EP1920040B1 - Granules regulateurs de mousse comme agents antidepot lors du lavage de textiles en machine - Google Patents

Granules regulateurs de mousse comme agents antidepot lors du lavage de textiles en machine Download PDF

Info

Publication number
EP1920040B1
EP1920040B1 EP06776697A EP06776697A EP1920040B1 EP 1920040 B1 EP1920040 B1 EP 1920040B1 EP 06776697 A EP06776697 A EP 06776697A EP 06776697 A EP06776697 A EP 06776697A EP 1920040 B1 EP1920040 B1 EP 1920040B1
Authority
EP
European Patent Office
Prior art keywords
group
use according
organopolysiloxane
carbon atoms
foam
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.)
Not-in-force
Application number
EP06776697A
Other languages
German (de)
English (en)
Other versions
EP1920040A1 (fr
Inventor
Erik BRÜCKNER
Eva-Maria Wikker
Lothar Zander
Doris Dahlmann
Birgit Middelhauve
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
Priority to PL06776697T priority Critical patent/PL1920040T3/pl
Publication of EP1920040A1 publication Critical patent/EP1920040A1/fr
Application granted granted Critical
Publication of EP1920040B1 publication Critical patent/EP1920040B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the preparation of such particulate foam control agents is carried out by spray-drying an aqueous slurry containing the support material and the defoaming mixture.
  • the defoamer performance of the defoamer mixture is reported to be insufficient when sprayed onto a particulate detergent.
  • Subject of the German patent application DE 23 38 468 is a detergent containing a silicone defoamer that is protected against interactions with the detergent ingredients.
  • aqueous melts containing the silicone defoamer and a carrier substance, for example polyglycol are first spray-dried and the resulting particles in a fluidized bed
  • the coating material used can be any of the conventional salts used in detergents, in particular tripolyphosphate or carboxymethylcellulose. Such a multi-stage production process is comparatively technically complicated.
  • the European patent application EP 097 867 describes a method for producing microencapsulated defoamer oils by mixing a silicone emulsion with an aqueous solution of carboxymethylcellulose and precipitating the microcapsules by adding electrolytes, especially polyvalent salts or organic solvents. There is considerable difficulty in homogeneously distributing the small quantities of silicone microcapsules required for adequate foam damping in a comparatively large quantity of washing powder.
  • polysiloxane block polymers which comprises liquid polydimethylsiloxane and spatially crosslinked polysiloxane having Si-bonded phenyl, phenylethyl or alkyl radicals having from 2 to 8 carbon atoms and optionally methyl radicals in the presence of Lewis acid or a basic substance heated and a silica airgel admits.
  • the polysiloxane block polymers can be used as foam inhibitors, especially in detergents, dishwashing detergents and cleaners.
  • the paraffin wax is not used alone but in combination with a bis-fatty acid amide which is known to enhance its foam regulator action but is generally solid at room temperature, it can be used according to International Patent Application WO 00/36063 the problem of clogging of the piping and nozzles used because of the risk of solidification of the Bisfettklamids by the use of an aqueous foam regulator emulsion, the 16 wt .-% to 70 wt .-% foam regulator active paraffin wax and / or silicone oil-based, 2 wt .-% to 15 wt.% Nonionic and / or anionic emulsifier and not more than 80 wt .-% water, dissolve. Particles with even greater stability can be made in accordance with international standards Patent application WO 02/074894 when solid support material containing alkali carbonate and a Br ⁇ nsted acid is used.
  • the invention relates to the use of a particulate formulated foam regulator comprising a combination of an organopolysiloxane (A) having at least one silicon-bonded substituent of the formula X-Ph, wherein X is a divalent organic group which is bonded via a carbon atom to silicon, and Ph a aromatic group means containing an organosilicon resin (B) and a hydrophobic filler (C), for preventing deposits on hydrophobic areas of a washing machine in the foam control of detergents used in automatic washing processes.
  • A organopolysiloxane
  • X-Ph a divalent organic group which is bonded via a carbon atom to silicon
  • Ph a aromatic group means containing an organosilicon resin (B) and a hydrophobic filler (C), for preventing deposits on hydrophobic areas of a washing machine in the foam control of detergents used in automatic washing processes.
  • Suitable components (A), (B) and (C) are in particular in the European patent specification EP 1 075 864 described.
  • the sum of the components (A), (B) and (C) is optionally also referred to below as silicone oil.
  • the combination additionally contains foam-regulating Paraffin wax (D), which is solid at room temperature and in 100 ° C in completely liquid form.
  • the particulate foam regulator granules are preferably prepared by spraying an aqueous foam regulator emulsion comprising 6% to 75% by weight of the foam regulator active ingredient combination of (A), (B) and (C), and optionally (D) and 2% by weight to Contains 15 wt .-% nonionic and / or anionic emulsifier in water, on a solid support material, which optionally followed by a drying step prepared.
  • the carrier material preferably contains alkali carbonate and a Br ⁇ nsted acid.
  • a Br ⁇ nsted acid used as part of the support material is in solid form at 25 ° C. It has at 25 ° C a water solubility of preferably at least 100 g / l. Preferably, it is selected from the di- and tricarboxylic acids, their acidic salts, the acidic salts of inorganic acids, in particular NaHSO 4 , Na 2 HPO 4 and NaH 2 PO 4 , and mixtures thereof.
  • the Br ⁇ nsted acid is citric acid.
  • the support material used preferably contains alkali carbonate and a Br ⁇ nsted acid in weight ratios of 1: 1 1 to 100: 1, in particular from 20: 3 to 80: 3.
  • the support material preferably has 40% by weight to 90% by weight, in particular 60% by weight to 80% by weight, of alkali carbonate and 1-20% by weight, in particular 3% by weight to 9% by weight.
  • a Br ⁇ nsted acid It may consist solely of alkali metal carbonate and Br ⁇ nsted acid or additionally contain other particulate components, solid and / or formulated in solid form washing or cleaning agent components come into question.
  • the carrier material comprises a combination of alkali metal bicarbonate and alkali carbonate, the weight ratio of which is preferably 99: 1 to 10:90, in particular 95: 5 to 50:50.
  • alkali metal in the salts mentioned as well as in the alkali carbonate is sodium.
  • a build-up granulation in such a way that one mixes an amount of 40 to 110 parts by weight, in particular 60 to 90 parts by weight of support material, which may preferably additionally contain alkali metal sulfate and / or alkali metal bicarbonate, intensive and granulating an amount of 15 to 50 parts by weight , in particular 25 to 35 parts by weight of the foam regulator emulsion, optionally heated to a temperature in the range of 70 ° C to 180 ° C.
  • Small amounts of water preferably not more than 10 parts by weight, in particular from 1 to 5 parts by weight of water, may, if desired, also be added after or preferably before the addition of the foam regulator emulsion.
  • a foam regulator emulsion containing paraffin wax which can be used according to the invention is preferably prepared by melting the paraffin wax in the presence of the emulsifier, optionally cooling the melt to at most about 100 ° C. and stirring in water. If mixtures of nonionic emulsifier and anionic emulsifier are used, it is preferred to incorporate the nonionic emulsifier as described in the melt of paraffin wax and the anionic emulsifier not the melt, but before stirring the melt added to the water. When using paraffin wax in molten, uncooled form, it is preferable to use cold water having a maximum room temperature To use temperature.
  • melt is cooled before stirring in water to a temperature of at most about 100 ° C, it is preferred to use water at a temperature of about 50 ° C to 80 ° C.
  • Conventional stirring devices are usually sufficient to achieve the uniform distribution of all components and thus to produce the aqueous emulsion useful in this invention;
  • high-speed mixers or homogenizers for example Ultra Turrax®
  • the incorporation of silicone oil is possible at any point of this process.
  • foam regulator emulsions are to be prepared which contain silicone oil as the sole foam regulator active ingredient or in comparison with the amount of paraffin wax in a higher amount, it is preferred to first mix the silicone oil with the nonionic and / or anionic emulsifier, add a portion of the water quantity with stirring so that a Forms emulsion of the type of water in silicone, continues to add more water until it comes to an inversion of the emulsion, stirred vigorously and then with stirring, the remaining water to.
  • the emulsion thus obtained may optionally have partially multiple character, that is, in the outer water phase may also be droplets of the original core emulsion type water in silicone.
  • the group Ph is a moiety containing at least one benzene ring -C 6 R 5 wherein each R is independently hydrogen, halogen, hydroxyl, an alkoxy group of 1 to 6 carbon atoms or a monovalent hydrocarbon group with 1 to 12 carbon atoms or wherein two or more R groups together represent a divalent hydrocarbon group.
  • the average number of siloxane units per molecule preferably ranges from 5 to 5,000.
  • the organopolysiloxane (A) at least 50% of diorganosiloxane units of the formula -SiYY'O- and up to 50% diorganosiloxane units Y is an alkyl group having 1 to 4 carbon atoms and Y 'is an aliphatic hydrocarbon group having 1 to 24 carbon atoms, especially 1 to 6 carbon atoms.
  • the group X is an alkylene group having 1 to 24 carbon atoms and Ph is a phenyl group.
  • the group is -X-Ph 2-phenylpropyl.
  • the organopolysiloxane (A) preferably contains at least one crosslink site between siloxane polymer chains corresponding to the formula -X'- or -X'-Sx-X'-, wherein X 'is a divalent aliphatic organic group bonded to carbon via silicon, and Sx is an organosiloxane group.
  • the organosilicon resin (B) is preferably a non-linear silicone consisting of siloxane units of the formula R ' a SiO (4-a) / 2 wherein R' represents a hydroxyl, hydrocarbyl or hydrocarbonoxy group and a has an average value of 0.5 until 2.4 has. It consists in particular of monovalent trihydroxycarbonsiloxy groups of the formula R "SiO 1/2 and tetrafunctional groups SiO 4/2 in the numerical ratio range from 0.4: 1 to 1.1: 1, where R" denotes an alkyl group. It preferably has an average particle size in the range from 2 ⁇ m to 50 ⁇ m.
  • the hydrophobic filler (C) is preferably selected from the group consisting of silica, titania, ground quartz, alumina, aluminosilicates, polyethylene waxes, microcrystalline waxes, zinc oxide, magnesium oxide, salts of aliphatic carboxylic acids, cyclohexylamine, alkylamides, SiO 2 and mixtures thereof.
  • pyrogenic or precipitated, in particular hydrophobicized silica having a surface area of at least 50 m 2 / g is particularly preferred, as it is commercially available, for example, under the names Aerosil® or Sipemat®.
  • Silicas preferably have an average particle size of 0.5 .mu.m to 30 .mu.m.
  • the viscosity of the silicone oil is preferably in the range from 1,000 mPa.s to 30,000 mPa.s, in particular from 1,500 mPa.s to 3,000 mPa.s.
  • paraffin waxes in question in accordance with the invention are generally complex mixtures without a sharp melting point.
  • the characterization is usually determined their melting range by differential thermal analysis (DTA) as described in "The Analyst” 87 (1962), 420, and / or their solidification point. This is the temperature at which the wax passes from the liquid to the solid state by slow cooling.
  • DTA differential thermal analysis
  • paraffins which are completely liquid at room temperature ie those having a solidification point below 25.degree. C.
  • solid paraffins which are solid at room temperature are useful.
  • the paraffin wax is solid at room temperature and is at 100 ° C in a completely liquid form.
  • paraffin wax mixtures of, for example, 26 wt .-% to 49 wt .-% microcrystalline paraffin wax having a freezing point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C. up to 40 ° C.
  • paraffins or paraffin mixtures are used, which solidify in the range of 30 ° C to 90 ° C.
  • paraffin wax mixtures may contain different proportions of liquid paraffin.
  • the liquid fraction at 40 ° C. is as high as possible without being 100% beautiful at this temperature.
  • Preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt.%, In particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-% to.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is achieved is, with particularly preferred paraffin wax mixtures, still below 85 ° C., in particular at 75 ° C. to 82 ° C.
  • paraffin waxes contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions.
  • Paraffin waxes which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.
  • silicone oil is preferably used in mixtures of paraffin wax and silicone oil in amounts such that the foam regulator emulsion used in the process according to the invention has a content of silicone oil in the range from 0.1% by weight to 10% by weight, in particular 1% by weight. -% to 5 wt .-% has.
  • the foam regulator emulsion to be sprayed onto the carrier material contains a mixture of paraffin wax and silicone oil in a weight ratio of 11: 1 to 1.8: 1, in particular 5: 1 to 2: 1.
  • a foam regulator emulsion used with particular preference contains from 5% by weight to 40% by weight, in particular from 10% by weight to 35% by weight of silicone oil, from 1% by weight to 10% by weight, in particular 2% by weight 5 wt .-% paraffin wax and 50 wt .-% to 94 wt .-% water.
  • the foam regulator emulsion useful according to the invention and a foam regulator used according to the invention are preferably free of bis-fatty acid amides.
  • Nonionic emulsifiers which can be used in emulsions which can be used according to the invention are, in particular, the alkoxylates, preferably the ethoxylates and / or propoxylates of alcohols, alkylamines, vicinal diols, carboxylic acids and / or carboxamides, the alkyl groups having 8 to 22 C atoms, preferably 12 to 18 carbon atoms, understood.
  • the average degree of alkoxylation of these compounds is generally from 1 to 10, preferably 2 to 5. They can be prepared in a known manner by reaction with the corresponding alkylene oxides.
  • Suitable alcohol alkoxylates include the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 8 to 22 C atoms, preferably 12 to 18 C atoms. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers can be used for the preparation of usable alkoxylates.
  • the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are useful.
  • the use of corresponding alkoxylates of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and eruca alcohol, is also possible.
  • esters or partial esters of carboxylic acids corresponding C chain length with polyols such as glycerol or oligoglycerol can be used.
  • Preferred anionic emulsifiers are alkali metal salts of alkylbenzenesulfonic acids having 9 to 13 carbon atoms in the alkyl group, in particular sodium dodecylbenzenesulfonate.
  • small amounts, optionally up to 4% by weight, of anionic and / or nonionic cellulose ethers, such as carboxymethylcellulose and / or hydroxyethylcellulose, may be present.
  • Essential for the preparation according to the invention useful emulsions is that one uses a homogeneous mixture of foam control system and in particular nonionic emulsifier. These can advantageously be achieved in a simple manner by melting the paraffin solid at room temperature in the presence of the silicone oil and the emulsifier, expediently with stirring or homogenization. Subsequent to the preferably at temperatures in the range of 60 ° C to 150 ° C, in particular 80 ° C to 150 ° C made formation of the mixture of defoamer and emulsifier this is, optionally after cooling, mixed with the water, wherein the water previously a in particular anionic emulsifier may have been added. In this case, the concentration of anionic emulsifier in water is preferably 5 wt% to 15 wt%.
  • the emulsion obtainable in this way is storage-stable at room temperature and preferably 3 to 60% by weight, in particular 15 to 45% by weight, of the carrier material is applied to it.
  • a drying step for example using conventional fluidized bed dryer, be connected, or bringing the emulsion with simultaneous drying, for example, also in a fluidized bed, on.
  • the foam regulator granules according to the invention or obtainable by the process according to the invention preferably contain 5% by weight to 50% by weight, in particular 8% by weight to 35% by weight, of foam regulator active ingredient.
  • the granules were incorporated into particulate universal detergents and used in machine washing processes. After 250 and in particular after 450 washes, the rubber cuffs of the washing machine were visually inspected:

Landscapes

  • 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)
  • Detergent Compositions (AREA)

Abstract

L'objectif de cette invention est d'empêcher, lors d'opérations de lavage en machine, l'apparition de dépôts sur des zones hydrophobes d'une machine à laver, qui apparaissent lorsque des détergents sont utilisés. A cet effet, l'invention consiste à utiliser un régulateur de mousse sous forme de particules, qui contient une combinaison d'un organopolysiloxane présentant au moins un substituant à liaison silicium de formule X-Ph, dans laquelle X représente un groupe organique divalent lié au silicium par l'intermédiaire d'un atome de carbone, et Ph représente un groupe aromatique, d'une résine d'organosilicium et d'une charge hydrophobe.

Claims (15)

  1. Utilisation d'un régulateur de mousse confectionné pour prendre une forme particulaire, qui contient une combinaison d'un organopolysiloxane (A) comprenant au moins un substituant lié à un atome de silicium répondant à la formule X-Ph où X représente un groupe organique divalent qui est lié à l'atome de silicium via un atome de carbone et Ph représente un groupe aromatique, d'une résine d'organosilicium (B) et d'une matière de charge hydrophobe (C), pour s'opposer aux dépôts dans des zones hydrophobes d'un lave-linge lors de la régulation de la mousse de détergents qui interviennent dans le processus de lavage en machine.
  2. Utilisation selon la revendication 1, caractérisée en ce que, dans l'organopolysiloxane (A), le groupe Ph représente une unité qui contient au moins 1 noyau benzénique -C6R5, formule dans laquelle chaque R représente, de manière réciproquement indépendante, un atome d'hydrogène, un atome d'halogène, un groupe hydroxyle, un groupe alcoxy contenant de 1 à 6 atomes de carbone ou bien un groupe d'hydrocarbure monovalent contenant de 1 à 12 atomes de carbone ou dans laquelle deux groupes R ou plus représentent ensemble un groupe d'hydrocarbure divalent.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que, dans l'organopolysiloxane (A), le nombre moyen d'unités siloxane par molécule s'élève de 5 à 5.000.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que, dans l'organopolysiloxane (A), sont contenus au moins 50 % d'unités de diorganosiloxane répondant à la formule -SiYY'O- et jusqu'à 50 % d'unités de diorganosiloxane répondant à la formule -SiYXPhO-, où Y représente un groupe alkyle contenant de 1 à 4 atomes de carbone et Y' représente un groupe d'hydrocarbure aliphatique contenant de 1 à 24 atomes de carbone, en particulier de 1 à 6 atomes de carbone.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que, dans l'organopolysiloxane (A), le groupe X représente un groupe alkylène contenant de 1 à 24 atomes de carbone et Ph représente un groupe phényle.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que, dans l'organopolysiloxane (A), le groupe X-Ph représente un groupe 2-phénylpropyle.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'organopolysiloxane (A) possède un endroit de réticulation entre des chaînes polymères siloxane, qui répond à la formule -X'- ou à la formule -X'-Sx-X'-, X' représentant un groupe organique aliphatique divalent qui est lié à l'atome de carbone via un atome de silicium, et Sx représente un groupe d'organosiloxane.
  8. Utilisation selon l'une quelconque des revendications 1 à 7, caractérisée en ce que la résine d'organosilicium (B) représente une silicone non linéaire qui est constitué par des unités siloxane répondant à la formule R'aSiO(4-a)/2 dans laquelle R' représente un groupe hydroxyle, un groupe d'hydrocarbure ou un groupe hydrocarbone-oxy et a possède une valeur moyenne de 0,5 à 2,4.
  9. Utilisation selon l'une quelconque des revendications 1 à 8, caractérisée en ce que la résine d'organosilicium (B) représente une résine de siloxane qui est constituée par des groupes trihydroxycarbone-siloxy monovalents répondant à la formule R"SiO1/2 et par des groupes tétrafonctionnels SiO4/2 dans la plage d'un rapport numéral de 0,4:1 à 1,1:1, R" représentant un groupe alkyle.
  10. Utilisation selon l'une quelconque des revendications 1 à 9, caractérisée en ce que la résine d'organosilicium (B) présente une granulométrie moyenne dans la plage de 2 µm à 50 µm.
  11. Utilisation selon l'une quelconque des revendications 1 à 10, caractérisée en ce que la matière de charge hydrophobe (C) est choisie parmi le groupe constitué par l'acide silicique, le dioxyde de titane, du quartz broyé, l'oxyde d'aluminium, des aluminosilicates, des cires de polyéthylène, des cires microcristallines, l'oxyde de zinc, l'oxyde de magnésium, des sels d'acides carboxyliques aliphatiques, la cyclohexylamine, des alkylamides, du SiO2 ainsi que leurs mélanges.
  12. Utilisation selon l'une quelconque des revendications 1 à 11, caractérisée en ce que la matière de charge hydrophobe (C) représente un acide silicique dont la granulométrie moyenne s'élève de 0,5 µm à 30 µm.
  13. Utilisation selon l'une quelconque des revendications 1 à 12, caractérisée en ce que la combinaison dans le régulateur de mousse confectionné pour prendre une forme particulaire comprend en outre une cire de paraffine régulatrice de mousse (D) qui est présente sous forme solide à la température ambiante et sous forme complètement liquide à 100 °C.
  14. Utilisation selon la revendication 13, caractérisée en ce que la cire de paraffine présente, à 40 °C, une fraction liquide d'au moins 50 % en poids, en particulier de 55 % en poids à 80 % en poids, et à 60 °C, une fraction liquide d'au moins 90 % en poids.
  15. Utilisation selon l'une quelconque des revendications 1 à 14, caractérisée en ce que la combinaison est présente sur une matière de support qui contient un carbonate de métal alcalin et un acide de Bronsted, l'acide de Bronsted étant présent sous forme solide à 25 °C.
EP06776697A 2005-08-24 2006-08-09 Granules regulateurs de mousse comme agents antidepot lors du lavage de textiles en machine Not-in-force EP1920040B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06776697T PL1920040T3 (pl) 2005-08-24 2006-08-09 Granulaty regulatora pienienia jako środki zapobiegające osadom przy maszynowym praniu tekstyliów

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005040273A DE102005040273B4 (de) 2005-08-24 2005-08-24 Verwendung von Schaumregulatorgranulaten als Ablagerungsverhinderer bei der maschinellen Textilwäsche
PCT/EP2006/007866 WO2007022866A1 (fr) 2005-08-24 2006-08-09 Granules regulateurs de mousse comme agents antidepot lors du lavage de textiles en machine

Publications (2)

Publication Number Publication Date
EP1920040A1 EP1920040A1 (fr) 2008-05-14
EP1920040B1 true EP1920040B1 (fr) 2012-05-16

Family

ID=37198829

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06776697A Not-in-force EP1920040B1 (fr) 2005-08-24 2006-08-09 Granules regulateurs de mousse comme agents antidepot lors du lavage de textiles en machine

Country Status (5)

Country Link
EP (1) EP1920040B1 (fr)
DE (1) DE102005040273B4 (fr)
ES (1) ES2383819T3 (fr)
PL (1) PL1920040T3 (fr)
WO (1) WO2007022866A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0901662D0 (en) 2009-02-04 2009-03-11 Dow Corning Foam control composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2952287A1 (de) 1979-12-24 1981-07-02 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines polysiloxan-blockpolymerisates sowie dessen verwendung als schauminhibitor
DE3128631A1 (de) 1981-07-20 1983-02-03 Henkel Kgaa "verfahren zur herstellung eines schaumgedaempften, silikone enthaltenden waschmittels"
DE3224135A1 (de) 1982-06-29 1983-12-29 Th. Goldschmidt Ag, 4300 Essen Pulverfoermiger entschaeumer und verfahren zu seiner herstellung
DE3436194A1 (de) 1984-10-03 1986-04-10 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines schuettfaehigen entschaeumerpraeparates
DD248600A1 (de) * 1986-04-23 1987-08-12 Genthin Waschmittelwerk Schaumdaempfendes mittel fuer pulverfoermige waschmittel
DE60017223T2 (de) * 1999-08-13 2005-12-08 Dow Corning S.A. Schaumregulierungsmittel auf Basis von Silikon
DE10108459A1 (de) * 2001-02-22 2002-09-12 Henkel Kgaa Schaumregulatorgranulat

Also Published As

Publication number Publication date
WO2007022866A1 (fr) 2007-03-01
ES2383819T3 (es) 2012-06-26
EP1920040A1 (fr) 2008-05-14
PL1920040T3 (pl) 2012-10-31
DE102005040273B4 (de) 2007-08-30

Similar Documents

Publication Publication Date Title
EP1137751B1 (fr) Emulsion aqueuse regulatrice de mousse
DE19962859A1 (de) Feste Waschmittel
DE19958398A1 (de) Verwendung von Partialgyceridpolyglycolethern
DE19953796A1 (de) Feste Wasch-, Spül- und Reinigungsmittel
DE2646127A1 (de) Wasch- und reinigungsmittelzusammensetzungen
EP1090102B1 (fr) Procede pour preparer des granulats antimousse
EP0708817B1 (fr) Agent regulateur de mousse coulant, sans phosphate
EP1920040B1 (fr) Granules regulateurs de mousse comme agents antidepot lors du lavage de textiles en machine
EP1362090B1 (fr) Granules regulateurs de mousse
EP1917338B1 (fr) Granulat regulateur de mousse
WO1993017772A1 (fr) Agent regulateur de moussage a base de paraffine
WO2000031221A1 (fr) Granulats antimoussants comportant des esters de polyethyleneglycols d'acides gras
WO2001034746A1 (fr) Granules d'antimousse
WO1997034983A1 (fr) Agent particulaire regulateur de mousse a base de paraffine
DE4240166A1 (de) Silikonfreies Schaumregulierungsmittel
DE4323411A1 (de) Schüttfähiges, phosphatfreies Schraumregulierungsmittel
DE19837196A1 (de) Herstellung von Entschäumergranulaten im Dünnschichtverdampfer
DE19953794A1 (de) Formkörper mit verbesserter Wasserlöslichkeit
WO2000027962A1 (fr) Granulats antimoussants contenant des cetones
DE19854531A1 (de) Entschäumergranulate mit Ether
DE19942538A1 (de) Waschmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080119

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

17Q First examination report despatched

Effective date: 20091228

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 558105

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2383819

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120626

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502006011452

Country of ref document: DE

Effective date: 20120712

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120516

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Effective date: 20120530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120916

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120917

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120817

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20120831

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

26N No opposition filed

Effective date: 20130219

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120816

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502006011452

Country of ref document: DE

Effective date: 20130219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120816

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120809

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120816

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 558105

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120809

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060809

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20160825

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20160822

Year of fee payment: 11

Ref country code: CZ

Payment date: 20160808

Year of fee payment: 11

Ref country code: PL

Payment date: 20160722

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20160810

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170809

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170809

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170831

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181029

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170809

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170810

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190822

Year of fee payment: 14

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502006011452

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210302