• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a cleaning composition comprising (a) from 10 to 70% by weight of carbamide; (b) 5 to 70% by weight of one or more electrolytes; (c) from 0.1% to 35% by weight of one or more surfactants; (d) 0.1 to 10% by weight of one or more enzymes and (e) 0.1 to 20% by weight of one or more complexing agents.
    公开号:AT14818U1
    申请号:TGM50158/2015U
    申请日:2010-03-17
    公开日:2016-06-15
    发明作者:
    申请人:Bbt Bergedorfer Biotechnik Gmbh；
    IPC主号:
    专利说明:

    description
    CLEANING AGENTS CONTAINING CARBAMIDE AND / OR AT LEAST ONE DERIVATIVE HIERVON
    The invention relates to a detergent containing 10 to 70 wt .-% of carbamide, in particular as a detergent for closed systems, especially as a dishwashing detergent, as a detergent for washing machines (especially for cleaning textiles), as a means for cleaning, Sanitizing and / or disinfecting a device in the food processing industry and for a medical device, as a hand dishwashing detergent or as a sanitary cleaner or as a hand cleaner (for washing hands).
    According to the invention, closed systems refer to facilities which are either completely closed to the environment during operation, for example dishwashers, washing machines or the like, or are hermetically sealed from the environment before start-up and are only opened at start-up. For example, a device for food processing or as a medical device, such as scavengers for operating rooms and dental chairs, dialysis machines, heart-lung machines, endoscopes and similar medical device. While in the former systems, the cleaning agent is circulated in the device during operation, in the latter systems, the system is flushed with the detergent. Here, the cleaning agent is not only used for cleaning, but also for sanitizing and / or optionally disinfecting.
    Closed-system detergents, such as dishwashing detergents, laundry detergents, hand dishwashing detergents, and sanitary cleaners are agents used in almost all households. Modern dishwashing detergents, as described in WO 2007/141257, typically contain surfactants, detergent builders, bleaching agents and enzymes as important ingredients.
    Enzymes are molecules, especially proteins that can catalyze a particular chemical reaction. Enzymes play an important role in the metabolism of all living organisms; they catalyze and direct many biochemical reactions, for example, copying (DNA polymerase) or transcribing (RNA polymerase) the genetic information. Enzymes used in dishwashing detergents are, for example, proteases, amylases, catalases, peroxidases, cellulases and / or lipases. Preference is given to the use of proteases and amylases.
    Enzymes are relatively expensive compared to other components of a modern closed-system detergent, dishwashing detergent or sanitary cleaner. Despite the use of expensive enzymes, the cleaning effect of modern detergents, such as dishwashing detergents, is often only satisfactory. In addition, the use of enzymes often has disadvantages; For example, dishwashing detergents can only be used within a certain temperature and pH range. And stability problems can occur, especially during prolonged storage. Finally, considering environmental considerations, it is problematic when uncontrolled amounts of enzyme enter the wastewater. Also, the handling of enzymes in the manufacture or use of enzyme-containing products is not without problems (for example allergenic potential).
    It was therefore an object of the invention to reduce the disadvantages presented above.
    It was a particular object of the invention to provide a cleaning agent, for example, for closed systems, a hand dishwashing detergent or a sanitary cleaner that shows a high cleaning effect. Despite the high cleaning effect, the detergent or the dishwashing detergent or the sanitary cleaner should be gentle on the surface. Furthermore, it should be possible to use it over a wide pH range (neutral, alkaline, acidic).
    In the case of the dishwashing agent, it was a further object of the invention to provide an agent which is applicable over a wide temperature range, in particular from 15 to 70 ° C or 15 to 80 * C, and which has an advantageous cleaning effect on a possible wide temperature range achieved. It should be usable for household dishwashers as well as commercial dishwashers. The agent should also lead to a gentle lens cleaning.
    Carbamide (urea) is a neutral, odorless, very well water-soluble, non-toxic product, which is excreted by the human organism as the end product of nitrogen metabolism in amounts of 20 to 30 g per day and is one of the most environmentally friendly substances in nature , Here it can be broken down into its building blocks by chemical degradation or stored in the form of water-soluble or insoluble salts (for example as Ca carbonate and / or Mg carbonate).
    In this aspect, carbamide - which is to be regarded chemically as diamide of carbonic acid - as a bonded form of the two gaseous components NH3 and CO2 (in the ratio 2: 1) are considered, from which it is because of its use in the field of fertilizers and synthetic resins produced on a large scale commercially on a large scale.
    By the invention proposed use of carbamide in cleaning agents is by the increased use of large amounts of carbamide in the cleaning sector by the binding of CO 2 gas in the industrial production, use as a cleaner and disposal in nature to harmless salts (especially carbonates and hydrogen carbonates) made a not inconsiderable contribution to environmental protection.
    Furthermore, it should be possible from an environmental and cost point of view, to reduce the amount of enzymes and bleaching agents that are commonly used in conventional detergents.
    Only biodegradable and / or bio-regenerable substances should be used, in particular those which are biodegradable according to EN ISO 14593: 199 (CO2 headspace test).
    The objects of the present invention have been unexpectedly solved by the use of a high carbamide (urea) agent.
    Furthermore, the objects of the present invention could be achieved by the use of carbamide (urea) as a cleaning agent.
    The present invention relates to a detergent containing 10 to 70 wt .-% of carbamide, as a cleaning agent, for example, for closed systems, especially as a dishwashing detergent, as a detergent for washing machines, as a means for cleaning, sanitizing and / or disinfecting a device in the food processing industry or for a medical device, as a hand-dishwashing detergent or as a sanitary cleaner, in particular as a toilet sanitary cleaner.
    More particularly, the present invention relates to a cleaning composition comprising: (a) 10 to 70% by weight of carbamide; (B) 5 to 70% by weight of one or more electrolytes; (C) 0.1 to 35% by weight of one or more surfactants; (D) 0.01 to 10% by weight of one or more enzymes; and (e) 0.01 to 20% by weight of one or more complexing agents.
    With regard to the use of the agent as a sanitary cleaner should be mentioned that the sanitary cleaner remains only during the actual cleaning process on the surface to be cleaned, for example, on the ceramic surface of the toilet and after the cleaning is completely rinsed off, so that the emergence odors that occur, for example, during the possible decomposition of the carbamide is prevented.
    The detergents according to the invention are preferably used as dishwashing agents, in particular for dishwashers. These detergents may be in solid or liquid form. The cleaning agents are preferably present in solid form, in particular in the form of a powder, granules or tablets (dishwasher tablets or tabs).
    In addition, the cleaning agents according to the invention are used as sanitary cleaners (in particular as toilet cleaners). These detergents may be in solid form (for example as powders or granules) or more liquid (for example as gel). The cleaning agents are preferably in solid form, in particular in the form of a powder.
    The explanations / definitions given below relate to detergents according to the present invention, for example for closed systems (in particular as a means for cleaning, sanitizing and / or disinfecting), the dishwashing detergent according to the invention and the sanitary cleaner according to the invention, unless otherwise stated. For the sake of clarity, reference is made to "means according to the invention" or "detergent according to the invention".
    The composition of the invention contains 10 to 70 wt .-%, most preferably 20 to 70 wt .-% and in particular 20 to 60 wt .-% of carbamide (urea), based on the total weight of the composition.
    Dishwashing agents preferably contain 15 to 65 wt .-%, in particular powdery dishwashing in 30 to 60 wt .-% carbamide.
    Sanitary cleaner preferably contain 10 to 40 wt .-%, in particular 10 to 30 wt .-%, carbamide.
    In contrast to these high levels, carbamide has been used in dishwashing detergents and sanitary cleaners of the prior art merely as an additive in minor amounts. For example, DE 199 23 943 A1 discloses a sanitary cleaner in which carbamide was used as a germ-promoting organic substance in an amount of about 0.5% by weight. However, carbamide was not used in this case to improve the cleaning effect or to achieve the above-mentioned objects.
    Carbamide (also known as urea) has the chemical structure of the formula (I).
    According to the invention, the agent according to the invention can be used as a detergent for closed systems, such as dishwashers or washing machines, as a means for cleaning, sanitizing and / or disinfecting a device in the food industry or a medical device, as a dishwashing detergent or as a sanitary cleaner ,
    The cleaning agent according to the invention may e.g. be used for closed systems. With appropriate dosage of the carbamide it can also be used as a means of cleaning, sanitizing and / or disinfecting a device in the food industry or medical devices.
    Dishwashing agents are generally used as a means of cleaning dishes. The agent according to the invention can be used both as a machine dishwashing detergent or as a dishwashing detergent. It is preferably used as a dishwashing detergent, especially for both commercial dishwashers and domestic dishwashers.
    Sanitary cleaners are generally used for cleaning sanitary surfaces. The agent according to the invention is preferably used for cleaning toilet bowls or in urine bowls. The sanitary cleaner is thus preferably a toilet sanitary cleaner.
    In addition to carbamide, the composition according to the invention contains one or more surfactants, such as anionic, nonionic, cationic and / or amphoteric surfactants. Likewise, any mixtures of all the surfactants described below are possible.
    The agent according to the present invention contains 0.1 to 35 wt .-%, more preferably 0.5 to 30 wt .-%, particularly preferably 1 to 30 wt .-% of one or more surfactants, based on the total weight of the agent.
    In general, anionic surfactants are surfactants which have a negatively charged functional group. Anionic surfactants are usually composed of a polar and a non-polar part. The nonpolar part is preferably a Ce-Cao-alkyl radical. The polar functional group is preferably -COO '(carboxylate), -SOa ^ sulfonate) or -O-SOa' (sulfate).
    Examples of these are: [0040] Alkylcarboxylates of the formula R-COO Na "", where R is an organic radical having 6 to 30, preferably 8 to 16 carbon atoms; Alkylbenzenesulfonates (ABS) of the formula CnH2rH-i-C6H4-SOs Na "^, where n is 6 to 30, preferably 8 is 16, (eg sodium dodecylbenzenesulfonate); secondary alkanesulfonates (SAS) of the formula CnH2rH.i-S03 ' Na '·, where n is 6 to 30, preferably 8 is 16;
    Fatty Acid Sulfates (FAS) of the formula H3C- (CH2) n -CH2-O-S03'Na'x, where n is 6 to 30, preferably 8 to 16 (for example, sodium lauryl sulfate).
    Suitable surfactants of the sulfonate type are preferably Cg-is-alkylbenzenesulfonates and olefinsulfonates into consideration. Also suitable are alkanesulfonates which are obtained from C 12-2o-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Furthermore, the esters of α-sulfo fatty acids (ester sulfonates), e.g. the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable. A specific example is Ufaryl (e.g., Ufaryl DL 90 C), an alkyl benzene sulfonate.
    Further suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof. Preferred sulfonated fatty acid glycerol esters are the sulfonated products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, myristic acid, palmitic acid, stearic acid or behenic acid.
    Another class of anionic surfactants is the class of ether carboxylic acids obtainable by reaction of fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. Suitable anionic surfactants are also the partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycols with the ene adducts of maleic anhydride with at least monounsaturated carboxylic acids having a chain length of 10 to 25 carbon atoms and preferably with an acid number of 15 to 130. Alternatively usable anionic surfactants are the sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates.
    Nonionic surfactants are usually surfactants which contain essentially no dissociable functional groups and therefore do not separate into ions in water. Like any other surfactant, the nonionic surfactants are composed of one unpoetic and one polar part. As a more non-polar part, the nonionic surfactants preferably contain a fatty alcohol (e.g., C12-Cis) or z. As an octyl or nonylphenol. As the polar part, the nonionic surfactants preferably contain hydroxyl groups or ether groups.
    Examples of nonionic surfactants are: [0046] polyalkylene glycol ethers; Fatty alcohol ethoxylates (FAEO), in particular of the formula CH3- (CH2) io-i6- (O-C2Fl4) i_25-OH; Fatty alcohol propoxylates (FAPO), in particular of the formula CFIII- (CH2) io-i6- (O-C3F16) i-25-OFI alkylglucosides; Alkylpolyglucosides (APG), in particular the formula CFIII- (CFl2) io-i6- (0-glycoside) i-3 -OFI; Octylphenolethoxylates, in particular of the formula C8Fli7- (C6Fl4) - (O-C2H4) i.25-0H; and / or nonylphenol ethoxylates, in particular of the formula C9Hig- (C6Fl4) - (O-C2H4) i.25-0H.
    Cationic surfactants are surfactants which have a positively charged functional group. Preference is given to quaternary ammonium compounds of the formula RiaR2aR3aR4aN "^ X, Wherein Ria bls R4a olo are organic radical having 4 to 20 carbon atoms, preferably stearyl, palmityl, methyl, benzyl, butyl radicals and X is a counterion, preferably a halide , is.
    Amphoteric surfactants are surfactants which possess both a negatively and positively charged functional group. The nonpolar part is preferably an alkyl group, and the polar part is preferably a carboxylate group (R-COO) and a quaternary ammonium group.
    In the case of dishwashing detergents, in a preferred embodiment, in particular polyoxyethylene sorbitan fatty acid esters (available, for example, as Span® or Tween® 80) and / or a C 12 -C 16 -alcohol polyethylene glycol ether (obtainable, for example, as Marlox® MO 154) are used as surfactants. In the case of liquid dishwashing detergents, advantageous stability has been demonstrated here.
    Other preferred surfactants are nonionic low-foaming or solid surfactants, e.g. sold under the trademarks Genapol (e.g., Genapol EP 2584), Lutensol (e.g., Lutensol AT 25), and Plurafac (e.g., Plurafac LF 901) and belonging to the class of alkylpolyglycol ethers and fatty alcohol ethoxylates, respectively.
    The agent of the invention contains 0.01 to 20 wt .-%, more preferably 0.5 to 20 wt .-%, and even more preferably 0.5 to 15 wt .-%, particularly preferably 0.2 to 15 Wt .-% of one or more complexing agents, based on the total weight of the composition.
    Chelating agents are ligands that have two or more binding sites. As a result, they form particularly stable complexes with polyvalent metal ions. Examples of complexing agents are nitrilotriacetate (NTA), ethylenediamine triacetate (TED), ethylenediaminetetraacetate (EDTA), methylglycine diacetate (MGDA) (e.g., Trilon M), oxalate, maleate, tartrate, and / or citrate, most preferred are sodium salts thereof. Even if in the case of citrate / citric acid, these can be used as electrolytes (and / or pH regulators), it is preferred that the above-mentioned complexing agents are present in the stated amounts.
    Further examples of complexing agents are polyacrylic acid and salts thereof (e.g., so-calanic PA 30 CL, a low molecular weight polyacrylic acid completely neutralized as the sodium salt) and the natural polysaccharide alginate and salts thereof.
    Most of such chelating agents are often combined in detergents with other electrolyte type additives under the general term "builders".
    Frequently, these water-soluble substances or non-water-soluble substances, such as aluminosilicates and in particular zeolites, can be used as builders.
    Zeolites suitable as builders include, for example, zeolite A, zeolite X, zeolite Y and zeolite P.
    Other suitable builders are, for example, polyacetals obtained by reaction of
    Dialdehydes can be obtained using Polyolcarboxylsäure, preferably having 5 to 7 carbon atoms and at least three hydroxyl groups. Preferred polyacetals are obtained with dialdehydes, such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and of polyol carboxylic acids, such as gluconic acid and / or glucoheptonic acid.
    Other suitable organic builders are dextrins, i. Oligomers or polymers of carbohydrates which can be obtained by partial hydrolysis of starch. Furthermore, polyacrylates, pectinates and alginates can be used as builders, which in the context of the present invention can also be regarded as "complexing agents".
    Alternatively, phosphate-based builders may be used. However, these are not preferred for reasons of environmental protection. Examples are sodium tri-polyphosphate, sodium pyrophosphate and sodium orthophosphate.
    Phosphonates, which may also be considered as suitable builders or chelating agents, are mentioned only as a specific example sold under the trademark Bayhibit (e.g., Bayhibit S). The detergent of the invention is preferably phosphate-free or contains only small amounts (e.g., up to 0.19% by weight of phosphonate).
    The aforementioned complexing agents as well as the following electrolyte-type agents can be considered as suitable builders capable of supporting the observed cleaning effect of the carbamide.
    In a preferred embodiment, the agent according to the invention also contains one or more stabilizers. Stabilizers are usually used as a solution and / or dispersion-promoting component. Preference is given to using polyalcohols as stabilizers. Polyalcohol is understood as meaning substances which comprise two or more alcohol groups. Examples of suitable stabilizers are glycol, propylene glycol, polyalkylene glycol, in particular polyethylene glycol (for example Pluriol®), polypropylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
    The composition of the invention may additionally contain stabilizers in an amount of 0.01 to 20 wt .-%, preferably from 0.1 to 5 wt .-%, in particular, if it is an inventive composition in liquid form.
    In a preferred embodiment, the agent according to the invention may further contain one or more antibacterial and / or antimycotic and / or antimicrobial additives, in particular in the case of a liquid preparation.
    The antibacterial and / or antifungal and / or antimicrobial additive is typically included in an amount of 0.01 to 5 wt.%, Preferably 0.1 to 2 wt.%, For example, food chemically approved preservatives such as Sodium formate, sodium sorbate or PHB esters and suitable additives with an antimicrobial spectrum of activity.
    In the case of a hand dishwashing detergent or a hand cleaner, so a cleaner such as a washing paste for cleaning the skin surfaces, especially the hand, it is also preferred that the inventive composition contains one or more skin-care components. This is usually contained in an amount of 0.1 to 5 wt .-%, preferably from 1 to 3 wt .-%. As skin-care component z. As amino acids or fruit acids suitable. Preference is given to using proline.
    The detergent according to the invention contains enzymes. These enzymes are in an amount of 0.01 to 10 wt .-%, preferably up to 5 wt .-% (eg 0.01 to 5 wt .-%, in particular 1 to 5 wt .-%), particularly preferably 0 , 1 to 3 wt .-%, in particular 0.5 to 2.5 wt .-%, based on the total amount of the agent included.
    Examples of suitable enzymes are proteases, lipases, amylases and cellulases. Examples of commercially available coated enzyme preparations in solid form are e.g. Savinase 6.0T, Lipolase 100T and Termamyl 120T.
    Further examples of enzymes include: proteases such as BLAP® 140 (Henkel), Optimase® M-440, Optimase® M-330,
    Opticlean® -M-375, Opticlean® -M-250 (company: Solvay Enzymes); Maxacal® CX 450,000, Maxapem® (company: Ibis); Savinase® 4.0T, 6.0T, 8.0T (Novo); Esperase! (Company: Ibis); - Amylases such as Termamyl® 60 T, 90 T, Duramyl® (company: Novo); Amylase-LT® (company:
    Solvay enzyme); Purafect OxAm® (company: Genencor); Maxamyl® P 5000, CXT 5000 or CXT 2900 (company: Ibis); in particular α-amylases such as Termamyl®, Termamyl®ultra, Duramyl® (company: Novozymes); Purastar®ST, Purastar®OxAm (company: Genencor); Keistase® (company: Daiwa Seiko); Lipases such as Lipolase® 30 T (company: Novo).
    In addition to the aforementioned components, the agent according to the invention may also contain one or more odorous substances. Odors are natural or synthetic substances that have a smell, especially a pleasant smell. Examples of fragrances are: ambrettolide, [alpha-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthanucleanic acid, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, [alpha] bromostyrene, n -Decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydraquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole , Jasmine, camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, p-methoxy-acetophenone, methyl-n-amyl ketone, methyl-anthranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-ss-naphthylketone, methyl-n nonylacetaldehyde, methyl n-nonyl ketone, muskon, ss-naphthol ethyl ether, ss-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octyl aldehyde, p-oxyacetophenone, pentadecanolide, ss-phenylethyl alcohol, phenylacetaldehyde-dimethyl acetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, methyl salicylate, salicylic acid hexyl ester, cyclohexyl salicylate, santalol, skatole, terpineol, thymes, thymol, [gamma] undelac-ton, vanilin, Veratraldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl esters, alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, Li-nayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral and / or citronellal.
    Also, essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, champaceae oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjunbal seed oil, helichrysum oil, Ho oil, Ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, ka-naga oil, cardamom oil, cassia oil, pine needle oil, copa [iota] vabalsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lemongrass oil, musk kernel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, Origanum oil, Palmarosa oil, Patchouli oil, Peruvian balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Star aniseed oil, Thuja oil, Thyme oil, Verbena oil, Vetiver oil, Juniper berry oil, Vermouth oil, Wintergreen oil, Ylang-ylang oil, Hyssop oil, cinnamon oil, cinnamon leaf oil and / or cypress oil.
    Particularly preferred odorants limonenterpene and / or orange terpenes are used.
    Odorants are usually used in an amount of 0.01 to 3 wt .-%, preferably from 0.01 to 2 wt .-%, based on the total weight of the composition. If desired, a combination of 2 or more fragrances, e.g. 2 to 10, used.
    A combination of odorous substances may be advantageous for covering a possibly occurring urea odor.
    In addition to the odorous substances, the agent according to the invention may also contain dyes (e.g., Kiwi Fruit Green or TAED Green).
    When the detergent according to the invention is in liquid form, it may contain water and / or one or more non-aqueous solvents.
    Suitable non-aqueous solvents are derived, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethyl-englykolmono-n-butyl ether , Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl 3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents can usually be used in the liquid dishwashing detergent or sanitary cleaner in amounts of from 0.1 to 90% by weight, preferably from 1 to 60% by weight, based on the total weight.
    In a further preferred embodiment, the agent according to the invention is present as a solid agent which is present in particulate form or in the form of compressed tablets or tablets. The composition according to the invention contains from 5 to 70% by weight, and most preferably from 5 to 60% by weight of electrolytes, based on the total weight of the composition.
    Depending on the powdery or liquid form, the dishwashing detergent preferably contains from 5 to 60% by weight of electrolytes.
    Salts, such as sodium sulfate or sodium chloride, influence physicochemical parameters, e.g. ionic strength, which may be beneficial to the cleaning activity of the agent used according to the ability to break intermolecular and intramolecular bonds (e.g., in proteins or carbohydrates).
    Preferred electrolytes are alkali metal or alkaline earth metal salts, more preferably alkali metal salts, in particular sodium salts. Examples are sodium sulfate or sodium chloride, sodium bicarbonate, sodium carbonate, trisodium citrate, sodium phosphate, sodium phosphonate, sodium acetate, sodium alginate, sodium maleate etc. According to the complexing and / or pH-controlling ability of the anions, trisodium citrate and sodium carbonate are preferably used in addition to pH-controlling buffer systems (eg, citric acid / sodium hydroxide and / or sodium carbonate / sodium bicarbonate). Therefore, it is a preferred embodiment that at least some of the electrolytes may be one or more substances capable of adjusting the pH (pH regulator). Such pH regulators are used to set a suitable pH of the cleaning agent (or, if an agent is in solid form, to adjust the pH of a 1 molar solution of the agent in water).
    Preferably, a pH of 7 to 12, in particular from 8 to 11, set in dishwashing detergents.
    In this case, the pH regulator is preferably an alkaline agent. Preferably, the alkaline agent is present in the form of a basic alkali salt and / or an alkaline earth salt and / or an alkali and / or alkaline earth metal hydroxide. Among these compounds, sodium is the preferred alkali metal. It is particularly preferred if the alkaline agent contains a mixture of sodium hydrogencarbonate (sodium bicarbonate) and sodium carbonate. Particularly advantageous results are achieved when sodium carbonate and sodium bicarbonate (sodium bicarbonate) are mixed so that about 2 to 4, especially 2.8 to 3.3 parts by weight of sodium bicarbonate (sodium bicarbonate) are added to two parts by weight of sodium carbonate. This mixture is then able to
    Range to about 8 to 11, in particular about 9 to 10, eingelegeln.
    Preferably, the acidic pH is adjusted from 1 to 6, especially from 2 to 4, in sanitary cleaners to dissolve limescale.
    In this case, the pH regulator is preferably an acidifying agent. Preferably, both inorganic and organic water-soluble free acids and anhydrides and their acid salts are used. In addition to the sodium or potassium hydrogen sulfate and / or carbamide phosphate, organic α-hydroxycarboxylic acids (fruit acids), such as citric acid, succinic acid, etc., for example, and / or their anhydrides may advantageously be used. These are also preferably usable in mixtures with amidosulfonic acids (e.g., citric acid and sulfamic acid in the ratio of 3 to 1).
    It is also possible that a raised viscosity of the agent according to the invention is expedient. For example, the agent according to the invention may be in the form of a gel. In this case, water or an organic liquid, e.g. Alcohol, as a filler and additionally added as a thickener.
    The viscosity of the composition according to the invention can be determined by conventional standard methods (for example Brookfield viscometer RVD-VII at 20 rpm and 20 ° C., spindle 3). Preferred liquid gelled agents may have viscosities of 20 to 4000 mPa.s, with values between 40 and 2000 mPa.s being particularly preferred.
    Suitable thickeners are inorganic or polymeric organic compounds. Mixtures of different thickeners can also be used.
    The inorganic thickeners include, for example, polysilicic acids, clay minerals, such as montmorillonites, zeolites, silicas, phyllosilicates and bentonites. The organic thickeners are derived from the groups of natural polymers, modified natural polymers and fully synthetic polymers. Naturally derived polymers which are used as thickeners are, for example, xanthan gum, agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, gellan gum, locust bean gum, starch, dextrins, gelatin and casein. In the case of liquid toilet sanitary cleaners preferably xanthan is used as a thickener. In the case of liquid dishwashing detergents, alginate, in particular sodium alginate, is preferably used as thickener.
    Modified natural substances come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose and methylhydroxyethylcellulose.
    If the agent according to the invention is in solid particulate form, the volume-average particle size (D50) is preferably 50 to 800 μm, more preferably 100 to 600 μm, in particular 150 to 450 μm. The particle size is determined as described above. It is likewise preferred that the agent according to the invention in particulate form has a "Hausner factor" of 1.03 to 1.3, more preferably of 1.04 to 1.20 and in particular of 1.04 to 1.15. By "Hausner factor" is meant the ratio of tamped density to bulk density. A corresponding particle size and a corresponding Hausner factor lead z. B. to an advantageous dissolution behavior and corresponding to a better cleaning result. (Information about the "Hausner Factor" can be found, for example, in: "Dosage Form II, Work Instructions for Laboratory, Pharmaceutical Technology", Eberhard Karls University, Tübingen, Germany).
    In the above statements, the possible constituents of the agent according to the invention were explained in detail. The individual constituents can in principle be combined as desired within the stated proportions and serve on a broad basis the development of effective cleaning agents. In particular, the preferred ranges of one component may be combined with the preferred ranges of the other component. Therefore, for the three areas of application machine dishwashing detergent, hand dishwashing detergent and toilet sanitary cleaner, more detailed investigations were carried out and surprisingly good cleaning results were achieved. These are described below both generally and by means of specific examples with test results.
    According to the present invention, the use of carbamide (urea) alone (100%) shows a surprisingly good cleaning performance and gloss of the glass and the dishes.
    The cleaning effect of the carbamide is significantly increased by the addition of electrolytes. In particular, the use of neutral salts such as sodium sulfate and / or sodium chloride or the use of trisodium citrate and / or the use of a basic buffer mixture of sodium carbonate and sodium bicarbonate is advantageous.
    The addition of surfactants enhances the cleaning activity especially with regard to the increased removal of grease and oil from the dishes.
    The addition of e.g. 1 to 2% enzymes (especially of enzymes with a high hydrolase activity at pH 8 to 10 and 40 to 50 Ό) further increases the cleaning performance in dishwashers. Among the commercially available enzymes (company: NOVOZYMES), enzyme preparations with amylase, lipase and protease activity bound to a carrier have been successfully used in dishwashing powders.
    Further improvements, e.g. In the removal of tea, coffee or rice contaminants, by adding small amounts (1 to 2%) Trilon M, a complexing agent that is readily biodegradable, polycarboxylate (Sokalan) and phosphonate (Bayhibit, preferably in amounts of only up to 0.19%).
    In particular, the preferred ranges of one component may be combined with the preferred ranges of the other components.
    It has further been shown that the use of a clear rinsing agent is not required. Furthermore, the addition of a bleaching agent is not necessary, which is particularly environmentally friendly.
    Another advantage is that the detergent according to the invention shows an ideal cleaning activity between 35 and 45 ° C. This leads to a significant reduction in energy consumption.
    Finally, the cleaning agent according to the invention shows a high storage stability.
    A preferred cleaning agent, in particular for use as a powdery dishwashing detergent, in particular as a dishwashing detergent, contains the following constituents: Carbamide: 25 to 70% by weight; Electrolyte: 10 to 50% by weight; Surfactant (especially nonionic): 1 to 5% by weight; Enzymes: 1 to 5 wt .-%; Complexing agent: 1 to 15% by weight; Odor substances: up to 0.1% by weight.
    According to the inventive method, the skilled person is able to partially replace the enzyme content of the enzyme-containing detergent for closed systems (in particular an enzyme-containing agent for cleaning, sanitizing and / or disinfecting), an enzyme-containing dishwashing detergent or an enzyme-containing sanitary cleaner. For example, if the enzyme-containing starting agent contains 10 g of enzyme, then when fully replaced, this amount is preferably replaced by 50 g to 500 g of carbamide. Due to the changed volume of the exchanged material, the adjustment of the further components could be required, e.g. a reduction in filler content.
    The process according to the invention leads to a cleaning agent, a sanitary napkin or a dishwashing detergent with a reduced enzyme content or to an enzyme-free cleaning agent.
    Thus, the object of the invention is also an enzyme-containing cleaning agent for closed systems, in particular an enzyme-containing agent for cleaning, sanitizing and / or disinfecting, with a content of 10 to 70 wt .-%, particularly preferably 20 to 70 wt .-% and in particular 20 to 60 wt .-% of carbamide, based on the total weight of the enzyme-containing detergent for closed systems.
    In summary, it should be noted that the agent according to the invention is a versatile source for countless applications due to its unexpectedly advantageous properties. The agent of the invention exhibits excellent solubility and containment for many fabrics. The main component of the composition according to the invention is very well tolerated by the skin as a neutral, toxicologically harmless natural substance and readily biodegradable. It has been found that carbamide is an unexpectedly good solubilizer, particularly in closed-system detergents (especially in cleaners, sanitizers and / or disinfectants), as well as in dishwashing detergents and sanitary cleaners. Despite the high amount of carbamide, the agent according to the invention is unexpectedly compatible with the surfaces to be cleaned, for example dishes and in particular with glasses. There is no unwanted etching on the surfaces to recognize. In addition, the agent according to the invention unexpectedly has no unpleasant odor.
    On the basis of the toxicologically and ecologically harmless carbamide the combination with other aforementioned biologically also harmless additives, e.g. also formulations with the claim "bio-cleaner".
    The invention will be illustrated by the following examples.
    EXAMPLES: [00124] An experiment based on the quality recommendations of the Industrial Association for Personal Care and Detergent e.V. was carried out. Test series A shows the advantageous properties of the composition according to the invention as a dishwashing detergent.
    Test Series A: Dishwashing Detergent [00126] AI: Methods The dishwashing agents were used according to the methods for determining the cleaning performance of automatic dishwashing detergents, IKW (Industrieverband Körperpflege und Waschmittel e.V.), Frankfurt a.M .; Special edition from SÖFW-Journal, 124th volume 11/98) tested.
    The cleaning performance of formulations according to the invention was tested in the following apparatus: [00129] Dishwashing machine: Mannmann table dishwasher TSG 704 [00130] The following parameters were selected: [00131] Program: Fast
    Water temperature: wash 49'C / rinse 55'C
    [00133] Program duration + holding time: 60 minutes [00134] Water consumption: 9.6 liters [00135] Dosing detergent: 10 g per rinse [00136] Dosing Rinse aid: no rinse aid used [00137] Dosing Ballast dirt: 15 g per rinse [00138 ] In order to achieve better differentiation of individual test products, in addition to the described individual soiling, ballast contamination was added to the cleaning cycle. This Ballastanschmutzung in the form of a frozen cube consists mainly of fat-like ingredients and protein and starchy foods. This additional dirt should simulate a dirt entry on easy-to-remove food particles and thus additionally burden the dishwasher.
    Before it could be started with the application of the individual stains, the various dishes had to undergo a thorough cleaning. This is particularly necessary because, due to the great persistence of some soiling, residues from previous tests could still be present on the dishes. Also newly inserted crockery parts should be subjected to a three-time basic cleaning before first use in the test. The test soils were prepared as follows: 1. Minced meat on porcelain plates - Mix 225g minced meat (half / half) and 75g whole egg [00142] - Mix minced meat / egg mixture (300 g) with 80 ml water and then Homogenize with a kitchen blender for 2 minutes [00143] - Weigh out 3 g ± 0.1 g of this mixture per plate and distribute evenly [00144] - 2 h dry at 70 in a drying oven [00145] Evaluation: Visually according to IKW photo catalog after staining with Carbolgentiana Violet 2. Starch Blend Preparation for 6 plates: [00148] Dissolve 2.6 g starch mix (potato and corn starch) in 200 ml of water [00149] - this 1.3% starch solution for 10 min heat at 95 ° C (cover beaker with aluminum foil) [00150] - Weigh out 29.5 g ± 0.1 g of this solution per plate [00151] - 4 h dry at 70 ° C. in drying oven [00152] - weigh plate after drying [ 00153] Evaluation:
    For better visual control, iodine (2.5 mM) was stained.
    [00156] 3. Oatmeal preparation for 6 plates: [00157] - Boil 25 ml of milk (1.5% fat), 75 ml of water and 5 g of oatmeal for 10 min. [00158] - 3 g of hot oatmeal soup evenly on the inner surface of the plate distribute [00159] - 2 h dry at 70 'in a drying oven [00160] evaluation: visually according to IKW photo catalog after staining with iodine (2.5 mM) [00161] 4. egg yolk [00162] - separate egg yolk from raw eggs [00163 ] - Weigh 1.0 g ± 0.1 g egg yolk mass per stainless steel dish and distribute evenly [00164] - 30 min dry at 70 ° C in a drying oven [00165] - weigh plate after drying [00166] Evaluation:
    [00167] A2: Evaluation The cleaning performance of different formulations was evaluated. The higher the score, the better the cleaning performance.
    A3: Formulation The following solid cleaning formulation was prepared:
    As standard, a commercially available powdered dishwashing detergent from a leading manufacturer (content> 30% phosphates, 5-15% acid-based bleach, less than 5% nonionic surfactants, polycarboxylates, enzymes (proteases, amylases)) was used.
    A4: Results The formulation described under A3 was tested according to the method described in AI and evaluated according to A2. It was found that the proposed formulation meets the requirements of a commercial dishwashing detergent.
    [00174] The cleaning performance of the particularly preferred formulation A3-1 was evaluated as an example:
    It could be shown that the cleaning performance of the formulation A3-5 in all categories (minced meat, oatmeal, starch mix and egg yolk) was significantly higher than the comparison standard.
    A5: Discussion In summary, it should be noted that the cleaning performance of the formulation according to the invention corresponds to the comparison standard and often even exceeds it. It has also been found that due to the present invention enzymes can be greatly reduced.
    B. Further examples: [00179] B1: dishwashing detergent
    权利要求:
    Claims (13)
    [1]
    claims
    A cleaning composition comprising (a) 10 to 70% by weight of carbamide; (b) 5 to 70% by weight of one or more electrolytes; (c) from 0.1% to 35% by weight of one or more surfactants; (d) 0.01 to 10% by weight of one or more enzymes; and (e) 0.01 to 20% by weight of one or more complexing agents.
    [2]
    2. Cleaning agent according to claim 1, comprising 20 to 60 wt .-% of carbamide.
    [3]
    3. Cleaning agent according to claim 1 or 2, comprising proteases, lipases, amylases and / or cellulases.
    [4]
    4. Cleaning agent according to one of claims 1 to 3, comprising nonionic surfactants.
    [5]
    5. Cleaning agent according to one of claims 1 to 4, comprising 5 to 60% by weight of electrolytes.
    [6]
    6. Cleaning agent according to one of claims 1 to 5, characterized in that the electrolytes alkali or alkaline earth salts, in particular sodium salts, are.
    [7]
    7. Cleaning agent according to one of claims 1 to 6, characterized in that the complexing agents are present as nitrilotriacetate (NTA), ethylenediamine triacetate (TED), ethylenediaminetetraacetate (EDTA), methylglycine diacetate (MGDA), and / or citrates, in particular sodium salts thereof.
    [8]
    8. Cleaning agent according to one of claims 1 to 7, comprising one or more stabilizer / s, in particular in an amount of 0.1 to 5 wt .-%.
    [9]
    9. Cleaning agent according to claim 8, characterized in that the stabilizers are glycol, propylene glycol, polyalkylene glycol, in particular polyethylene glycol, polyethylene glycol and polypropylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
    [10]
    10. Cleaning agent according to one of claims 1 to 9, characterized in that it is in the form of powder, granules or tablets.
    [11]
    11. Cleaning agent according to claim 10, characterized in that the tablets are present as pressed tablets.
    [12]
    12. Cleaning agent according to one of claims 1 to 11, characterized in that it contains pH regulator for adjusting a suitable pH of the cleaning agent.
    [13]
    13. Use of the cleaning agent according to one of claims 1 to 8 for closed systems, in particular as a dishwashing detergent or as a detergent for washing machines.
    类似技术:
    公开号 | 公开日 | 专利标题
    AT14818U1|2016-06-15|CLEANING AGENTS CONTAINING CARBAMIDE AND / OR AT LEAST ONE DERIVATIVE HIERVON
    EP1812542B1|2011-06-08|Fragrance combination comprising 3,7-dimethyloct-6-ene nitrile | as geranonitrile substitute
    KR101660304B1|2016-09-27|Dishwashing detergent composition comprising spinach extract and manufacturing method thereof
    WO2012035156A1|2012-03-22|Cleaning agent having a urea content
    WO2000065007A2|2000-11-02|Cleaning agents for hard surfaces
    CN108359543A|2018-08-03|The aerobic foam washing compound powder of environment-friendly highly efficient decontamination that safe pro-skin, profession are sterilized
    KR101565097B1|2015-11-02|liquid detergent composition
    DE2217021A1|1972-10-26|Cleaning agent containing stabilized fragrance mixtures
    WO2000031232A1|2000-06-02|Encapsulated detergent
    EP0994178B1|2003-02-05|Cleaning compositions and their use
    EP3083911B1|2018-03-21|Michael systems for odor stabilization
    DE60104512T2|2005-08-04|Lime soap dispersant and detergent and cleaning composition containing the same
    CN106544177A|2017-03-29|A kind of silver carboxymethyl chitosan antimicrobial laundry liquid and preparation method thereof
    DE19961660A1|2001-07-12|Care products for washing machines and dishwashers
    RU2038366C1|1995-06-27|Powdery detergent
    JP6905968B2|2021-07-21|Detergent composition for textile products
    KR20180112493A|2018-10-12|Liquid bleaching agent composition
    EP3083910B1|2017-09-06|Use of cnga2 agonists for enhancing the olfactory effect of an odorant
    EP1171560A1|2002-01-16|Cleaning agents for hard surfaces
    WO2005017084A1|2005-02-24|Dishwashing liquid with improved flavour perception
    JP6045942B2|2016-12-14|Solid detergent
    CN108567585A|2018-09-25|A kind of antibacterial moisturizing foam hand cleanser of easy wash type and preparation method thereof
    DE102009001486A1|2010-09-16|Biodegradable builders and co-surfactants
    同族专利:
    公开号 | 公开日
    US8252122B2|2012-08-28|
    US20120108484A1|2012-05-03|
    DE202010018137U1|2014-04-03|
    LT3192860T|2021-07-12|
    EP3192860A1|2017-07-19|
    EP3192860B1|2021-05-19|
    JP2012520910A|2012-09-10|
    WO2010105816A1|2010-09-23|
    CA2755644C|2016-01-19|
    JP2015212396A|2015-11-26|
    JP6137741B2|2017-05-31|
    HUE034365T2|2018-02-28|
    PL2408894T3|2017-12-29|
    ES2636615T3|2017-10-06|
    EP2408894B1|2017-05-10|
    US20100240759A1|2010-09-23|
    PL3192860T3|2021-11-22|
    DK2408894T3|2017-08-28|
    CA2755644A1|2010-09-23|
    EP2408894A1|2012-01-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE3833047A1|1988-09-29|1990-04-05|Henkel Kgaa|Acidic dishwashing compositions|
    WO1995018211A1|1993-12-30|1995-07-06|Ecolab Inc.|Method of making a solid alkaline cleaning composition|
    WO1998055582A1|1997-06-06|1998-12-10|Unilever Plc|Cleaning compositions in tablet form|
    WO2002044309A2|2000-12-01|2002-06-06|Bbt Bergedorfer Biotechnik Gmbh|Detergent|
    WO2002077149A2|2001-03-23|2002-10-03|Ecolab Inc.|Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment|
    BE678396A|1967-05-26|1966-05-31|S P R L Apiel|
    BE755475A|1968-11-19|1971-02-01|Fmc Corp|COMPOSITIONS FOR CLEANING AND DISINFECTING UTENSILS FOR SERVING FOOD AND BEVERAGE|
    US3957967A|1973-07-27|1976-05-18|Blendax-Werke R. Schneider & Co.|Agent for the care and the cleaning of teeth and dentures|
    DE2404494A1|1974-01-31|1975-08-14|Blendax Werke Schneider Co|Dentrifice cleaning compsn in tablet/powder form - contains urea and acts rapidly|
    DE2449354C3|1974-10-17|1980-04-30|Basf Ag, 6700 Ludwigshafen|
    JPS51144743A|1975-06-06|1976-12-13|Blendax Werke Schneider Co|Compound for artificial tooth washing|
    US4181621A|1975-07-08|1980-01-01|Blendax-Werke R. Schneider & Co.|Cleaning agents for dentures|
    NZ206210A|1982-11-16|1986-05-09|Unilever Plc|Foaming liquid detergent compositions containing sulphosuccinic acid esters and magnesium ions|
    NZ206212A|1982-11-16|1986-04-11|Unilever Plc|Foaming liquid detergent compositions containing sulphosuccinic acid esters and alkyl ether sulphates|
    GB8405266D0|1984-02-29|1984-04-04|Unilever Plc|Detergent compositions|
    GB8520550D0|1985-08-16|1985-09-25|Unilever Plc|Detergent compositions|
    DE3628406A1|1986-08-21|1988-02-25|Henkel Kgaa|TABLET SHAPED GLASS CLEANER|
    US4800038A|1988-01-21|1989-01-24|Colgate-Palmolive Company|Acetylated sugar ethers as bleach activators detergency boosters and fabric softeners|
    US5320783A|1992-11-04|1994-06-14|The Procter & Gamble Company|Detergent gels containing ethoxylated alkyl sulfate surfactants in hexagonal liquid crystal form|
    NZ278722A|1993-12-30|1997-03-24|Ecolab Inc|Solid cleaning composition comprising a hardening amount of urea and an effective amount of a cleaning agent|
    GB9407944D0|1994-04-21|1994-06-15|Procter & Gamble|Cationic bleach activators|
    CA2167971C|1995-02-01|2008-08-26|Paula J. Carlson|Solid acid cleaning block and method of manufacture|
    EP0807158A1|1995-02-02|1997-11-19|The Procter & Gamble Company|Automatic dishwashing compositions comprising cobalt catalysts|
    GB2318800A|1996-11-01|1998-05-06|Unilever Plc|Detergent composition|
    US6544944B1|1998-07-17|2003-04-08|Procter & Gamble Company|Detergent tablet|
    RU2131914C1|1998-07-17|1999-06-20|Всероссийский научно-исследовательский институт ветеринарной санитарии, гигиены и экологии|Washing and disinfecting composition|
    DE19921443A1|1999-05-10|2000-11-23|Bbt Bergedorfer Biotech Gmbh|Process for cleaning drain pipes for fatty wastewater|
    DE19923943A1|1999-05-25|2000-11-30|Bbt Bergedorfer Biotech Gmbh|Sanitary cleaning method and a sanitary cleaner|
    US6351486B1|1999-05-25|2002-02-26|Conexant Systems, Inc.|Accelerated selection of a base station in a wireless communication system|
    US6468956B1|2000-05-24|2002-10-22|Huish Detergents, Inc.|Composition containing α-sulfofatty acid ester and hydrotrope and methods of making and using the same|
    GB0207483D0|2002-03-28|2002-05-08|Unilever Plc|Fabric conditioning compositions|
    EP1354938A1|2002-04-18|2003-10-22|Unilever N.V.|Laundry tablets with improved dissolution behaviour|
    DE10260903A1|2002-12-20|2004-07-08|Henkel Kgaa|New perhydrolases|
    DE10311852A1|2003-03-17|2004-10-14|Henkel Kgaa|Textile treatment agents|
    DE102004029475A1|2004-06-18|2006-01-26|Henkel Kgaa|New enzymatic bleaching system|
    DE102004054620A1|2004-11-11|2006-06-08|Henkel Kgaa|Geranonitrile substitute|
    US20060293212A1|2005-05-05|2006-12-28|Ecolab Inc.|Stable solid compositions of spores, bacteria, fungi and/or enzyme|
    DE102005043188A1|2005-09-09|2007-03-22|Henkel Kgaa|Consumable products with changing odor images|
    DE102005043189A1|2005-09-09|2007-03-15|Henkel Kgaa|Consumable products with fragrance variety|
    CA2633163C|2005-12-12|2013-11-19|Vitech International, Inc.|Multipurpose, non-corrosive cleaning compositions and methods of use|
    DE102006021401A1|2006-05-08|2007-12-13|Henkel Kgaa|Amadoriases in detergents and cleaners|
    EP2035553A1|2006-06-06|2009-03-18|Total Raffinage Marketing|Lysophosphatidic acid acyltransferase genes and uses thereof|
    DE102007019428A1|2006-07-07|2008-10-30|Henkel Ag & Co. Kgaa|Washing, cleaning and care products 2|
    DE102007029643A1|2006-09-08|2009-01-15|Henkel Ag & Co. Kgaa|cleaning supplies|
    DE102007006630A1|2007-02-06|2008-08-07|Henkel Ag & Co. Kgaa|cleaning supplies|
    WO2008101810A1|2007-02-20|2008-08-28|Henkel Ag & Co. Kgaa|Use of urea derivatives in washing and cleaning compositions|
    US7915213B2|2007-04-27|2011-03-29|Church & Dwight Co., Inc.|High ash liquid laundry detergents comprising a urea and/or glycerine hygroscopic agent|
    US7828905B2|2007-05-04|2010-11-09|Ecolab Inc.|Cleaning compositions containing water soluble magnesium compounds and methods of using them|
    MX2009011622A|2007-05-04|2009-11-10|Ecolab Inc|Water soluble magnesium compounds as cleaning agents and methods of using them.|
    US7521412B2|2007-05-25|2009-04-21|Ecolab Inc.|Dimensionally stable solid rinse aid|
    WO2009059630A1|2007-11-05|2009-05-14|Ecolab Inc.|Solid block acid containing cleaning composition for clean-in-place milking machine cleaning system|
    US8252122B2|2009-03-17|2012-08-28|Bbt Bergedorfer Biotechnik Gmbh|Use of an agent that contains carbamide and/or at least a derivative thereof as a cleaning agent|US8951956B2|2008-01-04|2015-02-10|Ecolab USA, Inc.|Solid tablet unit dose oven cleaner|
    US8252122B2|2009-03-17|2012-08-28|Bbt Bergedorfer Biotechnik Gmbh|Use of an agent that contains carbamide and/or at least a derivative thereof as a cleaning agent|
    WO2012035156A1|2010-09-17|2012-03-22|Bbt Bergedorfer Biotechnik Gmbh|Cleaning agent having a urea content|
    IN2014CN03470A|2011-10-19|2015-07-03|Basf Se|
    US9574163B2|2012-10-26|2017-02-21|Ecolab Usa Inc.|Caustic free low temperature ware wash detergent for reducing scale build-up|
    US9605236B2|2012-10-26|2017-03-28|Ecolab Usa Inc.|Low alkaline low temperature ware wash detergent for protein removal and reducing scale build-up|
    US9394508B2|2012-10-26|2016-07-19|Ecolab Usa Inc.|Phosphorus free low temperature ware wash detergent for reducing scale build-up|
    US9133420B2|2013-01-08|2015-09-15|Ecolab Usa Inc.|Methods of using enzyme compositions|
    DE102013007024A1|2013-04-24|2014-10-30|Bbt Bergedorfer Biotechnik Gmbh|Pelletized cleaning agent, a process for its preparation and its uses|
    US9267096B2|2013-10-29|2016-02-23|Ecolab USA, Inc.|Use of amino carboxylate for enhancing metal protection in alkaline detergents|
    JP6468738B2|2014-06-26|2019-02-13|ライオン株式会社|Liquid cleaning agent|
    US9765286B2|2014-12-22|2017-09-19|Ecolab Usa Inc.|Warewashing composition containing alkanol amine phosphonate and methods of use|
    DE102015110425A1|2015-06-29|2016-12-29|Bbt Bergedorfer Biotechnik Gmbh|Pelletized cleaning agent, a process for its preparation and its use|
    WO2017004177A1|2015-06-30|2017-01-05|Ecolab Usa Inc.|Metal silicate and organic deposit inhibitor/dispersant for thermal recovery operations of hydrocarbon fuels|
    US10035949B2|2015-08-18|2018-07-31|Ecolab Usa Inc.|Fluoro-inorganics for well cleaning and rejuvenation|
    US10221376B2|2016-04-18|2019-03-05|Ecolab Usa Inc.|Solidification process using low levels of coupler/hydrotrope|
    EP3266860B1|2016-07-08|2020-04-08|The Procter and Gamble Company|Process for making a particle|
    US10421926B2|2017-01-20|2019-09-24|Ecolab Usa Inc.|Cleaning and rinse aid compositions and emulsions or microemulsions employing optimized extended chain nonionic surfactants|
    AU2018227530B2|2017-03-01|2020-06-25|Ecolab Usa Inc.|Mechanism of urea/solid acid interaction under storage conditions and storage stable solid compositions comprising urea and acid|
    法律状态:
    2018-11-15| MM01| Lapse because of not paying annual fees|Effective date: 20180331 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09003835|2009-03-17|
    EP09007638|2009-06-09|
    [返回顶部]