EP2473592B1 - Utilisation des agents de traitement de surfaces dures - Google Patents

Utilisation des agents de traitement de surfaces dures Download PDF

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Publication number
EP2473592B1
EP2473592B1 EP10743172.8A EP10743172A EP2473592B1 EP 2473592 B1 EP2473592 B1 EP 2473592B1 EP 10743172 A EP10743172 A EP 10743172A EP 2473592 B1 EP2473592 B1 EP 2473592B1
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EP
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Prior art keywords
alkyl
independently
another
groups
aryl
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EP10743172.8A
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German (de)
English (en)
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EP2473592A1 (fr
Inventor
Birgit Veith
Mirko Weide
Nadine Warkotsch
Brigitte Giesen
Stefan Stumpe
Roland Breves
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL10743172T priority Critical patent/PL2473592T3/pl
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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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/16—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
    • 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

Definitions

  • the invention relates to the use of a composition comprising a copolymer of quaternary ammonium acrylamide and acrylic acid and a multi-arm star-shaped polyalkoxylate and / or a polyester amide for reducing the adhesion of microorganisms to a hard surface or to the bacteriostatic finish of a hard surface.
  • copolymers which consist of at least one anionic vinyl monomer, one vinyl monomer having a quaternary ammonium group or one 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.
  • 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.
  • polyesteramides can be used to finish surfaces.
  • the present invention therefore provides the use of a composition comprising a copolymer of quaternary ammonium acrylamide and acrylic acid and a multi-arm star-shaped polyalkoxylate and / or a polysteramide for reducing the adhesion of microorganisms to a hard surface
  • a mixture of a multi-arm silyl polyalkoxylate and a copolymer of quaternary ammonium acrylamide and acrylic acid is used.
  • a mixture of a polyesteramide and a copolymer of quaternary ammonium acrylamide and acrylic acid is used.
  • a mixture of a multi-arm silyl polyalkoxylate, a polyester amide and a copolymer of quaternary ammonium acrylamide and acrylic acid is used.
  • Multi-armed star-shaped polyalkoxylates in the context of this invention contain polymer arms which are essentially star-shaped or radially bonded to a central unit and each comprise polyoxyalkylene units, preferably polyoxyethylene units and / or polyoxypropylene units.
  • the number of polymer arms is preferably 3 to 20, in particular 3 to 8.
  • the weight average molecular weight is preferably 500 to 100,000, in particular 1000 to 50,000, and particularly preferably 2,000 to 30,000.
  • Peripherals on the polymer arms may optionally also contain functional groups, such as positively or negatively charged groups or reactive groups.
  • Multi-arm star-shaped polyalkoxylates which can be used according to the invention are described, for example, in the patents WO2003 / 063926 . WO2007 / 096056 and DE102008063070 described.
  • a silyl polyalkoxylate or a mixture of several of these compounds wherein the silyl group is preferably located peripherally on the polymer arms.
  • 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.
  • the peripheral silyl groups themselves are preferably bonded to alkoxy and alkyl groups; instead or in turn, further functional groups may in turn be attached to the silyl groups.
  • 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.
  • D is preferably selected from poly-C 2 -C 4 -alkylene oxides, particularly 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 to to 30 wt .-% and particularly preferably of up to 20 wt .-%, which may be random and / or block copolymers.
  • D is - (CHR 3 -CHR 4 -O) q -, where R 3 and R 4 independently of one another denote hydrogen, methyl or ethyl and q is an integer of 2 to 10,000 means.
  • E stands in particular for 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.
  • E 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.
  • radicals -Si (OR 1 ) r (R 2 ) 3-r are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyldimethoxysilyl
  • trimethoxysilyl and triethoxysilyl radicals are most preferred.
  • R 1 and R 2 are the same and are methyl or ethyl.
  • r stands for the number 3.
  • the sum o + p 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.
  • o is 0.
  • the ratio o / p 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 used, they are generally present in a quantitative ratio of from 99: 1 to 1:99, preferably from 49: 1 to 1:49, and more preferably from 9: 1 to 1: 9.
  • Suitable polyalkoxylate precursors for preparing silyl polyalkoxylates which can be used according to the invention are obtainable, for example, under the trade names Voranol 4053, Wanol R420 or Voranol CP 1421.
  • Voranol 4053 is a polyether polyol (poly (ethylene oxide-co-propylene oxide)) from DOW Chemicals.
  • Wanol R420 from WANHUA, China, which is a mixture of a linear poly (propylene / ethylene) diethylene glycol and an 8-arm polyether polyol (poly (propyleneoxy / ethyleneoxy) sucrose) in a ratio of about 15 -25: 85-75 represents.
  • polyether polyol Voranol CP 1421 from DOW Chemicals, which is a 3-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of about 75/25 and a weight average (Weight average molecular weight) of about 5000 is.
  • silyl polyalkoxylates which can be used according to the invention are obtainable starting from these polyalkoxylate precursors by reacting the hydroxy end groups of these polyhydric polyalkoxylate precursors with functional silanes which have a functional group which is reactive with the hydroxy end groups of the polyalkoxylate precursor.
  • Examples are tetraalkoxy silanes such as tetramethyl silicate and tetraethyl silicate, (meth) acrylate silanes such as (3-methacryloxypropyl) trimethoxysilane, (methacryloxymethyl) triethoxysilane, (meth-acryloxymethyl) methyldimethoxysilane and (3-acryloxypropyl) trimethoxysilane, isocyanato-silanes such as Isocyanatopropyl) trimethoxysilane, (3-isocyanato-propyl) triethoxysilane, (isocyanatomethyl) methyl-dimethoxysilane and (isocyanato-methyl) trimethoxysilane, aldehyde-silanes such as triethoxysilylundecanal and triethoxysilyl-butyraldehydes, epoxy-silanes such as (3-glycidoxypropy
  • the multi-armed, star-shaped polyalkoxylate, and in particular the silyl polyalkoxylate, in the composition according to the invention preferably in an amount of 0.001 to 5 wt .-%, in particular 0.005 to 2 wt .-%, particularly preferably 0.02 to 0.5 wt .-% and especially 0.05 to 0.3 wt .-% used, each based on the total weight of the composition.
  • the polyesteramide is particularly preferably a polymer of the formula (IV) in which W is for H, C 1-20 -alkyl, C 6-10 -aryl or stands, A for OH or stands, B is C 2-24 -alkylene or C 6-24 -arylene, X 1 for stands, X 2 for H, X 1 , or stands, R 1, R 2 , R 3, R 4, R 5 and R 6 independently of one another represent H, C 1-8 -alkyl, C 6-10 -aryl or -CH 2 -OX 2 , R7 and R8 independently of one another represent optionally substituted by heteroatoms and / or heteroatom-containing groups substituted C 1-28 alkyl or C 6-10 aryl.
  • W is for H, C 1-20 -alkyl, C 6-10 -aryl or stands, A for OH or stands
  • B is C 2-24 -alkylene or C 6-24 -arylene
  • the polyesteramide is a polymer of the formula (V) in which A for OH or stands, B is C 2-24 -alkylene or C 6-24 -arylene, X 1 for stands, X 2 is hydrogen, X 1 , or stands, R 3 and R 6 independently of one another represent H, C 1-8 -alkyl or C 6-10 -aryl, R7 and R8 independently of one another represent optionally substituted by heteroatoms and / or heteroatom-containing groups substituted C 1-28 alkyl or C 6-10 aryl.
  • V formula (V) in which A for OH or stands, B is C 2-24 -alkylene or C 6-24 -arylene, X 1 for stands, X 2 is hydrogen, X 1 , or stands, R 3 and R 6 independently of one another represent H, C 1-8 -alkyl or C 6-10 -aryl, R7 and R8 independently of one another represent optionally substituted by heteroatoms and / or heteroatom-containing groups substituted C 1-28 alkyl or
  • R3 and R6 are preferably C 1-4 alkyl, more preferably methyl or ethyl.
  • R 7 and R 8 are preferably C 1-20 -alkyl which is optionally substituted by heteroatoms and / or groups containing heteroatoms, more preferably C 2 -, C -substituted by heteroatoms and / or by heteroatom-containing groups 3 or C 6 alkyl.
  • R 7 and R 8 may in particular be mono- or polysubstituted by groups selected from alcohols, ethers, polyethers, esters, cyanide, carbonate, urethane, urea, amide, imide, amine, imine, imidazole, oxime, sulfide, thiol, thiourea, sulfone , Sulfone oxide, sulfate, phosphate, phosphine, phosphine oxide, silane, silicone, silicate, fluorine, chlorine, bromine or iodine and groups containing at least one of the aforementioned functional groups.
  • radicals R7 and R8 are di (m) ethylaminoethyl, di (m) ethylaminopropyl and di (m) ethylaminohexyl and quaternized forms of these radicals; Tri (m) ethylsilylpropyl, tri (m) ethoxysilylpropyl, perfluorooctyl, perfluorooctyl (m) ethyl, (M) ethoxyethyl, (M) ethoxy-2-propyl, maleimidopropyl, maleimidohexyl, octenylsuccinimidohexyl, hexahydrophthalimidohexyl, 2- (benz) imidazolethyl, diphenylphosphinoethyl , Furfuryl, cyanoethyl, cyanopropyl and optionally substituted
  • the radicals R7 and R8 contain independently quaternized amino groups or polyether groups, in particular polyoxyethylene groups, or any mixtures thereof, wherein in the same molecule some radicals R7 and R8 only quaternized amino groups and other radicals R7 and R8 only polyether groups, especially polyoxyethylene , may contain.
  • the polyoxyethylene groups here preferably contain 3 to 20, particularly preferably 5 to 15, in particular 6 to 10 oxyethylene units, where the hydroxy end group of the oxyethylene units can be etherified with a short-chain alcohol, in particular methanol.
  • At least 10%, preferably at least 20% or 30%, of the radicals R 7 and R 8 are tri (m) ethylammoniumalkyl radicals, in particular selected from tri (m) ethylammoniumethyl, tri (m ) ethylammoniumpropyl and tri (m) ethylammoniumhexyl.
  • At least 10%, preferably at least 20% or 30%, of the radicals R7 and R8 are polyoxyethylene groups having 6 to 10, preferably 7, 8 or 9, oxyethylene units which are optionally terminal may be etherified with methyl or ethyl.
  • B may optionally be substituted, preferably by a radical C 1-26 alkyl, more preferably by methyl, octenyl, nonenyl, decenyl, undecenyl or dodecenyl.
  • B may in particular be a radical optionally substituted by one of the abovementioned radicals selected from among ethylene, ethenylene, 1,3-propylene, 1,2-cyclohexyl, 1,2-phenylene, 1,3-phenylene, 1, 4-phenylene, 2,3-norbornyl, 2,3-norbornen-5-yl and 1,2-cyclohex-4-enyl.
  • the molecular weight of the polyesteramides according to the invention is preferably from 600 g / mol to 50,000 g / mol, more preferably from 1000 g / mol to 40,000 g / mol, especially from 5000 g / mol to 35,000 g / mol.
  • the polyesteramide according to the invention may be both linear and branched, but it is preferably a branched polymer, more preferably a highly branched polymer.
  • polyesteramides which can be used according to the invention and in particular with regard to their preparation, particular reference is also made to the disclosure content of US Pat WO 99/16810 and WO 00/58388 directed.
  • Polyesteramides which can be used according to the invention are obtainable, for example, under the trade names Hybrane DAEO 5000 28037 or Hybrane Quat 48 from DSM.
  • the polyesteramides are preferably present in the compositions according to the invention in an amount of 0.02 to 5.0% by weight, more preferably in an amount of 0.05 to 2.0% by weight, in particular in an amount of 0.1 to 1.0 wt .-%, especially in an amount of 0.1 to 0.8 wt .-%, included.
  • copolymers of Quaternary Ammonium Acrylamide and Acrylic Acid are preferably copolymers of diallyldimethyl ammonium acrylamide and acrylic acid.
  • Such copolymers are available, for example, under the trade name Mirapol Surf from Rhodia. Above all, Mirapol Surf-S100, Mirapol Surf-S110, Mirapol Surf-S210 or Mirapol Surf-S500 and mixtures thereof can be used according to the invention.
  • copolymers of quaternary ammonium acrylamide and acrylic acid are preferably used in the compositions which can be used according to the invention in an amount of from 0.1 to 5.0% by weight, more preferably in an amount of from 0.2 to 2.0% by weight, in particular an amount of 0.3 to 1.0 wt .-%, especially in an amount of 0.4 to 0.8 wt .-%, included.
  • 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.
  • Embodiments of the present invention include the use of all known and / or appropriate administration forms of the agents which can be used according to the invention. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions.
  • the agent which can be used according to the invention is preferably a WC cleaner, a bath cleaner or an all-purpose cleaner.
  • an agent which can be used according to the invention preferably has a pH of from 1 to 5, in particular from 1 to 3; when used as a bath cleaner preferably has a pH of 1 to 6, in particular from 3 to 5; and when used as a general-purpose cleaner preferably has a pH of 8 to 12, in particular from 9 to 11.
  • the treatment of a surface all conventional methods are suitable, with which the agent can be applied to the surface.
  • the agent is liquid at room temperature
  • 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.
  • reducing the adhesion is here preferably to be understood that at least 20, 40 or 60%, more preferably at least 80, 90 or 95% less microorganisms adhere to the hard surface than when using a treatment agent without addition according to the invention polymers to be used.
  • the percentages here refer to the difference in the total mass of the adhered material.
  • microorganisms whose adhesion is reduced are preferably selected from bacteria, fungi, especially molds, viruses, especially bacteriophages, and algae.
  • the bacteria whose adhesion is reduced are preferably selected from the group consisting of Gram-negative and Gram-positive bacteria, especially pathogenic bacteria selected from Propionibacterium acnes, Staphylococcus aureus, Streptococcus spp., Corynebacterium spp., Micrococcus spp. (especially M. sedentarius), Bacillus anthracis, Neisseria spp., Pseudomonas aeruginosa, P.
  • Gram-negative and Gram-positive bacteria especially pathogenic bacteria selected from Propionibacterium acnes, Staphylococcus aureus, Streptococcus spp., Corynebacterium spp., Micrococcus spp. (especially M. sedentarius), Bacillus anthracis, Neisseria spp., Pseudomonas aeruginosa, P.
  • Microorganisms that are particularly relevant to biofilm formation, and whose adhesion is particularly preferably reduced, are for example Aeromonads, Agrobacterium, Aquabacterium, Bradyrhizobium japonicum, Burkholderia cepacia, Chromobacterium violaceum, Dermacoccen, Enterobacter agglomerans, Erwinia carotovora, Erwinia chrysanthemi, Escherichia coli, Nitrosomona europaea, Obesumbacterium proteus, Pantoea stewartii, Pseudomonas, Ralstonia solanacearum, Rhizobium, Rhodobacter sphaeroides, Salmonella enterica, Serratia, Vibrio anguillarum, Vibrio fischeri, Xanthomonas, Xenorhabdus nematophilus, Yersinia, Zooshikella gangwhensis, Cythophaga sp.
  • biofilm-forming agents are also relevant in the marine field, as they can contribute to the so-called fouling on submerged surfaces.
  • the agent preferably prevents the formation of biofilms without having a biocidal activity. It is believed that the effectiveness of the biofilm formation agents of the present invention is due to a bacteriostatic effect of the polymers used, thereby inhibiting colonization of the surfaces with microorganisms and hindering their adhesion and proliferation 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 used in 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.
  • polymer mixtures which can be used according to the invention as additives in surfactant-containing cleaning agents makes it possible to not only 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 to achieve a sufficient cleaning effect, i. without the need for the use of a conventional cleaning agent.
  • the polymers of the polymer mixtures which can be used according to the invention can be formulated easily and simply with the other constituents of the composition and, in particular, can be incorporated very easily 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.
  • the agent which can be used according to the invention furthermore 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 other components contained in the agent used according to the invention are to be selected according to their type and the amount used in such a way that there are no undesired interactions with the polymers to be used according to the invention.
  • the agents which can be used according to the invention preferably contain at least one surfactant which is selected from the anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof.
  • surfactants which can be used according to the invention, reference is made in particular to the published patent application WO2008 / 10190 directed.
  • Suitable anionic surfactants are preferably C 8 -C 18 -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C 8 -C 20 -alkanesulfonates, C 8 -C 18 -monoalkyl sulfates, C 8 -C 18 -alkyl polyglycol ether sulfates 2 to 6 ethylene oxide units (EO) in the ether portion and sulfosuccinic mono- and di-C 8 -C 18 alkyl esters.
  • C 8 -C 18 -alkylbenzenesulfonates in particular having about 12 C atoms in the alkyl moiety
  • C 8 -C 20 -alkanesulfonates C 8 -C 18 -monoalkyl sulfates
  • C 8 -C 18 - ⁇ -olefinsulfonates sulfonated C 8 -C 18 -fatty acids, in particular dodecylbenzenesulfonate, C 8 -C 22 -Carbonklamid ether sulfates, C 8 -C 18 -Alkylpolyglykolethercarboxylate, C 8 -C 18 -N Acyltauride, C 8 -C 18 -N sarcosinates and C 8 -C 18 -Alkylisethionate or mixtures thereof.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali metal 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.
  • C 8 -C 18 -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 - are especially nonionic surfactants.
  • 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.
  • 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.
  • Particular preference is given to using C 8-18 -fatty alcohol polyglycol ethers having in particular 2 to 8 EO, for example C 12 -fatty alcohol + 7-EO ether, and C 8-10 -alkyl polyglucosides having 1 to 2 glycoside units.
  • 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 iii ) (R iv ) (R v ) N + CH 2 COO - , in which R iii 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 the same or different Alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 alkyl dimethylcarboxymethylbetain and C 11 -C 17 -Alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix are 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 alkyl polyglucosides having 1 to 2 glycoside units.
  • the agents which can be used according to the invention contain at least one nonionic surfactant which is in particular selected from the 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) 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
  • the agents which can be used according to the invention preferably comprise 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.
  • the agents which can be used according to the invention comprise 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 usable 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 the total weight of the agent.
  • water is present in the composition which can be used according to the invention in amounts of from 1 to 98% by weight, in particular from 50 to 95% by weight, and particularly preferably from 80 to 93% by weight, based in each case on the total weight of the composition.
  • the agent which can be used according to the invention contains a thickener.
  • a thickener Suitable for this purpose are in principle all viscosity regulators used in detergents and cleaners in the state of the art, for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, guar, guaran, gellan, xanthan, 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, gum ethers and other derivatives of polysaccharides and heteropolysaccharides), organic fully synthetic thickeners (polyacrylic and polymethacrylic) Compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysili
  • agent which can be used according to the invention contains a thickener, this is generally contained in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.
  • the viscosity of the agents which can be used 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.
  • the viscosity of the agents which can be used according to the invention is in the range from 1 to 3000 mPas, preferably from 200 to 1500 mPas and particularly preferably from 400 to 900 mPas (Brookfield viscometer Rotovisco LV-DV II plus, spindle 31, 20 ° C., 20 U / min).
  • the agent which can be used 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 which can be used 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 They 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.
  • agents which can be used according to the invention can contain customary other constituents of agents, in particular cleaning agents, 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.
  • the agents which can be used according to the invention may contain film formers which can contribute to a better wetting of the surface.
  • film formers which can 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.
  • Agents which can be used according to the invention can furthermore comprise one or more antimicrobial active substances, 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% by weight.
  • Suitable examples are 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 their derivatives 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-
  • Water-soluble and / or water-insoluble builders can be used in the compositions which can be used according to the invention.
  • Water-soluble builders are preferred since they are usually less tend to leave insoluble residue 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. With regard to further builders and / or cobuilders which can be used according to the invention and their preferred amounts used, reference is made to the published patent application WO2008 / 101909 directed.
  • 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.
  • further corrosion inhibitors which can be used according to the invention, in particular also glass
  • 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 Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides
  • Alkalis which may be used according to the invention may furthermore 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 agents useful in this 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 which can be used 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.
  • 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.
  • 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 in enzyme-containing agents in order to protect 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 cleavage.
  • 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
  • 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 which can be used 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 should not be substantive to the surfaces, especially compared to toilet ceramics, even with prolonged exposure , The choice of suitable perfume is also limited only by possible interactions with the other detergent components.
  • An inventive hard surface cleaner may also contain one or more propellants (INCI propellants), usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, especially 2 to 10% by weight. , more preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%, included.
  • ICI propellants usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, especially 2 to 10% by weight. , more preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%, included.
  • blowing agent is on the publication WO2008 / 101909 directed.
  • a further subject of the present invention is also a product comprising a hard surface cleaner to be used in accordance with the invention, and a spray dispenser.
  • the product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container.
  • the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (pressurized gas containers, also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate.
  • Spray dispensers are more detailed in the WO 96/04940 (Procter & Gamble) and the US patents cited therein to Sprühspendern, to which all reference is made in this regard and the contents of which are hereby incorporated into this application described.
  • Trigger spray dispensers and pump sprayers have the advantage over compressed gas tanks that no propellant must be used.
  • suitable particles-passing attachments, nozzles, etc. so-called “nozzle valves”
  • enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.
  • the agent which can be used according to the invention is preferably a cleaning agent, in particular a cleaning agent for ceramics, more preferably sanitary ceramics.
  • the preparation of the agents which can be used according to the invention can be carried out in a customary manner by mixing the components contained in the agent in a suitable manner.
  • a further subject of the present invention is a method for treating a hard surface, in which the surface is brought into contact with an agent which can be used according to the invention, as described in the preceding text.
  • This process may be carried out as a stand-alone treatment process for the surface, for example, to provide it with antisoiling properties or one or more of the other properties which effect the agents of the invention in accordance with the teachings of the present invention.
  • the surface is brought into contact with a composition according to the invention.
  • the 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 bringing into contact takes place at a temperature of 5 to 50 ° C, in particular 15 to 35 ° C.
  • the process 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.
  • the invention relates to the use of an agent which can be used according to the invention for protecting a hard surface against stains and / or for easier removal of new stains from the surface, the stain (s) in particular being faecal dirt and / or biofilms and / or protein deposits is.
  • agents which can be used according to the invention are used for improved removal of faecal dirt and / or biofilms from the surfaces of flush toilets and / or for reducing the re-soiling of such surfaces with faecal 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.
  • This feature is particularly useful where surfaces are particularly prone to limescale and dirt and biofilm deposits, such as typically toilet bowls, sinks, bathtubs and shower stalls.
  • Another benefit of this feature is that water drains from treated surfaces faster, allowing them to dry faster. In a cleaning process, a rinse with pure water is usually required after treating the surface with detergent. It is desirable that the surfaces after this rinse quickly dry again, for example, because a fast-drying surface in a consumer enhances the impression of cleanliness.
  • an agent for bacteriostatic finishing of a hard surface which can be used according to the invention.
  • a particular advantage of the polymer mixtures used according to the invention is that the colonization by and growth of microorganisms is suppressed on surfaces treated therewith 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.
  • the starting material used was a polyether polyol which is 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, obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as initiator.
  • the polyether polyol was heated in vacuo with stirring for 1 h at 80 ° C.
  • Voranol CP 1421 from DOW Chemicals was dried in vacuo with stirring for 1 h at 80 ° 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 dried in vacuo with stirring for 1 h at 80 ° C.
  • To 209 g (16.9 mmol) of the dried polyether polyol was slowly added 20.9 mg (0.01%) of dibutyltindilaurate and 30.3 g (1.0 eq) of (3-isocyanatopropyl) triethoxysilane.
  • dibutyltin dilaureate it is also possible to use DABCO (1,4-diazabicyclo [2.2.2] octane) as the catalyst.
  • the reaction mixture was further stirred under blanketing gas at room temperature for 2 days until the NCO band in the IR measurement had disappeared.
  • 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 (Hydrostellan S100).
  • Example 2 WC reactor test with individual polymers and polymer mixtures
  • the preventive effect with regard to the biofilm reduction of different polymers as a function of their concentration in a commercially available WC cleaner was investigated in an application-oriented dynamic test system.
  • the preventive effect of the individual polymers was also compared with the effect of mixtures of these polymers.
  • the so-called toilet reactor simulates the flushing cycles of a toilet and thus the periodic wetting and drying of ceramic surfaces. This system makes it possible to examine adhesion and biofilm formation in a test system on several different surfaces over a defined period of 48 h. Instead of water in a real toilet, fresh medium (TBY 1:50) is passed over the tiles in this model.
  • the reactor is first filled with 680 ml of medium and inoculated with 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.
  • the incubation takes place overnight, so that the germ flora can establish itself in the system.
  • the 'water rinses' are semi-automatically controlled by a pump and the time-delayed opening of a solenoid valve. Per wash, 680 ml of medium are used. The first and second days after incubation are rinsed 15 times each, with a single rinse lasting 20 minutes. The tiles are removed after a total of 30 rinses at the end of the reactor run.
  • the horizontally placed tiles were submerged in 15-20 ml of the polymer solutions with defined concentrations for three minutes before being clamped in the reactor, then rinsed briefly with water and dried at 60 ° C. for two hours.
  • the solvent used was a detergent formulation.
  • the ceramic tiles are 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 is filtered off, removed with H 2 O bidist non-bonded dye from the glasses and the colored tiles are dried.
  • the stained surfaces are scanned and evaluated with Corel Draw Paint 9.
  • the background value (caused by the ceramic) is measured from untreated surfaces and from the color intensity of the stained Tiles removed.
  • the intensity of the biofilm on tiles which were previously treated only with the cleaner without polymer addition, set to 100% biofilm formation and 0% biofilm reduction.
  • Table 1 Biofilm reducing effect of individual polymers and combinations of polymers formulated in a WC cleaner Polymer (s) Conc.
  • DSM Hybrane DAEO 5000 is a branched polyester amide containing quaternized ammonium groups and long-chain polyoxyethylene groups.
  • biocidal properties of the individual polymers were investigated in accordance with DIN standard EN 1276 on Staphylococcus aureus, Enterococcus hirae, Pseudomonas aeruginosa and Escherichia coli .
  • biocidal properties were then compared with the biorepulsive properties of the polymers determined as described in Example 2.
  • tiles were used, which were treated in advance with water to determine a biofilm reduction by the toilet cleaner itself.
  • the WC cleaner with the addition of the polymers HydroStellan, DSM Hybrane Quat and DSM Hybrane 5000 each showed an approximately 70% increase in biofilm reduction.
  • Both the 80% cleaner / polymer formulations under 'clean' and 'dirty' conditions, and the 10% formulations under 'clean' conditions showed the same biocidal effect as the toilet cleaner without polymer.
  • Table 2 Comparison of biocidal (EN1276) and biorepulsive efficacy (biofilm reduction) of various polymers formulated in WC cleaners EN1276 concentration experimental condition 80% biofilm reduction clean dirty [%] Toilet cleaner + 0.25 wt .-% Hydrostellan S. aureus 2,97E + 05 2,97E + 05 71 ⁇ 5 E. hirae 1,32E + 05 1,32E + 05 P. aeruginosa 2,73E + 05 2,73E + 05 E. coli 1,73E + 05 1,73E + 05 WC cleaner + 1% by weight AS DSM Hybrane DAEO Quat S. aureus 2,97E + 05 2,97E + 05 66 ⁇ 7 E.
  • the data in the table are in wt .-% of active substance based on the total composition.
  • the pH of the compositions was adjusted to 2.2.
  • the viscosity of the compositions at 20 ° C was 550 mPaxs (Brookfield LV-DV II +, spindle 31, 20 rpm).
  • the data in the table are in wt .-% of active substance based on the total composition.
  • the pH of the compositions was adjusted to 3.9.
  • the Viscosity of the compositions was less than 10 mPaxs at 20 ° C (Brookfield LV-DV II +, spindle 31, 20 rpm).
  • the data in the table are in wt .-% of active substance based on the total composition.
  • the pH of the compositions was adjusted to 10.0.

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Claims (13)

  1. Utilisation d'un produit contenant un copolymère composé d'un acrylamide d'ammonium quaternaire et
    d'un acide acrylique
    ainsi qu'un polyalcoxylate en forme d'étoile à plusieurs bras et/ou
    un polyesteramide visant à réduire l'adhérence de micro-organismes sur une surface dure.
  2. Utilisation d'un produit contenant un copolymère composé d'un acrylamide d'ammonium quaternaire
    et d'un acide acrylique
    ainsi qu'un polyalcoxylate en forme d'étoile à plusieurs bras et/ou un polyesteramide visant au traitement bactériostatique d'une surface dure.
  3. Utilisation selon l'une quelconque des revendications 1 à 2, caractérisée en ce qu'il s'agit, concernant le polyalcoxylate en forme d'étoile à plusieurs bras, d'un polyalcoxylate de silyle, notamment d'un composé de la formule (I)

            (H-D)p-Z-[D-E-Si(OR1)r(R2)3-r]o     (I)

    soit
    Z pour un résidu de valeur (o+p) comportant au moins trois atomes de carbone, préférablement pour un résidu d'hydrocarbure acyclique ou cyclique au moins trivalent, notamment de trivalent à hexavalent comportant 3 à 12 atomes de carbone,
    D symbolisant un résidu de polyoxyalkylène bivalent, les résidus de polyoxyalkylène o+p liés à Z pouvant être chacun différents, et un résidu D étant respectivement relié à un atome d'oxygène appartenant à Z par Z et à un atome d'oxygène appartenant à D par E resp. hydrogène, et D symbolisant préférablement -(CHR3-CHR4-O)q-, R3 et R4 symbolisant indépendamment l'un de l'autre de l'hydrogène, du méthyle ou de l'éthyle et q symbolisant un nombre entier allant de 2 à 10 000,
    E symbolisant une liaison chimique ou un résidu organique bivalent comportant 1 à 50 atomes de carbone, préférablement une liaison covalente ou le résidu -C(O)-NH-(CH2)3-,
    OR1 symbolise un groupe hydrolysable, R1 et R2 symbolisent indépendamment l'un de l'autre un groupe d'alkyle linéaire ou ramifié comportant 1 à 6 atomes de carbone et r représentant un nombre entier allant de 1 à 3 et
    o représentant un nombre entier ≥ 1 et p représentant 0 ou un autre nombre entier ≥ 1, et o+p possédant une valeur allant de 3 à 100, o représentent préférablement 1 ou 2 et p symbolisant un nombre allant de 3 à 8.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le polyesteramide contient au moins deux groupes selon la formule (II)
    Figure imgb0046
     où
    Y représente H, C1-20(Cyclo-)alkyle, C6-10-aryle ou
    Figure imgb0047
    B représente les alkyles C2-24 ou les aryles C6-24,
    R1, R2, R3, R4, R5 et R6 représentent indépendamment les uns des autres H, C1-8-(Cyclo)alkyle ou C6-10-aryle,
    R7 et R8 représentent indépendamment l'un de l'autre C1-28-alkyle ou C6-10-aryle, le cas échéant remplacés par des hétéroatomes,
    ainsi que m et n indépendamment l'un de l'autre admettent une valeur allant de 1 à 4.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le polyesteramide contient au moins deux groupes selon la formule (III)
    Figure imgb0048
     où
    Y représente H, C1-20-(Cyclo-)alkyle, C6-10-aryle ou
    Figure imgb0049
    B représente les C2-24-alkyles ou les C6-24-aryles,
    R1, R2, R3, R4, R5 et R6 représentent indépendamment les uns des autres H, C1-8-(Cyclo)alkyle ou C6-10-aryle,
    R7 représente C1-28-alkyle ou C6-10-aryle, le cas échéant remplacés par des hétéroatomes, ainsi que m et n indépendamment l'un de l'autre admettent une valeur allant de 1 à 4.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'il s'agit, concernant le polyesteramide, d'un polymère selon la formule (IV)
    Figure imgb0050
     où
    W représente H, C1-20-alkyle, C6-10-aryle ou
    Figure imgb0051
     A représente OH ou
    Figure imgb0052
     B représente les C2-24-alkyles ou les C6-24-alkyles,
    X1 représente
    Figure imgb0053
     X2 représente H, X1
    Figure imgb0054
     ou
    Figure imgb0055
     R1, R2, R3, R4, R5 et R6 représentent indépendamment les uns des autres H, C1-8-(Cyclo)alkyle, C6-10-aryle ou -CH2-OX2,
    R7 et R8 représentent indépendamment l'un de l'autre C1-28-alkyle ou C6-10-aryle, le cas échéant remplacés par des hétéroatomes.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'il s'agit, concernant le polyesteramide, d'un polymère selon la formule (V)
    Figure imgb0056
     où
    A représente OH ou
    Figure imgb0057
     B représente les C2-24-alkyles ou C6-24-aryles,
    X1 représente
    Figure imgb0058
     X2 représente l'hydrogène, X1
    Figure imgb0059
     ou
    Figure imgb0060
     R3 et R6 représentent indépendamment l'un de l'autre H, C1-8-alkyle ou C6-10-aryle,
    R7 et R8 représentent indépendamment l'un de l'autre C1-28-alkyle ou C6-10-aryle le cas échéant remplacés par des hétéoatomes et/ou par des groupes contenant des hétéroatomes.
  8. Utilisation selon l'une quelconque des revendications 4 à 7, caractérisée en ce que R7 et R8 indépendamment l'un de l'autre sont remplacés une ou plusieurs fois par des groupes sélectionnés parmi les alcools, les éthers, les polyéthers, les esters, le cyanure, le carbonate, l'uréthane, l'urée, l'amide, l'imide, l'amine, l'imine, l'imidazol, l'oxime, le sulfure, le thiocarbamide, le sulfone, l'oxyde de sulfone, le sulfate, le phosphate, la phosphine, l'oxyde de phosphine, le silane, le silicone, le silicate, le fluor, le chlore, le brome ou l'iode ainsi que parmi des groupes contenant au moins un des groupes fonctionnels précédemment mentionnés.
  9. Utilisation selon l'une quelconque des revendications 4 à 8, caractérisée en ce que R7 et R8 indépendamment l'un de l'autre contiennent des groupes aminés quaternaires ou des groupes de polyéther, notamment des groupes de polyoxyéthylènes ou des composés quelconques de ceux-ci, et sont notamment sélectionnés parmi les résidus d'alkyl de tri(m)éthylammonium ainsi que, le cas échéant, les groupes de polyoxyéthylène éthérifiés comportant 6 à 10 unités d'oxyéthylène.
  10. Utilisation selon l'une quelconque des revendications 1 à 9, caractérisée en ce qu'il s'agit, concernant l'acrylamide d'ammonium quaternaire du copolymère issu de l'acrylamide d'ammonium quaternaire et de l'acide acrylique, d'un acrylamide de diallyldiméthylammonium.
  11. Utilisation selon l'une quelconque des revendications 1 à 10, caractérisée en ce que le produit contient au moins un tensioactif.
  12. Utilisation selon l'une quelconque des revendications 1 à 11, caractérisée en ce que le produit possède une valeur pH inférieure à 9, notamment de 0 à 6, préférablement de 1 à 5 et très préférablement de 2 à 4.
  13. Utilisation selon l'une quelconque des revendications 1 à 12, caractérisée en ce qu'il s'agit, concernant le produit, d'un produit détergent, préférablement d'un produit détergent pour céramique, notamment pour la céramique sanitaire.
EP10743172.8A 2009-09-01 2010-08-19 Utilisation des agents de traitement de surfaces dures Not-in-force EP2473592B1 (fr)

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DE102009029060A DE102009029060A1 (de) 2009-09-01 2009-09-01 Mittel zur Behandlung harter Oberflächen
PCT/EP2010/062108 WO2011026735A1 (fr) 2009-09-01 2010-08-19 Agents de traitement de surfaces dures

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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2920763B1 (fr) * 2007-09-06 2011-04-01 Saint Gobain Technical Fabrics Composition d'ensimage sous forme de gel physique pour fils de verre, fils de verre obtenus et composites comprenant lesdits fils.
DE102010038340A1 (de) * 2010-07-23 2012-01-26 Henkel Ag & Co. Kgaa Verhinderung der bakteriellen Adhäsion
WO2013160216A1 (fr) * 2012-04-25 2013-10-31 Akzo Nobel Chemicals International B.V. Utilisation d'un alkanolamide éthoxylé en tant qu'hydrotrope pour un adduit d'oxyde d'alkylène et d'alcool
US9790456B2 (en) * 2012-12-20 2017-10-17 Ecolab Usa Inc. Citrate salt bathroom cleaners
US9534190B2 (en) * 2012-12-20 2017-01-03 Ecolab Usa Inc. Citrate salt bathroom cleaners
US20150225594A1 (en) * 2014-02-11 2015-08-13 Gregory E Robinson Surface treatment composition
AT515627B1 (de) * 2014-04-15 2015-12-15 Bmb Gebäudehygiene Gmbh Verfahren zur Bekämpfung von Schimmel, Algen sowie anderen Mikroorganismen auf unterschiedlichen von diesen Organismen befallenen Wand-, Boden- oder Deckenflächen sowie Mauerwerk im Allgemeinen
US20180030389A1 (en) * 2016-07-29 2018-02-01 Amit Garyali Multi-Purpose Cleaner System
BR112020011623A2 (pt) * 2017-12-19 2020-12-08 Colgate-Palmolive Company Composição de limpeza para proporcionar repelência à água de longa duração em superfícies
JP2021172715A (ja) * 2020-04-23 2021-11-01 山崎産業株式会社 防汚洗浄剤、清掃用品及び防汚洗浄方法
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 (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4861511A (en) * 1987-06-26 1989-08-29 Nalco Chemical Company Toilet bowl cleaner and stain-inhibiting composition
BR9508569A (pt) 1994-08-12 1997-12-23 Procter & Gamble Composição para reduzir a impressão de mau cheiro sobre as superficies inanimadas
NL1007186C2 (nl) 1997-10-01 1999-04-07 Dsm Nv ß-hydroxyalkylamide groepen bevattend condensatiepolymeer.
EP1038902A1 (fr) 1999-03-26 2000-09-27 Dsm N.V. Polycondensats contenant des groupes terminaux dialkylamine, leur procédé de préparation et leurs utilisations
WO2003063926A1 (fr) 2002-02-01 2003-08-07 Sustech Gmbh & Co. Kg Prepolymeres en etoile pour la production de revetements ultraminces formant des hydrogels
US6926745B2 (en) * 2002-05-17 2005-08-09 The Clorox Company Hydroscopic polymer gel films for easier cleaning
WO2006005358A1 (fr) 2004-07-10 2006-01-19 Henkel Kommanditgesellschaft Auf Aktien Compositions de nettoyage contenant des copolymeres
DE102006009004A1 (de) 2006-02-23 2007-09-06 Sustech Gmbh & Co. Kg Multifunktionelle sternförmige Präpolymere, deren Herstellung und Verwendung
DE102007039649A1 (de) 2006-12-05 2008-06-12 Henkel Kgaa Reinigungsmittel für harte Oberflächen
EP2109663B1 (fr) * 2006-12-05 2010-09-29 Henkel AG & Co. KGaA Agent de nettoyage pour surfaces en verre
DE102007039652A1 (de) 2006-12-05 2008-06-12 Henkel Kgaa Mittel zur Behandlung harter Oberflächen
DE102007008655A1 (de) 2007-02-20 2008-08-21 Henkel Ag & Co. Kgaa Siderophor-Metall-Komplexe als Bleichkatalysatoren
US7741265B2 (en) * 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
DE102007039665A1 (de) * 2007-08-22 2009-02-26 Sustech Gmbh & Co. Kg Silylfunktionelle lineare Präpolymere, deren Herstellung und Verwendung
DE102007058343A1 (de) 2007-12-03 2009-06-04 Henkel Ag & Co. Kgaa Verminderung der Adhäsion von Schmutz, Staub und biologischem Material durch Polyesteramide
DE102008063070A1 (de) 2008-12-23 2010-07-01 Henkel Ag & Co. Kgaa Verwendung sternförmiger Polymere mit peripheren negativ geladenen Gruppen und/oder peripheren Silyl-Gruppen zur Ausrüstung von Oberflächen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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HUE031859T2 (hu) 2017-08-28
EP2473592A1 (fr) 2012-07-11
PL2473592T3 (pl) 2017-06-30
ES2618862T3 (es) 2017-06-22
US20120156377A1 (en) 2012-06-21
WO2011026735A1 (fr) 2011-03-10

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