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WO1997036984A1 - PROCEDE POUR AJUSTER AUTOMATIQUEMENT LE pH D'UNE SOLUTION DE TRAITEMENT AQUEUSE ET DETERGENTS SOLIDES CONVENANT A CET EFFET - Google Patents

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

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Publication number
WO1997036984A1
WO1997036984A1 PCT/EP1997/001470 EP9701470W WO9736984A1 WO 1997036984 A1 WO1997036984 A1 WO 1997036984A1 EP 9701470 W EP9701470 W EP 9701470W WO 9736984 A1 WO9736984 A1 WO 9736984A1
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Prior art keywords
acid
surfactants
enzyme
substrate
treatment solution
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Application number
PCT/EP1997/001470
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German (de)
English (en)
Inventor
Christian Nitsch
Karl-Heinz Maurer
Jürgen Härer
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AT97914294T priority Critical patent/ATE213266T1/de
Priority to DE59706388T priority patent/DE59706388D1/de
Priority to EP97914294A priority patent/EP0891414B1/fr
Publication of WO1997036984A1 publication Critical patent/WO1997036984A1/fr

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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 of an aqueous treatment solution from acid to alkaline, which uses an enzymatic reaction.
  • the invention further relates to solid agents, in particular cleaning agents, which are suitable for such a method.
  • washing and cleaning processes can be carried out in the alkaline or neutral range, and special cleaning processes can also be carried out in acidic processes.
  • complex cleaning processes such.
  • B. machine dishwashing it has been shown that certain stains are treated better in acidic, others better in alkaline. It is generally possible to shift the pH from acid to alkaline during the cleaning process by adding alkalis, but this is associated with handling and metering problems.
  • cleaning processes in closed devices e.g. B. Household dishwashing machines would also require additional technical changes.
  • the manufacturer of cleaning agents has the task of providing products which are automatically subject to a pH shift in aqueous solution.
  • Tea stone is a complex, brown-colored soil composed of water hardness formers and coloring components of the tea. It has proven advantageous to remove tea stone by an acidic pretreatment.
  • the invention thus provides a process for the automatic relocation 'tion of the pH of an aqueous treatment solution of the AI Sauern quay, characterized in that the desired acidic starting pH is set in an aqueous liquor, an ammonia-generating and / or an organic-carboxylic acid-consuming enzyme and its substrate are added simultaneously or subsequently, and the enzymatic reaction is then carried out runs to achieve the desired final pH.
  • the invention furthermore relates to a cleaning agent in solid form
  • the method according to the invention makes use of an enzymatic reaction to shift the pH of an aqueous treatment solution. Enzymatic reactions were selected because they run safely, substrate-specifically and with sufficient speed in the temperature and concentration range of interest for cleaning operations.
  • urease is used as the enzyme and urea as the substrate.
  • Commercial ureas that can be present as pure protein or as a finished product can be used here.
  • a preferred urease is, for example, a urease from "Jack Beans” that is commercially available from Sigma Chemicals.
  • such enzymes are made from microorganisms or mushrooms, and made into technically manageable granules or liquid concentrates.
  • an initial pH of not less than 4, preferably> 4.3 should be set.
  • the starting pH can be adjusted by using a buffer system or by adding the appropriate amount of an inorganic or organic acid.
  • 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, the components of which are also used as builder components in cleaning agents for automatic dishwashing.
  • decarboxylases in particular oxaloacetate decarboxylase and oxalate decarboxylase, can be used as enzymes and carboxylic acids, in particular also oxaloacetic acid and oxalic acid, can be used as substrates.
  • carboxylic acids in particular also oxaloacetic acid and oxalic acid
  • the pH value is preferably adjusted here by introducing the enzyme substrate and, if desired, partially neutralizing it with alkali metal hydroxide solution or ammonia or the like.
  • an enzyme of the oxidase type (for example oxalate oxidase) is used and oxalic acid or its salts are used as the substrate.
  • a pH value> 3, in particular> 4 is preferably assumed. It is advisable to adjust this pH with the help of oxalic acid and its alkali or ammonium salts.
  • this method variant has proven itself either with to work lime-free water or to add dispersants such as polycarboxylic acids or detergent builders to counteract the precipitation of calcium oxalate.
  • the process according to the invention is preferably carried out at temperatures between 10 and 70 ° C. In individual cases, higher temperatures can also be used for a short time if the enzymes survive without denaturation. In particular, however, work is carried out at temperatures between 20 and 60 ° C, with particular preference between 30 and 40 ° C. In particular, the fact is exploited that the enzyme activity gradually increases due to the heating of the non-preheated water and the corresponding pH value is hereby adjusted with appropriate kinetics.
  • the process according to the invention is based on an acidic treatment solution.
  • the treatment solution can be made acidic on the one hand with strong or weak inorganic or organic acids.
  • the enzymatic reaction results in a very rapid change in the pH.
  • buffer solutions known to the chemist, which allow a pH value between approx. 3 and below 7, can be used here.
  • buffer solutions whose constituents are either suitable as substrates for the enzymatic process or which have an independent effect in the sense of the treatment process.
  • the buffer solutions z. B. from organic carboxylic acids and their alkali or ammonium salts.
  • decarboxylates it makes sense to use those acids which are attacked by the decarboxylase.
  • oxidases eg oxalate oxidase
  • oxaloacetate decarboxylase one works with oxaloacetic acid and its salts.
  • the treatment solution whose pH is to be influenced by the method according to the invention is a cleaning solution
  • citric acid and its alkali metal or ammonium salts as a buffer system.
  • the sodium or potassium salts are preferred among alkali salts.
  • the method according to the invention is suitable for influencing the pH of a large number of treatment solutions.
  • this treatment solution contains a dye which is readily soluble in acid and irreversibly absorbs on fibers, synthetic fibers, cotton, wool or even hair in alkaline.
  • Suitable here are, for example, azo dyes with trialkylamonium groups or other dye systems which are known to the person skilled in the art and which have ammonium, sulfonium or phosphonium groups.
  • the treatment solution according to the invention to be influenced in pH is a cleaning solution.
  • the treatment solution contains, in addition to enzyme and enzyme substrate, above all surfactants, often also solubilizers, fragrances and dyes.
  • Suitable surfactants from the class of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and in particular mixtures of the surfactant classes mentioned are suitable.
  • Polymers or salts can also be added as further constituents for thickening. It is usually preferred to store and portion the detergent as a solid.
  • 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 the remaining constituents are salts, polymers, dyes, fragrances from 100% by weight. -%. In special cases, 20 to 40% by weight of an abrasive material may still be present at the expense of the other constituents.
  • 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 alpha-sulfonated 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. 9
  • 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 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 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.
  • alkyl polyglucosides 3 This acetals from long-chain alcohols, in particular alcohols with 8 to 18 carbon atoms and sugar, where these sugar residues can be monomeric or oligomeric bound to one another via an acetal bond.
  • 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.
  • fatty acid methylglucamides having 6 to 14 carbon atoms in the fatty acid residue.
  • anionic surfactants such as fatty acid alkanolamides, alkyl glucosides or alkyl glucamides, provides foaming preparations such as that for some applications, for example manual dishwashing is.
  • surfactants are semi-polar surfactants.
  • semi-polar surfactants for example, trialkylamine oxides with a long chain residue are preferred.
  • substances with an alkyl radical with 6 to 20 C atoms and 2 short-chain radicals with 1 to 4 C atoms, which can also carry a hydroxyl group, can be used here.
  • cationic surfactants can also be used.
  • cationic surfactants for example, quaternary ammonium salts having a long-chain alkyl radical having 6 to 20, in particular 8 to 16, carbon atoms and 3 short-chain radicals having 1 to 3 carbon atoms, which can also be substituted by a hydroxyl group, are preferred.
  • hydrotropes can still be used.
  • organic substances that impart the solubility of other substances in water.
  • Substances such as cumene sulfate, but also solvents such as ethanol, isopropanol, ethylene glycol, ethylene glycol and the like are mentioned here.
  • abrasive substances can also be used.
  • Suitable abrasives can be soluble or non-soluble in nature.
  • mica and certain silicates are preferred among the soluble ones, for example sodium bicarbonate, potassium sulfate or similar salts.
  • Other salts which can be present as adjusting agents in the cleaners according to the invention are sodium sulfate or magnesium salt which have the advantageous effect on the cleaning performance to have.
  • the cleaning agents according to the invention can also contain additives as are customary below for machine dishwashing detergents which are particularly preferred in the sense of the invention.
  • a particularly preferred object of the invention are cleaning agents in solid form, in particular for automatic dishwashing.
  • These cleaning agents necessarily contain 2 to 30% by weight of enzyme and enzyme substrate, and 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.
  • the cleaning agents according to the invention for machine dishwashing further contain 1 to 50% by weight of a builder component.
  • a builder component here which is not inherently strongly alkaline.
  • organic polycarboxylic acids and their salts are particularly suitable here. in particular the combinations described above as buffers or enzyme substrates.
  • the citric acid / alkali citrate system can be used, which is adjusted in particular in such a way that the desired starting pH value between 4 and just under 7 is reached.
  • the cleaning agents according to the invention then further contain at least 100% by weight of at least one active ingredient selected from the group consisting of oxygen bleaches, bleach activators, builders, surfactants and special active ingredients.
  • soluble builders are used as builders in the cleaning agents according to the invention for machine dishwashing, which builders can be present as monomeric polycarbonate or polymeric carboxylates.
  • alkali phosphates, borates and silicates can also be present in small amounts if these are sufficiently stable under the initial pH conditions.
  • Polymeric carboxylates are understood here to mean copolymers of polymerizable mono- or dicarboxylic acids and their salts. Such polymers are usually produced 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 may also contain further monomers, for example acrylamide, but also vinyl acetate, which is hydrolyzed in particular in a further processing step to give polyvinyl alcohol.
  • Suitable polymeric carboxylic acids have a molecular weight between 2000 and 70,000, on the one hand products with a molecular weight in the range from 2000 to 5000 are preferred on the other hand those with a molecular weight range from 20,000 to 70,000.
  • Monomeric polycarboxylates are understood here to mean mono- or polycarboxylic acids with generally no more than 10 carbon atoms and one to six carboxyl groups.
  • the monomeric polycarboxylates described below can be used as acids or as their alkali or ammonium salts, in particular sodium salts, according to the desired pH. The mixtures of the acids and the salts are preferred.
  • Suitable monomeric polycarboxylates with an acid group are lactic acid and glycolic acid.
  • succinic acid malonic acid, ethylene dioxide acetic acid, maleic acid, fumaric acid, tartaric acid, tartronic acid
  • monomeric polycarboxylates with three acid groups in addition to citric acid, aconitic acid, citraconic acid and derivatives of succinic acid such as carboxymethyloxisuccinate, lac- toxysuccinate or 2-oxa 1, 1,3-propanetrycarboxylate should also be mentioned.
  • polycarboxylates with four carboxyl groups the oxidisuccinates, the 1, 1, 2,2-ethane tetracarboxylates, the 1,1, 3,3-propane tetracarboxylates and the 1, 1, 2,3-propane tetracarboxylates are to be mentioned.
  • carbocyclic or heterocyclic polycarboxylic acids can also be used, for example cyclopropantetracarboxylic acid, cyclopentadiene pentacarboxylic acid, tetrahydrofuran tetracarboxylic acid and their homologues.
  • Aromatic polycarboxylic acids, melitic acid, pyromelitic acid, phthalic acid and their isomers can be used.
  • Preparations according to the invention for machine dishwashing can furthermore contain a bleaching system.
  • Oxygen bleaching agents are suitable here.
  • hydrogen peroxide inclusion compounds are used.
  • the sodium salts are usually used, and these in 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 present as such in the preparation. In terms of storage stability, however, it is usually preferred to apply it in an encased form.
  • a preferred embodiment of the invention uses perborates, in particular sodium perborate monohydrate or tetrahydrate.
  • sodium percarbonate a salt that contains three molecules of hydrogen peroxide per two molecules of sodium carbonate.
  • Percarbonate is generally used in a coated form.
  • Other salts are often used as coating agents here, for example borates but also soaps and the like.
  • Another important salt is the potassium peroxomonopersulfate or the potassium or ammonium peroxidisulfate.
  • organic peracids for example diperoxidodecanedioic acid, diperoxitetradecanoic acid, diperoxyhexadecanedioic acid and their homologs. These peracids are usually 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 are also suitable IH as described for example in the international patent application cited above.
  • the detergents according to the invention for machine dishwashing can also contain surfactants in amounts of 0.5 to 10% by weight. Suitable surfactants are listed in the previous chapter. Anionic surfactants and low-foaming nonionic surfactants are preferred for the purposes of machine dishwashing.
  • a particularly suitable class of low-foaming surfactants are the end group-capped ethoxylated fatty alcohols. These are compounds with a long-chain alkyl group of 8 to 18 carbon atoms, a hydrophilic chain derived from ethylene oxide and a closing group of 1 to 4 carbon atoms, the long-chain alkyl group also being able to have a hydroxyl group in two positions.
  • the preparations according to the invention for machine dishwashing can furthermore contain special active ingredients, for. B. enzymes, fragrances, dyes, foam inhibitors, stabilizers, silver preservatives, corrosion protection agents and the like.
  • Manganese (II) salts for example, are to be mentioned as special active substances, these serve to prevent the black coloring of silver and are generally used in an amount of 0.01 to 4% by weight, in particular up to 1% by weight and preferably 0.02 up to 0.4 wt .-% used.
  • Suitable man- Goan compounds are inorganic salts which can also be present as a hydrate.
  • Manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate or manganese chloride should be mentioned. Salts of manganese complexes, in particular salts of chelate complexes with more than one electron donor atom in the molecule, can also be used.
  • Complexing agents for heavy metals can also be contained in the preparations according to the invention as further special active ingredients.
  • Suitable complexing agents are derivatives of iminoacetic acid such as 2-hydroxyethyliminodiacetic acid or gluceryliminodiacetic acid, but also ethylenediaminetetraacetic acid and the like.
  • Organic diphosphonic acids are also suitable here.
  • 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; suitable here are C 16 to C 18 dimethylamine oxides C 12 to C 18 alkyl ethoxysulfates with an average degree of ethoxylation of 1 to 5 as well as ethoxylated fatty alcohols with a degree of ethoxylation around 12 or around 30.
  • the preparations according to the invention can furthermore contain foam inhibitors. These are usually used in an amount of 0.1 to 5% by weight.
  • foam inhibitors can be used here, for example foam inhibitors based on silicone or based on 2-alkylalkanol or paraffin foam inhibitors.
  • Copolymers of ethylene oxide and propylene oxide, for example ethoxylated-propoxylated fatty alcohols with an alkyl chain length of 10 to 16 carbon atoms can also be used here. Atoms and a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.
  • alpha amylases are preferably, for example, alpha amylases from B. Lichiniformis which can be used in an amount of 0.01 to 2% by weight. Lipases from Pseudomonas pseudoalkaligenes or lipases from homiculananigunosa, for example, can be used as lipiases.
  • a suitable enzyme of this type is marketed by Novo Nordisk under the brand name Lipolase.
  • Proteases can be used in amounts of 0.005% by weight to 2% by weight of active enzyme.
  • Serine proteases in particular serine proteases of the subtilisin type, are suitable here.
  • Suitable products are known to the person skilled in the art of detergents and cleaning agents and are commercially available, for example, under the trade names Alkalase or Maxatase.
  • the automatic dishwashing detergents according to the invention can furthermore contain substances for preventing glass corrosion.
  • Inorganic zinc compounds which are used as water-soluble zinc salts or insoluble as zinc oxide or zinc hydroxide are suitable here, for example.
  • the preparations according to the invention can furthermore contain fluorides, for preventing 1? Change of brown decor discoloration through the aforementioned manganese compounds but also to remove silicate deposits on glasses.
  • the preparations according to the invention can furthermore contain an organic redox system to prevent the discoloration of silver.
  • Organic mostly heterocyclic compounds which can also contain nitrogen and sulfur are suitable here.
  • a particularly preferred compound are benzotriazole and isocyanuric acid.
  • Other suitable compounds are the amino acids system and cystine.
  • Example 1 Urea urease on a laboratory scale
  • a significantly increasing enzyme activity can be achieved by increasing the temperature up to 50 ° C. At 60 ° C there is approximately the same activity as at 50 ° C.
  • the example of a 50 mM urea (3 g / l) and 0.8 g urease (0.16 g / l) was used to test the pH shift in a commercially available dishwasher.
  • the starting pH of 4.5 was set with a 20 mM citric acid.
  • the enzymes were added at about 25 ° C. after the pre-rinse was complete.
  • the dishwasher was a Miele G 590.
  • the program was set to 65 ° C universal program. With normal loading, the program reached the target temperature of 64 ° C. within 15 minutes and held the temperature for a further 8 minutes until the end of the cleaning cycle.
  • 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.
  • Example 4 Oxalic acid or oxalate - oxalate decarboxylase on a laboratory scale 2 *
  • reaction products are formate and carbon dioxide. This reaction does not proceed spontaneously, the oxalate is a significantly more stable compound than the oxaloacetate.
  • the enzyme shows no activity at 65 ° C. Units of oxalate decarboxylase
  • Example 5 pH shift and generation of hydrogen peroxide by oxalate / oxalate oxidase
  • 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.
  • Preparation of the peroxide reagent 75 mM KH2PO4 125 mM NaH2PO4 x H2O 10 mM chromotropic acid 0.5 mM 4-aminophenanzone
  • the test approach includes:
  • the detection reaction is started by adding the hydrogen peroxide.
  • the measurement is carried out at 600 nm.
  • the evaluation is carried out against a calibration curve.
  • the standard solutions for this were determined potentiometrically.

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Abstract

Dans une solution de traitement aqueuse, le pH devrait automatiquement passer de la zone acide à la zone basique. Pour cela, on règle un bain sur le pH acide de départ désiré, on ajoute simultanément ou ultérieurement une enzyme générant de l'ammoniac et/ou consommant de l'acide carboxilique organique, et son substrat, puis on laisse la réaction enzymatique se poursuivre jusqu'au moment où le pH final désiré est atteint.
PCT/EP1997/001470 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 WO1997036984A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT97914294T ATE213266T1 (de) 1996-03-30 1997-03-22 Verfahren zur selbsttätigen verlagerung des ph- werts einer wässrigen reinigungsmittellösung und dafür geeignete feste reinigungsmittel
DE59706388T DE59706388D1 (de) 1996-03-30 1997-03-22 VERFAHREN ZUR SELBSTTÄTIGEN VERLAGERUNG DES pH-WERTS EINER WÄSSRIGEN REINIGUNGSMITTELLÖSUNG UND DAFÜR GEEIGNETE FESTE REINIGUNGSMITTEL
EP97914294A 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

Applications Claiming Priority (2)

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
DE19612866.8 1996-03-30

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WO1997036984A1 true WO1997036984A1 (fr) 1997-10-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7415983B2 (en) 2003-12-18 2008-08-26 Ecolab Inc. Method of cleaning articles in a dish machine using an acidic detergent

Families Citing this family (4)

* 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
WO2019148071A1 (fr) 2018-01-26 2019-08-01 Ecolab Usa Inc. Tensioactifs anioniques liquides solidifiants
MX2020007859A (es) 2018-01-26 2020-09-18 Ecolab Usa Inc Solidificacion de tensioactivos de oxido de amina, betaina y/o sultaina liquidos con un aglutinante y un portador opcional.
JP7485605B2 (ja) 2018-01-26 2024-05-16 エコラボ ユーエスエー インコーポレイティド 担体を用いる、液体アミンオキシド、ベタイン、および／またはスルタイン界面活性剤の固化

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR639378A (fr) * 1926-08-17 1928-06-20 Henkel & Cie Gmbh Procédé de lavage à des températures basses
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
EP0274701A2 (fr) * 1987-01-16 1988-07-20 HANS SCHWARZKOPF GmbH Composition et méthode de teinture des cheveux
WO1995011964A1 (fr) * 1993-10-26 1995-05-04 Novo Nordisk A/S Peroxydase de myxococcaceae

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR639378A (fr) * 1926-08-17 1928-06-20 Henkel & Cie Gmbh Procédé de lavage à des températures basses
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
EP0274701A2 (fr) * 1987-01-16 1988-07-20 HANS SCHWARZKOPF GmbH Composition et méthode de teinture des cheveux
WO1995011964A1 (fr) * 1993-10-26 1995-05-04 Novo Nordisk A/S Peroxydase de myxococcaceae

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7415983B2 (en) 2003-12-18 2008-08-26 Ecolab Inc. Method of cleaning articles in a dish machine using an acidic detergent

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DE19612866A1 (de) 1997-10-30
DE59706388D1 (de) 2002-03-21
EP0891414A1 (fr) 1999-01-20
ES2172775T3 (es) 2002-10-01
ATE213266T1 (de) 2002-02-15
EP0891414B1 (fr) 2002-02-13

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