EP3800239A1 - Liquid, acidic cleaning compositions for hard surfaces - Google Patents

Abstract

The present invention relates to the use of a carboxylic acid-containing cleaning agent for removing soiling of plant origin and / or for decontaminating surfaces contaminated with pesticides. The agent comprises 20-60% by weight of an aliphatic C ₁ -C ₁₀ carboxylic acid, preferably formic acid, or a mixture of two or more such aliphatic carboxylic acids, which are preferably Formic acid comprises at least one surfactant, preferably an anionic surfactant and / or at least one nonionic surfactant, and the remainder water and / or solvent. In a further aspect, the present invention relates to special carboxylic acid-containing cleaning agents for hard surfaces, which are particularly suitable for the intended use.

Description

The present invention relates to improved detergent compositions which can find particular use in cleaning hard surfaces. The invention relates in particular to liquid, acidic cleaning agent compositions for removing vegetable contaminants and / or for decontaminating surfaces such as glass or metal surfaces in greenhouses or transport surfaces and / or storage surfaces, but also Styrofoam trays.

The present invention very particularly preferably relates to a cleaning agent containing carboxylic acid, for example formic acid, and its use for removing soiling of plant origin and / or for decontaminating surfaces, in particular hard surfaces, which can also be contaminated with pesticides, for example.

The cleaning agent composition according to the invention is very effective in its effectiveness, but the use of highly water-polluting ingredients can be dispensed with, so that classification in water hazard class 1 can also be made. In addition, the cleaning agent composition according to the invention is distinguished by good biodegradability.

State of the art

Cleaning agents have to meet numerous requirements. Ideally, on the one hand, they should not pose any serious danger to people or the environment, but on the other hand, they should also have a high and efficient cleaning effect and be easy to use.

Various formulations for detergent compositions have been prepared and are known in the art. For example, strong acid detergents containing strong acids such as hydrochloric acid are useful in removing hard water stains. However, the presence of strong acids is known to be irritants to the skin and further offers the potential for toxicological hazards. Also, only a few cleaning agents provide any hygienic effect on the hard surfaces being treated.

In terms of their composition, soiling of plant origin differs significantly from inorganic soiling and soiling of animal origin, and thus pose different challenges to the composition of the cleaning agent. Pollution of animal origin that occurs on farms, for example, includes urine and feces, among others. For example, a wide range of cleaning agents are available to dairy farms to remove them. Practice has shown that these cleaning agents are only suitable for removing contaminants of vegetable origin to a limited extent.

Such contaminants of plant origin not only include plant extracts or plant juices, which can arise, for example, from damage to plant parts and fruits during harvest, storage and packaging in the relevant operations, they also include products with plant-based ingredients, such as shading paints for greenhouses. The shading colors available on the market often contain starch. Such starch-based paints are after their application on the glass surfaces of greenhouses, if desired, either difficult to remove with the cleaning agents available in the prior art, or the effective cleaning agents are halogen-containing formulations and thus highly toxic and not very environmentally friendly.

In summary, it can be said that previously known cleaning agents and methods used include the manual removal of dirt with a brush and heated water or the use of poly- or perfluorinated surfactants in the Cleaning solutions are. Because of the lack of degradability, persistence, toxicity and bioaccumulation of fluorosurfactants, the manufacture and use of this class of substances will be banned within the EU from July 2020.

Another group of contamination that can occur in gardening or arable farms is contamination with pesticides, such as mitosis inhibitors, for example on soil, storage and transport areas. For the decontamination of such surfaces or other objects, such as transport crates and processing machines, the trade either provides products that are problematic due to their toxicity and poor environmental hazard, or that are not very effective in their cleaning performance.

According to a first aspect, the invention is therefore based on the object of providing a cleaning agent, also referred to herein as a cleaning agent composition or agent, which can be used as universally as possible for the removal of soiling of plant origin and / or for the decontamination of surfaces, and that during use does not pose any serious health risks to humans or the environment. Furthermore, it is the object of the present invention to provide an efficient and safe method for removing soiling of plant origin and / or for decontaminating surfaces through the use of a suitable cleaning agent.

According to a further aspect, cleaning agent compositions are also to be provided in particular which are ideally suited for cleaning and removing shading soiling and which dispense with fluorosurfactants as the active ingredient.

According to a first aspect of the present invention, these objects are achieved by providing a cleaning agent composition for hard surfaces which has proven to be particularly advantageous for removing soiling of plant origin and / or for decontaminating surfaces contaminated with pesticides.

• 20-60 Gew.-% einer aliphatischen Carbonsäure mit 1 bis 10 Kohlenstoffatomen oder einer Mischung von zwei oder mehr solcher aliphatischer Carbonsäuren,
• 1-30 Gew.-% eines anionischen Tensids, vorzugsweise einer Alkansulfonsäure und/oder eines Alkansulfonats, oder einer Mischung von zwei oder mehr anionischer Tenside, wobei die Mischung vorzugsweise eine Alkansulfonsäure und/oder ein Alkansulfonat umfasst,
• 0,1-5 Gew.-% eines nichtionischen Tensids, vorzugsweise eines Fettalkoholethoxylats, oder einer Mischung von zwei oder mehr nichtionischer Tenside, wobei die Mischung vorzugsweise ein Fettalkoholethoxylat umfasst, und
• als Rest Wasser und/oder Lösungsmittel.

The acidic hard surface cleaner of the present invention comprises the following components:

• 20-60% by weight of an aliphatic carboxylic acid having 1 to 10 carbon atoms or a mixture of two or more 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, the mixture preferably comprising an alkanesulfonic acid and / or an alkanesulfonate,
• 0.1-5% by weight of a nonionic surfactant, preferably a fatty alcohol ethoxylate, or a mixture of two or more nonionic surfactants, the mixture preferably comprising a fatty alcohol ethoxylate, and
• the remainder is water and / or solvent.

The agent according to the invention (hereinafter also referred to as cleaning agent or cleaning agent composition) is distinguished by an advantageous effect in the removal of soiling of plant origin and / or for the decontamination of surfaces contaminated with pesticides. It is therefore used in particular to remove soiling of vegetable origin. Another application is for the decontamination of surfaces contaminated with pesticides, for example.

The cleaning agent compositions according to the invention are distinguished by high rates of detachment of the soiling, for example the incrustations from starch adhesions, 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 lead to the desired success in a significantly shorter time. In this context, the literature " Seifen, Fette, Öle, Wachse, SÖFW 10, 2001, pp. 108-114 "In detail about the type of cleaning solution as well as the temperature and time required to remove starch deposits on glass surfaces reported. In contrast, the compositions according to the invention are distinguished by a greatly improved effect. For example, a very high rate of detachment of the incrustations at room temperature within 3 to 5 minutes could be determined for starch adhesions.

The cleaning agent according to the invention is ideally suited for removing soiling of vegetable origin on hard surfaces and for decontaminating surfaces. Areas or areas to be decontaminated within the meaning of the present invention are not only floor areas, floor coverings, glass areas, film areas, storage areas and transport areas; the term also includes - but not exclusively - objects such as boxes, transport and / or storage devices, for example Styrofoam trays , Irrigation mats and gutters, ribbon fabric, peeling, cutting, weighing and processing machines. Such surfaces or objects are examples of surfaces or objects with a hard surface. The areas in question can be found, for example, in market gardens, arable farms, greengrocers and plants and fruit processing companies.

The agent according to the invention comprises at least one aliphatic carboxylic acid. Carboxylic acids are organic compounds that carry one or more carboxyl groups and thus have a more or less pronounced acidic character. Depending on the number of carboxyl groups present, a distinction is made between monocarboxylic acids, dicarboxylic acids and tricarboxylic acids. In contrast to the cyclic and aromatic carboxylic acids, the carboxyl group or groups in the aliphatic carboxylic acids is / are bound to an aliphatic radical R.

According to the invention, the aliphatic carboxylic acids are carboxylic acids having 1 to 10 carbon atoms. These include both alkanoic acids, alkenoic acids, and alkynoic acids. In the case of alkanoic acids, the radical R is saturated. Alkenoic acids have at least one double bond in the remainder and alkynoic acids have at least one triple bond in the remainder. The aliphatic carboxylic acids that can be used according to the invention, that is to say included in the composition, can be a mono-, di- or tricarboxylic acid, with monocarboxylic acids being preferred.

Aliphatic monocarboxylic acids particularly preferred according to the invention are formic acid, acetic acid, propionic acid, or mixtures thereof. Examples of dicarboxylic acids are, not exhaustively, oxalic acid and malonic acid, and citric acid may also be mentioned as exemplary tricarboxylic acids, likewise not exhaustively.

The above-described aliphatic carboxylic acids, for example the aliphatic monocarboxylic acids, can be included individually or in any desired mixture of such carboxylic acids in the cleaning agent according to the invention. It has surprisingly been found that the one or more aliphatic carboxylic acid (s), in particular monocarboxylic acids, has or have an effect on vegetable sugars and components such as chlorophyll, for example.

The proportion of the aliphatic carboxylic acid or the mixture of aliphatic carboxylic acids in the agent according to the invention is 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 are also made up of a polar and a non-polar part. An alkyl radical can act as the non-polar part. The polar, functional group can, for example, be a carboxylate group (-COO ^- ), a sulfonate group (-SO ₃ ^- ) or a sulfate group (-SO ₄ ^2- ).

In the case of the anionic surfactants, alkanesulfonic acids and / or alkanesulfonates in particular have proven to be particularly advantageous. Alkanesulfonates are the salts of the alkanesulfonic acids. Sodium salts are particularly preferred according to the invention. In accordance with the invention Particularly preferred anionic surfactants are therefore alkanesulfonic acids and / or alkanesulfonates, in particular sodium alkanesulfonates. Alkanesulfonates with 10 to 20 carbon atoms, most preferably with 12 to 18 carbon atoms, or their salts, preferably their sodium salts, are even more preferred.

The anionic surfactant included in the composition according to the invention or the anionic surfactant mixtures, in particular the alkanesulfonic acids, alkanesulfonates and / or any mixtures of alkanesulfonic acids and / or alkanesulfonates, are in the compositions according to the invention in a proportion of 1 to 30% by weight, in particular with a Proportion of 4 to 28% by weight, very particularly preferably with a proportion of 6 to 25% by weight.

Even if nonionic surfactants cannot dissociate in water, these are also compounds that have both hydrophilic (polar) and hydrophobic (apolar) structures in the molecule. Nonionic surfactants are characterized by their good washing performance and high dissolving power for vegetable contaminants, especially at lower temperatures.

In the case of nonionic surfactants, fatty alcohol ethoxylates in particular have proven to be particularly advantageous. Fatty alcohol ethoxylates can be produced by the addition of ethylene oxide to natural and synthetic fatty alcohols. Nonionic surfactants particularly preferred according to the invention are therefore fatty alcohol ethoxylates. According to the present invention, it is particularly preferred that the fatty alcohol ethoxylates used were produced from natural or synthetic fatty alcohols having 6 to 22 carbon atoms, preferably having 12 to 18 carbon atoms.

Suitable fatty alcohols include, for example, hexan-1-ol, octan-1-ol, decan-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 C ₈ - up to C ₂₂ chain cuts, such as coconut fatty alcohol and palm kernel oil alcohol, synthetic primary alcohols such as iso-C ₁₃ oxo alcohols, C ₁₃ / C ₁₅ oxo alcohols, Mixtures of linear, singly or multiply branched oxo alcohols 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 and linear and branched, secondary alkanols with 8 to 22 carbon atoms . The alcohols can be saturated and unsaturated.

According to the invention, the ethoxylates preferably have a degree of ethoxylation (EO) in the range from 3 to 9, even more preferably in the range from 4 to 8 and most preferably in the range from 5 to 7. In the context of the present disclosure, the indication EO 3 means, for example, that the fatty alcohol has been reacted with 3 mol of ethylene oxide.

The nonionic surfactants or the nonionic surfactant mixture included in the composition according to the invention, in particular one of the fatty alcohol ethoxylates described above or any mixture of these, is in a proportion of 0.1 to 5% by weight, in particular with a proportion of 0.5 to 5% by weight, very particularly preferably in a proportion of 1 to 3% by weight in the composition according to the invention.

In one embodiment, the agent according to the invention can also contain an aromatic carboxylic acid or a mixture of two or more aromatic carboxylic acids. The aromatic carboxylic acid is preferably benzoic acid. In the event that a mixture of aromatic carboxylic acids is included in the agent according to the invention, the mixture preferably contains benzoic acid, in particular in a proportion of at least 30% by weight, based on all aromatic carboxylic acids in this mixture. Benzoic acid is also characterized by a preservative property. The aromatic carboxylic acid, in particular benzoic acid, can also be used in an acidic medium in low concentration for the purpose of corrosion inhibition if a stronger acid almost completely suppresses the dissociation of the aromatic carboxylic acid, in particular benzoic acid.

The aromatic carboxylic acid or the mixture of aromatic carboxylic acids, for example the benzoic acid or a mixture containing benzoic acid, is preferably with a Contained in the composition according to the invention in a proportion of 0.3 to 3% by weight. The optional proportion of the one or more aromatic carboxylic acids is even more preferably 0.4 to 2.8% by weight, even more preferably 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 acid. Since any unavoidable impurities should be disregarded here, the statement "no aromatic carboxylic acid" means that one or more aromatic carboxylic acid (s) with a total proportion, based on the detergent composition, of 0% by weight to less than 0.01 % By weight are included in the detergent composition. The maximum permissible maximum limit is preferably 0.008% by weight, even more preferably 0.006% by weight and even more preferably 0.004% by weight, based in each case on the cleaning agent composition. The proportion of aromatic carboxylic acids in the composition is most preferably 0% by weight.

The cleaning agent according to the invention furthermore comprises water (as a solvent) and / or at least one further solvent besides water. Preferably the solvent is water or it comprises water in a solvent mixture. Solvents other than water are known to those skilled in the art. In particular, they include alcohols such as ethanol.

The proportion of the at least one solvent is the remainder to 100% by weight (ad. 100% by weight), based on the total composition of the cleaning agent according to the invention. That is to say, the percentages by weight of the essential and optionally present optional constituents of the composition are always selected such that the total is 100% by weight.

The cleaning agent according to the invention is preferably a liquid, acidic composition.

The cleaning agent according to the invention preferably has an acidic pH value Range from 2 to 4 on.

According to a preferred embodiment, the agent according to the invention can also contain one or more foam boosters or foam boosters, preferably selected from the group of amine oxides, in particular alkyl amine oxides.

The foam booster or boosters is or are preferably included in the agent according to the invention in a proportion of 0.3 to 5% by weight. The proportion is even more preferably 0.4 to 4% by weight.

The alkyl amine oxides preferably contain alkyl radicals with a chain length of 14 to 24 carbon atoms. According to the invention, a preferred foam booster is coconut propylamine oxide or coconut fatty acid amidopropyldimethylamine oxide or cocamido-propylamine 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, further foam boosters which are commercially available and known to the person skilled in the art can be used.

The use of a foam booster is advantageous because the foam that forms from the cleaning agent adheres well to the surface to be cleaned and thus leads to thorough cleaning. The combination of the above-mentioned surfactants, in particular with a high proportion of anionic surfactants, in combination with one or more foam boosters has surprisingly proven to be particularly advantageous.

Furthermore, it has surprisingly been found that with a view to the stability of the composition and / or the foam and with regard to the cleaning effect, in particular a combination of cocamidopropylamine oxide, preferably in a proportion in the range from 0.3 to 5% by weight, with formic acid, preferably with a proportion of formic acid in the range from 20, even more preferably from 25 to 60% by weight, based in each case on the composition according to the invention, provides particularly advantageous effects.

Compositions with such a combination of ingredients, and the foam optionally obtained therefrom, are stable in spite of the acidic conditions. In particular, inactivation of the carboxylic acid (s) can be counteracted by, for example, complex formation.

According to a preferred embodiment of the cleaning agent according to the invention, the aliphatic carboxylic acid is formic acid, which is preferably present in the composition according to the invention in a proportion of 20 to 60% by weight, even more preferably in a proportion of 25 to 58% by weight, even more preferably in 30% by weight to 55 wt .-% is included. In the event that the agent according to the invention contains a mixture of two or more aliphatic carboxylic acids as the aliphatic carboxylic acid component, the formic acid is preferably contained in such a mixture. The proportion of formic acid is even more preferably at least 30% by weight, preferably at least 40% by weight, based on the sum of the proportions of aliphatic carboxylic acids having 1 to 10 carbon atoms in this mixture.

The use of formic acid is particularly advantageous because it has surprisingly been shown that formic acid, especially in the use concentration according to the invention, has a very good and specific cleaning effect against, for example, vegetable mono-, di- and polysaccharides, but also against compounds of the vegetable secondary metabolism, such as Has pigments, including chlorophyll. Without wishing to be bound by this theory, formic acid is the simplest and shortest-chain alkanoic acid, and the carboxyl group determines its properties particularly strongly.

Further customary additives and auxiliaries for cleaning agents can optionally also be added to the agent according to the invention. Suitable substances and mixtures of substances are well known to the person skilled in the art and can be obtained commercially. The additives and auxiliaries can be, for example, customary formulation aids, dyes and fragrances, buffer substances, builders, preservatives, etc. that are acceptable for the intended purpose.

If necessary, one or more substances used for corrosion protection can be added to the agent according to the invention. In the context of the present disclosure, corrosion protection means measures to avoid damage caused by corrosion on metallic components, but also on materials such as glass, plastics, building materials, etc. The protective measures taken aim in particular to reduce the speed of the corrosive attack to such an extent that damage to the component or material can be avoided during its service life or at least the functionality of the component or material is not impaired. For a further definition, reference is made to the DIN EN ISO 8044 standard.

The anti-corrosion agents suitable for this purpose are known in principle to the person skilled in the art and are commercially available. In order to prevent or reduce corrosion processes, however, it is particularly preferred according to the invention to use the anti-corrosion agent benzotriazole. This has surprisingly proven to be particularly advantageous in combination with the other essential and optional components of the cleaning agent according to the invention. According to the invention, benzotriazole can be included in the cleaning agent according to the invention either individually or in combination with further corrosion protection agents and / or other additives and auxiliaries.

The anti-corrosion agent (s) is / are in the agent according to the invention preferably in a proportion of 0.05 to 1% by weight, more preferably 0.1 to 0.8% by weight, even more preferably 0.15 to 0, 6% by weight. The particularly preferred corrosion protection agent according to the invention, benzotriazole, is preferably present in a proportion of 0.05 to 1% by weight, even more preferably from 0.1 to 0.8% by weight, even more preferably from 0.15 to 0.6% by weight. -% contain.

According to a preferred embodiment according to the invention, the cleaning agent according to the invention is free from highly water-polluting ingredients. In this context, substances and mixtures that are highly hazardous to water mean substances and mixtures that are classified as hazardous to water in accordance with the provisions of the ordinance via systems for handling substances hazardous to water (AwSV) with an issue date of April 18, 2017. In the context of the present disclosure, the term “free of” means that the proportion of such constituents in the overall composition is from 0 to less than 0.01% by weight. The maximum permissible maximum limit is preferably 0.008% by weight, even more preferably 0.006% by weight and even more preferably 0.004% by weight, based in each case on the cleaning agent. The proportion of such constituents in the composition is most preferably 0% by weight. Any unavoidable contamination should be disregarded here.

The components of the cleaning agent according to the invention are therefore preferably to be selected in such a way that at least a classification in water hazard class 2, particularly preferably a classification in water hazard class 1, can take place. Water hazard classes 1, 2 and 3 are defined in the sense of the present disclosure in accordance with the Ordinance on Systems for Handling Substances Hazardous to Water (AwSV) with an issue date of April 18, 2017.

Furthermore, it is preferred according to the invention that the components of the cleaning agent are to 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 an aliphatic monocarboxylic acid, preferably formic acid, 0-3% by weight at least one aromatic carboxylic acid, preferably benzoic acid, 1-30% by weight an alkyl sulfonate with 12 to 18 carbon atoms or its sodium salt, 0.5-5% by weight of a fatty alcohol ethoxylate, the fatty alcohol having 15 to 30 carbon atoms, preferably with a degree of ethoxylation in the range from EO 3 to 9, 0-5% by weight, preferably 0.3-5% by weight at least one amine oxide, preferably cocamidopropylamine oxide, 0-1% by weight an anti-corrosion agent, preferably benzotriazole, and ad 100% by weight Water and / or another solvent.

In addition to the constituents mentioned for this preferred embodiment of the agent according to the invention, such a cleaning agent can optionally contain one or more customary additives and auxiliaries.

Also included in the scope of the present invention are those compositions or agents which, with the exception of customary impurities, consist only of the essentials mentioned above and optionally 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 an aliphatic monocarboxylic acid other than propionic acid, preferably formic acid, 1-15% by weight Propionic acid, 1-3% by weight at least one aromatic carboxylic acid, preferably benzoic acid, 1-25% by weight an alkyl sulfonate with 12 to 18 carbon atoms or its sodium salt, 0.5-5% by weight of a fatty alcohol ethoxylate, the fatty alcohol having 15 to 30 carbon atoms, preferably with a degree of ethoxylation in the range from EO 3 to 9, 0-5% by weight, preferably 0.3-5% by weight at least one amine oxide, preferably cocamidopropylamine oxide, 0-1% by weight an anti-corrosion agent, preferably benzotriazole, and ad 100% by weight Water and / or another solvent.

In addition to the constituents mentioned for this preferred embodiment of the agent according to the invention, such a cleaning agent can optionally contain one or more customary additives and auxiliaries.

Also included in the scope of the present invention are those compositions or agents which, with the exception of customary impurities, consist only of the essentials mentioned above and optionally one or more of the optional components.

The agent according to the invention is a liquid one-component product from which a dilute use solution can be produced which then contains 0.5 to 5% by weight, in particular 0.8 to 2.2% by weight, of the agent. The present application therefore also relates, according to a further aspect, to the one explained above diluted working solution. The agent is preferably diluted with water to make the ready-to-use solution.

• 20-60 Gew.-% einer aliphatischen Carbonsäure mit 1 bis 10 Kohlenstoffatomen, oder Mischung von zwei oder mehr solcher aliphatischer Carbonsäuren, welche vorzugsweise Ameisensäure oder wobei die Mischung vorzugsweise Ameisensäure umfasst,
• mindestens ein Tensid, wobei das mindestens eine Tensid vorzugsweise ein anionisches Tensid oder eine Mischung von zwei oder mehr anionischer Tenside, vorzugsweise mit einem Anteil des oder der anionischen Tenside von nicht mehr als 30 Gew.-%, und/oder ein nichtionisches Tensid oder eine Mischung von zwei oder mehr nichtionischer Tenside, vorzugsweise mit einem Anteil des oder der nichtionischen Tenside von nicht mehr als 5 Gew.-%, ist und
• als Rest Wasser und/oder Lösungsmittel.

Another aspect of the present invention relates to the use of a carboxylic acid-containing cleaning agent for removing soiling of plant origin and / or for decontaminating surfaces contaminated with pesticides, for example. The cleaning agent used in the present invention includes

• 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, which preferably comprises formic acid or wherein the mixture preferably comprises formic acid,
• at least one surfactant, the at least one surfactant preferably being an anionic surfactant or a mixture of two or more anionic surfactants, preferably with a proportion of the anionic surfactant or surfactants of not more than 30% by weight, and / or a nonionic surfactant or a Mixture of two or more nonionic surfactants, preferably with a proportion of the nonionic surfactant (s) of not more than 5% by weight, and
• the remainder is water and / or solvent.

The use of such an agent enables a gentle but effective removal of plant contamination and / or a decontamination of surfaces.

As already explained in connection with the composition as such, according to the invention, the aliphatic carboxylic acids are carboxylic acids having 1 to 10 carbon atoms. These include both alkanoic acids, alkenoic acids, and alkynoic acids. The aliphatic carboxylic acids which can be used according to the invention can be a mono-, di- or tricarboxylic acid, monocarboxylic acids being preferred. Aliphatic carboxylic acids particularly preferred according to the invention are formic acid, acetic acid and propionic acid. Such carboxylic acids can be used individually or in any desired mixture of such carboxylic acids, in particular of monocarboxylic acids, in the invention Cleaning agent or be included in the cleaning agent used according to the invention.

The proportion of the aliphatic carboxylic acid or the mixture of aliphatic carboxylic acids in the agent according to the invention is 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 includes formic acid as the aliphatic carboxylic acid. In the event that the agent used contains several aliphatic carboxylic acids, it is preferred that the proportion of formic acid in the aliphatic carboxylic acid component is at least 30% by weight.

The agent used according to the invention comprises at least one surfactant or a surfactant mixture, preferably in a proportion of 1 to 30% by weight. The at least one anionic surfactant and / or at least one nonionic surfactant used according to the invention also preferably comprises. The proportion of the anionic surfactant or the anionic surfactants in the agent used is preferably not more than 30% by weight, even more preferably the proportion is 1 to 30% by weight, in particular 4 to 28% by weight, entirely particularly preferably from 6 to 25% by weight. The proportion of the nonionic surfactant or surfactants in the agent used is preferably not more than 5% by weight, even more preferably 0.1 to 5% by weight, in particular 0.5 to 4% by weight, very particularly preferably 1 to 3% by weight. With regard to the surfactant system, a combination of one or more anionic surfactants with one or more nonionic surfactants is particularly advantageous for the reasons already described above.

In the case of such a combination, the proportion of the anionic surfactant (s), based on the total composition of the agent, is preferably 1 to 30% by weight, even more preferably 4 to 28% by weight, and the proportion of the nonionic surfactant (s) is based on the total composition of the agent, preferably 0.1 to 5% by weight, even more preferably 0.5 to 4% by weight.

In principle, all anionic surfactants known to the person skilled in the art for use in cleaning agents and any mixtures thereof can be used. However, it has surprisingly been found that alkanesulfonates and / or their salts, in particular their sodium salts, are preferred as the anionic surfactant. With regard to even more preferred embodiments for these anionic surfactants, reference is made to the statements above. With regard to the nonionic surfactant, in principle, all nonionic surfactants known to the person skilled in the art for use in cleaning agents and any mixtures thereof can be used. However, it has surprisingly been found that fatty alcohol ethoxylates, in particular those with a degree of ethoxylation (EO) in the range from 3 to 9, are preferred as nonionic surfactants. With regard to even more preferred embodiments for these nonionic surfactants, reference is made to the statements above.

The cleaning agent used according to the invention furthermore comprises water (as a solvent) and / or at least one further solvent besides water. Preferably the solvent is water or it comprises water in a solvent mixture. Solvents other than water are known to those skilled in the art. In particular, they include alcohols such as ethanol.

The proportion of the at least one solvent is the remainder to 100% by weight (ad. 100% by weight), based on the total composition of the cleaning agent according to the invention. That is to say, the percentages by weight of the essential and optionally present optional constituents of the composition are always selected such that the total is 100% by weight.

The cleaning agent used according to the invention preferably has an acidic pH, more preferably a pH in the range from 2 to 4.

The cleaning agent used in the present invention is preferably a liquid composition.

The agent used according to the invention can optionally also contain at least one aromatic carboxylic acid, preferably benzoic acid, and / or a corrosion protection agent, preferably benzotrialzene, and / or other auxiliaries and / or additives known to those skilled in the art of cleaning agents. With regard to preferred proportions of these optional components, reference is made to the above disclosure relating to the agent as such. These proportions apply accordingly.

According to a preferred embodiment of the use according to the invention, the cleaning agent used is one of the cleaning agents for a hard surface described above according to the first aspect of the invention. Reference is made to the corresponding disclosure of the individual components and their proportions, also with regard to particularly preferred embodiments.

According to a preferred form of the use according to the invention, the contamination to be removed is a starch-containing contamination or deposit.

The polysaccharide starch is the most important reserve substance in plant cells. Animal organisms and fungi use a different carbohydrate store. This polysaccharide is one of the reasons why soiling of plant origin differs significantly from soiling or deposits of animal origin. The effective removal of starch poses particular challenges for the cleaning agent to be used. The carboxylic acid-containing cleaning agents have surprisingly been found to be particularly preferred for removing starch-containing soiling or deposits.

A majority of the shading colors on the market for glass surfaces in greenhouses are based on starch. In one embodiment of the invention, the use according to the invention therefore relates to the use of one of the above-described carboxylic acid-containing cleaning agents for removing shading paint, in particular from glass surfaces of greenhouses. So far, halogen-containing formulations have been used for this, which are highly toxic and little are environmentally friendly. Surprisingly, the carboxylic acid-containing cleaning agents described here cause cleaning to be at least as effective, but they are significantly less toxic and therefore easier to handle. They are also characterized by a significantly better environmental compatibility. It has been shown in particular that incrustations from starch adhesions can be detached within 3 to 15 minutes, preferably within 3 to 5 minutes, at room temperature. These high rates of detachment of the incrustations at room temperature are surprising and advantageous.

In the case of the impurities of plant origin that are to be removed, according to the invention, or in addition to the starch-containing impurities, they can be sugar and / or amino acid-containing vegetable juices / extracts, in particular juices / extracts of tomato, Act paprika and / or cucumber.

Such juices or extracts are produced, for example, during the harvest, packaging, storage or processing of vegetable products, in particular tomatoes, peppers and / or cucumbers, in market gardens or at dealerships. Due to their chemical composition, these contaminants are difficult to remove from the soiled surfaces or objects. It has surprisingly been found that a carboxylic acid-containing cleaning agent as described above, and in particular a carboxylic acid-containing cleaning agent according to the first aspect of the present invention, is also particularly suitable for effectively and gently removing such contaminants. In addition, aspects relating to food law and / or the protection of employees can be taken into account by using the product. According to a further embodiment of the use according to the invention, the carboxylic acid-containing cleaning agent is thus used to remove sugar- and / or amino-acid-containing plant juices / extracts, in particular for removing juices / extracts from tomatoes, paprika and / or cucumber.

The group of soiling of vegetable origin which is problematic with regard to their removal also includes soiling or deposits containing chlorophyll and / or a colored component. Such deposits can be green deposits, for example Algae deposits.

Chlorophylls are natural dyes made by organisms that photosynthesize. They are therefore contained in all green parts of the plant. The term “colored components” as used in connection with the present invention means or includes further photosynthetic pigments and colored secondary herbal ingredients.

It has surprisingly been found that a carboxylic acid-containing cleaning agent as described above, and in particular a carboxylic acid-containing cleaning agent according to the first aspect of the present invention, is also particularly suitable for effectively and gently removing such contaminants. In addition, aspects relating to food law and / or the protection of employees can be taken into account by using the product. According to a further embodiment of the use according to the invention, the carboxylic acid-containing cleaning agent is thus used to remove soiling or deposits containing chlorophyll and / or another colored component, in particular to remove deposits from green deposits, for example from algae deposits.

The use according to the invention of a carboxylic acid-containing cleaning agent also includes the use or use of a carboxylic acid-containing cleaning agent as described above, and in particular a carboxylic acid-containing cleaning agent according to the first aspect of the present invention, for decontaminating surfaces contaminated with pesticides. The pesticides are in particular chlorpropham [(3-chlorophenyl) -carbamic acid-1-methylethyl ester] and / or maleic hydrazide. Chlorpropham is a herbicide that is widely used in agriculture. It degrades slowly or at a moderate rate in water or soil. Maleic hydrazide is also an active ingredient that is used extensively in plant cultivation. The residues or washed-off pesticides remaining on the plant parts can / can lead to contamination of surfaces that have to be decontaminated. Such contamination can represent a significant problem in manufacturing and selling companies, for example. It has surprisingly been found that a carboxylic acid-containing cleaning agent as described above, and in particular a carboxylic acid-containing cleaning agent according to the first aspect of the present invention, is also very particularly suitable for removing such contaminations. In addition, aspects relating to food law and / or the protection of employees can be taken into account by using the product.

According to one embodiment of the use according to the invention, the surface to be cleaned is preferably a surface selected from the group consisting of boxes, storage areas, transport surfaces, storage and / or transport devices, floor coverings, irrigation mats and / or gutters, glass surfaces , Foil surfaces, ribbon fabric, peeling, cutting, weighing and processing machines.

According to a further embodiment of the use according to the invention, the surface to be cleaned is a greenhouse surface, in particular a glass, plastic or metal surface in a greenhouse.

In the case of the use according to the invention, the agent is applied either directly as a liquid, preferably as a dilute, preferably aqueous, solution or as a foam or as a strongly foaming liquid. The cleaning agent, in particular the cleaning agent according to the first aspect of the present invention, can, according to the first variant, be applied as an aqueous solution to the objects or surfaces to be cleaned. A mechanical effect can subsequently trigger foam formation. It should be made clear here again that the foam formation is not essential for the effect of the agent. That is, the effect according to the invention can in principle also be achieved without foam formation.

If the agent according to the invention according to the second preferred variant is applied to the surfaces or objects as a foam or highly foaming liquid, this can be done done for example by means of a commercially available foam syringe. Corresponding devices are well known to the person skilled in the art. In particular, a device such as that described in European patent no. 2,476,481 is disclosed.

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, even more preferably at least 30 seconds and very particularly preferably at least 40 seconds. Furthermore, it is preferred that the maximum contact time of the agent according to the invention on the surface or the object is 30 minutes, preferably 20 minutes, 10 minutes or 8 minutes, even more preferably 6 minutes and very particularly preferably a maximum of 4 minutes. The high tolerance of the agent according to the invention, already mentioned above, has proven to be particularly advantageous and makes the long exposure times possible. After the exposure time, the agent or the foam is preferably at least partially washed off or removed in some other way from the surface or the object. Of course, several successive cleanings of the same surface or the same object are also possible and included in the scope of the present invention, as required.

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 diluted before its use. The agent can be diluted with water or another suitable solvent. Suitable solvents are known to the person skilled in the art. The use concentration of the cleaning agent is preferably 0.5 to 5%, preferably 0.8 to 2.2%, based on the cleaning agent.

The pH of the diluted, ready-to-use cleaning agent is preferably in the range from 2 to 4.

• Bereitstellen eines Carbonsäure-haltigen Reinigungsmittels, welches 20-60 Gew.-% einer aliphatischen Carbonsäure mit 1 bis 10 Kohlenstoffatomen, vorzugsweise Ameisensäure, oder eine Mischung von zwei oder mehr solcher aliphatischer Carbonsäuren, welche vorzugsweise Ameisensäure umfasst, mindestens ein Tensid und als Rest Wasser und/oder Lösungsmittel umfasst. Das mindestens eine Tensid ist vorzugsweise ein anionisches Tensid oder eine Mischung von zwei oder mehr anionischer Tenside, vorzugsweise mit einem Anteil des oder der anionischen Tenside von nicht mehr als 30 Gew.-%, und/oder ein nichtionisches Tensid oder eine Mischung von zwei oder mehr nichtionischer Tenside, vorzugsweiseweise mit einem Anteil des oder der nichtionischen Tenside von nicht mehr als 5 Gew.-%.
• Aufbringen des bereitgestellten Carbonsäure-haltigen Reinigungsmittels auf eine mit Verschmutzungen pflanzlichen Ursprungs verschmutzte und/oder eine mit Pflanzenschutzmittel kontaminierte Fläche, und
• Reinigen der Fläche.

In a further aspect, the present invention also provides a method for Removal of plant-based pollution and / or ready for decontamination of surfaces, the method comprising the steps of:

• Providing a carboxylic acid-containing cleaning agent which contains 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, which preferably comprises formic acid, at least one surfactant and the remainder water and / or solvents. The at least one surfactant is preferably an anionic surfactant or a mixture of two or more anionic surfactants, preferably with a proportion of the anionic surfactant or surfactants of not more than 30% by weight, and / or a nonionic surfactant or a mixture of two or more more nonionic surfactants, preferably with a proportion of the nonionic surfactant or surfactants of not more than 5% by weight.
• Applying the provided cleaning agent containing carboxylic acid to a surface that is soiled with soiling of vegetable origin and / or a surface contaminated with pesticides, and
• Cleaning the area.

According to a preferred embodiment of the method according to the invention, the cleaning agent composition is applied / applied in the method according to the invention either directly as a liquid, preferably as an aqueous solution, or as a foam or as a highly foaming liquid. According to the first variant, the cleaning agent composition can be applied as an aqueous solution. A mechanical effect can subsequently trigger foam formation. It should be made clear here again that the foam formation is not essential for the effect of the composition. That is, the effect according to the invention can in principle also be achieved without foam formation.

If the agent according to the second preferred variant is applied 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 the person skilled in the art. To the generation of the foam, a device such as that disclosed in European Patent No. 2,476,481 is disclosed.

With regard to the action time of the cleaning agent on the surface to be cleaned, reference is made - for both application forms - to the corresponding statements in conjunction with the use according to the invention. The times apply equally to the use according to the invention and the method according to the invention.

After the exposure time, the agent or the foam is preferably at least partially washed off or removed in some other way from the surface or the object. Of course, several successive cleanings are also possible as required and are included in the scope of the present invention. The method according to the invention can thus comprise the further steps of allowing the applied composition to act, preferably with the abovementioned contact times, and / or the step of washing off or removing the applied composition in some other way, if appropriate after it has acted.

It is also provided according to the invention that the cleaning agent composition is diluted to a desired application concentration in an upstream process step before it is applied as a solution, foam or highly foaming solution. The composition can be diluted with water or another suitable solvent. Suitable solvents are known to the person skilled in the art. The use concentration of the cleaning agent composition is then preferably 0.5 to 5% by weight, in particular 0.8 to 2.2% by weight of the original composition. The composition is preferably diluted to give the solution for use with water. The method according to the invention can thus comprise the further step, which precedes the application, of diluting the composition to be applied, preferably to the above-mentioned use concentrations.

• Bereitstellen einer Reinigungsmittelzusammensetzung, die wie vorstehend beschrieben zusammengesetzt ist,
• gegebenenfalls Verdünnen der bereitgestellten Reinigungsmittelzusammensetzung auf eine Anwendungskonzentration von vorzugsweise 0,5 bis 5 Gew.-%, vorzugsweise mit Wasser und/oder einem anderen geeigneten Lösungsmittel,
• Applizierens der, gegebenenfalls verdünnten, Reinigungsmittelzusammensetzung auf eine zu behandelnde Fläche,
• Einwirkenlassen der applizierten Reinigungsmittelzusammensetzung, vorzugsweise für einen Zeitraum von 10 Sekunden bis 30 Minuten, und
• Abwaschen oder Entfernen der applizierten Reinigungsmittelzusammensetzung.

In a preferred embodiment, the method according to the invention thus comprises the steps

• Providing a detergent composition which is composed as described above,
• optionally diluting the cleaning agent composition provided to an application concentration of preferably 0.5 to 5% by weight, preferably with water and / or another suitable solvent,
• Applying the cleaning agent composition, optionally diluted, to a surface to be treated,
• Allowing the applied detergent composition to act, preferably for a period of from 10 seconds to 30 minutes, and
• Washing off or removing the applied detergent composition.

With regard to preferred embodiments of the cleaning agent used in the method according to the invention, reference is made to the statements above. In particular, the cleaning agent according to the first aspect of the invention is used in such a method.

Preferably, the surface to be cleaned contains a starchy soiling or deposit, which is more preferably soiling caused by shading paint for the glass surfaces of greenhouses. In a preferred embodiment, a method is provided for removing starch-containing soiling or deposits, in particular a shading color, for example from the glass surfaces of a greenhouse.

It has surprisingly been shown that a carboxylic acid-containing cleaning agent as described above, and in particular a carboxylic acid-containing cleaning agent according to the first aspect of the present invention, is also particularly suitable for starch adhesions on surfaces such as glass, metal or plastics, effectively and to remove gently. According to a further embodiment of the method according to the invention, the carboxylic acid-containing cleaning agent is thus used to remove starch adhesion from surfaces, in particular from glass, metal and / or Plastic surfaces, used accordingly in the cleaning method according to the invention.

In a further preferred embodiment, a method for removing sugar and / or amino acid-containing vegetable juices / extracts, in particular juices or extracts from tomato, paprika and / or cucumber, is provided. Yet another embodiment is a method for removing soiling or deposits containing chlorophyll, in particular for removing deposited green deposits, for example algae deposits. Another embodiment according to the invention provides a method for decontaminating surfaces contaminated with crop protection agents, in particular with chlorpropham [(3-chlorophenyl) carbamic acid 1-methylethyl ester] and / or maleic hydrazide.

For further details regarding the surfaces to be cleaned, reference is made to the corresponding statements in connection with the use according to the invention. This disclosure applies both to the use according to the invention and to the method according to the invention.

The following examples explain the invention without, however, restricting it thereto; Unless otherwise stated, all data are in% by weight.

Examples Example 1: Carboxylic acid-containing cleaning agent (according to the invention)

Components Parts by weight (w / w) C12-C18 alkanesulfonate sodium 10.00 C15-C20 fatty alcohol ethoxylate [3EO] 2.00 Formic acid 30.00 Benzotriazole 0.30 water ad 100.00

Example 2: Carboxylic acid-containing cleaning agent (according to the invention)

Components Parts by weight (w / w) C12-C18 alkanesulfonate sodium 20.00 C15-C30 fatty alcohol ethoxylate [7EO] 2.50 Formic acid 25.00 Propionic acid 10.00 Benzoic acid 2.00 water ad 100.00

Example 3: Carboxylic acid-containing cleaning agent (according to the invention)

Components Parts by weight (w / w) C12-C18 alkanesulfonate sodium 20.00 Coconut fatty acid amidopropyldimethylammonium oxide 3.00 Formic acid 50.00 water ad 100.00

Example 4: Carboxylic acid-containing cleaning agent (according to the invention)

Components Parts by weight (w / w) C12-C18 alkanesulfonate sodium 20.00 C15-C20 fatty alcohol ethoxylate [3EO] 1.00 Coconut fatty acid amidopropyldimethylammonium oxide 3.00 Formic acid 50.00 water ad 100.00

When preparing example formulations 1 to 4, the procedure is such that the water, preferably purified water, is initially introduced and then one of the several carboxylic acids is dissolved therein. The components surfactants and, if present, the benzotriazole and / or the foam booster, are then added to this solution, possibly additional water up to 100% by weight is added and stirred. The result is a clear, strongly foaming liquid.

The example formulations described above, which each represent a liquid one-component product, are each diluted to an aqueous, dilute use solution containing 1.5% of the agent and then applied by means of a foam syringe and left to act briefly on the surfaces to be cleaned.

It has been shown that the exemplary cleaning agent compositions according to the invention enabled a starch-based shading color to be removed effectively and gently from a glass surface at room temperature and an exposure time of 4 minutes.

Comparable positive results could be achieved with the removal of plant sap from contaminated transport boxes. Here, too, the cleaning was very effective and gentle.

Claims (18)

A liquid acidic hard surface detergent composition comprising: - 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, 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, the mixture preferably comprising at least one alkanesulfonic acid and / or at least one alkanesulfonate, 0.1-5% by weight of a nonionic surfactant, preferably a fatty alcohol ethoxylate, or a mixture of two or more nonionic surfactants, the mixture preferably comprising at least one fatty alcohol ethoxylate, and - the remainder is water and / or solvent. Detergent composition according to claim 1, wherein the anionic surfactant C12-C18 alkanesulfonate sodium and / or the nonionic surfactant is or comprises a C13-C30 fatty alcohol ethoxylate with a degree of ethoxylation in the range from EO 3 to 9. A detergent composition according to claim 1 or claim 2, further comprising 0.3-3% by weight of an aromatic carboxylic acid, preferably benzoic acid, or 0.3-3% by weight of a mixture of two or more aromatic carboxylic acids, the mixture preferably being benzoic acid includes. Detergent composition according to one of the preceding claims, further comprising one or more foam boosters, preferably at least one foam booster from the group of the alkyl amine oxides, the foam booster or boosters preferably being present in a proportion of 0.3-5% by weight. Detergent composition according to one of the preceding claims, wherein the aliphatic carboxylic acid is formic acid or the mixture of aliphatic carboxylic acids contains formic acid. Detergent composition according to one of the preceding claims, wherein the detergent composition is free of highly water-polluting ingredients, wherein in particular the ingredients are selected so that a classification in water hazard class 1 takes place, and / or the detergent composition is readily biodegradable, and / or the detergent composition is a Has pH in the range of 2 to 4. Use of a cleaning agent containing carboxylic acid for removing soiling of vegetable origin and / or for decontaminating contaminated surfaces, the cleaning agent 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, the mixture preferably comprising 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 proportion of the anionic surfactant or surfactants of not more than 30 wt .-%, and / or a nonionic surfactant or a mixture of two or more nonionic surfactants, preferably with a proportion of the nonionic surfactant or surfactants of not more than 5% by weight, and - the remainder is water and / or solvent. Use according to claim 7, wherein the carboxylic acid-containing cleaning agent is or comprises a cleaning agent according to one of claims 1 to 6. Use according to claim 7 or claim 8, wherein it is the pollution It is a starchy contamination or deposit. Use according to any one of claims 7 to 9, wherein the pollution is a shading color for the glass surfaces of greenhouses. Use according to claim 9, wherein the soil or deposit is starch adhesion to surfaces such as glass or metal. Use according to claim 7 or claim 8, wherein the contamination to be removed is sugar and / or amino acid-containing vegetable juices / extracts, in particular juices / extracts of tomato, paprika and / or cucumber. Use according to Claim 7 or Claim 8, the contamination to be removed being a contamination or deposit containing chlorophyll, preferably a deposit of green deposits, in particular an algae deposit. Use according to Claim 7 or Claim 8 for the decontamination of surfaces contaminated with pesticides, in particular with chlorpropham [(3-chlorophenyl) carbamic acid 1-methylethyl ester] and / or maleic hydrazide. Use according to one of claims 7 to 14, 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, film surfaces, boxes, transport devices, storage devices, for example Styrofoam trays, irrigation mats, Irrigation channels, ribbon fabric, peeling machines, cutting machines, weighing machines and processing machines. Use according to claim 15, wherein the surface to be cleaned is a greenhouse surface, in particular a glass or metal surface in a greenhouse. Use according to one of Claims 7 to 16, the cleaning agent composition being applied as a dilute, aqueous solution or as a foam. Use according to Claim 17, the application concentration of the cleaning agent composition being 0.5 to 5% by weight, preferably 0.8 to 2.2% by weight, based on the cleaning agent composition.