EP3690012A1 - Cleaning composition - Google Patents

Abstract

The invention relates to a composition, in particular a cleaning agent, for cleaning copper-containing materials.

Description

The present invention relates to the technical field of cleaning agents for metallic materials, in particular for copper materials.

In particular, the present invention relates to a composition with a cleaning effect and the use thereof.

Finally, the present invention relates to a method for removing corrosion products and / or limescale deposits from metal surfaces.

Corrosion is the reaction of a metallic material with its environment, which causes a measurable change in the material and can impair the function of a component or an entire system. The corrosion products can adhere firmly, be loose or soluble. The measurable changes can relate, for example, to the color, the surface quality or the mass. Corrosion damage only occurs when a component or an entire system is impaired due to corrosion.

In chemistry, corrosion is defined by a chemical or electrochemical reaction of a mostly metallic material with at least one substance from the environment. The most common chemical corrosion processes are the oxidation of silver as so-called tarnishing, bacterial anaerobic corrosion, glass corrosion, oxygen corrosion, hydrogen or acid corrosion and hydrogen embrittlement.

The phenomena of corrosion damage are very diverse, while in the case of surface corrosion the entire surface is destroyed almost uniformly, in pitting corrosion - also called pitting - the surface is only destroyed in small areas, so that holes and cracks occur.

Corrosion protection is an important issue when using metal materials. Corrosion can never be completely avoided, which is why corrosion protection measures can only prevent or delay corrosion damage. The protective measures are intended to maintain the function of a component or system during the intended service life. Corrosion protection can be done by changing the reaction conditions and / or material partners, by separating the materials from the corrosion medium or by electrochemical measures. If corrosion products already exist on a material, they must first be removed before protective measures can be taken to prevent corrosion. The corrosion products are usually removed by mechanical or chemical processes. The appropriate process must be selected depending on the material and the amount of corrosion products.

A common material that has been used for several thousand years is copper. Copper is used both as a pure metal and as an alloy for a variety of applications, such as for electrical installations, piping for heating systems or for gas and water, coins, cutlery, art objects, musical instruments, roofs and much more.

Since copper is a semi-precious metal, it hardly dissolves in hydrogen acids and hardly attacks oxygen, which is an advantage for many applications. However, if copper comes into contact with a combination of oxygen and acid, it corrodes. The corrosion of copper is therefore generally a mixture of two types of corrosion, namely oxygen corrosion and acid corrosion, and is assigned to the field of chemical corrosion.

The copper grate, also called patina or incorrectly called verdigris, is not a copper oxide and is therefore not comparable to the more common iron grate (iron oxide). Copper rust is a poorly soluble mixed compound based on copper hydroxides. The mixture often contains copper carbonate hydroxide, copper sulfate hydroxide, copper chloride hydroxide, copper ureates and salts of other basic copper compounds. The patina forms a protective layer and prevents further corrosion of the copper.

The typical greenish color of, for example, bronze monuments and copper roofs is formed in the atmosphere under the influence of carbon dioxide, sulfur dioxide, water and other substances that are present in the air in addition to water vapor. The color tone depends on the environmental influences and the composition of the metal, but is mainly based on the water-insoluble oxidation products of copper, such as copper chloride hydroxide and copper hydroxide, which form a layer on the component. A use of Different copper alloys in one object lead to color effects and gradients. The formation of copper patina can also be artificially generated and / or accelerated and leads to a very uniform patina, which changes over time and can lead to the mentioned color effects.

The patina on historical coins and works of art, for example, largely contributes to their value and the removal leads to an immense loss of value, which is why cleaning is often left to the experts.

Verdigris is often confused with patina due to its green color, but is made of copper (II) acetate and does not form a protective layer. The crystals are green to blue-green and moderately soluble in water and ethanol. Verdigris is toxic when ingested orally and can cause health problems in large quantities. The formation of verdigris is not possible without acetic acid.

Although a uniform patina gives coins and monuments their value, they are not wanted on other objects. In brass instruments, it can affect the smoothness of trains and the sound quality. Furthermore, it is not desirable for optical and haptic reasons, for example on bronze coolers of vintage cars, lamps, taps, accessories and brass instruments. The typical shine and color of the copper is wanted here.

Mechanical cleaning to remove the patina is often out of the question because this process involves a high level of material removal. Preferably, only the undesired corrosion products should be removed and the material of the object should not be further reduced or damaged. Alternatively, cleaning with acids is very effective, but a longer exposure time is necessary for the impurities to be removed effectively. Simply washing or wiping is not sufficient. Smaller objects can easily be cleaned with the help of an immersion bath, but this is not possible with large and / or fixed objects. It is also not always possible to use an immersion bath for objects made from a combination of different materials. For example, hunting horns often have a leather wrap that must not be treated with acid. The use of pastes is also known, but wood flour or other particles are added to them, which can be found in a cleaning of, for example Can fix brass instruments in trains or valves. In addition, the cleaning agent must be able to be removed from the cleaned object in a simple and residue-free manner, which is often not possible for the use of pastes, in particular on detailed objects, such as brass instruments or radiator figures.

In addition, signs of corrosion are also observed on chrome-plated surfaces. Although the chromium surface is only slightly susceptible to corrosion due to the formation of a passivation layer made of chromium oxides, it usually has cracks through which corrosive substances or electrolytes can reach the chromium-plated material, which subsequently corrodes. Furthermore, the adherence of flash rust to chrome-plated components is also known, as well as the direct corrosion of chrome coatings under the action of calcium chloride solutions, such as those that occur when moisture comes into contact with road salt and specifically lead to the corrosion of chrome-plated vehicle parts.

In addition to corrosion products, lime deposits are often present on the same object. Lime deposits are sedimentations of calcium carbonate and are also called scale. Water that flows through calcareous soil absorbs carbonic acid, as well as calcium and magnesium compounds. When the water is heated, the carbon dioxide escapes, causing calcium carbonate to precipitate and to adhere to the walls of vessels, for example. In brass instruments, lime comes into the interior of the instrument via the condensed water and leads to problems especially in valves and guides. Limescale can be removed particularly well with acetic acid, but copper materials then form harmful verdigris (copper (II) acetate), making this preferred limescale removal unsuitable for copper-containing materials.

It is therefore an object of the present invention to provide a composition which gently and effectively removes heavy impurities from limescale deposits and oxidation products.

In addition, it is a further object of the present invention to provide a cleaning agent which has high adhesion to the has cleaning surfaces in order to minimize material consumption and expenditure of time with the same cleaning effect.

Another object of the present invention is to provide a composition which is easy to spread, but nevertheless does not spread in an uncontrolled manner and can be removed easily and without residue after the desired application time.

It is also an object of the present invention to provide a composition which does not contain any highly corrosive components, the handling of which is not harmful to health and the environment and which is easily degradable.
The subject of the present invention according to a first aspect of the present invention is thus a composition, in particular a cleaning agent, preferably with adhesiveness to metals according to claim 1; Further advantageous refinements of this aspect of the invention are the subject of the related subclaims.

Another object of the present invention according to a second aspect of the present invention is a composition, in particular a cleaning agent, preferably with adhesiveness to metals according to claim 10.

Yet another object of the present invention according to a third aspect of the present invention is the use of a composition according to the invention for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits on metal surfaces .12.

Furthermore, according to a fourth aspect of the present invention, a further object of the present invention is a cleaning method for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits on metal surfaces.

The present invention furthermore relates to a fifth aspect of the present invention, a composition in the form of a dry mixture of a cleaning agent according to claim 14.

Finally, a further aspect of the present invention is, according to a further aspect of the present invention, a cleaning method for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits from metal surfaces.

It goes without saying that special features, features, configurations and embodiments as well as advantages or the like, which are subsequently only carried out for one aspect of the invention - for the purpose of avoiding unnecessary repetitions - naturally apply correspondingly to the other aspects of the invention without this requires an explicit mention.

In addition, it is true that all the values or parameter specifications or the like mentioned below can in principle be determined or determined using standardized or standardized or explicitly specified determination methods or with determination methods which are known per se to the person skilled in the art in this field.

In addition, it goes without saying for the person skilled in the art that all percentages relating to weight or quantity are selected by the person skilled in the art in such a way that the sum is 100%.

That being said, the present invention is described in more detail below.

1. (a) mindestens eine Säure,
2. (b) mindestens ein Bindemittel und
3. (c) Wasser

enthält, wobei die Zusammensetzung frei von Holzmehl ist.The subject of the present invention - according to a first aspect of the present invention - is thus a composition, in particular a cleaning agent, preferably with adhesiveness to metals, which

1. (a) at least one acid,
2. (b) at least one binder and
3. (c) water

contains, the composition is free of wood flour.

Because of its high adhesive capacity, the composition according to the invention adheres directly to the surface of metals without the addition of further adhesion promoters, as a result of which the material consumption and time expenditure are reduced with a constant cleaning effect compared to immersion baths or washing or wiping.

Furthermore, the high adhesiveness makes it possible to apply the cleaning composition in a site-specific and in particular locally limited manner, so that only the desired part of an object is treated.

The composition according to the invention, in particular the cleaning agent, is free from wood flour, which means that it can also be used on sensitive objects such as brass instruments, without clogging of valves or cables.

Even sensitive chrome-plated surfaces can be easily cleaned and adhering rust film and corrosion products from the chrome coating or the underlying material, especially metal, can be removed without damaging the scratch-sensitive chrome surface.

The composition according to the invention can in particular be site-specific and smooth, i.e. Apply to a metal surface without accidental dripping or running. In addition, the use of a combination of acid and binder enables the composition to be applied simply and easily, for example by means of a brush or roller, the layer thicknesses being high enough to provide a sufficient amount of acid for the intended cleaning of the metal surface.

In addition, the composition according to the invention is preferably easy to remove with water and can therefore also be used for cleaning finely structured surfaces, in particular brass instruments or works of art made of copper-containing materials.

Due to the good removability and high cleaning effect, the composition according to the invention can also be applied in a location-selective manner to objects of art which consist of several materials without the Composition reaches for example on wood or leather parts on which it is not wanted and on which it could damage the material.

Surprisingly, the use of both inorganic acids, organic acids or their mixtures in the composition according to the invention is possible. A medium-strong acid, in particular a mineral acid or a fruit acid, which do not have any strongly caustic properties and whose handling is neither harmful to the environment nor healthy, is sufficient and preferred.

According to a particular embodiment of the composition according to the invention, when using a mineral acid, it is preferred according to the invention to use it in combination with a buffer system. In the context of the present invention, particularly preferred buffer systems include phosphate buffers and / or acetate buffers and / or carbonate buffers and / or citrate buffers.

According to the invention, it is particularly preferred if the acid is selected from the group of citric acid, malic acid, fumaric acid, maleic acid, oxalic acid, glycolic acid, lactic acid, tartaric acid, salicylic acid, ascorbic acid, acetic acid, propionic acid, formic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and their mixtures. Particularly good results are obtained in this composition if the acid is selected from the group of citric acid, malic acid, fumaric acid, maleic acid, oxalic acid, lactic acid, tartaric acid, salicylic acid, ascorbic acid and mixtures thereof.

According to a particularly preferred embodiment of the present invention, the acid is citric acid.

In the context of the present invention, it is preferred if the composition contains the acid in amounts in the range from 10% by weight to 60% by weight, in particular in the range from 20% by weight to 55% by weight, preferably in the range from 25% by weight to 50% by weight, preferably in the range from 30% by weight to 45% by weight, particularly preferably in the range from 35% by weight to 45% by weight, based on the composition, contains.

In the context of the present invention, a binder is preferably to be understood as a thickener. Thickeners are substances that are able to bind water. Withdrawing unbound water increases the viscosity. According to the invention, it is preferred if the binder is an acid-stable binder, preferably a binder obtained from a natural product, particularly preferably a polysaccharide. In the context of the present invention, an acid-stable binder is understood to mean a binder whose molecules are not or only very slowly decomposed or split in the acidic environment.

According to a preferred embodiment of the composition according to the invention, the binder is selected from the group of alginate, agar agar, carrageenan, locust bean gum, guar gum, tragacanth, gum arabic, xanthan gum, karaya gum, tara gum, gellan, konjac, cassia gum, pectins, cellulose, starch , and their mixtures and derivatives. The use of xanthan is very particularly preferred according to the invention. In the context of the present invention, a derivative is preferably to be understood as a functionalized structure of the parent substance.

In the context of the present invention, it is usually provided that the composition of the binder in amounts of 0.5 to 7% by weight, in particular in the range of 0.8 to 6.5% by weight, preferably in the range of 0, 5 to 5% by weight, preferably in the range from 1 to 5% by weight, particularly preferably in the range from 1 to 2% by weight, based on the composition.

If the binder is a starch or a starch derivative, it has proven useful if the composition contains the binder in amounts of 1 to 7% by weight, in particular in the range of 1.5 to 6.5% by weight, preferably in Contains range of 2 to 6 wt .-%, preferably in the range of 3 to 5 wt .-%, particularly preferably in the range of 3.5 to 4.5 wt .-%, based on the composition.

If binders other than starch, in particular xanthan, are used in the context of the present invention, particularly good results are obtained if the composition of the binder in amounts of 0.5 to 5% by weight, in particular 0.5 to 4% by weight. -%, preferably 1 to 3 wt .-%, preferably 1 to 2 wt .-%, based on the composition.

Particularly by using xanthan as a binder, highly viscous and well-adhering compositions can be obtained with a small amount-related use of binders.

In addition, it can be provided within the scope of the present invention that the composition according to the invention has at least one adhesion-promoting additive, preferably at least one sugar. According to a preferred embodiment of the present invention, the sugar is selected from the group of sucrose, glucose, fructose, invert sugar, galactose, mannose, raffinose, maltodextrin and mixtures thereof. In addition, it can be provided in particular that the aforementioned mixtures are used in the form of a sugar syrup, with particular preference being given to the use of glucose syrup and / or invert sugar syrup.

Particularly good results are obtained if the composition contains the adhesion-promoting additive, in particular the sugar, in amounts in the range from 5% by weight to 70% by weight, in particular in the range from 8% by weight to 60% by weight. preferably in the range from 10% by weight to 50% by weight, preferably in the range from 10% by weight to 45% by weight, particularly preferably in the range from 10% by weight to 40% by weight on the composition. When using a syrup, the aforementioned quantity also relates to the amount of sugar in the composition.

If starch or starch derivatives are used as binders in the context of the present invention, the composition usually contains the adhesion-promoting additive in amounts in the range from 10 to 70% by weight, in particular 15 to 60% by weight, preferably in the range from 10 to 50% by weight, preferably in the range from 35 to 45% by weight, particularly preferably in the range from 35 to 40% by weight, based on the composition.

If the composition contains xanthan or another polysaccharide as a binder, it has proven useful if the composition preferably contains the adhesion-promoting additive in amounts in the range from 5 to 25% by weight, in particular in the range from 8 to 20% by weight in the range of 10 to 15 wt .-%, based on the composition.

When using, in particular, xanthan as a binder, the use of adhesion-promoting additives can either be dispensed with or their proportion in the composition according to the invention is extremely small.

In general, it is provided that the composition can be applied to a substrate in a location-selective and / or localized manner with a brush, in particular with a doctor blade and / or with a spatula. The composition according to the invention should therefore have a highly viscous consistency, in particular a viscosity in the range from 10 ³ cP to 10 ⁵ cP, preferably from 5,000 cP to 50,000 cP, particularly preferably from 10,000 cP to 30,000 cP, preferably in the order of 10 ⁴ cP .

In the context of the present invention, location-selective, in particular location-selective application of the composition is understood to mean application of the composition to precisely intended points or locations on a substrate. In the context of the present invention, a substrate is preferably to be understood as the metallic surface to be treated.

It has surprisingly been found that a consistency of the composition according to the invention comparable to the consistency of honey is sufficient to ensure adequate adhesion.

The amount of water in the composition according to the invention can vary within wide limits. The composition usually has water in amounts in the range from 15% by weight to 70% by weight, in particular in the range from 15% by weight to 60% by weight, preferably in the range from 20% by weight to 55% by weight .-%, preferably in the range of 25 wt .-% to 50 wt .-%, based on the composition.

If it is provided in the context of the present invention that the composition contains an adhesion-promoting additive, it can be provided that the composition contains water in amounts in the range from 15 to 50% by weight, in particular 15 to 40% by weight, preferably 20 to 35 wt .-%, preferably 25 to 30 wt .-%, based on the composition.

However, if the composition does not contain any adhesion-promoting additive in the context of the present invention, it has proven useful if the composition has the water in amounts in the range from 15 to 70% by weight, in particular 25 to 70% by weight, preferably 30 to 60% by weight, preferably 40 to 50% by weight, based on the composition .

In addition, it can be provided in the context of the present invention that the composition contains additives, in particular preservatives and / or rheology adjusting agents. If the composition contains additives, it has proven useful if the composition in amounts in the range from 0.001% by weight to 2% by weight, in particular in the range from 0.005% by weight to 1.5% by weight. %, preferably in the range from 0.01% by weight to 1.2% by weight, preferably in the range from 0.05% by weight to 0.8% by weight, particularly preferably in the range from 0.1 Wt .-% to 0.5 wt .-%, based on the composition contains.

1. (a) mindestens eine Säure,
2. (b) mindestens ein Bindemittel,
3. (c) Wasser,
4. (d) mindestens einen adhäsionsfördernden Zusatz und
5. (e) mindestens ein Additiv;

wobei die Zusammensetzung frei von Holzmehl ist.Thus, according to a particular embodiment, the composition according to the invention, in particular the cleaning agent, preferably with adhesiveness to metals

1. (a) at least one acid,
2. (b) at least one binder,
3. (c) water,
4. (d) at least one adhesion promoting additive and
5. (e) at least one additive;

the composition being free from wood flour.

For this embodiment, all the advantages, special features and preferred features mentioned above apply, which are described above for the further embodiments.

Fig. 1a:

eine kupferne Bettpfanne in der Draufsicht vor Reinigung mit der erfindungsgemäßen Zusammensetzung;

Fig. 1b:

die kupferne Bettpfanne mit Draufsicht nach Behandlung mit der erfindungsgemäßen Zusammensetzung;

Fig. 2a:

die kupferne Bettpfanne in der Seitenansicht vor Behandlung mit der erfindungsgemäßen Zusammensetzung;

Fig. 2b:

die kupferne Bettpfanne in der Seitenansicht nach Behandlung mit der erfindungsgemäßen Zusammensetzung;

Fig. 3a:

eine Messingglocke vor Behandlung mit der erfindungsgemäßen Zusammensetzung;

Fig. 3b:

die Messingglocke nach Behandlung mit der erfindungsgemäßen Zusammensetzung;

Fig. 4a:

ein Detail eines Gestellrings aus Messing vor Behandlung mit der erfindungsgemäßen Zusammensetzung;

Fig. 4b:

ein Ausschnitt eines Gestellrings aus Messing nach Behandlung mit der erfindungsgemäßen Zusammensetzung;

Fig. 5a:

ein Lampengewicht aus Messing vor Behandlung mit der erfindungsgemäßen Zusammensetzung und

Fig. 5b:

das Lampengewicht aus Messing nach der Behandlung mit der erfindungsgemäßen Zusammensetzung.

The figures are shown in accordance with

Fig. 1a:

a copper bedpan in plan view before cleaning with the composition according to the invention;

Fig. 1b:

the copper bedpan with top view after treatment with the composition according to the invention;

Fig. 2a:

the copper bedpan in side view before treatment with the composition according to the invention;

Fig. 2b:

the copper bedpan in side view after treatment with the composition according to the invention;

Fig. 3a:

a brass bell before treatment with the composition according to the invention;

3b:

the brass bell after treatment with the composition according to the invention;

Fig. 4a:

a detail of a brass frame ring before treatment with the composition according to the invention;

Fig. 4b:

a section of a frame ring made of brass after treatment with the composition according to the invention;

5a:

a lamp weight made of brass before treatment with the composition according to the invention and

Fig. 5b:

the lamp weight made of brass after treatment with the composition according to the invention.

1. (a) mindestens einer Säure,
2. (b) mindestens einem Bindemittel,
3. (c) Wasser,
4. (d) mindestens einem adhäsionsfördernden Zusatz und
5. (e) mindestens einem Additiv,

besteht.Another object of the present invention - according to a second aspect of the present invention - is a composition, in particular a cleaning agent, preferably with adhesiveness to metals, which consists of

1. (a) at least one acid,
2. (b) at least one binder,
3. (c) water,
4. (d) at least one adhesion promoting additive and
5. (e) at least one additive,

consists.

For further details, advantages and embodiments relating to this aspect of the invention, reference may be made to the previous statements relating to the previous aspect of the invention, which apply accordingly with regard to the composition according to the invention. This aspect of the invention can be used to read all the advantages, special features, features and embodiments which have been mentioned above in connection with the composition according to the first aspect of the invention.

Another object of the present invention - according to a third aspect of the present invention - is the use of a composition described above for cleaning metal surfaces, which preferably consist of or contain copper, copper alloys, brass, bronze and / or chrome.

The composition is preferably used for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits on metal surfaces.

Particularly good results are obtained in this connection if the metal surfaces contain or consist of copper, copper alloys, brass, bronze and / or chromium.

Surprisingly, the composition according to the invention can be used both for removing oxidation products and for removing limescale deposits on metal surfaces.

Likewise, according to a further aspect of its use, the composition according to the invention can be used to remove oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or to remove limescale deposits on brass instruments.

For further details on this aspect of the invention, reference can be made to the above explanations regarding the other aspects of the invention, which apply accordingly with regard to the use according to the invention.

1. (a) auf eine Metalloberfläche aufgebracht wird,
2. (b) für eine chemische Entfernung der Oxidationsprodukte und/oder der Kalkablagerungen ausreichende Zeit auf der Metalloberfläche belassen wird und
3. (c) von der Metalloberfläche entfernt wird.

Yet another object of the present invention - according to a fourth aspect of the present invention - is a cleaning process for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits from metal surfaces, a composition described above

1. (a) is applied to a metal surface,
2. (b) is left on the metal surface sufficient time for chemical removal of the oxidation products and / or the lime deposits, and
3. (c) is removed from the metal surface.

According to an embodiment preferred according to the invention, it can be provided within the scope of the method according to the invention that the composition according to the invention is applied in a location-selective and / or localized manner, in particular with a brush, a squeegee or a spatula to the metal surface.

In the context of the present invention, it can be provided that the adhesiveness of the composition is increased by at least one adhesion-promoting additive, in particular at least one sugar, preferably a sugar syrup, as previously stated. It has been found that glucose syrup and / or invert sugar syrup are particularly preferred.

With regard to the time for which the composition is left on the metal surface, it has proven useful if the composition according to the invention is on the surface over a period of 2 to 30 minutes, in particular 5 to 25 minutes, preferably 10 to 20 minutes is left.

The cleaning process can be carried out as often as required until the desired cleaning effect is achieved. The process is usually carried out one to three times. In most cases, a single application of the composition or a single implementation of the method is sufficient to achieve very good cleaning results. This applies in particular to less pronounced signs of corrosion on copper-containing materials or the cleaning of chrome-plated surfaces. With a pronounced patina on copper-containing materials or intensive occurrence of verdigris, up to 3 applications are usually required to achieve complete removal of the corrosion products or oxidation products.

According to a preferred embodiment of the cleaning method according to the invention, the composition is removed without residue, preferably with water.

In this context, it can be provided in particular that the water is heated, in particular to temperatures in the range from 30 to 80 ° C., preferably 30 to 70 ° C., preferably 40 to 60 ° C. With warm water the composition can usually also be easily removed from detailed structures.

For further details on this aspect of the invention, reference can be made to the above explanations regarding the other aspects of the invention, which apply accordingly with regard to the method according to the invention.

1. (a) mindestens eine Säure und
2. (b) mindestens ein Bindemittel

enthält, wobei die Zusammensetzung frei von Holzmehl ist.The present invention - according to a fifth aspect - is a composition in the form of a dry mixture of a cleaning agent

1. (a) at least one acid and
2. (b) at least one binder

contains, the composition is free of wood flour.

In the context of the present invention, a dry mixture is preferably to be understood as a powdery mixture of ingredients. The dry mix is preferably water-free and has a long shelf life at room temperature with no air. An appropriate amount of liquid is added to the dry mix for use.

The dry mixture according to the invention, in particular the cleaning agent, is free from wood flour, which means that the composition can also be used on sensitive objects, such as brass instruments, without clogging of valves or cables.

After the addition of liquid, in particular water, the dry mixture preferably gives the composition described above, in particular the cleaning agent described above.

Because, as the applicant has found, mixtures of acids, in particular organic acids, preferably fruit acids, with a large number of binders can be stored for a long period of time with the exclusion of moisture.

The composition according to the invention in the form of a dry mixture is then mixed with an appropriate amount of liquid, in particular, before use Water is added in order to obtain a liquid mixture of the desired viscosity, which, as described above, can be applied to metal surfaces in a location-selective and localized manner without problems.

If the composition is in the form of a dry mixture, it has proven useful if the acid is used in powder form, in particular as a crystalline powder, in the composition.

The acids used for the dry mixture in the context of the present invention are preferably solids, in particular fruit acids, preferably selected from the group of citric acid, malic acid, fumaric acid, maleic acid, oxalic acid, glycolic acid, lactic acid, tartaric acid, salicylic acid, ascorbic acid and their mixtures.

In the context of the present invention, however, it is particularly preferred if the dry mixture according to the invention contains citric acid.

It is usually provided according to the invention that the acid in amounts in the range from 50% by weight to 98% by weight, preferably in the range from 65% by weight to 95% by weight, preferably in the range from 70% by weight. % to 80% by weight, particularly preferably in the range from 80% by weight to 90% by weight, based on the composition in the form of a dry mixture.

As already stated above, a binder in the context of the present invention is preferably to be understood as a thickener. In the context of the dry mixture according to the invention, an acid-stable, preferably a solid binder obtained from a natural substance is used.

As previously stated, the binder is preferably used in the form of a dry mixture as a solid.

In this context, the use of a polysaccharide is preferred. The binder is particularly preferably selected from the group consisting of alginate, agar, carrageenan, locust bean gum, guar gum, tragacanth, gum arabic, xanthan, karaya gum, tara gum, gellan, konjac, cassia gum, pectins, cellulose, starch, and mixtures and derivatives thereof .

The binder for the dry mixture is particularly preferably selected from xanthan or mixtures of xanthan and starch or starch derivatives.

Particularly good results are obtained if the binder is preferably a polysaccharide, in amounts in the range from 2% by weight to 20% by weight, in particular in the range from 3.5% by weight to 15% by weight, preferably in Range from 5% by weight to 15% by weight, preferably in the range from 6% by weight to 13% by weight, particularly preferably in the range from 8% by weight to 12% by weight, based on the Composition in the form of a dry mixture is used.

According to a particular embodiment, it can be provided in particular that the dry mixture according to the invention has at least one adhesion-promoting additive, preferably at least one sugar, in particular in the form of a solid. It is particularly preferred if the sugar is selected from the group of sucrose, dry glucose, fructose, dextrose, galactose, mannose, raffinose, maltodextrin and mixtures thereof.

The use of dry glucose and / or sucrose is very particularly preferred in connection with this.

In addition, it can be provided in the context of the present invention that the dry mixture has at least one additive, in particular preservative and / or rheology adjuster. The additives are preferably also present as solids. If the composition in the form of a dry mixture has an additive, the composition in the form of a dry mixture usually has the additive in amounts in the range from 0.001% by weight to 2% by weight, in particular in the range from 0.005% by weight to 1 .5% by weight, preferably in the range from 0.01% by weight to 1.2% by weight, preferably in the range from 0.05% by weight to 0.8% by weight, particularly preferably in Range from 0.1 wt .-% to 0.5 wt .-%, based on the composition.

1. (a) mindestens eine Säure,
2. (b) mindestens ein Bindemittel,
3. (c) mindestens einen adhäsionsfördernden Zusatz und
4. (d) mindestens ein Additiv

enthalten, wobei die Zusammensetzung frei von Holzmehl ist.According to a particular embodiment of the present invention, the composition according to the invention, in particular the dry mixture of the cleaning agent,

1. (a) at least one acid,
2. (b) at least one binder,
3. (c) at least one adhesion promoting additive and
4. (d) at least one additive

included, the composition is free of wood flour.

To this particular embodiment of the present invention, all the advantages, features and special features mentioned above, which were mentioned in connection with other embodiments of the composition in the form of a dry mixture, can be applied and read accordingly.

For further details on this aspect of the invention, reference can be made to the above statements regarding the other aspects of the invention, which apply correspondingly in relation to the composition according to the invention in the form of a dry mixture.

1. (a) mindestens einer Säure,
2. (b) mindestens einem Bindemittel,
3. (c) mindestens einem adhäsionsfördernden Zusatz und
4. (d) mindestens einem Additiv

besteht.Yet another object of the present invention - according to a sixth aspect of the present invention - is a composition, in particular a dry mixture of a cleaning agent, which consists of

1. (a) at least one acid,
2. (b) at least one binder,
3. (c) at least one adhesion promoting additive and
4. (d) at least one additive

consists.

For further details, advantages and embodiments relating to this aspect of the invention, reference can be made to the previous statements relating to the previous aspect of the invention, which apply correspondingly in relation to the composition according to the invention in the form of a dry mixture.

Yet another object of the present invention - according to a seventh aspect of the present invention - is the use of a dry composition according to the invention as described above for removing oxidation products, in particular patina and verdigris or oxidation products on chromium-plated surfaces, and / or for removing limescale deposits on metal surfaces, the dry composition being mixed with water before application to the metal surface to be cleaned.

Surprisingly, the dry composition according to the invention, after adding water, can be used both for removing oxidation products and for removing limescale deposits on metal surfaces.

In this context, it can in particular be provided that the metal surface contains or consists of copper, copper alloys, brass, bronze and / or chromium.

When using the composition in the form of a dry mixture, it is particularly provided that the composition in the form of a dry mixture is mixed with a corresponding amount of water and mixed as homogeneously as possible in order to obtain a liquid composition. The liquid composition has the necessary adhesiveness to metal surfaces. By changing the metered amount of water, the viscosity of the ready-to-use composition can be easily adjusted.

Yet another object of the present invention is the use of a composition according to the invention in the form of a dry mixture as described above for cleaning metal surfaces which preferably consist of or contain copper, copper alloys, brass, bronze or chromium. All of the aforementioned advantages, special features and embodiments of the use of a dry mixture according to the invention can be applied accordingly to this special aspect of the present invention.

In particular, the dry summary is suitable for cleaning metal surfaces, which preferably consist of or contain copper, copper alloys, brass, bronze and / or chromium.

After adding water, the dry composition according to the invention can very particularly preferably be used according to a further aspect of its use for removing oxidation products or oxidation products on chrome-plated surfaces, in particular patina and verdigris, and / or for removing limescale deposits on brass instruments.

For further details on this aspect of the invention, reference can be made to the above explanations regarding the other aspects of the invention, which apply accordingly to the use of a dry mixture according to the invention.

1. (a) mit Wasser vermengt wird,
2. (b) die in Verfahrensschritt (a) erhaltene Zusammensetzung auf eine Metalloberfläche aufgebracht wird,
3. (c) für eine chemische Entfernung der Oxidationsprodukte und/oder der Kalkablagerungen ausreichende Zeit auf der Metalloberfläche belassen wird und
4. (d) anschließend von der Metalloberfläche entfernt wird.

Finally, another object of the present invention - according to an eighth aspect of the present invention - is a cleaning process for removing oxidation products, in particular patina and verdigris or oxidation products on chromium-plated surfaces, and / or for removing limescale deposits from metal surfaces, the previously described invention Dry mix

1. (a) is mixed with water,
2. (b) the composition obtained in process step (a) is applied to a metal surface,
3. (c) leaving sufficient time on the metal surface for chemical removal of the oxidation products and / or the lime deposits, and
4. (d) is then removed from the metal surface.

According to the invention, it can in particular be provided that the amount of water is selected so that the cleaning composition has a highly viscous consistency.

According to a preferred embodiment of the cleaning process, the viscosity is set to values in the range from 10 ³ cP to 10 ⁵ cP, preferably from 5,000 cP to 50,000 cP, particularly preferably from 10,000 cP to 30,000 cP, preferably to approximately 10 ⁴ cP.

In general, it is provided that the composition obtained in process step (a) is applied to the metal surface with a brush, a squeegee and / or a spatula in process step (b).

In this connection, it has surprisingly been found that a consistency of the composition obtained in process step (a) comparable to the consistency of honey is sufficient to ensure adequate adhesion.

According to a particular embodiment of the cleaning process, in step (c) the composition is left on the surface for a period of 2 to 30 minutes, in particular 5 to 25 minutes, preferably 10 to 20 minutes.

Within the scope of the invention, the cleaning process can be carried out as often as desired. However, the process is preferably carried out once or twice, preferably once.

According to a preferred embodiment of the cleaning method according to the invention, the composition is removed without residue, preferably with water.

In this context, particularly good results are obtained when the water is heated, as stated above.

For further details on this aspect of the invention, reference can be made to the above explanations regarding the other aspects of the invention, which apply accordingly in relation to the cleaning method according to the invention.

The subject matter of the present invention is illustrated below in an exemplary and non-limiting manner by the exemplary embodiments.

Embodiments Manufacturing examples

The cleaning compositions are mixed mechanically at room temperature and can be applied directly to the surface to be cleaned. After the exposure time of 10 to 20 minutes, they are completely rinsed off the surface to be cleaned with lukewarm water.

Regular drinking water is used, which does not have to be further purified.

Stobigel XMH 143 is a modified starch from the Stockmeier company that swells cold and thus gelatinizes without being heated.

The sugar syrup used has 75% dry matter, a dry glucose content of 60% and an invert sugar content of 40% when dry.

Potassium sorbate is a preservative.

Composition 1

• 250 g citric acid
• 30 g Stobigel XMH 143
• 1 g potassium sorbate
• 580 g sugar syrup
• 139 g water

This composition shows all the desired properties, it can be used vertically on walls, even upside down, is easy to wash off and achieves good removal of impurities.

Composition 2

• 400 g Zitronensäure
• 1 g Kaliumsorbat
• 30 g Stobigel XMH 143
• 350 g Zuckersirup
• 219 g Wasser

To lower the pH, the concentration based on the composition is increased and that of the sugar syrup is reduced.

• 400 g citric acid
• 1 g potassium sorbate
• 30 g Stobigel XMH 143
• 350 g sugar syrup
• 219 g water

The application and cleaning effects of this composition are comparable to those from the previous composition.

Composition 3

• 400 g Zitronensäure
• 40 g Stobigel XMH 143
• 4 g Xanthan
• 556 g Wasser

A composition without sugar and preservatives is desirable so that they are not used, but a combination of two binders is used for higher adhesion.

• 400 g citric acid
• 40 g Stobigel XMH 143
• 4 g xanthan gum
• 556 g of water

The composition has a higher viscosity with constant adhesion and cleaning power. The use of sugar syrup is therefore only optional.

The results of a viscosity measurement at 22 ° C. using the Brookfield RVDV II + rotary viscometer and spindle 5 of composition 2 and composition 3 are listed in the table below: Table 1: Dynamic viscosities of compositions 2 and 3 RPM ¹ Composition 2 [cP] Composition 3 [cP] 2nd 29,700 5 16,280 5920 10th 10,600 4680 20 6990 3800 30th 5533 ¹ : Rounds per minute

Composition 4

• 400 g citric acid
• 10 g xanthan gum
• 150 g glucose syrup
• 440 g water

Composition 5

• 400 g citric acid
• 20 g xanthan
• 150 g glucose syrup
• 430 g water

Composition 6

• 400 g citric acid
• 16 g xanthan
• 150 g glucose syrup
• 430 g water

Composition 7

• 400 g citric acid
• 10 g xanthan gum
• 590 g water

Recipes 4 to 7 have in common that a very stable gel-like structure is formed, which can be easily brushed onto metallic surfaces, for example using a brush, and remains there without running.

This correlates well with the measured viscosity values, which were determined for formulation 4. Even after heating to 85 ° C and then cooling to 22 ° C, the viscosity remains almost constant. The solution is only made clearer by heating, since the air bubbles introduced during production are significantly reduced.

Table 2 shows the results of a viscosity measurement at 22 ° C. (Brookfield RVDV II + rotary viscometer, spindle 5) on composition 4 before and after heating to 85 ° C. Table 2: Dynamic viscosities of composition 4 before and after heating to 85 ° C RPM ¹ Composition 4 [cP] Composition 4 after heating [cP] 1.00 89,200 83,600 2.00 46,400 46,000 5.00 21,920 20,720 10.00 12,000 11,320 20.00 6,900 6,400 50.00 3,368 3,128 100.00 2,072 1,840 ¹ : Rounds per minute

The sharp decrease in the viscosity of compositions with increasing speed is due to the thixotropic gels with the binder xanthan. This is advantageous for cleaning purposes, since after stirring the composition can be applied to the surface to be treated without problems and in thin layers with a brush. After application, however, the composition remains on the treated areas and can develop its effect.

The addition of adhesion-promoting agents, such as glucose syrup, is not absolutely necessary, so that usually the three components, acid, in particular citric acid, binder, in particular xanthan, and water are sufficient.

The viscosity measurements of recipe 7 show that the influence of glucose syrup on the viscosity is relatively small. Furthermore, formulation 7 adheres well to metallic surfaces, the adhesion being somewhat worse than the adhesion of formulation 4, but being sufficient for most applications.

Table 3 shows the results of a viscosity measurement at 22 ° C. (Brookfield RVDV II + rotary viscometer, spindle 5) on composition 7. Table 3: Dynamic viscosities of compositions 7 RPM ¹ Composition 7 [cP] 1.00 81,600 2.00 44,200 5.00 19,200 10.00 10,960 20.00 6,060 50.00 2,840 100.00 1,600 ¹ : Rounds per minute

Composition 8 (dry mix)

• 900 g citric acid
• 90 g of Stobigel
• 10 g xanthan gum

Composition 9 (dry mix)

• 800 g citric acid
• 100 g of sugar
• 90 g of Stobigel
• 10 g xanthan gum

Dry mixtures 8 and 9 can be prepared by mixing thoroughly with warm water to form ready-to-use solutions or dispersions with a very high viscosity. The good adhesive properties of the modified starch achieve the desired adhesive properties. It is usually sufficient to use a dry composition without additives that promote adhesion, such as sugar, dry glucose or maltodextrin. If necessary, the adhesion to the metal surfaces can be increased by adding these additives.

Application example

The application example shown in the figure is explained in more detail below.

In the application examples illustrated in the figure, the composition according to Production Example 1 is applied with a brush to copper-containing materials and left there for about 10 minutes. The composition is then washed off with warm water and the surface is dried.

They show Figures 1a and 2a a copper bedpan, which is heavily soiled and has a strong partina. After treatment with the composition according to Production Example 1 is as in the Figures 1b and 2 B shown, the partina as well as usual other soiling has largely disappeared and the shiny metallic copper can be recognized again.

Figure 3a shows a brass bell before treatment with the composition according to production example 1. The bell is uneven and tarnished. After treatment with the composition according to the invention the bell shines metallic again and the dirt and build-up are almost completely removed, as if Figure 3b evident.

Figure 4a shows a section of a frame ring made of brass before treatment with the composition according to the invention according to Production Example 1.

Figure 4b shows the same section of the frame ring, which shines metallic again after treatment with the composition according to the invention. It can also be clearly seen that the fine details and contours of the ring frame have almost completely removed the dirt and oxidation products.

Figure 5a finally shows the weight of a brass lamp, which is also very dirty and tarnished. After treatment with the composition according to the invention according to Preparation Example 1, the heavy soiling is as if from Figure 5b visible, almost completely removed.

The composition according to the invention thus enables simple, reproducible and inexpensive cleaning of copper-containing materials, in particular also of detailed objects with fine structures.

Claims (15)

Composition, in particular detergent, preferably having adhesiveness to metals, comprising (a) at least one acid, (b) at least one binder and (c) water; the composition being free from wood flour. Composition according to claim 1, characterized in that the acid is an inorganic acid, an organic acid or a mixture thereof, in particular a mineral acid or a fruit acid. Composition according to Claim 1 or 2, characterized in that the composition contains the acid in amounts in the range from 10% by weight to 60% by weight, in particular in the range from 20% by weight to 55% by weight, preferably in the Range from 25% by weight to 50% by weight, preferably in the range from 30% by weight to 45% by weight, particularly preferably in the range from 35% by weight to 45% by weight, based on the Composition. Composition according to one of the preceding claims, characterized in that the binder is an acid-stable binder, preferably a binder obtained from a natural product, preferably a polysaccharide. Composition according to one of the preceding claims, characterized in that the binder is selected from the group consisting of alginate, agar agar, carrageenan, locust bean gum, guar gum, tragacanth, gum arabic, xanthan gum, karaya gum, tara gum, gellan, konjac, cassia gum, pectin, cellulose , Starch, and their mixtures and derivatives, very particularly preferably xanthan. Composition according to one of the preceding claims, characterized in that the composition of the binder in amounts in the range from 0.5% by weight to 7% by weight, in particular in the range from 0.5% by weight to 6.5% .-%, preferably in the range of 0.8 wt .-% to 5% by weight, preferably in the range from 1% by weight to 5% by weight, particularly preferably in the range from 1% by weight to 2% by weight, based on the composition. Composition according to the preceding claims, characterized in that the composition has at least one adhesion-promoting additive, preferably at least one sugar, preferably a sugar syrup, particularly preferably glucose syrup or invert sugar syrup. Composition according to the preceding claims, characterized in that the composition has a highly viscous consistency, in particular a viscosity in the range from 10 ³ cP to 10 ⁵ cP, preferably from 5,000 cP to 50,000 cP, particularly preferably from 10,000 cP to 30,000 cP, preferably in the Of the order of 10 ⁴ cP. Composition according to the preceding claims, characterized in that the composition comprises the water in amounts in the range from 15% by weight to 70% by weight, in particular in the range from 15% by weight to 60% by weight, preferably in the range from 20% by weight to 55% by weight, preferably in the range from 25% by weight to 50% by weight, based on the composition. Composition, in particular cleaning agent, preferably with adhesiveness to metals, consisting of (a) at least one acid, (b) at least one binder, (c) water, (d) at least one adhesion promoting additive and (e) at least one additive. Use of a composition according to one of claims 1 to 10 for cleaning metal surfaces, which preferably consist of or contain copper, copper alloys, brass, bronze and / or chromium. Use of a composition according to one of Claims 1 to 10 for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits on metal surfaces. Cleaning method for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits from metal surfaces, characterized in that a composition according to one of claims 1 to 10 (a) is applied to a metal surface, (b) is left on the metal surface sufficient time for chemical removal of the oxidation products and / or the lime deposits, and (c) is removed from the metal surface. A composition, in the form of a dry blend of a detergent, comprising (a) at least one acid and (b) at least one binder; the composition being free from wood flour. Cleaning method for removing oxidation products, in particular patina and verdigris or oxidation products on chrome-plated surfaces, and / or for removing limescale deposits from metal surfaces, characterized in that the dry mixture according to claim 14 (a) is mixed with water, (b) the composition obtained in process step (a) is applied to a metal surface, (c) leaving sufficient time on the metal surface for chemical removal of the oxidation products and / or limescale deposits, and (d) is then removed from the metal surface.

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