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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0017—Multi-phase liquid 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds

Definitions

• the invention relates to multiphase liquid, essentially chlorofluorocarbon (CFRP) -free cleaning agents which can be temporarily emulsified by rubble and can be used for cleaning hard surfaces, in particular glass, and a method for cleaning hard surfaces.
• CFRP chlorofluorocarbon
• the cleaning agents for hard surfaces which are customary today are generally aqueous preparations in the form of a stable solution or dispersion which, as essential active substances, have surface-active substances, organic solvents and, if appropriate, complexing agents for the hard constituents of water, abrasives and cleaning alkalis contain.
• Cleaning agents which are primarily intended for cleaning glass and ceramic surfaces, are often formulated as solutions of the active substances in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such agents can be found in German Offenlegungsschrift 22 20 540, US Pat. Nos. 3,839,234 and 3,882,038 and in European Patent Applications 344 847 and 393 772.
• German Offenlegungsschrift 39 10 170 describes compositions which serve as mouthwash for the desorption of bacteria from solid surfaces and living tissues and which are in the form of a 2-phase preparation and form a temporary oil-in-water emulsion of limited life when shaken, where the aqueous phase comprises about 50 to 97% by weight and the water-immiscible oil phase comprises about 3 to 50% by weight.
• Essential to the invention is a content of about 0.003 to 2% by weight of an amphiphilic cationic agent, for example a cationic surfactant, in an amount which enables the formation of the oil-in-water emulsion, this emulsion being about 10 seconds to 30 Minutes after their formation breaks down and separates.
• Anionic surfactants impair the antibacterial effect.
• European patent application 0 195 336 describes in two embodiments (1) and (2) care products for sensitive surfaces which can be emulsified by shaking, in particular (1) plastic surfaces or (2) compact disc disks which, in addition to an aqueous phase, also contain an organic phase consisting of the CFRP 1, 1, 2-trichloro-1, 2, 2-trifluoroethane.
• the agents are also free of wax and contain in the aqueous phase (1) at least one surfactant and a water-soluble liquid silicone oil or (2) the triethanolamine salt of a C 1 -C 2 -alkylsulfonic acid half -ester. No statement is made about the stability of the emulsion that can be generated by shaking.
• the surfactant content is usually 1 to 10% by weight, in particular 2 to 8% by weight, but if necessary also more than 10% by weight, anionic surfactants, in particular those having a sulfate or sulfonate group , are preferred. Due to their environmentally harmful properties, especially in connection with the ozone hole, the use of CFRP should be reduced or better avoided.
• the invention relates to a liquid, multi-phase, essentially CFRP-free cleaning agent with at least two continuous phases, which has at least one aqueous phase I and one non-aqueous liquid phase II which is immiscible with this aqueous phase and which is temporarily ingested by rubble an emulsion can be transferred and which contains anionic and / or nonionic surfactant.
• an agent according to the invention consists of a continuous aqueous phase which consists of the entire phase I consists, and a continuous non-aqueous liquid phase, which consists of the entire phase II.
• one or more continuous phases of an agent according to the invention can also contain parts of another phase in emulsified form, so that in such an agent, for example, phase I is partly present as continuous phase I, which is the continuous aqueous phase of the agent, and one other part than discontinuous phase I is emulsified in the continuous non-aqueous phase II.
• phase II and other continuous phases are examples of phase II and other continuous phases.
• immiscible, non-aqueous phase means phase which is not based on water as the solvent, in the non-aqueous phase II small amounts, based on phase II, of water of up to 10% by weight, usually not more than 5 wt .-%, may be contained in dissolved form.
• essentially CFRP-free is to be understood to mean that the non-aqueous liquid phase II is not based on CFRP.
• the agents according to the invention preferably contain no CFRP at all, although small amounts, based on the total agent, of up to about 5% by weight are still tolerable.
• the invention furthermore relates to a process for cleaning hard surfaces, in particular glass, in which a cleaning agent according to the invention is temporarily converted into an emulsion by rubble, in amounts of 1.5 to 10 g per m 2 onto the surface to be cleaned, preferably by Spray, applied and this surface is then optionally cleaned by wiping with an absorbent soft object.
• the agents according to the invention are notable for high storage stability.
• the individual phases are stable on average for a long time without, for example, deposits being formed, and the conversion into a temporary emulsion remains even after frequent rubble. reversibly.
• the physical form of the agents according to the invention eliminates the problem of stabilizing an agent formulated as an emulsion per se.
• the separation of ingredients into separate phases can additionally require the chemical stability of the agent.
• the agents according to the invention have excellent residue behavior. Greasy residues are largely avoided so that the gloss of the surfaces is maintained without the need for rinsing.
• the continuous phases I and II are delimited from one another by a sharp boundary surface.
• one or both of the continuous phases I and II contain parts, preferably 0.1 to 35% by volume, in particular 0.2 to 20% by volume, based on the volume of the respective continuous Phase, the other phase as dispersant.
• the continuous phase I or II is then reduced by the part by volume which is distributed as a dispersant in the other phase.
• Agents in which phase I is emulsified in phase II in amounts of 0.1 to 35% by volume, preferably 0.2 to 20% by volume, based on the volume of phase II, are particularly preferred.
• part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion not being present due to two sharp boundary surfaces, an upper and a lower one parts of phases I and II involved in the emulsion are delimited.
• the agents according to the invention preferably contain 5 to 95% by volume of phase I and 95 to 5% by volume of phase II.
• the agent contains 35 to 95% by volume of phase I and 5 to 65% by volume Phase II, in particular 55 to 95% by volume of phase I and 5 to 45% by volume of phase II, extremely preferably 70 to 95% by volume of phase I and 5 to 30% by volume of phase II.
• the continuous phase also constitutes I preferably the lower phase and the continuous phase II the upper phase.
• the water-immiscible phase II is based on aliphatic petroleum hydrocarbons and / or terpene hydrocarbons.
• Suitable terpene hydrocarbons are, for example, citrusols such as orange oil obtained from the peel of oranges, the orange terpenes contained therein, in particular limonene, or pine oil, the pine oil extracted from roots and stumps.
• Phase II can also consist exclusively of aliphatic petroleum hydrocarbons and / or terpene hydrocarbons.
• Phase II contains petroleum hydrocarbons preferably in amounts of at least 60% by weight, particularly preferably 90 to 100% by weight, in particular 95 to 100% by weight, extremely preferably 99 to 99.99% by weight.
• Suitable surfactants for the agents according to the invention are surfactants, in particular from the classes of anionic and nonionic surfactants.
• the agents preferably contain anionic and nonionic surfactants, the anionic surfactants in particular being contained in phase I.
• the amount of anionic surfactant, based on phase I is usually not more than 10% by weight, preferably between 0.01 and 5% by weight, in particular between 0.01 and 0.5% by weight, particularly preferably between 0.1 and 0.3% by weight. If the agents contain nonionic surfactants, their concentration in phase I, based on phase I, is usually not more than 3% by weight, preferably between 0.001 and 0.3% by weight and in particular between 0.001 and 0.1% by weight.
• phase II based on phase II, usually not more than 5 wt .-%, preferably between 0.001 and 0.5% by weight and in particular between 0.001 and 0.2% by weight, particularly preferably between 0.005 and 0.1% by weight, extremely preferably between 0.01 and 0.05% by weight.
• Suitable anionic surfactants are preferably C 8 -C ⁇ 8 - alkylbenzene sulphonates, particularly from about 12 carbon atoms in the alkyl part, C 8 -C 20 alkanesulfonates, C 8 -C ⁇ -Monoalkylsulfate 8, C 8 8 alkyl -C ⁇ polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid esters with 8 to 18 C atoms in the alcohol residues.
• EO ethylene oxide units
• 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 amine salts.
• surfactants examples include sodium cocoalkyl sulfate, sodium sec. -Alkanesulfonate with about 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkyl sulfates with 12 to 14 carbon atoms and sodium lauryl ether sulfate with 2 EO have proven particularly suitable.
• the nonionic surfactants are especially C 8 -C 18 alcohol polyglycol ethers, ie ethoxylated alcohols having 8 to 18 C atoms in the alkyl part and 2 to 15 ethylene oxide units (EO), C 8 -C 8 carboxylic acid polyglycol esters with 2 up to 15 EO, ethoxylated fatty acid amides with 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain ammoxides with 14 to 20 C atoms and long-chain alkyl polyglycosides with 8 to 14 C atoms in the alkyl part and 1 to 3 glycosidein to mention.
• EO ethylene oxide units
• C 8 -C 8 carboxylic acid polyglycol esters with 2 up to 15 EO
• ethoxylated fatty acid amides with 12 to 18 C atoms in the fatty acid part and 2 to 8 EO
• long-chain ammoxides with 14 to 20 C atom
• surfactants examples include oleyl-cetyl alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, coconut alkyl dimethylamine oxide and coconut alkyl polyglucoside with an average of 1.4 glucose units.
• nonionic surfactants in the aqueous phase in addition to ⁇ en addition products from ethylene oxide and fatty alcohols with in particular 4 to 8 ethylene oxide units, the alkyl polyglycosides, and of these in turn the representatives with 8 to 10 carbon atoms in the alkyl part and up to 2 glucose units.
• fatty alcohol polyglycol ethers with in particular 2 to 8 EO for example oleyl cetyl alcohol + 5-EO ether
• FSE fatty acid polyglycol esters
• nonionic surfactants - acidic + 6-EO esters particularly preferred.
• the degree of ethoxylation for phase II is matched to the length of the C chain in such a way that shorter C chains with lower degrees of ethoxylation or longer C chains with higher degrees of ethoxylation are combined ,
• Agents which contain anionic and nonionic surfactant are particularly preferred.
• Combinations of anionic surfactant in phase I and nonionic surfactant in phase II are particularly advantageous, for example combinations of fatty alkyl sulfates and / or fatty alcohol polyglycol ether sulfates in phase I with fatty alcohol polyglycol ethers and / or FSE in phase II.
• the cleaning agents according to the invention can contain water-soluble organic solvents in the form of lower alcohols and / or ether alcohols, but preferably mixtures of alcohols and ether alcohols.
• the amount of organic solvent is preferably 0.1 to 15% by weight, in particular 1 to 10% by weight, based on the aqueous phase I.
• ethanol, isopropanol and n-propanol are used as alcohols.
• Sufficiently water-soluble compounds with up to 10 carbon atoms in the molecule m are suitable as ether alcohols.
• ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotertiarbutyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether tyl ether and propylene glycol monobutyl ether are preferred.
• the weight ratio of the two is preferably between 1: 2 and 4: 1. Ethanol is particularly preferred in the context of the invention.
• compositions can be converted into the temporary emulsion according to the invention by preferably up to three times, in particular up to twice, particularly preferably once, the temporary emulsion, the temporary emulsion generated by Schuttein over a period of time of about 0.5 to 10 minutes sufficient for convenient use of the composition , preferably 1 to 5 min, in particular 1.5 to 3 min, ie on the one hand, does not collapse immediately after the rubble ends and, on the other hand, does not remain in the long term.
• a regulation for setting the latter properties of the agents according to the invention consists in controlling the viscosity of the individual phases.
• the aqueous phase I preferably has a Brookfield viscosity (model DV-II +, spindle 31, rotational frequency 20 min "1 , 20 C C) of 0.1 to 200 mPa-s, in particular 0.5 to 100 mPa-s, au - Most preferably 1 to 60 mPa.s.
• the agent or the phases it contains can contain viscosity regulators.
• the amount of viscosity regulator in phase I, based on phase I, is usually up to 0.5% by weight. preferably 0.001 to 0.3% by weight, in particular 0.01 to 0.2% by weight, extremely preferably 0.05 to 0.15% by weight.
• Suitable viscosity regulators include synthetic polymers such as homo- and / or copolymers of acrylic acid or its derivatives, for example the products available under the trade name Carbopol ® by Goodrich, in particular the cross-linked Acrylsaurecopolymer CarJbo- pol -ETD-262y.
• Carbopol ® by Goodrich
• WO 97/38076 is a number of other of the acrylic acid derived polymers led, which also represent suitable viscosity regulators.
• the agents according to the invention can furthermore contain volatile alkali in phase I.
• ammonia and / or alkanolamines which can contain up to 9 carbon atoms in the molecule, are used.
• the ethanolamines are preferred as alkanolamines, and the monoethanolamine in turn is preferred.
• the content of ammonia and / or alkanolamine, based on phase I, is preferably 0.01 to 3% by weight, in particular 0.02 to 1% by weight, particularly preferably 0.05 to 0.5% by weight ,
• the agents according to the invention can additionally contain carboxylic acid in phase I, the equivalent ratio of amine and / or ammonia to carboxylic acid preferably being between 1: 0.9 and 1: 0.1.
• Carboxylic acids with up to 6 carbon atoms are suitable, which may be mono-, di- or polycarboxylic acids.
• the content of carboxylic acid, based on phase I is preferably between 0.01 and 2.7% by weight, in particular between 0.01 and 0.9% by weight.
• carboxylic acids examples include acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, of which acetic acid, citric acid and lactic acid are preferably used.
• Acetic acid is particularly preferably used.
• the agents according to the invention can contain further auxiliaries and additives as are customary in such agents.
• auxiliaries and additives include in particular dyes, perfumes, pH regulators (e.g. citric acid, alkanolamines or NaOH), preservatives, complexing agents for alkaline earth ions, enzymes, bleaching systems and antistatic substances.
• the amount of such additives is usually not more than 2 Ge-l in the detergent. The lower limit of use depends on the type of additive and can, for example, be up to for dyes 0.001 wt .-% and below.
• the amount of auxiliaries is preferably between 0.01 and 1% by weight.
• the pH of the aqueous phase I can be varied over a wide range, but a range from 2.5 to 12, preferably 5 to 10.5, in particular 7 to 10 is preferred.
• the agents according to the invention contain 70 to 95% by volume of aqueous phase I, containing
• anionic surfactant 0.01 to 10% by weight of anionic surfactant
• nonionic surfactant 0 to 3% by weight of nonionic surfactant
• perfume 0 to 1% by weight of perfume, the details in% by weight being based on the respective phase, the sum of the gasoline and terpene hydrocarbons phase II to 100% by weight and the phases additionally comprising small amounts of dye can contain.
• the agents according to the invention are used in such a way that the agent temporarily converted into an emulsion by rubble in amounts of, for example, about 1.5 to 10 g per m 2 , preferably 3 to 7 g per m 2 , towards which applied cleaning surface and immediately wipes these surfaces with an absorbent soft object and thereby cleans them.
• the agents are preferably applied with the aid of suitable spray devices in order to achieve a distribution that is as uniform as possible. Sponges are primarily suitable for wiping or cloths that can be rinsed out with water from time to time when treating larger areas.
• the agents according to the invention are produced by separately mixing the individual phases directly from their respective raw materials, then combining and mixing the phases and finally standing the agent to separate the temporary emulsion. They can also be prepared directly from their raw materials by mixing, then mixing and finally standing the agent for separating the temporary emulsion. Insofar as a component is not completely insoluble in a phase other than the phase to which the respective component is attributed or with which it was introduced into the agent, this other phase can also contain corresponding proportions of the component in question as part of the adjustment of solubility equilibria by diffusion ,
• Phase I a) anionic surfactants ([1] Sodium C 12 -i4-fatty alkyl sulfate, [2] Sodium C 12. 14, fatty alkyl-2EO-sulfate), b) nonionic surfactants, c) water-soluble solvent (Ethanol), d) emulsifier (Carbopol 2643) e) alkali (aqueous ammonia solution, 25% by weight) f) perfume and g) water, and in phase II h) aliphatic petroleum hydrocarbons
• the experimental formulations contained neither perfume nor in phase II
• composition of the basic formulation R and the formulations E1 to E5 according to the invention (proportions of phases I and II in% by volume, amounts of components a) to i) in% by weight) and the pH and the viscosity determined as described the aqueous phase I of agents El to E5 are listed in Table 1.
• Table 1 The composition of the basic formulation R and the formulations E1 to E5 according to the invention (proportions of phases I and II in% by volume, amounts of components a) to i) in% by weight) and the pH and the viscosity determined as described the aqueous phase I of agents El to E5 are listed in Table 1.
• the formulations according to the invention had a clear lower phase I and an upper phase II, which was slightly milky due to a small amount of emulsified phase I.
• the light remission was measured on white PVC sheets (40 mm * 554 mm), which were provided with a test soiling, after standardized treatment in the Gardener test device. The test dirt was exposed
• agents according to the invention show a cleaning performance which is at least equivalent to that of conventional single-phase agents, or even exceed their cleaning performance as in the case of the examples according to the invention.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (6)

• 1999
  • 1999-09-21 HU HU0202861A patent/HUP0202861A3/hu unknown
  • 1999-09-21 AU AU61938/99A patent/AU6193899A/en not_active Abandoned
  • 1999-09-21 WO PCT/EP1999/006982 patent/WO2001021751A1/de active Search and Examination
  • 1999-09-21 PL PL353935A patent/PL191444B1/pl not_active IP Right Cessation

Patent Citations (6)

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