EP0891414B1 - PROCEDE POUR AJUSTER AUTOMATIQUEMENT LE pH D'UNE SOLUTION DE NETTOYANT AQUEUSE ET DETERGENTS SOLIDES CONVENANT A CET EFFET - Google Patents

PROCEDE POUR AJUSTER AUTOMATIQUEMENT LE pH D'UNE SOLUTION DE NETTOYANT AQUEUSE ET DETERGENTS SOLIDES CONVENANT A CET EFFET Download PDF

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Publication number
EP0891414B1
EP0891414B1 EP97914294A EP97914294A EP0891414B1 EP 0891414 B1 EP0891414 B1 EP 0891414B1 EP 97914294 A EP97914294 A EP 97914294A EP 97914294 A EP97914294 A EP 97914294A EP 0891414 B1 EP0891414 B1 EP 0891414B1
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EP
European Patent Office
Prior art keywords
acid
enzyme
surfactants
substrate
detergent
Prior art date
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EP97914294A
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German (de)
English (en)
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EP0891414A1 (fr
Inventor
Christian Nitsch
Karl-Heinz Maurer
Jürgen Härer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives 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
    • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase

Definitions

  • the invention relates to a method for automatically shifting the pH an aqueous treatment solution from acidic to alkaline that makes use of an enzymatic reaction.
  • the invention further relates to solid agents, especially detergents for such a method are suitable.
  • B. automatic dishwashing it has been shown that certain stains are better acidic than others be treated better in alkaline. It is generally possible while a cleaning process by adding alkalis the pH value shift from sour to alkaline, but this is with handling and dosing problems.
  • Tea stone is a complex, brown-colored soil from water hardness formers and coloring components of the tea. It has proven to be beneficial proven to remove tea stone by acid pretreatment.
  • the object of the invention is therefore to provide a method in which a aqueous treatment solution its pH value without replenishment of alkalis shifts from sour to alkaline, with the elaborate wrapping of individual components for the purpose of delayed release should be.
  • the invention thus relates to a method for automatic relocation the pH value of an aqueous detergent solution and a cleaning agent in solid form as set out in the claims.
  • the method according to the invention makes a shift in the pH to use an enzymatic reaction in an aqueous treatment solution.
  • Enzymatic reactions were chosen because they are used for cleaning operations interesting temperature and concentration range, Run substrate-specific and with sufficient speed.
  • Enzyme urease and used as substrate urea can be used here commercially available ureas as a pure protein or as a finished product can be present.
  • a preferred urease is, for example, a urease from "Jack Beans" which are commercially available from Sigma Chemicals is.
  • Such enzymes are made from microorganisms for industrial use or mushrooms, and in technically manageable granules or liquid concentrates assembled.
  • an initial pH value is established of not less than 4, preferably of> 4.3 should.
  • the starting pH can be adjusted using a buffer system or by adding the appropriate amount of an inorganic or organic Acid can be adjusted.
  • Suitable buffer systems are buffer systems based on weak organic or inorganic acids and their Salts.
  • a preferred buffer system is the citric acid / alkali citrate system its components also as builder components in cleaning agents for machine dishwashing is used.
  • decarboxylases can be used as enzymes especially oxaloacetate decarboxylase and oxalate decarboxylase are used and carboxylic acids as substrates, in particular also oxaloacetic acid and oxalic acid. It is also the case with these systems preferably starting from a pH value> 3, in particular> 4. Preferably the pH is adjusted here by using the enzyme substrate submitted and if necessary partially with alkali or ammonia or the like neutralized.
  • a Enzyme of the oxidase type e.g. oxalate oxidase
  • sets oxalic acid as the substrate or their salts e.g. oxalate oxidase
  • a pH value is preferably> 3, especially> 4.
  • this method variant has proven itself either with lime-free water to work or dispersants such as polycarboxylic acids or add detergent builder to prevent the precipitation of Counteract calcium oxalate.
  • the process according to the invention is preferably carried out at temperatures between 10 and 70 ° C performed. In individual cases, higher temperatures can also occur be applied briefly if this is the enzymes without denaturation survive. In particular, however, at temperatures between 20 and 60 ° C, worked with particular preference between 30 and 40 ° C. In particular takes advantage of the fact that the enzyme activity by heating of the non-preheated water gradually increases and the corresponding one This adjusts the pH value with the appropriate kinetics.
  • the method according to the invention is based on an acidic treatment solution the treatment solution can be strong or weak inorganic or organic acids are made acidic. At this Process variant becomes very rapid due to the enzymatic reaction Change in pH reached.
  • buffer solutions are particularly preferred use the components either as a substrate for the enzymatic Processes are suitable, or one in the sense of the treatment process have an independent effect.
  • buffer solutions z. B. from organic carboxylic acids and their Alkali or ammonium salts are built up.
  • decarboxylases it makes sense to use such acids by the decarboxylase to be attacked.
  • oxidases e.g. oxalate oxidase
  • a buffer system consisting of the substrate (e.g. oxalic acid) and its alkali salts proven.
  • oxaloacetate decarboxylase one works with Oxaloacetic acid and its salts.
  • the according to the invention Process should be influenced in its pH value, it has been proven citric acid and its alkali or ammonium salts to be used as a buffer system. Alkali salts are used here as well as in previous chapters preferred the sodium or potassium salts.
  • the detergent solution contains enzyme and enzyme substrate especially surfactants, often solubilizers, fragrances and dyes.
  • surfactants from the class of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and in particular Mixtures of the surfactant classes mentioned.
  • polymers or salts can also be added. It is usually preferred to store the detergent as a solid and to portion.
  • the solid preparation usually contains: 0.5 to 5 % By weight of enzymes, 2 to 25% by weight of enzyme substrate, 20 to 70% by weight of surfactant and as the remaining components salts, polymers, dyes, fragrances from 100 Wt .-%. In special cases, the other components may continue to be charged 20 to 40% by weight of an abrasive is present.
  • Anionic surfactants suitable for the purposes of the invention are in particular surfactants from the class of the sulfonates and sulfates. Suitable examples are alkylbenzenesulfonates with 5 to 15 carbon atoms in the alkyl radical and alphasulfonated fatty acid methyl esters whose fatty acid content has 6 to 18 carbon atoms. For the purposes of the invention, preference is given to alkyl sulfates having 6 to 18, in particular 8 to 10, carbon atoms in the alkyl radical. In general, it is preferred to use mixtures, in particular mixtures which differ with regard to the C chain lengths of the hydrophobic radical.
  • the alkyl sulfate to be used can be petrochemical in nature and oleochemical in nature.
  • Another important class of surfactants are alkyl ether sulfates with an alkyl chain length of C 8 to C 18, in particular C 10 to C 16 in the alkyl radical and a chain length of the ether unit derived from ethylene oxide of 1 to 10 ethylene oxide groups per alkyl radical.
  • the anionic surfactants mentioned are present at least in the alkaline range as a salt.
  • Suitable counterions are sodium, potassium, ammonium but also amines such as mono-, di- or triethanolamine.
  • surfactants suitable here are sarcosinates. These are, for example, the amides of amino acids with fatty acids, a C chain length of 8 to 18, in particular 10 to 14, to be used in the fatty acid portion.
  • sarcosinates are, for example, the amides of amino acids with fatty acids, a C chain length of 8 to 18, in particular 10 to 14, to be used in the fatty acid portion.
  • suitable anionic surfactants are the alkyl ester sulfate which can be prepared by reacting fatty acid esters, in particular fatty acid methyl esters, with SO 3 .
  • the alkyl ester sulfates mentioned can be present as such or in the form of the disalts of the alpha sulfo fatty acids.
  • Nonionic surfactants can also be used in the cleaning agents according to the invention.
  • An important class of nonionic surfactants are the reaction products of long-chain alkyl alcohols with 6 to 22 carbon atoms in the alkyl radical with ethylene oxide, propylene oxide or both. Preference is given to substances which are derived from alkyl alcohols of natural origin (fatty alcohols) and have a degree of ethoxylation of 3 to 100, in particular 3 to 20. For some problem solutions, it may be desirable to use non-ionic surfactants which are both ethoxylated and propoxylated and have a degree of ethoxylation of 5 to 30 and a degree of propoxylation of 1 to 10.
  • the long-chain alcohols to be used for the class of nonionic surfactants can, however, also be of synthetic origin, for example those such as are obtainable from Ziegler olefin oligomerization or from oxo synthesis. Ethoxylates of C 12 to C 15 alcohols of petrochemical origin or of coconut alcohol or palm kernel oil alcohol are preferred.
  • Another class of nonionic surfactants are the mono- and diethanolamides. Products with 8 to 12 carbon atoms in the fatty acid residue are preferred here.
  • Further suitable nonionic surfactants are the alkyl polyglucosides, these are acetals from long-chain alcohols, in particular alcohols with 8 to 18 carbon atoms and sugar.
  • Alkyl polyglycosides with a C chain length in the alkyl radical of 8 to 12 and a degree of oligomerization of 1.3 to 2.5, in particular 1.4 to 1.7, are preferred.
  • Other suitable nonionic surfactants are the fatty acid glucamides. These are amides from fatty acids with 8 to 22 carbon atoms and N-alkylamino sugars. Preferred among these are fatty acid methylglucamides having 6 to 14 carbon atoms in the fatty acid residue.
  • the person skilled in the art will ensure that the combination of anionic surfactants with certain nonionic surfactants, such as fatty acid alkanolamides, alkylglucosides or alkylglucamides, provides strongly foaming preparations, as is preferred for some applications, for example manual dishwashing.
  • nonionic surfactants such as fatty acid alkanolamides, alkylglucosides or alkylglucamides
  • surfactants are semi-polar surfactants.
  • these are for example, trialkylamine oxides with a long-chain radical are preferred.
  • substances with an alkyl radical with 6 to 20 carbon atoms and 2 short chain residue with 1 to 4 carbon atoms, which also carry a hydroxyl group can be used.
  • cationic surfactants can also be used.
  • cationic Surfactants are, for example, quaternary ammonium salts with a long chain Alkyl radical with 6 to 20, in particular 8 to 16 carbon atoms and 3 short-chain Residues with 1 to 3 carbon atoms, which are also substituted by a hydroxyl group can be preferred.
  • Hydrotropes are used. These are organic substances that have solubility convey other substances in water. Substances such as cumene sulfate should be mentioned here but also solvents such as ethanol, isopropanol, ethylene glycol, diethylene glycol and the same.
  • the product according to the invention is a cleaning agent with abrasive Abrasive materials can continue to be used.
  • suitable Abrasives can be soluble or non-soluble in nature.
  • Insoluble mica and certain silicates are preferred among the soluble ones can, for example, sodium bicarbonate, potassium sulfate or the like Salts are used.
  • Other salts used as adjusting agents in the invention Cleaners that can be present are sodium sulfate or magnesium salt have a beneficial effect on cleaning performance.
  • the cleaning agents according to the invention can also contain additives as subsequently preferred in the sense of the invention machine dishwashing detergents are common.
  • the invention relates to cleaning agents in solid form, especially for automatic dishwashing.
  • This detergent contain 2 to 30% by weight of enzyme and enzyme substrate, in the case of the urease / urea system 0.5 to 25% by weight. urea can be combined with 1.5 to 5% by weight urease.
  • Detergents for automatic dishwashing continue to contain 1 to 50% by weight of an organic polycarboxylic acid.
  • the person skilled in the art becomes a builder component here select that is not inherently strongly alkaline. Suitable here are, for example, organic polycarboxylic acids and their salts in particular those described above as a buffer or enzyme substrate Combinations.
  • the citric acid / alkali citrate system are used in particular is set so that the desired starting pH value is between 4 and just under 7 is reached.
  • the cleaning agents according to the invention contain then further ad 100 wt .-% at least one active ingredient selected from the group of oxygen bleaches, bleach activators, builders, surfactants and special active ingredients.
  • citrate soluble builders are used as monomeric polycarboxylates or polymeric carboxylates may be present.
  • borates and silicates are also present in small amounts, if they are sufficiently stable under the initial pH conditions.
  • Polymeric carboxylates are understood here to mean copolymers of polymerizable ones Mono- or dicarboxylic acids and their salts. Usually such polymers are made from acrylic acid, methacrylic acid, itaconic acid, Citraconic acid or crotonic acid, from maleic acid or fumaric acid and the anhydride of maleic acid.
  • the polymers mentioned can still further monomers contain, for example, acrylamide but also vinyl acetate which in particular in a further processing step to polyvinyl alcohol is hydrolyzed.
  • Suitable polymeric carboxylic acids have a molecular weight between 2000 and 70000, on the one hand products with are preferred a molecular weight in the range of 2000 to 5000 on the other hand with a molecular weight range of 20,000 to 70,000.
  • Mono- or polycarboxylic acids are used here as monomeric polycarboxylates generally no more than 10 carbon atoms and one to six carboxyl groups Roger that.
  • the monomeric polycarboxylates described below can according to desired pH as acids or as their alkali or Ammonium salts, especially sodium salts, are used. Are preferred mixtures of acids and salts.
  • Suitable monomeric polycarboxylates with an acid group are lactic acid and glycolic acid. Under substances with two acid groups are succinic acid, malonic acid, ethylenedioxyacetic acid, Maleic acid, fumaric acid, tartaric acid, tartronic acid too mention.
  • monomeric polycarboxylates with three acid groups in addition to citric acid, aconitic acid, citraconic acid and derivatives of Succinic acid such as carboxymethyloxisuccinate to mention, also lactoxysuccinate or 2-oxa 1,1,3-propane trycarboxylates.
  • monomers Polycarboxylates with four carboxyl groups are the oxidisuccinates that 1,1,2,2-ethane tetracarboxylates, the 1,1,3,3-propane tetracarboxylates and the Mention 1,1,2,3-propane tetracarboxylates.
  • carbocyclic or heterocyclic polycarboxylic acids are also used, for example the cyclopropane tetracarboxylic acid, the cyclopentadiene pentacarboxylic acid, the tetrahydrofuran tetracarboxylic acid and its homologues.
  • Aromatic polycarboxylic acids can be melitic acid, pyromelitic acid, phthalic acid and their isomers are used.
  • Preparations according to the invention for machine dishwashing can still contain a bleaching system.
  • Oxygen bleaches are suitable here.
  • hydrogen peroxide inclusion compounds are used.
  • the sodium salts and these are usually used Amounts of 1 to 40, in particular 5 to 20% by weight of the total preparation.
  • examples of inorganic peroxide salts are the perborates, percarbonates, Perphosphates, persulfates and persilicates.
  • the salts mentioned can be used as such are present in the preparation. However, it is in the sense of storage stability mostly preferred to apply them in an encased form.
  • a preferred in embodiment The invention uses perborates, in particular sodium perborate monohydrate or tetrahydrate.
  • sodium percarbonate a salt that is added to two molecules of sodium carbonate, contains three molecules of hydrogen peroxide.
  • Percarbonate is generally used in coated form used. Others are often used as wrapping agents Salts used for example borates but also soaps and the like. On another important salt is the potassium peroxomonopersulfate or the potassium or ammonium peroxydisulfate.
  • organic peracids can also be used, for example the diperoxidodecanedioic acid, the diperoxitetradecanoic acid, the diperoxihexadecanedioic acid and their homologues. Usually these peracids also used as salts, for example as alkali or magnesium salts.
  • the preparations according to the invention can furthermore contain bleach activators.
  • a preferred group of bleach activators are substances which react with the H 2 O 2 present in aqueous liquor after the persalts have been dissolved to give peracids.
  • Substances with N or O acyl groups are suitable here. Reference is made to the teaching of international application WO 95/12652, page 8, which contains a detailed compilation of suitable bleach activators of this type.
  • N, N, N-, N-, tetraacetylethylenediamine, the N-acylamides from Carprolacta or Valerolacta and their substitution products are particularly suitable here.
  • O-acyl compounds such as monobenzyl tetraacetyl glucose and anhydrides such as phthalic anhydride are also suitable.
  • Cationic peracid precursors such as are described, for example, in the international patent application cited above are also suitable.
  • the inventive agents for automatic dishwashing can also contain surfactants in quantities of 0.5 to 10% by weight. Suitable surfactants are listed in the previous chapter. For machine dishwashing purposes are anionic surfactants and low-foaming nonionic surfactants prefers.
  • a particularly suitable class of low foaming Surfactants are the end group-capped ethoxylated fatty alcohols. It these are compounds with a long-chain alkyl group of 8 to 18 carbon atoms, a hydrophilic chain derived from ethylene oxide and a locking group from 1 to 4 carbon atoms, the long-chain alkyl group also can have a hydroxyl group in the two position.
  • the preparations according to the invention for machine dishwashing can also contain special active ingredients, such.
  • Manganese (II) salts may be mentioned as special active ingredients, these serve to prevent the black coloring of silver and become generally in an amount of 0.01 to 4% by weight, in particular up to 1 % By weight and preferably 0.02 to 0.4% by weight.
  • Suitable manganese compounds are inorganic salts which can also be present as a hydrate.
  • complexing agents for heavy metals may also be present.
  • suitable Complexing agents are derivatives of iminoacetic acid such as 2-hydroxyethyliminodiacetic acid or gluceryliminodiacetic acid as well Ethylenediaminetetraacetic acid and the like. Organic ones are also suitable here Diphosphonic acids.
  • the preparations according to the invention can contain lime soap dispersants as further special active ingredients. It is preferred to choose surfactants that have the appropriate lime soap dispersing effect.
  • C 16 to C 18 dimethylamine oxides C 12 to C 18 alkyl ethoxysulfates with an average degree of ethoxylation of 1 to 5 are suitable, as are ethoxylated fatty alcohols with a degree of ethoxylation of around 12 or 30.
  • the preparations according to the invention can furthermore contain foam inhibitors contain. These are usually in an amount of 0.1 to 5 wt .-% used.
  • foam inhibitors can be used here are, for example, silicone-based or 2-alkylalkanol-based foam inhibitors or paraffin foam inhibitors.
  • Suitable other enzymes are amylases, lipases if appropriate but also cellulases, glutanases and optionally esterases or proteases. Among the above, proteases are less preferred because they sometimes attack other enzymes.
  • Amylases are alpha amylases, for example alpha Amylases from B. Lichiniformis used in an amount of 0.01 to 2 wt .-% can be.
  • Lipases can be, for example, lipases Pseudomonas pseudoalkaligenes can be used or lipases from Homikulalanigunosa.
  • a suitable enzyme of this type is sold under the brand name Lipolase marketed by Novo Nordisk.
  • Proteases can be found in Amounts of 0.005% by weight to 2% by weight of active enzyme are suitable here are serine proteases, especially subtilisin type serine proteases.
  • Proteases from Bacilus lentus, from Bacillus lichiniformis, are suitable here (Subtilisin Carlsberg) or Subtilisin BPN.
  • Suitable products are the Detergents and cleaning agents are known to those skilled in the art and are, for example marketed under the trade name Alkalase or Maxatase.
  • the automatic dishwashing detergents according to the invention can also Contain substances to prevent glass corrosion.
  • the preparations according to the invention can contain fluorides, for prevention of brown decor discoloration through the aforementioned manganese compounds but also for removing silicate deposits on glasses.
  • the preparations according to the invention can also be an organic redox system to prevent the discoloration of silver included.
  • Suitable here are organic, mostly heterocyclic compounds that also contain nitrogen and can contain sulfur.
  • a particularly preferred connection are benzotriazole and isocyanuric acid.
  • Other suitable connections are the amino acids cysteine and cystine.
  • Example 1 Urea urease on a laboratory scale
  • 30 ml of substrate solution are placed in a 50 ml beaker, tempered and adjusted to the required pH.
  • the reaction is started by adding the respective enzyme.
  • a significantly increasing enzyme activity can be achieved by increasing the temperature reach up to 50 ° C. At 60 ° C the same activity is shown as at 50 ° C.
  • Example 3 Oxaloacetic acid or oxaloacetate - oxaloacetate decarboxylase on a laboratory scale
  • the enzymatic decarboxylation of the oxaloacetate increases the present pH because a carboxyl group is broken down.
  • the reaction products are pyruvate and carbon dioxide, which for the most part escapes, the proportions of dissolved kohnen yarn do not have a great influence on the pH.
  • the decarboxylation of the unstable oxaloacetate described here also takes place spontaneously, especially at higher temperatures.
  • 30 ml of substrate solution are placed in a 50 ml beaker, tempered and adjusted to the required pH.
  • the reaction is started by adding the respective enzyme.
  • the standard concentration of 10 mM is used. A doubling Halving the substrate concentration shows no great effects.
  • Example 4 Oxalic acid or oxalate - oxalate decarboxylase on a laboratory scale
  • reaction products are formate and carbon dioxide. This reaction does not occur spontaneously, the oxalate is one significantly more stable compound than oxaloacetate.
  • 30 ml of substrate solution are placed in a 50 ml beaker, tempered and adjusted to the required pH.
  • the reaction is started by adding the respective enzyme.
  • the enzyme shows no activity at 65 ° C.
  • Example 5 pH shift and generation of hydrogen peroxide by oxalate / Oxalate oxidase
  • 30 ml of substrate solution are placed in a 50 ml beaker, tempered and adjusted to the required pH.
  • the reaction is started by adding the respective enzyme.
  • the concentration of hydrogen peroxide generated is determined by photometric determinations.
  • a hydrogen donor (4-aminophenanzone and chromotropic acid) produces a blue dye in the presence of peroxidase and hydrogen peroxide, the absorption maximum of which is 600 nm.
  • the detection reaction is started by adding the hydrogen peroxide.
  • the measurement takes place at 600 nm.
  • the evaluation takes place against a Calibration curve.
  • the standard solutions for this were determined potentiometrically.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Claims (15)

  1. Procédé d'ajustement automatique de la valeur du pH d'une solution aqueuse de produit de nettoyage allant de l'acide à l'alcalin,
    caractérisé en ce qu'
    on ajuste dans un jus aqueux la valeur de pH de départ acide désirée, on ajoute en même temps ou ensuite, un enzyme qui génère de l'ammoniac et/ou qui consomme un acide organique carboxylique et son substrat, après quoi on laisse se dérouler la réaction enzymatique jusqu'à l'obtention de la valeur de pH finale désirée.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on met en oeuvre comme enzyme de l'uréase et comme substrat de l'urée.
  3. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on met en oeuvre comme enzyme une dicarboxylase, et comme substrat un acide carboxylique, en particulier un acide dicarboxylique est présent.
  4. Procédé selon la revendication 1 ou 3,
    caractérisé en ce qu'
    on met en oeuvre comme enzyme une décarboxylase d'oxalacétate et comme substrat l'acide oxalacétique ou ses sels,
  5. Procédé selon la revendication 1 ou 3,
    caractérisé en ce qu'
    on met en oeuvre comme enzyme une décarboxylase d'oxalate et comme substrat de l'acide oxalique.
  6. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on met en oeuvre comme enzyme une oxydase et comme substrat de l'acide oxalique.
  7. Procédé selon les revendications 1 à 6,
    caractérisé en ce qu'
    on opère à des températures comprises entre 10 et 70°C.
  8. Procédé selon les revendications 1 à 7,
    caractérisé en ce qu'
    on met en oeuvre la valeur de pH acide à l'aide d'une solution tampon, en particulier à l'aide d'une solution tampon à base d'un acide carboxylique organique plurifonctionnel et de son sel de métal alcalin ou d'ammonium.
  9. Procédé selon les revendications 1 à 8,
    caractérisé en ce que
    la solution de traitement contient en outre un ou plusieurs additifs choisis dans le groupe des agents tensioactifs, des agents de structuration de produits de lavage, des agents de blanchiment, des activateurs de blanchiment, des enzymes comme des protéases, des lipases, des amylases, et des agents anti-mousse.
  10. Produit de nettoyage sous forme solide, en particulier pour le lavage de la vaisselle à la machine qui contient :
    de 2 à 30 % en poids d'enzyme qui génère de l'ammoniac et/ou qui consomme des acides carboxyliques et leur substrat d'enzyme,
    de 1 à 50 % en poids de mélange à base d'un acide polycarboxylique organique et de son sel, ainsi que
    qsp 100 % en poids d'au moins un principe actif choisi dans le groupe des agents blanchissants oxygénés, des agents de structuration d'activateur de blanchiment, des agents tensloactifs et des principes actifs spéciaux.
  11. Produit de nettoyage selon la revendication 10,
    caractérisé en ce qu'
    on met en oeuvre comme agent de blanchiment oxygéné, du tétrahydrate de perborate, du monohydrate de perborate, et/ou un percarbonate.
  12. Produit de nettoyage selon la revendication 10,
    caractérisé en ce qu'
    on met en oeuvre comme activateurs de blanchiment, des composés N-acylés et/ou O-acylés, de préférence des diamines N,N'-acylées comme la tétraacétyléthylène dlamine ou un acylcaprolactame.
  13. Produit de nettoyage selon la revendication 10,
    caractérisé en ce qu'
    on met en oeuvre comme agent de structuration supplémentaire, des polyphosphates de métal alcalin, en particulier du tripolyphosphate de sodium ou de potassium, un silicate de métal alcalin du type disilicate ou des agents de structuration insolubles comme de la zéolithe A.
  14. Produit de nettoyage selon la revendication 10,
    caractérisé en ce qu'
    on met en oeuvre comme agents tensioactifs, des agents tensloactifs anioniques, des agents tensioactifs non ioniques, ou des agents tensioactifs cationiques, parmi lesquels on préfère dans les produits pour le lavage de la vaisselle à la machine, des agents tensioactifs non ioniques faiblement moussants, et pour le lavage de la vaisselle à la main des mélanges fortement moussants à base d'agents tensioactifs anioniques, d'agents tensioactifs non ioniques et d'agents tensioactifs amphotères.
  15. Produit de nettoyage selon la revendications 10,
    caractérisé en ce qu'
    on met en oeuvre comme principes actifs spéciaux, d'autres enzymes, des parfums, des colorants, des agents anti-mousse, des agents stabilisants, des agents protecteurs de l'argent, et des agents protecteurs contre la corrosion.
EP97914294A 1996-03-30 1997-03-22 PROCEDE POUR AJUSTER AUTOMATIQUEMENT LE pH D'UNE SOLUTION DE NETTOYANT AQUEUSE ET DETERGENTS SOLIDES CONVENANT A CET EFFET Expired - Lifetime EP0891414B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19612866A DE19612866A1 (de) 1996-03-30 1996-03-30 Verfahren zur selbsttätigen Verlagerung des pH-Werts einer wäßrigen Behandlungslösung und dafür geeignete feste Reinigungsmittel
DE19612866 1996-03-30
PCT/EP1997/001470 WO1997036984A1 (fr) 1996-03-30 1997-03-22 PROCEDE POUR AJUSTER AUTOMATIQUEMENT LE pH D'UNE SOLUTION DE TRAITEMENT AQUEUSE ET DETERGENTS SOLIDES CONVENANT A CET EFFET

Publications (2)

Publication Number Publication Date
EP0891414A1 EP0891414A1 (fr) 1999-01-20
EP0891414B1 true EP0891414B1 (fr) 2002-02-13

Family

ID=7790060

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97914294A Expired - Lifetime EP0891414B1 (fr) 1996-03-30 1997-03-22 PROCEDE POUR AJUSTER AUTOMATIQUEMENT LE pH D'UNE SOLUTION DE NETTOYANT AQUEUSE ET DETERGENTS SOLIDES CONVENANT A CET EFFET

Country Status (5)

Country Link
EP (1) EP0891414B1 (fr)
AT (1) ATE213266T1 (fr)
DE (2) DE19612866A1 (fr)
ES (1) ES2172775T3 (fr)
WO (1) WO1997036984A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11214763B2 (en) 2018-01-26 2022-01-04 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier
US11377628B2 (en) 2018-01-26 2022-07-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
US11655436B2 (en) 2018-01-26 2023-05-23 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19860239C2 (de) * 1998-12-24 2000-11-30 Wella Ag Mittel und Verfahren zur schonenden dauerhaften Haarverformung mit Autostoppfunktion
US7415983B2 (en) 2003-12-18 2008-08-26 Ecolab Inc. Method of cleaning articles in a dish machine using an acidic detergent

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL20687C (fr) * 1926-08-17
US4002204A (en) * 1975-11-13 1977-01-11 Shell Oil Company Timing the deposition of an asphalt plugging material from an asphalt-cationic emulsion
DE2557623A1 (de) * 1975-12-20 1977-06-30 Henkel & Cie Gmbh Bleichendes wasch- und reinigungsmittel
DE3701098A1 (de) * 1987-01-16 1988-07-28 Beiersdorf Ag Haarfaerbemittel und verfahren zur haarfaerbung
EP0730641A1 (fr) * 1993-10-26 1996-09-11 Novo Nordisk A/S Peroxydase de myxococcaceae

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11214763B2 (en) 2018-01-26 2022-01-04 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier
US11377628B2 (en) 2018-01-26 2022-07-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
US11655436B2 (en) 2018-01-26 2023-05-23 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
US11834628B2 (en) 2018-01-26 2023-12-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
US11976255B2 (en) 2018-01-26 2024-05-07 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
US12006488B2 (en) 2018-01-26 2024-06-11 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier

Also Published As

Publication number Publication date
EP0891414A1 (fr) 1999-01-20
DE19612866A1 (de) 1997-10-30
DE59706388D1 (de) 2002-03-21
WO1997036984A1 (fr) 1997-10-09
ATE213266T1 (de) 2002-02-15
ES2172775T3 (es) 2002-10-01

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