EP3011002B1 - Mittel zur entfernung von flecken und ablagerungen - Google Patents

Mittel zur entfernung von flecken und ablagerungen Download PDF

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Publication number
EP3011002B1
EP3011002B1 EP14731263.1A EP14731263A EP3011002B1 EP 3011002 B1 EP3011002 B1 EP 3011002B1 EP 14731263 A EP14731263 A EP 14731263A EP 3011002 B1 EP3011002 B1 EP 3011002B1
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EP
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Prior art keywords
agent
weight
stains
styrene
acid
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EP14731263.1A
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German (de)
English (en)
French (fr)
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EP3011002A1 (de
Inventor
Joachim Leipold
Edgar Jaeschke
Antje Schirmer
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Buck Industries GmbH
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Buck Service GmbH
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • 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
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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

Definitions

  • the present invention relates to agents suitable for removing a variety of different stains and deposits on hard and soft surfaces.
  • the agent is particularly suitable for removing stains that are difficult to remove from soft, sensitive materials such as textiles.
  • the stains can be stains on the armpits of clothing, but also stains from chocolate, lipstick, shoe polish, red wine, turmeric, fat, lime, soap residues, feces, rust, blood and chewing gum.
  • the agent according to the invention is also suitable for removing stains or deposits from hard surfaces.
  • the agent according to the invention can also be used industrially to remove deposits, for example smoke gas resin in boiler systems and combustion chambers.
  • the agent according to the invention can also be used to remove contaminants on semiconductor surfaces. Use in etching processes is also possible. Another area of application is the removal of moss.
  • the US 4,931,207 teaches a liquid bleach with a polymeric matrix with hypochlorides.
  • the US 5,205,960 relates to an aqueous alkaline detergent solution with nonionic surfactants, a builder, hydrogen peroxide, water and a hydrolyzed polymer.
  • the US 4,968,447 teaches a detergent composition for removing stains with a high proportion of organic solvents, polyethylene and an abrasive material.
  • the US 5,449,473 teaches a detergent composition with surfactants, polybutene and bleach.
  • the US 2003/0083208 A1 concerns a furniture polish with mineral oil, styrene copolymers and organic solvents.
  • the US 2004/0229981 A1 relates to a means for removing bituminous material.
  • the US 2010/0300493 A1 concerns a soaking agent for pots and pans.
  • the US 5,965,512 relates to a liquid degreasing and cleaning agent with terpenes, surfactants and alkali.
  • the US 2005/238601 A1 relates to a liquid cosmetic cleaning agent which, in addition to surfactants, also contains alkylene styrene copolymer and oil and is used for good cleaning and skin improvement.
  • Acidic agents which are used in particular to remove stains on textiles in the armpit area, are from the WO 2011/077144 A1 known. These agents are strongly acidic (pH ⁇ 1) and include an acid, water and a surfactant. If desired, the agent can also be thickened with a gelling agent or a thickener such as, for example, ethoxylated fatty alcohols / ethoxylated fatty amines.
  • Acid containing agents for cleaning hard surfaces are from the WO 2009/085049 known.
  • the agents there include an organic acid, nonionic surfactants, water and a hydrophilic polymer that adsorbs on the hard surface.
  • This publication teaches the use of polybetaines as hydrophilic polymers which also adsorb on the hard surface.
  • stain remover which contains nonionic surfactants, anionic soaps and a polymer.
  • From the DE 199 35 259 A1 is a bleaching agent composition that can be used as a pre- or post-treatment agent for textiles.
  • the DE 10 2007 014 875 A1 teaches a liquid detergent that includes photocatalytic material, humectant, and surfactants.
  • the object of the invention is to provide a means which is suitable for the effective removal of stains and deposits on textiles, in particular in the armpit area, and for the removal of the above “difficult” stains, and at the same time which causes little or no damage to the surface to be treated becomes.
  • Another object is to provide an agent which is also suitable for removing deposits and stains on hard surfaces and in particular for removing deposits containing resin, grease or oil, also on an industrial scale and from moss.
  • the agent contains surfactants and an adhesion promoter in addition to the respective active substances such as acids, alkalis, bleaches and / or organic hydrophobic solvents not bound in a gel , wherein the coupling agent is selected from the group of alkylene styrene copolymers, where the polymers can also be hydrogenated.
  • active substances generally cause the actual stain removal.
  • the adhesion promoters serve to make the agent sticky, so that the agent adheres to the relevant stain or the deposit after application and does not flow or drip off.
  • the surfactants contained in the agent have a cleaning effect. They also help the hydrophobic coupling agent to dissolve in the presence of water.
  • the coupling agent which is generally hydrophobic, also has a protective and delaying effect. Water-soluble active ingredients are only released from the agent in the presence of water. Reactive active substances are previously protected in the hydrophobic matrix.
  • reactive active ingredients can also be formulated in the hydrophobic matrix without losing their effectiveness within a short time.
  • the agent for removing a wide variety of stains or deposits can be formulated.
  • the agent contains, in addition to surfactants and the adhesion promoter, at least 10% by weight of acid as the active ingredient.
  • Such an agent can be used to remove acid-soluble stains.
  • Such acidic agents for removing stains such as rust, blood or impurities on calcifications. Since the acidic agent does not attack the fibers, such an agent is suitable for removing stains and deposits, in particular on soft, sensitive surfaces such as woven, knitted or knitted fabrics, in particular on textiles, carpets or curtains.
  • the surfaces can, for example, be made of synthetic or natural fibers, natural or synthetic leather or also made of plastic.
  • the acidified agent according to the invention can of course also be used to remove such stains from hard, insensitive surfaces, for example on metal, ceramic, stone, glass, plastic or wood.
  • the agent comprises bleach as an active ingredient, for example salts of peracids such as perborates, percarbonates, persulfates or phthalimidoperoxohexanoic acid (PAP).
  • the bleaching agents are contained in the agent in a concentration of at least 5% by weight, preferably at least 8% by weight and particularly preferably at least 12% by weight.
  • a bleach activator such as, for example, tetraacetylenethylene diamine (TAED), nitrile quats, NOBS (nonanoyloxobenzenesulfonate) or DOBS (decanoyloxobenzenesulfonate) can be added to the agent.
  • TAED tetraacetylenethylene diamine
  • NOBS nonanoyloxobenzenesulfonate
  • DOBS decanoyloxobenzenesulfonate
  • the agent comprising bleach comprises at least 20% by weight of surfactants, at least 10% by weight of bleach and between 20% by weight and 60% by weight of adhesion promoter as a pure substance or as a solution in a hydrophobic solvent and, if appropriate, bleach activators and solubilizers, in a particularly preferred embodiment between 25% by weight and 40% by weight of surfactants, at least 10% by weight of salts of peroxyacids and between 30% by weight and 50% by weight of adhesion promoter, in particular alkylene-styrene copolymers, dissolved in hydrophobic solvents (Versagel).
  • Such agents are suitable for removing red wine, coffee or tea stains from soft, sensitive surfaces such as textiles and carpets, but also for removing red wine, coffee or tea stains from the aforementioned hard surfaces.
  • the agent is applied to the stain of the object in question, if necessary, waiting times or exposure times are observed, and the object is then washed, for example in a washing machine or also rinsed off.
  • the bleaching agents and the surfactants are gradually released from the agent on the stain and bleach the stain and transport the impurities into the wash liquor. Since the active ingredients are enclosed in the hydrophobic matrix of the coupling agent and are only released from it in the presence of water, overdoses of the active ingredients and thus damage to the tissue can be avoided.
  • the agent according to the invention can be formulated for removing fat-soluble and / or pigment-containing impurities such as lipstick, shoe polish, cocoa, fats or waxes.
  • the agent has, on the one hand, hydrophobic organic solvents which serve to dissolve the fats or waxes.
  • the hydrophobic organic solvents used for this purpose must therefore be freely available in the agent.
  • Solvents which are contained in the composition but which are necessary for gel formation, such as, for example, the hydrophobic solvents which act as solvents for gel formation in the failure which is particularly preferred as an adhesion promoter, are not freely available organic solvents in the sense of the invention.
  • Hydrophobic organic solvents for example terpenes, alkanes, mineral oils, long-chain alcohols (R> 10), esters or ethers, are therefore preferably added to the agent via the hydrophobic solvent required for gel formation.
  • the concentration of the free organic solvents in the composition is at least 10% by weight, preferably above 15% by weight and particularly preferably between 20% by weight and 40% by weight.
  • the agent should also contain alkalis, which on the one hand also serve to dissolve the fats and oils.
  • the alkalis also cause the fibers to swell and thus also make it easier for the Active ingredients penetrate sufficiently into the textiles and dissolved impurities can be removed again due to the swollen structure.
  • the concentration of alkalis in agents which additionally comprise hydrophobic organic solvents is at least 2% by weight and preferably at least 5% by weight.
  • Such alkaline agents with at least 2% by weight of alkalis, preferably NaOH or KOH, at least 20% by weight of free hydrophobic organic solvent, preferably terpenes, at least 10% by weight of coupling agent (preferably alkylene-styrene copolymer, dissolved in organic solvents such as failure) and at least 20% by weight of surfactants are suitable for removing grease and / or pigment-containing stains such as cocoa, lipstick, shoe polish, chewing gum and turmeric, preferably from soft, sensitive, in particular textile surfaces.
  • alkalis preferably NaOH or KOH
  • free hydrophobic organic solvent preferably terpenes
  • coupling agent preferably alkylene-styrene copolymer, dissolved in organic solvents such as failure
  • surfactants are suitable for removing grease and / or pigment-containing stains such as cocoa, lipstick, shoe polish, chewing gum and turmeric, preferably from soft, sensitive, in particular textile surfaces.
  • such an agent can also be used to remove stains from hard surfaces.
  • the agent is formulated with a very high proportion of alkalis, which is generally above 50% by weight and preferably above 60% by weight.
  • alkalis such as acrylic acid, styrene, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, greasy or oily contaminants or soot.
  • Such a strongly alkaline agent shows very good results when removing resin or fat deposits even on vertical surfaces (e.g. in slaughterhouses, with pipe clogging of fats (drain-opener), for removing keratinous substances (hair, horn)).
  • a strongly alkaline agent is only suitable in exceptional cases, eg for fabrics made of alkali-resistant fibers such as Teflon or PUR.
  • the agent according to the invention comprises surfactants, wherein anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants.
  • the surfactants not only serve for cleaning but also have the effect that the polymer adhering to the surface can be rinsed off again.
  • surfactants have a thickening effect on the polymers, i.e.
  • the viscosity of the agent can also be adjusted by adding surfactants, especially in powder form.
  • anionic and / or cationic and / or nonionic and / or amphoteric surfactants can be used as surfactants, powdered to highly pasty being preferred.
  • the surfactant content in the composition is 10% by weight to 60% by weight and particularly preferably 25% by weight to 45% by weight.
  • the anionic surfactants perform several tasks in the present invention. On the one hand, they serve to emulsify the polymer matrix without completely destroying the adhesive properties.
  • Preferred anionic surfactants are one or more substances from the group of the salts of the carboxylic acids, the sulfuric acid half-esters and the sulfonic acids, preferably from the group of the fatty acids Fatty alkyl sulfuric acids and the alkylarylsulfonic acids used.
  • the C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.
  • Carboxylic acids (C6-C22) in the form of their metal salts (preferably alkali salts) and their natural or synthetic mixtures as well as alkali salts of the sulfuric acid semiesters and longer-chain alcohols can also be used as anionic surfactants.
  • alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation gives the alkyl ether sulfuric acids concerned.
  • alkali metal salts of alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in the context of the present invention.
  • Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids).
  • Typical representatives are alkylbenzenesulfonates, particularly preferably linear alkylbenzenesulfonates (LAS).
  • anionic surfactants can be used in their neutralized form alone or in a mixture with one another.
  • the surfactant phase preferably contains 10% by weight to 90% by weight and particularly preferably 40% by weight to 85% by weight of lauryl sulfate, based on its weight.
  • Alkoxylated, preferably ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol can be used as nonionic surfactants are in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula alkyl-O (G) can also be used as further nonionic surfactants, alkyl being for a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol for a glycoside unit with 5 or 6 carbon atoms, preferably for glucose.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide or alkanolamides, can also be used.
  • the proportion of the nonionic surfactant or surfactants in the total surfactant phase can be up to 50%, preferably up to 30% and particularly preferably up to 25%.
  • the surfactant phase can also be provided with cationic or amphoteric and zwitterionic surfactants.
  • amphoteric surfactants are fatty acid amidopropyl betaines with C5-C21 fatty acid components, but also amphodiacetates.
  • Cationic surfactants are preferably also used as bactericidal substances in the present acidic formulation.
  • Zwitterionic surfactants can be described by way of example as quaternary ammonium, phosphonium or sulfonium components which are linked via an aliphatic bridge to another now anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
  • Olefin sulfonates, ether sulfates or methyl acid taurides can also be added to the agent as foaming agents. If strong foaming agents are to be used, preferably 1 to 50%, in particular 1 to 25%, of the surfactant phase can be passed through one or more foaming agents, e.g. from the group of betaines, the alkoxylated alkyl ether sulfates or lactobionic acid derivatives.
  • foaming agents can be selected from the fatty acid amidopropyl betaines with a C5-C21 fatty acid content such as, for example, coconut amidopropyl betaine, the alkali metal or ammonium salts of lauryl ether sulfates with 1 to 5 EO, the lactobionococoylamide, the lactobionooleylamide, the lactobionotalgamide, etc. or mixtures thereof.
  • These frothers can be easily incorporated into the agent according to the invention.
  • Those cosurfactants which are present in solid, preferably powdery or highly viscous form are preferably used.
  • adhesion promoters which are selected from a group of alkylene styrene copolymers, where the polymers can also be hydrogenated.
  • Diblock or triblock copolymers are selected as alkylene styrene copolymers, in particular from the group of styrene-butadiene-styrene copolymers (SBS), the styrene-isoprene-styrene copolymer (SIS), the styrene-ethylene-butylene-styrene copolymer (S-EB-S), the styrene-ethylene-propylene copolymer (S-EP), the styrene-ethylene-butylene copolymer (S-EB), the styrene-butadiene copolymers (SB) and styrene-isoprene copolymers (SI).
  • the alkylene styrene copolymers can also be hydrogenated or partially hydrogenated.
  • the hydrogenated or non-hydrogenated alkylene-styrene copolymers are preferably crosslinked.
  • the alkylene styrene copolymers are preferably dissolved in a solvent, in particular hydrophobic solvents such as mineral or vegetable oils, alkanes or aromatic hydrocarbons.
  • a solvent in particular hydrophobic solvents such as mineral or vegetable oils, alkanes or aromatic hydrocarbons.
  • the solvents should be aprotic and non-polar and preferably inert.
  • Such gels generally consist of about 1 to 20% by weight of polymers and 80 to 99% by weight of hydrophobic solvents such as mineral oil.
  • Alkylene styrene copolymers are offered, for example, in the form of a solution in a hydrophobic solvent from Penreco under the trade name Versagel, such as the Versagel M750 or the Versagel M1600.
  • Versagel such as the Versagel M750 or the Versagel M1600.
  • the company Kraton Performance Polymers offers alkylene-styrene copolymers as a solid under the trademark "Kraton”.
  • the agents are also sticky. It is hereby achieved that the agent adheres to the surface of the object in question and can thus act on the surface to be treated over a longer period of time when rinsing or washing.
  • the agent according to the invention further contains at least one active substance which is to be selected depending on the stain to be removed or the deposit to be removed.
  • Active substances in the sense of the present invention are acids, alkalis, bleaching agents and freely available organic hydrophobic solvents. Depending on the intended use, the agent may also contain several active substances.
  • the agent according to the invention contains acids as the active substance
  • the agent is suitable, for example, for removing stains from soft surfaces, such as stains from items of clothing in the armpit area, or from rust and blood stains or from impurities caused by calcifications.
  • Organic and inorganic acids can be used as acids.
  • Suitable organic acids are acetic acid, lactic acid, citric acid, levulinic acid, tartaric acid, formic acid, glycolic acid, succinic acid, glutaric acid, maleic acid, methanesulfonic acid, sulfamic acid or oxalic acid.
  • concentration of organic acids should be between 1% by weight and 60% by weight, preferably between 15% by weight and 40% by weight.
  • inorganic acids which can be used are sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid.
  • concentration of inorganic acids in the agent should be between 1% by weight and 40% by weight, preferably between 10% by weight and 30% by weight, in the case of an acidified agent.
  • the minimum content of acids (organic and / or inorganic) in the agent is at least 10% by weight.
  • the pH of a 1% solution of the agent with an acid should be pH 2 or less, preferably at most pH 1.5 and particularly preferably at most pH 1.
  • the agent comprises, as active substance, at least one oxidizing agent in addition to the at least one acid.
  • Such a variant is suitable for removing stains from rust, blood, sweat and oxidizable substances.
  • phosphoric acid with H 2 O 2 (stabilized) can be used.
  • the proportion of H 2 O 2 (absolute) in the average should preferably be between 2% by weight and 5% by weight.
  • An agent which comprises a high proportion of alkalis is suitable for removing resin stains, for example smoke resins.
  • alkalis for example oxides and hydroxides of alkali and alkaline earth metals such as NaOH, KOH or MgO or Na 2 O, preferably as a solid or as prills, can be used.
  • the proportion of alkalis in the composition can be 50% by weight and more, preferably at least 60% by weight and particularly preferably at least 70% by weight.
  • the pH of a 1% solution of an alkaline agent should be at least pH 9, preferably at least pH 10 and particularly preferably at least pH 11.
  • an agent which comprises alkalis and free hydrophobic organic solvents as active substance.
  • the alkalis serve to swell the fibers.
  • Alkali and hydrophobic solvents serve to make the fat-soluble To dissolve impurities and / or to modify them chemically, for example by ester cleavage.
  • the adhesion promoter is gelatinized in a hydrophobic solvent such as a mineral oil (for example as Versagel 1600) and the part of the mineral oil required for gel formation is not available as a hydrophobic solvent, the dissolution of fat-soluble ones Substances in the recipe only through "free", ie solvents not required for gel formation.
  • a hydrophobic solvent such as a mineral oil (for example as Versagel 1600) and the part of the mineral oil required for gel formation is not available as a hydrophobic solvent
  • additional hydrophobic solvents such as, for example, terpenes, in a proportion - depending on the stain to be removed - of at least 10% by weight and preferably up to 40% by weight. given.
  • the proportion of alkalis in such an agent is at least 2% by weight.
  • the free hydrophobic solvents already cause the oil-containing soiling to dissolve when the agent is applied to the stain.
  • the agent according to the invention can comprise alkalis and bleaching agents as the active substance.
  • bleaches which are stable in alkaline such as chlorine-releasing bleaches such as cyanurates or chlorine bleaching, preferably in a concentration of 0.01% by weight to 1% by weight, are additionally added to the agent described above with alkalis as the active substance.
  • Such an agent is suitable for removing stains from fabrics which are chlorine stable, preferably from undyed fibers.
  • the agent according to the invention can also comprise solubilizers in order to facilitate emulsification across phase boundaries.
  • Glycol ethers or sodium cumene sulfonate for example, can be used as solubilizers, preferably in a concentration between 1% by weight and 40% by weight.
  • agent according to the invention can also comprise humectants.
  • humectants Preferably polyalcohols such as. B. Glycerin or glycol used.
  • (co) thickeners can be added to the agent according to the invention in order to increase the plasticity of the agent.
  • (co) thickeners for example, bentonites, powder surfactants, xanthans, polybutadiene rubbers, polyisopropenes, block copolymers which comprise linked oligomers consisting of oligo or polyethylene oxide and / or oligo or propylene oxide and / or oligo or polybutylene oxide, and aryl ethoxylates or alkyl Aryl ethoxylates can be used.
  • the polymeric natural substances such as the lignins or their alkali or alkaline earth salts can also be used as (co) thickeners.
  • Sequestering agents such as sodium diphosphonate, which are useful, for example, for removing tea stains, can also be added to the agent.
  • Dispersants which, for example, keep Ca or Mg salts in the washing liquor in suspension, can also be present in the composition.
  • the agent can also comprise complexing agents such as phosphonates or EDTA.
  • hydrophobicizers such as Aerosil, in particular methylated Aerosil (from Carbot Carbon) can be added to the agent according to the invention as fillers.
  • the agent according to the invention can of course also comprise dyes, fragrances and enzymes (amylases, lipases, proteases, cellulases and peroxidases).
  • the agent can also contain malodor counteractants, which are preferably added to the fragrances.
  • malodor counteractants are for example in the US 7,288,507 B2 described.
  • the viscosity of the agent can be adjusted depending on the desired application and the type of application.
  • the viscosity of the agent should be so low that the agent can effectively wet the stain to be treated.
  • the viscosity of the agent should in turn be so high that it does not "run away" from the stain to be treated or the contamination and the amount applied can be metered.
  • the agents can be thin to viscous, depending on the type of surface or fabric on which they are applied and should adhere over a longer period of time.
  • the agent according to the invention is preferably pasty.
  • the agent has a viscosity of at least 30 Pa * s, in particular at least 100 Pa * s, measured with a Haake viscometer, plate / plate system, plate diameter 10 mm, with a shear rate of 2.62 s-1 and 20 ° C.
  • a paste can, for example, be spread onto the surface to be treated using a brush or spatula, where it adheres.
  • the stain remover according to the invention is applied to the area to be cleaned of the object to be treated, in particular the textiles, on the stain or in the armpit area with a brush or brush.
  • the stain remover adheres and then slowly releases the active substances in the presence of water in the alkaline wash liquor, which gradually dissolves the stain.
  • the residue from poorly soluble aluminum salts is present in the presence of water slowly decomposed by the acid released, without attacking the textile fiber.
  • the local medium around the stain is acidic, but the rest of the textiles are in an alkaline solution.
  • the agent according to the invention is generally suitable for removing stains from textiles of plant, animal or synthetic origin.
  • the agent is particularly suitable for removing deposits from deodorant with sweat on cotton textiles.
  • the stain remover according to the invention is first applied to the stain to be removed, where it adheres.
  • the applied stain remover is then removed again, for example by washing the treated article of clothing after a certain contact time of at least one minute in the washing machine or else by hand.
  • the water-soluble active substance i.e. the alkalis or bleach released locally around the stain and the stain removed.
  • the remaining "immaculate", in particular textile material, is mainly affected by the wash liquor or - if there is no washing in the washing machine with a detergent - water.
  • the active ingredient insofar as it is water-soluble, such as acids, alkalis or bleaching agents, is only released from the agent when it comes into contact with water, there is - compared to the agents known to date - tissue damage due to the fact that the stain remover is applied, but not then the necessary time is rinsed off, almost impossible.
  • the stain remover is completely removed from the surface, also as a result of the surfactants contained in the agent.
  • the agent according to the invention can also be used to remove blood, rust and iron stains or other acid-soluble stains.
  • the agent according to the invention can also be used to remove moss and other deposits, for example on stones.
  • benzalkonium chloride bronopol, glutaraldehyde, formaldehyde, triazine, dibromonitrile propionamide, perbutryn, IPBC, OIT and diuron can be used as the biocide.
  • the agent can also be used to remove impurities from copper or other metals on hard surfaces such as, for example, circuit boards.
  • the stain remover according to the invention is preferably applied to the object to be treated at room temperature and then rinsed off again with cold or warm water.
  • the agent according to the invention is particularly suitable for single use for removing stains and impurities, the entire agent being subsequently removed again with water after the application.
  • the composition should preferably be anhydrous or a water content of at most 5% by weight .% and particularly preferably have at most 1% by weight.
  • the following shows a frame formulation and an example formulation for an acidic agent according to the invention, which can be used, for example, to remove stains on textiles in the armpit area.
  • Area preferred area Polymer possibly dissolved in mineral oil
  • the agent based on the following recipe is referred to below as an "armpit cleaner”: Versagel 1600 (styrene copolymer dissolved in mineral oil) 15% surfactants Lutensol A05 (C13 / C15 oxo alcohol ethoxylate / 5 EO, BASF) 5% Lutensol A08 (C13 / C15 oxo alcohol ethoxylate / 8 EO, BASF) 15% Texapon SPN 70 (sodium lauryl ether sulfate, Cognis) 5% Solubilizer Eltesol SCS93 (cumene sulfonate, sodium salt, Rhodia) 15% acid amidosulfonic 30% Phosphoric acid (85%) 5% glycerin 10%
  • the armpit cleaner according to recipe II above was applied to stains on a blue multi-worn T-shirt in the armpit area.
  • Dr. Beck-mann's "Rost & Deo" stain devil applied according to instructions.
  • the washing conditions were as follows: 55 g washing powder per 4.5 kg washing, liquor ratio 1: 5, washing temperature 40 ° C., 250 mg / cm 2 armpit cleaner, exposure time 60 minutes, washing time 30 minutes, washing time 3 x 30 seconds, cold ,
  • FIG. 1 shows the starting material with the spots in the armpit area and the result after removal of the spot with the armpit cleaner according to the invention and with Dr. Beckmann's Spot Devil.
  • the stain in the armpit area is completely removed, whereas when treating the stain with Dr. Beckmann's stain devil clearly visible stains remain in the armpit area.
  • the respective test material was washed in a household washing machine based on DIN EN ISO 6330, on the one hand untreated, without paste and on the other hand with armpit cleaner.
  • 50 mg / cm 2 of the armpit cleaner paste was applied in the middle in a strip about 3 cm wide using a doctor blade and acted for 60 minutes.
  • the laundry was done at one Washing temperature of 40 ° C, normal wash, Laundry detergent: Mild detergent, Loading: 2 kg, Washer Type: Miele "Gala Grande”.
  • each test material was washed separately. The samples thus obtained were used as the basis for the further tests.
  • the tensile properties of the textile fabrics were determined in accordance with DIN EN ISO 13934-1, determination of the maximum tensile force and maximum tensile force elongation using the strip tensile test, date of issue: 1999-04 with clamping length 200 mm, strip width: 50 mm, test speed (chain) 100 mm / min, test speed (shot): 100 mm / min, preload force 2 N.
  • the tensile properties of the textile fabrics are determined in accordance with DIN EN ISO 13934-2, the maximum tensile force is determined using the grab tensile test, date of issue: 1999-04.
  • the following recipe is particularly suitable for removing the above stains on soft surfaces such as textiles.
  • Wt .-% Versagel M 1600 15 Lutensol TO3 (C13 oxo alcohol / 3 EO, BASF) 5 Lutensol AO 5 (C13 / C15 oxo alcohol ethoxylate / 5 EO, BASF) 5 Lutensol AO 8 (C13 / C15 oxo alcohol ethoxylate / 8 EO, BASF) 15 Eltesol SCS 93 (cumene sulfonate, sodium salt, Rhodia) 15 Sokalan PA30 CL (polyacrylate, BASF) 0.5 Orangenterpene 30 Glycerin (85%) 5 NaOH 5 Texapon SPN 70 (sodium lauryl ether sulfate, Cognis) 4.5 total 100
  • the NaOH contained in the agent acts as a fat dissolver and causes the fibers to swell, so that the constituents reach the fiber better and can be removed from it again.
  • the following agent can be used to remove stains with oxidative components such as dyes: Wt .-% Kelzan ASX (Xanthan Gum, Monsanto) 1.86 Eltesol 6.5
  • Tensopol USP94 Liauryl C12-C16 sulfate Na salt, manro) 31.64 Versagel M 1600 40 sodium 15 TAED 5 total 100
  • This formulation includes sodium perborate as a bleaching agent and TAED as an oxidation activator.
  • Figure 4 shows the removal of red wine stains with the agent according to the invention according to recipe X and for comparison with Dr. Beckmann's stain devil "Fruit &Beverages".
  • the figures show that the stain with the agent according to recipe X compared to Dr. Beckmann's stain devil is completely removed after one treatment.
  • the stain remover according to the invention according to recipe IX already removes the stain further and better stain removal after the first wash than with the Dr. also tested in the comparison Beckmann's Spot Devil "Fatty &Sauces". The comparison test is shown in FIG. 6 .
  • the stain paste according to the invention is applied evenly to the stain with the spatula.
  • the exposure time is 15 to 30 minutes.
  • Dr. Beckmann's stain devil is applied according to the instructions.
  • washing was carried out as follows in the concentration ratio: 55 g washing powder per 4.5 kg washing, liquor ratio 1: 5, washing temperature 40 ° C., ballast washing (BW terry cloth).
  • the washing time was 30 minutes and the washing time with cold water was 3 x 30 seconds.
  • washing process in a washing machine washing program 40 ° C without prewash.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Paints Or Removers (AREA)
  • Cleaning By Liquid Or Steam (AREA)
EP14731263.1A 2013-06-18 2014-06-18 Mittel zur entfernung von flecken und ablagerungen Active EP3011002B1 (de)

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EP3847229B1 (en) * 2018-09-05 2023-07-05 Unilever Global Ip Limited Foamable cleaning composition
JP2022505301A (ja) * 2018-11-16 2022-01-14 ザ プロクター アンド ギャンブル カンパニー 布地から染みを除去するための組成物及び方法
CN111518600B (zh) * 2019-12-23 2021-05-18 新疆中宇金盾碳基研究院(有限公司) 泛碱抑制剂、含有泛碱抑制剂的兰炭基型碳及其制备方法
EP4247926A1 (en) * 2020-11-17 2023-09-27 Unilever IP Holdings B.V. Composition
CN113122396A (zh) * 2021-03-12 2021-07-16 大连传奇化工有限公司 一种织物表面卟啉及共轭双键结构类污渍去除剂及其制备方法

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MY171321A (en) 2019-10-09
CN105324474A (zh) 2016-02-10
AU2014283324A1 (en) 2016-02-11
BR112015030856A2 (pt) 2017-07-25
SG11201509718VA (en) 2015-12-30
WO2014202651A1 (de) 2014-12-24
US10047322B2 (en) 2018-08-14
AU2014283324B2 (en) 2017-04-06
CA2913638C (en) 2018-11-20
NZ716097A (en) 2017-07-28
KR20160021773A (ko) 2016-02-26
CN105324474B (zh) 2019-09-13
MX2015017226A (es) 2016-11-10
DE102013106363B3 (de) 2014-12-11
PH12015502696A1 (en) 2016-03-14
US20160137955A1 (en) 2016-05-19
JP2016533412A (ja) 2016-10-27

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