WO1996037593A1 - Granules acides renfermant des substances a activite redox - Google Patents

Granules acides renfermant des substances a activite redox Download PDF

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Publication number
WO1996037593A1
WO1996037593A1 PCT/EP1996/002047 EP9602047W WO9637593A1 WO 1996037593 A1 WO1996037593 A1 WO 1996037593A1 EP 9602047 W EP9602047 W EP 9602047W WO 9637593 A1 WO9637593 A1 WO 9637593A1
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WO
WIPO (PCT)
Prior art keywords
redox
acid
active substance
weight
granules
Prior art date
Application number
PCT/EP1996/002047
Other languages
German (de)
English (en)
Inventor
Thomas Holderbaum
Jürgen Härer
Peter Jeschke
Christian Nitsch
Hans-Josef Beaujean
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 JP8535329A priority Critical patent/JPH11505290A/ja
Priority to EP96916058A priority patent/EP0827529A1/fr
Publication of WO1996037593A1 publication Critical patent/WO1996037593A1/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
    • C11D3/39—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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof

Definitions

  • the invention relates to acidic granules containing a redox-active substance; Cleaning agents for machine washing dishes containing such acidic granules are particularly claimed.
  • Redox-active substances must in general in the presence of atmospheric oxygen. be stabilized in order to prevent their premature oxidation.
  • they are usually admixed with reactive substances or substance mixtures, some of which can undesirably be catalytically decomposed prematurely in the presence of redox-active substances.
  • Redox-active substances in the sense of the present invention are those substances that have an easy-running, i.a. reversible, oxidation and / or reduction are accessible. These can be both organic and inorganic substances.
  • redox-active substances are metal salts or metal complexes which are added, for example, to machine dishwashing detergents for the purpose of preventing corrosion of silver cutlery, or metal salts or metal complexes which are added to detergents and cleaning agents as bleach activators.
  • the redox-active substances themselves, e.g. B. metal salts - for example nS04 - are generally slightly airborne, ie on the one hand a way must be found to effectively shield the redox-active substances from the surrounding atmospheric oxygen; on the other hand, the effective shielding from the environment is also necessary because redox-active substances are usually further substances or substance mixtures, e.g.
  • detergents or cleaning agents are admixed, wherein no chemical interaction between redox-active substances and other ingredients may occur during storage. Only when using the Mixtures of substances, such as washing or cleaning agents, the targeted release of the redox-active substances and chemical interactions with the environment are desired.
  • redox-active substances have been coated, i.e. completely covered with a waterproof but easily removable material.
  • Preferred coating materials which are applied by known processes are e.g. Paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids.
  • the object of the present invention is therefore to provide redox-active substances in such a way that a premature reaction of the redox-active substance with atmospheric oxygen is prevented as well as chemical interactions with ingredients of substance mixtures to which redox-active substances are admixed. In addition, segregation must not occur. As few steps as possible should be necessary to solve this task.
  • the object was achieved by providing granules based on a carrier substance, the 1% by weight aqueous solution of which has a pH of less than 7, preferably from 1.5 to 3.5, at 20 ° C., containing an acid and 0.001 to 50% by weight, preferably 0.1 to 20% by weight and in particular 1 to 10% by weight of a redox-active substance.
  • Granules in the sense of the present invention are particles which are formed from powdery substances by agglomeration processes.
  • granulate reference is expressly made here to the disclosure in “Winnacker, Küchler, Chemical Technology, Volume 1, Carl Hauser Verlag Kunststoff Vienna 1984, pages 384 to 387", and the methods of fluidized bed spray granulation described there, the granulation in the plate, the granulation in the mixer and the press and roller granulation.
  • the granules according to the invention are preferably produced by pelletizing in a commercially available mixer.
  • the carrier substance and the redox-active substance are placed in the mixer, granulated with water and / or aqueous solutions of further ingredients and / or further granulating liquids. If necessary, the granules are e.g. dried in a fluidized bed dryer and sieved the desired fraction.
  • the acid can be introduced into the granules as a solid and / or liquid component.
  • the solids usually used in detergents and cleaning agents come into question as carrier substances, e.g. B. soda, sodium citrate, citric acid, sodium bicarbonate and in particular Na2S ⁇ 4.
  • As a granulating aid e.g. to increase the grain stability e.g. Carboxylmethylcellulose or the polyacrylates sold by BASF under the trade name Sokalan are used.
  • the grain diameter of the granules according to the invention can vary over the entire spectrum disclosed in the abovementioned prior art, and is preferably about 0.2 to 1.8 mm.
  • the bulk density (according to DIN-IS0697, Jan. 1987) is around 300 to 1300 g / 1.
  • the redox-active substance is an organic or inorganic substance which is amenable to easy-running, generally reversible, oxidation and / or reduction.
  • typical complexation center such as B. EDTA or hydroxyethane diphosphonic acid or bleach activators of the TAED type, ie compounds which have a bleach-activating action due to easily cleavable NC bonds, and related compounds not covered by this definition.
  • Organic redox active substances are e.g. Ascorbic acid, indole, cysteine, cystine or methionine.
  • the coupler and developer compounds disclosed in the international application PCT / EP94 / 01387 are also suitable redox-active substances; p-Hydroxyphenylglycine, 2,4-diaminophenol, 5-chloro-2,3-pyridinediol, l- (p-aminophenyl) morpholine, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol and pyrogallol should be mentioned here in particular.
  • inorganic redox-active substances e.g. the substances a2S2 ⁇ 3 (sodium thiosulfate), a2S2 ⁇ (sodium dithionite) or Na2S2 ⁇ 5 (sodium disulfite), which are based on various levels of sulfur oxidation.
  • a2S2 ⁇ 3 sodium thiosulfate
  • a2S2 ⁇ sodium dithionite
  • Na2S2 ⁇ 5 sodium disulfite
  • the inorganic redox-active substances are preferably transition or main group metal salts or complexes which are amenable to easy oxidation and / or reduction.
  • transition or main group metal salts or complexes which are amenable to easy oxidation and / or reduction.
  • the salts or complexes of the transition metals especially the metals iron, titanium, manganese, tin, cobalt, nickel and copper, are preferred.
  • manganese (II), manganese (III) and manganese (IV) salts or complexes are preferred.
  • MnS04 is particularly suitable in an anhydrous or water-containing form.
  • the manganese complexes disclosed in international application W094 / 19445 are also suitable representatives. The following are particularly worth mentioning: [Me-TACN) Mn I ( ⁇ -0) 3Mn IV (Me-TACN)] 2+ (PF6 ⁇ ) 2, [Me-MeTACN) Mn IV ( ⁇ -0) 3Mn IV (Me -MeTACN)] 2+ (PF6-) 2- [Me-TACN) Mn ⁇ I ( ⁇ -0) ( ⁇ -0Ac) 2Mn ⁇ (Me-TACN)] 2+ (PF6-) 2 and [Me-MeTACN ) Mn III ( ⁇ -0) ( ⁇ -0Ac) 2Mn III (Me-MeTACN)] 2+ (PF6-) 2, where Me-TACN stands for l, 4,7-trimethyl-l, 4,7-triazacyclononane and Me-MeTACN stands for l, 2,4,7-tetramethyl-l, 4,7-
  • a 1% by weight aqueous solution of the granules according to the invention has a pH of less than 7 at 20 ° C. (i.e. in practice from 1.0 to 7), preferably from 1.5 to 3.5.
  • the granules according to the invention contain an acid.
  • all non-oxidizing acids can be used, e.g. mono- and bifunctional carboxylic acid or hydroxycarboxylic acids, especially maleic acid, glutaric acid, adipic acid, sulfuric acid, alkanobenzenesulfonic acids or fatty acids.
  • citric acid and tartaric acid or mixtures thereof are preferably used; Citric acid is particularly suitable.
  • a particularly preferred mixture is the combination of an acid other than maleic acid, glutaric acid or adipic acid (for example tartaric acid and in particular citric acid) and maleic acid, glutaric acid, adipic acid or mixtures thereof.
  • Maleic acid, glutaric acid, adipic acid or mixtures thereof are contained in this particular embodiment in an amount of at most 10% by weight, preferably at most 5% by weight, based on the total granulate.
  • the acids can be used in the form of a solid, as a melt or as an aqueous solution in the granulation.
  • Liquid acids such as H2SO4 are used as aqueous solutions.
  • the granules according to the invention can be stored as such and substances or substance mixtures with which the redox-active substance contained in the granules is to have a chemical interaction are only added at the moment of use.
  • the granules can also already be stored together with substances or substance mixtures, since the redox-active substances contained in the granules according to the invention are not only protected against atmospheric oxygen, but also against premature undesired chemical interactions with ingredients of the substance mixtures, e.g. Connections containing active oxygen are passivated; there are also no segregations. This applies regardless of whether the substance mixtures themselves are in granular form or as a conventional powder.
  • the redox-active substances contained in the granules according to the invention can, among other functions, e.g. perform the following functions:
  • Another object of the invention is an agent for machine washing dishes containing 15 to 60 wt .-%, preferably 30 to 50 wt .-% builder components, 5 to 25 wt .-%, preferably 10 to 15 wt .-% oxygen-based bleach and 0.3 to 20% by weight, preferably 1 to 10% by weight, of the above-described granules containing a redox-active substance.
  • the redox-active substance does not necessarily act, but preferably as a silver corrosion protection agent.
  • the redox-active substance fulfills the function as a silver corrosion inhibitor, in particular when using the preferred redox-active substances already described above, for example manganese (II), manganese (III) or manganese (IV) salts or complexes.
  • low-alkaline machine dishwashing detergents are understood to mean those whose 1% by weight aqueous solution has a pH of 8.0 to 11.5, preferably 9.0 to 10.5.
  • builders commonly used in machine dishwashing detergents are suitable as builder components, e.g. B. poly ere Alkali ⁇ phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts.
  • B. poly ere Alkali ⁇ phosphates which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are: tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • phosphate are in the range of up to about 60% by weight, based on the total agent; for ecological reasons, however, the agents according to the invention are preferably free of such phosphates.
  • Other possible, water-soluble, builder components are e.g. B. organic polymers native or synthetic origin, especially polycarboxylates, which act in particular in hard water systems as co-builders.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercial products include Sokalan ( R ) CP 5 and PA 30 from BASF, Alcosperse ( R ) 175 or 177 from Alco, LMW ( R ) 45 N and SP02 N from Norsohaas.
  • the native polymers include, for example, oxidized starch (see, for example, DE 4228786) and polyamino acids such as polyglutamic acid or polyaspartic acid, eg. B. from the companies Cygnus and SRCHEM.
  • Other possible builder components are naturally occurring hydroxy carboxylic acids such as. B. mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • Preferred builder components are the salts of citric acid, especially sodium citrate. Water-free trisodium citrate or preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to citrate can also be present.
  • Sodium perborate mono- and tetrahydrate or sodium percarbonate are primarily considered as oxygen-based bleaches.
  • the use of sodium percarbonate has advantages because it has a particularly favorable effect on the corrosion behavior on glasses.
  • the oxygen-based bleach is therefore preferably a percarbonate salt, in particular sodium percarbonate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are often used in amounts of up to 10% by weight, preferably 1 to 6% by weight, to activate it in the dishwasher.
  • Organic bleach activators containing 0- or N- (C 1 -C 12) -acyl groups e.g.
  • PAG penentaacetylglucose
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine
  • ISA isatoic anhydride
  • TAED isatoic anhydride
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate can also be useful.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates
  • magnesium salts such as magnesium sulfate
  • the dishwashing detergents according to the invention contain enzymes such as proteases, aylases, lipases and cellulases, for example proteases such as BLAP ( R ) 140 from Henkel; 0ptimase ( R ) -M-440, 0ptimase ( R ) -M-330, 0pticlean ( R ) -M-375, 0pticlean ( R ) -M-250 from Solvay Enzy es; Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis; Savinase ( R ) 4.0 T, 6.0 T, 8.0 T from Novo; Esperase ( R ) T from the company Ibis and amylases such as Termamyl ( R ) 60 T, 90 T from Novo; Amylase-LT () from Solvay Enzymes or Maxamyl ( R )
  • proteases such as BLAP ( R ) 140 from He
  • the agents according to the invention preferably additionally contain the alkali carriers contained in conventional machine dishwashing agents such as. B. alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 30% by weight, based on the total agent, may be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably avoided.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of essentially carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, in an amount of up to 60% by weight, preferably 10 to 40% by weight, based on the total agent , is included.
  • the ratio of carbonate and bicarbonate used varies; Usually, however, an excess of sodium hydrogen carbonate is used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • surfactants in particular low-foaming nonionic surfactants, can also be added to the agents according to the invention, which improve the detachment of fatty food residues, as wetting agents, as granulating aids or as dispersing aids for better, homogeneous distribution of the aforementioned silver corrosion inhibitors in the washing liquor and on the Silver surfaces serve.
  • Their amount is then up to 10% by weight, preferably up to 3% by weight.
  • Extremely low-foam connections are usually used. These preferably include C12-C18 ethylene oxide and propylene oxide units in the molecule.
  • nonionic surfactants known as low-foam such as.
  • Ci2-Ci8-alkyl polyethylene glycol polybutylene glycol ether each with up to 8 - 10 -
  • the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
  • a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
  • Other optional additives are e.g. B. Perfume oils.
  • the dishwashing detergents according to the invention are preferably in the form of powdered or granular preparations or tablet-shaped preparations which are produced by the granules containing the redox-active substance compacting the basic recipes produced in the customary manner, for example by mixing, granulating, rolling and / or by spray drying admixed and, if necessary, tabletted.
  • pH of a 10% by weight aqueous solution 1.76 2.06 2.07 1.69
  • Dicarboxylic acid mixture of adipic acid, glutaric acid and succinic acid (from BASF)
  • Citric acid, sodium sulfate and manganese (II) sulfate were placed in a 130 liter ploughshare mixer from Lödige, granulated with water or an aqueous Sokalan DCS R (BASF) and then dried in a fluidized bed dryer.
  • the manganese does not react to higher oxidation levels.
  • the active oxygen content was determined immediately after production and after 4 weeks of storage (at 30 ° C. and 80% relative humidity).
  • the content of active oxygen was determined in acidic solution by potentiometric titration with a 0.04 molar KMnO4 solution with a Titroprocessor 682 (Metrohm) determined.
  • a platinum electrode from Metrohm was used for this; a calomel electrode served as the reference electrode.
  • a mixture to a low-alkaline machine dishwashing detergent of composition I which contains 3.6% of the granules 1 to 4 mentioned, shows a clearly delayed oxidation of the manganese (II) sulfate and a stability of the bleaching component, which is comparable with the corresponding manganese salt-free, lower-alkaline cleaner is.
  • premixes 5 to 8 (according to the invention) and the premix V9 (not according to the invention) were produced in a ploughshare mixer, then compacted on a roller press from Alexanderwerke, type WP 50 N / 75 and the fine grain fraction (less than 0.2 mm) sieved.
  • Citric acid 91.5 89.5 - 90 - anhydrous
  • the granules 5 to 8 according to the invention were stable, the granules V9 not according to the invention turned yellow and split off NH3.
  • Agents according to the invention for machine washing dishes of the following compositions were produced (data in% by weight): the silver protection effect was evaluated as follows:
  • Silver spoons (type WMF, hotel cutlery, form Berlin) were cleaned with a silver cleaner, degreased with gasoline and dried.
  • a dishwashing solution was then prepared from 500 g of water at 35 ° C. with a hardness of 16 ° C. and 2.5 g of detergent I-VIII. Then the silver spoons were immersed and the solution was heated to 65 ° C. After about 20 minutes the final temperature of 65 ° C was reached; the silver spoons were then left in the solution for a further 10 minutes, then removed, rinsed with water and assessed visually.
  • the tarnishing colors in the range 0 to 5 were evaluated:
  • Amylase 1 0.5 0.5 1.5
  • Amylase 1 0.5 0.5 1.5

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention a pour objet des granulés acides renfermant une substance à activité redox. Sous cette forme, la substance à activité redox est protégée contre les interactions chimiques indésirables avec l'oxygène de l'air ou d'autres constituants. Les granulés selon l'invention sont de préférence contenus dans des agents détergents pour lave-vaisselle, où la substance à activité redox, par exemple, un sel ou un complexe d'un métal d'un groupe de transition ou d'un groupe principal, se comporte, en particulier, comme un agent anti-corrosion de l'argent.
PCT/EP1996/002047 1995-05-22 1996-05-13 Granules acides renfermant des substances a activite redox WO1996037593A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP8535329A JPH11505290A (ja) 1995-05-22 1996-05-13 酸化還元活性物質を含有する酸性顆粒
EP96916058A EP0827529A1 (fr) 1995-05-22 1996-05-13 Granules acides renfermant des substances a activite redox

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995118695 DE19518695A1 (de) 1995-05-22 1995-05-22 Redoxaktive Substanzen enthaltende saure Granulate
DE19518695.8 1995-05-22

Publications (1)

Publication Number Publication Date
WO1996037593A1 true WO1996037593A1 (fr) 1996-11-28

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EP (1) EP0827529A1 (fr)
JP (1) JPH11505290A (fr)
DE (1) DE19518695A1 (fr)
WO (1) WO1996037593A1 (fr)

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EP0927241A1 (fr) * 1996-08-26 1999-07-07 The Procter & Gamble Company Regulation de l'activite de la cellulase par un terminateur
WO2001009276A1 (fr) * 1999-07-28 2001-02-08 Ciba Specialty Chemicals Holding Inc. Complexes de manganese de type salen sous forme de granules hydrosolubles
US7109155B2 (en) 2002-12-07 2006-09-19 Clariant Gmbh Liquid bleaching composition components comprising amphiphilic polymers
WO2007030352A2 (fr) 2005-09-07 2007-03-15 Transitions Optical, Inc. Article optique multifocal photochrome
US7243664B2 (en) 2005-03-04 2007-07-17 The Procter & Gamble Company Automatic dishwashing composition with corrosion inhibitors
WO2012085534A1 (fr) 2010-12-21 2012-06-28 Reckitt Benckiser N.V. Particule de catalyseur de blanchiment
US8592617B2 (en) 2005-12-21 2013-11-26 Roche Diagnostics Operations, Inc. Redox mediators

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DE10242222A1 (de) * 2002-09-12 2004-03-25 Henkel Kgaa Unter Druck kompaktiertes Wasch- oder Reinigungsmittel
JP2009149778A (ja) * 2007-12-20 2009-07-09 Lion Corp 漂白活性化成分の造粒物およびそれを含有する洗浄剤組成物、ならびに漂白活性化成分の造粒物の製造方法
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin
EP3050952A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Procédé de lavage de vaisselle
EP3050951A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Procédé de lavage de vaisselle
PL3050953T3 (pl) 2015-02-02 2019-07-31 The Procter And Gamble Company Kompozycja detergentu

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EP0927241A1 (fr) * 1996-08-26 1999-07-07 The Procter & Gamble Company Regulation de l'activite de la cellulase par un terminateur
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WO2012085534A1 (fr) 2010-12-21 2012-06-28 Reckitt Benckiser N.V. Particule de catalyseur de blanchiment

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EP0827529A1 (fr) 1998-03-11
JPH11505290A (ja) 1999-05-18
DE19518695A1 (de) 1996-11-28

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