LIQUID ACID CLEANING AGENT COMPOSITIONS FOR HARD SURFACES

Abstract

The present invention relates to the use of a cleaning agent containing carboxylic acid for removing soils of plant origin and / or for decontaminating surfaces contaminated with plant protection products. The agent comprises 20-60% by weight of an aliphatic C1-C10 carboxylic acid, preferably formic acid, or a mixture of two or more such aliphatic carboxylic acids, preferably comprising formic acid, at least one surfactant, preferably an anionic surfactant and / or at least one nonionic surfactant, and the remainder being water and / or solvent. In another aspect, the present invention relates to special carboxylic acid-containing cleaning agents for hard surfaces that are particularly suitable for the intended use.

Description

The present invention relates to improved cleaning agent compositions that can be used particularly for cleaning hard surfaces. The invention relates specifically to liquid acidic cleaning agent compositions for removing plant contamination and / or for decontaminating surfaces, such as glass or metal surfaces in greenhouses, or transport and / or storage surfaces, as well as expanded polystyrene trays. The present invention relates in a very preferential way to a cleaning agent containing carboxylic acid, for example, a cleaning agent containing formic acid, and to its use for removing dirt of vegetable origin and / or for the decontamination of surfaces, in particular hard surfaces, which for example may also be contaminated with plant protection agents. The cleaning agent composition according to the invention is very effective in its efficacy; however, the use of ingredients highly hazardous to water can be dispensed with, so that a classification in water risk class 1 can also take place. In addition, the cleaning agent composition according to the invention is characterized by good biodegradability. State of the art Cleaning agents must meet numerous requirements. Ideally, on the one hand, they should not pose any serious risk to humans or the environment; on the other hand, they should also provide a high and efficient cleaning effect and be easy to handle. Several cleaning agent compositions have been prepared and are known in the prior art. For example, strongly acidic cleaning agents containing strong acids, such as hydrochloric acid, are useful for removing stains from hard water. However, strong acids are known to irritate the skin and pose potential toxicological risks. Furthermore, only a few cleaning agents provide any hygienic effect on the hard surfaces they treat. zzRrnn / zznz / e / Yi / u Plant-based soils differ significantly from inorganic and animal-based soils in their composition, and therefore present additional challenges to the composition of cleaning agents. Animal-based soils, such as those found on farms, include urine and feces, among other things. Dairy farms, for example, have a wide range of cleaning agents available for their removal. Experience has shown that these cleaning agents are only partially effective at removing plant-based contaminants. These contaminants of plant origin not only include plant extracts or juices that can be generated, for example, by damage to plant parts and fruits during harvesting, storage, and packaging on the farms, but also include products with plant-based ingredients, such as greenhouse shade paints. Specifically, commercially available shade paints often contain starch. After application to greenhouse glass surfaces, such starch-based paints can either be removed with difficulty using existing cleaning agents, or the effective cleaning agents are halogen-containing formulations that are therefore highly toxic and environmentally unfriendly. In summary, it can be established that the cleaning agents and methods currently known are manual removal of dirt with a brush and hot water or the use of polyfluorinated or perfluorinated surfactants in cleaning solutions. Due to the lack of degradability, persistence, toxicity, and bioaccumulation of fluorosurfactants, the production and use of this class of substances will be prohibited in the EU from July 2020. Another group of contaminants, which can appear in gardening or agriculture, are those contaminated with plant protection products, such as mitosis inhibitors, for example, on soil, storage, and transport surfaces. For the decontamination of such surfaces or other objects, such as transport crates and processing machinery, the market offers products that are either problematic due to their toxicity and environmental hazards, or that are ineffective in their cleaning performance. zzRrnn / zznz / e / Yi / u In its first aspect, the invention is based on the objective of providing a cleaning agent, also referred to herein as a cleaning agent composition or agent, that can be applied as universally as possible for removing soils of plant origin and / or for decontaminating surfaces, and that does not pose any serious risk to human health or the environment when used. Furthermore, the objective of the present invention is to provide an efficient and safe method for removing soils of plant origin and / or for decontaminating surfaces using a suitable cleaning agent. According to another aspect, cleaning agent compositions will also be provided in particular, which are best suited for cleaning and removing shading dirt and do not use fluorosurfactants as an active ingredient. These objectives are achieved according to a first aspect of the present invention by providing a hard surface cleaning agent composition, which has proven to be particularly advantageous for removing dirt of plant origin and / or for decontaminating surfaces contaminated with plant protection agents. The cleaning agent according to the invention comprises at least 20% by weight of an aliphatic carboxylic acid with 1 to 10 carbon atoms, in particular 20-60% by weight of formic acid or at least 20% by weight of a mixture of two or more such aliphatic carboxylic acids, wherein the mixture comprises formic acid. Furthermore, the cleaning agent according to the invention comprises one or more surfactants. The surfactant(s) are preferably anionic surfactants or a mixture of two or more anionic surfactants and / or nonionic surfactants or a mixture of two or more nonionic surfactants. The acid cleaning agent according to the invention for hard surfaces preferably comprises the following components: - 20-60% by weight of an aliphatic carboxylic acid with 1 to 10 carbon atoms, wherein the carboxylic acids are selected in particular from the group consisting of formic acid, acetic acid, propanoic acid, oxalic acid, malonic acid, citric acid and any mixture thereof or a mixture of two or more of such aliphatic carboxylic acids, - 1-30% by weight of an anionic surfactant, preferably an alkanesulfonic acid and / or an alkanesulfonate, or a mixture of two or more anionic surfactants, wherein the mixture preferably comprises an alkanesulfonic acid and / or an alkanesulfonate, - 0.1-5% by weight of a non-ionic surfactant, preferably a fatty alcohol ethoxylate, or a mixture of two or more non-ionic surfactants, wherein the mixture preferably comprises a fatty alcohol ethoxylate, and - as water and / or solvent residue. The agent according to the invention (hereinafter also referred to as the cleaning agent or cleaning agent composition) is characterized by its advantageous action in removing soils of plant origin and / or decontaminating surfaces contaminated with plant protection products. Therefore, it is used in particular for removing soils of plant origin. Another application is its use in decontaminating, for example, surfaces contaminated with plant protection products. The cleaning agent compositions according to the invention are characterized by high removal rates of dirt, for example, starch deposits, at room temperature within 3 to 15 minutes, preferably within 3 to 5 minutes. Compared to conventional cleaners, the cleaning agent compositions according to the invention achieve the desired result in a significantly shorter time. In this context, the bibliography Seifen, Fette, Ole, Wachse, SOFW 10, 2001, pages 108-114, provides detailed information on the type of cleaning solution, as well as the temperature and time required to remove starch deposits from glass surfaces. In contrast, the compositions according to the invention are characterized by a much improved effect.For example, a very high detachment rate of the deposits at room temperature could be determined in this way within 3 to 5 minutes for starch adhesions. The cleaning agent according to the invention is best suited for removing plant-based soils from hard surfaces and for surface decontamination. Surfaces to be decontaminated in the sense of the present invention are not only floor areas, floor coverings, glass surfaces, sheet surfaces, storage areas, and transport areas; the term also encompasses, but is not limited to, objects such as boxes, transport and / or storage devices, for example, expanded polystyrene trays, mats and irrigation channels, tape fabric, peeling, cutting, weighing, and processing machines. Such surfaces are examples of surfaces with a hard surface. The areas in question are found, for example, in gardening, agricultural operations, fruit shops, and plant and fruit processing companies. The agent according to the invention comprises at least one aliphatic carboxylic acid. Carboxylic acids are organic compounds that possess one or more carboxyl groups and, therefore, have a more or less pronounced acidic character. Depending on the number of carboxyl groups they contain, they are classified as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids. Unlike cyclic and aromatic carboxylic acids, the carboxyl group(s) is or are attached to an aliphatic residue R in aliphatic carboxylic acids. According to the invention, the aliphatic carboxylic acids are those with 1 to 10 carbon atoms. These include alkanoic, alkenoic, and alkynoic acids. In alkanoic acids, the R group is saturated. Alkenoic acids have at least one double bond in the R group, and alkynoic acids have at least one triple bond. The aliphatic carboxylic acids that can be used according to the invention, i.e., those included in the composition, can be mono-, di-, or tricarboxylic acids, with monocarboxylic acids being preferred. Preferred aliphatic monocarboxylic acids according to the invention are formic acid, acetic acid, propionic acid, or mixtures thereof. Examples of dicarboxylic acids are, but not conclusively, oxalic acid and malonic acid; citric acid is mentioned as an example of a tricarboxylic acid, also not conclusively. The aliphatic carboxylic acids described above, for example, the aliphatic monocarboxylic acids, may be comprised individually or in any mixture of such carboxylic acids in the cleaning agent according to the invention. Remarkably, it has been shown that one or more of the aliphatic carboxylic acid(s), in particular the monocarboxylic acid(s), act especially on plant sugars and constituents such as, for example, chlorophyll. The percentage of aliphatic carboxylic acid or mixture of aliphatic carboxylic acids in the agent according to the invention amounts to 20 to 60% by weight, preferably 25 to 58% by weight, even more preferably 30 to 55% by weight. The cleaning agent according to the invention contains at least one anionic surfactant in combination with at least one nonionic surfactant. The combination of these two surfactant groups has proven to be particularly advantageous. Anionic surfactants are surfactants that have a negatively charged functional group. Like all surfactants, anionic surfactants also consist of a polar and a nonpolar part. An alkyl group can act as the nonpolar part. The polar functional group can be, for example, a carboxylate group (-COO), a sulfonate group (-SO3), or a sulfate group (-SO42). In the case of anionic surfactants, alkanesulfonic acids and / or alkanesulfonates have proven particularly advantageous. Alkanesulfonates are the salts of alkanesulfonic acids. Sodium salts are especially preferred according to the invention. Therefore, the anionic surfactants most preferred according to the invention are alkanesulfonic acids and / or alkanesulfonates, particularly sodium alkanesulfonates. Even more preferred are alkanesulfonates with 10 to 20 carbon atoms, and most preferably those with 12 to 18 carbon atoms, or their salts, preferably their sodium salts. The anionic surfactant or mixtures of anionic surfactants comprising the composition according to the invention, in particular alkanesulfonic acids, alkanesulfonates and / or any mixture of alkanesulfonic acids and / or alkanesulfonates, are comprised in the compositions according to the invention in a percentage of 1 to 30% by weight, in particular in a percentage of 4 to 28% by weight, most preferably in a percentage of 6 to 25% by weight. Even though nonionic surfactants cannot dissociate in water, they are, in this sense, compounds that have both hydrophilic (polar) and hydrophobic (nonpolar) structures within the molecule. Nonionic surfactants are characterized by their good washing performance and high dissolving power for plant contaminants, especially at lower temperatures. In the case of nonionic surfactants, fatty alcohol ethoxylates have proven particularly advantageous. Fatty alcohol ethoxylates can be produced by adding ethylene oxide to natural and synthetic fatty alcohols. The particularly preferred nonionic surfactants according to the invention are therefore fatty alcohol ethoxylates. According to the present invention, it is especially preferred that the fatty alcohol ethoxylates used be prepared from natural or synthetic fatty alcohols with 6 to 22 carbon atoms, preferably with 12 to 18 carbon atoms. Suitable fatty alcohols include, for example, hexan-1-ol, octan-1-ol, decane-1-ol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, behenyl alcohol, hexadecenol, oleyl alcohol, linoleyl alcohol, decyl alcohol, stearyl alcohol, or mixtures of Cs to C22 chain cuts, such as coconut fatty alcohol and palm kernel oil alcohol, synthetic primary alcohols such as C13 iso-oxoalcohols, C13 / C15 oxoalcohols, mixtures of linear, once-branched, or many-times-branched oxoalcohols with an average carbon chain length of 10 to 15 carbon atoms, Ziegler alcohols with 8 to 22 carbon atoms, and Guerbet alcohols with 10, 12, 14, 16, or 18 carbon atoms. Carbon and linear and branched secondary alcohols with 8 to 22 carbon atoms. Alcohols can be saturated or unsaturated. According to the invention, the ethoxylates preferably have a degree of ethoxylation (DE) in the range of 3 to 9, more preferably in the range of 4 to 8, and most preferably in the range of 5 to 7. In this respect, for example, within the context of this disclosure, the indication DE 3 means that the fatty alcohol has reacted with 3 moles of ethylene oxide. The non-ionic surfactants or the mixture of non-ionic surfactants comprising the composition according to the invention, in particular one of the fatty alcohol ethoxylates described above or any mixture thereof, comprises a percentage of 0.1 to 5% by weight, in particular a percentage of 0.5 to 5% by weight, most preferably zzRrnn / zznz / e / YiAi with a percentage of 1 to 3% by weight in the composition according to the invention. In one embodiment, the agent according to the invention may also contain an aromatic carboxylic acid or a mixture of two or more aromatic carboxylic acids. The aromatic carboxylic acid is preferably benzoic acid. If the agent according to the invention comprises a mixture of aromatic carboxylic acids, the mixture preferably contains benzoic acid, in particular at least 30% by weight of all the aromatic carboxylic acids in the mixture. Benzoic acid is also characterized by a preservative property. The aromatic carboxylic acid, in particular benzoic acid, can be used in acidic media at low concentrations to inhibit corrosion when a stronger acid almost completely suppresses the dissociation of the aromatic carboxylic acid, particularly benzoic acid. The aromatic carboxylic acid or mixture of aromatic carboxylic acids, for example, benzoic acid or a mixture containing benzoic acid, is preferably contained in the composition according to the invention in a percentage of 0.3 to 3% by weight. Even more preferably, the optional percentage of one or more of the aromatic carboxylic acids is from 0.4 to 2.8% by weight, and even more preferably from 0.5 to 2.6% by weight. In another embodiment according to the invention, the cleaning agent according to the invention does not contain any aromatic carboxylic acids. Since unavoidable impurities are not to be considered here, the statement "no aromatic carboxylic acids" means that one or more aromatic carboxylic acids are present with a total percentage, with respect to the cleaning agent composition, of from 0% by weight to less than 0.01% by weight. Preferably, the maximum permissible upper limit is 0.008% by weight, more preferably 0.006% by weight, and even more preferably 0.004% by weight, in each case with respect to the cleaning agent composition. Most preferably, the percentage of aromatic carboxylic acids in the composition is 0% by weight. The cleaning agent according to the invention further comprises water (as a solvent) and / or at least one other solvent besides water. Preferably, the solvent is water or comprises water in a mixture of solvents. Other solvents besides water are known to the skilled trade. They include, in particular, alcohols, for example, ethanol. The percentage of at least one solvent is the remainder up to 100% by weight (up to 100% by weight) of the total composition of the cleaning agent according to the invention. That is, the percentages, % by weight, of the essential and, where applicable, optional constituents present in the composition are always selected so that the total is 100% by weight. In the case of the cleaning agent according to the invention, it is preferably a liquid acidic composition. The cleaning agent according to the invention preferably has an acidic pH value in the range of 2 to 4. According to a preferred embodiment, the agent according to the invention may also contain one or more foam boosters or foam enhancers, preferably selected from the group of amine oxides, in particular alkylamine oxides. The foam booster(s) are preferably comprised in the agent according to the invention at a percentage of 0.3 to 5% by weight. Even more preferably, the percentage is from 0.4 to 4% by weight. Alkylamine oxides preferably contain alkyl moieties with a chain length of 14 to 24 carbon atoms. According to the invention, a preferred foam booster is coconut propylamine oxide, coconut fatty acid amidopropyldimethylamine oxide, cocamidopropylamine oxide, or coconut fatty acid amidopropyldimethylammonium oxide with different chain lengths (CAS No. 68155-09-9). In addition to the foam boosters explicitly mentioned above, other commercially available foam boosters known to those skilled in the art may be used. Therefore, using a foam booster is advantageous because the foam formed from the cleaning agent adheres well to the surface being cleaned, thus leading to thorough cleaning. The combination of the aforementioned surfactants, particularly those with a high percentage of anionic surfactants, along with one or more foam boosters, has proven surprisingly beneficial. zzRrnn / zznz / e / YiAi Furthermore, it has been surprisingly found that, with regard to the stability of the composition and / or the foam, as well as the cleaning effect, a combination of cocamidopropylamine oxide, preferably in the range of 0.3 to 5% by weight, with formic acid, preferably in the range of 20%, and even more preferably 25%, to 60% by weight, in each case with respect to the composition according to the invention, provides particularly advantageous effects. Compositions with such a combination of ingredients, and the foam obtained from them, are stable under acidic conditions. In particular, the inactivation of the carboxylic acid(s) can be counteracted, for example, by complexation. According to a preferred embodiment of the cleaning agent according to the invention, the aliphatic carboxylic acid is formic acid, which is included in the composition according to the invention in a percentage of 20 to 60% by weight, more preferably in a percentage of 25 to 58% by weight, and even more preferably in a percentage of 30 to 55% by weight. If the agent according to the invention contains a mixture of two or more aliphatic carboxylic acids as an aliphatic carboxylic acid component, the formic acid is preferably contained in said mixture. Even more preferably, the percentage of formic acid is at least 30% by weight, and preferably at least 40% by weight, with respect to the sum of the percentages of aliphatic carboxylic acids with 1 to 10 carbon atoms in this mixture. Therefore, the use of formic acid is particularly advantageous because, surprisingly, formic acid, especially at the concentration used according to the invention, has been shown to exhibit very good and specific cleaning action against, for example, plant mono-, di-, and polysaccharides, as well as against compounds of plant secondary metabolism, such as pigments, including chlorophyll. While not explicitly stating this, it is worth noting that formic acid is the simplest and shortest-chain alkanoic acid, and the carboxyl group strongly influences its cleaning properties. Optionally, other common additives and processing aids for cleaning agents may also be added to the agent according to the invention. Suitable substances and mixtures of substances are well known to those skilled in the art and are commercially available. The additives and processing aids zzRrnn / zznz / e / YiAi may include, for example, common formulation aids acceptable for the intended purpose, colorants and fragrances, buffering agents, structural agents, preservatives, etc. In this case, one or more substances for corrosion protection may be added to the agent according to the invention. For the purposes of this disclosure, corrosion protection means measures to prevent damage caused by the corrosion of metallic components, but also of materials such as glass, plastics, building materials, etc. The protective measures adopted are aimed, in particular, at reducing the rate of corrosive attack to such an extent that damage to the component or material can be prevented during its service life, or at least its functionality is not impaired. For a more detailed definition, please refer to DIN EN ISO 8044. Suitable anti-corrosion agents for this purpose are generally known to those skilled in the art and are commercially available. However, to prevent or reduce corrosion processes, the anti-corrosion agent benzotriazole is preferably used according to the invention. Surprisingly, this has proven to be particularly advantageous in combination with the other essential and optional constituents of the cleaning agent according to the invention. According to the invention, benzotriazole may be included in the cleaning agent according to the invention individually or in combination with other corrosion protection agents and / or other additives and adjuvants. The anti-corrosion agent(s) are present in the agent according to the invention, preferably in a concentration of 0.05 to 1% by weight, more preferably from 0.1 to 0.8% by weight, and even more preferably from 0.15 to 0.6% by weight. The particularly preferred anti-corrosion agent according to the invention, benzotriazole, is preferably present in a concentration of 0.05 to 1% by weight, more preferably from 0.1 to 0.8% by weight, and even more preferably from 0.15 to 0.6% by weight. According to a preferred embodiment of the invention, the cleaning agent according to the invention is free from highly hazardous ingredients for water. In this context, highly hazardous ingredients for water means substances and mixtures that are classified, according to their hazard, in water hazard class 3 according to the requirements of the Water Hazardous Substances Management Systems Ordinance (AwSV) issued on April 18, 2017. For the purposes of this disclosure, the indication "free from" means that the percentage of such constituents in the total composition is from 0 to less than 0.01% by weight. Preferably, the maximum permissible upper limit is 0.008% by weight, more preferably 0.006% by weight, and even more preferably 0.004% by weight, in each case with respect to the cleaning agent.Ideally, the percentage of these constituents in the composition should be 0% by weight. In this respect, any unavoidable contaminants will not be taken into account. Therefore, the components of the cleaning agent according to the invention shall preferably be selected so that at least one classification in water hazard class 2 may take place, and more preferably one classification in water hazard class 1. Water hazard classes 1, 2 and 3 are defined for the purposes of this disclosure in accordance with the Water Hazardous Substances Handling Systems Ordinance (AwSV) issued on April 18, 2017. Furthermore, it is preferred according to the invention that the components of the cleaning agent be selected so that the agent is readily biodegradable. According to a preferred embodiment, the agent according to the invention / the cleaning agent composition according to the invention comprises the following components: 25-55% by weight of an aliphatic monocarboxylic acid, preferably formic acid, 0-3% by weight of at least one aromatic carboxylic acid, preferably benzoic acid, 1-30% by weight of an alkylsulfonate with 12 to 18 carbon atoms or its sodium salt, 0.5-5% by weight of a fatty alcohol ethoxylate, wherein the fatty alcohol has 15 to 30 carbon atoms, preferably with a degree of ethoxylation in the OE range 3 to 9, 0-5% by weight preferably 0.3-5% by weight zzRrnn / zznz / e / YiAi 0-1% by weight up to 100% of at least one amine oxide, preferably cocamidopropylamine oxide, of an anti-corrosion agent, preferably benzotriazole, and by weight of water and / or other solvent. In addition to the constituents mentioned for this preferred embodiment of the agent according to the invention, a cleaning agent of this type may optionally contain one or more common additives and adjuvants. Also included within the scope of the present invention are those compositions or agents which, with the exception of usual impurities, are composed only of the essential components mentioned above, and in some cases one or more of the optional components. According to another preferred embodiment, the agent according to the invention / the cleaning agent composition according to the invention comprises the following components: 24-45% by weight 1-15% by weight -3% by weight -25% by weight 0.5-5% by weight 0-5% by weight preferably 0.3-5% by weight 0-1% by weight of an aliphatic monocarboxylic acid other than propionic acid, preferably formic acid, of propionic acid, of at least one aromatic carboxylic acid, preferably benzoic acid, of an alkylsulfonate having 12 to 18 carbon atoms or its sodium salt, of a fatty alcohol ethoxylate, the fatty alcohol having 15 to 30 carbon atoms, preferably with a degree of ethoxylation in the range of EO 3 to 9, of at least one amine oxide, preferably cocamidopropylamine oxide, of an anti-corrosion agent, preferably benzotriazole, and up to 100% by weight of water and / or other solvent. In addition to the constituents mentioned for this preferred embodiment of the agent according to the invention, a cleaning agent of this type may optionally contain one or more common additives and adjuvants. Also included within the scope of the present invention are those compositions or agents which, with the exception of usual impurities, are composed only of the essential components mentioned above, and in some cases one or more of the optional components. In the case of the agent according to the invention, it is a single-component liquid product from which a diluted solution for use can be prepared, containing from 0.5 to 5% by weight, and in particular from 0.8 to 2.2% by weight, of the agent. Therefore, this application also relates, in another respect, to the diluted solution for use described above. The dilution of the agent for the solution for use is preferably carried out with water. Another aspect of the present invention relates to the use of a cleaning agent containing carboxylic acid for removing soils of plant origin and / or for decontaminating surfaces contaminated, for example, with plant protection products. The cleaning agent used according to the invention comprises at least 20% by weight of an aliphatic carboxylic acid with 1 to 10 carbon atoms or at least 20% by weight of a mixture of two or more such aliphatic carboxylic acids. Furthermore, the cleaning agent used according to the invention comprises one or more surfactants. The surfactant(s) are preferably anionic surfactants or a mixture of two or more anionic surfactants and / or nonionic surfactants or a mixture of two or more nonionic surfactants. The cleaning agent used according to the invention preferably comprises - 20-60% by weight of an aliphatic carboxylic acid with 1 to 10 carbon atoms, or a mixture of two or more such aliphatic carboxylic acids, preferably comprising formic acid or wherein the mixture preferably comprises formic acid, - at least one surfactant, wherein the at least one surfactant is preferably an anionic surfactant or a mixture of two or more anionic surfactants, preferably with a percentage of the anionic surfactant(s) not exceeding 30% by weight, and / or a non-ionic surfactant or a mixture of two or more non-ionic surfactants, preferably with a percentage of the non-ionic surfactant(s) not exceeding 5% by weight, and - as water and / or solvent residue. The use of such an agent allows for gentle but effective removal of plant dirt and / or decontamination of surfaces. As explained in the section on composition, according to the invention, the aliphatic carboxylic acids are those with 1 to 10 carbon atoms. These include alkanoic, alkenoic, and alkynoic acids. The aliphatic carboxylic acids that can be used according to the invention may be mono-, di-, or tricarboxylic acids, with monocarboxylic acids being preferred. Particularly preferred aliphatic carboxylic acids are formic acid, acetic acid, and propionic acid. These carboxylic acids may be contained individually or in any mixture of such carboxylic acids, particularly monocarboxylic acids, in the cleaning agent according to the invention or in the cleaning agent used according to the invention. The percentage of aliphatic carboxylic acid or mixture of aliphatic carboxylic acids in the agent according to the invention amounts to 20 to 60% by weight, preferably 25 to 58% by weight, even more preferably 30 to 55% by weight. In a particularly preferred embodiment, the aliphatic carboxylic acid is formic acid. That is, the agent used comprises formic acid as the aliphatic carboxylic acid. If the agent used contains several aliphatic carboxylic acids, it is preferred that the percentage of formic acid in the aliphatic carboxylic acid component be at least 30% by weight. The agent used according to the invention comprises at least one surfactant or a mixture of surfactants, preferably in a percentage of 1 to 30% by weight. Furthermore, preferably, the agent used according to the invention comprises at least one anionic surfactant and / or at least one non-ionic surfactant. The percentage of the anionic surfactant or surfactants in the agent used preferably does not exceed 30% by weight; more preferably, the percentage is from 1 to 30% by weight, particularly from 4 to 28% by weight, and most preferably from 6 to 25% by weight. The percentage of non-ionic surfactant or non-ionic surfactants in the agent used preferably amounts to no more than 5% by weight, even more preferably from 0.1 to 5% by weight, in particular from 0.5 to 4% by weight, most preferably from 1 to 3% by weight.Regarding the surfactant system, a combination of one or more anionic surfactants with one or more non-ionic surfactants is particularly advantageous for the reasons already described above. In the case of such a combination, the percentage of the anionic surfactant(s) is, with respect to the total composition of the agent, preferably from 1 to 30% by weight, even more preferably from 4 to 28% by weight, and the percentage of the non-ionic surfactant(s) is, with respect to the total composition of the agent, preferably from 0.1 to 5% by weight, even more preferably from 0.5 to 4% by weight. In principle, all anionic surfactants known to those skilled in the art may be used in cleaning agents and any mixtures thereof. However, surprisingly, it has been found that alkanesulfonates and / or their salts, particularly their sodium salts, are preferred as anionic surfactants. Reference is made to the preceding embodiments regarding even more preferred embodiments of these anionic surfactants. Similarly, with regard to nonionic surfactants, in principle, all nonionic surfactants known to those skilled in the art may be used in cleaning agents and any mixtures thereof. However, surprisingly, fatty alcohol ethoxylates, particularly those with a degree of ethoxylation (DE) in the range of 3 to 9, have been found to be preferred as nonionic surfactants.With regard to even more preferred embodiments for these non-ionic surfactants, reference is made to the above embodiments. The cleaning agent used according to the invention further comprises water (as a solvent) and / or at least one other solvent besides water. Preferably, the solvent is water or comprises water in a mixture of solvents. Other solvents besides water are known to the skilled trade. They include, in particular, alcohols, such as, for example, ethanol. The percentage of at least one solvent is the remainder up to 100% by weight (up to 100% by weight) of the total composition of the cleaning agent according to the invention. That is, the percentages, % by weight, of the essential and, where applicable, optional constituents present in the composition are always selected so that the total is 100% by weight. The cleaning agent used according to the invention preferably has an acidic pH value, even more preferably a pH value in the range of 2 to 4. The cleaning agent used according to the invention is preferably a liquid composition. The agent used according to the invention may optionally also contain at least one aromatic carboxylic acid, preferably benzoic acid, and / or an anti-corrosion agent, preferably benzotriazole, and / or other additives and / or adjuvants known to the skilled worker in the art for cleaning agents. Regarding the preferred percentages of these optional constituents, reference is made to the prior disclosure relating to the agent itself. These percentages apply accordingly. According to a preferred embodiment of the invention, the cleaning agent used is one of the hard surface cleaning agents described above in accordance with the first aspect of the invention. Reference is made to the corresponding disclosure regarding the individual constituents and their percentages, also with respect to particularly preferred embodiments. According to a preferred form of use according to the invention, in the case of the dirt to be removed, it is a dirt or deposit that contains starch. Starch is the most important storage substance in plant cells. Animal organisms and fungi use a different carbohydrate reserve. This polysaccharide is one of the reasons why soils of plant origin differ significantly from soils or deposits of animal origin. Effective starch removal presents particular challenges for the cleaning agent to be used. Surprisingly, it has been shown that cleaning agents containing carboxylic acid are especially preferred for removing soils or deposits containing starch. The vast majority of shade cloths on the market for greenhouse glass surfaces are starch-based. Therefore, the use according to the invention relates, in one embodiment of the invention, to the use of one of the carboxylic acid-containing cleaning agents described above to remove shade cloth, particularly from greenhouse glass surfaces. Until now, halogen-containing formulations, which are highly toxic and environmentally unfriendly, have been used for this purpose. Surprisingly, the carboxylic acid-containing cleaning agents described herein achieve at least the same level of cleaning effectiveness, yet are significantly less toxic and therefore easier to handle. They are also characterized by significantly better environmental compatibility.In particular, it has been shown that starch deposits can be removed at room temperature within 3 to 15 minutes, preferably within 3 to 5 minutes. These high rates of deposit removal at room temperature are surprising and advantageous. In the case of soils of vegetable origin, which must be removed, it is possible to treat according to the invention, instead of or in addition to soils containing starch, vegetable juices / extracts containing sugar and / or amino acid, in particular tomato, pepper and / or cucumber juices / extracts. Such juices or extracts are generated, for example, during the harvesting, packing, storage, or processing of plant products, particularly tomatoes, peppers, and / or cucumbers, in gardening or at distribution centers. Due to their chemical composition, these impurities are difficult to remove from soiled surfaces or objects. It has been surprisingly shown that a cleaning agent containing carboxylic acid, as described above, and in particular, a cleaning agent containing carboxylic acid according to the first aspect of the present invention, is also very well suited for effectively and gently removing such impurities. Furthermore, aspects related to food legislation and / or worker protection can be taken into account through the use of the agent.According to another form zzRrnn / zznz / e / YiAi of embodiment of the use according to the invention, the cleaning agent containing carboxylic acid is therefore used to remove vegetable juices / extracts containing sugar and / or amino acid, in particular to remove juices / extracts from tomato, pepper and / or cucumber. The group of plant-based soils that are problematic to remove also includes soil or deposits containing chlorophyll and / or colored components. Such deposits can be green coatings, for example, algae coatings. Chlorophylls are natural pigments produced by photosynthetic organisms. Therefore, they are found in all parts of green plants. The term "colored components," as used in connection with the present invention, means or includes other photosynthetic pigments and colored secondary plant ingredients. It has been surprisingly shown that a cleaning agent containing carboxylic acid, as described above, and in particular a cleaning agent containing carboxylic acid according to the first aspect of the present invention, is also very well suited for effectively and gently removing such soils. Furthermore, aspects related to food legislation and / or worker protection can be taken into account through the use of the agent. According to another embodiment of the invention, the cleaning agent containing carboxylic acid is therefore used to remove soils or deposits containing chlorophyll and / or other colored components, particularly for removing deposits from green coatings, for example, algae deposits. The use, according to the invention, of a cleaning agent containing carboxylic acid also includes the use of a cleaning agent containing carboxylic acid as described above, and in particular a cleaning agent containing carboxylic acid according to the first aspect of the present invention, for decontaminating surfaces contaminated with plant protection agents. The plant protection agents in question are chlorpropham [1-methylethyl ester of (3-chlorophenyl)carbamic acid] and / or maleic acid hydrazide. Chlorpropham is a herbicide widely used in agriculture. It degrades slowly or at a moderate rate in water or soil. Maleic acid hydrazide is also an active ingredient used on large areas in agricultural production.Residues left on plant parts or washed-off plant protection products can lead to surface contamination that requires decontamination. Such contamination can pose a considerable problem in production and marketing companies, for example. It has been surprisingly shown that a cleaning agent containing carboxylic acid, as described above, and in particular a cleaning agent containing carboxylic acid according to the first aspect of the present invention, is also particularly well-suited for removing such contamination. Furthermore, considerations related to food legislation and / or worker protection can be addressed through the use of this agent. According to one embodiment of the use according to the invention, in the case of the surface to be cleaned, it is preferably a surface selected from the group consisting of boxes, storage surfaces, transport surfaces, storage and / or transport devices, floor coverings, mats and / or irrigation channels, glass surfaces, sheet surfaces, tape fabric, peeling, cutting, weighing and processing machines. According to another embodiment of the use according to the invention, in the case of the surface to be cleaned it is a greenhouse surface, in particular it is a glass, plastic or metal surface in a greenhouse. The agent is applied, in the case of use according to the invention, either directly as a liquid, preferably as a diluted solution, preferably aqueous, or as a foam or a highly foaming liquid. The cleaning agent, in particular the cleaning agent according to the first aspect of the present invention, can be applied to the objects or surfaces to be cleaned as an aqueous solution corresponding to the first variant. Subsequently, foam formation can be triggered by a mechanical action. It should be made clear again here that foam formation is not essential for the action of the agent. That is to say, in principle, the action according to the invention can also be achieved without foam formation. zzRrnn / zznz / e / YiAi If the agent according to the invention, in the second preferred embodiment, is applied to surfaces or objects as a foam or highly foaming liquid, this can be done, for example, by means of a commercially available foam syringe. Corresponding devices are well known to those skilled in the art. In particular, a foam-generating device, as disclosed in European patent no. 2476481, can be used. For both application variants, the contact time of the agent according to the invention on the surface to be cleaned or the object to be cleaned is preferably at least 10 seconds, preferably at least 20 seconds, more preferably at least 30 seconds, and most preferably at least 40 seconds. Furthermore, the maximum contact time of the agent according to the invention on the surface or object is preferably 30 minutes, preferably 20 minutes, 10 minutes, or 8 minutes, more preferably 6 minutes, and most preferably a maximum of 4 minutes. The high compatibility of the agent according to the invention, mentioned above, has proven to be particularly advantageous in this respect and enables extended contact times. After the contact time, the agent or foam is preferably at least partially washed off or otherwise removed from the surface or object.Naturally, several successive cleanings of the same surface or the same object are also possible, as required, and are included within the scope of the present invention. According to a preferred embodiment of the use according to the invention, the carboxylic acid-containing cleaning agent, and in particular the carboxylic acid-containing cleaning agent according to the first aspect of the present invention, is dissolved prior to use. The dilution of the agent may be carried out with water or another suitable solvent. Suitable solvents are known to those skilled in the art. The application concentration of the cleaning agent is preferably from 0.5 to 5%, and preferably from 0.8 to 2.2%, with respect to the cleaning agent. The pH value of the diluted, ready-to-use cleaning agent is preferably in the range of 2 to 4. In another additional provision, the present invention also provides a method for removing soils of plant origin and / or for the decontamination of surfaces, the method comprising the steps of: zzRrnn / zznz / e / Yi / u - to provide a cleaning agent containing carboxylic acid, comprising 20-60% by weight of an aliphatic carboxylic acid with 1 to 10 carbon atoms, preferably formic acid, or a mixture of two or more such aliphatic carboxylic acids, preferably comprising formic acid, comprising at least one surfactant and the remainder being water and / or solvent. The at least one surfactant is preferably an anionic surfactant or a mixture of two or more anionic surfactants, preferably with a percentage of the anionic surfactant(s) not exceeding 30% by weight, and / or a non-ionic surfactant or a mixture of two or more non-ionic surfactants, preferably with a percentage of the non-ionic surfactant(s) not exceeding 5% by weight. - apply the cleaning agent containing carboxylic acid provided to a surface soiled with plant-based dirt and / or a surface contaminated with plant protection agents, and - clean the surface. According to a preferred embodiment of the process according to the invention, the application of the cleaning agent composition in the process according to the invention takes place either directly as a liquid, preferably as an aqueous solution, or as a foam or a highly foaming liquid. Corresponding to the first embodiment, the cleaning agent composition can be applied as an aqueous solution. Subsequently, foam formation can be triggered by a mechanical action. It should be made clear again in this case that foam formation is not essential for the action of the composition. That is, in principle, the action according to the invention can also be achieved without foam formation. If the agent according to the second preferred variant is applied as a foam or a highly foaming liquid, this can be done, for example, by means of a commercially available foam syringe. Corresponding devices are well known to those skilled in the art. In particular, a foam-generating device, as disclosed in European patent no. 476 481, can be used. Regarding the contact time of the cleaning agent on the surface to be cleaned, reference is made, for both application methods, to the corresponding embodiments in relation to the use according to the invention. The times apply equally to the use according to the invention and to the procedure according to the invention. After the contact time, the agent or foam is preferably at least partially washed off or otherwise removed from the surface or object. Naturally, several successive cleanings are also possible as required and are included within the scope of the present invention. That is, the procedure according to the invention may comprise the additional steps of allowing the applied composition to act, preferably for the contact times mentioned above, and / or the step of washing off or otherwise removing the applied composition, if necessary, after its action. It is also provided according to the invention that the cleaning agent composition, prior to its application as a solution, foam, or high-foaming solution, is diluted to a desired application concentration in a previous procedural step. The dilution of the composition may take place with water or another suitable solvent. Suitable solvents are known to those skilled in the art. The application concentration of the cleaning agent composition then preferably ranges from 0.5 to 5% by weight, particularly from 0.8 to 2.2% by weight of the original composition. The dilution of the composition for the application solution preferably takes place with water. That is to say, the process according to the invention may comprise the additional step, prior to application, of diluting the composition to be applied, preferably to the application concentrations mentioned above. In a preferred embodiment, the process according to the invention therefore comprises the following steps - provide a cleaning agent composition, which is composed as described above, - if necessary, dilute the provided cleaning agent composition to an application concentration of preferably 0.5 to 5% by weight, preferably with water and / or another suitable solvent, - Apply the cleaning agent composition, diluted if necessary, to the surface to be treated, - allow the applied cleaning agent composition to act, preferably for a period of time from 10 seconds to 30 minutes, and - wash or remove the applied cleaning agent composition. With regard to preferred embodiments of the cleaning agent used in the process according to the invention, reference is made to prior embodiments. In particular, the cleaning agent according to the first aspect of the invention is used in such a process. Preferably, the surface to be cleaned contains a starch-containing dirt or deposit, which is even more preferably dirt caused by shading paint for greenhouse glass surfaces. That is, in a preferred embodiment, a method is provided for removing starch-containing dirt or deposits, in particular shading paint, for example, from greenhouse glass surfaces. It has been surprisingly shown that a cleaning agent containing carboxylic acid, as described above, and in particular a cleaning agent containing carboxylic acid according to the first aspect of the present invention, is also very well suited for effectively and gently removing starch from surfaces such as glass, metal, or plastics. According to another embodiment of the process according to the invention, the cleaning agent containing carboxylic acid is therefore used to remove starch from surfaces, particularly glass, metal, and / or plastic surfaces, in the cleaning process according to the invention. In another preferred embodiment, a process is provided for removing plant juices / extracts containing sugar and / or amino acids, particularly from tomato, pepper, and / or cucumber juices or extracts. Yet another embodiment is a process for removing dirt or deposits containing chlorophyll, particularly for removing green deposits, for example, from an algae coating. Another embodiment according to the invention provides a process for decontaminating surfaces contaminated with plant protection agents, particularly with chlorpropham [1-methylethyl ester of (3-chlorophenyl)carbamic acid] and / or maleic acid hydrazide. For further details on the surfaces to be cleaned, please refer to the corresponding embodiments in relation to the use according to the invention. zzRrnn / zznz / e / Yi / u This disclosure applies both to the use according to the invention and to the process according to the invention. The following examples explain the invention, however, without limiting it to them; all data are, unless otherwise indicated, in % by weight. zzRrnn / zznz / e / Yi / u Examples Example 1: Cleaning agent containing carboxylic acid (according to the invention) Components Parts by weight (w / w) sodium C12-C18 alkanesulfonate 10.00 C15-C20 fatty alcohol ethoxylate [3OE] 2.00 formic acid 30.00 benzotriazole 0.30 water up to 100.00 Example 2: Cleaning agent containing carboxylic acid (according to the invention) Components Parts by weight (w / w) sodium C12-C18 alkanesulfonate 20.00 C15-C30 fatty alcohol ethoxylate [7OE] 2.50 formic acid 25.00 propionic acid 10.00 benzoic acid 2.00 water up to 100.00 Example 3: Cleaning agent containing carboxylic acid (according to the invention) Components Parts by weight (w / w) sodium C12-C18 alkanesulfonate 20.00 cocco fatty acid amidopropyldimethylammonium oxide formic acid 50.00 water up to 100.00 Example 4: Cleaning agent containing carboxylic acid (according to the invention) Components Parts by weight (w / w) zzRrnn / zznz / e / Yi / u sodium C12-C18 alkanesulfonate20.00 sodium C12-C18 alkanesulfonate20.00 amidopropyldimethylammonium oxide of fatty acidθθ of coconut] formic acid50.00 water up to 100.00 In preparing the example formulations 1 to 4, the procedure is as follows: first, water, preferably purified water, is added, and then one of the various carboxylic acids is dissolved in it. The surfactant components are added to this solution, and if benzotriazole and / or foam booster are present, additional water may be added to bring the total volume to 100% by weight, and the mixture is stirred. A clear, highly foaming liquid is generated. The example formulations described above, which in each case represent a single-component liquid product, are diluted in each case to give a diluted aqueous solution containing 1.5% of the agent and are then applied by foam syringe and left to act briefly on the surfaces to be cleaned. It has been shown that, by means of the cleaning agent compositions according to the invention, by way of example, a starch-based shading paint can be effectively and gently removed from a glass surface at room temperature and an acting time of 4 minutes. Positive results comparable to the removal of vegetable juices from dirty transport crates were achieved. In this case as well, the cleaning was very effective and gentle.

Claims

1. Use of a liquid acid cleaning agent composition containing carboxylic acid for the removal of soils of vegetable origin and / or for the decontamination of contaminated surfaces, wherein the cleaning agent comprises: - 20-60% by weight of formic acid or a mixture of two or more aliphatic carboxylic acids with 1 to 10 carbon atoms, the mixture comprising formic acid, and the carboxylic acids with 1 to 10 carbon atoms being selected from the group consisting of acetic acid, propanoic acid, oxalic acid, malonic acid, citric acid and any mixture thereof, - 1-30% by weight of an anionic surfactant, preferably an alkanesulfonic acid and / or an alkanesulfonate, or a mixture of two or more anionic surfactants, wherein the mixture preferably comprises at least one alkanesulfonic acid and / or at least one alkanesulfonate, - 0.1 -5% by weight of a fatty alcohol ethoxylate, or a mixture of two or more non-ionic surfactants,wherein the mixture preferably comprises at least one fatty alcohol ethoxylate, and the remainder being water and / or solvent.

2. Use according to claim 1, wherein the percentage of formic acid in the aliphatic carboxylic acid mixture amounts to at least 30% by weight, with respect to the sum of the percentages of aliphatic carboxylic acids with 1 to 10 carbon atoms in this mixture.

3. Use according to any of the preceding claims, wherein the anionic surfactant is or comprises C12-C18 sodium alkanesulfonate and / or the nonionic surfactant is or comprises a C13-C30 fatty alcohol ethoxylate with a degree of ethoxylation in the range of OE 3 to 9.

4. Use according to any of the preceding claims, further comprising 0.3-3% by weight of an aromatic carboxylic acid, or 0.3-3% by weight of a mixture of two or more aromatic carboxylic acids.

5. Use according to claim 4, wherein the aromatic carboxylic acid is benzoic acid, or the mixture comprises benzoic acid.

6. Use according to one of the preceding claims, further comprising one or more foam boosters.

7. Use according to claim 6, wherein the at least one foam booster is from the alkylamine oxide group.

8. Use according to claim 6 or claim 7, wherein the foam booster(s) is / are preferably found in a percentage of 0.3-5% by weight.

9. Use according to any of the preceding claims, wherein the cleaning agent composition is free from ingredients highly hazardous to water, and / or the cleaning agent composition is readily biodegradable, and / or the cleaning agent composition has a pH value in the range of 2 to 4.

10. Use according to claim 9, wherein the ingredients are selected so that a classification of the cleaning agent composition takes place in water hazard class 1.

11. Use according to any one of claims 1 to 10, wherein in the case of dirt it is dirt or deposit containing starch.

12. Use according to any one of claims 1 to 10, wherein the dirt is a shading paint for greenhouse glass surfaces.

13. Use according to claim 11, wherein the dirt or deposit is a starch adhesion on surfaces. zzRrnn / zznz / e / YiAi 14. Use according to claim 13, wherein the surface is a glass or metal surface.

15. Use according to claim 14, wherein in the case of the dirt to be removed it is vegetable juices / extracts containing sugar and / or amino acid.

16. Use according to claim 15, wherein the juices / extracts are from tomato, pepper and / or cucumber.

17. Use according to claim 16, wherein in the case of the dirt to be removed it is a dirt or deposit that contains chlorophyll.

18. Use according to claim 17, wherein in the case of the dirt to be removed it is a deposit of green linings.

19. Use according to claim 18, wherein in the case of the deposit to be removed it is an algae coating.

20. Use according to claim 19 for the decontamination of surfaces contaminated with plant protection agents.

21. Use according to claim 20, wherein the phytoprotective agent is chlorpropham [1-methylethyl ester of (3-chlorophenyl)-carbamic acid] and / or maleic acid hydrazide.

22. Use according to any one of claims 1 to 21, wherein the surface to be cleaned or decontaminated is selected from the group consisting of storage surfaces, transport surfaces, floor surfaces, floor coverings, glass surfaces, sheet surfaces, boxes, transport devices, storage devices, for example expanded polystyrene trays, irrigation mats, irrigation channels, tape fabric, peeling machines, cutting machines, weighing machines, and processing machines. zzRrnn / zznz / e / Yi / u 23. Use according to claim 22, wherein in the case of the surface to be cleaned zzRrnn / zznz / e / Yi / u it is a greenhouse surface.

24. Use according to claim 23, wherein the greenhouse surface is a glass or metal surface.

25. Use according to any one of claims 1 to 24, wherein the cleaning agent composition is applied as a diluted aqueous solution or as a foam.

26. Use according to claim 25, wherein the application concentration of the cleaning agent composition is from 0.5 to 5% by weight, with respect to the cleaning agent composition.

27. Use according to claim 26, wherein the application concentration of the cleaning agent composition ranges from 0.8 to 2.2% by weight, with respect to the cleaning agent composition.