EP1141226A1 - Produit de nettoyage multiphase contenant du sulfonate de lignine - Google Patents

Produit de nettoyage multiphase contenant du sulfonate de lignine

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Publication number
EP1141226A1
EP1141226A1 EP99965459A EP99965459A EP1141226A1 EP 1141226 A1 EP1141226 A1 EP 1141226A1 EP 99965459 A EP99965459 A EP 99965459A EP 99965459 A EP99965459 A EP 99965459A EP 1141226 A1 EP1141226 A1 EP 1141226A1
Authority
EP
European Patent Office
Prior art keywords
weight
phase
agent according
volume
amounts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99965459A
Other languages
German (de)
English (en)
Inventor
Thomas Möller
Heinz-Dieter Soldanski
Stefanie Küch
Jürgen Noglich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1141226A1 publication Critical patent/EP1141226A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/30—Sulfonation products derived from lignin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • Multi-phase cleaning agent with lignin sulfonate Multi-phase cleaning agent with lignin sulfonate
  • the invention relates to multi-phase liquid cleaning agents with lignin sulfonate, which can be temporarily emulsified by shaking and can be used for cleaning hard surfaces, in particular glass, and to a method for cleaning hard surfaces.
  • the cleaning agents for hard surfaces that are common today are usually aqueous preparations in the form of a stable solution or dispersion which contain, as essential active ingredients, surface-active substances, organic solvents and, if appropriate, complexing agents for the hardness constituents of water, abrasives and cleaning alkalis.
  • Detergents 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 serving as mouthwash for the bacterial desorption of solid surfaces and living tissues, which are in the form of a 2-phase preparation and form a temporary oil-in-water emission of limited life when shaken, 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 after about 10 seconds to 30 minutes their education breaks down and separates.
  • Anionic surfactants impair the antibacterial effect.
  • European patent application 0 195 336 describes in two embodiments (1) and (2) rubbing agents for care products for sensitive surfaces, in particular (1) plastic surfaces or (2) compact disc disks, which contain an organic phase in addition to an aqueous phase , which consists of chlorofluorocarbon (CFRP) 1, 1, 2-tr ⁇ chlor-1, 2,2-tr ⁇ fluorethane. Furthermore, the agents are 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 10 . 12- Alkylsulfuric acid half-esters No statement is made about the stability of the emulsion that can be generated by rubble.
  • CFRP chlorofluorocarbon
  • the surfactant content is usually from 1 to 10% by weight, in particular from 2 to 8% by weight, but if necessary also above 10% by weight %, preference being given to anionic surfactants, in particular those having a sulfate or sulfonate group. Because of their environmentally harmful properties, in particular in connection with the ozone hole, however, the use of CFRP should be reduced or better avoided
  • Hair treatment agents in the form of a 2-phase system are known from the German Offenlegungsschnfte 195 01 184, '187 and' 188 (Henkel KGaA), which have an oil phase and a water phase, the oil phase preferably being based on Sihkonol and briefly miscible by mechanical action are
  • Substantive polymers are in particular polycarboxylates such as poly (vinyl pyrrolidon-co-acrylic acid), but also Poly (styrene sulfonate), cationic sugar and starch derivatives, and block copolymers composed of ethylene oxide and propylene oxide, the latter polyethers in particular having less substantivity
  • the object of the present invention was therefore to provide powerful, stable and easy-to-use agents for cleaning hard surfaces, which show separate phases, can be emulsified for use, remain homogeneous during use and then form separate phases again and after Counteract application on the hard surface of the rain or fogging effect, ie bring about an anti-rain effect or anti-fogging effect.
  • the invention in a first embodiment, relates to a liquid, multi-phase cleaning agent with at least two continuous phases, which has at least one aqueous phase I and a non-aqueous liquid phase II which is immiscible with this aqueous phase and which can be temporarily converted into an emulsion by shaking, and which contains at least one lignin sulfonate.
  • immiscible, nonaqueous phase means a phase which is not based on water as the solvent, in the nonaqueous phase II small amounts, based on phase II, of water of up to 10% by weight, usually not more than 5 wt .-%, can be contained in solution.
  • an agent according to the invention consists of a continuous aqueous phase consisting of the entire phase I and a continuous non-aqueous liquid phase consisting 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.
  • the invention relates to the use of at least one lignin sulfonate in a cleaning agent for hard surfaces to reduce the rain effect and / or the fogging effect.
  • the invention relates to a method for reducing the rain effect and / or the fogging effect on a hard surface treated with a liquid cleaning agent, the surface being treated with a liquid cleaning agent containing at least one lignin sulfonate in concentrated or diluted form.
  • the invention further relates to a method for cleaning hard surfaces, in particular glass, in which a cleaning agent according to the invention is shaken temporarily transferred to an emulsion, applied in amounts of 1.5 to 10 g per m 2 to the surface to be cleaned, preferably by spraying, and this surface is then optionally cleaned by wiping with an absorbent soft object.
  • a particular advantage of the present invention is that the lignin sulfonate according to the invention has an anti-rain and an anti-fog effect at the same time.
  • the agents according to the invention are also distinguished by an overall high storage stability.
  • the individual phases are stable on average for a long time without deposits being formed, for example, and the conversion into a temporary emulsion remains reversible even after frequent shaking.
  • the physical form of the agents according to the invention does not address the problem of stabilizing an agent formulated as an emulsion.
  • the separation of ingredients into separate phases can also promote 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 retained without the need for rinsing.
  • the content of at least one lignin sulfonate in the agent according to the invention is usually 0.001 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.05 to 5% by weight, particularly preferably 0.1 to 1.5% by weight and most preferably 0.15 to 0.5% by weight.
  • Ligninsulfonates are the salts of ligninsulfonic acid and have surface-active properties.
  • Lignin sulfonic acid is the reaction product of native lignin and sulfurous acid that results from the sulfite digestion of wood to obtain cellulose. In this digestion process, lignin is sulfonated on the C 3 side chains of the basic phenylpropane units. Depending on the bases used in the digestion process, water-soluble sodium, ammonium, calcium or magnesium salts of lignin sulfonic acid result. Data on the molar mass of the lignosulfonic acid vary with values from approx.
  • Ligninsulfonic acid or its salts, the ligninsulfonates are the main constituent of the sulfite waste liquors, from which they are isolated as a brown powder can (softwood lignin sulfonates, molecular weight 500 to 50,000 g / mol, hardwood lignin sulfonates, molecular weight 500 to 10,000 g / mol).
  • Suitable according to the invention are, for example, the alkali metal and alkaline earth metal sulfonates and the ammoniumignin sulfonates or mixtures thereof.
  • ligninsulfonate includes the use of ligninsulfonic acid, which may be neutralized in situ with an appropriate base.
  • Lignin sulfonates suitable according to the invention are, for example, under the trade name Zewa ® from Ligninchemie, for example the sodium lignin sulfonates Zewa ® EF, Zewa ® S, Zewa ® S 2, Zewa ® SL and Zewa ® SL 2 and the ammonium lignosulfonate Zewa ® DIS TR, under the Trade names Totanin ® from Nike Baeck Industries GmbH, for example the ammonium lignin sulfonate Totanin ® AM 5025-T2 and the calcium lignin sulfonate Totanin ® CA 2032, as well as under the trade names Borresperse ® (about 25% of the molecules have a molecular weight of more than 20,000 g / mol), Borrewell ® , Borrebond ® , Ultrazine ® , Ufoxane ® (Ultrazine ® , Ufoxane
  • the agent is essentially CFK-free, i.e. the non-aqueous liquid phase II is not based on CFRP. Due to the negative environmental influences of these compounds, 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 continuous phases I and II are delimited from one another by a sharp interface.
  • 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 a dispersant.
  • the continuous phase I or II is then reduced by the volume that 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 interfaces, 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 composition contains 35 to 95% by volume of phase I and 5 to 65% by volume of 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 I preferably represents the lower phase and the continuous phase II the upper phase.
  • the water-immiscible phase II is based on aliphatic gasoline hydrocarbons and / or terpene hydrocarbons.
  • the gasoline hydrocarbons preferably have a boiling point range from 130 to 260 ° C, in particular from 140 to 240 ° C, particularly preferably from 150 to 220 ° C, such as that with a boiling point range of 184 to 217 ° C, available for example as Shellsol ® T from Deutsche Shell Chemie AG (Eschborn).
  • Suitable terpene hydrocarbons are, for example, citrus oils such as the orange oil obtained from the peel of oranges, the orange terpenes contained therein, in particular limes, or pine oil, the pine oil extracted from roots and stumps.
  • Phase II can also consist exclusively of aliphatic gasoline hydrocarbons and / or terpene hydrocarbons.
  • phase II preferably contains gasoline hydrocarbons in amounts of at least 60% by weight, particularly preferably 90 to 99.99% by weight, in particular 95 to 99.9% by weight, extremely preferably 97 to 99% by weight
  • Suitable surfactants for the agents according to the invention are, in particular, from the classes of anionic and nonionic surfactants.
  • the agents preferably contain anionic and nonionic surfactants, the anionic surfactants being contained in phase I in particular.
  • the amount of anionic surfactant is based on that Phase I, 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
  • Containing agents containing nonionic surfactants, their concentration is preferably in phase I, based on phase I, 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, and in Phase II, based on phase II, usually not more than 5% by weight, 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, most preferably between 0.01 and
  • Suitable anionic surfactants are preferably C 8 -C 18 alkylbenzenesulfonates, in particular with about 12 C atoms in the alkyl part, C 8 -C 20 alkanesulfonates, C 8 -C 18 monoalkyl sulfates, C 8 -C 18 alkyl polyglycol ether sulfates 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid esters with 8 to 18 C atoms in the alcohol residues
  • EO ethylene oxide units
  • 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 coconut alkyl sulfate, sodium sec-alkane sulfonate with about 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkyl sulfates with 12 to 14 carbon atoms as well as sodium lauryl ether sulfate with 2 EO have proven to be particularly suitable
  • the nonionic surfactants are, above all, C 8 -C 18 alcohol polyglycol ethers, ie ethoxy-etherified alcohols having 8 to 18 C atoms in the alkyl part and 2 to 15 ethylene oxide units (EO), C 8 -C 18 carboxylic acid polyglycol esters with 2 to 15 EO, ethoxy-etherified fatty acid amides with 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides with 14 to 20 C atoms and long-chain alkylene polyglycosides with 8 to 14 C atoms in the alkyl part and 1 to 3 To mention glycoside units.
  • C 8 -C 18 alcohol polyglycol ethers ie ethoxy-etherified alcohols having 8 to 18 C atoms in the alkyl part and 2 to 15 ethylene oxide units (EO)
  • C 8 -C 18 carboxylic acid polyglycol esters with 2 to 15 EO ethoxy
  • 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.
  • Preferred nonionic surfactants in the aqueous phase are, in addition to the addition products of 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
  • 2 to 10 EO for example tallow fatty acid + 6-EO
  • the degree of ethoxylation for phase II is tailored to the length of the C chain in such a way that shorter C chains are combined with lower degrees of ethoxylation or longer C chains with higher degrees of ethoxylation
  • 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 are suitable as ether alcohols.
  • 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 ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred.
  • ratio of both preferably between 1: 2 and 4: 1.
  • Ethanol is particularly preferred in the context of the invention.
  • the agents can be converted into the temporary emulsion according to the invention by shaking preferably up to three times, in particular up to twice, particularly preferably once, the temporary emulsion generated by shaking over a period of time of about 0.5 to 10 minutes being sufficient for convenient use of the agent , preferably 1 to 5 min, in particular 1, 5 to 4 min, is stable, ie on the one hand, does not collapse immediately after the end of the chute and, on the other hand, does not persist in the long term.
  • constant is to be understood to mean that, after the respective time, at least 90% by volume of the agent is still present as the temporary emulsion generated by shaking.
  • 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) of 0.1 to 200 mPa-s, in particular 0.5 to 100 mPa s, extremely preferred
  • the agent or the phases contained can contain viscosity regulators, and the amount of viscosity regulator in phase I, based on phase I, is usually up to 0.5% by weight, preferably 0.001 up 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 the 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 acrylic acid copolymer Carbopol ® ETD 2623.
  • Carbopol ® by Goodrich
  • WO 97/38076 lists a number is further from the acrylic acid off-led polymers listed that also s 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 of these in turn the monoethanolamine.
  • 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.
  • At least one lignin sulfonate is used together with at least one further additive, which likewise has the effect of reducing the rain and / or fogging effect.
  • This can be one or more water-soluble additives and / or one or more additives which are essentially dissolved in the non-aqueous phase II in an agent according to the invention.
  • additives within the meaning of this particular embodiment which are essentially dissolved in an aqueous phase I in an agent according to the invention, are in particular (i) the noun polymers with hydrophilic groups of WO 96/04358 A1 (Procter & Gamble), in particular polycarboxylates such as poly (vinylpyrrolidone-co-acrylic acid), but also poly (styrene sulfonate), cationic sugar and starch derivatives and block copolymers composed of ethylene oxide and propylene oxide, with an average molecular weight of 10,000 to 3,000,000 g / mol, preferably 20,000 to 2,500,000 g / mol mol, in particular 300,000 to 2,000,000 g / mol, extremely preferably 400,000 to 1,500,000 g / mol, (ii) the amine oxide polymers, in particular poly (4-vinylpyridine-N-oxides), of WO 97/33963 A1 (Procter & Gamble) with an average molar
  • R 1 is a linear, aliphatic hydrocarbon radical having 1 to about 22 carbon atoms or a mixture of various such radicals
  • R 2 is a hydrogen atom or a lower alkyl radical having 1 to 6 carbon atoms
  • R 3 is a linear or branched, saturated or unsaturated, aliphatic see, optionally aryl-substituted, aeych or cyclic, hydrocarbon radical with 1 to about 78 carbon atoms and optionally one or more hydroxyl groups and / or ether groups -O- or a mixture of different such radicals
  • p a number from 0 to about 15 and q a number of Represents 0 to about 50 and the sum of p and q is at least 1, in particular epoxy-sealed polyalkoxylated alcohols of the aforementioned formula, in which R 1 is a linear, aliphatic hydrocarbon radical having 1 to about 22 carbon atoms or a mixture of various such radicals
  • R 2 is a hydrogen
  • the low molecular weight sodium salts L Omar ® LS, Lomar ® PW, Lomar ® PWFA 40 and Lomar ® PL 4 the high molecular weight sodium salts Lomar ® D and Lomar ® D SOL, the potassium salt Lomar ® HP as well as the ammonium salt Lomar ® PWA, and under the trade name Tamol ® from Fa.
  • X is a single bond, a C L s-alkylene group, a carbonyl group or a group CR 1 , where R 1 is a hydrogen atom or a C ⁇ s-alkyl group, Y is a single bond, a C ⁇ .s-alkylene group, a carbonyl group , a group CR 2 , where R 2 is a hydrogen atom or a C ⁇ alkyl group, or two hydrogen atoms, where the group "-Y-" then corresponds to "-H H-", R is a hydrogen atom, a C ⁇ - 6 - Alkyl group or mixtures thereof, m represents a number from 0 to about 20 and n represents a number from 0 to about 20 and the sum m + n> 0.
  • each alkoxylated dihydroxyaromatic is based on its solubility in the non-aqueous phase II, preferably non-more alkoxylated dihydroxyaromatic being used than is homogeneously soluble in the non-aqueous base of phase II.
  • Particularly preferred alkoxylated dihydroxyaromatics have a high solubility in aliphatic gasoline hydrocarbons which, as will be described below, represent a preferred basis for the non-aqueous phase II.
  • Dihydroxyaromatics ie formula A without the groups H [OCH (R) CH 2 ] m O- and -O [CH2CH (R)] n H, are, for example, biphenyl, diphenylmethane, 1, 1-diphenylethane, 1, 2-diphenylethane, 1,2-diphenylpropane, 1,3-diphenylpropane, 2,2-diphenyipropane, 1,2-diphenylbutane, 1,4-diphenylbutane, 2,2-diphenylbutane, 1,5-diphenyipentane, 3,3-diphenylpentane, fluorene, Fluorenone, anthracene and anthraquinone.
  • Known dihydroxyaromatics are, for example, the o, o'-biphenol and the bisphenols bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol B (2,2-bis - (4-hydroxyphenyl) butane) and bisphenol F (2,2'-methylenediphenol).
  • the alkoxylation of the dihydroxyaromatics to the invented Alkoxylated dihydroxyaromatics of the formula A according to the invention are possible by known alkoxylation methods and are usually carried out under basic or acid catalysis at elevated temperatures and under elevated pressure, a normal or a narrowed homolog distribution being obtained, depending on the conditions selected.
  • n represents the average total degree of alkoxylation of the alkoxylated dihydroxyaromatics of the formula A according to the invention and assumes values in the range of real numbers from above 0 to approximately 40, m and n at the molecular level for corresponding integers from 0 to approximately 20 according to the respective homolog distribution.
  • the corresponding average degrees of alkoxylation m and n are generally the same, while m and n can be the same or different at the molecular level.
  • the average total degree of alkoxylation is preferably 0.1 to 30, in particular 0.5 to 25, particularly preferably 1 to 20 and extremely preferably 1 to 5 to 15.
  • the ethoxylated and / or propoxylated dihydroxyaromatics of the formula A (R H and / or CH 3 ) preferred.
  • These can be mixed alkoxylates with ethyleneoxy (EO) and propyleneoxy (PO) units, preferably pure ethoxylates or, in particular, pure propoxylates.
  • dihydroxyaromatics of the formula A can also be used, in which R represents an ethyl, propyl, isopropyl, butyl, se ⁇ butyl, tert- butyl, pentyl and / or hexyl radical.
  • Preferred alkoxylated dihydroxyaromatics of the formula A have as group "-Y-" two hydrogen atoms "-H H-” and carry the alkoxylated hydroxy groups in particular in the 4- and 4'-position (with respect to X) according to formula B,
  • -X- is preferably a C 1-4 alkylene group -C (R 3 ) (R 4 ) -, in which R 3 and R 4 are H, CH 3 , CH 2 CH 3 or CH 2 CH 2 CH 3 , in particular a 2, 2-propylene or 2,2-butylene group.
  • Alkoxylation products of bisphenol A, which is also known under the name Dian, of the formula C, are particularly preferred,
  • Alkoxylated bisphenols A of the formula C for example, sold under the trade name Dianof ® by the company. Akzo Nobel, such as Dianol ® 22, Dianof 220 Dianof 22 D, Dianof 240 1, Dianof 264, Dianof 285, Dianof 33, Dianof 320 Dianof 340 and Dianof 33. and Dianof 3130.
  • At least one lignin sulfonate is used together with at least one alkoxylated dihydroxyaromatic compound of the formula A.
  • at least one lignin sulfonate is used together with at least one of the aforementioned water-soluble additives (i) to (vii).
  • at least one lignin sulfonate is used together with at least one alkoxylated dihydroxyaromatic compound of the formula A and at least one of the abovementioned water-soluble additives (i) to (vii).
  • the content of at least one of these further additives in an agent according to the invention is 0.001 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.05 to 5% by weight, particularly preferably 0.1 to 1 , 5% by weight and most preferably 0.15 to 0.5% by weight.
  • the agents according to the invention can contain further auxiliaries and additives as are customary in such agents.
  • auxiliaries and additives include dyes, perfume oils, 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% by weight in the cleaning agent. The lower limit of use depends on the type of additive and can be up to 0.001% by weight and below, for example in the case of dyes.
  • 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
  • anionic surfactant 0.01 to 10% by weight of anionic surfactant
  • nonionic surfactant 0 to 3% by weight of nonionic surfactant, 0.1 to 1.5% by weight of at least one lignin sulfonate,
  • nonionic surfactant 0 to 5% by weight of nonionic surfactant
  • Phases can also contain small amounts of dye.
  • the agent according to the invention is sprayable and can therefore be used in a spray dispenser.
  • Another object of the invention is accordingly a product containing an agent according to the invention and a spray dispenser.
  • the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers, self-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate.
  • Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US cited therein for spray dispensers. Patents, all of which are referred to in this regard and the contents of which are hereby incorporated into this application, are described.
  • the agents according to the invention are used in such a way that the agent temporarily converted into an emulsion by shaking is applied in amounts of, for example, about 1.5 to 10 g per m 2 , preferably 3 to 7 g per m 2 applies 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 particular a spray dispenser or a product according to the invention, in order to achieve a distribution which is as uniform as possible. Sponges or cloths are primarily suitable for wiping, which 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 by mixing them directly from their raw materials, then mixing them and then 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 relevant component as part of the division of solubility balances by diffusion .
  • Agents E1 to E3 according to the invention and comparative agent V1 were prepared by simply stirring the components according to Table 1 together.
  • E1 to E3 according to the invention containing the lignin sulfonate Zewa ® EF in different amounts, while V1 had no additive.
  • Cg. Served as an aliphatic gasoline hydrocarbon. 13 -lsoparaff ⁇ ne. All agents had a pH of 10 and contained a clear and transparent aqueous phase I at the bottom and a creamy whitish non-aqueous phase II at the top in a phase I to phase II volume ratio of 80 to 20 and separated by a sharp interface.
  • the aqueous phase I was slightly thickened by the polymer, so that the temporary emulsions generated by Scierein remained stable for about 3 minutes each, which was sufficient for the convenient application of the agent, and the phases were then separated again.
  • test rain prepared from tap water and 8 g / l of wfk carpet pigment dirt (55% by weight of kaolin, 43% by weight of quartz, 1.5% by weight of carbon black 101) were produced within about 4 seconds , 0.5% by weight iron oxide black; wfk code wfk-09 W) from w / Tc-Testgewebe GmbH (http://www.wfk.de), evenly sprayed onto the pretreated mirror surface. Immediately afterwards, wetting and droplet formation were evaluated and, after drying, dirt distribution and stain formation.
  • agents E1 to E3 according to the invention show both an anti-rain effect and an anti-fog effect.

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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)

Abstract

Les sulfonates de lignine peuvent (i) être continus dans un produit de nettoyage multiphase liquide qui contient au moins deux phases continues, à savoir une phase I aqueuse et une phase II liquide non aqueuse non miscible avec cette phase aqueuse, et qui se transforme temporairement en une émulsion par secouage ; ils peuvent (ii) être utilisés dans un produit de nettoyage destiné à des surfaces dures afin de réduire l'effet pluie et/ou l'effet condensation et (iii) être utilisés dans un procédé de réduction de l'effet pluie et/ou de l'effet condensation sur une surface dure traitée avec un produit de nettoyage liquide, la surface étant traitée avec un produit de nettoyage liquide sous forme concentrée ou diluée contenant au moins un composé aromatique dihydroxy alcoxylé de la formule (I). Enfin, ils peuvent (iv) être utilisés dans un procédé de nettoyage de surfaces dures, notamment de verre, selon lequel un produit de nettoyage selon (i) se transforme temporairement en une émulsion par secouage et est appliqué en quantité de 1,5 à 10 g pro m2 sur la surface à nettoyer, de préférence par pulvérisation. Ensuite, cette surface est nettoyée éventuellement par essuyage avec un objet doux absorbant.
EP99965459A 1998-12-23 1999-12-14 Produit de nettoyage multiphase contenant du sulfonate de lignine Withdrawn EP1141226A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19859808A DE19859808A1 (de) 1998-12-23 1998-12-23 Mehrphasiges Reinigungsmittel mit Ligninsulfonat
DE19859808 1998-12-23
PCT/EP1999/009889 WO2000039267A1 (fr) 1998-12-23 1999-12-14 Produit de nettoyage multiphase contenant du sulfonate de lignine

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EP1141226A1 true EP1141226A1 (fr) 2001-10-10

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EP (1) EP1141226A1 (fr)
AU (1) AU2096700A (fr)
CA (1) CA2292427A1 (fr)
DE (1) DE19859808A1 (fr)
WO (1) WO2000039267A1 (fr)

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DE19859808A1 (de) 2000-06-29
CA2292427A1 (fr) 2000-06-23
US6288015B1 (en) 2001-09-11
WO2000039267A1 (fr) 2000-07-06
AU2096700A (en) 2000-07-31

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