EP0845524A2 - Utilisation de tungstates et de molybdates pour améliorer les performances de blanchiment - Google Patents

Utilisation de tungstates et de molybdates pour améliorer les performances de blanchiment Download PDF

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Publication number
EP0845524A2
EP0845524A2 EP97120141A EP97120141A EP0845524A2 EP 0845524 A2 EP0845524 A2 EP 0845524A2 EP 97120141 A EP97120141 A EP 97120141A EP 97120141 A EP97120141 A EP 97120141A EP 0845524 A2 EP0845524 A2 EP 0845524A2
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EP
European Patent Office
Prior art keywords
weight
molybdate
cleaning
ammonium tungstate
alkali
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.)
Withdrawn
Application number
EP97120141A
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German (de)
English (en)
Other versions
EP0845524A3 (fr
Inventor
Helmut Dipl.-Ing. Blum
Christian Dr. Dipl.-Chem. Nitsch
Siglinde Chem.-Ab. Erpenbach
Peter Dr. Dipl.-Chem. Jeschke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0845524A2 publication Critical patent/EP0845524A2/fr
Publication of EP0845524A3 publication Critical patent/EP0845524A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to the use of tungstates and molybdate to enhance the bleaching effect of, in particular, inorganic peroxygen compounds when bleaching colored stains on hard Surfaces, and cleaning agents for hard surfaces, the tungstates or Molybdate included.
  • Inorganic peroxygen compounds especially hydrogen peroxide and solid peroxygen compounds, which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
  • the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic anhydrides, especially phthalic acid anhydride.
  • Carboxylic acid esters in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxybenzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose, have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.
  • the present invention has the improvement of the oxidation and bleaching effect of inorganic Peroxygen compounds at low temperatures below 80 ° C, especially in the temperature range of approx. 15 ° C to 45 ° C.
  • the invention relates to the use of alkali metal or ammonium tungstate and / or molybdate as an activator for in particular inorganic peroxygen compounds in aqueous cleaning solutions for hard surfaces, in particular for dishes.
  • the ammonium salts include those with the cation N + R 1 R 2 R 3 R 4 , in which R 1 to R 4 are independently hydrogen or a C 1-3 alkyl radical.
  • the alkali salts which can be used include in particular the sodium, potassium and lithium salts of tungstic acid and molybdic acid, alone or in mixtures.
  • bleaching refers to both the bleaching of itself on the hard Dirt, especially tea, as well as bleaching in the surface Dirt detached from the hard surface Understood.
  • the invention further relates to a method for cleaning hard surfaces, in particular of dishes using aqueous, optionally further detergent components, in particular oxidizing agents based on peroxygen, containing solution, and cleaning agents for hard surfaces, in particular cleaning agents for dishes and among these preferably those for use in mechanical cleaning processes which contain alkali metal or ammonium tungstate and / or - contain molybdate in combination with polycarboxylate and / or enzyme.
  • the use according to the invention consists essentially in the presence of a hard surface contaminated with colored stains create, among which a peroxidic oxidizing agent and the monomeric tungstates and / or molybdates can react with one another with the aim of being more oxidizing to obtain effective secondary products.
  • a peroxidic oxidizing agent and the monomeric tungstates and / or molybdates can react with one another with the aim of being more oxidizing to obtain effective secondary products.
  • Such conditions exist in particular when the reactants meet in aqueous solution. This can be done through separate Add the peroxygen compound and the tungstate and / or molybdate a solution containing detergent if necessary.
  • the method according to the invention is performed using an inventive method Detergent for hard surfaces, the alkali or Ammonium tungstate and / or molybdate in combination with polycarboxylate and / or Enzyme and optionally contains an oxidizing agent containing peroxy.
  • the peroxygen compound can also be separate, in bulk or as preferred aqueous solution or suspension, added to the solution if a peroxide-free Detergent is used.
  • the conditions can be varied widely depending on the intended use. So come in addition to purely aqueous solutions, also mixtures of water and suitable organic Solvents as a reaction medium in question.
  • the quantities of peroxygen compounds used are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm Active oxygen is present.
  • the amount of bleach enhancer used Tungsten or molybdate depends on the application. Depending on what you want Degree of activation, it is used in such amounts that 0.00001 mol to 0.5 mol, preferably 0.0001 mol to 0.2 mol of tungstate or molybdate per mole of peroxygen compound can be used, but in special cases these limits are also exceeded or undershot.
  • Cleaning agents according to the invention preferably contain 0.005% by weight to 5% by weight, in particular 0.05% by weight to 2% by weight of alkali metal or ammonium tungstate and / or molybdate in combination with 0.5% by weight to 60% by weight, in particular 1% by weight to 50 wt .-% monomeric and / or polymeric polycarboxylate and / or 0.01 wt .-% to 15% by weight, in particular 0.05% by weight to 10% by weight, of enzyme, in particular protease, Lipase and / or amylase.
  • the cleaning agents according to the invention in the form of granules, in powder or tablet form Solids, as other shaped bodies, homogeneous solutions or suspensions are present can, in addition to the combination mentioned, in principle all known and in such Contain common ingredients.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, contain additional peroxygen activators as well as colors and fragrances.
  • a cleaning agent for hard surfaces according to the invention can also abrasive components, in particular from the group comprising quartz flours, Wood flour. Plastic flours, chalks and micro glass balls and their mixtures, contain. Abrasives are preferred in the cleaning agents according to the invention do not contain more than 20% by weight, in particular from 5% by weight to 15% by weight.
  • Another object of the invention is a means for machine cleaning Tableware containing 15% to 65% by weight, in particular 20% to 60% by weight water-soluble builder component, 5% by weight to 25% by weight, in particular 8% by weight up to 17% by weight of bleaching agent based on oxygen, in each case based on the total agent, and 0.01 wt .-% to 5 wt .-% tungsten and / or molybdate contains, wherein at water-soluble builder also in combination with the tungstate and / or molybdate contained polycarboxylates.
  • Such a means is particular lower alkaline, i.e. its 1% by weight solution has a pH of 8 to 11.5, preferably 9 to 11.
  • alkali phosphates in the form their alkaline, neutral or acidic sodium or potassium salts may be present.
  • Examples include trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate and the corresponding potassium salts or mixtures from sodium and potassium salts. Their amounts can range up to about 60 wt .-%, in particular 5 wt .-% to 20 wt .-%, based on the total agent.
  • Other possible water-soluble builder components are polyphosphonates and phosphonate alkyl carboxylates, for example, organic polymers native or synthetic Origin of the type of polycarboxylates, particularly in hard water regions act as a co-builder.
  • Examples include polyacrylic acids and copolymers from maleic anhydride and acrylic acid and the sodium salts thereof Polymer acids.
  • Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • origin include oxidized starch, such as from the International patent application WO 94/05762 known, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • the preferred builder components and preferably with tungstate or molybdate Combining polycarboxylates include the salts of citric acid, in particular Sodium citrate.
  • Trisodium citrate dihydrate can be fine or coarse crystalline Powder can be used.
  • the pH adjusted to the co-builder salts mentioned can also be used corresponding acids are present.
  • the enzymes contained in agents according to the invention include proteases, amylases, Pullulanases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®
  • amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramy
  • the used Enzymes can, as for example in international patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or in Envelope substances are embedded to protect them against premature inactivation.
  • she are in the cleaning agents according to the invention preferably in amounts of up to Contain 10 wt .-%, in particular from 0.05 wt .-% to 5 wt .-%, being particularly preferably enzymes stabilized against oxidative degradation, for example from the international ones Patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.
  • conventional bleach activators can be used known transition metal complexes and / or conventional bleach activators, that is Compounds that are optionally substituted under perhydrolysis conditions Perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms result, are used.
  • the usual ones cited at the beginning are suitable Bleach activators, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • acylates are preferred Alkylenediamines, especially tetraacerylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyl sulfonates, in particular nonanoyl or isononanoyloxybenzenesulfonate, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetyl
  • the connection to tungsten and / or molybdate is preferably in the range of 1000: 1 up to 1: 4, especially from 800: 1 to 1: 1.
  • the main bleaches used are oxygen-based or alkali perborate mono tetrahydrate and / or alkali percarbonate into consideration, where sodium is the preferred alkali metal is.
  • the use of sodium percarbonate has in particular Dishwashing detergent benefits as it is particularly beneficial on the Corrosion behavior affects glasses.
  • the oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate.
  • known peroxycarboxylic acids for example Dodecanediperic acid or phthalimidopercarboxylic acids, optionally on aromatics may be substituted.
  • the addition of small amounts known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as Magnesium sulfate may be useful.
  • the machine dishwashing detergents according to the invention preferably contain the customary alkali carriers such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 40% by weight, in particular 3% by weight to 30% by weight, based on the total composition, can be present.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which are contained in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight can.
  • agents according to the invention are 20% by weight to 60% by weight of water-soluble organic builder, in particular alkali citrate, 3% by weight to Contain 20 wt .-% alkali carbonate and 3 wt .-% to 40 wt .-% alkali disilicate.
  • surfactants in particular anionic surfactants, zwitterionic surfactants and preferably low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulating aids in the preparation of the cleaning agents.
  • Their amount can be up to 20% by weight, in particular up to 10% by weight, and is preferably in the range from 0.5% by weight to 5% by weight.
  • Extremely low-foaming compounds are usually used in particular in cleaning agents for use in automatic dishwashing processes.
  • C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • you can also use other known low-foaming nonionic surfactants such as C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-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 to 4 (e.g.
  • surfactants from the family of glucamides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably originates from a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
  • silver corrosion inhibitors can be used for dishes.
  • Preferred silver corrosion inhibitor are organic sulfides like cystine and cysteine, bi- or trivalent phenols, optionally alkyl- or aryl-substituted triazoles such as Benzotriazole, isocyanuric acid, manganese, titanium, zirconium, hafnium, vanadium or Cerium salts and / or complexes in which the metals mentioned, depending on the metal, in one of the Oxidation levels II, III, IV, V or VI are present.
  • the cleaning agents for example in the presence of anionic surfactants, at the Application foam too much, they can still up to 6 wt .-%, preferably about 0.5 wt .-% to 4 wt .-% of a foam suppressing compound, preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides, and other other known commercially available defoamers will.
  • a foam suppressing compound preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides, and other other known commercially available defoamers will.
  • Other optional ingredients in the agents according to the invention are for example perfume oils.
  • usable organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, Diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and their mixtures and the ethers derived from the compound classes mentioned.
  • Such water-miscible solvents are in the cleaning agents according to the invention preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, available.
  • the agents according to the invention cannot system and pH environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, however also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • pH regulators are preferably not more than 10% by weight, in particular, in the agents according to the invention from 0.5% by weight to 6% by weight.
  • the preparation of the solid compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, take place, the peroxygen compound and bleaching catalyst possibly later be added separately.
  • Cleaning agents according to the invention in the form of aqueous or other conventional Solutions containing solvents are particularly advantageous by simple Mixing the ingredients in bulk or as a solution in an automatic Mixers can be made.
  • the agents according to the invention are preferably powdered, granular or tablet-shaped preparations in a known manner, for example by Mixing, granulating, roller compacting and / or by spray drying the thermally resilient components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and the bleaching catalyst are to be counted, can be produced.
  • the procedure is preferably such that all 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 1 500 ⁇ 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 1 500 ⁇ 10 5 Pa pressed.
  • unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally over 150 N.
  • a tablet manufactured in this way 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.
  • agents according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 up to 1000 g / l can be achieved in that the Builder components with at least a portion of liquid mixture components mixed by increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other components of the agent, including the bleach catalyst, combined with the premix obtained in this way.
  • Means for cleaning dishes according to the invention can be used both in household dishwashers as used in commercial dishwashers. The addition is done by hand or by means of suitable dosing devices.
  • the application concentrations in the cleaning liquor are usually about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program is generally followed by some on the Cleaning cycle following intermediate rinse cycles with clear water and one Rinse aid supplemented with a customary rinse aid and ended. After this Drying gives a completely clean and in when using agents according to the invention hygienically perfect dishes.
  • the agent M7 was tested according to Example 1 in comparison to an agent V2 which was otherwise composed like M7 and which lacked the molybdate, an agent V3 which was otherwise composed like M7 and which lacked the amylase granules, and an agent V4 which otherwise how M7 was composed and which lacked both the molybdate and the amylase granules. It can be seen that the agent M7 according to the invention has a higher cleaning performance than would have been expected from the results of the agents V2 and V3 . Sheet removal marks medium Removal of deposits M7 17th V2 11 V3 10th V4 6

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97120141A 1996-11-27 1997-11-18 Utilisation de tungstates et de molybdates pour améliorer les performances de blanchiment Withdrawn EP0845524A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19649078 1996-11-27
DE1996149078 DE19649078A1 (de) 1996-11-27 1996-11-27 Verwendung von Wolframaten und Molybdaten zur Verstärkung der Bleichwirkung

Publications (2)

Publication Number Publication Date
EP0845524A2 true EP0845524A2 (fr) 1998-06-03
EP0845524A3 EP0845524A3 (fr) 1999-03-10

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EP97120141A Withdrawn EP0845524A3 (fr) 1996-11-27 1997-11-18 Utilisation de tungstates et de molybdates pour améliorer les performances de blanchiment

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DE (1) DE19649078A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004081159A1 (fr) * 2003-03-12 2004-09-23 Ecolab Inc. Traitement predetachant utilisant de l'oxygene singulet

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2697401C1 (ru) * 2018-07-23 2019-08-14 Общество с ограниченной ответственностью "Вайт-Смайл" (ООО "Вайт-Смайл") Способ отбеливания эмали зубов

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8525047D0 (en) * 1985-10-10 1985-11-13 Interox Chemicals Ltd Waste treatment
JPH0525498A (ja) * 1991-07-18 1993-02-02 Kao Corp 住居用漂白剤組成物
JPH0641593A (ja) * 1992-07-27 1994-02-15 Central Glass Co Ltd 漂白活性剤および漂白剤組成物
US5904734A (en) * 1996-11-07 1999-05-18 S. C. Johnson & Son, Inc. Method for bleaching a hard surface using tungsten activated peroxide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004081159A1 (fr) * 2003-03-12 2004-09-23 Ecolab Inc. Traitement predetachant utilisant de l'oxygene singulet
US7018967B2 (en) 2003-03-12 2006-03-28 Ecolab Inc. Prespotting treatment employing singlet oxygen

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Publication number Publication date
EP0845524A3 (fr) 1999-03-10
DE19649078A1 (de) 1998-05-28

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