EP2109664A1 - Agents pour le traitement de surfaces dures - Google Patents

Agents pour le traitement de surfaces dures

Info

Publication number
EP2109664A1
EP2109664A1 EP07847714A EP07847714A EP2109664A1 EP 2109664 A1 EP2109664 A1 EP 2109664A1 EP 07847714 A EP07847714 A EP 07847714A EP 07847714 A EP07847714 A EP 07847714A EP 2109664 A1 EP2109664 A1 EP 2109664A1
Authority
EP
European Patent Office
Prior art keywords
composition according
formula
radical
silyl
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07847714A
Other languages
German (de)
English (en)
Other versions
EP2109664B1 (fr
Inventor
Haitao Rong
Stefan Stumpe
Matthias LÜKEN
Mirko Weide
Jürgen GROLL
Peter Greiwe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL07847714T priority Critical patent/PL2109664T3/pl
Publication of EP2109664A1 publication Critical patent/EP2109664A1/fr
Application granted granted Critical
Publication of EP2109664B1 publication Critical patent/EP2109664B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/24—Mineral surfaces, e.g. stones, frescoes, plasters, walls or concretes

Definitions

  • the present invention relates to the technical field of hard surface treating agents, particularly to hard surface cleaners and to agents which protect surfaces from soiling and / or facilitate the removal of soil contaminants.
  • agents have been found with which surfaces can be retrofitted and equipped in a way that can be carried out in a household so that they less easily pollute or easier to clean, at least for a certain period of use.
  • copolymers which consist of at least one each of an anionic vinyl monomer, a vinyl monomer having a quaternary ammonium group or a tertiary amino group, and a nonionic hydrophilic vinyl monomer or a polyfunctional vinyl monomer. These copolymers are useful as anti-soiling components in detergents and are effective, for example, against fecal contamination.
  • toilet cleaners for better lime solution are often after application for a long time, often several hours or even overnight, left to act on the ceramic.
  • the formulations are usually thickened to improve the adhesion to the ceramic. When prolonged exposure then forms on the surface of a film that is usually colored due to the product coloring and after drying is difficult to remove.
  • Biofilms consist of a thin layer of mucus (film) in which microorganisms (e.g., bacteria, algae, fungi, protozoa) are embedded. This can be not only a hygienic but also an aesthetic problem. As an antidote biocidal substances are often used. However, this is not always unproblematic in view of the ecotoxicological properties of many of these substances and the associated limitations in their application. In addition, biofilms contribute to the formation of unpleasant-smelling substances and are therefore a source of undesirable bad odors, especially in the sanitary sector.
  • microorganisms e.g., bacteria, algae, fungi, protozoa
  • agents for the treatment of hard surfaces must fulfill further requirements. So it is important that after the treatment of the surface their appearance is not affected. This is in particular the preservation of the gloss of surfaces which have a gloss in the original or clean state, and the avoidance of residues of the treatment agent, for example in the form of stripes or streaks.
  • there has been a need for methods and means to provide a hard surface with soil repellency and / or to facilitate the release of soil and / or reduce the formation or adhesion of biofilms where these effects can be achieved optionally in a stand-alone surface treatment process, or in the course of a cleaning process, in which a surface is cleaned and at the same time provided with the aforementioned properties.
  • US 2003/0153712 A1 discloses a polyurethane prepolymer having terminal alkoxysilane and hydroxyl groups.
  • a polyether-diol is first reacted with stoichiometric diisocyanate, and the resulting isocyanate-hydroxy compound is then further treated with an aminosilane to introduce the silyl groups.
  • the described, two-armed polyalkoxylates representing prepolymers are used for the production of sealants and adhesives.
  • US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a completely silyl-terminated derivative which can be prepared starting from sorbitol as the central unit.
  • the polyethylene glycol derivatives described in the document are said to be suitable for the preparation of biodegradable polymeric hydrogels and for medical-pharmaceutical use, for example for implants.
  • the object of the invention was therefore to remedy the above-described disadvantages of the prior art, at least partially.
  • the object was to provide means for improving the removability of dirt and biofilms of hard surfaces, especially toilet ceramics, as well as the prevention of new formation of such soiling on such surfaces.
  • silyl-polyalkoxylate-containing agents are particularly suitable to protect a surface treated therewith from contamination and / or to facilitate the removal of contaminants from the surface.
  • the present invention therefore provides an agent for the treatment of a hard surface, in particular for the cleaning and / or dirt-repellent treatment of a hard surface, comprising a) at least one multi-arm silyl polyalkoxylate of the formula (I)
  • Z is an (m + n) -valent radical having at least three carbon atoms
  • A is a divalent polyoxyalkylene radical, where the m + n attached to Z
  • Polyoxyalkylenreste may be different from each other, and wherein a radical A in each case via an oxygen atom belonging to Z with Z and one belonging to A.
  • Oxygen atom is connected to B or hydrogen
  • OR 1 is a hydrolyzable group
  • R 1 and R 2 are independently a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer of 1 to 3, and m is an integer> 1 and n is 0 or is an integer> 1, and m + n has a value of 3 to 100
  • hard surfaces are in particular surfaces of stone or ceramic materials, hard plastics, glass or metal. It can be hard surfaces such as walls, work surfaces, floors or sanitary items.
  • the invention relates to surfaces of ceramics, preferably sanitary ceramics, and more particularly of toilet bowls.
  • the agent can be applied to the surface.
  • the treatment of the surface is preferably carried out so that the agent is transferred to the surface by means of an absorbent fabric or that the agent is sprayed onto the surface.
  • the treatment can also be done, for example, by immersing the surface in the agent.
  • dirt or soiling are in particular fecal dirt and / or biofilms.
  • the agent By treating a hard surface with the agent according to the invention, it is protected against contamination and / or facilitates the detachment of dirt from the surface.
  • the agent prevents the formation of biofilms without having a biocidal effect. It is believed that the effectiveness of the biofilm formation agents of the present invention is due to a bacteriostatic effect of the silyl polyalkoxylates used, thereby inhibiting the colonization of surfaces with microorganisms and hindering their attachment and propagation to the surfaces. On the other hand, since no biocidal effects were observed for the agents, they are not subject to the disadvantages mentioned in the introduction of biocides.
  • the agents of the present invention provide for easier soil removability and reduced tendency to re-soak and, in particular, improve the cleaning performance of hard surface cleaners. As a result, appropriately treated or cleaned surfaces are perceived longer than clean.
  • silyl polyalkoxylates of the formula (I) as additives in surfactant-containing cleaning agents makes it possible not only to clean one surface in a single work step, but at the same time provides it with protection against dirt. In this way, for example, a calcification, an adhesion of protein or fat-containing dirt and the growth of bacteria is prevented. The treated surfaces stay clean longer and, moreover, the subsequent cleaning is greatly facilitated. This means that you need to clean the surfaces less often without sacrificing cleanliness, and their subsequent cleaning is associated with less effort insofar as it can be done in a time-saving manner and / or requires milder detergents. So it is possible in favorable cases, for a certain time alone with the help of water a sufficient To achieve cleaning effect, ie without the need for the use of a conventional cleaning agent.
  • silyl polyalkoxylates of the formula (I) can be easily and simply formulated in the other constituents of the composition and, in particular, can be incorporated in a very simple manner into conventional detergent formulations.
  • the advantageous solubility properties of these substances mean that their incorporation into customary cleaning agents does not entail any restrictions, such as a reduced sprayability.
  • multi-armed silyl polyalkoxylates contain polymer arms which are essentially star-shaped or radially bonded to a central unit.
  • a silyl polyalkoxylate of the formula (I) or a mixture of several of these compounds is used, wherein the weight average molecular weight is from 500 to 50,000, preferably from 1,000 to 20,000, and more preferably from 2,000 to 10,000.
  • the silyl polyalkoxylate preferably contains 0.3 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% silicon, based on the total weight of the silyl polyalkoxylate.
  • Z preferably represents an at least trihydric, in particular tri-to octahedral, acyclic or cyclic hydrocarbon radical having 3 to 12 carbon atoms, where the radical may be saturated or unsaturated and in particular also aromatic.
  • Z is particularly preferably the trivalent radical of glycerol or the trihydric to hexahydric radical of a sugar, for example the hexavalent radical of sorbitol or the octahedral radical of sucrose.
  • the x-valent radical of one of the abovementioned polyols is to be understood as meaning that molecule fragment which remains from the polyol after removal of the hydrogen atoms from x alcoholic or phenolic hydroxyl groups.
  • Z can stand for any central unit which is known from the literature for the preparation of star-shaped (pre) polymers.
  • n 0, 1 or 2 and m is a number from 3 to 8.
  • A is preferably selected from poly-C 2 -C 4 -alkylene oxides, more preferably a (co) polymer of ethylene oxide and / or propylene oxide, in particular a copolymer having a propylene oxide content of up to 60% by weight, preferably up to to 30 wt .-% and particularly preferably of up to 20 wt .-%, which may be random and / or block copolymers.
  • B is in particular a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50, in particular 2 to 20 carbon atoms.
  • divalent low molecular weight organic radicals are short-chain aliphatic and heteroaliphatic radicals such as - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (O) -NH- (CH 2 ) 3 - and -C (O) -NH-X-NH-C (O) -NH- (CH 2 ) 3 -, wherein X is a bivalent aromatic radical such as the phenylene radical or an alkylidene radical.
  • B is a bond or the radical -C (O) -NH- (CH 2 ) 3 -.
  • R 1 and R 2 independently of one another are methyl or ethyl, and r is 2 or 3.
  • Examples of radicals -Si (OR 1 ) r (R 2 ) 3 . r are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl, trimethoxysilyl, triethoxysilyl or tri-t-butoxysilyl radicals, but very particular preference is given to trimethoxysilyl and triethoxysilyl radicals.
  • R 1 and R 2 are the same and are methyl or ethyl.
  • r stands for the number 3.
  • the sum m + n is preferably 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, and coincides with the number of arms which is bound in the compound (I) to the central unit Z.
  • the central unit therefore preferably has 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, oxygen atoms which serve as attachment points for the arms.
  • n is 0.
  • the ratio n / m is between 99/1 and 1/99, preferably 49/1 and 1/49, and especially 9/1 and 1 /.
  • the agent contains a mixture of at least two, in particular two to four, different multi-armed silyl polyalkoxylates of the formula (I).
  • the at least two different multi-armed silyl polyalkoxylates differ in the number of their arms.
  • a first silyl polyalkoxylate having 3 to 6 arms is combined with a second silyl polyalkoxylate having 6 to 10 arms.
  • two different multi-arm silyl polyalkoxylates are usually present in a quantitative ratio of from 99: 1 to 1:99, preferably from 49: 1 to 1:49, and especially from 9: 1 to 1: 9.
  • the agent according to the invention further contains at least one hydrolyzable silicic acid derivative.
  • Hydrolyzable silicic acid derivatives are to be understood as meaning in particular the esters of orthosilicic acid, in particular the tetraalkoxysilanes and very particularly preferably tetraethoxysilane.
  • hydrolyzable silicic acid derivatives are also compounds which also carry a carbon residue on the silicon atom in addition to three alkoxy groups, for example N- (triethoxysilylpropyl) -O-polyethylene oxide-urethane, dimethyl-octadecyl- (3- (trimethoxysilylpropyl) ammonium chloride, diethylphosphatoethyltriethoxysilane and the trisodium salt of N- (trimethoxysilylpropyl) ethylenediaminetriacetic acid.
  • the quantitative ratio of SiIyI polyalkoxylate or silyl polyalkoxylate mixture to the at least one hydrolyzable silicic acid derivative 90:10 to 10:90, preferably 50:50 to 10:90, and in particular 40:60 to 20:80.
  • the at least one silyl polyalkoxylate of the formula (I) is usually present in the composition according to the invention in an amount of 0.001 to 20% by weight, in particular 0.01 to 10% by weight, preferably 0.05 to 5% by weight and more particularly preferably used from 0.1 to 1 wt .-%, in each case based on the total weight of the composition.
  • the two-armed polyurethane prepolymer with terminal alkoxysilane and hydroxyl groups described in US 2003/0153712 A1 is prepared by first reacting a polyether-diol with stoichiometric diisocyanate, and then further reacting the obtained isocyanate-hydroxy compound with an aminosilane for the introduction of silyl groups is treated.
  • the synthesis principles used there can be basically transferred to the preparation of multi-armed polyalkoxylates according to the teachings of the present invention.
  • US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a completely silyl-terminated derivative which can be prepared starting from sorbitol as a central unit and which falls under the general formula (I) of the present invention.
  • Suitable polyalkoxylate precursors for the preparation of the SiIyI-polyalkoxylates used according to the invention are themselves multi-arm polyalkoxylates which already have the above-described multi-arm structure and which each have a hydroxyl group at the ends of the polymer arms which is partially or completely group (n) -B -Si (OR 1 ) r (R 2 ) 3 - r can be converted.
  • the polyalkoxylate precursors of the silyl polyalkoxylates used according to the invention can be represented by the general formula (II)
  • suitable polyalkoxylate precursors are known from the literature under the name star-shaped or multi-arm polyether polyols. These polyalkoxylate precursors are prepared by polymerization of the appropriate monomers, especially ethylene oxide and / or propylene oxide, using polyfunctional small molecules such as glycerol or sorbitol as initiator. Examples of polyhydric polyether polyols are ethoxylates or propoxylates of glycerol, sucrose and sorbitol, as described in US Pat. No. 6,423,661.
  • Suitable polyalkoxylate precursors are also commercially available in part.
  • An example of this is Voranol 4053, a polyether polyol (poly (ethylene oxide-co-propylene oxide)) from DOW Chemicals. It is a mixture of two different polyether polyols, consisting of a 3-arm polyether polyol with glycerol as the central unit and an 8-arm polyether polyol with cane sugar as the central unit.
  • the arms represent random copolymers of about 75% EO and about 25% PO, the OH functionality (hydroxy end groups) is an average of 6.9 at a weight average molecular weight of about 12000.
  • Triethoxysilyl butyraldehydes epoxy silanes such as (3-glycidoxypropyl) trimethoxysilane, anhydride silanes such as 3- (triethoxysilyl) propyl succinic anhydride, halogen silanes such as
  • TEOS tetraethyl silicate
  • the group B is in such a case, for example, exclusively in a bond, or it comprises, when an isocyanatosilane was used as a functional silane, together with the terminal oxygen atom of group A, for example, a urethane group and the atomic group, in the starting isocyanatosilane between the isocyanato group and the silyl group stands.
  • group B in such a case, together with the terminal oxygen atom of group A, comprises an ester group and the atomic group which in the starting anhydride silane is between the anhydride group and the silyl group.
  • a polyalkoxylate precursor of the general formula (II) is reacted with a relation to the total of the terminal hydroxy groups substoichiometric amount of a functional silane, ie there are as described above first -B-Si (OR 1 ) r (R 2 ) 3 .
  • multi-armed polyalkoxylates which contain both hydroxy and -Si (OR 1 ) r (R 2 ) 3 . carry r groups.
  • R 1 OH
  • the remaining or a part of the remaining hydroxyl groups can be modified as described to give radicals B-Si (OR 1 ) r (R 2 ) 3 - r .
  • the other components present in the aqueous composition according to the invention in addition to the at least one silyl polyalkoxylate are to be selected according to their type and the amount used in such a way that no undesired interactions with the silyl polyalkoxylate occur.
  • compositions according to the invention contain at least one surfactant which is selected from the anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof.
  • Suitable anionic surfactants are preferably C 8 -C 8 -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C 8 -C 2 0-alkanesulfonates, C 8 -C 8 -monoalkyl sulfates, C 8 -C 8 -alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide (EO) in the ether moiety and sulfosuccinic steinklado- and di-C 8 -C 18 alkyl esters.
  • EO ethylene oxide
  • C 8 -C 18 - ⁇ -olefinsulfonates sulfonated C 8 -C 8 -fatty acids, in particular dodecylbenzenesulfonate, C 8 -C 22 -Carbonklamid- ethersulfate, Cs-C-alkylpolyglykolethercarboxylate, C 8 -C 8 N-Acyltauride, C 8 -C- 8 -N-sarcosinates and Cs-C-is-alkylisethionate or mixtures thereof.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg dodecylbenzenesulfonic acid.
  • examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and Sodium dioctylsulfosuccinate.
  • Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven to be particularly suitable.
  • Particularly suitable nonionic surfactants are Cs-C-is-alcohol polyglycol ethers, ie ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), C 8 - C 18 -carboxylic acid polyglycol esters having 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides having 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain alkylpolyglycosides with 8 to mention 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units.
  • Cs-C-is-alcohol polyglycol ethers ie ethoxylated and / or propoxylated alcohols having 8 to 18 C
  • surfactants examples include oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, Kokosalkyldimethylaminoxid and Kokosalkylpolyglucosid with an average of 1, 4 glucose units.
  • Particularly preferred are C 8 -i 8 fatty alcohol polyglycol ethers having, in particular 2 to 8 EO, for example, C- ⁇ 2 fatty alcohol + 7 EO ether, and C 8 -io alkyl polyglucosides with 1 to 2 glycoside units used.
  • the nonionic surfactant is selected from the group comprising polyalkylene oxides, in particular alkoxylated primary alcohols, where the polyalkylene oxides may also be end-capped, alkoxylated fatty acid alkyl esters, amine oxides and alkyl polyglycosides and mixtures thereof.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R '") (R IV ) (R V ) N + CH 2 COO - , in which R'" is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R IV and R V are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl dimethylcarboxymethylbetain and C 1 -C 4 -alkylamidopropyl-dimethylcarboxymethylbetaine.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R VI ) (R V ") (R VI ") (R IX ) N + X " , in which R v ⁇ to R ⁇ x for four identical or different, in particular two long, and two short-chain, alkyl radicals and X 'are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • the surfactant component comprises only one or more anionic surfactants, preferably C 8 -C 18 -alkyl sulfates and / or C 8 -C 18 -alkyl ether sulfates, and / or one or more nonionic surfactants, preferably C 8 . 18 - fatty alcohol polyglycol ethers having 2 to 8 EO and / or C 8 . 10- Alkylpolyglucoside with 1 to 2 glycoside units.
  • compositions according to the invention contain at least one nonionic surfactant which is (s) selected in particular from the ethoxylated and / or propoxylated alcohols having 8 to 18 carbon atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and or propylene oxide units (PO) and the alkyl polyglycosides having 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units.
  • EO ethylene oxide
  • PO propylene oxide units
  • compositions according to the invention preferably contain surfactants in amounts of from 0.01 to 20% by weight, in particular from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight and more preferably from 0.2 to 1% by weight. %, in each case based on the total weight of the agent.
  • compositions of the invention contain water and / or at least one non-aqueous solvent.
  • Suitable non-aqueous solvents are preferably those solvents which are miscible in any ratio with water.
  • the nonaqueous solvents include, for example, monohydric or polyhydric alcohols, alkanolamines, glycol ethers and mixtures thereof.
  • the alcohols used are in particular ethanol, isopropanol and n-propanol.
  • ether alcohols are sufficiently water-soluble compounds having up to 10 carbon atoms in the molecule into consideration.
  • ether alcohols examples include ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred.
  • ethanol is used as the nonaqueous solvent.
  • Non-aqueous solvents may be present in the composition according to the invention in amounts of from 0.01 to 99.9% by weight, in particular from 0.1 to 50% by weight, and particularly preferably from 2 to 20% by weight, based in each case on Total weight of the agent.
  • Water is contained in the composition according to the invention generally in amounts of 1 to 98 wt .-%, in particular 50 to 95 wt .-%, and particularly preferably 80 to 93 wt .-%, each based on the total weight of the composition.
  • the agent according to the invention contains a thickening agent.
  • a thickening agent Suitable for this purpose are in principle all viscosity regulators used in detergents and cleaners in the prior art, for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins , Gelatin, casein), organic modified natural products (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, core flour ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (Polysilicic acids, clay minerals like Montmorillonite, zeolites, silicas).
  • organic natural thickeners agar-agar, carrageenan,
  • polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): carbomers), also referred to as carboxyvinyl polymers.
  • polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ® such as Polygel ® DA, and by the company.
  • Carbopol ® such as Carbopol ® 940 (molecular weight about 4,000,000), Carbopol ® 941 (molecular weight approximately 1,250,000) or Carbopol ® 934 (molecular weight approximately 3,000,000).
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C- ⁇ - 4 alkanols formed esters (INCI acrylates copolymer), to which about Copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and the example of the Fa.
  • Rohm & Haas under the trade name Aculyn polymer are available ® and Acusol ®, and from Degussa (Goldschmidt) under the trade name Tego ®, for example the anionic non-associative polymers Aculyn ® 22, Aculyn ® 28, Aculyn ® 33 (crosslinked), Acusol ® 810, Acusol ® 823 and Acusol ® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C 10 - 30 alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably d- 4 - Alkanols formed, esters (INCI acrylates / C 10-30 alkyl acrylate crosspolymer) include and which are available, for example, from the company BFGood
  • Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide gums for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • a particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15x10 6 and for example, by Fa. Kelco under the trade names Keltrol ® and Kelzan ® or available from Rhodia under the trade name Rhodopol ®. As thickeners, it is also possible to use phyllosilicates.
  • the agent according to the invention contains xanthan gum and succinoglycan gum.
  • agent according to the invention contains a thickener, it is generally present in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.
  • the viscosity of the compositions according to the invention can be adjusted within a wide range depending on the intended use. Thus, for general-purpose and bathroom cleaners, generally low, almost water-thin formulations may be preferred, while for other uses, for example, toilet bowl cleaners, higher-viscosity, thickened formulations may be preferred. In general, the viscosity of the compositions according to the invention in the range of 1 to 3000 mPas 20, preferably from 200 to 1500 mPas and particularly preferably from 400 to 900 mPas (Brookfield viscometer, Rotovisco LV-DV Il plus, spindle 31, 2O 0 C, U / min).
  • the agent according to the invention has a pH of less than 9, in particular a pH of 0 to 6, preferably 1 to 5 and particularly preferably 2 to 4.
  • the agent according to the invention contains at least one acid.
  • Suitable acids are in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • acetic acid is not used as the acid.
  • the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or mixtures thereof.
  • acids selected from the group comprising amidosulfonic acid, citric acid, lactic acid and formic acid are preferably used in amounts of 0.01 to 30 wt .-%, particularly preferably 0.2 to 15 wt .-%, each based on the total weight of the composition.
  • compositions according to the invention may contain customary other constituents of agents, in particular detergents, for the treatment of hard surfaces, provided that they do not interact in an undesired manner with the substances used according to the invention.
  • compositions should preferably contain not more than 30% by weight of further ingredients, preferably from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.
  • compositions according to the invention may contain film formers which may contribute to a better wetting of the surface.
  • film formers which may contribute to a better wetting of the surface.
  • the film former is selected from the group comprising polyethylene glycol, polyethylene glycol derivatives and mixtures thereof, preferably having a molecular weight between 200 and 20,000,000, more preferably between 5,000 and 200,000.
  • the film former is advantageously used in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.
  • Compositions according to the invention may furthermore comprise one or more antimicrobial active ingredients, preferably in an amount of from 0.01 to 1% by weight, in particular from 0.05 to 0.5% by weight, particularly preferably from 0.1 to 0.3 wt .-%.
  • antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carba
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octan-amine) dihydrochloride, N, N'-bis ( 4-chlorophenyl) -3,12-diimino-2,4,11,13-
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleansing agent.
  • particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite and mixtures thereof.
  • Water-soluble and / or water-insoluble builders can be used in the compositions according to the invention.
  • water-soluble builders are preferred because they usually less so tend to leave insoluble residues on hard surfaces.
  • Typical builders which may be present in the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and its salts, the carbonates, phosphates and silicates.
  • Water-insoluble builders include the zeolites, which may also be used, as well as mixtures of the aforementioned builders.
  • Suitable corrosion inhibitors are, for example, the following substances named according to INCI: cyclohexylamines, diammonium phosphates, dilithium oxalates, dimethylamino methylpropanol, dipotassium oxalates, dipotassium phosphates, disodium phosphates, disodium pyrophosphates, disodium tetrapropenyl succinates, hexoxyethyl diethylammonium, phosphates, nitromethanes, potassium silicates, sodium aluminates, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.
  • Chelants also called sequestering agents, are ingredients that are capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the agents, for example clouding.
  • it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness.
  • the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents.
  • the complexing agents support the cleaning effect.
  • Suitable examples are the following according to INCI called complexing agents: aminotrimethylene, phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrates, diammonium EDTA, diethylenetriamines pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptanes diphosphonates , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pen
  • alkalis it is also possible for alkalis to be present.
  • Suitable bases in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide.
  • ammonia and / or alkanolamines having up to 9 C atoms in the molecule preferably the ethanolamines, in particular monoethanolamine.
  • Preservatives may also be included in compositions of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.
  • the agents may further contain bleaching agents.
  • Suitable bleaching agents include peroxides, peracids and / or perborates, particularly preferred is hydrogen peroxide.
  • Sodium hypochlorite is less suitable for acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline detergents.
  • a bleach activator may be included in addition to the bleaching agent.
  • the agent according to the invention may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They may be added to the composition in any form established in the art. In the case of liquid or gel-containing compositions, these include, in particular, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shelled form.
  • enzymes preferably proteases, lipases, amylases, hydrolases and / or cellulases.
  • an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • enzyme stabilizers may be present to prevent an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic To protect division.
  • Suitable enzyme stabilizers are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12 such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars.
  • benzamidine hydrochloride borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups
  • stabilizers for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the agent according to the invention may finally contain one or more fragrances and / or one or more dyes.
  • dyes both water-soluble and oil-soluble dyes can be used, on the one hand the compatibility with other ingredients, such as bleaches, is observed and on the other hand, the dye used against the surfaces, especially to toilet ceramics, even with prolonged exposure should not be substantive ,
  • suitable perfume is also limited only by possible interactions with the other detergent components.
  • the agent according to the invention is preferably a cleaning agent, in particular a cleaning agent for ceramics, more preferably sanitary ceramics.
  • compositions according to the invention can be carried out in a customary manner by mixing the components contained in the composition in a suitable manner.
  • the present invention likewise provides a process for preparing a composition according to the invention, in which the individual components are mixed with one another.
  • Another object of the present invention is a method for treating a hard surface, wherein the surface is brought into contact with an agent according to the invention, as described in the preceding text.
  • This process can be carried out as a stand-alone treatment process for the surface, for example with dirt-repellent properties or one or more to provide the other properties which cause the agents according to the invention according to the teaching of the present invention.
  • the surface is brought into contact with a composition according to the invention.
  • the inventive method is carried out so that the agent is distributed over the surface area and advantageously then either after a contact time of 1 second to 20 minutes, preferably 1 to 10 minutes, rinsed or left to dry.
  • the method in the contacting occurs at a temperature of from 5 to 5O 0 C, in particular 15 to 35 0 C.
  • the process according to the invention represents a purification process which serves to clean the surface.
  • the inventive method is used to treat a surface of ceramic, glass, stainless steel or plastic.
  • a further embodiment of the invention relates to the use of a composition according to the invention for protecting a hard surface against stains and / or for easier removal of new stains from the surface, wherein the stain (s) are in particular faecal dirt and / or biofilms and / or or protein deposits.
  • means according to the invention are used for improved removal of fecal dirt and / or biofilms from the surfaces of flush toilets and / or for reducing the re-soiling of such surfaces with fecal dirt and / or biofilms.
  • the agent is advantageously distributed over the surface area and either rinsed after a contact time of preferably 1 to 10 minutes or left to dry. After treating the surface in this manner, fecal soiling is easier to remove, often without the aid of mechanical aids such as a toilet brush. In addition, any dried-up detergent residues can be rinsed off more easily.
  • a further embodiment of the invention relates to the use of an agent according to the invention for water-repellent finishing of a hard surface and / or for shortening the drying time of a hard surface after exposure to water.
  • the treatment of a surface with the agents according to the invention makes this surface hydrophilic. This facilitates wetting and the removal of dirt, while at the same time “softening" the surface of a film of water, thus avoiding the formation of water droplets and thus the retention of residual soils. and dirt and biofilm deposits, such as toilet bowls, wash basins, bathtubs and shower cubicles, etc.
  • Another advantage of this feature is that water from treated surfaces drains faster and dries faster, and a cleaning process is usually after treatment It is desirable that the surfaces dry quickly after this rinse, for example because a fast-drying surface enhances the appearance of cleanliness to a consumer.
  • an agent according to the invention for the bacteriostatic finishing of a hard surface.
  • a particular advantage of the silyl polyalkoxylates of the formula (I) used in accordance with the invention lies in the fact that colonization by and growth of microorganisms is suppressed on surfaces treated with them without the need for biocides. This achieves a surface finish on which bacteria can not multiply or only in a much slower way. This is a clear advantage over the prior art, especially in view of the fact that the use of biocides is becoming increasingly critical with regard to environmental and consumer protection.
  • a further embodiment of the invention therefore relates to the use of a multi-arm silyl polyalkoxylate of the formula (I)
  • Z is an (m + n) -valent radical having at least three carbon atoms
  • A is a divalent polyoxyalkylene radical, where the m + n attached to Z
  • Polyoxyalkylenreste may be different from each other, and wherein a radical A is in each case connected via an oxygen atom belonging to Z with Z and an oxygen atom belonging to A with B or hydrogen,
  • OR 1 is a hydrolyzable group
  • R 1 and R 2 independently of one another represent a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer from 1 to
  • the starting material used was a polyether polyol containing a 6-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of 80/20 and a molecular weight of 12,000 g / mol prepared by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as initiator. Before further reaction, the polyether polyol was heated under vacuum for 1 h at 80 0 C with stirring.
  • Voranol CP 1421 from DOW Chemicals was dried under vacuum with stirring for 1 h at 80 0 C.
  • To 2.04 g (0.41 mmol) of the dried polyether polyol was slowly added 317 mg (1.0 equivalents) of (3-isocyanatopropyl) triethoxysilane.
  • the reaction mixture was further stirred under inert gas at 100 ° C. for 2 days until the vibration band of the NCO group disappeared upon IR measurement.
  • Voranol 4053 from DOW Chemicals was vacuum with stirring for 1 h at 80 0 C dried.
  • To 209 g (16.9 mmol) of the dried polyether polyol was added 20.9 mg (0.01%) of dibutyltin dilaurate and 30.3 g (1.0 equivalents) of (3-isocyanatopropyl) triethoxysilane slowly added.
  • the reaction mixture was further stirred under inert gas at room temperature for 2 days until the NCO band disappeared on IR measurement.
  • the product was obtained, which in each case has a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol and represents a mixture of a 3-armed and an 8-armed polyalkoxylate in a ratio of about 20/80, as a colorless viscous liquid.
  • IKW ballast dirt was prepared according to the literature S ⁇ FW-Journal, 1998, 124, 1029.
  • the test surfaces were overcoated with ballast soil and dried overnight at room temperature. After drying, the surfaces were rinsed with running water. The amount and distribution of residual debris remaining on the surfaces (white fat layer) was used as a criterion for the easy-to-clean effect.
  • Shoe polish dirt was made as follows: A mixture of black shoe polish (6.5% by weight), Mazola oil (3.5% by weight), gravy (26% by weight) and tap water (64% by weight) became 100 0 C cooked for 2 min. Subsequent stirring for 20 minutes and cooling to room temperature gave the shoe cream stain. The test surfaces were dipped in the shoe cream soil for 2 minutes. After removal, the test surfaces were dried at room temperature for 1 min and then rinsed with running water. The amount and distribution of residual debris left on the surfaces (white fat layer) were used as criteria for the easy-to-clean effect.
  • a synthetic Desikalanschmutzung according to the patent DE 103 57 232 B3 was prepared. Similar to the test procedure described there, the fecal soiling was applied punctiform (diameter 10 mm) to the test surfaces using a metal template and dried at room temperature for 15 min. After drying, the surfaces were rinsed in a laboratory rinse, which simulates the flushing of a toilet flush toilet, with evenly flowing water. The time (in seconds) that elapses from the start of the rinse to the time when the yellowish brown fecal stain was completely removed from the surfaces and the amount and distribution of residual debris (white fat layer) were used as criteria for the Easy -to-clean effect used. In addition, it was also taken into account whether the surfaces become dry again quickly after rinsing off.
  • a calcium-magnesium-rich mineral water brand Contrex was used.
  • the test surfaces were immersed in this water at room temperature for 24 hours. After removal, the test surfaces were dried in air for 2 hours and then in dist. Water immersed for 20 min. After removal, the test surfaces were air dried for an additional 2 hours. It was only followed by a qualitative visual assessment of whether and with what amount of lime the surfaces are covered. Thereafter, a quantitative determination of the amount of lime deposited on the surfaces was carried out. For this purpose, the accumulated lime was dissolved with dilute hydrochloric acid and the amount of calcium and magnesium ions in the resulting aqueous solution was determined by titration (standard method from Metrohm). The normalized amount of lime (mg / cm 2 ) was used as a criterion for the anti-lime effect.
  • the biorepulsive performance of a test substance was determined in an adhesion test for microorganisms with the organisms Staphylococcus aureus DSM799 and Pseudomonas aeruginosa DSM939.
  • the substances to be tested were applied to hard surfaces, which have relevance in the household, such.
  • Specimens of 18x18 mm format were first washed with sterile and distilled water and dried. The thus prepared specimens were overlaid with a germ suspension and incubated for one hour. Subsequently, the seed suspensions were filtered off with suction and the test pieces were washed twice. After having been transferred into sterile test panels, the test specimens for S.
  • aureus were overlayed with nutrient agar, and then incubated for 48 hours at 30 0 C.
  • the specimens were shaken in buffer, then overlaid with nutrient agar plus 10% TZC and then incubated for 24 hours at 30 0 C.
  • the shaking fluid was filtered through a membrane and the filters were incubated on Caso agar for 24 hours at 30 0 C.
  • the extent of seed growth indicative of colonization of the specimens with nuclei is reported relative to an untreated surface, thereby setting the microbial load of the control specimen as 100%.
  • coated surfaces (2 ⁇ 2 cm) were exposed to biofilm growth for 24 hours.
  • the test specimens were placed in a microtiter plate consisting of 6 chambers.
  • a germ mixture consisting of Dermacoccus nishinomiyaensis DSMZ 20448, Bradyrhizobium japonicum DSMZ 1982 and Xanthomonas campestris DSMZ 1526, which forms a stable biofilm in aqueous environments, was added at a bacterial count of 106 cfu / ml.
  • the germs in the above-mentioned concentration together with a diluted complete medium 50 times DGHM-water-diluted TBY
  • a diluted complete medium 50 times DGHM-water-diluted TBY
  • test specimens were removed from the microtiter chambers for drying at room temperature and then stained with 6 ml of 0.01% safranine solution for 15 minutes. Thereafter, the dyeing solution was sucked off, and the test pieces were rinsed to remove the unbonded dye from the test pieces. After drying, the dyed test specimens were evaluated.
  • test specimens were examined in an almost automatically running, application-oriented WC reactor, which simulates the function of a toilet from its construction.
  • This system makes it possible to examine adhesion and biofilm formation in a test system on several different surfaces over a short and long period of time (in this case: total running time of two days).
  • fresh medium TY / DGHM water 1:50
  • the surfaces fall dry in phases and are then covered with liquid again. This change is very similar to the processes in a toilet, where the ceramic surfaces can also be alternately wetted or dried.
  • the biofilms produced in the reactor correspond to those of microtiter plates in terms of strength and homogeneity.
  • the reactor was first filled with 680 ml of medium, inoculated with the germ mixture described in 1.6.2 and incubated overnight, so that the bacterial flora could establish in the system.
  • water flushing was done from a storage vessel by opening a solenoid valve, which in turn was controlled by a timer.
  • the curvature of the toilet bowl was adjusted by clamping the specimens by means of an adapter in the reactor interior.
  • Per Rinse was usually used about 600 ml_ of water.
  • the first and second day post-incubation were each rinsed 15 times, with the single rinse lasting 20 minutes.
  • the first specimen was taken in the morning on the first day, after there were no or few rinses.
  • the second withdrawal took place in the afternoon after the rinses, overnight the reactor was filled with medium without rinsing.
  • the specimens were dried after removal from the reactor at room temperature and then stained with 6 ml of 0.01% safranine solution for 15 minutes. Thereafter, the dyeing solution was sucked off, then the dyeing solution was sucked off, and the test pieces rinsed to remove the unbound dye from the test specimens. After drying, the dyed test specimens were scanned and evaluated with Corel Draw Paint 9. In order to be able to deduct the background value caused by the surfaces of the substrates used from the measured value, untreated surfaces were additionally scanned.
  • Formulation A prepared in 2.1 was sprayed onto a cleaned tile or glass surface. After brief exposure, the surface was rinsed with running water. This gave a coating which is hydrophilic (water contact angle about 40 °) and at the same time water-wicking (low hysteresis). Because of this water-wicking property, the surface becomes instantly dry when rinsed with water.
  • a cleaned slide (26 cm x 76 cm) was immersed in formulation D3 prepared in 2.6. After brief exposure, the surface was rinsed with running water. This gave a coating on both sides of the slide.
  • the anti-lime test on the prepared surfaces was performed according to protocol 1.5, using as reference an untreated slide. Under identical conditions, it was found that hardly any calcification could be observed on the produced coating, whereas on uncoated surfaces a clear white layer of lime remained. Further quantitative determination by titration revealed a reduction of calcification by using the formulation according to the invention by about 90%.
  • Formulation F1 Another formulation (Formulation F2) was prepared in an analogous manner but additionally containing tetraethoxysilane (on a weight basis double the amount of silyl polyalkoxylate). Coverslips (20mm x 20mm) were dipped in the respective formulation for 1 min, followed by rinsing with running water. The reference was an untreated cover glass. The results showed that both inventive formulations against both test organisms used (Staphylococcus aureus and Pseudomonas aeruginosa) compared to the uncoated control a comparably strong and compared to the reference a significant adhesion reduction on glass caused.
  • the tests were carried out according to the procedure 1.6.2.
  • the formulation F1 already described under 3.6.1 was used.
  • the ceramic tiles 25 mm x 25 mm) were cleaned with ethanol, then dried. From about 15 cm distance, the formulation F1 was sprayed onto the cleaned tile, left for 15 minutes and then rinsed with water. After 15 minutes, the procedure was repeated to produce 4x, 5x and 7x sprayed tiles as a result.
  • tiles were used as controls, which were sprayed only with the surfactant-containing agent (consisting of: C 8 -io-alkyl polyglycoside 2.5 g, lactic acid 2.0 g, water to 100 g).
  • the tiles were then dried for 2 hours at 6O 0 C and then used for the tests.
  • Tiles treated with Formulation F1 showed a marked visible biofilm reduction compared to control, with 7 fold sprayed tiles the effect was most pronounced. These effects were not based on biocidal effects, according to cultural analyzes.
  • hydrophobic, especially superhydrophobic surfaces are often used to achieve easy-to-clean properties.
  • a typical example is hydrophobic, rainwater repellent formulations for car windshields.
  • a hydrophobic surface with a water contact angle of about 100 °, made of perfluorosilane was compared with a surface treated according to the invention with regard to its easy-to-clean effects.
  • two formulations were first prepared: a mixture of the silyl polyalkoxylate of Synthesis Example 1 (0.50 wt%), water (0.25 wt%), acetic acid (0.25 wt%), and ethanol ( ad 100% by weight) was stirred at room temperature for 2 days (formulation G).
  • the formulation prepared in 2.1 was tested in terms of appearance (cloudiness, precipitation, etc.) and its ability to produce the hydrophilic and water repellent surfaces of the present invention under real conditions (room temperature and normal humidity). The test was conducted one month apart. For this purpose, the formulation was applied to tile and glass surfaces as described above, and the resulting surfaces were evaluated for their wetting and dewetting with water. The results showed that the formulation did not change from appearance to effect within the test period (about 1 year), suggesting that it is stable under the conditions indicated.
  • the formulation A prepared in 2.1 was sprayed onto a cleaned tile or glass surface. After brief exposure, the surface was rinsed with running water. This gave a coating which is hydrophilic (water contact angle about 40 °) and at the same time water-wicking (low hysteresis).
  • the treated tile or glass surface was stored under normal conditions (room temperature and normal humidity) and evaluated for watering and dewetting one month apart. The results showed that no change in water wettability and water drainage behavior on the surface could be detected within the test period (about 8 months), indicating that the coating is stable under the conditions indicated.
  • silyl polyalkoxylates from Synthesis Examples 2 and 3 Similar results were achieved both in the test with IKW ballast soil (see 1.2.) And in the test with shoe cream soil (see 1.3.) As with the silyl polyalkoxylate from Synthesis Example 1. All these substances were clearly superior to the reference in these tests to very clearly superior.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne des agents pour le traitement de surfaces dures, notamment pour le nettoyage et/ou le traitement anti-taches d'une surface dure, lesdits agents contenant a) au moins un silyle-polyalcoxylate à plusieurs branches de formule (I) (H-A)n-Z-[A-B-Si(OR1)r(R2)3-r]m, dans laquelle Z représente un radical (m+n) valent comprenant au moins trois atomes de carbone, A représente un radical polyoxyalkylène bivalent, les m+n radicaux polyoxyalkylène reliés à Z pouvant être différents les uns des autres et un radical A étant relié avec B ou l'hydrogène par à chaque fois un atome d'oxygène appartenant à Z et un atome d'oxygène appartenant à A, B représente une liaison chimique ou un radical organique bivalent ayant de 1 à 50 atomes de carbone, OR1 représente un groupement hydrolysable, R1 et R2 représentent indépendamment l'un de l'autre un groupement alkyle linéaire ou ramifié ayant de 1 à 6 atomes de carbone et r représente un nombre entier de 1 à 3, m représente un nombre entier ≥ 1, n représente 0 ou un nombre entier ≥ 1, et m+n représente une valeur de 3 à 100, b) au moins un tensioactif, c) de l'eau et/ou au moins un solvant non aqueux, d) éventuellement d'autres composants habituels compatibles avec les autres éléments des agents de nettoyage et/ou de traitement de surface.
EP07847714A 2006-12-05 2007-12-04 Agents pour le traitement de surfaces dures Not-in-force EP2109664B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07847714T PL2109664T3 (pl) 2006-12-05 2007-12-04 Środek do obróbki twardych powierzchni

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102006057632 2006-12-05
DE102007039652A DE102007039652A1 (de) 2006-12-05 2007-08-22 Mittel zur Behandlung harter Oberflächen
PCT/EP2007/063204 WO2008068236A1 (fr) 2006-12-05 2007-12-04 Agents pour le traitement de surfaces dures

Publications (2)

Publication Number Publication Date
EP2109664A1 true EP2109664A1 (fr) 2009-10-21
EP2109664B1 EP2109664B1 (fr) 2010-10-27

Family

ID=39059363

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07847714A Not-in-force EP2109664B1 (fr) 2006-12-05 2007-12-04 Agents pour le traitement de surfaces dures

Country Status (8)

Country Link
US (1) US7998919B2 (fr)
EP (1) EP2109664B1 (fr)
JP (1) JP2010511763A (fr)
KR (1) KR20090087905A (fr)
AT (1) ATE486120T1 (fr)
DE (2) DE102007039652A1 (fr)
PL (1) PL2109664T3 (fr)
WO (1) WO2008068236A1 (fr)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2851572B1 (fr) * 2003-02-20 2007-04-06 Rhodia Chimie Sa Composition nettoyante ou rincante pour surfaces dures
US8513305B2 (en) 2007-05-14 2013-08-20 Research Foundation Of State University Of New York Induction of a physiological dispersion response in bacterial cells in a biofilm
US8741158B2 (en) 2010-10-08 2014-06-03 Ut-Battelle, Llc Superhydrophobic transparent glass (STG) thin film articles
DE102007039648A1 (de) * 2007-08-22 2009-02-26 Sustech Gmbh & Co. Kg Mischungen, multifunktioneller sternförmiger Präpolymere, deren Herstellung und Verwendung sowie Beschichtungen daraus
CA2748533C (fr) * 2009-01-30 2016-10-11 Ecolab Inc. Mise au point d'un adjuvant a base d'hydroxycarboxylate d'aluminium
US8202830B2 (en) * 2009-01-30 2012-06-19 Ecolab Usa Inc. Development of an aluminum hydroxydicarboxylate builder
DE102009029060A1 (de) * 2009-09-01 2011-03-03 Henkel Ag & Co. Kgaa Mittel zur Behandlung harter Oberflächen
WO2011051385A2 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Formulations durcissant à l'humidité à modification dans le temps
DE102010032780A1 (de) 2010-07-26 2012-01-26 Helfried Haufe Hydrophile Schicht und Beschichtungszusammensetzung zur Herstellung der Schicht sowie Verfahren zur Herstellung der Beschichtungszusammensetzung
US11292919B2 (en) 2010-10-08 2022-04-05 Ut-Battelle, Llc Anti-fingerprint coatings
DE102011002809A1 (de) 2011-01-18 2012-07-19 Henkel Ag & Co. Kgaa 2K-PU-Zusammensetzung mit verzögerter Vernetzung
US20120189485A1 (en) * 2011-01-21 2012-07-26 Ppg Idustries Ohio, I Nc. Methods of removing rust from a ferrous metal-containing surface
FI20115276A0 (fi) * 2011-03-22 2011-03-22 3S Cosmetics Oy Kynsilakanpoistokoostumus ja sen käyttö
DE102011007504A1 (de) 2011-04-15 2012-10-18 Henkel Ag & Co. Kgaa PU-Zusammensetzungen mit komplexierten Katalysatoren
US8852357B2 (en) 2011-09-30 2014-10-07 Ppg Industries Ohio, Inc Rheology modified pretreatment compositions and associated methods of use
KR101358448B1 (ko) * 2011-11-23 2014-02-06 극동제연공업 주식회사 음이온성 계면활성제 및 주석산을 포함하는 자동차 유리 세정액 조성물
US20130216631A1 (en) 2012-02-17 2013-08-22 The Clorox Company Targeted performance of hypohalite compositions thereof
US9771656B2 (en) 2012-08-28 2017-09-26 Ut-Battelle, Llc Superhydrophobic films and methods for making superhydrophobic films
AU2013308540A1 (en) 2012-08-31 2015-03-19 3M Innovative Properties Company Multi-functional compositions and methods of use
US20150239773A1 (en) 2014-02-21 2015-08-27 Ut-Battelle, Llc Transparent omniphobic thin film articles
US10030216B2 (en) 2015-06-12 2018-07-24 Crossford International, Llc Systems and methods for cooling tower fill cleaning with a chemical gel
US9404069B1 (en) 2015-06-12 2016-08-02 Crossford International, Llc Systems and methods for cooling tower fill cleaning with a chemical gel
KR102508822B1 (ko) * 2016-04-28 2023-03-10 (주)덕산테코피아 포토레지스트 박리액 조성물
KR101789251B1 (ko) * 2017-03-17 2017-10-26 영창케미칼 주식회사 화학적 기계적 연마 후 세정용 조성물
MX2020007163A (es) 2017-09-26 2020-08-17 Ecolab Usa Inc Composiciones de acidos/anionicos antimicrobianos y viricidas y usos de estas.
US11541105B2 (en) 2018-06-01 2023-01-03 The Research Foundation For The State University Of New York Compositions and methods for disrupting biofilm formation and maintenance
JP7075657B2 (ja) * 2018-06-29 2022-05-26 エフエーティシステム株式会社 うろこ状皮膜の除去方法
CA3136356A1 (fr) 2019-04-12 2020-10-15 Ecolab Usa Inc. Nettoyant antimicrobien multi-usages et procedes de fabrication et d'utilisation de celui-ci
CN114652898A (zh) * 2022-03-25 2022-06-24 华南理工大学 一种用于慢性肾病修复的亲水负电多孔纳米薄膜及其制备方法与应用
GR20220100628A (el) * 2022-08-01 2024-03-12 Παπαδοπουλος Νικολαος-Ξαφακης Σωτηριος Ομορρυθμη Εταιρεια, Μεθοδος αναπτυξης ανθεκτικων αντιρρυπαντικων νανοεπικαλυπτικων συστηματων με επιπροσθετη ισχυρη αντιμικροβιακη δραση

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0639592B2 (ja) * 1985-11-06 1994-05-25 ライオン株式会社 毛髪用液体洗浄剤組成物
US5254284A (en) * 1992-04-13 1993-10-19 Miles Inc. Glass cleaner having antifog properties
DE4415556C1 (de) 1994-04-27 1995-06-01 Goldschmidt Ag Th Organosilyl- bzw. Organosiloxanyl-Derivate von Glycerinethern und deren Verwendung
AU699888B2 (en) 1994-12-15 1998-12-17 Colgate-Palmolive Company, The Microemulsion light duty liquid cleaning compositions
BR9608342A (pt) 1995-06-21 1999-01-05 Henkel Corp Composição de limpeza desinfetante e processos para aumentar e eficácia de um agente de conter odor ou mascarar odor e preparar uma composição de limpeza desinfetante
US6117830A (en) * 1996-05-07 2000-09-12 Kao Corporation Liquid detergent composition for hard surface and method for cleaning hard surface
DE19642623A1 (de) * 1996-10-16 1998-04-23 Wella Ag Haarreinigungsmittel mit Festigungseigenschaften
US6352582B1 (en) * 1997-10-22 2002-03-05 S.C. Johnson & Son, Inc. Composition and process for treating hard surfaces
EP0983332A4 (fr) * 1997-12-12 2002-10-23 Church & Dwight Co Inc Compositions de nettoyage de surface dures
AR019107A1 (es) * 1998-04-27 2001-12-26 Dow Global Technologies Inc Polioles de alto peso molecular, proceso para su preparacion y uso de los mismos.
FR2779641B1 (fr) * 1998-06-16 2000-07-21 Oreal Compositions cosmetiques detergentes et utilisation
US6329353B1 (en) * 1999-05-12 2001-12-11 Goldschmidt Chemical Corporation Clear personal care formulations containing quaternary ammonium compounds and other nitrogen-containing compounds
US20020037822A1 (en) * 2000-07-19 2002-03-28 Foley Peter Robert Cleaning composition
DE10045289A1 (de) * 2000-09-13 2002-03-28 Henkel Kgaa Schnell trocknendes Wasch- und Reinigungsmittel, insbesondere Handgeschirrspülmittel
US6528070B1 (en) * 2000-09-15 2003-03-04 Stepan Company Emulsion comprising a ternary surfactant blend of cationic, anionic, and bridging surfactants, oil and water, and methods of preparing same
EP1245667B1 (fr) * 2001-03-26 2005-10-26 The Procter & Gamble Company Procédé de nettoyage de surfaces dures avec un produit liquide comprenant un agent de blanchiment
DE10204523A1 (de) * 2002-02-05 2003-08-07 Bayer Ag Alkoxysilan- und OH-Endgruppen aufweisende Polyurethanprepolymere mit erniedrigter Funktionalität, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung
US20050202178A1 (en) * 2002-05-02 2005-09-15 Hussmann Corporation Merchandisers having anti-fog coatings and methods for making the same
US20040033924A1 (en) * 2002-08-14 2004-02-19 Murphy Dennis Stephen Methods for conferring fabric care benefits during laundering
TW200407172A (en) * 2002-10-17 2004-05-16 Unilever Nv Scalp treatment
KR20040040782A (ko) * 2002-11-08 2004-05-13 선바이오(주) 신규한 헥사-암 폴리에틸렌글리콜과 유도체 및 그의합성방법
DE10357232B3 (de) 2003-12-09 2005-06-30 Henkel Kgaa Artifizielle Fäkalanschmutzung
WO2006005358A1 (fr) 2004-07-10 2006-01-19 Henkel Kommanditgesellschaft Auf Aktien Compositions de nettoyage contenant des copolymeres
DE102005057857A1 (de) * 2005-12-03 2010-02-25 Evonik Goldschmidt Gmbh Polyethermodifizierte Polysiloxane mit Blockcharakter und deren Verwendung zur Herstellung von kosmetischen Formulierungen
US20070277697A1 (en) * 2006-06-06 2007-12-06 Keri Diamond Product for treating vehicle surfaces

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008068236A1 *

Also Published As

Publication number Publication date
JP2010511763A (ja) 2010-04-15
WO2008068236A1 (fr) 2008-06-12
KR20090087905A (ko) 2009-08-18
EP2109664B1 (fr) 2010-10-27
US7998919B2 (en) 2011-08-16
DE502007005503D1 (de) 2010-12-09
DE102007039652A1 (de) 2008-06-12
ATE486120T1 (de) 2010-11-15
US20100056415A1 (en) 2010-03-04
PL2109664T3 (pl) 2011-04-29

Similar Documents

Publication Publication Date Title
EP2109664B1 (fr) Agents pour le traitement de surfaces dures
EP2129763B1 (fr) Agent de traitement de surfaces dures
EP2487231B1 (fr) Moyen de traitement de surfaces dures
EP2473592B1 (fr) Utilisation des agents de traitement de surfaces dures
EP2108037B1 (fr) Agents de nettoyage pour surfaces dures
EP1781765B1 (fr) Utilisation d'un agent de nettoyage presentant des proprietes de repulsion des souillures fecales
EP2109663B1 (fr) Agent de nettoyage pour surfaces en verre
WO2009156254A1 (fr) Produit de nettoyage antisalissure
DE102007038452A1 (de) Mittel zur Behandlung harter Oberflächen
EP2414495A1 (fr) Agent de nettoyage pour sols
DE102007023871A1 (de) Mittel zur Behandlung harter Oberflächen
WO2016102389A1 (fr) Polymères pour nettoyant à effet de modification de surface
DE102007039654A1 (de) Reinigungsmittel für Glasoberflächen

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090212

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 20091111

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502007005503

Country of ref document: DE

Date of ref document: 20101209

Kind code of ref document: P

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20101027

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20101027

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E009733

Country of ref document: HU

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

Ref country code: LT

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

Effective date: 20101027

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: FI

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

Effective date: 20101027

Ref country code: PT

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

Effective date: 20110228

Ref country code: SE

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

Effective date: 20101027

Ref country code: IS

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

Effective date: 20110227

Ref country code: LV

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

Effective date: 20101027

Ref country code: BG

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

Effective date: 20110127

Ref country code: NL

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

Effective date: 20101027

Ref country code: SI

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

Effective date: 20101027

BERE Be: lapsed

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

Effective date: 20101231

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

Ref country code: GR

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

Effective date: 20110128

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

Ref country code: EE

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

Effective date: 20101027

Ref country code: ES

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

Effective date: 20110207

Ref country code: IE

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

Effective date: 20101027

Ref country code: MC

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

Effective date: 20101231

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

Ref country code: SK

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

Effective date: 20101027

Ref country code: DK

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

Effective date: 20101027

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: BE

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

Effective date: 20101231

26N No opposition filed

Effective date: 20110728

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502007005503

Country of ref document: DE

Effective date: 20110728

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

Ref country code: MT

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

Effective date: 20101027

Ref country code: IT

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

Effective date: 20101204

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: CY

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

Effective date: 20101027

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

Ref country code: LU

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

Effective date: 20101204

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

Ref country code: LI

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

Effective date: 20111231

Ref country code: CH

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

Effective date: 20111231

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

Ref country code: RO

Payment date: 20141112

Year of fee payment: 8

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

Ref country code: AT

Payment date: 20141125

Year of fee payment: 8

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 486120

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151204

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

Ref country code: AT

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

Effective date: 20151204

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

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

Ref country code: RO

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

Effective date: 20151204

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

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

Ref country code: TR

Payment date: 20171204

Year of fee payment: 11

Ref country code: FR

Payment date: 20171221

Year of fee payment: 11

Ref country code: DE

Payment date: 20171211

Year of fee payment: 11

Ref country code: CZ

Payment date: 20171201

Year of fee payment: 11

Ref country code: HU

Payment date: 20171212

Year of fee payment: 11

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

Ref country code: GB

Payment date: 20171221

Year of fee payment: 11

Ref country code: PL

Payment date: 20171123

Year of fee payment: 11

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

Ref country code: IT

Payment date: 20171221

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502007005503

Country of ref document: DE

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

Ref country code: CZ

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

Effective date: 20181204

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

Effective date: 20181204

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

Ref country code: FR

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

Effective date: 20181231

Ref country code: DE

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

Effective date: 20190702

Ref country code: IT

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

Effective date: 20181204

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

Ref country code: HU

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

Effective date: 20181205

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

Ref country code: GB

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

Effective date: 20181204

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

Ref country code: PL

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

Effective date: 20181204

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

Ref country code: TR

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

Effective date: 20181204