EP0215451A2 - Cleaning product for hard surfaces - Google Patents
Cleaning product for hard surfaces Download PDFInfo
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- EP0215451A2 EP0215451A2 EP86112626A EP86112626A EP0215451A2 EP 0215451 A2 EP0215451 A2 EP 0215451A2 EP 86112626 A EP86112626 A EP 86112626A EP 86112626 A EP86112626 A EP 86112626A EP 0215451 A2 EP0215451 A2 EP 0215451A2
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- European Patent Office
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- cleaning agent
- floor cleaning
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
Definitions
- the present invention relates to the cleaning and care of hard surfaces, in particular floors, in the household and in commercial cleaning with the aid of aqueous cleaning agents.
- numerous methods and agents have already been developed for the various purposes. The choice of agents is essentially determined by whether cleaning or preservation of the surface should be achieved as a matter of priority.
- the compositions contain, usually in emulsified form, waxes or film-forming polymers and crosslinking active ingredients, as a rule heavy metal salts, which together form self-glossy or polishable films on the treated surfaces after drying.
- a rule heavy metal salts which together form self-glossy or polishable films on the treated surfaces after drying.
- a disadvantage of these agents is that removal of the firmly adhering films, if it becomes necessary, for example because of dirt or damage, is only possible under extreme conditions.
- 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 followed.
- agents that contain the usual film formers in very low concentrations together with surfactants often lead to a disruptive film addition, which requires additional cleaning after certain times.
- the present invention offers a solution to this problem in the form of an agent consisting of: 0.5-10% by weight of surfactant from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof, 0.1 - 4.5% by weight of alkali-soluble, non-metal-crosslinked polymer compound with a minimum film-forming temperature between 0 and 70 ° C, 0.01 - 5% by weight of alkaline complexing agents, 0-3% by weight of alkalizing agent, 0 - 40% by weight of water-miscible organic solvent, 0 - 5 wt .-% additives and Rest of water.
- surfactant from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, alkylbenzenesulfonates, alkylsulfates, alkanesulfonates,
- This agent is used in such a way that a preferably one to three percent solution of the agent is first prepared by dilution with water which is then applied to the surfaces to be cleaned with the help of wipers, sponges or similar aids and partly removed from the surface with the dirt. After this treatment, the surface is 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 large number of soiling and at the same time forms a resistant film which forms excellent protection against re-soiling. In contrast to other agents, this film is completely transparent and allows the color and structure of the treated surfaces to appear 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 preferably suitable for the caring cleaning of floors and delivers excellent results on stone, sealed parquet, tiles, linoleum and plastic floors.
- Use on high-gloss floor coverings is particularly advantageous because the film formed does not reduce the gloss due to its high transparency.
- An agent of the following composition is preferably used.
- surfactant from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, Alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof, 0.2-2.9% by weight of alkali-soluble, non-metal-crosslinked polymer compound with a minimum film-forming temperature between 0 and 70 ° C, 0.05 - 3% by weight of alkaline complexing agents, 0.05-2% by weight of alkalizing agent, 0-20% by weight of water-miscible organic solvent, 0.05 - 2 wt .-% additives and Rest of water.
- the water-soluble, non-hardness-sensitive surfactants from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof are suitable for the agents according to the invention.
- the amounts used are 0.5 to 10% by weight, preferably 1 to 6% by weight, based on the undiluted medium.
- Nonionic and anionic surfactants are preferably used together.
- the nonionic surfactants mentioned are addition compounds of 4-40, preferably 8-20, moles of ethylene oxide (EO) with 1 mole of an aliphatic alcohol or alkylphenol with 10-20 C atoms.
- EO ethylene oxide
- the aliphatic alcohols can be branched or unsaturated and have primary and / or secondary hydroxyl groups.
- nonionic surfactants are nonylphenol + 13 EO, internal C15-C17 alkanediol + 9 EO, C14 / C15 oxo alcohol + 11 EO, coconut alcohol + 7 EO, tallow alcohol + 14 EO.
- Adducts of 8-20 mol EO with fatty alcohols with 12-18 C atoms are preferably used as nonionic surfactants.
- anionic surfactants come from the classes of sulfonates and sulfates and are used consistently as salts, preferably as sodium salts.
- the surfactants of the sulfonate type are the alkylbenzenesulfonates with C 9-15 -alkyl groups, the esters of alpha-sulfofatty acids, e.g. B.
- Suitable sulfate-type surfactants are the sulfuric acid monoesters of primary alcohols natural and synthetic origin, ie from fatty alcohols, such as. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C10-C20 oxo alcohols, and those of secondary alcohols of these chain lengths.
- Alkylbenzenesulfonates and alkanesulfonates are preferably used as anionic surfactants.
- nonionic and anionic surfactants good to very good cleaning results are achieved throughout, but in many cases it is possible, without loss of cleaning performance, to use a smaller proportion, ie up to about 50%, of these surfactants by other types, such as ethylene oxide adducts Polypropylene oxide or to replace fatty acid amides or olefin sulfonates, sulfosuccinates and alkyl ether sulfates.
- all polymer compounds soluble in water in the alkaline range are suitable, provided they are not metal-crosslinked and have a minimum film-forming temperature between 0 and 70 ° C. These are generally copolymers of at least three different monomers.
- the solubility is at least 0.1%, preferably 0.2%, at a pH between 8 and 10.5, in particular between 8.5 and 9.5.
- the polymers used preferably contain, as the most important constituent, 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 C1-C8 alcohols and / or methacrylic acid with C4 to C8 alcohols and 30 to 70 parts by weight of Comono mers that form homopolymers with glass transition temperatures above room temperature, preferably methacrylic acid esters of C1 to C3 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 C1-C8 alcohols and / or methacrylic acid with C4 to C8 alcohols
- ethylenically unsaturated carboxylic acids can be used; acrylic acid and methacrylic acid are primarily suitable.
- esters of acrylic acid with C1-C8 alcohols are esters of acrylic acid with C1-C8 alcohols and esters of methacrylic acid with C4-C8 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 C1-C3 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 copolymers 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 general knowledge of polymer chemistry applies.
- the film formation temperatures mentioned relate to the plasticizer-free system, i. H. on the polymers without further additives.
- the polymers are preferably soluble in water only in the alkaline range, while they remain undissolved in the acidic range.
- Corresponding products are often offered by the trade in emulsified form.
- 0.1 to 4.5% by weight of the polymers, calculated as pure polymer, are used in the agents according to the invention.
- Preferred contents are 0.2 to 2.9% by weight, in particular 0.2 to 1.0% by weight.
- Suitable for the agents according to the invention are water-soluble, preferably low molecular weight complexing agents (builders) which are able to prevent disturbances due to the water hardness when the agents are used.
- Pentasodium triphosphate, trisodium citrate, sodium gluconate, tetrasodium ethylenediaminetetraacetate (EDTA-Na) and trisodium nitrilotriacetate (NTA-Na) are particularly suitable.
- EDTA-Na and / or sodium gluconate are preferably used.
- the amounts are 0.01 to 5% by weight, preferably 0.05 to 3% by weight and in particular not more than 1% by weight, based on the total composition.
- the alkalizing agents together with the complexing agents serve to give the agents in the undiluted state a pH of 8 to 10.5, preferably 8.5 to 9.5. At these pH values, the polymers are at least partially in the salt form.
- the choice of these agents is not critical insofar as they are compatible with the other ingredients. For example, ammonia, alkanolamines, alkaline salts such as Na2CO3 or NaOH are suitable. Ammonia is preferably used.
- the alkalizing agents are used in amounts of up to 3% by weight, preferably 0.05 to 2% by weight.
- water-miscible organic solvents can be present, with solvents that are highly fat-dissolving preferred.
- solvents are lower mono- and dialcohols, ether alcohols, polyethers and amines. Typical representatives of these solvent groups are isopropanol, butyl glycol, dimethyl diglycol and methyl pyrrolidone.
- Lower ether alcohols for example mono- or diethylene glycol monoalkyl ethers having 1 to 4 carbon atoms in the alkyl group, are preferably used.
- the solvent content is not more than 40% by weight, preferably not more than 20% by weight and in particular between 0.5 and 10% by weight.
- customary substances can additionally achieve effects such as are particularly desired in floor cleaning, for example a pleasant smell or a disinfectant effect. Furthermore, they can serve the Stabilize means yourself and make them appealing.
- additives examples include inorganic neutral salts, dyes, fragrances, foam inhibitors and antimicrobial agents. It goes without saying that only those representatives of these substances who are compatible with the other constituents of the agents and do not impair the action of the agents are selected.
- the total amount of additives is not more than 5% by weight, preferably not more than 2% by weight and in particular between 0.05 and 0.5% by weight of the composition.
- Tables 1 and 2 below show the composition of five agents according to the invention and three agents of the prior art. The contents of the individual raw materials are given in percent by weight, based on the finished agent and anhydrous raw materials.
- Polymer 1 Primal® 644, polymer dispersion from Rohm and Haas, Philadelphia, USA
- Neocryl ® BT 20 polymer dispersion from Polyvinylchemie, Waalwijk, NL
- Polymer 3 Copolymer of 58% by weight methyl methacrylate 30% by weight ethyl acrylate 10% by weight acrylic acid 2 wt% styrene
- the cleaning effect of the wiping care products was determined with the help of a Gardner washability and abrasion tester, as described in the quality standards of the industrial association cleaning and care products e. V. (Seifen- ⁇ le-Fette-Wwachs, 108 , pages 526-528 (1982)).
- a white PVC film is soiled with soot and grease and, under standardized conditions, is wiped mechanically with a sponge soaked in the cleaning agent.
- the cleaning performance is measured by photoelectric determination of the reflectance.
- the care effect is shown, among other things, by the fact that a film from previous treatments with the same agent facilitates the detachment of subsequently applied soiling.
- test method specified above was therefore modified in such a way that the film was wiped with the wiping agent to be tested and then dried before the same stain was applied. After this The application of the soiling was then carried out in the same way as the cleaning performance:
- the wiping agents 1-5 according to the invention have an excellent cleaning performance both with respect to non-pretreated and to pretreated film. Soiling from pretreated film is removed even better than from the original film.
- the means 6 - 8 used for comparison show good cleaning performance either only on untreated film (6) or only on pretreated film (7, 8).
- the care effect of the agent 8 is quite comparable to that of the agents according to the invention, but unlike these, after multiple use leads to a film addition which adversely affects the natural appearance of the treated surfaces.
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Abstract
Das wäßrige Mittel enthält im wesentlichen Tenside, nicht metallvernetzte Polymere und alkoholisch reagierende Komplexbildner und eignet sich zur pflegenden Reinigung insbesondere von Fußböden. Es wird in stark verdünnter Form angewendet und hinterläßt einen festen, aber leicht wieder ablösbaren, transparenten Schutzfilm.The aqueous agent essentially contains surfactants, non-metal-crosslinked polymers and alcohol-reacting complexing agents and is suitable for caring cleaning, especially of floors. It is used in a highly diluted form and leaves a firm, but easily removable, transparent protective film.
Description
Auf dem Gebiet der Reinigung und Pflege von harten Oberflächen sind neben hygienischen und ästhetischen Aspekten vor allem wirtschaftliche Überlegungen und die Materialbeschaffenheit maßgebend für die Auswahl der Reinigungsverfahren und der einzusetzenden Mittel. Da jedem dieser Kriterien im Einzelfall unterschiedliche Bedeutung zukommt, ist es nicht erstaunlich, daß für diese Aufgaben bereits eine Vielzahl unterschiedlichster Verfahren und Mittel entwickelt worden sind.In the field of cleaning and maintenance of hard surfaces, in addition to hygienic and aesthetic aspects, economic considerations and the material properties are decisive for the selection of cleaning methods and the agents to be used. Since each of these criteria has different meanings in individual cases, it is not surprising that a multitude of different methods and means have already been developed for these tasks.
Die vorliegende Erfindung betrifft die Reinigung und Pflege von harten Oberflächen, insbesondere Fußböden, im Haushalt und in der gewerblichen Reinigung mit Hilfe wäßriger Reinigungsmittel. Auch auf diesem Gebiet sind bereits zahlreiche Verfahren und Mittel für die verschiedenen Anwendungszwecke entwickelt worden. Dabei wird die Auswahl der Mittel wesentlich dadurch bestimmt, ob vordringlich eine Reinigung oder eine Konservierung der Oberfläche erreicht werden soll.The present invention relates to the cleaning and care of hard surfaces, in particular floors, in the household and in commercial cleaning with the aid of aqueous cleaning agents. In this area too, numerous methods and agents have already been developed for the various purposes. The choice of agents is essentially determined by whether cleaning or preservation of the surface should be achieved as a matter of priority.
So verwendet man zur Pflege und Konservierung von Oberflächen in erster Linie solche Mittel, die mehr oder weniger harte, widerstandsfähige Filme erzeugen. Die Mittel enthalten zu diesem Zweck, meist in emulgierter Form, Wachse oder filmbildende Polymere und vernetzende Wirkstoffe, in der Regel Schwermetallsalze, die zusammen nach dem Abtrocknen auf den behandelten Flächen selbstglänzende oder polierbare Filme bilden. Auf diese Weise läßt sich eine lang anhaltende Konservierung der Oberflächen erreichen, wobei je nach Qualität des Films auch starke mechanische Beanspruchungen gut vertragen werden. Nachteilig ist bei diesen Mitteln, daß eine Entfernung der festhaftenden Filme, wenn sie, etwa wegen Verschmutzung oder Beschädigung, notwendig wird, nur unter extremen Bedingungen möglich ist.For the care and preservation of surfaces, primarily those agents are used that produce more or less hard, resistant films. For this purpose, the compositions contain, usually in emulsified form, waxes or film-forming polymers and crosslinking active ingredients, as a rule heavy metal salts, 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, and, depending on the quality of the film, strong mechanical loads can also be tolerated well. A disadvantage of these agents is that removal of the firmly adhering films, if it becomes necessary, for example because of dirt or damage, is only possible under extreme conditions.
Im Gegensatz dazu enthalten Mittel, deren Wirkungsschwerpunkt bei der Reinigung liegt, hohe Anteile an Tensiden, oft zusammen mit alkalisch reagierenden Stoffen, organischen Lösungsmitteln oder Abrasivstoffen. Mit diesen Mitteln ist in vielen Fällen eine gründliche Entfernung von Verschmutzungen und alten Belägen möglich, doch sind die so gereinigten Oberflächen danach in der Regel der Wiederanschmutzung schutzlos ausgesetzt, sofern nicht eine Konservierungsbehandlung angeschlossen wird.In contrast, 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 followed.
Da in vielen Fällen Reinigung und Pflege von Oberflächen gleichermaßen erwünscht sind, hat es nicht an Versuchen gefehlt, aus Gründen der Arbeitsvereinfachung Mittel zu entwickeln, mit denen Reinigung und Konservierung in einem Arbeitsgang erreicht werden können. Die bisherigen Lösungsvorschläge befriedigen jedoch nicht.Since in many cases cleaning and care of surfaces are equally desirable, there has been no shortage of attempts to develop means to simplify work and to achieve cleaning and preservation in one operation. However, the previous proposed solutions are unsatisfactory.
So führen beispielsweise Mittel, die die üblichen Filmbildner in sehr niedriger Konzentration zusammen mit Tensiden enthalten, häufig zu einer störenden Filmaddition, die nach gewissen Zeiten eine Zusatzreinigung erforderlich macht. Andere Mittel erfordern spezielle, teure Polymere oder bilden zu weiche Filme, die nur geringen Schutz gegen Wiederanschmutzung bieten. Auch Mittel auf Seifenbasis, die ebenfalls in diese Kategorie gehören, liefern recht weiche Filme und sind zudem anfällig gegen Wasserhärte.For example, agents that contain the usual film formers in very low concentrations together with surfactants often lead to a disruptive film addition, which requires additional cleaning after certain times. Require other means special, expensive polymers or form too soft films that offer little protection against re-soiling. Soap-based agents, which also belong to this category, also produce very soft films and are also prone to water hardness.
Es bestand daher nach wie vor die Aufgabe, zur gleichzeitigen Reinigung und Konservierung von harten Oberflächen, insbesondere Fußböden, Mittel mit verbesserter Wirkung zu entwickeln.It was therefore still the task to develop agents with improved effectiveness for the simultaneous cleaning and preservation of hard surfaces, in particular floors.
Die vorliegende Erfindung bietet eine Lösung dieser Aufgabe in Form eines Mittels, bestehend aus:
0,5 - 10 Gew.-% Tensid aus der Gruppe Additionsverbindungen von Ethylenoxid mit Alkoholen oder Alkylphenolen, Alkylbenzolsulfonate, Alkylsulfate, Alkansulfonate, Fettsäureestersulfonate und deren Mischungen,
0,1 - 4,5 Gew.-% alkalilösliche, nicht metallvernetzte Polymerverbindung mit einer minimalen Filmbildetemperatur zwischen 0 und 70 °C,
0,01 - 5 Gew.-% alkalisch reagierende Komplexbildner,
0 - 3 Gew.-% Alkalisierungsmittel,
0 - 40 Gew.-% wassermischbares organisches Lösungsmittel,
0 - 5 Gew.-% Zusatzstoffe sowie
Rest Wasser.The present invention offers a solution to this problem in the form of an agent consisting of:
0.5-10% by weight of surfactant from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof,
0.1 - 4.5% by weight of alkali-soluble, non-metal-crosslinked polymer compound with a minimum film-forming temperature between 0 and 70 ° C,
0.01 - 5% by weight of alkaline complexing agents,
0-3% by weight of alkalizing agent,
0 - 40% by weight of water-miscible organic solvent,
0 - 5 wt .-% additives and
Rest of water.
Die Anwendung dieses Mittels erfolgt in der Weise, daß zunächst durch Verdünnen mit Wasser eine vorzugsweise ein- bis dreiprozentige Lösung des Mitels hergestellt wird, die dann mit Hilfe von Wischtüchern, Schwämmen oder ähnlichen Hilfsmitteln auf die zu reinigenden Oberflächen aufgetragen und zum Teil mit dem Schmutz wieder von der Oberfläche abgenommen wird. Nach dieser Behandlung wird die Oberfläche nicht abgespült, so daß die verbleibende Reinigungsmittellösung zu einem gleichmäßig schützenden Film auftrocknen kann. Wegen dieses Anwendungsverfahrens werden derartige Mittel auch als Wischpflegemittel bezeichnet. Das erfindungsgemäße Mittel zeichnet sich dabei trotz seiner einfachen Zusammensetzung durch eine optimale Reinigungswirkung gegenüber einer Vielzahl von Anschmutzungen aus und bildet gleichzeitig einen widerstandsfähigen Film, der einen hervorragenden Schutz gegen Wiederanschmutzung bildet. Im Gegensatz zu anderen Mitteln ist dieser Film hier vollständig transparent und läßt Farbe und Struktur der behandelten Flächen unverändert erscheinen, ohne daß ein zusätzlicher Glanz auftritt . Bei erneuter Anwendung des Mittels löst sich der Film auf und erleichtert dadurch den Reinigungsvorgang. Eine störende Filmaddition findet nicht statt.This agent is used in such a way that a preferably one to three percent solution of the agent is first prepared by dilution with water which is then applied to the surfaces to be cleaned with the help of wipers, sponges or similar aids and partly removed from the surface with the dirt. After this treatment, the surface is 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. Despite its simple composition, the agent according to the invention is distinguished by an optimal cleaning action against a large number of soiling and at the same time forms a resistant film which forms excellent protection against re-soiling. In contrast to other agents, this film is completely transparent and allows the color and structure of the treated surfaces to appear unchanged without additional gloss. When the agent is used again, the film dissolves, making the cleaning process easier. There is no annoying film addition.
Das erfindungsgemäße Mittel eignet sich vorzugsweise zur pflegenden Reinigung von Fußböden und liefert dabei sowohl auf Stein, versiegeltem Parkett, Kacheln, Linoleum und Kunststoffböden ausgezeichnete Ergebnisse. Besonders vorteilhaft ist die Anwendung auf hochglänzenden Fußbodenbelägen, da der gebildete Film durch seine hohe Transparenz den Glanz nicht mindert. Vorzugsweise wird ein Mittel der folgenden Zusammensetzung verwendet. :
1 - 6 Gew.-% Tensid aus der Gruppe Additionsverbindungen von Ethylenoxid mit Alkoholen oder Alkylphenolen, Alkylbenzolsulfonate, Alkylsulfate, Alkansulfonate, Fettsäureestersulfonate und deren Mischungen,
0,2 - 2,9 Gew.-% alkalilösliche, nicht metallvernetzte Polymerverbindung mit einer minimalen Filmbildetemperatur zwischen 0 und 70 °C,
0,05 - 3 Gew.-% alkalisch reagierende Komplexbildner,
0,05 - 2 Gew.-%Alkalisierungsmittel,
0 - 20 Gew.-% wassermischbares organisches Lösungsmittel,
0,05 - 2 Gew.-% Zusatzstoffe sowie
Rest Wasser.The agent according to the invention is preferably suitable for the caring cleaning of floors and delivers excellent results on stone, sealed parquet, tiles, linoleum and plastic floors. Use on high-gloss floor coverings is particularly advantageous because the film formed does not reduce the gloss due to its high transparency. An agent of the following composition is preferably used. :
1-6% by weight of surfactant from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, Alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof,
0.2-2.9% by weight of alkali-soluble, non-metal-crosslinked polymer compound with a minimum film-forming temperature between 0 and 70 ° C,
0.05 - 3% by weight of alkaline complexing agents,
0.05-2% by weight of alkalizing agent,
0-20% by weight of water-miscible organic solvent,
0.05 - 2 wt .-% additives and
Rest of water.
Die einzelnen Bestandteile des Mittels, die durch ihr Zusammenspiel dessen Eigenschaften bewirken, lassen sich wie folgt näher beschreiben:The individual components of the agent, which through their interaction bring about its properties, can be described in more detail as follows:
Generell eignen sich für die erfindungsgemäßen Mittel die wasserlöslichen, nicht härteempfindlichen Tenside aus der Gruppe Additionsverbindungen von Ethylenoxid mit Alkoholen oder Alkylphenolen, Alkylbenzolsulfonate, Alkylsulfate, Alkansulfonate, Fettsäureestersulfonate und deren Mischungen. Die Einsatzmengen betragen 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 6 Gew.-%, bezogen auf das unverdünnte Mittel. Vorzugsweise werden nichtionische und anionische Tenside zusammen verwendet.In general, the water-soluble, non-hardness-sensitive surfactants from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof are suitable for the agents according to the invention. The amounts used are 0.5 to 10% by weight, preferably 1 to 6% by weight, based on the undiluted medium. Nonionic and anionic surfactants are preferably used together.
Bei den genannten nichtionischen Tensiden handelt es sich um Additionsverbindungen von 4 - 40, vorzugsweise 8 - 20 Mol Ethylenoxid (EO) mit 1 Mol eines aliphatischen Alkohols oder Alkylphenols mit 10 - 20 C-Atomen. Die aliphatischen Alkohole können verzweigt oder ungesättigt sein und primäre und/oder sekundäre Hydroxylgruppen aufweisen. Bevorzugt werden die Ethylenoxidaddukte an unverzweigte primäre und sekundäre Alkohole, insbesondere Fettalkohole und Oxoalkohole.The nonionic surfactants mentioned are addition compounds of 4-40, preferably 8-20, moles of ethylene oxide (EO) with 1 mole of an aliphatic alcohol or alkylphenol with 10-20 C atoms. The aliphatic alcohols can be branched or unsaturated and have primary and / or secondary hydroxyl groups. The ethylene oxide adducts with unbranched primary and secondary alcohols, in particular fatty alcohols and oxo alcohols, are preferred.
Typische Vertreter geeigneter Niotenside sind Nonylphenol + 13 EO, innenständiges C₁₅-C₁₇-Alkandiol + 9 EO, C₁₄/C₁₅-Oxoalkohol + 11 EO, Kokosalkohol + 7 EO, Talgalkohol + 14 EO.Typical representatives of suitable nonionic surfactants are nonylphenol + 13 EO, internal C₁₅-C₁₇ alkanediol + 9 EO, C₁₄ / C₁₅ oxo alcohol + 11 EO, coconut alcohol + 7 EO, tallow alcohol + 14 EO.
Vorzugsweise werden als nichtionische Tenside Addukte von 8 - 20 Mol EO an Fettalkohole mit 12 - 18 C-Atomen eingesetzt.Adducts of 8-20 mol EO with fatty alcohols with 12-18 C atoms are preferably used as nonionic surfactants.
Die oben genannten Aniontenside stammen aus den Klassen der Sulfonate und Sulfate und werden durchweg a ls Salze, vorzugsweise als Natriumsalze eingesetzt. Bei den Tensiden vom Sulfonattyp handelt es sich um die Alkylbenzolsulfonate mit C 9-15-Alkylgruppen, die Ester von alpha-Sulfofettsäuren, z. B. die alpha-sulfonierten Methyl- oder Ethylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren sowie um die Alkansulfonate, die aus C₁₂-C₁₈-Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation oder durch Bisulfitaddition an Olefine erhältlich sind. Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester von primären Alkoholen natürlichen und synthetischen Ursprungs, d. h. von Fettalkoholen, wie z. B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, oder den C₁₀-C₂₀-Oxoalkoholen, und solche von sekundären Alkoholen dieser Kettenlängen. Vorzugsweise werden als anionische Tenside Alkylbenzolsulfonate und Alkansulfonate eingesetzt.The above-mentioned anionic surfactants come from the classes of sulfonates and sulfates and are used consistently as salts, preferably as sodium salts. The surfactants of the sulfonate type are the alkylbenzenesulfonates with C 9-15 -alkyl groups, the esters of alpha-sulfofatty acids, e.g. B. the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids and the alkane sulfonates that are available from C₁₂-C₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Suitable sulfate-type surfactants are the sulfuric acid monoesters of primary alcohols natural and synthetic origin, ie from fatty alcohols, such as. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C₁₀-C₂₀ oxo alcohols, and those of secondary alcohols of these chain lengths. Alkylbenzenesulfonates and alkanesulfonates are preferably used as anionic surfactants.
Mit den vorgenannten nichtionischen und anionischen Tensiden werden durchweg gute bis sehr gute Reinigungsergebnisse erzielt, doch ist es in vielen Fällen möglich, ohne Einbußen an Reinigungsleistung einen kleineren Teil, daß heißt bis etwa 50 %, dieser Tenside auch durch andere Typen, wie etwa Ethylenoxidaddukte an Polypropylenoxid oder an Fettsäureamide oder Olefinsulfonate, Sulfosuccinate und Alkylethersulfate zu ersetzen.With the aforementioned nonionic and anionic surfactants, good to very good cleaning results are achieved throughout, but in many cases it is possible, without loss of cleaning performance, to use a smaller proportion, ie up to about 50%, of these surfactants by other types, such as ethylene oxide adducts Polypropylene oxide or to replace fatty acid amides or olefin sulfonates, sulfosuccinates and alkyl ether sulfates.
Generell eignen sich alle in Wasser im alkalischen Bereich löslichen Polymerverbindungen, soweit sie nicht metallvernetzt sind und eine minimale Filmbildungstemperatur zwischen 0 und 70 °C aufweisen. Es handelt sich dabei in der Regel um Copolymerisate aus wenigstens drei verschiedenen Monomeren. Die Löslichkeit beträgt wenigstens 0,1 %, vorzugsweise 0,2 %, bei einem pH-Wert zwischen 8 und 10,5, insbesondere zwischen 8,5 und 9,5.In general, all polymer compounds soluble in water in the alkaline range are suitable, provided they are not metal-crosslinked and have a minimum film-forming temperature between 0 and 70 ° C. These are generally copolymers of at least three different monomers. The solubility is at least 0.1%, preferably 0.2%, at a pH between 8 and 10.5, in particular between 8.5 and 9.5.
Die vorzugsweise eingesetzten Polymeren enthalten als wichtigsten Bestandteil ein Acrylat-Copolymer aus 1 bis 30 Gewichtsteilen, bezogen auf Copolymer an carbonsäuregruppenhaltigen Monomeren, 30 bis 70 Gewichtsteilen Monomeren, die Homopolymere mit Glastemperaturen unter 20 °C bilden, vorzugsweise Estern der Acrylsäure mit C₁ -C₈ Alkoholen und/oder der Methacrylsäure mit C₄ bis C₈-Alkoholen und 30 bis 70 Gewichtsteile Comono meren, die Homopolymere mit Glastemperaturen über Raumtemperatur bilden,
vorzugsweise Methacrylsäureester von C₁ bis C₃-Alkoholen oder Styrol.The polymers used preferably contain, as the most important constituent, 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 C₁-C₈ alcohols and / or methacrylic acid with C₄ to C₈ alcohols and 30 to 70 parts by weight of Comono mers that form homopolymers with glass transition temperatures above room temperature,
preferably methacrylic acid esters of C₁ to C₃ alcohols or styrene.
Als säuregruppenhaltige Comonomere können ethylenisch ungesättigte Carbonsäuren eingesetzt werden; in erster Linie kommen Acrylsäure und Methacrylsäure in Frage.As comonomers containing acid groups, ethylenically unsaturated carboxylic acids can be used; acrylic acid and methacrylic acid are primarily suitable.
An Comonomeren mit Glastemperaturen unter 20 °C, also Glastemperaturen unter Raumtemperatur (bezogen jeweils auf Homopolymere eines Monomeren) sind Ester der Acrylsäure mit C₁-C₈-Alkoholen und Ester der Methacrylsäure mit C₄-C₈-Alkoholen zu nennen. So können hier der Methyl-, Ethyl-, Propyl-, Butyl- oder 2-Ethylhexylester der Acrylsäure wie auch der Butyl-, Hexyl-oder 2-Ethylhexylester der Methacrylsäure eingesetzt werden. Comonomere, deren Homopolymere Glastemperaturen über Raumtemperatur aufweisen, sind Ester der Methacrylsäure mit C₁-C₃-Alkoholen, wie beispielsweise Methylmethacrylat oder Ethylmethacrylat. Ein besonders wichtiges Comonomer, dessen Homopolymer eine Glastemperatur über Raumtemperatur aufweist, ist Styrol.Comonomers with glass transition temperatures below 20 ° C, that is glass transition temperatures below room temperature (based in each case on homopolymers of a monomer) are esters of acrylic acid with C₁-C₈ alcohols and esters of methacrylic acid with C₄-C₈ alcohols. Thus, 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 C₁-C₃ alcohols, such as methyl methacrylate or ethyl methacrylate. A particularly important comonomer whose homopolymer has a glass transition temperature above room temperature is styrene.
Vorzugsweise werden Copolymerisate von Acrylsäure und/oder Methacrylsäure mit Styrol, Acrylsäureestern und/oder Methacrylsäureestern eingesetzt. Besonders bevorzugt werden die Copolymerisate aus Acrylsäure oder Methacrylsäure mit unterschiedlichen Acryl- und/oder Methacrylsäureestern und/oder Styrol, beispielsweise Copolymerisate aus Acrylsäuremethylester, Acrylsäureethylester, Methacrylsäure und Styrol.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 copolymers of methyl acrylate, ethyl acrylate, methacrylic acid and styrene.
Die jeweiligen Verhältnisse von Comonomeren, deren Homopolymere Glastemperaturen unter Raumtemperatur aufweisen und Monomeren, deren Homopolymere Glastemperaturen über Raumtemperatur aufwei sen, sind so einzustellen, daß die Filmbildungstemperatur der Polymerdispersion im Bereich zwischen 0 und 70 °C liegt. Dabei gilt das allgemeine Wissen der Polymerchemie. Die genannten Filmbildungstemperaturen beziehen sich auf das weichmacherfreie System, d. h. auf die Polymeren ohne weitere Zusätze.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 general knowledge of polymer chemistry applies. The film formation temperatures mentioned relate to the plasticizer-free system, i. H. on the polymers without further additives.
Die Polymeren sind vorzugsweise nur im alkalischen Bereich in Wasser löslich, während sie im sauren Bereich ungelöst bleiben. Entsprechende Produkte werden vom Handel vielfach in emulgierter Form angeboten.The polymers are preferably soluble in water only in the alkaline range, while they remain undissolved in the acidic range. Corresponding products are often offered by the trade in emulsified form.
In den erfindungsgemäßen Mitteln werden im allgemeinen 0,1 bis 4,5 Gew.-% der Polymeren, gerechnet als reines Polymeres, verwendet. Bevorzugte Gehalte sind 0,2 bis 2,9 Gew.-%, insbesondere 0,2 bis 1,0 Gew.-%.In general, 0.1 to 4.5% by weight of the polymers, calculated as pure polymer, are used in the agents according to the invention. Preferred contents are 0.2 to 2.9% by weight, in particular 0.2 to 1.0% by weight.
Für die erfindungsgemäßen Mittel eignen sich wasserlösliche, vorzugsweise niedermolekulare Komplexbildner (Builder), die in der Lage sind, Störungen durch die Wasserhärte bei der Anwendung der Mittel zu verhindern. Geeignet sind insbesondere Pentanatriumtriphosphat, Trinatriumcitrat, Natriumgluconat,Tetranatriumethylendiamintetraacetat (EDTA-Na) und Trinatriumnitrilotriacetat (NTA-Na). Vorzugsweise werden EDTA-Na und/oder Natriumgluconat verwendet. Die Mengen betragen 0,01 bis 5 Gew.-%, vorzugsweise 0,05 bis 3 Gew.-% und insbesondere nicht mehr als 1 Gew.-%, bezogen auf das gesamte Mittel.Suitable for the agents according to the invention are water-soluble, preferably low molecular weight complexing agents (builders) which are able to prevent disturbances due to the water hardness when the agents are used. Pentasodium triphosphate, trisodium citrate, sodium gluconate, tetrasodium ethylenediaminetetraacetate (EDTA-Na) and trisodium nitrilotriacetate (NTA-Na) are particularly suitable. EDTA-Na and / or sodium gluconate are preferably used. The amounts are 0.01 to 5% by weight, preferably 0.05 to 3% by weight and in particular not more than 1% by weight, based on the total composition.
Die Alkalisierungsmittel dienen zusammen mit den Komplexbildnern dazu, den Mitteln im unverdünnten Zustand einen pH-Wert von 8 bis 10,5, vorzugsweise 8,5 bis 9,5 zu geben. Bei diesen pH-Werten liegen die Polymeren wenigstens partiell in der Salzform vor. Die Wahl dieser Mittel ist unkritisch, soweit sie mit den übrigen Bestandteilen verträglich sind. Geeignet sind beispielsweise Ammoniak, Alkanolamine, alkalisch reagierende Salze wie Na₂CO₃ oder NaOH. Vorzugsweise wird Ammoniak verwendet. Die Alkalisierungsmittel werden in Mengen bis zu 3 Gew.-%, vorzugsweise 0,05 bis 2 Gew.-% eingesetzt.The alkalizing agents together with the complexing agents serve to give the agents in the undiluted state a pH of 8 to 10.5, preferably 8.5 to 9.5. At these pH values, the polymers are at least partially in the salt form. The choice of these agents is not critical insofar as they are compatible with the other ingredients. For example, ammonia, alkanolamines, alkaline salts such as Na₂CO₃ or NaOH are suitable. Ammonia is preferably used. The alkalizing agents are used in amounts of up to 3% by weight, preferably 0.05 to 2% by weight.
Zur Verstärkung der Reinigungskraft können wassermischbare organische Lösungsmittel enthalten sein, wobei gut fettlösende Lösungsmittel bevorzugt werden. Beispiele für derartige Lösungsmittel sind niedere Mono- und Dialkohole, Etheralkohole, Polyether und Amine. Typische Vertreter dieser Lösungsmittelgruppen sind etwa Isopropanol, Butylglykol, Dimethyldiglykol und Methylpyrrolidon. Vorzugsweise werden niedere Etheralkohole , beispielsweise Mono- oder Diethylenglykolmonoalkylether mit 1 bis 4 C-Atomen in der Alkylgruppeverwendet. Der Gehalt an Lösungsmitteln liegt nicht über 40 Gew.-%, vorzugsweise nicht über 20 Gew.-% und insbesondere zwischen 0,5 und 10 Gew.-%.To increase the cleaning power, water-miscible organic solvents can be present, with solvents that are highly fat-dissolving preferred. Examples of such solvents are lower mono- and dialcohols, ether alcohols, polyethers and amines. Typical representatives of these solvent groups are isopropanol, butyl glycol, dimethyl diglycol and methyl pyrrolidone. Lower ether alcohols, for example mono- or diethylene glycol monoalkyl ethers having 1 to 4 carbon atoms in the alkyl group, are preferably used. The solvent content is not more than 40% by weight, preferably not more than 20% by weight and in particular between 0.5 and 10% by weight.
Durch die Einarbeitung dieser üblichen Stoffe können zusätzlich Effekte, wie sie insbesondere bei der Fußbodenreinigung erwünscht sind, beispielsweise ein angenehmer Geruch oder eine desinfizierende Wirkung, erreicht werden. Weiterhin können sie dazu dienen, die Mittel selbst zu stabilisieren und ansprechend zu gestalten.The incorporation of these customary substances can additionally achieve effects such as are particularly desired in floor cleaning, for example a pleasant smell or a disinfectant effect. Furthermore, they can serve the Stabilize means yourself and make them appealing.
Beispiele derartiger Zusatzstoffe sind anorganische Neutralsalze, Farbstoffe, Duftstoffe, Schauminhibitoren und antimikrobielle Wirkstoffe. Es ist selbstverständlich, daß bei der Auswahl nur solche Vertreter dieser Stoffe gewählt werden, die mit den übrigen Bestandteilen der Mittel verträglich sind und die Wirkung der Mittel nicht beeinträchtigen. Die Mengen an Zusatzstoffen betragen insgesamt nicht mehr als 5 Gew.-%, vorzugsweise nicht mehr als 2 Gew.-% und insbesondere zwischen 0,05 und 0,5 Gew.-% der Mittel.Examples of such additives are inorganic neutral salts, dyes, fragrances, foam inhibitors and antimicrobial agents. It goes without saying that only those representatives of these substances who are compatible with the other constituents of the agents and do not impair the action of the agents are selected. The total amount of additives is not more than 5% by weight, preferably not more than 2% by weight and in particular between 0.05 and 0.5% by weight of the composition.
Die folgenden Tabellen 1 und 2 geben die Zusammensetzung von fünf erfindungsgemäßen Mitteln und drei Mitteln des Standes der Technik wieder. Die Gehalte an den einzelnen Rohstoffen sind in Gewichtsprozent angegeben, bezogen auf das fertige Mit tel und wasserfreie Rohstoffe.Tables 1 and 2 below show the composition of five agents according to the invention and three agents of the prior art. The contents of the individual raw materials are given in percent by weight, based on the finished agent and anhydrous raw materials.
Folgende alkalilösliche Copolymere wurden verwendet:The following alkali-soluble copolymers were used:
Polymer 1:
Primal® 644, Polymerdispersion von Rohm und Haas, Philadelphia, USAPolymer 1:
Primal® 644, polymer dispersion from Rohm and Haas, Philadelphia, USA
Polymer 2:
Neocryl ® BT 20, Polymerdispersion von Polyvinylchemie, Waalwijk, NLPolymer 2:
Neocryl ® BT 20, polymer dispersion from Polyvinylchemie, Waalwijk, NL
Polymer 3:
Copolymerisat aus 58 Gew.-% Methylmethacrylat
30 Gew.-% Ethylacrylat
10 Gew.-% Acrylsäure
2 Gew.-% Styrol
Copolymer of 58% by weight methyl methacrylate
30% by weight ethyl acrylate
10% by weight acrylic acid
2 wt% styrene
Die Reinigungswirkung der Wischpflegemittel wurde mit Hilfe eines Gardner-Waschbarkeits- und Scheuerprüfgerätes ermittelt, wie es in den Qualitätsnormen des Industrieverbandes Putz- und Pflegemittel e. V. beschrieben ist (Seifen-Öle-Fette-Wachse, 108, Seiten 526 - 528 (1982)). Bei dieser Methode wird eine weiße PVC-Folie mit einer Testanschmutzung aus Ruß und Fett versehen und unter standardisierten Bedingungen mit einem mit dem Reinigungsmittel getränkten Schwamm maschinell gewischt. Die Reinigungsleistung wird durch photoelektrische Bestimmung des Remissionsgrades gemessen.The cleaning effect of the wiping care products was determined with the help of a Gardner washability and abrasion tester, as described in the quality standards of the industrial association cleaning and care products e. V. (Seifen-Öle-Fette-Wwachs, 108 , pages 526-528 (1982)). In this method, a white PVC film is soiled with soot and grease and, under standardized conditions, is wiped mechanically with a sponge soaked in the cleaning agent. The cleaning performance is measured by photoelectric determination of the reflectance.
Die Pflegewirkung zeigt sich unter anderem darin, daß durch einen aus früheren Behandlungen mit demselben Mittel stammenden Film die Ablösung von nachträglich aufgebrachten Anschmutzungen erleichtert wird.The care effect is shown, among other things, by the fact that a film from previous treatments with the same agent facilitates the detachment of subsequently applied soiling.
Das oben angegebene Prüfverfahren wurde deshalb in der Weise modifiziert, daß die Folie vor dem Aufbringen der gleichen Anschmutzung mit dem zu prüfenden Wischpflegemittel gewischt und dann getrocknet wurde. Nach dem Aufbringen der Anschmutzung erfolgte die Prüfung dann wie die Prüfung der Reinigungsleistung:The test method specified above was therefore modified in such a way that the film was wiped with the wiping agent to be tested and then dried before the same stain was applied. After this The application of the soiling was then carried out in the same way as the cleaning performance:
Tabelle 3 führt die Ergebnisse der Prüfungen an allen acht Mitteln auf. Sie sind in Prozent Lichtremission bezogen auf weiß = 100 % angegeben. In allen Prüfungen wurden die Mittel in verdünnter Form mit einer Konzentration von 2 Gewichtsprozent angewendet.Table 3 lists the results of the tests on all eight agents. They are given in percent light emission based on white = 100%. In all tests, the agents were used in a diluted form with a concentration of 2 percent by weight.
Aus den Ergebnissen wird deutlich, daß die erfindungsgemäßen Wischpflegemittel 1 - 5 eine ausgezeichnete Reinigungsleistung sowohl gegenüber nicht vorbehandelter als auch gegenüber vorbehandelter Folie aufweisen. Von vorbehandelter Folie wird dabei die Anschmutzung noch besser entfernt als von der ursprünglichen Folie.It is clear from the results that the wiping agents 1-5 according to the invention have an excellent cleaning performance both with respect to non-pretreated and to pretreated film. Soiling from pretreated film is removed even better than from the original film.
Die zum Vergleich herangezogenen Mittel 6 - 8 zeigen dagegen gute Reinigungsleistungen entweder nur an unvorbehandelter Folie (6) oder nur an vorbehandelter Folie (7, 8). Das Mittel 8 ist dabei in seiner Pflegewirkung durchaus mit den erfindungsgemäßen Mitteln vergleichbar, führt aber anders als diese, nach mehrfacher Anwendung zu einer Filmaddition, die das natürliche Aussehen der behandelten Flächen beeinträchtigt.
Claims (9)
0,5 - 10 Gew.-% Tensid aus der Gruppe Additionsverbindungen von Ethylenoxid mit Alkoholen oder Alkylphenolen, Alkylbenzolsulfonate, Alkylsulfate, Alkansulfonate, Fettsäureestersulfonate und deren Mischungen,
0,1 - 4,5 Gew.-% alkalilösliche, nicht metallvernetzte Polymerverbindung mit einer minimalen Filmbildetemperatur zwischen 0 und 70 °C,
0,01 - 5 Gew.-% alkalisch reagierende Komplexbildner,
0 - 3 Gew.-% Alkalisierungsmittel,
0 - 40 Gew.-% wassermischbares organisches Lösungsmittel,
0 - 5 Gew.-% Zusatzstoffe sowie
Rest Wasser.1. Floor cleaning agent, consisting of:
0.5-10% by weight of surfactant from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof,
0.1 - 4.5% by weight of alkali-soluble, non-metal-crosslinked polymer compound with a minimum film-forming temperature between 0 and 70 ° C,
0.01 - 5% by weight of alkaline complexing agents,
0-3% by weight of alkalizing agent,
0 - 40% by weight of water-miscible organic solvent,
0 - 5 wt .-% additives and
Rest of water.
1 - 6 Gew.-% Tensid aus der Gruppe Additionsverbindungen von Ethylenoxid mit Alkoholen oder Alkylphenolen, Alkylbenzolsulfonate, Alkylsulfate, Alkansulfonate, Fettsäureestersulfonate und deren Mischungen,
0,2 - 2,9 Gew.-% alkalilösliche, nicht metallvernetzte Polymerverbindung mit einer minimalen Filmbildetemperatur zwischen 0 und 70 °C,
0,05 - 3 Gew.-% alkalisch reagierende Komplexbildner,
0,05 - 2 Gew.-% Alkalisierungsmittel,
0 - 20 Gew.-% wassermischbares organisches Lösungsmittel,
0,05 - 2 Gew.-% Zusatzstoffe sowie
Rest Wasser.2. Floor cleaning agent according to claim 1, consisting of:
1-6% by weight of surfactant from the group of addition compounds of ethylene oxide with alcohols or alkylphenols, alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, fatty acid ester sulfonates and mixtures thereof,
0.2-2.9% by weight of alkali-soluble, non-metal-crosslinked polymer compound with a minimum film-forming temperature between 0 and 70 ° C,
0.05 - 3% by weight of alkaline complexing agents,
0.05-2% by weight of alkalizing agent,
0-20% by weight of water-miscible organic solvent,
0.05 - 2 wt .-% additives and
Rest of water.
1 - 6 Gew.-% Tensidgemisch aus mindestens einer Additionsverbindung von 8 - 20 Mol Ethylenoxid mit C₁₂-C₁₈-Fettalkoholen und/oder Alkylbenzolsulfonat und/oder Alkansulfonat,
0,2 - 1 Gew.-% Copolymerisat aus Acrylsäuremethylester, Acrylsäureethylester, Methacrylsäureund Styrol,
0,05 - 1 Gew.-% Ethylendiamintetraacetat,
0,5 -10 Gew.-% wassermischbares organisches Lösungsmittel aus der Gruppe der Mono- oder Diethylenglykolmonoalkylether mit 1 bis 4 C-Atomen in der Alkylgruppe
0,1 - 0,5 Gew.-% Zusatzstoffe sowie
Rest Wasser.Floor cleaning agent according to one of claims 1 to 7, consisting of:
1-6% by weight surfactant mixture of at least one addition compound of 8-20 moles of ethylene oxide with C₁₂-C₁₈ fatty alcohols and / or alkylbenzenesulfonate and / or alkanesulfonate,
0.2-1% by weight of copolymer of methyl acrylate, ethyl acrylate, methacrylic acid and styrene,
0.05-1% by weight of ethylenediaminetetraacetate,
0.5-10% by weight of water-miscible organic solvent from the group of mono- or diethylene glycol monoalkyl ethers with 1 to 4 carbon atoms in the alkyl group
0.1-0.5% by weight of additives and
Rest of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86112626T ATE58751T1 (en) | 1985-09-20 | 1986-09-12 | HARD SURFACE CLEANER. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853533531 DE3533531A1 (en) | 1985-09-20 | 1985-09-20 | CLEANER FOR HARD SURFACES |
| DE3533531 | 1985-09-20 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0215451A2 true EP0215451A2 (en) | 1987-03-25 |
| EP0215451A3 EP0215451A3 (en) | 1988-05-18 |
| EP0215451B1 EP0215451B1 (en) | 1990-11-28 |
Family
ID=6281452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86112626A Expired - Lifetime EP0215451B1 (en) | 1985-09-20 | 1986-09-12 | Cleaning product for hard surfaces |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4725319A (en) |
| EP (1) | EP0215451B1 (en) |
| JP (1) | JPH0823038B2 (en) |
| AT (1) | ATE58751T1 (en) |
| DE (2) | DE3533531A1 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GR910100312A (en) * | 1990-07-16 | 1992-08-26 | Colgate Palmolive Co | Liquid cleaning composition for rough surfaces |
| WO1993020174A1 (en) * | 1992-03-27 | 1993-10-14 | Henkel Kommanditgesellschaft Auf Aktien | Liquid cleaning products |
| WO1993020173A1 (en) * | 1992-03-27 | 1993-10-14 | Henkel Kommanditgesellschaft Auf Aktien | Liquid products for cleaning hard surfaces |
| WO1994014943A1 (en) * | 1992-12-22 | 1994-07-07 | Henkel-Ecolab Gmbh & Co. Ohg | Neutral cleaning agents (ii) |
| WO1994020595A1 (en) * | 1993-03-05 | 1994-09-15 | Henkel Kommanditgesellschaft Auf Aktien | Floor-cleaning agents |
| WO1994020594A1 (en) * | 1993-03-10 | 1994-09-15 | Henkel-Ecolab Gmbh & Co. Ohg | Floor-care agents |
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| DE10357389A1 (en) * | 2003-12-07 | 2005-07-07 | Benda, Jürgen Michael | Non-mechanical cleaning of soapstone and other stones, using aqueous cleaner, applied first, and a non-aqueous cleaner |
| US6979371B1 (en) | 1997-10-07 | 2005-12-27 | The Procter & Gamble Company | Detergent composition for hard surfaces comprising hydrophilic shear-thinning polymer at very low level |
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| US5008030A (en) * | 1989-01-17 | 1991-04-16 | Colgate-Palmolive Co. | Acidic disinfectant all-purpose liquid cleaning composition |
| JPH02274800A (en) * | 1989-04-14 | 1990-11-08 | Manritsu:Kk | floor cleaning agent |
| JP2796535B2 (en) * | 1990-06-01 | 1998-09-10 | ライオン株式会社 | Zeolite-containing liquid detergent composition |
| SE469058B (en) * | 1991-10-10 | 1993-05-10 | Berol Nobel Ab | APPLICATION OF A TRIETANOLAMINE-CONTAINING PRODUCT MIXTURE IN COSMETIC PRODUCTS AND CLEANING COMPOSITIONS |
| WO1993023793A1 (en) * | 1992-05-12 | 1993-11-25 | Eastman Kodak Company | Addenda for an aqueous photographic stabilizing solution |
| US5837665A (en) * | 1996-05-02 | 1998-11-17 | Young; Robert | Spot cleaner for carpets |
| WO1997042296A1 (en) * | 1996-05-07 | 1997-11-13 | Kao Corporation | Liquid detergent composition for hard surface and method for cleaining hard surface |
| US5770548B1 (en) * | 1996-05-14 | 1999-06-29 | Johnson & Son Inc S C | Rinseable hard surface cleaner comprising silicate and hydrophobic acrylic polymer |
| US5955413A (en) * | 1997-10-24 | 1999-09-21 | 3M Innovative Properties Company | Carpet cleaning and reapplication system based on methacrylic acid polymer, sequestrant, and anionic surfactant |
| DE19751859A1 (en) * | 1997-11-22 | 1999-07-29 | Henkel Ecolab Gmbh & Co Ohg | Means for cleaning hard surfaces |
| CA2260607C (en) | 1998-02-02 | 2007-01-23 | Playtex Products, Inc. | Stable compositions for removing stains from fabrics and carpets |
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Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6900307A (en) * | 1969-01-08 | 1969-10-27 | ||
| BE759066A (en) * | 1969-11-17 | 1971-05-17 | Atlantic Richfield Co | SHAMPOO COMPOSITIONS |
| US3716488A (en) * | 1970-09-04 | 1973-02-13 | Stevens & Co Inc J P | Textile fabric cleaning compositions |
| US3723358A (en) * | 1971-02-22 | 1973-03-27 | Johnson & Son Inc S C | Fabric treating shampoo compositions |
| US3901727A (en) * | 1971-03-08 | 1975-08-26 | Minnesota Mining & Mfg | Process and composition for cleaning and imparting water and oil repellency and stain resistance to a substrate |
| US3723323A (en) * | 1971-04-22 | 1973-03-27 | Johnson & Son Inc S C | Fabric treating shampoo compositions |
| US4002571A (en) * | 1972-03-08 | 1977-01-11 | S. C. Johnson & Son, Inc. | Cleaning compositions |
| GB1430204A (en) * | 1973-09-18 | 1976-03-31 | Johnson & Son Inc S C | Aqueous cleaning composition |
| US3994744A (en) * | 1973-10-01 | 1976-11-30 | S. C. Johnson & Son, Inc. | No-scrub cleaning method |
| US3976501A (en) * | 1974-09-18 | 1976-08-24 | Blue Maurice R | Process for cleaning and polishing a floor |
| GB1528592A (en) * | 1974-12-10 | 1978-10-11 | Procter & Gamble | Floor care and cleaning composition |
| JPS5326804A (en) * | 1976-08-23 | 1978-03-13 | Aaru Buruu Moorisu | Liquid detergent for floor and its using method |
| US4230605A (en) * | 1978-12-13 | 1980-10-28 | Armstrong Cork Company | Cleaning composition for no-wax vinyl composition floor covering |
| PH17613A (en) * | 1981-05-29 | 1984-10-05 | Unilever Nv | General-purpose cleaning composition |
| US4347151A (en) * | 1981-06-30 | 1982-08-31 | S. C. Johnson & Son, Inc. | Cleaner-polish for fiberglass and ceramic surfaces |
| DE3316876A1 (en) * | 1983-05-07 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | MEANS OF REMOVING FILM-FORMING POLYMER PROTECTIVE COATS |
| US4537802A (en) * | 1984-08-31 | 1985-08-27 | Flanagan John J | Floor finishing, cleaning and burnishing compositions containing ucon polymers, and method of use |
| US4609406A (en) * | 1984-09-05 | 1986-09-02 | Pennzoil Company | Rust conversion coatings |
| US4565644A (en) * | 1985-01-04 | 1986-01-21 | Creative Products Resource Associates, Ltd. | Floor cleaning and waxing composition |
-
1985
- 1985-09-20 DE DE19853533531 patent/DE3533531A1/en not_active Withdrawn
-
1986
- 1986-09-09 US US06/905,713 patent/US4725319A/en not_active Expired - Lifetime
- 1986-09-12 EP EP86112626A patent/EP0215451B1/en not_active Expired - Lifetime
- 1986-09-12 DE DE8686112626T patent/DE3675861D1/en not_active Expired - Fee Related
- 1986-09-12 AT AT86112626T patent/ATE58751T1/en not_active IP Right Cessation
- 1986-09-20 JP JP61223489A patent/JPH0823038B2/en not_active Expired - Lifetime
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0467472A3 (en) * | 1990-07-16 | 1993-06-02 | Colgate-Palmolive Company | Hard surface liquid cleaning composition with anti-soiling polymer |
| GR910100312A (en) * | 1990-07-16 | 1992-08-26 | Colgate Palmolive Co | Liquid cleaning composition for rough surfaces |
| US5507971A (en) * | 1992-03-27 | 1996-04-16 | Henkel Kommanditgesellschaft Auf Aktien | Liquid cleaners for hard surfaces |
| WO1993020174A1 (en) * | 1992-03-27 | 1993-10-14 | Henkel Kommanditgesellschaft Auf Aktien | Liquid cleaning products |
| WO1993020173A1 (en) * | 1992-03-27 | 1993-10-14 | Henkel Kommanditgesellschaft Auf Aktien | Liquid products for cleaning hard surfaces |
| WO1994014943A1 (en) * | 1992-12-22 | 1994-07-07 | Henkel-Ecolab Gmbh & Co. Ohg | Neutral cleaning agents (ii) |
| WO1994020595A1 (en) * | 1993-03-05 | 1994-09-15 | Henkel Kommanditgesellschaft Auf Aktien | Floor-cleaning agents |
| WO1994020594A1 (en) * | 1993-03-10 | 1994-09-15 | Henkel-Ecolab Gmbh & Co. Ohg | Floor-care agents |
| US5683975A (en) * | 1993-03-10 | 1997-11-04 | Henkel Ecolab Gmbh & Co Ohg | Floor wiping composition |
| WO1995010589A1 (en) * | 1993-10-14 | 1995-04-20 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous floor cleaning agent |
| US5753604A (en) * | 1993-10-14 | 1998-05-19 | Henkel Kommanditgesellschaft Auf Aktien | Water-containing floor cleaning composition |
| EP0790286A1 (en) * | 1996-02-13 | 1997-08-20 | Unilever N.V. | Surface treating process and device |
| US5782991A (en) * | 1996-02-13 | 1998-07-21 | Diversey Lever, Inc. | Surface treating process |
| WO1999018182A1 (en) * | 1997-10-07 | 1999-04-15 | The Procter & Gamble Company | Detergent composition for hard surfaces comprising hydrophilic shear-thinning polymer at very low level |
| US6979371B1 (en) | 1997-10-07 | 2005-12-27 | The Procter & Gamble Company | Detergent composition for hard surfaces comprising hydrophilic shear-thinning polymer at very low level |
| DE10357389A1 (en) * | 2003-12-07 | 2005-07-07 | Benda, Jürgen Michael | Non-mechanical cleaning of soapstone and other stones, using aqueous cleaner, applied first, and a non-aqueous cleaner |
| DE10357389B4 (en) * | 2003-12-07 | 2005-12-15 | Benda, Jürgen Michael | Process for cleaning soapstone |
Also Published As
| Publication number | Publication date |
|---|---|
| US4725319A (en) | 1988-02-16 |
| EP0215451A3 (en) | 1988-05-18 |
| JPS6272800A (en) | 1987-04-03 |
| EP0215451B1 (en) | 1990-11-28 |
| DE3675861D1 (en) | 1991-01-10 |
| DE3533531A1 (en) | 1987-04-02 |
| ATE58751T1 (en) | 1990-12-15 |
| JPH0823038B2 (en) | 1996-03-06 |
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