EP3011002A1 - Agent for removing spots and deposits - Google Patents

Abstract

The invention relates to an agent for removing spots or deposits from hard or soft surfaces, which agent comprises surfactants, an adhesion promoter, and at least one active substance, wherein the adhesion promoter is selected from the group of the alkylene-styrene copolymers, the olefin homopolymers or olefin copolymers of two or more olefins, wherein the polymers can also be hydrogenated, and the polyalkylene derivatives, the active substance is an acid, an alkali, a bleaching agent, and/or hydrophobic organic solvent not bound in a gel, and the agent comprises either at least 10 wt% of at least one acid or at least 10 wt% of at least one alkali and/or at least 5 wt% of a bleaching agent and/or comprises at least 10 wt% of hydrophobic organic solvent not bound in a gel.

Description

 Agent for removing stains and deposits

The present invention relates to agents useful for removing a variety of different stains and deposits on hard and soft surfaces.

In particular, the agent is suitable for removing hard-to-remove stains from soft, delicate materials such as textiles. The stains can be spots on the underarm area of garments, but also stains of chocolate, lipstick, shoe polish, red wine, turmeric, fat, lime, soap scum, feces, rust, blood and chewing gum.

In addition, the composition according to the invention is also suitable for removing stains or deposits of hard surfaces. par- Moreover, the agent according to the invention can also be used industrially to remove deposits, for example of smoke gas resin in boiler plants and combustion chambers. In a further variant, the agent according to the invention can also be used to remove impurities on semiconductor surfaces. The use in Etching- method is possible. Another application is the removal of moss.

Various stains remover for stains of chocolate, lipstick, shoe polish, red wine, turmeric, fat, lime, soap residue, feces, rust and blood are known in the art. In addition, there are several home remedies that are used to remove such stains.

With the means known hitherto, however, either no adequate removal of difficult spots such as cocoa, lipstick or turmeric is possible or the tissue shows damage after application of the agent.

Another problem in the removal of stains, for which no satisfactory and tissue-preserving solution has been found so far, is the removal of stains in the underarm area of textiles. Such stains are due to the formation of poorly soluble deposits that partially harden. It is believed that these deposits are reaction products of sweat, aluminum chlorohydrates contained in the deodorants, and the metabolites of the bacteria. For the complete removal of such stains, no suitable fabric-preserving agent has heretofore been known.

Means for cleaning sanitary objects, such as toilet bowls, which can be applied directly to a sanitary object such as a toilet, adhere there and can only be rinsed off after a relatively large number of rinsing operations and which are so sticky that further means can be attached thereto, are known from EP 2 275 524 Bl. These agents are used for maintenance cleaning and not for the one-time removal of stains or impurities.

Acid agents which are intended in particular to remove stains on textiles in the underarm area are described in WO 2011/077144 A1. known. These agents are highly acidic (pH <1) and include, besides an acid, water and a surfactant. If desired, the agent may still be thickened with a gelling agent or a thickener such as ethoxylated fatty alcohols / ethoxylated fatty amines.

In practice, however, it has been shown that such agents either do not allow sufficient removal of the stains in the underarm area of the textiles or indeed remove the stains, but at the same time damage the textiles.

Acid-containing agents for cleaning hard surfaces are known from WO 2009/085049. The local agents include an organic acid, nonionic surfactants, water and a hydrophilic polymer which adsorbs to the hard surface. As hydrophilic polymers that also adsorb to the hard surface, this document teaches the use of polybetaines.

Means for removing stains from textiles containing lightly colored crystalline clay minerals are known from EP 1 238 050 B1. WO 03/066797 teaches a stain remover, which i.a. a hydrophobic component.

EP 0 786 514 A2 discloses a stain remover which contains nonionic surfactants, anionic soaps and a polymer.

DE 199 35 259 A1 discloses a bleaching composition which can be used as a pre-treatment or after-treatment agent for textiles.

DE 10 2007 014 875 A1 teaches a liquid cleaning agent which comprises photocatalytic material, humectants and surfactants.

The object of the invention is to provide an agent which is suitable for the effective removal of stains and deposits on textiles, especially in the underarm area, and for the removal of the above "difficult" stains and at the same time little or no damage to the surface to be treated becomes. A further object is to provide an agent which is also suitable for the removal of deposits and stains on hard surfaces, and in particular the removal of resin, grease or oil-containing deposits on an industrial scale and moss.

These objects are achieved by a means having the features of claim 1 and claim 11.

Surprisingly, it has been found that both effective and gentle stain removal can be achieved even on sensitive surfaces, if the agent also contains surfactants and a coupling agent in addition to the respective active substances such as acids, alkalis, bleaches and / or not bound in a gel organic hydrophobic solvents in which the adhesion promoter is selected from the group of the alkylene-styrene copolymers, the olefin homopolymers or olefin copolymers of two or more olefins, where the polymers may also be hydrogenated and the polyalkylene derivatives are selected.

In this case, the "active substances" generally cause the actual stain removal.

The adhesion promoters serve to make the agent sticky so that the agent will adhere to the spot or deposit after application and will not flow away or drip off.

The surfactants contained in the agent cause on the one hand a cleaning effect. In addition, they help to dissolve the hydrophobic coupling agent in the presence of water.

The primer, which is generally hydrophobic, also provides a protective and delaying effect. Water-soluble active substances are only released from the product in the presence of water. Previously, reactive agents are protected in the hydrophobic matrix.

This prolongs the effectiveness of the agent. In addition, reactive agents can also be formulated in the hydrophobic matrix without losing the effect within a short time. Depending on the active ingredient added, the agent can be formulated to remove a wide variety of stains or deposits.

In a first variant, the agent contains, in addition to surfactants and the adhesion promoter as the active ingredient, at least 10% by weight of acid. Such an agent can be used to remove acid soluble stains.

Surprisingly, it has been found that such an acid stain remover, in particular with alkylene styrene copolymers dissolved in hydrophobic solvents as adhesion promoters, surfactants and at least 10 wt.%, Preferably at least 15 wt.% And particularly preferably at least 20 wt.% Acid, conventional removal means of stains from textiles in the underarm area is superior. The stain can be effectively removed with the agent of the invention without damaging the tissue.

In addition, it is possible to use such acidic agents to remove stains such as rust, blood or impurities on calcifications. Since the acidified agent does not attack the fibers, such a stain and debris removal agent is particularly useful on soft, delicate surfaces such as woven, knit, or walkwear, particularly on textiles, carpets, or curtains. The surfaces can z. B. of synthetic or natural fibers, natural or artificial leather or plastic.

In addition, the inventive set sour agent can of course also be used to remove such stains from hard, insensitive surfaces, such as metal, ceramic, stone, glass, plastic or wood.

In a further variant, which is particularly suitable for removing colored stains such as red wine, the agent comprises bleach as active ingredient, for example salts of peracids such as perborates, percarbonates, persulfates or Phthalimidoperoxohexansäure (PAP). Preferably, the bleaching agents are contained in the composition in a concentration of at least 5% by weight and preferably at least 8% by weight and more preferably at least 12% by weight. If desired, the agent may also contain a bleach activator such as tetrahydrofuran. raacetylenethylenediamine (TAED), nitrile quats, NOBS (nonanoyloxobenzene sulfonate) or DOBS (docanoyloxobenzene sulfonate).

In a preferred variant, the agent comprising bleach comprises at least 20% by weight of surfactants, at least 10% by weight of bleaching agent and between 20% by weight and 60% by weight of adhesion promoter as 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 peroxoacids and between 30% by weight and 50% by weight of adhesion promoters, 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.

For this purpose, the agent is applied to the spot of the object in question, if necessary. Waiting or action times are met, and then washed the object, for example, in a washing machine or rinsed. In the presence of the water, the bleaches and surfactants are then gradually released from the agent at the stain and bleach the stain and transport the contaminants to the wash liquor. Since the active ingredients are enclosed in the hydrophobic matrix of the adhesion promoter and only dissolved in the presence of water from this, overdoses of the active ingredients and thus damage to the tissue can be avoided.

In a further variant, the inventive composition for the removal of fat-soluble and / or pigment-containing impurities such as lipstick, shoe polish, cocoa, fats or waxes can be formulated.

To remove such impurities, the agent comprises a hydrophobic organic solvent which serves to dissolve the fats or waxes. The hydrophobic organic solvents used for this purpose must thus be freely available in the agent. solu- However, semides which are contained in the composition but which are required for gelation, such as, for example, the hydrophobic solvents which act as solvents for gelation in the bond particularly preferred as 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 additionally added to the agent via the hydrophobic solvent required for gelation.

In general, the concentration of the free organic solvents in the composition is at least 10% by weight, preferably above 15% by weight, and more preferably between 20% by weight and 40% by weight.

In addition to the freely available organic hydrophobic solvents, the agent should still contain alkalis, which on the one hand also serve to dissolve the fats and oils. On the other hand, the alkalis also cause the fibers to swell and thus also facilitate that the active ingredients penetrate sufficiently into the textiles and dissolved impurities can be removed again as a result of the structured structure.

The concentration of alkalis in such agents, which additionally comprise hydrophobic organic solvents, is generally at least 2% by weight and preferably at least 5% by weight.

Such alkalized agents with at least 2% by weight alkali, preferably NaOH or KOH, at least 20% by weight free hydrophobic organic solvent, preferably terpenes, at least 10% by weight adhesion promoter (preferably alkylene styrene copolymer, dissolved in organic solvents such as Versagel) and At least 20% by weight of surfactants are suitable for removing stains containing grease and / or pigment such as cocoa, lipstick, shoe polish, chewing gum and turmeric, preferably of soft, sensitive, in particular textile surfaces. Of course, such an agent can also be used to remove stains from hard surfaces.

In a further variant, the agent is formulated with a very high proportion of alkalis, which is generally above 50% by weight and preferably above 60% by weight. Such adhesive, pasty, strongly alkaline agents stick to vertical surfaces and, in the presence of water, for example, by rinsing, release the alkalis, which then deposits of resins, fats, oils or the like. attack. Such agents can be used, for example, in industrial plants and combustion chambers to remove fumes, fats or oily impurities or soot. Such a highly alkaline agent shows very good results in removing resin or grease deposits even on vertical surfaces (e.g., in slaughterhouses, in pipe-plugging of fats (drain-opener), for removal of keratinous substances (hair, horn)). For the cleaning of sensitive soft surfaces, however, such a strongly alkaline agent is only suitable in exceptional cases, e.g. for fabrics made of alkali-resistant fibers such as Teflon or PUR.

surfactants

The composition according to the invention comprises surfactants, it being possible to use anionic, cationic, nonionic and amphoteric surfactants as surfactants.

The surfactants are not only used in the compositions according to the invention for cleaning but also cause the polymer adhering to the surface to be rinsed off again. In addition, surfactants have a thickening effect on the polymers, i. By adding surfactants, especially in powder form, it is also possible to adjust the viscosity of the agent.

As surfactants, it is possible in principle to use all known anionic and / or cationic and / or nonionic and / or amphoteric surfactants, powdery to highlypasteose being preferred.

The proportion of surfactant in the composition can be up to 80% by weight, preferably 10% by weight to 60% by weight and more preferably 25% by weight to 45% by weight. The anionic surfactants perform several tasks in the present invention. First, they serve to emulsify the polymeric matrix without completely destroying the adhesiveness.

On the other hand, they contribute significantly to the plasticization of the starting polymer by serving as viscosity enhancers (thickeners). Last but not least, a good cleaning action of the surfactants is desired, which is supported by the good wetting properties.

As anionic surfactants it is preferred to use one or more substances from the group of the salts of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids. Usually, the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

Carboxylic acids (C6-C22) in the form of their metal salts (preferably alkali metal salts) and their natural or synthetic mixtures and alkali metal salts of sulfuric monoesters and longer-chain alcohols can also be used as anionic surfactants.

Another class of anionic surfactants which can be used according to the invention are the alkali metal salts of the alkyl ether sulfuric acids. Like the alkyl sulfuric acids, alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates concerned. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation provides the relevant alkyl ether sulfuric acids.

The alkali metal salts of alkanesulfonic acids and olefinsulfonic acids can also be used as anionic surfactants in the context of the present invention. Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids). Typical representatives are alkylbenzenesulfonates, particularly preferably linear alkylbenzenesulfonates (LAS). The above-mentioned anionic surfactants may be used in their neutralized form alone or in admixture with each other.

According to the invention, the surfactant phase contains, based on its weight, preferably 10% by weight to 90% by weight and particularly preferably 40% by weight to 85% by weight of lauryl sulfate.

As nonionic surfactants, it is possible to use alkoxylated, preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol and on average 2 to 8 EO per mole of alcohol preferred. In addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and Alkylg lykoside the general formula alkyl-O (G) can be used, wherein alkyl is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol for a glycosidic structure with 5 or 6 C atoms, preferably for glucose.

Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-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%.

If desired, the surfactant phase can also be provided with cationic or amphoteric and zwitterionic surfactants. Examples of amphoteric surfactants are fatty acid amidopropyl betaines with C5-C21 fatty acid moieties, but also amphodiacetates.

Cationic surfactants are preferably used in the present acidic formulation as bactericidal substances. Zwitterionic surfactants can be described by way of example as quaternary ammonium, phosphonium or sulfonium components which are connected via an aliphatic bridge with another now anionic group such as Carbboxy, sulfonate, sulfate, phosphate or phosphonate.

As foaming agent, olefin sulfonates, ether sulfates or acid methyl taurides can furthermore be added to the agent. If strong foaming agents are to be used, preferably 1 to 50, in particular 1 to 25%, of the surfactant phase can be obtained by one or more frothers, e.g. from the group of betaines, the alkoxylated alkyl ether sulfates or Lactobi- onsäurederivate be replaced. These foaming agents may be selected from fatty acid amidopropyl betaines having a C 5 -C 21 fatty acid moiety, such as cocoamido proplybetaine, the alkali metal or ammonium salts of the lauryl ether sulfates containing 1 to 5 EO, the lactobionococoylamide, the lactobionooleylamide, the lactobionotalgamide, etc., or mixtures thereof. These foaming agents can be incorporated well into the composition according to the invention. Preference is given to using such cosurfactants which are present in solid, preferably pulverulent or highly viscous form.

bonding agent

An essential constituent of the agent according to the invention are adhesion promoters which are selected from a group of the alkylene styrene copolymers, the olefin homopolymers or olefin copolymers of two or more olefins, where the polymers may also be hydrogenated, and the polyalkylene derivatives. Preferred alkylene-styrene copolymers are diblock or tri-block copolymers, in particular from the group consisting of styrene-butadiene-styrene copolymers (SBS), styrene-isoprene-styrene copolymer (SIS) and styrene-ethylene-butylene-styrene Copolymers (S-EB-S), styrene-ethylene-propylene copolymers (S-EP), styrene-ethylene-butylene copolymers (S-EB), styrene-butadiene copolymers (SB) and styrene-isoprene copolymers ( SI). The alkylene styrene copolymers may also be hydrogenated or partially hydrogenated. Preferably, the hydrogenated or non-hydrogenated alkylene-styrene copolymers are crosslinked.

The alkylene styrene copolymers, in particular the polymers from the group of the alkylene styrene copolymers, are preferably dissolved in 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.

This often forms hydrophobic gels that are sticky. Such gels generally consist of about 1 to 20% by weight of polymers and 80 to 99% by weight of hydrophobic solvents, such as, for example, 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. Kraton Performance Polymers offers alkylene-styrene copolymers as a solid under the trademark "Kraton".

By the addition of the polymers - optionally dissolved in hydrophobic solvents - the agents are also sticky. This ensures that the agent adheres to the surface of the object in question and can thus act on the surface to be treated during the rinse or during the washing process over a longer period of time.

As olefin homopolymers or copolymers can be used polybutadiene rubbers, styrene-butadiene block and copolymers and the polyisopropenes, but also random (block) polymers, which are obtained by 1,3-addition of butadiene or isoprene to styrene or alpha-methylstyrene , Homopolymers or copolymers of ethylene or propylene, such as ethylene-propylene-diene terpolymers, which are natural The rubbers and the norbornene polymers or polydicyclopentadiene can be used. The compounds from the group of olefin homopolymers and copolymers can also be partially hydrogenated, partially oxidized or further functionalized via graft molecules.

Another possible class of adhesion promoters from the group of polyalkylene derivatives comprises polyalkylene chains with randomly distributed functional groups. The polyalkylene chains are preferably polybutadiene, polyisopropylene and polypropylene chains.

The randomly distributed on the polyalkylene functional groups are preferably reactive groups, in particular from the group of anhydrides, thiols, epoxides or primary amines. Of course, the functional groups should be selected so that the coupling agents do not react with the other components of the agent.

Particular preference is given to polymers having randomly attached to the polybutadiene chain maleic anhydride groups. The particularly preferred maleic anhydride adduct on 1,4-cis-polybutadiene is available from Degussa under the name Polyvest.

active substance

The agent according to the invention furthermore contains at least one active substance which is to be selected according to the stain to be removed or the deposit to be removed.

Active substances for the purposes of the present invention are acids, alkalis, bleaches and freely available organic hydrophobic solvents. Depending on the intended use, the agent may also contain a plurality of active substances.

Acids as active substance

If the agent according to the invention contains acids as active substance, the agent is suitable, for example, for removing stains from soft surfaces, such as stains of clothing pieces in the underarm area or rust and blood stains or impurities on calcifications.

As acids, organic and inorganic acids, also in combination, can be used.

Examples of 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 else oxalic acid. The concentration of organic acids should be between 1% by weight and 60% by weight, preferably between

15% by weight and 40% by weight.

As inorganic acids, for example, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid can be used. The concentration of inorganic acids in the composition should be between 1% and 40% by weight, preferably between 10% and 30% by weight, at an acidified level.

If no further active substances are contained in the composition, the minimum content of acids (organic and / or inorganic) in the composition should be 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 most preferably at most pH 1.

Preference is given to the use of solid anhydrous acids such as sulfamic acid.

Acids and bleach as active substance

In a further variant, the agent as active substance in addition to the at least one acid comprises at least one oxidizing agent.

Such a variant is suitable for removing stains from rust, blood, sweat and oxidizable substances. For an acidic, oxidizing agent, phosphoric acid can be used with H2O2 (stabilized). The proportion of H2O2 (absolute) in the agent should preferably be between 2% by weight and 5% by weight.

Alkalis as active substance

To remove resin stains, such as fumes, an agent comprising a high proportion of alkalis is suitable.

As alkalis, for example, oxides and hydroxides of alkali and alkaline earth metals such as NaOH, KOH or MgO or Na2Ü, preferably as a solid or prills, can be used.

For the removal of resin stains or oily stains, especially on hard surfaces, the proportion of alkalis in the composition can be

50% by weight and more, preferably at least 60% by weight and more preferably at least 70% by weight.

The pH of a 1% solution of an alkaline admixed agent should be at least pH 9, preferably at least pH 10 and more preferably at least pH 11.

Alkalis and hydrophobic solvents as active substance

To remove greasy stains such as shoe polish or chocolate, especially sensitive soft surfaces such as textiles, an agent that comprises alkalis and free hydrophobic organic solvents as the active substance is suitable. The alkalis serve to swell the fibers. Alkalis and hydrophobic solvents serve to dissolve and / or chemically modify the fat-soluble impurities, e.g. by ester cleavage.

Since in some variants of the composition according to the invention the adhesion promoter in a hydrophobic solvent such as a mineral oil is gelelt (eg as Versagel 1600) and the part of the mineral oil, which is required for the gel formation is not available as a hydrophobic solvent, the dissolution of fat-soluble Substances in the recipe only by "free", that is, not required for gelation solvents occur.

In a preferred variant, therefore, to the mineral oil-containing Versagel required for gelation in the agent still additional hydrophobic solvents such as terpenes in a proportion - depending on the stain to be removed - of at least 10 wt.% And preferably up to 40 wt.% given. In such an agent, the proportion of alkalis is at least 2% by weight.

The free hydrophobic solvents cause already when applying the agent on the stain a dissolving oil-containing contamination.

Alkalis and bleach as active substance

In a further variant, the inventive agent as

Active substance alkalies and bleach include. In this variant, bleaching agents which are stable in the alkaline, such as chlorine-releasing bleaching agents such as cyanurates or chlorine bleaches, preferably in a concentration of 0.01 wt.% To 1 wt.% Additionally added to the agent described above with alkalis as active substance.

Such an agent is useful for removing stains from fabrics that are chlorine stable, preferably undyed fibers.

The composition according to the invention may additionally comprise solubilizers in order to facilitate the emulsification via phase boundaries. As solubilizers, for example, glycol ethers or sodium cumene sulfonate can be used, preferably in a concentration between 1 wt.% And 40 wt.%.

Furthermore, the agent according to the invention may also comprise humectants. Preferably, polyalcohols such. As glycerol or glycol used.

In addition, co-thickeners may be added to the composition according to the invention in order to increase the plasticity of the composition. As (co) - Thickeners may include, for example, bentonites, powder surfactants, xanthans, polybutadiene rubbers, polyisopropenes, block copolymers comprising linked oligomers consisting of oligo- or polyethylene oxide and / or oligo- or propylene oxide and / or oligo- or polybutylene oxide and also arylethoxylates or alkyl-aryl-ethoxylates become. The polymeric natural substances such as lignins or their alkali metal or alkaline earth metal salts can also be used as (co) thickeners.

Sequestering agents, such as sodium diphosphonate, useful, for example, to remove tea stains may also be added to the composition. Also, dispersants that hold, for example, Ca or Mg salts in the wash liquor in suspension, may be included in the composition as a component. In addition, the agent may also include complexing agents such as phosphonates or EDTA.

Furthermore, hydrophobicizers such as, for example, Aerosil, in particular methylated Aerosil (Carobo Carbon) can be added to the composition according to the invention as fillers.

Of course, the agent according to the invention - if desired - also include dyes, fragrances and enzymes (amylases, lipases, proteases, cellulases and peroxidases).

In order to bind unpleasant odors, the agent may further contain odoriferous agents (malodor counteractants) which are preferably added to the fragrances. Such odor binders are described, for example, in US Pat. No. 7,288,507 B2.

The viscosity of the agent can be adjusted depending on the desired application and the type of application.

The viscosity of the agent should on the one hand be so low that the agent can effectively wet the spot to be treated. On the other hand, the viscosity of the agent should again be so high that it does not "run away" from the spot or the contaminant to be treated and the amount applied can be metered. Depending on the intended use, the agents can be thin to viscous, depending on which type of surface or fabric they are applied and which should adhere for a relatively long time.

The agent according to the invention is preferably pasty. In a particularly preferred embodiment, the composition has a viscosity of at least 30 Pa * s, in particular at least 100 Pa * s, measured with a Haake viscometer, system plate / plate, plate diameter 10 mm, with a shear rate of 2.62 s-1 and 20 ° C on. Such a paste can for example be painted on the surface to be treated by means of a brush or a spatula, where it adheres.

The stain remover according to the invention is applied to the point to be cleaned of the object to be treated, in particular the textiles, on the stain or in the underarm area with brush or brush. The stain remover sticks and slowly releases in the presence of water then in the alkaline wash the active ingredients that gradually dissolve the stain.

In the case of the acid stain remover for the underarm area of textiles, the residue of sparingly soluble aluminum salts in the presence of water is slowly decomposed by the liberated acid without attacking the textile fiber. In this case, the local medium around the stain is acidic, but the rest of the textiles are in an alkaline solution.

The composition according to the invention is generally suitable for removing stains from textiles of plant, animal or synthetic origin. In particular, the deodorant removal agent is suitable for removing sweat from cotton textiles.

When removing stains from textiles, the stain remover according to the invention is first applied to the stain to be removed, where it adheres.

Subsequently, the applied stain remover is removed again, for example, by washing the treated garment after a certain exposure time of at least one minute in the washing machine or even by hand. By washing, the water-soluble active substance, ie the alkalis or the bleaching agent, is released locally in the vicinity of the stain and the stain is removed. The rest of the "non-stained" material, especially textiles, is mainly affected by the washing liquor or - if no washing is done in the washing machine with a detergent - water.

After the active ingredient, as far as water-soluble, such as acids, alkalis or bleach, only in contact with water are released from the agent, in comparison to the previously known means damage to the tissue in that the stain remover applied, but not within the required time is rinsed off again, almost impossible.

Upon contact with water, the stain remover is completely removed from the surface, also as a result of the surfactants contained in the composition.

In addition to the removal of sweat stains, the composition according to the invention can also be used to remove blood, rust and iron stains or other acid-soluble stains.

In a variant with at least 5% by weight of an acid and / or at least 1% by weight of a biocide as active substance, the composition according to the invention can also be used for removing moss and other deposits, for example on stones.

For example, benzalkonium chloride, bronopol, glutaraldehyde, formaldehyde, triazine, dibromonitrilepropionamide, perbutryn, IPBC, OIT and diuron can be used as the biocide.

In a variant with the alkali ammonium hydroxide or dilute organic or inorganic acids, the agent can also be used to remove impurities from copper or other metals on hard surfaces such as 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 the removal of stains and impurities, the entire agent subsequently being removed again with water after application.

In order to protect water-soluble active ingredients in the composition against premature decomposition and to ensure that the active ingredients are released in the composition, as far as water soluble, only when washing or rinsing with water, the agent should preferably be anhydrous or a water content of at most 5 wt % and more preferably at most 1% by weight.

The invention will be described in more detail below with reference to exemplary embodiments.

In the following, a frame formulation and an example formulation for an acid agent according to the invention are shown, which can serve, for example, for removing stains on textiles in the underarm area.

I. Framework for an acidified agent

Range preferred range

Polymer 0.5 to 50% (based on 15 to 20% of Versagel

(optionally in mineral oil on the polymer) (i.e., styrene-dissolving) copolymer dissolved in

 Mineral oil)

Surfactants 5 to 60% 10 to 50% Solubilizer 0 to 30% 10 to 20%

Acid (s) 10 to 50% 20 to 40%

Feuchtha Item ittel 0 to 30% to 15%

Formulation of an acid remedy to remove stains in the armpits ("Armpit Cleaner")

The remedy based on the following recipe is referred to below as "Armpit Cleaner":

III. Attempts at the effectiveness of the removal of stains in the armpit area

The Armpit Cleaner according to Formulation II above was applied to patches of a blue multiply worn T-shirt in the underarm area. On the adjacent stain in the armpit was Dr. med. Beckmann's spot devil "rust &deodorant" applied according to instructions.

The washing conditions were as follows: 55 g washing powder to 4.5 kg laundry, liquor ratio 1: 5, washing temperature 40 ° C, 250 mg / cm ² Armpit Cieaner, exposure time 60 minutes, washing time 30 minutes, washout 3 x 30 seconds, cold ,

Figure 1 shows the starting material with the stains in the armpit area and the result after removal of the stain the armpit Cieaner invention and with Dr. med. Beckmann's spot devil.

With the Armpit Cieaner according to the invention, the spot in the underarm area is completely removed, whereas in the treatment of the spot with Dr. med. Beckmann's spot devil clearly visible stains remain in the underarm area.

IV. Investigation of possible quality losses of various tissues by the Armpit-Cleaner according to Experiment II

The German Textile Research Institute North-West (Krefeld) has investigated the effect of the agent for the removal of stains in the axillary region from experiment II on the following tissues: a) examined tissue

PM Sample Identification Material (%) Tint

Cotton silk gloss CO (100) white (4000361010017)

 Cotton silk gloss CO (100) green (4000364014404)

 Cotton light (2000000059396) PES / CO (65/35) white

Cotton light (2000000059488) PES / CO (65/35)

5 Fabrics Stretch PES / CV / EL white (2000000061764) (65/32/3)

 6 Clothing fabric Stretch PES / CV / EL cherry (2000000061757) (65/32/3)

 7 Microfiber Peach (2000000032051) PES (100) white

8 Microfiber Peach (2000000062099) PES (100) red

9 Lycra Dancewear PA / EL (80/20) white (4000302010017)

 10 Lycra Dance Garment PPAA // EELL ((8800 // 2200)) orange (4000302011403)

 PM = number of the test material;

 Source of supply of the examined fabrics: www.Stoff4you.de

CA = acetate, CO = cotton, PA = polyamide, PAN = polyacrylic, PES = polyester, WO = wool, CV = viscose, EL = Lycra; * visually brightened, As part of the investigations, approximately 50 mg / cm ^{2 of} the Armpit Cleaner according to Formulation II were applied to each sample by means of a doctor blade. b) Test method for the determination of color fastness:

The determination of color fastness in household and commercial laundry was carried out according to DIN EN ISO 105-C06 (Linitest plus), AIS, 40 ° C, with steel balls, Date of issue: 2010-08, multi-fiber backing fabric type "DW" and ECE detergent with phosphate

Evaluation: Authenticity -1- (bad) to -5- (good) c) For the untreated tissue samples, the following results were obtained:

Bleeding from

 ΡΜ change of color

 WO PAN PES PA CO CA

 1 -5-5-5-5-5-5-5-5-

2 4-5 -5-5-5-5-5- -3- -5-

3 -5-5-5-5-5-5- 4-5 * -5-

4 -5- -5- -5- -5- -4- -5- 4-5

5 -5-5-5-5-5-5-5-5-

6 -5- -3- 4-5 -3- -3- -3- -3-

7 -5-5-5-5-5-5-5-5-

8 -5- 4-5 -5- 4-5 3-4 4-5 4-5

9 -5-5-5-5-5-5-5-5-

10 -5-5-5-5-5-5-5-5-

Table 1

CA = acetate, CO = cotton, PA = polyamide, PAN = polyacrylic, PES = polyester, WO = wool, * optically brightened d) For the tissue samples with Armpit-Cleaner (paste exposure: 50 mg / cm ² and 60 minutes) the following results were obtained:

Change of color bleeding from

 WO PAN PES PA CO CA

 1 -5-5-5-5-5-5-5-5-

2 4-5 -4- 4-5 4-5 -3- -3- 4-5

3 -5-5-5-5-5-5- 4-5 * -5-

4 -5-5-5-5-5-5- 4-5 -5-

5 -5-5-5-5-5-5-5-5-

6 -5- -2- -4- -3- -2- -2- -3-

7 -5-5-5-5-5-5-5-5-

8 -5- 4-5 -5- 4-5 4-5 4-5 4-5

9 -5-5-5-5-5-5-5-5-

10 -5-5-5-5-5-5-5-5-

Table 2

 CA = acetate, CO = cotton, PA = polyamide, PAN = polyacrylic, PES = polyester, WO = wool, * optically brightened

V. Washing test in household washing machine

Based on DIN EN ISO 6330, the respective test material was washed in a domestic washing machine, on the one hand untreated, without paste and on the other hand with Armpit Cleaner. For this purpose, 50 mg / cm ² of Armpit Cleaner paste was applied in the middle in a strip of about 3 cm wide by means of a doctor and worked for 60 minutes.

The laundry took place at one

Washing temperature of 40 ° C, normal washing,

Detergent: mild detergent,

Load: 2 kg,

 Washing machine type: Miele "Gala Grande".

To prevent contamination by other test material, each test material was washed separately. The samples thus obtained were used 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 with the strip tensile test, issuing date: 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.

Condition of the sample: adjusted, standard climate: 20 ° C, 65% relative humidity

 Number of test samples: each direction 3

a) Original blank: PM Product direction Maximum tensile strength Maximum tensile elongation at break

 [N] [%]

2 chain 415 ± 9.04 7.5 ± 0.2

 Shot 447 ± 7.52 20.8 ± 0.2

4 chain 934 ± 30.8 21.4 ± 0.1

 Shot 539 ± 16.2 19.5 ± 0.3

6 chain 901 ± 22.2 60.0 ± 2.0

 Shot 647 ± 22.4 58.5 ± 3.0

8 chain 748 ± 2.3 48.5 ± 2.3

 Shot 599 ± 4.45 27.2 ± 2.3

 Table 3

b) washed:

PM goods direction maximum tensile force maximum tensile strength elongation

 [N] [%]

₂ chain 330 ± 19.7 18.8 ± 0.8

 Shot 326 ± 3.78 26.8 ± 1.0

4 chain 841 ± 23.4 22.4 ± 0.6 Shot 552 ± 15.2 22.6 ± 0.3

₆ chain 1060 ± 27.9 55.2 ± 1.5

 Shot 989 ± 20.6 92.1 ± 6.1

₈ chain 820 ± 3.94 49.3 ± 1.7

 Shot 708 ± 11.7 23.4 ± 0.4

Table 4

c) with Armpit-Cleaner (paste effect: 50 mg / cm ² and 60 minutes) and washed:

PM goods direction maximum tensile force maximum tensile strength elongation

 [N] [%]

2 chain 451 ± 24.5 14.7 ± 1.2

 Shot 445 ± 5.21 21.9 ± 0.3

4 chain 822 ± 23.0 21.2 ± 1.0

 Shot 510 ± 11.4 21.3 ± 0.2

6 chain 1170 ± 30.0 47.4 ± 0.4

 Shot 1180 ± 5.68 61.0 ± 1.9

8 Chain 844 ± 0.88 47.5 ± 0.8

 Shot 727 ± 159 22.2 ± 1.2

 Table 5

VI. Determination of tensile properties

The determination of the tensile properties of the textile fabrics is carried out in accordance with DIN EN ISO 13934-2, determination of the maximum tensile strength with the grab tensile test, issuing date: 1999-04.

a) Original blank PM goods direction maximum tensile force maximum tensile strength elongation

 [N] [o / o]

10 ^years 9 ^s 224 ± 9.73 139.2 ± 1.3

 transverse 312 ± 9.62 99.2 ± 2.3

Table 6

b) washed

Maximum tensile force Maximum tensile strength PM goods direction

 [N] [%]

₁₀ along 218 ± 10,8 135,1 ± 3,1

 transverse 319 ± 7.38 95, 4 ± 2.5

Table 7 c) with Armpit Cleaner (paste action: 50 mg / cm ² and 60 minutes) and washed:

PM goods direction maximum tensile force maximum tensile strength elongation

 [N] [%]

 along 219 ± 13.2 129.0 ± 2.1

10

 transverse 290 ± 19.3 82.8 ± 3.3

Table 8

VII. Supports and fillers according to DIN 54278-1, determination of the substances soluble in organic solvents,

Date of issue: 1995-10 Solvent: Water Original - Blank: PM solute [%] Individual values mean value

 1 1.23 1.10 1.17

 3 0.68 0.72 0.70

 5 0.17 0.20 0.19

 7 0.17 0.17 0.17

 9 0.19 0.17 0.18

 Table 9

I): p _M solute [%]

 Individual values mean value

1 0.32 0.29 0.31

 3 0.92 0.79 0.86

 5 0.28 0.21 0.24

 7 0.14 0.15 0.15

 9 0.40 0.27 0.33

 Table 10

II) with PM 11 (paste exposure: 50 mg / cm ² and 60 minutes) and washed:

PM solute [%]

 Individual values mean value

1 0.40 0.47 0.44

 3 1.52 1.51 1.52

 5 0.29 0.27 0.28

 7 0.30 0.28 0.29

 9 0.75 0.77 0.76

Table 11 VIII. Result

Under the test conditions described by treatment with Armpit Cleaner, neither yellowing of the different substrates (PM 1, PM 3, PM 5, PM 7 and PM 9) nor a change in hue of the stained samples could be detected. Two samples showed greater bleeding of the accompanying tissues when washing out the Armpit Cleaner (PM 2 and PM 6) (see Table 2).

In addition, no appreciable impairment of the maximum tensile force of the different substrates could be recorded by using Armpit Cleaner (see Table 3 to Table 8).

The washout of the applied Armpit Cleaner by household washing with the "Delicates" program at 40 ° C is good for both the stretch and microfiber materials (PM 5 and PM 7), however, the polyester / cotton (PM 3) and the lyrics (PM 9) higher residual restraints determined, ie that the washout under the experimental conditions is slightly lower (see Tables 9 to Table 11).

As a result, it should be noted that, due to the use of Armpit Cleaner under the above test conditions, no yellowing or hue changes of the tested textiles occurred. Likewise, no negative influence on the material strengths could be determined.

IX. Formulation for an agent with alkali and hydrophobic solvents as an active substance for the removal of fat, wax and lipstick

The following recipe is particularly suitable for removing the above stains on soft surfaces such as textiles.

Wt .-%

Versagel M 1600 15 Lutensol T03 (C13-oxoalcohol / 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, Na salt, Rhodia) 15

 Sokalan PA30 CL (polyacrylate, BASF) 0.5

Orange terpenes 30

 Glycerol (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 grease and causes a swelling of the fibers, so that the ingredients can get better to the fiber and be transported away from it again.

The mixture of short-chain, oil-soluble surfactants (Lutensol T03 and Lutensol AO 5) and longer-chain water-soluble surfactants and the solubilizer Eltesol cause the impurity enters the aqueous phase.

X. Formulation for an acid bleaching stain remover, for example for removing red wine stains from textiles

To remove stains with oxidative components such as dyes, the following acidic agent may be used:

Wt .-%

Kelzan ASX (Xanthan Gum, Monsanto) 1.86 Eltesol 6.5

Tensopol USP94 (Lauryl C12-C16 sulfate Na salt, Manro) 31,64 Versagel M 1600 40

Sodium perborate 15

TAED 5

Total 100

This formulation includes as sodium bleach sodium perborate and TAED as oxidation activator.

XI. Further washing experiments with the invention

 funds

In order to check the effectiveness of the compositions according to the invention, further washing tests were carried out with material of different stains under laboratory conditions and by washing in the household washing machine and with Dr. med. Beckmann's spot devil compared.

In the following, the washing results are discussed in detail.

a) shoe polish stains

The comparison of the stain removal of shoe polish with the composition according to the invention according to Formulation IX (Alkali with terpenes) and Dr. med. Beckmann's patch devil "lubricant / oils" is shown after a single treatment in Figure 2.

The results show that with the composition of the invention according to Formulation IX at least as good stain removal as with Dr. med. Beckmann's tainting devil is achieved, both under laboratory conditions and in household washing. b) chocolate cream stains The removal of chocolate cream stains with the composition of the invention according to Formulation IX (alkali and terpene) and Dr. med. Beckmann's patch devil "Fatty &Sauces" is shown in Figure 3. After a single application, the means of the invention only a small "shadow" can be seen, whereas after removal with Dr. med. Beckmann's spot devil the spot is still clearly recognizable.

c) red wine stains

FIG. 4 shows the removal of red wine stains with the composition according to the invention in accordance with recipe X and for comparison with Dr. med. Beckmann's tainted devil "Fruits & Beverages." The illustrations show that the stain with the composition according to Formulation X is completely removed in a single treatment, compared to Dr. Beckmann's tainted devil d) Lipstick stains

The removal of lipstick stains is generally very difficult. In comparison with Dr. Beckmann's tainted devil "Nature & Cosmetics", however, shows the agent according to the invention as per Recipe IX visibly better results than the stain remover (Figure 5), under laboratory conditions as well as in the household linen e) Kurkuma stains

With the removability of turmeric or curry comes with the stain remover according to the invention according to Formulation IX already after the first wash to a further removal of the stain and a better stain removal than with the tested in comparison also Dr.. Beckmann's Blot Devil "Fatty and Sauce" The comparative test is shown in FIG.

XII. washing conditions The stain paste of the invention is applied evenly to the stain with the spatula. The exposure time is 15 to 30 minutes. Dr. Beckmann's patch devil is applied according to instructions.

a) Laboratory: beaker washing

Under laboratory conditions, the laundry was carried out as follows in the concentration ratio: 55 g of washing powder to 4.5 kg of laundry, liquor ratio 1: 5, washing temperature 40 ° C, ballast wash (BW terry).

The washing time was 30 minutes and the washout time with cold water 3 × 30 seconds. b) Household linen

The washing process in a washing machine, washing program 40 ° C without prewash.

PAGE INTENDED EMPTY

Claims

claims Means for removing stains or deposits of hard or soft surfaces, which agent comprises surfactants, an adhesion promoter and at least one active substance, wherein the coupling agent is selected from the group of the alkylene-styrene copolymers, the olefin homopolymers or olefin copolymers of two or more olefins, where the polymers may also be hydrogenated and the polyalkylene derivatives are selected, the active substance is an acid, an alkali, a bleach and / or non-gel bound hydrophobic organic solvent, and the agent is either at least 10% by weight of at least one acid or at least 10% by weight of at least one alkali and / or comprises at least 5% by weight of a bleaching agent and / or comprises at least 10% by weight of non-gel-bound hydrophobic organic solvent. Composition according to Claim 1, characterized in that the alkylene-styrene copolymers are selected from the group consisting of diblock or triblock copolymers and in particular from the group of the styrene-butadiene-styrene copolymers (SBS), the styrene-isoprene copolymer. Styrene-ethylene-butylene-styrene copolymers (S-EB-S), styrene-ethylene-propylene copolymers (S-EP), styrene-ethylene-butylene copolymers (S-EB), styrene-styrene copolymers (SIS); Butadiene copolymers (SB) and styrene-isoprene copolymers (SI), where the alkylene styrene copolymers may also be hydrogenated or partially hydrogenated, and the olefin homopolymers or copolymers from the group of polybutadiene rubbers, styrene-butadiene block and copolymers, and the polyisopropenes and random (block) polymers obtained by 1,3-addition of butadiene or isoprene to styrene or alpha-methylstyrene which are selected from homopolymers or copolymers of ethylene or propylene such as ethylene-propylene-terpolymers, natural rubbers and norbornene polymers or polydicyclopentadiene. 3. Composition according to one of the preceding claims, characterized in that the pH of a 1% solution of an acid-containing agent is pH 2 or less, preferably at most pH 1.5 and more preferably at most pH 1. 4. Composition according to one of the preceding claims, characterized in that the pH of a 1% solution of an alkali-containing agent is at least pH 9, preferably at least pH 10 and more preferably at least pH 11. 5. Composition according to one of the preceding claims, characterized in that the surfactant content up to 80 wt.%, Preferably 10 wt.% To 60 wt.% And particularly preferably 25 wt.% To 45 wt.%. 6. Composition according to one of the preceding claims, characterized in that the agent is pasty and preferably a viscosity of at least 30 Pa * s, and more preferably of at least 100 Pa * s, measured with a Haake viscometer, system plate / plate, plate diameter 10 mm, with a shear rate of 2.62 s-1 and 20 ° C, has. 7. Use of a composition according to any one of the preceding claims comprising at least 10% by weight of acid, preferably at least 20% by weight of acid and preferably at least 30% by weight of a mixture of an organic acid and an inorganic acid to remove stains from textiles in the underarm area or stains of blood, rust and scumming on calcifications. 8. Use of a composition according to any one of claims 1, 2, 4, 5 o- 6, the at least 50 wt.%, Preferably at least 60% by weight, and more preferably at least 70% by weight, of alkalis comprises deposits of hard surfaces and / or for etching of surfaces, in particular in industry, containing resin, oil, carbon black or fat. Use of an agent according to any one of claims 1, 2, 4, 5 or 6, wherein the agent comprises alkalis and at least 10% by weight of hydrophobic organic solvents for the removal of stains from cocoa / chocolate, shoe polish, lipstick, chewing gum, turmeric or other stains containing grease or pigment. 10. Use of a composition according to any one of claims 1 to 6, which comprises at least 10 wt.% Bleaching agent, preferably from the group of peroxo compounds, for the removal of colored stains, in particular of red wine stains. 11. Use of a moss removal agent, wherein the composition comprises surfactants, an adhesion promoter and at least one active substance,  wherein the coupling agent is selected from the group of the alkylene-styrene copolymers, the olefin homopolymers or olefin copolymers of two or more olefins, where the polymers may also be hydrogenated and the polyalkylene derivatives are selected, the active substance is at least 5% of an acid and / or at least 1% of a biocide. PAGE INTENDED EMPTY