DE102014218502A1 - Protein-containing detergent - Google Patents

Abstract

A hard surface cleaner containing a spider silk protein can be used for cleaning and simultaneously stain resistant hard surface modification.

Description

The invention relates to a hard surface cleaner containing certain proteins.

All-purpose cleaners have long been firmly established in many households. They are used in the cleaning of hard surfaces and are able to remove a large number of soiling, especially greasy soiling. However, it is desirable that the surface be given further positive properties. This includes an improved water drain as well as dirt-repellent properties. These positive properties should result in both concentrated and dilute application of the detergent.

Object of the present invention was to provide a cleaning agent in particular liquid form, which causes an improvement of dirt-repellent properties and the water drainage on cleaned with him surfaces with consistently good or even improved cleaning performance.

An object of this application is a hard surface cleaner containing spider silk protein.

Spider silk proteins are polymers that exhibit exceptional physical properties. However, limited information is available on the composition of the various silks produced by different spiders. For example, the hedgehogs of the golden silk spider (Nephila clavipes) and the garden spider (Araneus diadematus) are examined; these spider silk are usually composed of two large proteins, and it may be possible that other proteins play a role in the composition and final structure of the spinel silk. The two key protein components of the Araneus diadematus safety line are called ADF-3 and ADF-4.

In the context of the present invention, the term "spider silk protein" encompasses not only all natural sequences but also all artificial or synthetic sequences derived therefrom.

Accordingly, the spider silk amino acid sequences can be derived from so-called "authentic" sequences. This term means that the underlying nucleic acid sequences have been isolated from their natural environment without substantial alteration of the sequence. However, it is acceptable to alter the authentic nucleic acid sequence so that its expression in a host organism, for example E. coli, is facilitated without any change in the encoded amino acid sequence.

The authentic non-repeating sequences are preferably derived from the amino-terminal non-repetitive region and / or the carboxy-terminal non-repetitive region of a naturally occurring spider silk protein.

Particularly preferred are the proteins of one or more of the spiders Arachnura higginsi, Araneus circulissparsus, Araneus diadematus, Argiope picta, Argiope trifasciata, Nephila antipodiana, Cyrtophora beccarii, Celaenia excavata, Gasteracantha kuhlii, Argiope aurantia, Ordgarius furcatus, Ordgarius magnificus, Neoscona nautica, Neoscona rufofemorata, Zygiella calyptrata, Parawixia dehaani, Neoscona oxancensis, Gasteracantha cancriformis (elipsoides) Gasteracantha arcuata, Cyrtophora moluccensis, Cyrtophora parnasia, Dolophones conifera, Dolophones turrigera, Gasteracantha doriae, Gasteracantha mammosa, Cyrtophora exanthematica, Aculeperia ceropegia, eriophora pustulosa, Anepsion depressium , Gasteracantha Quadrispinosa, Eriophora transmarina, Araneus bicentenarius, Nephila maculata, Gasteracantha hasseltii, Tegenana atrica, Heurodes turrita, Cyclosa insulana, Astracantha minax, Araneus mitificus, Eriovixia laglaisei, Cyclosa bifida, Nephilengys malabarensis, Argiope versicolor, Herennia ornatissima, Argiope aemula, Cyrtophora unicolor, Cyrtophora hirta, Argiope keyserlingi, Acusilas coccineus, Argiope argentata, Neoscona domiciliorum, Argiope aetheria, Poltys illepidus, Arkys clavatus, Arkys lancearius, Poecilopachys australasia), Nephila species such as Nephila clavipes, Nephila senegalensis, Nephila madagascariensis.

In the present invention, a recombinant spider silk protein may not only be derived from protein sequences of one species, but may also contain sequences derived from different spider species. It is also possible to use a recombinant spider silk protein having more than one type of repeating sequence, which different types may be derived from different species.

Preferably, the spider silk protein, optionally multiply, in particular 1-fold to 5-fold, an amino acid sequence which is at least 60%, in particular at least 90% identical to NR4 (ADF-4) with SEQ ID No.1 (corresponding to SEQ ID No. 11 in WO 2007/014755 ) is the amino acid sequence disclosed.

The spider silk protein contained in the cleaning agent leads to a hydrophilization of surfaces treated with the agent, in particular tile or glass surfaces. The surfaces show a higher gloss; In addition, water residues run better from the surface, so that the formation of droplets is prevented. After the use of the agent were Soil-release effects on surfaces such as glass and ceramic already with a single pre-cleaning. In addition, an improved cleaning performance against grease contamination was observed.

A further subject of this application is accordingly the use of a hard surface cleaner according to the invention containing spider silk protein for the cleaning and simultaneous dirt-repellent modification of hard surfaces.

When applying agents according to the invention, it may be helpful to apply a liquid cleaning agent to the surface to be cleaned or to the surface part to be cleaned by spraying. A further subject of this application is therefore a product comprising a liquid detergent according to the invention containing spider silk protein and a spray dispenser.

A detergent according to the invention can be used in a process for cleaning and simultaneously dirt-repellent modification of hard surfaces. In this case, the agent can be used both in concentrated form and diluted, preferably diluted with water, wherein solid compositions according to the invention are used in the form of dilute aqueous solutions. Another object of the invention is therefore a process for the cleaning and simultaneous dirt-repellent modification of hard surfaces, consisting of the steps of applying a cleaning agent according to the invention, in concentrated or diluted form, on the surface to be cleaned, optionally by spraying, wiping with a cloth, a sponge or another suitable substrate for this purpose, to distribute the agent over the entire surface or the part of the surface to be cleaned, if necessary, exposure, rinsing with clear water and optionally dry rubbing the surface with another cloth, a sponge or another suitable for this purpose substrate.

Spider silk protein is preferably contained in compositions of the invention in an amount in the range of 0.001 wt .-% to 20 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%. Preferably, a detergent according to the invention, which may be, for example, an all-purpose cleaner, a machine or manual dishwashing or glass cleaning agent, is liquid and contains from 0.1% to 99.9% by weight, in particular from 50% by weight to 99% by weight and particularly preferably from 55% by weight to 95% by weight of water. In addition to spider silk protein, a hard surface cleaner of the present invention may contain any of the ingredients commonly found in such agents, and is preferably an aqueous composition containing nonionic surfactant, for example, a short chain fatty alcohol polyglycol ether, and anionic surfactant.

An agent according to the invention preferably comprises a short-chain nonionic surfactant of the formula I R ¹ O (CH ₂ CH ₂ O) _n -H (I) in which R ^{1 is} a straight-chain or branched C _1-8 -alkyl radical or C _2-8 -alkenyl radical and n is a number between 1 and 10. These are preferably pentaethylene glycol monohexyl ethers, ie a compound of the formula I where R ¹ = C ₆ -alkyl and n = 5; occasionally abbreviated as "C6E5". Short-chain nonionic surfactant is preferably used in an amount of from 0.1% by weight to 10% by weight, in particular from 0.2% by weight to 5% by weight, particularly preferably from 0.5% by weight to 4 wt .-% used.

The agent according to the invention preferably contains 0.1% by weight to 30% by weight, in particular 0.6% by weight to 15% by weight, particularly preferably 0.8% by weight to 5% by weight, another nonionic surfactant.

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 preferred as further nonionic surfactants -C ₁₈ -Carbonsäurepolyglykolester with 2 to 15 EO, for example, tallow fatty acid + 6-EO ester, ethoxylated fatty acid amides having 12 to 18 carbon atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides having 14 to 20 carbon atoms and long-chain alkylpolyglycosides with 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units to mention. Examples of such surfactants are 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 fatty alcohol alkoxylates, preferably C _8-20 fatty alcohol polyglycol ethers having, in particular, 5 to 14 EO, for example C _12-18 fatty alcohol + 7 EO ethers. The agent should, however, be free of those nonionic surfactants derived from glycerol.

The agent according to the invention preferably further comprises at least one anionic surfactant, preferably in an amount of 0.1 to 30 wt .-%, preferably 0.6 to 15 wt .-%, in particular 1 to 10 wt .-%.

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 (fatty alcohol ether sulfates) with 2 to 6 ethylene oxide units (EO) in the ether portion and sulfosuccinic mono- and di-C ₈ -C ₁₈ alkyl esters. Furthermore, C ₈ -C _{18 α-} olefinsulfonates, sulfonated C ₈ -C ₁₈ -fatty acids, in particular dodecylbenzenesulfonate, C ₈ -C ₂₂ -carboxylic acid amide ether sulfates, C ₈ -C ₁₈ -alkyl polyglycol ether carboxylates, C ₈ -C ₁₈ -N-acyltaurides , Fatty acid cyanamides, C ₈ -C ₁₈ N-sarcosinates and C ₈ -C ₁₈ -alkyl isethionates or mixtures thereof.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. The former are particularly preferred because of their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them. In particular, the oxo alcohols or derivatives thereof obtainable, for example, by the ROELEN's oxo synthesis can also be used accordingly.

Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably the longer-chain alcohols for the purposes of the present invention. As a rule, n moles of ethylene oxide and one mole of alcohol give rise, depending on the reaction conditions, to a complex mixture of addition products of different degrees of ethoxylation. Another embodiment is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. For the purposes of the present invention, very particular preference is given to lower ethoxylated fatty alcohols (0.5 to 4 mol of EO, preferably 1 to 2.5 mol of EO).

The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.

The anionic surfactant used is preferably an alkylbenzenesulfonic acid, in particular a C _10-13 -alkylbenzenesulfonic acid

In the composition according to the invention, the weight ratio of short-chain nonionic surfactant to anionic surfactant is preferably 1: 100 to 100: 1, in particular 1: 5 to 5: 1, particularly preferably 1: 4 to 1: 1.5. The weight ratio of anionic surfactant to further nonionic surfactant is preferably 1: 100 to 100: 1, in particular 5: 1 to 1: 5, particularly preferably 3: 1 to 1: 1.

In addition to the surfactants mentioned, an agent according to the invention may contain further ingredients usually used in cleaning agents. These are preferably selected from the group comprising other surfactants, bases, acids, viscosity modifiers, fatty acids, solvents, other polymers, antibacterial agents, preservatives, solubilizers, complexing agents, enzymes, dyes, fragrances and mixtures thereof.

In addition to the surfactant types mentioned above, the composition according to the invention may also contain cationic surfactants and / or amphoteric surfactants.

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} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetain 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.

In compositions according to the invention, it is furthermore possible for bases to be present. As such, alkalis from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide, are preferably used. In addition, however, it is also possible to use ammonia and / or alkanolamines having up to 9 C atoms in the molecule, preferably the ethanolamines, in particular monoethanolamine.

Detergents according to the invention can be used to enhance the cleaning performance Lime and urine contain one or more acids. 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. In addition, however, it is also possible to use the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid and mixtures thereof.

In order to allow longer adherence of liquid detergents to the surface to be cleaned, it may also be advantageous to increase the viscosity of the composition by using a thickening agent. Suitable for this purpose are all viscosity regulators customarily used in detergents and cleaners, 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 (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose 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 such as montmorillonites, zeolites, silicas).

Examples of 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. Such polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ^® such as Polygel ^® DA, and by the company. BFGoodrich under the tradename 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). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C _1-4 -alkanols (INCI acrylates copolymer), such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and, for example, by the company Rohm & Haas under the trade names Aculyn ^®. and Acusol ^®, and from Degussa (Goldschmidt) under the trade name Tego ^® polymers are available, for example the anionic non-associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® 33 (crosslinked), Acusol ^® 810, Acusol ^® 823 and Acusol ^® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C _10-30 alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 alkanols formed, esters (INCI acrylates / C _10-30 alkyl acrylate Crosspolymer) and which are for example available from the company. BFGoodrich under the tradename Carbopol ^®, for example hydrophobized Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI acrylates / C10 -30 alkyl acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473). 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. Other polysaccharide thickeners, such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl -, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate. A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 × 10 ^6, and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® or from Rhodia is available under the trade name Rhodopol ^®.

As thickeners, it is also possible to use phyllosilicates. These include, for example, available under the trade name Laponite ^® magnesium or sodium magnesium phyllosilicates from Solvay Alkali, in particular the Laponite ^® RD or Laponite ^® RDS, and the magnesium silicates Süd-Chemie, especially the Optigel ^® SH.

Another ingredient of cleaning agents according to the invention may be fatty acids. For the purposes of this invention, this term is taken to mean branched or unbranched, saturated or mono- or polyunsaturated carboxylic acids having preferably 6 to 22 carbon atoms.

Another preferred component of liquid agents according to the invention are solvents, in particular water-soluble organic solvents. These include, for example, lower alcohols and / or ether alcohols, which are understood as lower alcohols in the context of this invention straight-chain or branched C _1-6 alcohols. The alcohols used are in particular ethanol, isopropanol and n-propanol. As ether alcohols are sufficiently water-soluble compounds having up to 10 carbon atoms in the molecule into consideration. Examples of such ether alcohols are 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. In a preferred embodiment, however, ethanol is used as the solvent.

The composition of the invention may further comprise one or more additional polymers. These may include, for example, polymers which increase the critical micelle concentration (cmc) by interaction with the surfactants, in particular anionic surfactants, and thereby positively influence the cleaning performance. These polymers include, for example, high molecular weight polyethylene glycols (PEG having a molecular weight of over 400,000), but also derivatives of polyvinylpyrrolidone (PVP derivatives) such as PVP-K15 (ISP Corp). Polymers with builder properties can also have a positive effect on the cleaning performance. For this example, polyacrylic acids and / or polyacrylates are expected, such as Sokalan ^® types of BASF (Sokalan ^® PA 15/20/25/30 CL), also acrylic acid-maleic anhydride copolymers such as Acusol ^® 448 or Acusol ^® 460 N (both Rohm & Haas), maleic acid-olefin Copolymerisat- sodium salt, for example Sokalan ^® CP 9 (BASF), or nitrogen-containing polymers. The latter group includes, for example, alkoxylated polyvinylamines, alkoxylated, acylated or alkylated polyaminoamides and polyurethane ureas having tertiary amino groups.

In addition, it is also possible to use other polymers which raise and modify surfaces, for example by imparting hydrophilic properties or by modifying the wetting behavior on hydrophobic surfaces. Among these are, for example, those known as "soil-release polymers" amphiphilic and nonionic oligoesters, which are obtainable by polycondensation of dicarboxylic acids, polyols and alkylene oxides. Also, for the surface modification can polyether siloxanes, polymethylsiloxanes and therefore copolymers of ethylene or propylene oxide units, or other derivatives such as polysiloxane Tegopren ^® 6922 and 6924 serve (Degussa-Goldschmidt), further improve the liquid flow. Can also for surface modification of film-forming polymers such as the acrylic copolymer Primal ^® NT 2624 (Rohm & Haas) or the acrylate resin Wokamer ^® C3303 (Worlee), and waxes such as polyethylene waxes, serve as Poligen ^® WE. 1

Disinfection and sanitation constitute a particular form of purification. In a corresponding particular embodiment of the invention, the cleaning agent therefore contains one or more antimicrobial active substances, preferably in an amount of from 0.01% by weight to 1% by weight preferably 0.02 wt.% to 0.8 wt.%, in particular 0.05 wt.% to 0.5 wt.%, particularly preferably 0.1 wt.% to 0.3 wt. %, most preferably 0.2% by weight.

The terms disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention. While disinfection in the narrower sense of the medical practice means the killing of - in theory all - infectious germs, sanitation is to be understood as the greatest possible elimination of all - including the saprophytic - normally harmless to humans saprophytic - germs. Here, the extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial content or increasing dilution of the agent for use.

Antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention 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-carbamate, iodine, iodophores and peroxides. 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-octanamine) dihydrochloride, N, N'-bis (4- chlorophenyl) -3.12-diimino-2,4,11,13- tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleaning agent. However, 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.

Preservatives may also be included in compositions of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.

In addition to the substances already mentioned, the compositions according to the invention can also contain solubilizers, so-called hydrotropes. In this case, it is possible to use all substances customarily used for this purpose in cleaning compositions, preferably sodium cumene sulphonate or sodium xylene sulphonate.

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. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. In addition, 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, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, S orodium dihydroxyethylglycinate, sodium EDTMP, sodium glutamate, sodium gluconate, sodium glycereth-1 polyphosphate, sodium hexametaphosphate, sodium metaphosphate, sodium metasilicate, sodium phytate, sodium polydimethylglycinophenolsulfonate, sodium trimetaphosphate, TEA-EDTA, TEA polyphosphate, tetrahydroxyethyl ethylene diamine, tetrahydroxypropyl ethylene diamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

The agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They can be added to the composition according to the invention in any form established according to the prior 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 may be encapsulated, for example, by spray-drying or extruding 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-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, 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. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. In addition, 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.

Finally, an agent according to the invention can contain all scents and dyes customary in detergents and cleaners.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2007/014755 [0011]

Claims (8)

 Hard surface cleaner containing spider silk protein. Detergent according to claim 1, characterized in that it contains spider silk protein in an amount in the range of 0.001 wt .-% to 20 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%. Cleaning agent according to claim 1 or 2, characterized in that it is liquid and contains 0.1 wt .-% to 99.9 wt .-%, in particular 50 wt .-% to 99 wt .-% water. Detergent according to one of Claims 1 to 3, characterized in that it is an aqueous composition containing nonionic surfactant and anionic surfactant.  Use of a hard surface cleaner containing spider silk protein for cleaning and simultaneously stain resistant hard surface modification.  Product of a liquid detergent containing spider silk protein and a spray dispenser.  Process for the cleaning and simultaneous dirt-repellent modification of hard surfaces, comprising the steps of applying a cleaning agent according to the invention, in concentrated or diluted form, to the surface to be cleaned, optionally by spraying, wiping with a cloth, a sponge or another suitable substrate for this purpose in order to distribute the agent over the entire surface or the part of the surface to be cleaned, optionally exposing to it, rinsing with clear water and optionally rubbing the surface dry with a further cloth, a sponge or another suitable substrate. Agent according to one of claims 1 to 4, use according to claim 5, product according to claim 6 or method according to claim 7, characterized in that the spider silk protein, optionally multiply, in particular 1 to 5 times, has an amino acid sequence of at least 60%, in particular at least 90% identical to the amino acid sequence disclosed as SEQ ID NO: 11 in WO 2007/014755.