EP0846155B1 - Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine - Google Patents

Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine Download PDF

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Publication number
EP0846155B1
EP0846155B1 EP96930089A EP96930089A EP0846155B1 EP 0846155 B1 EP0846155 B1 EP 0846155B1 EP 96930089 A EP96930089 A EP 96930089A EP 96930089 A EP96930089 A EP 96930089A EP 0846155 B1 EP0846155 B1 EP 0846155B1
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EP
European Patent Office
Prior art keywords
weight
surfactants
lipases
dishwashing detergents
lipase
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.)
Expired - Lifetime
Application number
EP96930089A
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German (de)
English (en)
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EP0846155A2 (fr
Inventor
Christian Nitsch
Peter Jeschke
Jürgen Härer
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Henkel AG and Co KGaA
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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
Priority claimed from DE19531197A external-priority patent/DE19531197A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0846155A2 publication Critical patent/EP0846155A2/fr
Application granted granted Critical
Publication of EP0846155B1 publication Critical patent/EP0846155B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention relates to a new use of the known lipases in Framework of low alkaline agents for machine washing dishes and as a means of supporting the bleaching systems for removing Tea stains.
  • lipolytic enzymes in machine Dishwashing detergents are known per se. The expert knows that they are in the Cleavage of triglycerides and fatty ester contamination are helpful. So EP-B-271 155 teaches the use of lipases in dishwashing detergents and in rinse aid. It is stated there that the formation of films and Stains is significantly reduced. Under the diminution of film formation the reduction in greasy films is understood here, not the reduction of tea toppings.
  • European patent application 346 136 describes the Reduction of stains and film formation through a special, genetically modified lipase.
  • German published patent application DE 43 32 170 describes the use of lipase in lower alkaline agents for automatic dishwashing.
  • the lipase is used simultaneously with the agents.
  • International application WO94 / 07985 claims the use of a combination of lipases and lime soap dispersants in dishwashing detergents.
  • the patent application assumes that the mode of action of the lipase releases fatty acids which react with the existing water hardness to form lime soaps. These in turn are deposited on the items to be washed.
  • the application claims the use of 0.001% by weight to 2% by weight of a lipolytically active enzyme. In the examples, however, the use of slightly more than 2% by weight of a lipase enzyme is described. It is clear to the person skilled in the art in this field that, under normal conditions of use, an effect of the lipase, as described in WO94 / 07985, is more likely to be expected in the higher dosage range.
  • the present invention therefore relates to the use of Esterases, preferably lipases, in or together with lower alkaline Detergents for automatic dishwashing which have a pH in 1% by weight solution have between 8.5 and 10.5, containing 15 to 70% by weight of a builder component, 0.5 to 20% by weight of an oxygen-based bleach and, if desired, bleach activators, Surfactants, anti-corrosion agents, hydrotropes, foam inhibitors and other components customary in machine dishwashing detergents, characterized in that that 0.001 to 1.5 wt .-% esterase, if desired in combination with 1 to 25 wt .-% polyfunctional, organic carboxylic acids are used, the lower alkaline Agents can be brought into effect after the esterases.
  • lower alkaline Agents can be brought into effect after the esterases.
  • the active ingredient can be cleaned in a first step use different ways. So the esterase in dissolved form or wash in, spread on or spray on as a suspension. It also comes in Question, the hard surfaces to be cleaned for a certain time, by the effectiveness of the dosage form can be dependent, in an immersion bath to leave and the effectiveness of the esterases if necessary by acting and leave to increase. But also other usual procedures for manual or mechanical pre-rinsing can be used.
  • esterases used according to the invention can be in the a wide variety of dosage forms are used, with powder, Blocks, tablets, compacts, granules, pastes, viscous liquids, and aqueous and non-aqueous solutions can be used. Especially granules and tablets are preferred. But you can also as Components along with other substances in the above Dosage forms are used.
  • the lipases to be used according to the invention are enzymes lipolytic activity, as used for example in detergents become.
  • Preferred lipases are of bacterial origin and can be used for Example in strains like Humicola sp. or Thermomyces sp. or Pseudomonas pseudoalkaligenes or Pseudomonas fluorescens occur.
  • Lipases which are derived from basic enzymes can also be used genetic change can be generated. Even lipase mixtures that also enzymes that have both proteolytic and lipolytic activities are suitable.
  • lipases sold under the brand name Lipomax® CXT 1000 from Gist Brocades, or Lipolase® from Novo Nordisk im Trading is (see EP 258 068).
  • a lipase is also preferred Pseudomonos fluorescens, under the brand name Lipase P Amano by can be obtained from Amano.
  • the agents according to the invention in addition to the lipase as an essential component a multifunctional, organic acid.
  • Suitable multifunctional, Organic acids are primarily citric acid, but also tartaric acid as well as the dicarboxylic acids with 3 to 8 carbon atoms.
  • the multifunctional, Organic acid is the agents according to the invention as such, i. H. not in Salt form added. It should be ensured that the organic acid as such, d. H. not in salt form. Since the invention too dishwashing detergents are generally not spontaneously soluble, it is believed that the release kinetics, i.e. H. through the comparative faster solubility of the acid component, some kind of effect the tea contamination is achieved, which then leads to an improved Removability leads.
  • the dishwashing detergents to be used according to the invention are set so that that they have a pH between 8.5 in 1% by weight aqueous solution and 10.5, in particular 8.5 and 9.5.
  • the formulations according to the invention contain an essential component a builder component.
  • Dishwashing agents commonly used builders in question, especially water-soluble builder components, e.g. B. polymeric alkali phosphates, which in Form of their alkaline neutral or acidic sodium or potassium salts can be present.
  • water-soluble builder components e.g. B. polymeric alkali phosphates, which in Form of their alkaline neutral or acidic sodium or potassium salts can be present. Examples include: tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate and the corresponding potassium salts or Mixtures of sodium hexametaphosphate and the corresponding Potassium salts or mixtures of sodium and potassium salts.
  • the amounts of Phosphate is in the range of up to about 30 wt .-%, based on the total funds; the agents according to the invention are for ecological reasons but preferably free of such phosphates.
  • More possible Builder components are e.g. B. Native or organic polymers of synthetic origin, especially polycarboxylates, particularly in Hard water systems act as a co-builder. Consider, for example Polyacrylic acids and copolymers of maleic anhydride and acrylic acid as well as the sodium salts of these polymer acids. Commercial products are e.g. Sokalan® CP 5 and PA 30 from BASF, Alcosperse® 175 or 177 from Alco, LMW® 45 N and SPO2 N from Norsohaas.
  • About the native polymers include, for example, oxidized starch and polyamino acids such as Polyglutamic acid or polyaspartic acid, e.g. B. from the companies Cygnus or SRCHEM.
  • Crystalline layered silicates such as by Hoechst AG under the Trade names Na-SKS-6 distributed products come into question.
  • Further possible builder components are naturally occurring hydroxycarboxylic acids such as B. mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and Gluconic acid.
  • Preferred builder components are the salts of citric acid, especially trisodium citrate, either as the sole builder or can be used in a mixture with other builder substances.
  • the Salts of citric acid are preferably in an amount of 15 to 70% by weight, in particular 20 to 60, very particularly preferably 25 to 45% by weight, based on the total mean.
  • Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder be used.
  • trisodium citrate in a mixture with sodium or Potassium hydrogen carbonate used. It can be trisodium citrate, in particular in the form of the dihydrate, in amounts of 20 to 60 wt .-% with Sodium bicarbonate in amounts of 5 to 50 wt .-%, preferably of 20 to 40 wt .-%, are used, with up to 40 wt .-%, preferably from 5 to 10% by weight, sodium carbonate may be present.
  • the agents to be used according to the invention contain further mandatory ones Component is an oxygen-based bleach.
  • Usual bleach on Oxygen bases are, for example, sodium perborate mono- and tetrahydrate or Sodium percarbonate in an amount of up to 10 wt .-%, based on the entire means.
  • bleach activators such as PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine), ISA (isatoic anhydride) or N, N, N ', N'-tetraacetylethylenediamine (TAED) is possible in principle, but not necessary. This one Bleach activators will often favor silver corrosion preferably dispensed with them.
  • the agents to be used according to the invention can optionally also be added surfactants, in particular low-foaming nonionic surfactants, which serve to better detach fatty food residues, as wetting agents, as granulating aids or as dispersing aids for better, homogeneous distribution of the aforementioned silver corrosion inhibitors in the washing liquor and on the silver surfaces.
  • surfactants in particular low-foaming nonionic surfactants, which serve to better detach fatty food residues, as wetting agents, as granulating aids or as dispersing aids for better, homogeneous distribution of the aforementioned silver corrosion inhibitors in the washing liquor and on the silver surfaces.
  • Their amount is then preferably up to 10% by weight, in particular 0.5 to 5% by weight.
  • Extremely low-foam connections are usually used. These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene
  • low-foam nonionic surfactants such as.
  • B. 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-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14 alkyl polyglucosides with a degree of polymerization of about 1-4 (z. B. APG® 225 and APG® 600 from Henkel) and / or C 12 -C 14 alkyl polyethylene glycols with 3 - 8 ethylene oxide units in the molecule. Bleached quality should be used, otherwise brown granules will result.
  • the cleaning agents foam too much during use, them up to 6% by weight, preferably about 0.5 to 4% by weight of one foam-suppressing compound, preferably from the group of silicone oils, Mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols, Paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers added become.
  • foam-suppressing compound preferably from the group of silicone oils
  • silicone oils preferably from the group of silicone oils
  • the agents to be used according to the invention additionally contain the alkali carriers present in conventional machine dishwashing agents, such as. B. alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 30% by weight. %, based on the total, may be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably avoided.
  • the alkali carrier system preferably used in the agents to be used according to the invention is a mixture of essentially carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, in an amount of up to 60% by weight, preferably 10 to 40% by weight, based on the total Means, is included.
  • the ratio of carbonate and bicarbonate used varies; Usually, however, an excess of sodium hydrogen carbonate is used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • the dishwashing detergents according to the invention preferably enzymes such as Proteases, amylases, lipases, cutinases and cellulases in an amount of contain up to 5 wt .-%, preferably 1 to 3 wt .-%, for example Proteases such as BLAP® 140 from Henkel; Optimase® -M-440, Optimase®-M-330, Optidean® -M-375, Opticlean® -M-250 from Solvay Enzymes; Maxacal® CX 450,000, Maxapem® from 1bis; Savinase® 4.0 T, 6.0 T, 8.0 T from Novo; Esperase® T from Ibis and amylases such as Termamyl® 60 T, 90 T and Duramyl® from Novo; Amylase-LT® from Solvay Enzymes, Purafect OxAm® from Genencor or Maxamyl®
  • the dishwashing detergents to be used according to the invention are preferably located as powdery, granular or tablet-like preparations, which in themselves customary, for example by mixing, granulating, roller compacting and / or can be produced by spray drying.
  • the preparation of the preparations to be used according to the invention in tablet form is preferably carried out in such a way that all of the constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • conventional tablet presses for example eccentric presses or rotary presses
  • compression pressures in the range from 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • the agents to be used according to the invention can be used both in Household dishwashers as in commercial dishwashers be used. The addition is done by hand or with a suitable one Dosing devices.
  • the application concentrations in the cleaning liquor are about 2 to 8 g / l, preferably 2 to 5 g / l.
  • the rinse program is generally followed by some on the cleaning cycle following intermediate rinse cycles with clear water and a rinse cycle with supplemented with a common rinse aid and finished. After this Drying is not only a completely clean and hygienic one flawless crockery, but above all bright silver silver cutlery.
  • the agents to be used according to the invention can be used as further substances Corrosion protection agents, especially corrosion protection agents against the Silver corrosion included. Please refer to the relevant status of the Technology, for example on international application W094 / 26859 and on W095 / 10588. Nitrogen-containing agents are particularly preferred Substances. In a special embodiment, substances are made of the group of benzotriazoles and their derivatives. But also inorganic salts and complexes of manganese and cobalt and their related elements can be used in a preferred embodiment become.
  • agents used according to the invention can also be hydrotropic Contain substances if desired.
  • lime soap dispersants can be used in principle; however, this is only with high water hardness and higher amounts of lipase recommended.
  • Lime soap dispersants should be used in amounts of 1 to 10% by weight, preferably 2 to 4% by weight.
  • fatty alcohol ether sulfates such as C 16 -4EO sulfate, are suitable, but nonionic surfactants with a dispersing action.
  • Further lime soap dispersants are described in the aforementioned W094 / 07985.
  • the agents according to the invention contain oxygen-based bleaches, Chlorine- or hypochlorite-based bleaching agents can only be used if, then extremely small amounts are used.
  • teacups are prepared 25 times in one-minute intervals at 70 ° C Tea brew dipped. Then the cups are removed and with the opening down to dry on a tray.
  • lipase Lipomax® CXT 1000 was used from the company Gist Brocades, Delft, Netherlands
  • citric acid was used from the other hand, in the amounts mentioned under (3) below.
  • the teen note lies without lipase / citric acid or other additives in the pre-rinse cycle at 2 with the additives according to the invention [e.g. according to recipe (11.2)] in the pre-rinse cycle at 7.

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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)
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  • Health & Medical Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (10)

  1. Utilisation d'estérases, de préférence de lipases, dans ou conjointement avec des agents pour le lavage de la vaisselle en machine, qui présentent en solution à 1 % en poids un pH compris entre 8,5 et 10,5, qui renferment
    15 à 70 % en poids d'un composant adjuvant,
    0,5 à 20 % en poids d'un agent de blanchiment à base d'oxygène,
    ainsi que le cas échéant, des activateurs de blanchiment, des tensioactifs, des agents anti-corrosifs, des substances hydrotropes, des inhibiteurs de mousse et d'autres composants usuels des agents pour le lavage de la vaisselle,
    caractérisée en ce l'on met en oeuvre
    0,001 à 1,5 % en poids d'estérase,
    le cas échéant en association avec
    1 à 15 % en poids d'acides carboxyliques organiques polyfonctionnels, les agents faiblement alcalins étant activés après les estérases.
  2. Forme de réalisation selon la revendication 1, caractérisée en ce que les agents pour le lavage de la vaisselle en machine présentent un pH de 8,5 à 9,5 en solution aqueuse à 1 % en poids.
  3. Forme de réalisation selon une des revendications 1 ou 2, caractérisée en ce que l'on met en oeuvre comme composant adjuvant, des sels de l'acide citrique, le cas échéant en mélange avec de l'hydrogénocarbonate de sodium.
  4. Forme de réalisation selon une des revendications 1 à 3, caractérisée en ce que l'on met en oeuvre 20 à 60 % en poids de citrate trisodique (en particulier sous forme de dihydrate) conjointement avec 5 à 50 % en poids, de préférence 20 à 40 % en poids d'hydrogénocarbonate de sodium et jusqu'à 40 % en poids, de préférence 5 à 10 % en poids de carbonate de sodium.
  5. Forme de réalisation selon une des revendications 1 à 4, caractérisée en ce que l'on met en oeuvre en plus des tensioactifs, en particulier des surfactifs non ioniques, en proportions allant jusqu'à 10 % en poids, comprises de préférence entre 0,5 et 5 % en poids.
  6. Forme de réalisation selon la revendication 5, caractérisée en ce que l'on met en oeuvre des tensioactifs non ioniques peu moussants.
  7. Forme de réalisation selon n'importe laquelle des revendications 1 à 6, caractérisée en ce que l'on met en oeuvre comme autre enzyme, des amylases et/ou des protéases et/ou des cellulases.
  8. Forme de réalisation selon une des revendications 1 à 7 caractérisée en ce que l'on met en oeuvre dans un cycle de prélavage, des estérases, en particulier des lipases en association avec des acides carboxyliques de fonctionnalité plus élevée, de préférence de l'acide citrique et/ou de l'acide tartrique, et/ou avec des tensioactifs, de préférence des surfactifs non ioniques.
  9. Forme de réalisation selon la revendication 8, caractérisée en ce que l'on met en oeuvre comme autre enzyme dans le cycle de prélavage, des cellulases et/ou des protéases et/ou des amylases.
  10. Utilisation de lipases dans des agents pour le lavage de la vaisselle en machine, qui présentent en solution à 1 % en poids un pH compris entre 8,5 et 10,5, qui renferment 15 à 70 % en poids d'un composant adjuvant, 0,5 à 20 % en poids d'un agent de blanchiment à base d'oxygène, ainsi que le cas échéant, des activateurs de blanchiment, des tensioactifs, des agents anti-corrosifs, des substances hydrotropes, des inhibiteurs de mousse et d'autres composants usuels des agents pour le lavage de la vaisselle, caractérisée en ce l'on met en oeuvre 0,001 à 1,5 % en poids de lipase, le cas échéant en association avec 1 à 15 % en poids d'acides carboxyliques organiques polyfonctionnels pour l'élimination des salissures de thé, les agents faiblement alcalins étant mis en oeuvre en même temps que les estérases ou après celles-ci.
EP96930089A 1995-08-25 1996-08-23 Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine Expired - Lifetime EP0846155B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19531197A DE19531197A1 (de) 1995-08-25 1995-08-25 Verwendung von Lipasen in niederalkalischen Mitteln zum maschinellen Geschirrspülen
DE19531197 1995-08-25
DE19632283 1996-08-09
DE19632283A DE19632283A1 (de) 1995-08-25 1996-08-09 Verwendung von Lipasen in niederalkalischen Mitteln zum Vorspülen im Rahmen des maschinellen Geschirrspülens
PCT/EP1996/003727 WO1997008281A1 (fr) 1995-08-25 1996-08-23 Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine

Publications (2)

Publication Number Publication Date
EP0846155A2 EP0846155A2 (fr) 1998-06-10
EP0846155B1 true EP0846155B1 (fr) 2000-02-09

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EP (1) EP0846155B1 (fr)
AT (1) ATE189696T1 (fr)
ES (1) ES2143777T3 (fr)
WO (1) WO1997008281A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0525314D0 (en) * 2005-12-13 2006-01-18 Reckitt Benckiser Nv Method and composition
DE102011118037A1 (de) 2011-06-16 2012-12-20 Henkel Ag & Co. Kgaa Geschirrspülmittel mit Bleichkatalysator und Protease
EP3770240A1 (fr) 2019-07-22 2021-01-27 Henkel AG & Co. KGaA Lave-vaisselle pourvu de catalyseur de blanchiment et protéase de bacillus gibsonii

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007985A1 (fr) * 1992-09-25 1994-04-14 The Procter & Gamble Company Composition de detergent contenant un dispersant de savon de chaux et des lipases

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1767567A1 (de) * 1968-05-24 1971-09-09 Henkel & Cie Gmbh Geschirrspuelmittel
GB8629538D0 (en) * 1986-12-10 1987-01-21 Unilever Plc Enzymatic dishwashing & rinsing composition
AU655274B2 (en) * 1991-05-31 1994-12-15 Colgate-Palmolive Company, The Nonaqueous liquid, phosphate-free, improved automatic dishwashing composition containing enzymes
DE59208478D1 (de) * 1991-08-29 1997-06-19 Benckiser Gmbh Joh A Neutrales maschinelles Geschirrspülmittel
DE4232170C2 (de) * 1992-09-25 1999-09-16 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
WO1994025556A1 (fr) * 1993-04-27 1994-11-10 The Procter & Gamble Company Compositions de detergent liquide ou granulaire pour lave-vaisselle
EP0628625B1 (fr) * 1993-06-07 1999-05-06 The Procter & Gamble Company Protéase compatible avec lipase dans les compositions solides de blanchiment
ES2133775T3 (es) * 1994-06-23 1999-09-16 Unilever Nv Composiciones para el lavado de vajillas.
DE4437486A1 (de) * 1994-10-20 1996-04-25 Henkel Kgaa Kristalline Schichtsilikate in maschinellen Geschirrspülmitteln
CN1094516C (zh) * 1994-11-18 2002-11-20 普罗格特-甘布尔公司 含有特种脂解酶的洗涤剂组合物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007985A1 (fr) * 1992-09-25 1994-04-14 The Procter & Gamble Company Composition de detergent contenant un dispersant de savon de chaux et des lipases

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ES2143777T3 (es) 2000-05-16
EP0846155A2 (fr) 1998-06-10
WO1997008281A1 (fr) 1997-03-06

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