EP0687290B1 - Nettoyant pour sols - Google Patents
Nettoyant pour sols Download PDFInfo
- Publication number
- EP0687290B1 EP0687290B1 EP94909043A EP94909043A EP0687290B1 EP 0687290 B1 EP0687290 B1 EP 0687290B1 EP 94909043 A EP94909043 A EP 94909043A EP 94909043 A EP94909043 A EP 94909043A EP 0687290 B1 EP0687290 B1 EP 0687290B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- composition
- agents
- floor cleaning
- cleaning composition
- 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.)
- Expired - Lifetime
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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to an aqueous agent which can be used in a diluted state for cleaning and maintaining hard surfaces, in particular floors.
- agents Numerous new processes and agents have been developed for cleaning and maintaining floors in recent years and decades, not least due to the development of new materials for floor coverings.
- the choice of agents is essentially determined by whether cleaning or preservation of the surface is to be achieved as a matter of priority.
- the agents usually contain heavy metal salts, mostly in emulsified form, waxes or film-forming polymers and crosslinking agents, which together form self-glossy or polishable films on the treated surfaces after drying. In this way, long-lasting preservation of the surfaces can be achieved, with strong mechanical loads being well tolerated, depending on the quality of the film.
- agents that focus on cleaning contain high levels of surfactants, often together with alkaline substances, organic solvents or abrasives. In many cases, these agents can be used to thoroughly remove dirt and old coverings, but the surfaces cleaned in this way are usually exposed to re-soiling without protection, unless a preservation treatment is connected.
- the appropriately set agents are often not stable to segregation in the cold and show less good residue behavior when used on smooth floors, with occasional increased re-soiling of the films. To achieve an improvement here without impairing the otherwise good properties of known agents was one of the objects of the present invention.
- the invention relates to an aqueous agent for cleaning floors, which contains nonionic surfactant, anionic surfactant and at least 1% by weight of alkali-soluble polymeric polycarboxylate with a minimum film-forming temperature between 0 and 70 ° C, at least 25% by weight of those in these Agents contained nonionic surfactants consist of alkyl polyglycosides.
- the new agents have excellent cleaning properties and, after drying on the floor surface, deliver very even films with extremely high transparency and very little tendency to re-soiling. Particularly noteworthy is the high stability against segregation when stored in the cold, which exists even when non-foaming nonionic surfactants with relatively low solubility in water are used in view of the particular low-foaming nature and / or the agents have very high surfactant concentrations.
- the surfactants contained in the compositions are based on a mixture of non-ionic and anionic surfactants.
- the nonionic surfactants make up at least 50% by weight of the total surfactant content in the agents according to the invention; their proportion is preferably between 65 and 95% by weight.
- nonionic surfactants are suitable as nonionic surfactants for the agents according to the invention, provided that they meet the requirements regarding low foam.
- EO ethylene oxide
- the corresponding ethoxylation products of other long-chain compounds are also suitable, for example the fatty acids and the fatty acid amides with 12 to 18 carbon atoms and the alkylphenols with 8 to 16 carbon atoms in the alkyl part.
- propylene oxide (PO) can also be added instead of part of the ethylene oxide.
- nonionic surfactants are mono- and diethanolamides of fatty acids and long-chain amine oxides or sulfoxides, for example the compound N-cocoalkyl-N, N-dimethylamine oxide.
- water-soluble addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of ethylene oxide with polypropylene glycol, alkylenediamine polypropylene glycol and with alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic residue.
- nonionic surfactants the addition products of 3 to 10 mol of ethylene oxide with long-chain primary alcohols having 10 to 16 carbon atoms from the group of the oxo alcohols and the natural fatty alcohols are preferred in the agents according to the invention, the fatty alcohol ethoxylates being very particularly preferred.
- the agents according to the invention always also contain alkyl polyglycosides as nonionic surfactants.
- These are surfactants of the general formula I. RO (-G) n I in which R is a long-chain alkyl radical having 8 to 22 carbon atoms, G is a glycosidically bonded radical of a monosaccharide and n is a value between 1 and 10.
- Alkyl polyglycosides have been known as surface-active substances for more than 50 years and can be produced in various ways. In this context, reference should only be made to European patent application 362 671, which also cites literature on older processes.
- a synthesis which is important on an industrial scale today consists essentially in the acid-catalyzed condensation of monosaccharides of the aldose type (HO-G) with long-chain alcohols (R-OH) which contain 8 to 22, preferably 8 to 18, C atoms.
- alkyl glycosides of the formula I When water escapes, alkyl glycosides of the formula I are formed RO (-G) n the value of n can be varied within wide limits by the choice of reaction conditions.
- alkyl glycosides In the production of the alkyl glycosides, one can also start from oligosaccharides or polysaccharides, which are then depolymerized to lower fragments in the course of the acid-catalyzed reaction by hydrolysis and / or alcoholysis before the alkyl glycosides of the formula I form. Mixtures of different reducing monosaccharides or polysaccharides which contain different monosaccharide units can also be used as starting materials, and if n is greater than 1, appropriately mixed alkylglycoside molecules can be formed.
- the following monosaccharides are preferably suitable as starting materials: glucose, mannose, galactose, arabinose, apiose, lyxose, gallose, altrose, idose, ribose, xylose and talose as well as the oligo- and polysaccharides composed of these monosaccharides, for example maltose, lactose, maltotriose, hemicellulose , Starch, partial hydrolyzates of starch and sugar syrup.
- alkyl glycosides are preferred which are composed of the same monosaccharide units.
- Alkyl glycosides in which the rest (-G) is derived from glucose are preferred.
- glucose, maltose, starch and other oligomers of glucose are used accordingly as starting materials.
- the alkyl part R is derived from long-chain, optionally unsaturated, preferably primary alcohols which can be branched, but are preferably not branched.
- Examples are the synthetic oxo alcohols with 9 to 15 C atoms and the fatty alcohols obtained from natural fatty acids with 8 - 22 C atoms.
- the fatty alcohols with 8 to 18 carbon atoms and the oxo alcohols with 11 to 15 carbon atoms are preferred, but in particular the fatty alcohols with 8 to 10 carbon atoms or with 12 to 14 carbon atoms.
- alkyl glycosides of formula I In addition to the actual alkyl glycosides of formula I, technically manufactured products generally also contain certain proportions of free alcohol R-OH and non-acetalized saccharides, optionally in oligomerized form. In most cases, these technical impurities do not interfere with the intended use. If alcohol mixtures are used in the production of the alkyl glycosides, for example alcohols based on natural fats, the alkyl glycosides are of course also mixtures with a correspondingly larger meaning of R in formula I.
- alkyl polyglycosides are preferably used whose glycoside part consists of 1 to 2 glucose units and whose alkyl part is derived from fatty alcohols having 8 to 10 carbon atoms.
- the alkyl polyglycosides in the agents according to the invention make up at least 25% by weight of the total of nonionic surfactants present. In the limit, alkyl polyglycosides alone can be included as nonionic surfactants.
- the agents according to the invention primarily contain synthetic anionic surfactants as anionic surfactants. These are primarily of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are alkylbenzenesulfonates with a C 9 -C 15 -alkyl radical and olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
- alkanesulfonates which are obtainable from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of ⁇ -sulfofatty acids, e.g. B. the ⁇ -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- Suitable sulfate-type surfactants are the sulfuric acid monoesters of long-chain primary alcohols of natural or synthetic origin, ie of fatty alcohols, such as, for. As coconut fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols or secondary alcohols of this chain length.
- the sulfuric acid monoesters of the aliphatic long-chain primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol of ethylene oxide (EO) are also suitable.
- Sulfated fatty acid alkanolamides, sulfated fatty acid monoglycerides and long-chain sulfosuccinic acid esters are also suitable.
- the anionic surfactants are preferably used as alkali salts, in particular sodium salts, but ammonium salts or the salts of alkanolamines having 2 to 6 carbon atoms can also be used.
- particularly preferred anionic surfactants are the fatty alcohol sulfates and the fatty alcohol ether sulfates, for example C 12 / C 18 coconut alcohol sulfate Na and C 12 / C 14 coconut alcohol + 2E0 sulfate.
- the Agents according to the invention also contain smaller amounts of other surfactants, in particular amphoteric surfactants and soaps, if this is expedient to achieve special effects and the other good properties of the agents are not thereby impaired.
- the soaps are the water-soluble salts of long-chain fatty acids with preferably 12 to 18 carbon atoms, for example coconut fatty acid sodium salt and tallow fatty acid sodium salt.
- the amphoteric surfactants are long-chain compounds whose hydrophilic part consists of a cationically charged center (usually a tertiary amino or a quaternary ammonium group) and an anionically charged center (usually a carboxylate or a sulfonate group). Examples of such surfactants are N-cocoalkyl-N, N-dimethylaminoacetate and N-dodecyl-N, N-dimethyl-3-aminopropanesulfonate.
- the total content of surfactants in the agents according to the invention is preferably between 4 and 25% by weight, in particular between 8 and 16% by weight, based on the total agent in the undiluted state.
- alkali-soluble polymeric polycarboxylate with a minimum film formation temperature between 0 and 70 ° C is essential for the care properties of the agents.
- carboxylates can be resin-like compounds, for example copolymers of styrene and maleic anhydride, which can be partially saponified and, if appropriate, also partially esterified or amidated. Soluble polymer compounds, which are copolymers of at least 3 different monomers, are preferred, the polycarboxylates not being metal-crosslinked.
- the polymers used preferably contain an acrylate copolymer of 1 to 30 parts by weight, based on the copolymer, of monomers containing carboxylic acid groups, 30 to 70 parts by weight of monomers which form homopolymers with glass transition temperatures below 20 ° C., preferably esters of acrylic acid with C 1 - C 8 alcohols and / or methacrylic acid with C 4 -C 8 alcohols, and 30 to 70 parts by weight of comonomers which form homopolymers with glass transition temperatures above room temperature, preferably methacrylic acid esters of C 1 -C 3 alcohols or styrene.
- an acrylate copolymer of 1 to 30 parts by weight, based on the copolymer, of monomers containing carboxylic acid groups, 30 to 70 parts by weight of monomers which form homopolymers with glass transition temperatures below 20 ° C., preferably esters of acrylic acid with C 1 - C 8 alcohols and / or methacrylic acid with C 4 -C 8 alcohol
- ethylenically unsaturated carboxylic acids can be used; acrylic acid and methacrylic acid are primarily suitable.
- Comonomers with glass transition temperatures below 20 ° C. include esters of acrylic acid with C 1 -C 8 alcohols and esters of methacrylic acid with C 4 -C 8 alcohols.
- esters of acrylic acid with C 1 -C 8 alcohols include esters of acrylic acid with C 1 -C 8 alcohols and esters of methacrylic acid with C 4 -C 8 alcohols.
- the methyl, ethyl, propyl, butyl or 2-ethylhexyl ester of acrylic acid can be used here, as can the butyl, hexyl or 2-ethylhexyl ester of methacrylic acid.
- Comonomers whose homopolymers have glass transition temperatures above room temperature are esters of methacrylic acid with C 1 -C 3 alcohols, such as methyl methacrylate or ethyl methacrylate.
- a particularly important comonomer whose homopolymer has a glass transition temperature above room temperature is styrene.
- Copolymers of acrylic acid and / or methacrylic acid with styrene, acrylic acid esters and / or methacrylic acid esters are preferably used.
- the copolymers of acrylic acid or methacrylic acid with different acrylic and / or methacrylic acid esters and / or styrene are particularly preferred, for example terpolymers of methyl acrylate, ethyl acrylate, methacrylic acid and styrene.
- the respective ratios of comonomers whose homopolymers have glass transition temperatures below room temperature and monomers whose homopolymers have glass transition temperatures above room temperature must be set so that the film-forming temperature of the polymer dispersion is in the range between 0 and 70 ° C.
- the polycarboxylates used if they are not already water-soluble as such, should be able to be converted into a soluble form with the aid of alkalis.
- alkalis In particular, NaOH, KOH and non-volatile amines, such as, for example, alkanolamines, come in as alkalis Question.
- Aqueous ammonia is preferred, with the aid of which the desired clarification of the polycarboxylates can be carried out particularly safely without the risk of overbasing.
- the finished compositions should preferably have a pH between about 7 and about 11 in the undiluted state; the ranges with pH values between 8 and 9, but also between 10 and 10.5 are particularly preferred.
- the amount of polymeric polycarboxylates in the agents according to the invention is preferably chosen so that the weight ratio between polycarboxylate and the total content of surfactants is between 1: 6 and 2: 3, in particular between 1: 4 and 1: 2. If a mixture of several polymeric polycarboxylates is used, these values apply to the total polycarboxylate content.
- the agents according to the invention can contain further auxiliaries and additives, as are customary in such agents. It is a prerequisite, of course, that this does not impair the positive properties of the agents.
- additives are organic, completely water-miscible solvents which are used to increase the performance and, if appropriate, to improve the wetting capacity. Lower alcohols having 2 or 3 carbon atoms are preferably used, amounts not exceeding 10% by weight, preferably between about 0.2 and 5% by weight, based on the total weight of the undiluted agent.
- other additives are perfume oils, dyes, viscosity regulators and preservatives. These substances are usually used in amounts of not more than 5% by weight, preferably between 0.01 and 2% by weight.
- the agents are used in such a way that a solution of the agent is first prepared by dilution with water, in which the content of non-volatile constituents is between about 0.2 and about 1 g / l. Depending on the concentration of the original agent, this concentration is achieved by dilution between about 1: 1000 and about 1: 50.
- the diluted solution is then applied to the surface to be cleaned with the aid of an absorbent article, for example with the aid of a wipe or a sponge, and z. T. removed with the dirt from the surface again. After this treatment the Surface not rinsed off, so that the remaining cleaning agent solution can dry out to form an evenly protective film. Because of this application method, such agents are also referred to as wiping agents.
- the agent according to the invention is distinguished by an optimal cleaning action against a multitude of soiling and at the same time forms a resistant film which forms excellent protection against re-soiling.
- the film is completely transparent and allows the color and structure of the treated surfaces to appear largely unchanged without additional gloss. When the agent is used again, the film dissolves, making the cleaning process easier. There is no annoying film addition.
- the agent according to the invention is particularly low-foaming even when it is used in higher concentration or undiluted for the local removal of stains. Even in high concentrations, it has excellent storage stability at the usual storage temperatures, but especially in the cold.
- the product is particularly suitable for cleaning floors and provides excellent results on stone, sealed parquet, tiles, linoleum and plastic floors, but it is also suitable for cleaning other hard surfaces, even for glass. Use on high-gloss floor coverings is particularly advantageous because the film formed does not reduce the gloss due to its high transparency.
- the preparation of the agent in its various embodiments presents no difficulties.
- the polymeric polycarboxylate is first dissolved in water, if appropriate with the addition of the alkalizing agents, and the surfactants are then mixed in at the desired concentration. Finally, the additives follow.
- compositions No. 1 to 3 according to the invention and the compositions No. 4 to 10 not according to the invention which are given in Table 1.
- the figures for the ingredients mean% by weight; the rest 100% by weight is water. 3 g of these agents were each diluted to one liter and used in this form to test the cleaning ability and the re-soiling behavior. The transparency of the residue remaining after drying was checked with a 3 times stronger concentration of the agents; The cold stability was tested on the undiluted agents. The test results are also shown in Table 1.
Claims (8)
- Agent aqueux pour le nettoyage des sols, renfermant du tensioactif non ionique, du surfactif anionique et au moins 1 % en poids de polycarboxylate polymère soluble dans les alcalis avec une température de formation de film minimale comprise entre 0 et 70 °C, caractérisé en ce qu'au moins 25 % en poids de la proportion de tensioactifs non ioniques contenue est constituée d'alkylpolyglycosides.
- Agent pour le nettoyage des sols selon la revendication 1, dans lequel la proportion des tensioactifs non ioniques dans la concentration totale en surfactifs représente au moins 50 % en poids, en étant comprise de préférence entre 65 et 95 % en poids.
- Agent pour le nettoyage des sois selon une des revendications 1 ou 2, dans lequel le rapport pondéral entre le polymère et la concentration totale en surfactifs est compris entre 1:6 et 2:3, de préférence, entre 1:4 et 1:2.
- Agent pour le nettoyage des sols selon une des revendications 1 à 3, dans lequel la concentration totale en surfactifs est comprise entre 4 et 25, de préférence entre 8 et 16 % en poids, par rapport au poids du produit prêt à l'emploi.
- Agent pour le nettoyage des sols selon une des revendications 1 à 4, contenant1 à 10, de préférence 2 à 6 % en poids d'éthoxylate d'alcool gras (3 à 10 EO)1 à 10, de préférence 4 à 8 % en poids de polyglucoside d'alcool gras,0,5 à 4, de préférence 1 à 3 % en poids de tensioactif anionique faisant partie du groupe du sulfate d'alcool gras, de l'éther sulfate d'alcool gras et des mélanges de ceux-ci,1 à 8, de préférence 3 à 5 % en poids de polycarboxylate polymère soluble dans les alcalis, avec une température de formation de film minimale comprise entre 0 et 70 °C,0 à 10, de préférence 0,2 à 5 % en poids de solvants organiques miscibles avec l'eau et0 à 5, de préférence 0,01 à 2 % en poids d'autres adjuvants et additifs.
- Agent pour le nettoyage des sols selon une des revendications 1 à 5, dans lequel on utilise comme alkylpolyglycoside, un alkylpolyglycoside présentant une chaîne alkyle constituée de 8 à 10 atomes de C et une fraction polyglycosidique constituée de 1 à 2 unités de glucose.
- Utilisation d'un agent selon une des revendications 1 à 6 à l'état dilué pour le nettoyage et l'entretien simultanés des surfaces dures, en particulier des sols.
- Procédé de nettoyage et d'entretien simultanés des sols, dans lequel un agent selon une des revendications 1 à 6 est tout d'abord dilué avec de l'eau à une concentration en constituants non volatiles de 0,2 à 1 g/l et le sol est ensuite essuyé avec cette solution diluée de l'agent à l'aide d'un objet absorbant.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4306899A DE4306899A1 (de) | 1993-03-05 | 1993-03-05 | Fußbodenreinigungsmittel |
DE4306899 | 1993-03-05 | ||
PCT/EP1994/000530 WO1994020595A1 (fr) | 1993-03-05 | 1994-02-25 | Nettoyant pour sols |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0687290A1 EP0687290A1 (fr) | 1995-12-20 |
EP0687290B1 true EP0687290B1 (fr) | 1997-09-17 |
Family
ID=6482006
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94909043A Expired - Lifetime EP0687290B1 (fr) | 1993-03-05 | 1994-02-25 | Nettoyant pour sols |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0687290B1 (fr) |
AT (1) | ATE158341T1 (fr) |
CA (1) | CA2157570A1 (fr) |
CZ (1) | CZ286846B6 (fr) |
DE (2) | DE4306899A1 (fr) |
DK (1) | DK0687290T3 (fr) |
ES (1) | ES2107195T3 (fr) |
GR (1) | GR3025103T3 (fr) |
HU (1) | HU218506B (fr) |
PL (1) | PL177230B1 (fr) |
SK (1) | SK280885B6 (fr) |
WO (1) | WO1994020595A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4335046A1 (de) * | 1993-10-14 | 1995-04-20 | Henkel Kgaa | Wäßriges Fußbodenreinigungsmittel |
DE19501145A1 (de) * | 1995-01-17 | 1996-07-18 | Huels Chemische Werke Ag | Verwendung von Alkylpolyglycosiden als Reibungsminderer |
DE19714424A1 (de) | 1997-04-08 | 1998-10-15 | Beiersdorf Ag | Kosmetische und dermatologische waschaktive Zubereitungen, enthaltend Acrylatcopolymere, Alkylglucoside und Alkohole |
DE19717950A1 (de) * | 1997-04-29 | 1998-11-05 | Henkel Kgaa | Tensidgemische |
DE19908563C2 (de) * | 1999-02-27 | 2002-11-14 | Cognis Deutschland Gmbh | Reinigungsmittel für harte Oberflächen |
EP2179018A2 (fr) * | 2007-08-17 | 2010-04-28 | Reckitt Benckiser Inc. | Compositions de traitement de surfaces dures, acceptables d'un point de vue environnemental |
DE102013210273A1 (de) * | 2013-06-03 | 2014-12-04 | Henkel Ag & Co. Kgaa | Wasch-, Reinigungs- oder Vorbehandlungsmittel mit erhöhter Reinigungskraft IV |
MA49244A (fr) | 2017-05-11 | 2020-04-15 | Ecolab Usa Inc | Compositions et procédé de nettoyage ou de restauration de sol |
CN116507710A (zh) * | 2020-12-04 | 2023-07-28 | 巴斯夫欧洲公司 | 免擦洗清洁组合物 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0491531A1 (fr) * | 1990-12-18 | 1992-06-24 | Unilever Plc | Compositions détérgentes |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8310529D0 (en) * | 1983-04-19 | 1983-05-25 | Unilever Plc | General-purpose cleaning composition |
DE3533531A1 (de) * | 1985-09-20 | 1987-04-02 | Henkel Kgaa | Reinigungsmittel fuer harte oberflaechen |
DE4116807A1 (de) * | 1991-05-23 | 1992-11-26 | Henkel Kgaa | Konzentriertes waessriges fluessigwaschmittel |
DE4216410A1 (de) * | 1992-05-18 | 1993-11-25 | Henkel Kgaa | Verfahren zur Fußbodenreinigung |
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1993
- 1993-03-05 DE DE4306899A patent/DE4306899A1/de not_active Withdrawn
-
1994
- 1994-02-22 SK SK1102-95A patent/SK280885B6/sk unknown
- 1994-02-25 HU HU9502589A patent/HU218506B/hu not_active IP Right Cessation
- 1994-02-25 EP EP94909043A patent/EP0687290B1/fr not_active Expired - Lifetime
- 1994-02-25 WO PCT/EP1994/000530 patent/WO1994020595A1/fr active IP Right Grant
- 1994-02-25 ES ES94909043T patent/ES2107195T3/es not_active Expired - Lifetime
- 1994-02-25 DK DK94909043.5T patent/DK0687290T3/da active
- 1994-02-25 PL PL94310530A patent/PL177230B1/pl unknown
- 1994-02-25 DE DE59404098T patent/DE59404098D1/de not_active Expired - Fee Related
- 1994-02-25 AT AT94909043T patent/ATE158341T1/de not_active IP Right Cessation
- 1994-02-25 CA CA002157570A patent/CA2157570A1/fr not_active Abandoned
- 1994-02-25 CZ CZ19952132A patent/CZ286846B6/cs not_active IP Right Cessation
-
1997
- 1997-10-20 GR GR970402745T patent/GR3025103T3/el unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0491531A1 (fr) * | 1990-12-18 | 1992-06-24 | Unilever Plc | Compositions détérgentes |
Also Published As
Publication number | Publication date |
---|---|
WO1994020595A1 (fr) | 1994-09-15 |
CZ286846B6 (en) | 2000-07-12 |
HU9502589D0 (en) | 1995-10-30 |
EP0687290A1 (fr) | 1995-12-20 |
CZ213295A3 (en) | 1996-01-17 |
ATE158341T1 (de) | 1997-10-15 |
DK0687290T3 (da) | 1998-05-04 |
CA2157570A1 (fr) | 1994-09-15 |
SK110295A3 (en) | 1997-07-09 |
HUT72022A (en) | 1996-03-28 |
PL310530A1 (en) | 1995-12-27 |
SK280885B6 (sk) | 2000-09-12 |
ES2107195T3 (es) | 1997-11-16 |
HU218506B (hu) | 2000-09-28 |
DE59404098D1 (de) | 1997-10-23 |
GR3025103T3 (en) | 1998-01-30 |
PL177230B1 (pl) | 1999-10-29 |
DE4306899A1 (de) | 1994-09-08 |
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