EP1111035A2 - Combinaison d'agents actifs à incorporer dans des compositions détergentes - Google Patents

Combinaison d'agents actifs à incorporer dans des compositions détergentes Download PDF

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Publication number
EP1111035A2
EP1111035A2 EP00127120A EP00127120A EP1111035A2 EP 1111035 A2 EP1111035 A2 EP 1111035A2 EP 00127120 A EP00127120 A EP 00127120A EP 00127120 A EP00127120 A EP 00127120A EP 1111035 A2 EP1111035 A2 EP 1111035A2
Authority
EP
European Patent Office
Prior art keywords
weight
active ingredient
agents
ingredient combination
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Withdrawn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
EP00127120A
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German (de)
English (en)
Other versions
EP1111035A3 (fr
Inventor
Helmut Blum
Siglinde Erpenbach
Horst-Dieter Dr. Speckmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1111035A2 publication Critical patent/EP1111035A2/fr
Publication of EP1111035A3 publication Critical patent/EP1111035A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/38672—Granulated or coated enzymes
    • 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
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • 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 an active ingredient combination for incorporation in washing or Detergent, which is an active ingredient applied to an inert proppant contains, as well as a method for producing the active ingredient combination and a method for cleaning hard surfaces.
  • Active ingredients in washing and cleaning formulations only in small quantities are often first processed into so-called intermediate products then with the other ingredients for the finished formulation (for the finished Medium) are processed.
  • Such pre-formulated products are also referred to as compounds.
  • Active ingredients incorporated into detergents and cleaning agents in the form of compounds are surfactants, bleaches, bleach activators, bleach catalysts, enzymes. Fragrances, etc. These active ingredients are often applied to carrier materials.
  • Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate. have long been used as an oxidizing agent 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.
  • 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, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, Hydrotriazine, urazoles, diketopiperazines, sulfuryl amides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, Carbonklareester, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, are known in the literature.
  • bleach activators for which numerous suggestions, especially from the substance
  • transition metal salts which as such make essentially no contribution to improving the oxidation and bleaching action of inorganic peroxygen compounds at low temperatures, have a clear bleach-catalyzing effect on colored soils which are located on hard surfaces , if the transition metal salts are used in the form of a combination of active ingredients which additionally contains an ammonium salt and, if appropriate, an oxidizing agent.
  • active substance combinations are produced starting from transition metal salts in solid form.
  • the active ingredients described above are only in the finished formulations very small amounts are included, because of these small amounts there is often Risk that they are not evenly distributed in it. Therefore, the active ingredients are common pre-assembled, d. H. converted into solid intermediate products.
  • the active ingredients are often in liquid form, it occurs in the manufacture of the Intermediate products in the reactors often cause caking, including the bulk behavior and the Free flow of the preliminary products containing the active ingredients are not always satisfactory.
  • the present invention was accordingly based on the object of active ingredients in such To provide preparation forms that can be easily prepared as well have good pouring behavior and good flow properties.
  • the present invention accordingly relates to an active ingredient combination for the Use in washing and / or cleaning agents, in which the active ingredient on an inert Support material is applied, characterized in that at least part of the Supporting substance has a particle size of 2 to 1000 nm.
  • Supports in the sense of the present invention are substances in solid form are present and serve as carrier material for the active ingredient, the stability of the Support active ingredient or if the active ingredient, for example, in situ at the Production of the active ingredient combination according to the invention is formed, the formation of Can support active ingredient.
  • the proppants are inert, i.e. they do not react with the active ingredient and any other components contained in the active ingredient combination.
  • the Support is preferably an inorganic material, e.g. can be selected from Alkali sulfate, alkali carbonate, alkali hydrogen carbonate, alkali percarbonate, alkali chloride, Alkali silicate, alkali phosphate and mixtures thereof, with the sodium salts particularly are preferred.
  • Nanoparticulate inorganic compounds can be prepared by known methods, e.g. according to EP 0 711 217 A1 (Nanophase Technologies Corp.). Suitable oxides are commercially available under the Nano Tek® trademark, suitable silicates under the trademark Optigel® or Laponite®. Also by hydrolysis of organometallic compounds oxide hydrates and hydroxides are accessible in a very fine distribution. Such Materials are e.g. available under the name Disperal Sol P3 ®.
  • Suitable nanoparticulate oxides for use in the agents according to the invention are e.g. Magnesium oxide, aluminum oxide, titanium dioxide, zirconium dioxide and zinc oxide.
  • suitable oxide hydrate is e.g. B. alumina hydrate (boehmite).
  • a suitable silicate is e.g. B. magnesium silicate.
  • Suitable phosphates include e.g. B. the apatite.
  • Layer silicates such as are particularly suitable nanoparticulate inorganic compounds Montmorillonite, bentonite, hectorite, smectite or talc, as well as aluminosilicates such as Zeolites.
  • Other suitable silicates are precipitated silicas, which are commercially available e.g. More colorful the product names Aerosil® (Degussa), Lutrasil® (Freudenberg), Sipernat® (Degussa), etc. are available.
  • the support substances used have at least some particles Particle size in the nanoscale range, the particle size preferably below 500 nm and is particularly preferably in the range between 7 and 100 nm is in particular between 10 and 50 nm. Can also be particularly advantageous Use supports with a particle size of 10 and 30 nm.
  • the proportion of the nanoscale particles is preferably from 0.1 to 5% by weight, in particular from 0.25 to 2.5% by weight, based on the active ingredient combination.
  • the active ingredient combination according to the invention can be used as active ingredients in any washing and Contain detergents that can be used, in particular those Substances are incorporated that are found in washing and cleaning agents only in small quantities Amount included or which are pre-assembled due to their low stability become.
  • suitable active substances are bleach-catalytically active substances, Enzymes, fragrances, perfume carriers, fluorescent agents, dyes, electrolytes, pH adjusting agents, Hydrotopes, foam regulators, soil release compounds, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, Antioxidants, sequestering agents, corrosion inhibitors, deposit inhibitors, swelling and Anti-slip agents, antistatic agents, ironing aids, phobing and impregnating agents and UV absorber.
  • Preferred combinations of active ingredients contain bleach-catalytically active ones Active ingredients, fragrances and / or enzymes.
  • the bleach-catalytically active substances include, in particular, transition metal salts, which are preferably selected from the water-soluble salts of a Transition metal, selected from cobalt, iron, copper and ruthenium, in Combination with a water-soluble ammonium salt, especially for this Ammonium halide, sulfate, carbonate, hydrogen carbonate, phosphate, phosphonate, nitrate, -perchlorate and / or -citrate.
  • transition metal salts are preferably selected from the water-soluble salts of a Transition metal, selected from cobalt, iron, copper and ruthenium, in Combination with a water-soluble ammonium salt, especially for this Ammonium halide, sulfate, carbonate, hydrogen carbonate, phosphate, phosphonate, nitrate, -perchlorate and / or -citrate.
  • Cobalt (II) chloride which can be used in anhydrous form or can be used as hexahydrate, cobalt (II) sulfate, cobalt (II) carbonate and cobalt (II) acetate, alone or in mixtures.
  • the ones used in the process according to the invention preferably have aqueous solutions of the transition metal salts contents of at least 35% by weight, in particular 40% by weight to 75% by weight and particularly preferably 50% by weight to 70% by weight Transition metal salt. If the water absorption capacity of the inert proppant is not sufficient to do this via the solution of the transition metal salt in the Active ingredient combination to bring in water so that a particulate Product is formed, a drying step can follow the mixing step connect.
  • bleach-catalytically active substances are used as active substances, these are in Active ingredient combinations according to the invention are preferably 0.01% by weight to 1% by weight, in particular 0.1 wt .-% to 0.5 wt .-%, transition metal from the Transition metal salt included.
  • the ammonium salt content is preferably 0.5% by weight to 25% by weight, in particular 1% by weight to 10% by weight.
  • the rest on 100% by weight can consist of an inert carrier material.
  • the active ingredient combination can contain an oxidizing agent Peroxygen base, preferably in an amount of 1% by weight to 20% by weight, contain in particular 2% by weight to 10% by weight.
  • fragrance oils or fragrances can be made from all known fragrance compounds can be selected either individually or as mixtures.
  • fragrance compounds count e.g. synthetic products of the ester, ether, aldehyde, ketone, Alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g.
  • the ethers include, for example, benzyl ethyl ether and the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal.
  • Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil are suitable.
  • suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and Labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandal oil.
  • Enzymes in particular come in the active substance combinations according to the invention those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of mentioned enzymes in question. All of these hydrolases contribute to the removal of Soiling such as stains containing protein, fat or starch.
  • To bleach can also be used oxidoreductases.
  • Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified variants obtained enzymatic active ingredients.
  • proteases of the subtilisin type and in particular proteases which are preferred Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytically acting Enzymes or protease, lipase or lipolytically active enzymes, in particular however, protease and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest.
  • lipolytic acting enzymes are the well-known cutinases. Also have peroxidases or oxidases proved to be suitable in some cases.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the active ingredient combination according to the invention can be produced in a simple manner.
  • the active ingredients or their Starting compounds optionally as aqueous solutions or Suspensions / emulsions exist with the solid or as a solution respectively Suspension present proppant and possibly other carrier material mixed and then dried if necessary.
  • the active substances are in solid form mixed, then an aqueous solution or suspension of the proppant added and the mixture obtained is dried in a manner known per se and assembled.
  • Transition metal salts are used as active ingredients in combination with ammonium salts used, it is preferred to first with the ammonium salt and if necessary to mix the peroxygen-based oxidizing agent, then the Add aqueous transition metal salt solution and then by adding a aqueous granulation aid solution, in particular an alkali silicate solution Perform granulation step.
  • the active ingredient is in situ educated.
  • the aqueous and powdery components used including a build-up granulation, optionally using granulation aids such as aqueous Alkali silicate solutions or solutions of salts of polymeric polycarboxylates, to facilitate the handling of the active ingredient combination.
  • granulation aids such as aqueous Alkali silicate solutions or solutions of salts of polymeric polycarboxylates
  • the flowability of such granules can be achieved by adding fine-particle inert Material, for example of silica, towards the end of the granulation respectively can be further improved in a subsequent powdering step if desired.
  • fine-particle inert Material for example of silica
  • the mixing or granulation preferably follows Ingredients that are essentially at room temperature or at which resulting from the energy input of the mixer or granulator Temperature is usually not above 30 ° C, a thermal Post-treatment of the active ingredient combination over a period of, for example, up to to 120 minutes, especially 15 minutes to 60 minutes. If such thermal aftertreatment is carried out, the above mentioned Drying process is not necessary. It is preferred if one looks after the mixing or Granulation step another combination of active ingredients obtained certain time, for example 1 hour to 5 hours, at the temperature of the mixer or Granulation step before leaving the thermal Performs post-treatment. In the process step of thermal Post-treatment is heating to temperatures in the range from 40 ° C to 90 ° C, in particular 60 ° C to 80 ° C normally completely sufficient.
  • the nitrogen content decreases, based on the transition metal before the thermal aftertreatment (annealing) preferably in the atomic ratio range from about 6: 1 to about 4: 1 after the thermal aftertreatment in the atomic ratio range from about 2: 1 to below 3: 1.
  • this procedure presumably forms polynuclear transition metal complexes in which ammonia, the anions of the ammonium salt and the anions of the carrier material salts assume the role of the ligands.
  • Co (II) salts it is known that, particularly in the presence of peroxidic oxidizing agent, there is known to be significantly more stable Co (III) complexes, which are known as multinuclear complexes, possibly of the type of the surface-linked trinuclear complex exemplified below are present, the replacement of at least individual bridging ⁇ -OH groups by bridging ⁇ -imino or ⁇ -amino groups and further linking to even higher-nucleus complexes is also conceivable.
  • Such formation of polynuclear complexes presumably also takes place when the constituents are mixed intimately without subsequent tempering or when the non-tempered combination of active ingredients is used in the aqueous system.
  • transition metal salts in combination with an ammonium compound is preferably mixed 0.5 parts by weight to 10 parts by weight, in particular 2 parts by weight up to 7.5 parts by weight ammonium salt with 50 parts by weight up to 150 parts by weight, in particular 70 parts by weight to 100 parts by weight of support material and up to 20 parts by weight, in particular 2 parts by weight to 10 parts by weight of oxidizing agent Peroxygen basis and then gives 1 part by weight of the divalent transition metal salt in aqueous solution.
  • further proppant can be added.
  • Mixing step of commercially available proppants with a particle size above 1000 nm used, while the subsequently added proppant has a particle size between 2 and 1,000 nm.
  • a bleach-enhancing active ingredient combination preferably produced according to the invention is preferably used in cleaning solutions for hard surfaces, especially for dishes, in the presence of, in particular, inorganic peroxygen compounds Bleaching of stained stains used.
  • the invention further relates to cleaning agents for hard surfaces, in particular Detergents for dishes and preferably those for use in mechanical cleaning processes which contain an active ingredient combination described above, and a method for cleaning hard surfaces, in particular of Dishes using such a combination of active ingredients in an aqueous, optionally further solution containing detergent components.
  • 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 bleaching enhancer Active ingredient combinations can react with each other, with the aim of being more oxidizing to obtain effective secondary products.
  • a peroxidic oxidizing agent and the bleaching enhancer Active ingredient combinations can react with each other, with the aim of being more oxidizing to obtain effective secondary products.
  • Such conditions exist in particular when both reactants meet in aqueous solution. This can be done by separate addition of the peroxygen compound and the active ingredient combination to one if necessary, detergent-containing solution.
  • the active ingredient combination produced according to the invention and optionally contains an oxidant containing peroxygen.
  • the active ingredient combination according to the invention is an oxidizing agent based on peroxygen.
  • the peroxygen compound can also be used separately, in substance or as a preferably aqueous solution or suspension, added to the solution if a peroxide-free cleaning agent 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 Active ingredient combination depends on the application. Depending on the desired level of activation the combination of active ingredients is used in such amounts that 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.02 mol, of transition metal per Moles of peroxygen compound can be used, but in special cases this can Limits can also be exceeded or fallen short of.
  • Detergents used as powder or tablet solids or suspensions can be present in addition to the active ingredient combination produced according to the invention in principle contain all known and usual ingredients in such agents.
  • the Agents can include, in particular, builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, Electrolytes, pH regulators and other auxiliaries, such as Silver corrosion inhibitors, foam regulators, additional peroxygen activators as well as dyes and fragrances.
  • a cleaning agent for hard surfaces can also contain abrasive components, especially from the group comprising quartz flours, wood flours, Plastic flours, chalks and micro glass balls and their mixtures.
  • Abrasives are preferably not present in the cleaning agents according to the invention 20 wt .-%, in particular from 5 wt .-% to 15 wt .-%, contain.
  • an agent for machine cleaning of dishes containing 15% by weight to 60% by weight, in particular 20% by weight to 50% by weight, of water-soluble Builder component, 5% by weight to 25% by weight, in particular 8% by weight to 17% by weight Oxygen-based bleach, in each case based on the total agent which the Bleach-activating active ingredient combination produced according to the invention, in particular in Amounts from 1 wt .-% to 10 wt .-%, the details of Amount of bleaching agent the amount possibly contained in the active ingredient combination Include oxidizing agents.
  • a medium is particularly low alkaline, that His 1% by weight solution has a pH of 8 to 11.5, preferably from 9 to 11.
  • water-soluble builder components are for example organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, especially in hard water regions Act.
  • polyacrylic acids and copolymers of maleic anhydride are suitable and acrylic acid and the sodium salts of these polymer acids.
  • Commercial products are, for example, Sokalan® CP 5 and PA 30 from BASF.
  • Polymers of native origin that can be used as co-builders include, for example oxidized starch, such as from the international patent application WO 94/05762 known, and polyamino acids such as polyglutamic acid or Polyaspartic acid.
  • the preferred builder components include Salts of citric acid, especially sodium citrate.
  • sodium citrate come anhydrous Trisodium citrate and preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the co-builder salts mentioned are also present.
  • an oxygen-based bleach come primarily hydrogen peroxide as well Alkali perborate or tetrahydrate and / or alkali percarbonate into consideration, with sodium being the preferred alkali metal. Hydrogen peroxide can also with the help of an enzymatic system, i.e. an oxidase and its substrate, be generated.
  • 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.
  • Bleach activators that is, compounds that operate under perhydrolysis conditions optionally substituted perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular result in 2 to 4 carbon atoms. They are suitable usual bleach activators cited at the beginning, the O- and / or N-acyl groups of mentioned number of carbon atoms and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine, are preferred (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyl sulfonates, especially nonanoyl or Isononanoyloxybenzenesulfonat, acylated polyhydric alcohols, especially triacetin.
  • TAED acylated glycolurils, especially tetraacetylglycoluril
  • DADHT acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • DADHT acylated phenyl s
  • PAG pentaacetyl glucose
  • PEG pentaacetyl fructose
  • Tetraacetylxylose Tetraacetylxylose
  • Octaacetyllactose as well as acetylated, if necessary N-alkylated glucamine and gluconolactone.
  • agents according to the invention in addition to the bleach-enhancing active ingredient combination 0.5% by weight to 6% by weight, in particular 2% by weight to 4% by weight of such under perhydrolysis conditions Peroxocarboxylic acid releasing compound present.
  • the weight ratio of compound releasing peroxocarboxylic acid under perhydrolysis conditions Transition metal from the active ingredient combination is preferably in the range of 2000: 1 to 20: 1, in particular from 800: 1 to 100: 1.
  • the machine dishwashing detergents are low-alkaline and 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 30% by weight. %, based on the total, may be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably completely avoided.
  • An alkali carrier system preferably used in the agents is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight. Depending on which pH is ultimately desired. the ratio of the carbonate used and the hydrogen carbonate used varies, but an excess of sodium hydrogen carbonate is usually used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • these are 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to Contain 15 wt .-% alkali carbonate and 20 wt .-% to 40 wt .-% alkali disilicate.
  • surfactants in particular low-foaming nonionic surfactants, can also be added to the compositions, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulation aids in the course of the production of the cleaning compositions.
  • Their amount can be up to 10% by weight, in particular up to 5% by weight, and is preferably in the range from 0.5% by weight to 3% by weight.
  • Extremely low-foaming compounds are usually used in particular in cleaning agents for use in automatic dishwashing processes. These preferably include 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.
  • 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. APG® 225 and APG® from Henkel) and / or C 12 -C 14 -alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule.
  • 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.
  • transition metals are known to counteract the corrosion of silver can, the bleach-boosting produced according to the invention Transition metal-containing active ingredient combinations are generally used in amounts that are too small to be able to provide silver corrosion protection, so that in the invention Dishwashing detergents still silver corrosion inhibitors can also be used.
  • Preferred silver corrosion inhibitors are organic disulfides, di- or trihydric phenols, optionally alkyl and / or aryl-substituted triazoles such as benzotriazole, manganese, titanium, zirconium, hafnium, Bismuth, vanadium or cerium salts and / or complexes in which the metals mentioned are in one of the oxidation states II, III, IV, V or VI.
  • enzymes are not already contained in the active ingredient combination according to the invention they can also be used in the form of their known preparation forms.
  • the optionally used enzymes can, as for example in the international Patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or be embedded in coating substances to protect them against premature Protect inactivation.
  • detergents preferably in amounts up to 5 wt .-%, in particular from 0.1 wt .-% to 2 wt .-%, contain, especially 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.
  • the cleaning agents foam too much during use, they can still up to 6% by weight, preferably about 0.5% to 4% by weight of a foam suppressant Compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, more hydrophobic Silicic acid, the bis fatty acid amide, and other other well-known in the trade available defoamers can be added.
  • a foam suppressant Compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, more hydrophobic Silicic acid, the bis fatty acid amide, and other other well-known in the trade available defoamers can be added.
  • Other optional ingredients in the invention Agents are, for example, perfume oils.
  • the agent can not be used under conditions of self-resulting pH System and environmentally compatible acids, especially citric acid, acetic acid. Tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or Adipic acid, but also mineral acids, especially sulfuric acid or Alkali hydrogensulfates, or bases, especially ammonium or alkali hydroxides. contain.
  • Such pH regulators are preferred in the agents according to the invention do not contain more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • agents for machine cleaning from dishes 50% by weight to 60% by weight sodium phosphate, 15% by weight to 25% by weight Sodium carbonate or its mixture with polymeric polycarboxylate, 5 wt .-% to 15% by weight sodium perborate or percarbonate, 0.5% by weight to 5% by weight below Perhydrolysis conditions
  • Peroxocarboxylic acid-releasing bleach activator 0.5% by weight up to 7.5 wt% surfactant, 2 wt% to 10 wt% sodium silicate and 0.1 wt% to 0.75 wt .-% silver corrosion inhibitor, especially benzotriazole or a Benzotriazole derivative.
  • the agents are preferably in powder, granular, tablet or as other moldings prepared solids, which in a manner known per se, for example by mixing, granulating, roller compacting and / or by Spray drying the thermally resilient components and admixing the more sensitive components, in particular enzymes, bleaches and the Active substance combination produced according to the invention are to be expected can.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 10 5 Pa to 1 500 10 5 Pa .
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • 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 by using 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 active ingredient combination produced according to the invention, with the thus obtained Premix combined.
  • the means of cleaning dishes can be found in both domestic dishwashers as used in commercial dishwashers. The addition takes place by hand or by means of suitable dosing devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
  • the product according to the invention produced according to Example 2 had a better one Free flowing on than the product from Example 1, which is particularly evident in the lighter Dosing of the component affected during further processing.
  • the residual moisture is an indicator of the improved free-flowing properties.
  • the comparison shows. that the addition of the nanoscale particles according to the invention reduces the residual moisture by approximately 4%. Residual moisture (%) Example 1 (comparison) 15.2 Example 2 11.5

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
EP00127120A 1999-12-21 2000-12-12 Combinaison d'agents actifs à incorporer dans des compositions détergentes Withdrawn EP1111035A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19961687 1999-12-21
DE1999161687 DE19961687A1 (de) 1999-12-21 1999-12-21 Wirkstoffkombination zur Einarbeitung in Wasch- und Reinigungsmittel

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EP1111035A2 true EP1111035A2 (fr) 2001-06-27
EP1111035A3 EP1111035A3 (fr) 2003-04-23

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711748A (en) * 1985-12-06 1987-12-08 Lever Brothers Company Preparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation
GB8926644D0 (en) * 1989-11-24 1990-01-17 Unilever Plc Detergent composition
GB9113675D0 (en) * 1991-06-25 1991-08-14 Unilever Plc Particulate detergent composition or component
WO1995002724A1 (fr) * 1993-07-14 1995-01-26 The Procter & Gamble Company Compositions detersives contenant du percarbonate et procede de production
DE19609953A1 (de) * 1996-03-14 1997-09-18 Basf Ag Feste Zusammensetzung aus heterocyclischen Verbindungen und/oder Oximestern und inerten porösen Trägermaterialien und ihre Verwendung als stabile Bleichaktivator-Komponente in Wasch-, Bleich- und Reinigungsmitteln
DE19709284A1 (de) * 1997-03-07 1998-09-10 Henkel Kgaa Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung
DE19925511A1 (de) * 1999-06-04 2000-12-07 Henkel Kgaa Herstellung einer bleichkatalytisch aktiven Wirkstoffkombination

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DE19961687A1 (de) 2001-07-05

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