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 lipases known per se in the context of low-alkaline agents for the automatic washing of dishes and as a means for supporting the bending systems for removing tea stains.
• Bleachable soiling is generally the case when washing dishes by machine at today's cleaning temperatures of approx. 55 ° to 65 ° C. easily removed. In the course of saving energy, dishwasher manufacturers are now starting to offer low-temperature cleaning programs with temperatures of around 40 ° C.
• Eliminate bleachable stains such as tea stains / tea deposits, coffee residues, dyes from vegetables, lipstick residues and the like.
• lipolytic enzymes in automatic dishwashing detergents is known per se. Those skilled in the art know that they are helpful in cleaving triglycerides and fatty ester contaminants.
• EP-B-271 155 teaches the use of lipases in dishwashing detergents and in rinse aids. It is stated there that the formation of films and stains is significantly reduced. The reduction in film formation here means the reduction in greasy films, not the reduction in tea deposits.
• European patent application 346 136 describes the reduction of stains and film formation by a special, genetically modified lipase.
• the present invention therefore relates to the use of esterases, preferably lipases, in or together with lower alkaline agents for automatic dishwashing, containing 15 to 70% by weight of a builder component, 0.5 to 20% by weight of an oxygen-based bleaching agent and, if desired Bleach activators, surfactants, corrosion inhibitors, hydrotropic substances, foam inhibitors and other components customary in machine dishwashing detergents, characterized in that 0.001 to 1.5% by weight of lipase, if desired in combination with 1 to 25% by weight of multifunctional, organic carboxylic acids, are used , whereby the lower alkaline agents are brought into effect simultaneously or after the esterases.
• esterases preferably lipases
• lower alkaline agents for automatic dishwashing containing 15 to 70% by weight of a builder component, 0.5 to 20% by weight of an oxygen-based bleaching agent and, if desired Bleach activators, surfactants, corrosion inhibitors, hydrotropic substances, foam inhibitors and other components customary in machine dishwashing detergents, characterized
• the active ingredient can be used in a variety of ways in a first cleaning step.
• the esterase can be washed in, spread on or sprayed on in dissolved form or as a suspension. It is also possible to immerse the hard surfaces to be cleaned for a certain time, which may depend on the effectiveness of the dosage form to leave and to increase the effectiveness of the esterases if necessary by acting and leaving standing. However, other common procedures for manual or machine pre-rinsing can also be used.
• the esterases used according to the invention can be used in a wide variety of dosage forms, v. a. Powders, blocks, tablets, compacts, granules, pastes, viscous liquids, and aqueous and non-aqueous solutions can be used. Granules and tablets are particularly preferred. However, they can also be used as components together with other substances in the dosage forms mentioned above.
• the lipases to be preferably used according to the invention are enzymes with lipolytic activity, such as are also used in detergents, for example.
• Preferred lipases are of bacterial origin and can be found, for example, in strains such as Humicola sp. or Thermomyces sp. or Pseudomonas pseudoalkaligenes or Pseudomonas fluorescens occur.
• Lipases which can be generated from basic enzymes by genetic modification can also be used. Lipase mixtures which also have enzymes which have both proteolytic and lipolytic activities are also suitable.
• lipases which are commercially available under the brand name Lipomax® CXT 1000 from Gist Brocades, or Lipolase® from Novo Nordisk (see EP 258 068). Also preferred is a lipase from Pseudomonos fluorescens, which can be obtained from Amano under the brand name Lipase P Amano.
• the agents according to the invention contain, apart from the lipase, a multifunctional, organic acid as an essential component.
• Suitable multifunctional, organic acids are primarily citric acid, but also tartaric acid and dicarboxylic acids with 3 to 8 carbon atoms.
• the multifunctional, organic acid is the agents according to the invention as such, i. H. not added in salt form. It is important to ensure that the organic acid as such, i.e. H. not in salt form. Since the dishwashing detergents to be used according to the invention are generally not spontaneously soluble, it is assumed that the kinetics of dissolution, i.e. H. due to the comparatively quicker solubility of the acid component, an effect of some kind on the soiling of tea is achieved, which then leads to improved removability.
• the dishwashing detergents to be used according to the invention are adjusted so that they have a pH value between 8.5 and 10.5, in particular 8.5 and 9.5, in 1% by weight aqueous solution.
• the preparations according to the invention contain a builder component as an essential component.
• builder components especially water-soluble builder components, e.g. B.
• polymeric alkali phosphates in the 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 are in the range of up to about 30% by weight, based on the total agent; for ecological reasons, however, the agents according to the invention are preferably free of such phosphates.
• Other possible builder components are e.g. B. organic polymers of native or synthetic origin, especially polycarboxylates, which act in particular in hard water systems as a co-builder.
• polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
• Commercial products include Sokalan® CP 5 and PA 30 from BASF, Alcosperse® 175 or 177 from Alco, LMW® 45 N and SPO2 N from Norsohaas.
• 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 and SRCHEM.
• Crystalline layered silicates such as the product sold by Hoechst AG under the trade name Na-SKS-6 are suitable.
• Other 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, in particular trisodium citrate, which can be used either as the sole builder substance or in a mixture with other builder substances.
• the salts of citric acid are preferably present 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 agent.
• Trisodium citrate anhydrous trisodium citrate or preferably trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
• trisodium citrate in a mixture with sodium or potassium hydrogen carbonate is used as the builder component.
• Trisodium citrate, in particular in the form of the dihydrate, in amounts of 20 to 60% by weight with sodium bicarbonate in amounts of 5 to 50% by weight, preferably 20 to 40% by weight, can be used, with up to 40 % By weight, preferably from 5 to 10% by weight, of sodium carbonate may be present.
• the agents to be used according to the invention contain an oxygen-based bleaching agent as a further mandatory component.
• Customary oxygen-based bleaching agents are, for example, sodium perborate mono- and tetrahydrate or sodium percarbonate in an amount of up to 10% by weight, based on the total agent.
• 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) in principle possible, but not necessary. Since these bleach activators often favor silver corrosion, they are preferably avoided.
• 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 ether, each with 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 ( e.g. 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.
• APG® 225 and APG® 600 from Henkel
• Bleached quality should be used, otherwise brown granules will result.
• the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
• a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
• Other optional additives are e.g. B. Perfume 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 agent, 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 up to 5% by weight, preferably 1 to 3% by weight, can be used to better remove protein, fat or starch-containing food residues.
• enzymes such as proteases, amylases, lipases, cutinases and cellulases in an amount of up to 5% by weight, preferably 1 to 3% by weight, can be used to better remove protein, fat or starch-containing food residues.
• proteases such as BLAP® 140 from Henkel; Optimase® -M-440, Optimase® - M-330, Opticlean® -M-375, Opticlean® -M-250 from Solvay Enzymes; Maxacal® CX 450,000, Maxapem® from Ibis; 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® P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipolase® 30 T from Firm Novo; Cellulases such as Celluzym® 0.7 T from Novo Nordisk.
• the dishwashing agents preferably contain proteases and / or amylases.
• the dishwashing detergents to be used according to the invention are preferably in the form of powdery, granular or tablet-like preparations which can be prepared in a conventional manner, for example by mixing, granulating, roller compacting and / or by spray drying.
• the preparation of the present invention applicable preparations in tablet form, the procedure is preferably such that mixing all ingredients together in a mixer and the mixture using conventional tablet presses, for example eccentric presses or rotary presses with press pressures in the range of 200 • 10 5 Pa to 1,500 ⁇ 10 5 Pa pressed. In this way, unbreakable tablets are obtained with a flexural strength of normally more than 150 N that are sufficiently quickly soluble under conditions of use.
• 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 and in commercial dishwashers. They are added by hand or using suitable 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 supplemented and ended with a few intermediate rinse cycles with clear water and a rinse cycle with a common rinse aid following the cleaning cycle. After drying, not only a completely clean and hygienically perfect tableware is obtained, but above all also bright silver parts.
• the agents to be used according to the invention can contain, as further substances, anti-corrosion agents, in particular anti-corrosion agents against silver corrosion.
• anti-corrosion agents in particular anti-corrosion agents against silver corrosion.
• Substances containing nitrogen are particularly preferred.
• substances from the group of benzotriazoles and their derivatives are contained. But also Inorganic salts and complexes of manganese and cobalt and their related elements can be used in a preferred embodiment.
• the agents used according to the invention can furthermore contain hydrotropic substances, if desired.
• Lime soap dispersants can also be used in principle; however, this is only recommended if the water hardness and lipase levels are high.
• 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 WO94 / 07985.
• the agents according to the invention contain bleaching agents based on oxygen, bleaching agents based on chlorine or hypochlorite, can, if then, only be used in extremely small amounts.
• 16 l of cold city water (16 ° d) are briefly heated to boiling in a water treatment boiler.
• 96 g of black tea are drawn in the nylon net with the lid closed for 5 minutes and the tea is transferred to a diving apparatus with heating and agitator.
• teacups are immersed 25 times in one-minute intervals at 70 ° C in the prepared tea infusion.
• the cups are then removed and placed on a tray with the opening facing down to dry.
• the following low-alkaline base product was first prepared, whose 1% by weight solution in distilled water gave a pH of 9.5:
• nonionic surfactants such as APG 225 (C 8 -C 10 alkyl oligoglucoside), Dehydol® LS2 (C 12 -C 14 fatty alcohol 2EO ethoxylate) and Dehypon LT 104 (butyl-locked C 12 -
• lipase Lipomax® CXT 1000 from Gist Brocades, Delft, The Netherlands was used
• citric acid in the amounts mentioned below were added in the pre-rinse cycle.
• non-ionic surfactants such as APG 225 (C 8 -C 10 alkyl oligoglucoside), Dehydol® LS2 (C 12 -C 14 - fatty alcohol 2EO ethoxylate) and Dehypon LT 104 (butyl-locked C 12 -C 18 - Fatty alcohol-10 EO ethoxylate).

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• Chemical & Material Sciences (AREA)
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• 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)

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• 1996
  • 1996-08-23 EP EP96930089A patent/EP0846155B1/fr not_active Expired - Lifetime
  • 1996-08-23 WO PCT/EP1996/003727 patent/WO1997008281A1/fr active IP Right Grant
  • 1996-08-23 ES ES96930089T patent/ES2143777T3/es not_active Expired - Lifetime
  • 1996-08-23 AT AT96930089T patent/ATE189696T1/de active

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