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.
• 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
• 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.
• 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.
• 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.
• 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)
• 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
• 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 .
• 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.
• 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
• 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.
• 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
• 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.
• 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.
• 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.

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• Oil, Petroleum & Natural Gas (AREA)
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• 2007
  • 2007-08-22 DE DE102007039652A patent/DE102007039652A1/de not_active Withdrawn
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