight hydrogen peroxide are particularly preferably used. If a cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, are preferred (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso, phonohydride), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE
  • Patent applications WO 94/27970, WO 94/28102, WO 94/281 03, WO 95/00626, WO 95/14759 and WO 95/17498 are known.
  • the hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0453 003 can also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which are described in German patent application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium known from German patent application DE 196 20411 - Amine complexes, the manganese, copper and cobalt complexes described in German patent application DE 44 16 438, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • C 2 -C 8 -alkyl polyethylene glycol polypropylene glycol ether each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • nonionic surfactants such as C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end group capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14 alkyl polyglucoside with one Degree of polymerization of about 1 to 4 (e.g.
  • 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 saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are used in the reaction of corresponding monoolefins with sulfur trioxide arise, as well as ⁇ -sulfofatty acid esters, which " arise in the sulfonation of fatty acid methyl or ethyl esters.
  • the enzymes which can be used in the compositions are those from the class of proteases, lipases, cutinases, amylases, pullulanases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean® , Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and or Purafect® OxAm, lipases such as Lipolase® , Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean® , Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia, enzymatic active substances obtained.
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia, enzymatic active substances obtained.
  • These optionally additionally used enzymes as described for example in European patent EP 0 564476 or in international patent applications WO 94/23005, can also be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trivalent phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, manganese, titanium, zirconium, hafnium, cobalt or cerium salts and / or complexes , in which the metals mentioned are in one of the oxidation states II, III, IV, V or VI, depending on the metal.
  • the cleaning agents foam too much during use, for example in the presence of anionic surfactants, they can still contain up to 6% by weight, preferably about 0.5% by weight to 4% by weight, of a foam-suppressing compound the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, bis-fatty acid amides, and other other known commercially available defoamers.
  • Other optional ingredients in the agents according to the invention are, for example, perfume oils.
  • the agents 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 contain mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are preferably not contained in the agents according to the invention in excess of 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • Cleaning agents according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the agents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which are known in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally resilient components and admixing of the more sensitive components, which include in particular the enzymes and, if appropriate, bleaching agents, can be produced.
  • Agents according to the invention can be produced 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 / 1 by adding the builder components with at least a portion of liquid mixture components in a first process stage Increasing the bulk density of this premix is mixed and subsequently - if desired after an intermediate drying - the further components of the agent, including the bleaching catalyst, are combined with the premix obtained in this way.
  • Agents according to the invention for cleaning dishes can be used both in household dishwashers and in commercial dishwashers. It is added by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / 1, preferably 2 to 5 g / 1.
  • a machine wash program is generally supplemented and ended by a few intermediate rinse cycles with clear water and a rinse cycle with a customary rinse aid after the cleaning cycle. After drying, when using the agents according to the invention, a completely clean and hygienically perfect tableware is obtained. Examples
  • a cleaning agent (VI) for the automatic cleaning of dishes containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium arbonate, 31 parts by weight of sodium hydrogen carbonate, 1 part by weight of protease and 2 parts by weight of amylase Granules (Termamyl® 60T), 2 parts by weight of nonionic surfactant and 10 parts by weight of sodium perborate monohydrate and 4 parts by weight of N, N, N'N'-tetraacetylethylenediamine (TAED), an agent according to the invention ( Ml), which was otherwise composed as VI, but additionally contained 1.7 parts by weight of Cereflo® 200 L, and an agent (M2) likewise according to the invention, which instead had twice the activity of ⁇ -glucanase from Bacillus alkalophilus (DSM 9956 ) were tested as follows:
  • agent according to the invention is significantly superior to the agent not according to the invention in cleaning performance.

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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)
  • Detergent Compositions (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Abstract

L'invention concerne des produits destinés au nettoyage de surfaces dures comme, par exemple, au nettoyage mécanique de la vaisselle. Pour améliorer le pouvoir nettoyant vis-à-vis des salissures de polysaccharide, on développe un produit permettant de nettoyer les surfaces dures, notamment la vaisselle, et contenant non seulement des substances habituellement tolérables avec cet enzyme mais aussi de la β-glucanase.
EP98943758A 1997-07-30 1998-07-21 Produit detergent contenant de la glucanase et destine aux surfaces dures Revoked EP1000136B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19732750A DE19732750A1 (de) 1997-07-30 1997-07-30 Glucanasehaltiges Reinigungsmittel für harte Oberflächen
DE19732750 1997-07-30
PCT/EP1998/004566 WO1999006515A1 (fr) 1997-07-30 1998-07-21 Produit detergent contenant de la glucanase et destine aux surfaces dures

Publications (2)

Publication Number Publication Date
EP1000136A1 true EP1000136A1 (fr) 2000-05-17
EP1000136B1 EP1000136B1 (fr) 2003-01-22

Family

ID=7837328

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98943758A Revoked EP1000136B1 (fr) 1997-07-30 1998-07-21 Produit detergent contenant de la glucanase et destine aux surfaces dures

Country Status (8)

Country Link
US (1) US6703357B1 (fr)
EP (1) EP1000136B1 (fr)
AT (1) ATE231542T1 (fr)
DE (2) DE19732750A1 (fr)
ES (1) ES2191330T3 (fr)
HU (1) HUP0003055A2 (fr)
PL (1) PL338419A1 (fr)
WO (1) WO1999006515A1 (fr)

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DE102006038448A1 (de) 2005-12-28 2008-02-21 Henkel Kgaa Enzym-haltiges Reinigungsmittel
KR101160802B1 (ko) 2010-11-25 2012-06-29 주식회사 토일러 생화학 물질을 활용한 수세를 필요치 않은 세제 조성물
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US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US20140308162A1 (en) 2013-04-15 2014-10-16 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
MX2017016883A (es) 2015-07-06 2018-09-18 Ecolab Usa Inc Remocion de mancha a traves de oxidante novedoso y combinacion de quelante.
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US11518966B2 (en) * 2019-11-07 2022-12-06 Envirox, L.L.C. Peroxide-based multi-purpose cleaning, degreasing, sanitizing, and disinfecting solutions and methods for preparing the same

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ATE231542T1 (de) 2003-02-15
WO1999006515A1 (fr) 1999-02-11
ES2191330T3 (es) 2003-09-01
HUP0003055A2 (hu) 2001-01-29
DE19732750A1 (de) 1999-02-04
PL338419A1 (en) 2000-11-06
EP1000136B1 (fr) 2003-01-22
DE59807025D1 (de) 2003-02-27
US6703357B1 (en) 2004-03-09

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