EP0876460B1 - Cleaning agent for hard surfaces - Google Patents

Cleaning agent for hard surfaces Download PDF

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Publication number
EP0876460B1
EP0876460B1 EP96942274A EP96942274A EP0876460B1 EP 0876460 B1 EP0876460 B1 EP 0876460B1 EP 96942274 A EP96942274 A EP 96942274A EP 96942274 A EP96942274 A EP 96942274A EP 0876460 B1 EP0876460 B1 EP 0876460B1
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EP
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Prior art keywords
cleaner
weight
group
formula
surfactants
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EP96942274A
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German (de)
French (fr)
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EP0876460A1 (en
Inventor
Rainer Jeschke
Ludwig Schieferstein
Katica Bocarac
Paul Birnbrich
Herbert Fischer
Rainer Kade
Eva Kiewert
Dieter Nickel
Horst-Dieter Speckmann
Juan-Carlos Wuhrmann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to the use of cationic polymers as soil release compounds in cleaning agents for hard surfaces.
  • cleaning agents are essentially aqueous Solutions of surfactants used as additives builders, water-soluble solvents, Solubilizers, water-soluble abrasives, etc. may contain. To meet the requirements To be able to do justice to the consumer, these cleaning agents should be compared all types of soiling can be effective.
  • the detergent components that contained the dirt removal in the second and subsequent applications are called soil release connections designated.
  • Most of these are polymeric Links. These polymers affect the surface of those to be cleaned Objects in such a way that they get rid of the dirt on the second and all influence further cleaning processes positively. They act in such a way that they first cleaning cycle have a certain tendency to focus on the cleaned To set surfaces (substantivity) and thus their surface properties change.
  • the polymers do not form permanent films, they can be with aqueous solutions e.g. B. in subsequent cleaning under certain circumstances very easily remove again.
  • a combination of high tendency to wet hard surfaces due to a soil release polymer with high stability against detachment (in Combination with stabilization of the dirt in the fleet) without the cleaning effect reducing detergents would be beneficial from the consumer's point of view judge.
  • the water-soluble anionic contains cationic or nonionic polymers.
  • the quaternized ammonium alkyl methacrylate groups contained in the molecule.
  • the cleaning agents described in this publication only show their dirt-repellent effect when the product has already been used was applied to the hard surface.
  • the object of the present invention is to provide connections put in use in aqueous surfactant solutions for manual cleaning of hard surfaces act as soil-release compounds, which remove dirt and Stabilization of the loosened dirt in the cleaning liquor already at the Positively influence first use or at least do not reduce it, and show an increased substantivity to the surface compared to aqueous solutions, which increases the cleaning ability of the detergent when used repeatedly is improved.
  • the cationic polymers according to the invention in Hard surface cleaners act as soil release compounds. Dirt detachment is particularly important when cleaning hard surfaces manually and the stabilization of the detached dirt in the cleaning liquor is positive influenced and improved substantivity on surfaces achieved.
  • the polymers contain the monomer units of the formula I preferably in a proportion of 40 mol% to 100 mol%, particularly preferably more than 50 mol%. As a result, the polymers have a significant soil release effect.
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like
  • olefins such as ethylene, propylene and butene
  • alkyl esters of unsaturated carboxylic acids in particular esters of acrylic acid and methacrylic acid, and their alcohol components, of alkyl groups from 1 to 6
  • C atoms such as methyl acrylate, ethyl acrylate, methyl methacrylate and their hydroxy derivatives such as 2-hydroxyethyl methacrylate
  • unsaturated groups such as styrene, methyl styrene, vinyl styrene and hetero
  • the polymers used according to the invention can in the cleaning agents in a Amount of 0.01 to 10 wt .-%, preferably from 0.02 to 5 wt .-%, in particular from 0.05 to 2 wt .-%, based on the all cleaning agents are included.
  • US-A-4 454 060 describes liquid detergent mixtures of non-cationic surfactants and cationic polymers which contain monomer units of the present formula I.
  • the cationic polymers act as foam stabilizers.
  • nonionic surfactants which may be contained in the agents according to the invention, z. B. alkyl polyglycosides and C 8 -C 18 alkyl alcohol ethers and nitrogenous surfactants.
  • Alkyl polyglycosides are known nonionic surfactants and can be described by formula II R 5 O- [G] p wherein R 5 is an alkyl radical having 8 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms, preferably a glucose radical, and p are numbers from 1 to 10.
  • Alkyl polyglycosides (APG) with the formula II can according to the relevant procedures of preparative organic chemistry can be obtained. Representing the extensive Literature is referred to EP-A1-0 301 298 and WO 90/3977.
  • the alkyl polyglycosides can differ from aldoses or ketoses with 5 or 6 carbon atoms, preferably derive the glucose.
  • the preferred alkyl polyglycosides are thus Alkyl polyglucosides.
  • Alkyl polyglycosides with an average degree of oligomerization are preferred p used from 1.1 to 3.0. From an application point of view, such alkyl polyglycosides are preferred, the degree of oligomerization is less than 1.7.
  • C 8 -C 18 alkyl alcohol polypropylene glycol / polyethylene glycol ether are also known nonionic surfactants. They can be described by formula III wherein R 6 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 18 carbon atoms, c is 0 or numbers from 1 to 3 and d is numbers from 1 to 20.
  • the C 8 -C 18 alkyl alcohol polypropylene / polyethylene glycol ether with the formula III can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols.
  • Typical examples are polyglycol ethers of the formula III in which R6 is an alkyl radical having 8 to 18 carbon atoms, c is 0 to 2 and d is a number from 2 to 7.
  • End-capped C 8 -C 18 -alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula III is etherified.
  • the end-capped C 8 -C 18 alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry.
  • C 8 -C 18 -Alkyl alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride.
  • Typical examples are mixed ethers of the formula III in which R 6 is for a technical fatty alcohol residue, preferably C 12/14 coconut alkyl residue, c for 0 and d stand for 5 to 10, which are closed with a butyl group.
  • Nitrogen-containing surfactants serve as further nonionic surfactants.
  • the particularly suitable compounds include lauric acid, Myristic acid and palmitic acid monoethanolamides.
  • the cleaning agent contains nonionic nitrogen-containing surfactants in amounts of 0.05% by weight to 10% by weight, preferably 0.1 % By weight to 5% by weight.
  • the cleaning agent preferably contains nitrogenous surfactants from the group of amphoteric surfactants, fatty acid alkanolamides, fatty acid polyhydroxyamides and alkylamine oxides.
  • the cleaning agent preferably contains nitrogenous surfactants and the cationic Polymers with units of the formula I in one Weight ratio of 40: 1 to 1:10, preferably 20: 1 to 1: 5.
  • surfactant components which are considered nonionic in the sense of this application
  • Surfactants can be used are amphoteric or zwitterionic surfactants, e.g. B. Mention betaine surfactants or fatty amine oxides.
  • the cleaning agents according to the invention can be used as an additional surfactant component Anionic surfactants included.
  • the anionic surfactants can be used in amounts of 0.05 to 10% by weight, preferably 0.1 to 7.0% by weight, based on the total agent, may be present.
  • Anionic surfactants and cationic polymers are preferably in a ratio of 20: 1 to 1:20, especially 10: 1 to 1:10.
  • Suitable anionic surfactants are e.g. C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, C 8 -C 18 alkane sulfonates, C 8 -C 18 ⁇ -olefin sulfonates, sulfonated C 8 -C 18 fatty acids, C 8 -C 18 alkyl benzene sulfonates , Sulfonic succinic acid mono- and di-C 1 -C 12 alkyl esters, C 8 -C 18 alkyl polyglycol ether carboxylates, C 8 -C 18 -N-acyl taurides, C 8 -C 18 -N-sarcosinates and C 8 -C 18 alkyl isethionates .
  • C 8 -C 18 alkyl sulfates C 8 -C 18 alkyl ether sulfates, C 8 -C 18 alkan
  • the agents according to the invention can also contain soaps, ie alkali metal or ammonium salts of saturated or unsaturated C 6 -C 22 fatty acids.
  • the soaps can be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.
  • the liquid cleaning agents for hard surfaces e.g. B. All-purpose cleaners and manual dishwashing detergents, contain common auxiliaries his. These substances are builders, such as. B. salts of glutaric acid, Succinic acid, adipic acid, tartaric acid, benzene hexacarboxylic acid, gluconic acid, Citric acid; Solvents such as B. ethanol, isopropanol, glycol ether; Hydrotropes like e.g. B. cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol; Cleaning booster; Viscosity regulators, such as B.
  • the cleaning agent according to the invention lies as ready-to-use solution, which is used in particular as a spray cleaner can.
  • the cleaning agent according to the invention is located as a pourable detergent concentrate, which is also a water-soluble Abrasive component can contain.
  • Such cleaning agents contain a water-soluble Salt, and are concentrated as an abrasive and diluted as an all-purpose cleaner suitable.
  • the inventive ones are suitable Means both as an all-purpose cleaner and for manual cleaning of dishes, especially of heavily soiled cookware.
  • water-soluble abrasive components are alkali metal carbonates, preferably sodium bicarbonate, which has an average grain size of about 200 microns ⁇ 100 microns exhibit.
  • the abrasive component is preferably present in an amount 50% by weight, particularly preferably 50 to 65% by weight, based on the invention Means, before.
  • the agent according to the invention is used to stabilize the abrasive component preferably as a gel.
  • the viscosity and thus the flow properties of the Cleaning agents according to the invention can be added by adding up to 5% by weight, preferably from about 0.3 to 3% by weight of polyols of the formula HO-R-OH, in which R is one alkyl radical optionally substituted by hydroxyl groups with about 2 to 6, preferably means 2 to 4 carbon atoms.
  • R is one alkyl radical optionally substituted by hydroxyl groups with about 2 to 6, preferably means 2 to 4 carbon atoms.
  • To the polyols include, for example, ethylene glycol, n- and iso-propylene glycols and glycerin.
  • Another possible additive consists of naturally occurring polymers and their derivatives such as xanthan gum, other polysaccharides and / or gelatin in Amounts up to 2% by weight, preferably about 0.1 to 1.0% by weight.
  • the agents according to the invention are particularly suitable for cleaning hard surfaces such as B. enamel, glass, porcelain, PVC and other plastics, linoleum, ceramic tiles, Marble and metals.
  • hard surfaces such as B. enamel, glass, porcelain, PVC and other plastics, linoleum, ceramic tiles, Marble and metals.
  • the Hand dishwashing detergents which are usually used to clean dishes, glasses, cutlery, Pots, bowls, etc. are used, and the all-purpose cleaner, which is usually be used to clean larger areas in the household, distinguished.
  • the dynamic interfacial tension ⁇ G was determined for various oils using the drop / volume tensiometer (TVT1, Lauda, according to the operating instructions) in order to be able to investigate the short-term kinetics when the interfacial tension was reduced.
  • the following is representative of the time course of the interfacial tension ⁇ G [mN / m] for Mazola, a commercially available vegetable oil.
  • the ingredients of the cleaning formulations are shown in Table 1 and the test results for Examples B1 to B5 are shown in Table 2.
  • test results show that the hydrophilizing on the PVC surface Effect of the drying layer when polymer is added even after a rinsing process is clearly noticeable. This effect occurs with cleaning agents which are described in EP-A-467 472 known polymers contain, to a significantly lesser extent, which is also a shows significantly better soil release effect of the polymers according to the invention.
  • a plastic sponge was each with 10 ml of the detergent solution to be tested soaked and mechanically on the also with 10 ml of the cleaning agent to be tested coated test surface moves. After 10 wiping movements, the cleaned test area Held under running water and the loose dirt removed.
  • the cleaning effect i.e. the whiteness of the so-called plastic surface was included a color difference measuring device "Microcolor" (Dr. Lange) measured. As a white standard served the clean untreated white plastic surface.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

Cationic polymers comprising at least 40 mole percent monomer units of the formula (I):wherein n is 2 to 4, R1 is hydrogen or methyl, and R2, R3 and R4 independently are hydrogen, C1-4 alkyl or C1-4 alkenyl, and X- is an anion selected from the group consisting of halide anions and monoalkyl anions of sulfuric acid semiester are used as soil-release compounds in hard surface cleaners.

Description

Die vorliegende Erfindung betrifft die Verwendung von kationischen Polymeren als Soil-Release-Verbindungen in Reinigungsmitteln für harte Oberflächen. Außerdem betrifft die Erfindung Reinigungsmittel für harte Oberflächen, die diese kationischen Polymere als Soil-Release-Verbindungen enthalten.The present invention relates to the use of cationic polymers as soil release compounds in cleaning agents for hard surfaces. In addition, the Invention detergent for hard surfaces that these cationic polymers as Soil release connections included.

Für die Reinigung harter Oberflächen, die im Haushalt und im Gewerbesektor auftreten, werden unterschiedliche Reinigungsmittel verwendet, die sich sowohl in der Konzentration der Reinigungswirkstoffe und in der Anbietungsform, z. B. Konzentrate, Sprühreiniger, Gele, Pulver, als auch im pH-Wert, z. B. saure, neutrale und alkalische Reiniger, unterscheiden. Es handelt sich bei den Reinigungsmitteln im wesentlichen um wäßrige Lösungen von Tensiden, die als Zusatzstoffe Builder, wasserlösliche Lösungsmittel, Lösungsvermittler, wasserlösliche Abrasivstoffe, etc. enthalten können. Um den Anforderungen der Verbraucher gerecht werden zu können, sollen diese Reinigungsmittel gegenüber allen Arten von auftretenden Verschmutzungen wirksam sein.For cleaning hard surfaces that occur in the household and in the commercial sector, different detergents are used, both in concentration the cleaning agents and in the form of supply, for. B. concentrates, spray cleaners, Gels, powders, as well as in pH, e.g. B. acidic, neutral and alkaline cleaners, differentiate. The cleaning agents are essentially aqueous Solutions of surfactants used as additives builders, water-soluble solvents, Solubilizers, water-soluble abrasives, etc. may contain. To meet the requirements To be able to do justice to the consumer, these cleaning agents should be compared all types of soiling can be effective.

Darüber hinaus wäre es wünschenswert, wenn die Reinigungsmittel Komponenten enthielten, die die Schmutzentfernung bei der zweiten und den nachfolgenden Anwendungen der Mittel erleichtern. Solche Komponenten werden als Soil-Release-Verbindungen bezeichnet. Überwiegend handelt es sich dabei um polymere Verbindungen. Diese Polymere beeinflussen die Oberfläche der zu reinigenden Gegenstände in der Weise, daß sie die Schmutzablösung bei dem zweiten und allen weiteren Reinigungsvorgängen positiv beeinflussen. Sie wirken derart, daß sie beim ersten Reinigungsgang eine gewisse Neigung besitzen, sich auf den gereinigten Oberflächen abzusetzen (Substantivität) und damit deren Oberflächeneigenschaften zu verändern. Die Polymere bilden dabei keine dauerhaften Filme, sondern sie lassen sich mit wäßrigen Lösungen z. B. beim nachfolgenden Reinigen unter Umständen sehr leicht wieder entfernen. Eine Kombination von hoher Benetzungstendenz harter Oberflächen durch ein Soil-Release-Polymer mit einer hohen Stabilität gegenüber Ablösung (in Verbindung mit Stabilisierung des Schmutzes in der Flotte) ohne die Reinigungswirkung von Reinigungsmitteln zu reduzieren, wäre vom Standpunkt des Verbrauchers günstig zu beurteilen. In addition, it would be desirable if the detergent components that contained the dirt removal in the second and subsequent applications the means lighten. Such components are called soil release connections designated. Most of these are polymeric Links. These polymers affect the surface of those to be cleaned Objects in such a way that they get rid of the dirt on the second and all influence further cleaning processes positively. They act in such a way that they first cleaning cycle have a certain tendency to focus on the cleaned To set surfaces (substantivity) and thus their surface properties change. The polymers do not form permanent films, they can be with aqueous solutions e.g. B. in subsequent cleaning under certain circumstances very easily remove again. A combination of high tendency to wet hard surfaces due to a soil release polymer with high stability against detachment (in Combination with stabilization of the dirt in the fleet) without the cleaning effect reducing detergents would be beneficial from the consumer's point of view judge.

Stand der TechnikState of the art

In der europäischen Patentanmeldung EP-A 0 467 472 wird ein Reinigungsmittel für harte Oberflächen beschrieben, das als Soil-Release-Verbindungen wasserlösliche anionische, kationische oder nichtionische Polymere enthält. Als Beispiele für derartige Polymere werden insbesondere Polymere angegeben, die quatemisierte Ammoniumalkylmethacrylatgruppen im Molekül enthalten. Die in dieser Druckschrift beschriebenen Reinigungsmittel weisen ihre schmutzabweisende Wirkung erst dann auf, wenn das Mittel bereits einmal auf die harte Oberfläche aufgetragen wurde.In European patent application EP-A 0 467 472 a cleaning agent for hard Surfaces described, the water-soluble anionic, contains cationic or nonionic polymers. As examples of such polymers particularly indicated polymers, the quaternized ammonium alkyl methacrylate groups contained in the molecule. The cleaning agents described in this publication only show their dirt-repellent effect when the product has already been used was applied to the hard surface.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Verbindungen zur Verfügung zu stellen, die in der Anwendung in wäßrigen Tensidlösungen zur manuellen Reinigung von harten Oberflächen als Soil-Release-Verbindungen wirken, die Schmutzablösung und Stabilisierung des abgelösten Schmutzes in der Reinigungsflotte bereits bei der Erstanwendung positiv beeinflussen oder zumindest sie nicht herabgesetzen, und gegenüber wässrigen Lösungen eine erhöhte Substantivität zur Oberfläche zeigen, wodurch das Reinigungsvermögen des Reinigungsmittels bei wiederholter Anwendung verbessert wird.The object of the present invention is to provide connections put in use in aqueous surfactant solutions for manual cleaning of hard surfaces act as soil-release compounds, which remove dirt and Stabilization of the loosened dirt in the cleaning liquor already at the Positively influence first use or at least do not reduce it, and show an increased substantivity to the surface compared to aqueous solutions, which increases the cleaning ability of the detergent when used repeatedly is improved.

Gegenstand der Erfindung ist die Verwendung von kationischen Polymeren, die Monomereinheiten der Formel I

Figure 00020001
   worin

  • n eine Zahl zwischen 2 und 4, bevorzugt 3, ist
  • R1 für Wasserstoff oder eine Methylgruppe steht und
  • R2, R3 und R4 gleich oder verschieden sein können und für Wasserstoff oder eine C1-4-Alk(en)ylgruppe stehen,
  • X- ein Anion aus der Gruppe der Halogenidanionen oder ein Monoalkylanion der Schwefelsäurehalbester repräsentiert,
    • enthalten, als Soil-Release-Verbindungen in Reinigungsmitteln für harte Oberflächen.The invention relates to the use of cationic polymers, the monomer units of the formula I.
    Figure 00020001
    wherein
  • n is a number between 2 and 4, preferably 3
  • R 1 represents hydrogen or a methyl group and
  • R 2 , R 3 and R 4 may be the same or different and represent hydrogen or a C 1-4 alk (en) yl group,
  • X - represents an anion from the group of halide anions or a monoalkyl anion of sulfuric acid half-esters,
    • included as soil release compounds in cleaning agents for hard surfaces.

    Es wurde festgestellt, daß die erfindungsgemäßen kationischen Polymere in Reinigungsmitteln für harte Oberflächen als Soil-Release-Verbindungen wirken. Insbesondere bei der manuellen Reinigung von harten Oberflächen wird die Schmutzablösung und die Stabilisierung des abgelösten Schmutzes in der Reinigungsflotte positiv beeinflußt und eine verbesserte Substantivität an Oberflächen erreicht.It was found that the cationic polymers according to the invention in Hard surface cleaners act as soil release compounds. Dirt detachment is particularly important when cleaning hard surfaces manually and the stabilization of the detached dirt in the cleaning liquor is positive influenced and improved substantivity on surfaces achieved.

    Die Polymere enthalten die Monomereinheiten mit der Formel I bevorzugt in einem Anteil von 40 Mol-% bis 100 Mol-%, besonders bevorzugt über 50 Mol-%. Die Polymere weisen dadurch eine signifikante Soil-Release-Wirkung auf. Neben den Monomereinheiten mit der Formel I können als Comonomere ungesättigte Monocarbonsäuren, wie Acrylsäure, Methacrylsäure, Crotonsäure und dergleichen, Olefine, wie Ethylen, Propylen und Buten, Alkylester von ungesättigten Carbonsäuren, insbesondere Ester der Acrylsäure und Methacylsäure, deren Alkoholkomponenten Alkylgruppen von 1 bis 6 C-Atomen enthalten, wie Methylacrylat, Ethylacrylat, Methylmethacrylat, sowie deren Hydroxyderivate wie 2-Hydroxy-Ethytmethacrylat, mit ungesättigten Gruppen versehene, gegebenenfalls weiter substituierte, aromatische Verbindungen wie Styrol, Methylstyrol, Vinylstyrol und heterocyclische Verbindungen wie Vinylpyrrolidon eingesetzt werden. Als Comonomere werden bevorzugt Acrylsäure, Methacrylsäure und ihre C1-C6-Esterverwendet.The polymers contain the monomer units of the formula I preferably in a proportion of 40 mol% to 100 mol%, particularly preferably more than 50 mol%. As a result, the polymers have a significant soil release effect. In addition to the monomer units of the formula I, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and the like, olefins, such as ethylene, propylene and butene, alkyl esters of unsaturated carboxylic acids, in particular esters of acrylic acid and methacrylic acid, and their alcohol components, of alkyl groups from 1 to 6, can be used as comonomers C atoms, such as methyl acrylate, ethyl acrylate, methyl methacrylate and their hydroxy derivatives such as 2-hydroxyethyl methacrylate, contain unsaturated groups, optionally further substituted aromatic compounds such as styrene, methyl styrene, vinyl styrene and heterocyclic compounds such as vinyl pyrrolidone. Acrylic acid, methacrylic acid and their C 1 -C 6 esters are preferably used as comonomers.

    Die erfindungsgemäß verwendeten Polymere können in den Reinigungsmitteln in einer Menge von 0,01 bis 10 Gew.-%, vorzugsweise von 0,02 bis 5 Gew.-%, insbesondere von 0,05 bis 2 Gew.-%, bezogen auf das gesamte Reinigungsmittel enthalten sein.The polymers used according to the invention can in the cleaning agents in a Amount of 0.01 to 10 wt .-%, preferably from 0.02 to 5 wt .-%, in particular from 0.05 to 2 wt .-%, based on the all cleaning agents are included.

    Ein weiterer Gegenstand der vorliegenden Erfindung sind wäßrige Reinigungsmittel für harte Oberflächen, die

  • a) von 0,01 bis 10 Gew.-%, vorzugsweise von 0,05 bis 2 Gew.-%, kationische Polymere, die Monomereinheiten mit der Formel I
    Figure 00030001
       worin
  • n eine Zahl zwischen 2 und 4, bevorzugt 3, ist
  • R1 für Wasserstoff oder eine Methylgruppe steht und
  • R2, R3 und R4 gleich oder verschieden sein können und für Wasserstoff oder eine C1-4Alk(en)ylgruppe stehen,
  • X- ein Anion aus der Gruppe der Halogenidanionen oder ein Monoalkylanion der Schwefelsäurehalbester repräsentiert,
    • enthalten
    wobei die Polymere
  • (i) Monomereinheiten der Formel I in einem Anteil von 40 bis 100 mol-% und/oder
  • (ii) als Comonomere ein oder mehrere Monomere aus der Gruppe der Olefine, der mit ungesättigten Gruppen versehenen, gegebenenfalls weiter substituierten, aromatischen und heterocyclischen Verbindungen, der ungesättigten Monocarbonsäuren, der Alkylester von ungesättigten Carbonsäuren sowie von deren Hydroxyderivaten, ausgenommen die C8_24-Ester der Acryl- und Methacrylsäure,
    •  enthalten,
    und
  • b) 0,1 bis 50 Gew.-% von einem nichtionischen Tensid oder mehreren nichtionischen Tensiden
    enthalten.
    • Another object of the present invention are aqueous cleaning agents for hard surfaces, the
  • a) from 0.01 to 10 wt .-%, preferably from 0.05 to 2 wt .-%, cationic polymers, the monomer units with the formula I.
    Figure 00030001
    wherein
  • n is a number between 2 and 4, preferably 3
  • R 1 represents hydrogen or a methyl group and
  • R 2 , R 3 and R 4 may be the same or different and represent hydrogen or a C 1-4 alk (en) yl group,
  • X - represents an anion from the group of halide anions or a monoalkyl anion of sulfuric acid half-esters,
    • contain
    being the polymers
  • (i) monomer units of the formula I in a proportion of 40 to 100 mol% and / or
  • (ii) as comonomers one or more monomers from the group of the olefins, the unsaturated groups, optionally further substituted aromatic and heterocyclic compounds, the unsaturated monocarboxylic acids, the alkyl esters of unsaturated carboxylic acids and their hydroxy derivatives, with the exception of C 8 _ 24 -Ester of acrylic and methacrylic acid,
    • contain,
    and
  • b) 0.1 to 50% by weight of one or more nonionic surfactants
    contain.

    • US-A-4 454 060 beschreibt flüssige Detergenzgemische aus nicht-kationischen Tensiden und kationischen Polymere, die monomereinheiten der vorliegenden Formel I enthalten. Die kationischen Polymere fungieren als Schaumstabilisatoren.US-A-4 454 060 describes liquid detergent mixtures of non-cationic surfactants and cationic polymers which contain monomer units of the present formula I. The cationic polymers act as foam stabilizers.

    Als nichtionische Tenside, die in den erfindungsgemäßen Mitteln enthalten sein können, eignen sich z. B. Alkylpolyglykoside und C8-C18-Alkylalkoholether und stickstoffhaltige Tenside.As nonionic surfactants, which may be contained in the agents according to the invention, z. B. alkyl polyglycosides and C 8 -C 18 alkyl alcohol ethers and nitrogenous surfactants.

    Alkylpolyglykoside sind bekannte nichtionische Tenside und können durch die Formel II beschrieben werden R5O-[G]p worin R5 für einen Alkylrest mit 8 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen, vorzugsweise einen Glucoserest, und p für Zahlen von 1 bis 10 stehen.Alkyl polyglycosides are known nonionic surfactants and can be described by formula II R 5 O- [G] p wherein R 5 is an alkyl radical having 8 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms, preferably a glucose radical, and p are numbers from 1 to 10.

    Alkylpolyglykoside (APG) mit der Formel II können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP-A1-0 301 298 und WO 90/3977 verwiesen.Alkyl polyglycosides (APG) with the formula II can according to the relevant procedures of preparative organic chemistry can be obtained. Representing the extensive Literature is referred to EP-A1-0 301 298 and WO 90/3977.

    Die Alkylpolyglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkylpolyglykoside sind somit Alkylpolyglucoside.The alkyl polyglycosides can differ from aldoses or ketoses with 5 or 6 carbon atoms, preferably derive the glucose. The preferred alkyl polyglycosides are thus Alkyl polyglucosides.

    Die Indexzahl p in der allgemeinen Formel II gibt den Oligomerisierungsgrad (DP-Grad), d.h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahlen zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß, und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylpolyglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkylpolyglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist. The index number p in the general formula II indicates the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p must always be an integer in a given connection, and here above all the values p = 1 to 6 can be the value p for a certain alkyl oligoglycoside an analytically calculated quantity, usually a fraction Represents number. Alkyl polyglycosides with an average degree of oligomerization are preferred p used from 1.1 to 3.0. From an application point of view, such alkyl polyglycosides are preferred, the degree of oligomerization is less than 1.7.

    C8-C18-Alkylalkoholpolypropylenglykol/polyethylenglykolether stellen ebenfalls bekannte nichtionische Tenside dar. Sie können durch die Formel III beschrieben werden

    Figure 00060001
    worin R6 für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen, c für 0 oder Zahlen von 1 bis 3 und d für Zahlen von 1 bis 20 steht.C 8 -C 18 alkyl alcohol polypropylene glycol / polyethylene glycol ether are also known nonionic surfactants. They can be described by formula III
    Figure 00060001
    wherein R 6 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 18 carbon atoms, c is 0 or numbers from 1 to 3 and d is numbers from 1 to 20.

    Die C8-C18-Alkylalkoholpolypropylen/polyethylenglykolether mit der Formel III kann man durch Anlagerung von Propylenoxid und/oder Ethylenoxid an Alkylalkohole, vorzugsweise an Fettalkohole, erhalten. Typische Beispiele sind Polyglykolether der Formel III, in der R6 für einen Alkylrest mit 8 bis 18 Kohlenstoffatomen, c für 0 bis 2 und d für Zahlen von 2 bis 7 steht.The C 8 -C 18 alkyl alcohol polypropylene / polyethylene glycol ether with the formula III can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols. Typical examples are polyglycol ethers of the formula III in which R6 is an alkyl radical having 8 to 18 carbon atoms, c is 0 to 2 and d is a number from 2 to 7.

    Es können auch endgruppenverschlossene C8-C18-Alkylalkoholpolyglykolether eingesetzt werden, d.h. Verbindungen in denen die freie OH-Gruppe in der Formel III verethert ist. Die endgruppenverschlossenen C8-C18-Alkylalkoholpolyglykolether können nach einschlägigen Methoden der präparativen organischen Chemie erhalten werden. Vorzugsweise werden C8-C18-Alkylalkohopolyglykolether in Gegenwart von Basen mit Alkylhalogeniden, insbesondere Butyl- oder Benzylchlorid, umgesetzt Typische Beispiele sind Mischether der Formel III, in der R6 für einen technischen Fettalkoholrest, vorzugsweise C12/14-Kokosalkylrest, c für 0 und d für 5 bis 10 stehen, die mit einer Butylgruppe verschlossen sind.End-capped C 8 -C 18 -alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula III is etherified. The end-capped C 8 -C 18 alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry. C 8 -C 18 -Alkyl alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride. Typical examples are mixed ethers of the formula III in which R 6 is for a technical fatty alcohol residue, preferably C 12/14 coconut alkyl residue, c for 0 and d stand for 5 to 10, which are closed with a butyl group.

    Als weitere nichtionische Tenside dienen stickstoffenthaltende Tenside z. B. Fettsäurepolyhydroxyamide, beispielsweise Glucamide, und Ethoxylate von Alkylaminen, vicinalen Diolen und/oder Carbonsäureamiden, die Alkylgruppen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, besitzen. Der Ethoxylierungsgrad dieser Verbindungen liegt dabei in der Regel zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Bevorzugt sind Ethanolamid-Derivate von Alkansäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 16 C-Atomen. Zu den besonders geeigneten Verbindungen gehören die Laurinsäure-, Myristinsäure- und Palmitinsäuremonoethanolamide.Nitrogen-containing surfactants serve as further nonionic surfactants. B. Fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides, the alkyl groups with 10 to 22 carbon atoms, preferably have 12 to 18 carbon atoms. The degree of ethoxylation of these compounds is usually between 1 and 20, preferably between 3 and 10. Preferred are ethanolamide derivatives of alkanoic acids with 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The particularly suitable compounds include lauric acid, Myristic acid and palmitic acid monoethanolamides.

    In einer bevorzugten Ausführungsform enthält das Reinigungsmittel nichtionische stickstoffhaltige Tenside in Mengen von 0,05 Gew.-% bis 10 Gew.-%, vorzugsweise 0,1 Gew.-% bis 5 Gew.-%.In a preferred embodiment, the cleaning agent contains nonionic nitrogen-containing surfactants in amounts of 0.05% by weight to 10% by weight, preferably 0.1 % By weight to 5% by weight.

    Vorzugsweise enthält das Reinigungsmittel stickstoffhaltige Tenside aus der Gruppe der amphoteren Tenside, Fettsäurealkanolamide, Fettsäurepolyhydroxyamide und Alkylaminoxide. The cleaning agent preferably contains nitrogenous surfactants from the group of amphoteric surfactants, fatty acid alkanolamides, fatty acid polyhydroxyamides and alkylamine oxides.

    Vorzugsweise enthält das Reinigungsmittel stickstoffhaltige Tenside und die kationischen Polymere mit Einheiten der Formel I in einem Gewichsverhältnis von 40:1 bis 1:10, vorzugsweise 20:1 bis 1:5.The cleaning agent preferably contains nitrogenous surfactants and the cationic Polymers with units of the formula I in one Weight ratio of 40: 1 to 1:10, preferably 20: 1 to 1: 5.

    Als weitere tensidische Bestandteile, die im Sinne dieser Anmeldung als nichtionische Tenside eingestzt werden können, sind amphotere oder zwitterionische Tenside, z. B. Betaintenside oder Fettaminoxide zu erwähnen.As further surfactant components, which are considered nonionic in the sense of this application Surfactants can be used are amphoteric or zwitterionic surfactants, e.g. B. Mention betaine surfactants or fatty amine oxides.

    Weiterhin können die erfindungsgemäßen Reinigungsmittel als zusätzliche Tensidkomponente Aniontenside enthalten. Die Aniontenside können in Mengen von 0,05 bis 10 Gew.-%, vorzugsweise 0,1 bis 7,0 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Aniontenside und kationische Polymere liegen vorzugsweise in einem Verhältnis von 20:1 bis 1 : 20, insbesondere 10:1 1 bis 1 : 10 vor.Furthermore, the cleaning agents according to the invention can be used as an additional surfactant component Anionic surfactants included. The anionic surfactants can be used in amounts of 0.05 to 10% by weight, preferably 0.1 to 7.0% by weight, based on the total agent, may be present. Anionic surfactants and cationic polymers are preferably in a ratio of 20: 1 to 1:20, especially 10: 1 to 1:10.

    Geeignete Aniontenside sind z .B. C8-C18-Alkylsulfate, C8-C18-Alkylethersulfate, C8-C18-Alkansulfonate, C8-C18-α-Olefinsulfonate, sulfonierte C8-C18-Fettsäuren, C8-C18-Alkylbenzolsulfonate, Sulfonbemsteinsäuremono- und -di-C1-C12-Alkylester, C8-C18-Alkylpolyglykolethercarboxylate, C8-C18-N-Acyltauride, C8-C18-N-Sarkosinate und C8-C18-Alkylisethionate.Suitable anionic surfactants are e.g. C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, C 8 -C 18 alkane sulfonates, C 8 -C 18 α-olefin sulfonates, sulfonated C 8 -C 18 fatty acids, C 8 -C 18 alkyl benzene sulfonates , Sulfonic succinic acid mono- and di-C 1 -C 12 alkyl esters, C 8 -C 18 alkyl polyglycol ether carboxylates, C 8 -C 18 -N-acyl taurides, C 8 -C 18 -N-sarcosinates and C 8 -C 18 alkyl isethionates .

    Wegen ihrer schaumdämpfenden Eigenschaften können die erfindungsgemäßen Mittel auch Seifen, d. h. Alkali- oder Ammoniumsalze gesättigter oder ungesättigter C6-C22-Fettsäuren, enthalten. Die Seifen können in einer Menge bis zu 5 Gew.-%, vorzugsweise von 0,1 bis 2 Gew.-%, eingesetzt werden.Because of their foam-suppressing properties, the agents according to the invention can also contain soaps, ie alkali metal or ammonium salts of saturated or unsaturated C 6 -C 22 fatty acids. The soaps can be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.

    Fakultativ können weiterhin die in flüssigen Reinigungsmitteln für harte Oberflächen, z. B. Allzweckreinigern und manuellen Geschirrspülmitteln, enthaltenen üblichen Hilfsstoffe enthalten sein. Bei diesen Stoffen handelt es sich um Builder, wie z. B. Salze der Glutarsäure, Bernsteinsäure, Adipinsäure, Weinsäure, Benzolhexacarbonsäure, Gluconsäure, Citronensäure; Lösungsmittel, wie z. B. Ethanol, Isopropanol, Glykolether; Hydrotrope, wie z. B. Cumolsulfonat, Octylsulfat, Butylglucosid, Butylglykol; Reinigungsverstärker; Viskositätsregler, wie z. B. synthetische Polymere wie Polysaccharide, Polyacrylate; pH-Regulatoren, wie z. B. Citronensäure, Alkanolamine oder NaOH; Konservierungsmittel; Desinfektionswirkstoffe; Farb- und Duftstoffe sowie Trübungsmittel oder auch Hautschutzmittel, wie sie in EP-A-522 556 beschrieben sind. Der pH-Wert der Reinigungsformulierungen kann dabei über einen weiten Bereich variiert werden, bevorzugt ist jedoch ein Bereich von 2,5 bis 10,5.The liquid cleaning agents for hard surfaces, e.g. B. All-purpose cleaners and manual dishwashing detergents, contain common auxiliaries his. These substances are builders, such as. B. salts of glutaric acid, Succinic acid, adipic acid, tartaric acid, benzene hexacarboxylic acid, gluconic acid, Citric acid; Solvents such as B. ethanol, isopropanol, glycol ether; Hydrotropes like e.g. B. cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol; Cleaning booster; Viscosity regulators, such as B. synthetic polymers such as polysaccharides, polyacrylates; pH regulators, such as B. citric acid, alkanolamines or NaOH; Preservatives; Disinfectants; Dyes and fragrances as well as opacifiers or Skin protection agents as described in EP-A-522 556. The pH of the Cleaning formulations can be varied over a wide range, however, a range from 2.5 to 10.5 is preferred.

    In einer bevorzugten Ausführungsform liegt das erfindungsgemäße Reinigungsmittel als anwendungsfertige Lösung vor, die insbesondere als Sprühreiniger eingesetzt werden kann. In a preferred embodiment, the cleaning agent according to the invention lies as ready-to-use solution, which is used in particular as a spray cleaner can.

    In einer weiteren bevorzugten Ausführungsform liegt das erfindungsgemäße Reinigungsmittel als gießfähiges Reinigungsmittelkonzentrat vor, das zusätzlich eine wasserlösliche Abrasivkomponente enthalten kann. Derartige Reinigungsmittel enthalten ein wasserlösliches Salz, und sind in konzentrierter Form als Scheuermittel und verdünnt als Allzweckreinigungsmittel geeignet. In dieser Ausführungsform eignen sich die erfindungsgemäßen Mittel sowohl als Allzweckreiniger als auch zur manuellen Reinigung von Geschirr, insbesondere von stark verschmutztem Kochgeschirr.In a further preferred embodiment, the cleaning agent according to the invention is located as a pourable detergent concentrate, which is also a water-soluble Abrasive component can contain. Such cleaning agents contain a water-soluble Salt, and are concentrated as an abrasive and diluted as an all-purpose cleaner suitable. In this embodiment, the inventive ones are suitable Means both as an all-purpose cleaner and for manual cleaning of dishes, especially of heavily soiled cookware.

    Als wasserlösliche Abrasivkomponente eignen sich insbesondere Alkalimetallcarbonate, vorzugsweise Natriumbicarbonat, die eine mittlere Korngröße von etwa 200 µm ± 100 µm aufweisen. Die Abrasivkomponente liegt in einer Menge von vorzugsweise über 50 Gew-%, besonders bevorzugt 50 bis 65 Gew.-%, bezogen auf das erfindungsgemäße Mittel, vor.Particularly suitable as water-soluble abrasive components are alkali metal carbonates, preferably sodium bicarbonate, which has an average grain size of about 200 microns ± 100 microns exhibit. The abrasive component is preferably present in an amount 50% by weight, particularly preferably 50 to 65% by weight, based on the invention Means, before.

    Zur Stabilisierung der Abrasivkomponente liegt das erfindungsgemäße Mittel vorzugsweise als Gel vor. Die Viskosität und damit die Fließeigenschaften der erfindungsgemäßen Reinigungsmittel lassen sich durch Zusatz von bis zu 5 Gew.-%, vorzugsweise von etwa 0,3 bis 3 Gew.-% Polyolen der Formel HO-R-OH, worin R einen gegebenenfalls durch Hydroxylgruppen substituierten Alkylrest mit etwa 2 bis 6, vorzugsweise 2 bis 4 Kohlenstoffatomen bedeutet, positiv beeinflussen. Zu den Polyolen gehören zum Beispiel Ethylenglykol, n- und iso-Propylenglykole sowie Glycerin.The agent according to the invention is used to stabilize the abrasive component preferably as a gel. The viscosity and thus the flow properties of the Cleaning agents according to the invention can be added by adding up to 5% by weight, preferably from about 0.3 to 3% by weight of polyols of the formula HO-R-OH, in which R is one alkyl radical optionally substituted by hydroxyl groups with about 2 to 6, preferably means 2 to 4 carbon atoms. To the polyols include, for example, ethylene glycol, n- and iso-propylene glycols and glycerin.

    Ein weiterer möglicher Zusatz besteht aus in der Natur vorkommenden Polymeren und deren Derivate wie etwa Xanthangum, weiteren Polysacchariden und/oder Gelatine in Mengen von bis zu 2 Gew.-%, vorzugsweise etwa 0,1 bis 1,0 Gew.-%.Another possible additive consists of naturally occurring polymers and their derivatives such as xanthan gum, other polysaccharides and / or gelatin in Amounts up to 2% by weight, preferably about 0.1 to 1.0% by weight.

    Die erfindungsgemäßen Mittel eignen sich besonders zum Reinigen von harten Oberflächen wie z. B. Emaille, Glas, Porzellan, PVC und anderen Kunststoffen, Linoleum, Keramikfliesen, Marmor und Metallen. Im Handel wird dabei zwischen den Handgeschirrspülmitteln, die in der Regel zum Reinigen von Geschirr, Gläser, Bestecken, Töpfen, Schüsseln etc. eingesetzt werden, und den Allzweckreinigem, die in der Regel zum Reinigen von im Haushalt vorhandenen größeren Flächen eingesetzt werden, unterschieden.The agents according to the invention are particularly suitable for cleaning hard surfaces such as B. enamel, glass, porcelain, PVC and other plastics, linoleum, ceramic tiles, Marble and metals. In trade there is between the Hand dishwashing detergents, which are usually used to clean dishes, glasses, cutlery, Pots, bowls, etc. are used, and the all-purpose cleaner, which is usually be used to clean larger areas in the household, distinguished.

    Die Vorteile der vorliegenden Erfindung werden in den nachfolgenden Beispielen näher erläutert. The advantages of the present invention are illustrated in the examples below explained.

    BeispieleExamples Physikalische UntersuchungenPhysical examinations

    Die Wirkung der Polymere auf den Reinigungsvorgang wurde mit verschiedenen physikalischen Methoden charakterisiert.
    Bei den Untersuchungen wurde der in Tabelle 1, Beispiel 1 genannte Allzweckreiniger (AZR) als Basis verwendet, dem jeweils 0,2 Gew.-% Polymer aus der im folgenden aufgezählten Gruppe zugesetzt wurden.

    Polymer a:
    Poly-Methacrylamidopropyltrimethylammoniumchlorid
    Polymer b:
    Poly-Methacrylamidopropyltrimethylammoniumchlorid-co-Natriumacrylat-co-Ethylacrylat im Verhältnis 8 : 3 : 6 Mol-Teile
    Polymer c:
    Poly-Methacrylamidopropyltrimethylammoniumchlorid-co-2-Ethylhexylacrylat im Verhältnis 9 : 1 Gewichtsteile
    Polymer d:
    Poly[beta(N-methyl-NN-diethylammonium)ethylmethacrylat] (aus EP-A-467 472)
    The effect of the polymers on the cleaning process was characterized by different physical methods.
    The tests were carried out using the all-purpose cleaner (AZR) mentioned in Table 1, Example 1, to which 0.2% by weight of polymer from the group listed below was added in each case.
    Polymer a:
    Poly-methacrylamidopropyltrimethylammonium chloride
    Polymer b:
    Poly-methacrylamidopropyltrimethylammonium chloride-co-sodium acrylate-co-ethyl acrylate in a ratio of 8: 3: 6 mol parts
    Polymer c:
    Poly-methacrylamidopropyltrimethylammonium chloride-co-2-ethylhexyl acrylate in a ratio of 9: 1 parts by weight
    Polymer d:
    Poly [beta (N-methyl-NN-diethylammonium) ethyl methacrylate] (from EP-A-467 472)

    Prüfung der dynamischen Grenzflächenspannunq σG am Beispiel von ÖlschmutzTesting the dynamic interfacial tension σ G using the example of oil dirt

    Die dynamische Grenzflächenspannung σG wurde für verschiedene Öle mit dem Tropfen/Volumen-Tensiometer (TVT1, Fa. Lauda, gem. Bedienungsanleitung) bestimmt, um die Kurzzeitkinetik bei der Senkung der Grenzflächenspannung untersuchen zu können. Im folgenden ist stellvertretend der zeitliche Verlauf der Grenzflächenspannung σG [mN/m] für Mazola, ein handelsübliches Pflanzenöl, bestimmt. Die Inhaltsstoffe der Reinigerformulierungen sind in Tabelle 1 und die Versuchsergebnisse für die Beispiele B1 bis B5 sind in Tabelle 2 wiedergegeben. Inhaltsstoff B1 B2 B3 B4 B5 C8/10-Alkylpolyglucosid p = 1,5 4,00 4,00 4,00 4,00 4,00 C12/14-Fettalkoholether mit 6 EO 1,00 1,00 1,00 1,00 1,00 Kokosfettsäure 0,5 0,5 0,5 0,5 0,5 NaHCO3 3,5 3,5 3,5 3,5 3,5 Polymer a 0,20 Polymer b 0,20 Polymer c 0,20 Polymer d 0,20 Konservierungsmittel 0,20 0,20 0,20 0,20 0,20 Wasser ad 100 ad 100 ad 100 ad 100 ad 100 Zeit [sec.] Dynamische Grenzflächenspannung σG [mN/m] B1 (Vergleich) B2 B3 B4 B5 (Vergleich) 25 7,8 4,4 4,5 7,2 7,8 35 7,2 4,2 4,2 6,1 7,2 45 6,75 3,9 3,9 5,4 6,7 55 6,5 3,8 3,8 4,7 6,6 65 6,3 3,6 3,6 4,2 6,4 75 6,0 3,5 3,4 4,0 6,0 85 5,8 3,2 3,2 3,9 5,8 95 5,7 2,9 3,2 3,8 5,4 The dynamic interfacial tension σ G was determined for various oils using the drop / volume tensiometer (TVT1, Lauda, according to the operating instructions) in order to be able to investigate the short-term kinetics when the interfacial tension was reduced. The following is representative of the time course of the interfacial tension σ G [mN / m] for Mazola, a commercially available vegetable oil. The ingredients of the cleaning formulations are shown in Table 1 and the test results for Examples B1 to B5 are shown in Table 2. ingredient B1 B2 B3 B4 B5 C 8/10 alkyl polyglucoside p = 1.5 4.00 4.00 4.00 4.00 4.00 C 12/14 fatty alcohol ether with 6 EO 1.00 1.00 1.00 1.00 1.00 Coconut fatty acid 0.5 0.5 0.5 0.5 0.5 NaHCO 3 3.5 3.5 3.5 3.5 3.5 Polymer a 0.20 Polymer b 0.20 Polymer c 0.20 Polymer d 0.20 Preservative 0.20 0.20 0.20 0.20 0.20 water ad 100 ad 100 ad 100 ad 100 ad 100 Time [sec.] Dynamic interfacial tension σ G [mN / m] B1 (comparison) B2 B3 B4 B5 (comparison) 25th 7.8 4.4 4.5 7.2 7.8 35 7.2 4.2 4.2 6.1 7.2 45 6.75 3.9 3.9 5.4 6.7 55 6.5 3.8 3.8 4.7 6.6 65 6.3 3.6 3.6 4.2 6.4 75 6.0 3.5 3.4 4.0 6.0 85 5.8 3.2 3.2 3.9 5.8 95 5.7 2.9 3.2 3.8 5.4

    Aus den in Tabelle 2 dargestellten Ergebnissen wird deutlich, daß die Reinigerformulierungen, die die erfindungsgemäß verwendeten, kationischen Polymere enthielten, einen für die Schmutzentfernung deutlich günstigeren Verlauf zeigen, als die polymerfreien oder auch die Reinigerformulierungen, die die aus der EP-A-467 472 bekannten Polymere enthalten.From the results shown in Table 2 it is clear that the Detergent formulations containing the cationic polymers used according to the invention contained, show a significantly more favorable course for dirt removal than that polymer-free or also the cleaner formulations which are derived from EP-A-467 472 known polymers contain.

    BenetzungsversucheWetting attempts

    Um den unterschiedlichen Soil-Release-Effekt der, verschiedene Polymere enthaltenden, Reinigerlösungen auf Oberflächen zu beweisen, wurden Benetzungsversuche mit wässrigen Lösungen an PVC durchgeführt. Die Versuche wurden nach der Wilhelmy-Methode mittels einem Kontaktwinkel- und Adsorptionsmeßsystem der Fa. Krüss GmbH, Hamburg durchgeführt. Dazu wurden die Substrate in die jeweiligen Reiniger-Lösungen getaucht, woraufhin man die Lösungen abtropfen und den verbleibenden Rest der Reinigerlösung eingetrocknen ließ. Die Benetzungsspannung σB[mN/m] wird danach beim Eintauchen der Substrate in Wasser detektiert. Zur Bestimmung der Soil-Release-Wirkung vergleicht man nun mit Substraten, bei denen die eingetrocknete Schicht des Restes der Reinigerlösung ein oder ggf. mehrmals mit Wasser abgespült und wiederum getrocknet wurde. Die in Tabelle 3 aufgeführten Ergebnisse zeigen die Ergebnisse nach einem solchen zusätzlichen Spülschritt. Die Benetzungsspannung σB [mN/m], als Oberflächeneffekt, wurde dabei für verschiedene Eintauchtiefen [mm] gemessen und aus diesen Daten der Grenzwert extrapoliert. In order to demonstrate the different soil release effect of the cleaning solutions containing different polymers on surfaces, wetting tests were carried out with aqueous solutions on PVC. The tests were carried out according to the Wilhelmy method using a contact angle and adsorption measurement system from Krüss GmbH, Hamburg. For this purpose, the substrates were immersed in the respective cleaning solutions, whereupon the solutions were drained off and the remainder of the cleaning solution was allowed to dry. The wetting tension σ B [mN / m] is then detected when the substrates are immersed in water. To determine the soil release effect, a comparison is now made with substrates in which the dried-on layer of the rest of the cleaning solution has been rinsed off with water one or more times and dried again. The results listed in Table 3 show the results after such an additional rinsing step. The wetting tension σ B [mN / m], as a surface effect, was measured for different immersion depths [mm] and the limit value was extrapolated from this data.

    Als Reinigerformulierungen wurden verwendet:

  • Reiniger 1  analog Tabelle 1 Beispiel 1 (ohne Polymerzusatz)
  • Reiniger 2  analog Tabelle 1 Beispiel 3 (mit einem erfindungsgemäßem Polymer)
  • Reiniger 3  analog Tabelle 1 Beispiel 5 (Polymer gemäß EP-A 0 467 472)
    • Benetzungsspannung σB [mN/m] Reiniger 1 aus Lösung Reiniger 1
    1x Wasser     Reiniger 2 aus Lösung Reiniger 2
    1x Wasser     Reiniger 3 aus Lösung Reiniger 3
    1x Wasser         44 17,5 43 31 44 18,5     The following were used as cleaner formulations:
  • Cleaner 1 analogous to Table 1 Example 1 (without polymer addition)
  • Cleaner 2 analogous to Table 1 Example 3 (with a polymer according to the invention)
  • Cleaner 3 analogous to Table 1 Example 5 (polymer according to EP-A 0 467 472)
    • Wetting tension σ B [mN / m] Cleaner 1 from solution Cleaner 1
    1x water     Cleaner 2 from solution Cleaner 2
    1x water     Cleaner 3 from solution Cleaner 3
    1x water     44 17.5 43 31 44 18.5

    Die Versuchsergebnisse zeigen, daß an der PVC-Oberfläche die hydrophilierende Wirkung der Eintrocknungschicht bei Polymerzusatz auch nach einem Spülprozeß noch deutlich feststellbar ist. Dieser Effekt tritt bei Reinigungsmitteln, die die aus EP-A-467 472 bekannten Polymere enthalten, in signifikant geringerem Maße auf, wonach sich auch ein erheblich besserer Soil-Release-Effekt der erfindungsgemäßen Polymeren zeigen läßt.The test results show that the hydrophilizing on the PVC surface Effect of the drying layer when polymer is added even after a rinsing process is clearly noticeable. This effect occurs with cleaning agents which are described in EP-A-467 472 known polymers contain, to a significantly lesser extent, which is also a shows significantly better soil release effect of the polymers according to the invention.

    Prüfung des ReinigungsvermögensChecking the cleaning ability

    Zur Prüfung des Reinigungsvermögens der erfindungsgemäß formulierten Reinigerzusammensetzungen diente die unten nach "Seifen-Öle-Fette-Wachse", 112, 371 (1986) beschriebene Testmethode, die sehr gut reproduzierbare Ergebnisse liefert. Danach wurde das zu prüfende Reinigungsmittel auf eine künstlich angeschmutzte Kunststoffoberfläche gegeben. Als künstliche Anschmutzung für die verdünnte Anwendung des Reinigungsmittels wurde ein Gemisch aus Ruß, Maschinenöl, Triglycerid aus gesättigten Fettsäuren und niedersiedendem aliphatischen Kohlenwasserstoff verwendet. Die Testfläche von 26 x 28 cm wurde mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künstlichen Anschmutzung beschichtet.The test method described below according to "Soap-Oil-Fat-Waxes", 112 , 371 (1986), which provides very reproducible results, was used to test the cleaning ability of the cleaner compositions formulated according to the invention. The cleaning agent to be tested was then placed on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride of saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent. The test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.

    Ein Kunststoffschwamm wurde jeweils mit 10 ml der zu prüfenden Reinigungsmittellösung getränkt und mechanisch auf der ebenfalls mit 10 ml der zu prüfenden Reinigungsmittel beschichteten Testfläche bewegt. Nach 10 Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung, d.h. der Weißgrad der sogenannten Kunststoffoberfläche wurde mit einem Farb-Differenz-Meßgerät "Microcolor" (Dr. Lange) gemessen. Als Weiß-Standard diente die saubere unbehandelte weiße Kunststoffoberfläche.A plastic sponge was each with 10 ml of the detergent solution to be tested soaked and mechanically on the also with 10 ml of the cleaning agent to be tested coated test surface moves. After 10 wiping movements, the cleaned test area Held under running water and the loose dirt removed. The cleaning effect, i.e. the whiteness of the so-called plastic surface was included a color difference measuring device "Microcolor" (Dr. Lange) measured. As a white standard served the clean untreated white plastic surface.

    Die Messung der sauberen Oberfläche entsprach 100 % und die der angeschmutzten Fläche 0 %, so daß die abgelesenen Werte der gereinigten Kunststoff-Flächen mit dem Prozentgehalt Reinigungsvermögen (% RV) gleichgesetzt werden konnten. Bei den nachstehenden Versuchen sind die angegebenen % RV-Werte die nach dieser Methode ermittelten Werte für das Reinigungsvermögen der untersuchten Reinigungsmittel. Sie stellen jeweils Mittelwerte aus drei gleichen Versuchen dar.The measurement of the clean surface corresponded to 100% and that of the soiled Area 0%, so that the read values of the cleaned plastic surfaces with the Percentage of cleaning ability (% RV) could be equated. Both The experiments below are the% RV values given using this method determined values for the cleaning ability of the investigated cleaning agents. she represent mean values from three identical experiments.

    Die Meßwerte wurden in Relation zum Reinigungsergebnis als Standard benutzten, die erfindungsgemäßen Polymere nicht enthaltenden, AZR-Rezeptur gesetzt. Meßwerte Probe x 100/ Meßwert Standard = % RV relativ The measured values were used in relation to the cleaning result as the standard, AZR recipe not containing the polymers according to the invention. Measured values sample x 100 / measured value standard =% RV relative

    Einige ausgewählte Beispiele für Reinigerformulierungen (B6 bis B22) sowie die mit ihnen erhaltenen Reinigungsergebnisse sind in den Tabellen 4 bis 7 wiedergegeben. Allzweckreiniger Verdünnungskonzentrat im schwachalkalischen Bereich Inhaltsstoff B6 B7 B8 B9 B10 C8/10-Alkylpolyglucosid p = 1,5 4,00 4,00 4,00 4,00 4,00 C12/14-Fettalkoholether mit 6 EO 1,00 1,00 1,00 1,00 1,00 Kokosfettsäure 0,5 0,5 0,5 0,5 0,5 NaHCO3 3,5 3,5 3,5 3,5 3,5 Polymer a 0,8 Polymer b 0,6 0,40 Polymer c 0,40 Konservierungsmittel 0,20 0,20 0,20 0,20 0,20 Wasser ad 100 ad 100 ad 100 ad 100 ad 100 Reinigungsvermögen (%) bei Konzentration 9 ml/l 100 148 158 139 135 Allzweckreiniger mit Aniontensid im schwachalkalischen Bereich Inhaltsstoff B11 B12 B13 B14 Na-Dodecylbenzolsulfonat 1,00 1,00 1,00 1,00 C12/14-Fettalkoholether mit 6 EO 3,00 3,00 3,00 3,00 C8/10-Alkylpolyglucosid p = 1,5 4,00 4,00 4,00 4,00 Kokosfettsäure 0,5 0,5 0,5 0,5 Citronensäure 3,00 3,00 3,00 3,00 NaOH 1,90 1,90 1,90 1,90 Polymer a 1,0 Polymer b 1,0 Polymer c 1,0 Konservierungsmittel 0,20 0,20 0,20 0,20 Wasser ad 100 ad 100 ad 100 ad 100 Reinigungsvermögen (%) bei Konzentration 9 ml/l 100 156 137 138 Badreiniger im schwachsauren Bereich Inhaltsstoff B15 B16 B17 B18 C8/10-Alkylpolyglucosid p = 1,5 3,85 3,85 3,85 3,85 C12/14-Fettalkoholether mit 6 EO 1,00 1,00 1,00 1,00 Citronensäure 4,80 4,80 4,80 4,80 NaOH 1,00 1,00 1,00 1,00 Ethanol 1,00 1,00 1,00 1,00 Polymer a 0,30 Polymer b 0,30 Polymer c 0,30 Konservierungsmittel 0,20 0,20 0,20 0,20 Parfümöl 0,90 0,90 0,90 0,90 Wasser ad 100 ad 100 ad 100 ad 100 Reinigungsvermögen (%) bei Konzentration 8 ml/l 100 139 150 145 Allzweckreiniger mit wasserlöslichem Abrasivstoff im schwachalkalischen Bereich Inhaltsstoff B19 B20 B21 B22 Na-C12-C14-Fettalkoholsulfat 5,00 5,00 5,00 5,00 C12/14-Fettalkoholether mit 2,5 EO (NRE) 3,50 3,50 3,50 3,50 C12-C14-Fettalkoholether mit 4 EO 0,30 0,30 0,30 0,30 Kokosfettsäure 1,00 1,00 1,00 1,00 Natriumbicarbonat 50,00 50,00 50,00 50,00 Polymer a 0,30 Polymer b 0,30 Polymer c 0,30 Propylenglykol 0,50 0,50 0,50 0,50 Konservierungsmittel 0,20 0,20 0,20 0,20 Parfümöl 0,40 0,40 0,40 0,40 Wasser ad 100 ad 100 ad 100 ad 100 Reinigungsvermögen (%) bei Konzentration 3 ml/l 100 123 120 122 A few selected examples of cleaning formulations (B6 to B22) and the cleaning results obtained with them are shown in Tables 4 to 7. All-purpose cleaner Dilution concentrate in the weakly alkaline range ingredient B6 B7 B8 B9 B10 C 8/10 alkyl polyglucoside p = 1.5 4.00 4.00 4.00 4.00 4.00 C 12/14 fatty alcohol ether with 6 EO 1.00 1.00 1.00 1.00 1.00 Coconut fatty acid 0.5 0.5 0.5 0.5 0.5 NaHCO 3 3.5 3.5 3.5 3.5 3.5 Polymer a 0.8 Polymer b 0.6 0.40 Polymer c 0.40 Preservative 0.20 0.20 0.20 0.20 0.20 water ad 100 ad 100 ad 100 ad 100 ad 100 Cleaning power (%) at a concentration of 9 ml / l 100 148 158 139 135 All-purpose cleaner with anionic surfactant in the weakly alkaline range ingredient B11 B12 B13 B14 Na dodecylbenzenesulfonate 1.00 1.00 1.00 1.00 C 12/14 fatty alcohol ether with 6 EO 3.00 3.00 3.00 3.00 C 8/10 alkyl polyglucoside p = 1.5 4.00 4.00 4.00 4.00 Coconut fatty acid 0.5 0.5 0.5 0.5 Citric acid 3.00 3.00 3.00 3.00 NaOH 1.90 1.90 1.90 1.90 Polymer a 1.0 Polymer b 1.0 Polymer c 1.0 Preservative 0.20 0.20 0.20 0.20 water ad 100 ad 100 ad 100 ad 100 Cleaning power (%) at a concentration of 9 ml / l 100 156 137 138 Bathroom cleaner in the weakly acidic area ingredient B15 B16 B17 B18 C 8/10 alkyl polyglucoside p = 1.5 3.85 3.85 3.85 3.85 C 12/14 fatty alcohol ether with 6 EO 1.00 1.00 1.00 1.00 Citric acid 4.80 4.80 4.80 4.80 NaOH 1.00 1.00 1.00 1.00 Ethanol 1.00 1.00 1.00 1.00 Polymer a 0.30 Polymer b 0.30 Polymer c 0.30 Preservative 0.20 0.20 0.20 0.20 Perfume oil 0.90 0.90 0.90 0.90 water ad 100 ad 100 ad 100 ad 100 Cleaning power (%) at a concentration of 8 ml / l 100 139 150 145 All-purpose cleaner with water-soluble abrasive in the weakly alkaline range ingredient B19 B20 B21 B22 Na-C 12 -C 14 fatty alcohol sulfate 5.00 5.00 5.00 5.00 C 12/14 fatty alcohol ether with 2.5 EO (NRE) 3.50 3.50 3.50 3.50 C 12 -C 14 fatty alcohol ether with 4 EO 0.30 0.30 0.30 0.30 Coconut fatty acid 1.00 1.00 1.00 1.00 Sodium bicarbonate 50.00 50.00 50.00 50.00 Polymer a 0.30 Polymer b 0.30 Polymer c 0.30 Propylene glycol 0.50 0.50 0.50 0.50 Preservative 0.20 0.20 0.20 0.20 Perfume oil 0.40 0.40 0.40 0.40 water ad 100 ad 100 ad 100 ad 100 Cleaning power (%) at a concentration of 3 ml / l 100 123 120 122

    Aus den Beispielen wird deutlich, daß die Reinigungswirkung der erfindungsgemäßen Reinigungsmittel gegenüber ölhaltigem Schmutz bei der verdünnten -Anwendung von Allzweckreiniger-Konzentraten und bei der unverdünnnten Anwendung bei Sprühreinigem deutlich höher liegt als die des Mittels, das keine kationischen Polymere enthält.From the examples it is clear that the cleaning effect of the invention Detergent against oily dirt when using - diluted All-purpose cleaner concentrates and when used undiluted with spray cleaners is significantly higher than that of the agent that contains no cationic polymers.

    Claims (14)

    1. The use of cationic polymers containing monomer units corresponding to formula I:
      Figure 00180001
      in which
      n is a number of 2 to 4, preferably 3,
      R1 is hydrogen or a methyl group and
      R2, R3 and R4 may be the same or different and represent hydrogen or a C1-4 alk(en)yl group,
      X- is an anion from the group of halide anions or a monoalkyl anion of sulfuric acid semiester,
      as soil release compounds in cleaners for hard surfaces.
    2. The use claimed in claim 1, characterized in that the monomers corresponding to formula I make up 40 to 100 mole-% of the cationic polymers.
    3. A cleaner for hard surfaces containing
      a) from 0.01 to 10% by weight and preferably from 0.02 to 2% by weight of cationic polymers containing monomer units corresponding to formula I:
      Figure 00180002
      in which
      n is a number of 2 to 4, preferably 3,
      R1 is hydrogen or a methyl group and
      R2, R3 and R4 may be the same or different and represent hydrogen or a C1-4 alk(en)yl group,
      X- is an anion from the group of halide anions or a monoalkyl anion of sulfuric acid semiester,
      the polymers containing
      (i) 40 to 100 mole-% monomer units corresponding to formula I and/or
      (ii) as comonomers one or more monomers from the group of olefins, optionally further substituted aromatic and heterocyclic compounds provided with unsaturated groups, unsaturated monocarboxylic acids, alkyl esters of unsaturated carboxylic acids and hydroxy derivatives thereof except for the C8-24 esters of acrylic and methacrylic acid
      and
      b) 0.1 to 50% by weight of one or more nonionic surfactants.
    4. A cleaner as claimed in claim 3, characterized in that it contains as nonionic surfactants alkyl polyglycosides corresponding to formula II: R5O-[G]p in which R5 is an alkyl group containing 8 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms, preferably a glucose unit, and p is a number of 1 to 10,
      and/or
      fatty alcohol polypropylene glycol/polyethylene glycol ethers corresponding to formula III:
      Figure 00200001
      in which R6 is a linear or branched aliphatic alkyl and/or alkenyl group containing 8 to 18 carbon atoms, c is 0 or a number of 1 to 3 and d is a number of 1 to 20.
    5. A cleaner as claimed in claim 3 or 4, characterized in that it contains anionic surfactants in a quantity of 0.05% by weight to 10% by weight and preferably in a quantity of 0.1% by weight to 7% by weight, based on the cleaner as a whole.
    6. A cleaner as claimed in claim 5, characterized in that it contains anionic surfactants and the cationic polymers corresponding to formula I in a ratio by weight of 20:1 to 1:20 and preferably in a ratio by weight of 10:1 to 1:10.
    7. A cleaner as claimed in any of claims 3 to 6, characterized in that it contains nonionic nitrogen-containing surfactants in quantities of 0.05% by weight to 10% by weight and preferably in quantities of 0.1% by weight to 5% by weight.
    8. A cleaner as claimed in claim 7, characterized in that it contains nitrogen-containing surfactants from the group of amphoteric surfactants, fatty acid alkanolamides, fatty acid polyhydroxyamides and alkylamine oxides.
    9. A cleaner as claimed in claim 7 or 8, characterized in that it contains nitrogen-containing surfactants and the cationic polymers corresponding to formula I in a ratio by weight of 40:1 to 1:10 and preferably in a ratio by weight of 20:1 to 1:5.
    10. A cleaner as claimed in any of claims 3 to 9, characterized in that it contains an abrasive component from the group of alkali metal carbonates.
    11. A cleaner as claimed in claim 10, characterized in that the abrasive component has an average particle size of about 200 µm ∀ 100 µm.
    12. A cleaner as claimed in claim 10 or 11, characterized in that the abrasive component is sodium bicarbonate.
    13. A cleaner as claimed in any of claims 3 to 12, characterized in that it is a multipurpose cleaner.
    14. A cleaner as claimed in any of claims 3 to 12, characterized in that it is a manual dishwashing detergent.
    EP96942274A 1995-12-07 1996-11-28 Cleaning agent for hard surfaces Expired - Lifetime EP0876460B1 (en)

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    DE19545630A DE19545630A1 (en) 1995-12-07 1995-12-07 Detergent for hard surfaces
    DE19545630 1995-12-07
    PCT/EP1996/005266 WO1997020908A1 (en) 1995-12-07 1996-11-28 Cleaning agent for hard surfaces

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    Families Citing this family (50)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE60032597T2 (en) * 1999-05-26 2007-10-04 The Procter & Gamble Company, Cincinnati USE OF ZWITTERIONIC POLYMER FOAM IMAGES
    US7241729B2 (en) 1999-05-26 2007-07-10 Rhodia Inc. Compositions and methods for using polymeric suds enhancers
    ATE374235T1 (en) * 1999-05-26 2007-10-15 Procter & Gamble LIQUID DETERGENT COMPOSITIONS CONTAINING BLOCK POLYMERS FOAM FORMERS
    US20050124738A1 (en) * 1999-05-26 2005-06-09 The Procter & Gamble Company Compositions and methods for using zwitterionic polymeric suds enhancers
    WO2000071591A1 (en) 1999-05-26 2000-11-30 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
    US6827795B1 (en) 1999-05-26 2004-12-07 Procter & Gamble Company Detergent composition comprising polymeric suds enhancers which have improved mildness and skin feel
    MXPA01012191A (en) * 1999-05-26 2003-06-30 Procter & Gamble Compositions and methods for using polymeric suds enhancers.
    AU5444100A (en) * 1999-05-26 2000-12-12 Procter & Gamble Company, The Detergent compostitions comprising polymeric suds enhancers which have improved mildness and skin feel
    AU5163400A (en) * 1999-05-26 2000-12-12 Procter & Gamble Company, The Liquid detergent compositions comprising polymeric suds enhancers
    US7939601B1 (en) 1999-05-26 2011-05-10 Rhodia Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses, and coagulants
    DE19927633A1 (en) * 1999-06-17 2000-12-21 Wella Ag Water-based liquid cosmetic composition useful for hair care comprises a water-soluble cationic polymer and a nonionic surfactant and is free of waxes, cationic surfactants, silicones and water-miscible solvents
    FR2796391B1 (en) * 1999-07-15 2003-09-19 Rhodia Chimie Sa CLEANING COMPOSITION FOR HARD SURFACES
    FR2797381B1 (en) * 1999-08-09 2001-11-02 Rhodia Chimie Sa USE OF A WATER-SOLUBLE POLYMER IN A BIOCIDAL COMPOSITION FOR THE TREATMENT OF HARD SURFACES
    DE19953457A1 (en) * 1999-11-05 2001-05-23 Rwe Dea Ag Methods for cleaning surfaces
    US7511006B2 (en) * 2000-12-14 2009-03-31 The Clorox Company Low residue cleaning solution comprising a C8 to C10 alkylpolyglucoside and glycerol
    DE10107772A1 (en) * 2001-02-16 2002-09-05 Christ Otto Ag Vehicle care emulsion allowing good drying and/or hot wax application in car washes contains a cationic surfactant, solvent, silicone wax, emulsifiers, oils and water
    US7070854B2 (en) * 2001-03-22 2006-07-04 Kimberly-Clark Worldwide, Inc. Water-dispersible, cationic polymers, a method of making same and items using same
    GB2385597B (en) * 2002-02-21 2004-05-12 Reckitt Benckiser Inc Hard surface cleaning compositions
    JP4230153B2 (en) * 2002-02-22 2009-02-25 花王株式会社 Antifouling cleaner for hard surfaces
    US7544649B2 (en) * 2002-02-22 2009-06-09 Kao Corporation Antifouling detergent for hard surfaces
    US6926745B2 (en) * 2002-05-17 2005-08-09 The Clorox Company Hydroscopic polymer gel films for easier cleaning
    US20030216281A1 (en) * 2002-05-17 2003-11-20 The Clorox Company Hard surface cleaning composition
    EP1375633B1 (en) * 2002-06-25 2006-09-27 Cognis IP Management GmbH Detergent compositions comprising polymers
    US6694804B1 (en) * 2002-09-23 2004-02-24 Ppg Industries Ohio, Inc. Method and device for evaluating and/or adjusting the cleaning performance of a cleaning liquid
    US6762162B1 (en) 2003-06-18 2004-07-13 S. C. Johnson & Son, Inc. Disinfecting cationic polymer cleaner comprising an acrylate cationic polymer
    US7048806B2 (en) * 2003-12-16 2006-05-23 The Clorox Company Cleaning substrates having low soil redeposition
    DE102006009138A1 (en) * 2006-02-24 2007-08-30 Henkel Kgaa Detergent for removing greasy or oily soil and cleaning and conditioning hard surface, e.g. washing machine or automatic dishwasher contains nonionic surfactant mixture of (poly)alkylene oxide mono- or di-ether and amine oxide
    ES2549257T3 (en) * 2006-11-14 2015-10-26 The Procter & Gamble Company Liquid cleaning compositions for hard surfaces
    US8093199B2 (en) * 2006-11-17 2012-01-10 Basf Se Premoistened cleaning disposable substrate and method of incorporation of a cleaning composition into said substrate
    US7741265B2 (en) * 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
    EP2216391A1 (en) * 2009-02-02 2010-08-11 The Procter & Gamble Company Liquid hand dishwashing detergent composition
    CA2751171A1 (en) * 2009-02-02 2010-08-05 The Procter & Gamble Company Liquid hand dishwashing detergent composition
    EP2213715A1 (en) * 2009-02-02 2010-08-04 The Procter & Gamble Company Liquid hand dishwashing detergent composition
    EP2216392B1 (en) * 2009-02-02 2013-11-13 The Procter and Gamble Company Liquid hand dishwashing detergent composition
    ES2488117T3 (en) * 2009-02-02 2014-08-26 The Procter & Gamble Company Liquid detergent composition for dishwashing by hand
    EP2216390B1 (en) * 2009-02-02 2013-11-27 The Procter and Gamble Company Hand dishwashing method
    PL2213713T3 (en) * 2009-02-02 2014-07-31 Procter & Gamble Liquid hand dishwashing detergent composition
    DE102010038340A1 (en) * 2010-07-23 2012-01-26 Henkel Ag & Co. Kgaa Prevention of bacterial adhesion
    PT2677022E (en) * 2012-06-19 2016-01-22 Weigert Chem Fab Machine cleaning of plastic parts
    EP2914544A4 (en) * 2012-10-30 2016-06-15 Clorox Co Anionic micelles with cationic polymeric counterions compositions, methods and systems thereof
    US8728454B1 (en) 2012-10-30 2014-05-20 The Clorox Company Cationic micelles with anionic polymeric counterions compositions thereof
    US8883706B2 (en) 2012-10-30 2014-11-11 The Clorox Company Anionic micelles with cationic polymeric counterions systems thereof
    US8728530B1 (en) 2012-10-30 2014-05-20 The Clorox Company Anionic micelles with cationic polymeric counterions compositions thereof
    US8883705B2 (en) 2012-10-30 2014-11-11 The Clorox Company Cationic micelles with anionic polymeric counterions systems thereof
    US8765114B2 (en) 2012-10-30 2014-07-01 The Clorox Company Anionic micelles with cationic polymeric counterions methods thereof
    JP2017527661A (en) * 2014-08-19 2017-09-21 ゲオ‐テック ポリマーズ，エルエルシー Corrosive aqueous alkyl glycoside removal composition
    EP3309243B1 (en) * 2016-10-11 2020-03-25 The Procter & Gamble Company Hard surface cleaners
    CA3039483C (en) * 2016-11-18 2021-05-04 The Procter & Gamble Company Fabric treatment compositions and methods for providing a benefit
    US10870816B2 (en) 2016-11-18 2020-12-22 The Procter & Gamble Company Fabric treatment compositions having low calculated cationic charge density polymers and fabric softening actives and methods for providing a benefit
    EP3766952A1 (en) 2019-07-16 2021-01-20 The Procter & Gamble Company Disinfectant composition

    Family Cites Families (17)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    JPS5378288A (en) * 1976-12-22 1978-07-11 Sanyo Chem Ind Ltd Preparation of water in oil type polymer emulsion having improved flowability
    GB2006811B (en) 1977-10-26 1982-04-28 Unilever Ltd Soil-release compositions
    JPS5813700A (en) 1981-07-17 1983-01-26 花王株式会社 Detergent composition
    JPS5920396A (en) * 1982-07-27 1984-02-02 花王株式会社 Liquid detergent composition
    US4454060A (en) 1983-06-09 1984-06-12 Colgate-Palmolive Company Liquid detergent composition with a cationic foam stabilizing copolymer containing pendant quaternary nitrogen groups and pendant hydrophobic groups
    GB8504862D0 (en) * 1985-02-26 1985-03-27 Unilever Plc Liquid detergent composition
    US4885102A (en) * 1987-07-17 1989-12-05 Kao Corporation Cloth-softening liquid composition containing quaternary ammonium compound and a polyether derivative or cationic surfactant polymer
    DE3723826A1 (en) 1987-07-18 1989-01-26 Henkel Kgaa METHOD FOR PRODUCING ALKYL GLYCOSIDES
    US5576425A (en) 1988-10-05 1996-11-19 Henkel Kommanditgesellschaft Auf Aktien Process for the direct production of alkyl glycosides
    DE3833780A1 (en) 1988-10-05 1990-04-12 Henkel Kgaa METHOD FOR THE DIRECT PRODUCTION OF ALKYL GLYCOSIDES
    EP0467472A3 (en) * 1990-07-16 1993-06-02 Colgate-Palmolive Company Hard surface liquid cleaning composition with anti-soiling polymer
    FR2671352B1 (en) * 1991-01-09 1993-04-23 Hoechst Francaise Ste NEW CATIONIC COPOLYMERS, NEW EMULSIONS AND THEIR APPLICATION.
    US5293976A (en) 1991-07-11 1994-03-15 Masuyuki Naruse Brake-and accelerator pedal assembly
    GB9210500D0 (en) * 1992-05-13 1992-07-01 Robert Mcbridge Group The Limi Cleaning compositions
    US5433863A (en) * 1993-11-17 1995-07-18 Nalco Chemical Company Method for clarifying wastewater containing surfactants
    US5686024A (en) * 1995-12-18 1997-11-11 Rhone-Poulenc Surfactants & Specialties, L.P. Aqueous dispersion of a surface active polymer having enhanced performance properties
    US5756436A (en) * 1996-03-27 1998-05-26 The Procter & Gamble Company Conditioning shampoo compositions containing select cationic conditioning polymers

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    EP0876460A1 (en) 1998-11-11
    DE19545630A1 (en) 1997-06-12
    ATE198764T1 (en) 2001-02-15
    BR9611692A (en) 1999-02-17
    DE59606352D1 (en) 2001-02-22
    ES2154422T3 (en) 2001-04-01
    WO1997020908A1 (en) 1997-06-12
    US6251849B1 (en) 2001-06-26
    PT876460E (en) 2001-06-29

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