DE19536353A1 - Antimicrobial acid cleaner for removal of crusts, deposits and contamination with microorganisms - Google Patents

Abstract

Antimicrobial, acid cleaners, suitable for the simultaneous removal of crusts, deposits and contamination with microorganisms, contain (a) an acid system comprising Al<3>+ salts, Fe<3>+ salts, inorganic acids and/or organic acids and (b) anionic tensides.

Description

1. Problem, state of the art 1.1. Germination problems with crusts, deposits

Smooth surfaces can be made relatively easily with antimicrobial treatments sanitize, but are in areas that are more or less complex aqueous solutions, e.g. B. drinking and waste water, food and fruit juices, Drinks such as As beer, organic liquids such. B. urine, come into contact rather the exception. Mostly there are deposits or crusts on the contact surfaces, such as B. lime, water stone, oxal stone, beer stone, urine stone etc., which is a very good one Represent a settlement surface for microorganisms (bacteria, fungi, yeasts), especially since such coatings are mostly porous and therefore also inside can be settled. Simple cleaning procedures like the non-antimicrobial, pure crust solution or surface disinfection without dissolution of crusts cannot solve these problems in a script.

1.2. State of the art

There are various means and processes for dissolving lime and other crusts known, e.g. B. (Quick) descaler for tea and coffee machines, washing and Dishwashers. Disinfectant additives that the under 1.1. shown These products are lacking in eliminating problems. On the other hand, from the Dairy farming, as well as the beverage and food industry products for Ober surface disinfection known, the inorganic or organic acids and anionic Contain surfactants.

It is known that anionic surfactants, such as. B. fatty alcohol sulfates or alkyl aryl Sulfonates at low pH values (<3) already in concentrations around 200 mg / l (0.02%) have good microbicidal effects.

With the acidic surface disinfectants mentioned above, the acidity is only added to set the desired low pH. The potency of such Products for lime solution or crust dissolution are not sufficient, and probably also not intended. In addition to the acid concentration, there is also the type of acid used Acids or their composition with acidic mixtures are not good Crust or lime solution optimized. Modern descaling mixtures are not considered. Furthermore, these products are often clouded, i. H. the anionic Surfactants are not in a clear solution, so that an optimal microbicide and a residue-free effect is also not ensured.

Usually only either inorganic acids or organic acids, however mixtures of these acid types are not used.

When using fatty alcohol sulfates that are unstable to hydrolysis, the Lang is time stability in solution not guaranteed. The ones formed by hydrolysis Fatty alcohols are no longer antimicrobial.  

Practically all common acidic microbicidal cleaners are made with tap water mixed and used in diluted form. It comes through Incompatibility reactions between the anionic surfactants and the Hardeners in the dilution water often cause turbidity, precipitates, which Severely impair cleaning effect.

2. Solution according to the invention of the problems described

The means explained below and their application solve the described under 1. problems.

2.1. Formulation principle of the agents according to the invention

The fundamentals are based on the following principle

• - Selection of an effective acid system for lime and crust solution.
• - Mix in a well-suited, solution and application compatible surfactant in optimal concentration to the additional function, the antimicrobial Effect to introduce parallel to descaling.

2.1.1. Acid systems used according to the invention a) Al ³⁺ , Fe ³⁺ -containing acid systems

While when using alkylbenzenesulfonates by reaction with the M ³⁺ cations cloudy, precipitate and therefore unsuitable, acidic and microbicidal cleaners are formed in any case, by using fatty alcohol sulfates, phosphates and sulfosuccinates or their ethoxylated derivatives Build M ³⁺ -insensitive, clear, long-term stable cleaning systems.

The following acid systems are possible:

• - Exclusively Al ³⁺ , Fe ³⁺ salts such as B. the chlorides, nitrates, sulfates, hydrogen sulfates, amidosulfonates. When dissolved in water, the M ³⁺ (H₂O) ₆ complexes are formed, which act as weak acids.
• - Optimized mixtures of Fe ³⁺ and Al ³⁺ salts with inorganic acids, such as. B. sulfuric acid, sodium hydrogen sulfate, amidosulfonic acid, nitric acid, hydrochloric acid, phosphoric acid, phosphonic and phosphinic acid.
• - Optimized mixtures of the Al ³⁺ and Fe ³⁺ salts listed above with organic acids, such as. B. citric acid, tartaric acid, formic acid, acetic acid, glycolic acid, malic acid, grape acid. Sugar acids (mono- and dicarboxylic acids of triosen, tetroses, pentoses, hexoses), organic phosphonic acids (e.g. 2-phosphonobutane-1,2,4-tricarboxylic acid; 1-hydroxyethane-1,1-dimethylene-phosphonic acid etc.) .
• - Optimized mixtures of the Al ³⁺ and Fe ³⁺ salts listed above with combinations of the inorganic acids and the organic acids listed below.

b) Inorganic acids alone

All acid systems listed under 2.1.1, point a) are used here.

c) Organic acids alone

Stable, non-cloudy application solutions of anionic surfactants with the organic acids listed under 2.1.1., Point a) in water containing Ca ²⁺ are generally only available with large excesses of anionic detergents (<0.2 to 0.5% ) producible. Glycolic acid is an exception.

Among the anionic surfactants form ethoxylated fatty alcohol sulfates, which are due to their insensitivity to hardness agents even with small ones Clear surfactant concentrations (<= 0.02%) with organic acids Allow application solutions, an exception.

d) Optimized mixtures of inorganic acids and organic acids

All under 2.2. 1 a) described inorganic and organic acids can also as mixtures, their composition optimized and the intended use is adjusted, use.

2.1.2. Anionic surfactants used according to the invention

The following anionic surfactants are used together with the under 2.1.1. defined Acid systems used:

• - Fatty alcohol sulfates, such as. B. sodium lauryl sulfate (C₁₂).
• - Ethoxylated fatty alcohol sulfates or fatty alcohol ether sulfates (with 1 to 100 Ethylene oxide groups or -oxy-ethylene groups and their C-substituted Derivatives)
• - Fatty alcohol ether phosphates with 1-100 oxyethylene groups and their C-substituted derivatives.
• - fatty alcohol sulfosuccinates
• - Fatty acid methyl ester sulfonates
• - Alkylbenzenesulfonates: As described above, this group is not compatible with Al ³⁺ or Fe ³⁺ -containing acid systems.

The number of carbon atoms in the alkyl chains of the anionic enumerated above Surfactants is between 8 and 18, mainly C₁₀-C₁₄, mainly C₁₂ (Lauryl residue).

Na⁺ generally acts as the cation of the surfactant anions. Theories are also theoretical Cations in the surfactant salts possible, e.g. B. K⁺, NH₄⁺. Free sulfonic acids are also applicable.

2.1.3. Areas of application of the antimicrobial cleaners according to the invention

The antimicrobial acidic cleaners defined according to the invention can be used anywhere be used where it is about the simultaneous cleaning of surfaces, vessels, Machines, pipe systems, objects, installations of crusts, such as B. lime, Water stone, oxal stone, beer stone, urine stone, tartar or deposits from these Materials with organic additives (fat, protein, carbohydrates) and adherent or stored microorganisms such. B. bacteria, yeasts, fungi goes.

This, parallel removal of two classes of contamination is carried out by the cleaners according to the state of the art, or only insufficiently enabled.

Typical areas of application for the new cleaners are:

• - Microbicidal descaling of tea and coffee machines (in private households and commercial area).
• - Microbicide descaling of washing machines and dishwashers (private and commercial).
• - Microbicidal cleaning and scale removal in the kitchen (sink) and bathroom (shower, Tub, toilet, tiles).
• - Microbicidal cleaning and removal of lime or other crusts in Systems and lines for the dairy, food and beverage industries as well as in slaughterhouses.
• - Microbicidal cleaning of beer lines in the brewery and gastronomy: Here - and also in the previously mentioned area of application - the use of sodium lauryl sulfate in Al ³⁺ -containing acid systems with NaHSO₄, H₂SO₄, amido sulfonic acid is particularly suitable due to its harmlessness and freedom from taste and organic acids.
• - Microbicidal limescale removal from private water pipes households and industry.
• - Microbicidal cleaning of lime residues in public and private Swimming pools.

2.1.4. Antimocrobial acidic solutions for dental hygiene

To our knowledge, the following purpose is completely new, regardless of Cleaners used:

Permanent cleaning of toothbrushes

Toothbrushes are cleaned superficially with water after use, however kept in the air in the moist state. Until they dry, they will deposits still adhering to the bristles to a large increase in micro organisms (from the oral flora and the outside air) so that when renewed Use a correspondingly strongly contaminated toothbrush.

The constant new and further contamination of the toothbrush is a reliable one Oral hygiene is not beneficial.

This problem is solved in that the toothbrush, the interdental brush and if necessary, also floss in a solution of antimicrobial acid cleaner is kept. Acidic because limescale is always on the toothbrush the tap water, but also from toothpastes, and be removed have to.

Acid systems containing sodium lauryl sulfate in a long term are particularly suitable use a stable recipe. Sodium lauryl sulfate is already used extensively in teeth pastes are completely harmless and tasteless.

Before reusing the in the antimicrobial acid storage solution stored toothbrush is enough to rinse briefly under running water. The so pretreated toothbrush or the dental care system is always germ-free!

Removable dental prostheses, partial dentures can also be used in this invention appropriate solutions are kept and cleaned and disinfected at the same time, e.g. B. overnight.

2.2. General description of the agents according to the invention

Depending on the components, liquid microbicidal acidic cleaners can be used or develop solid mixtures.

Liquid products

In general, all mixtures that are possible in solid form can also be used here dissolved, liquid form are manufactured, of course, all cleaners, too liquid components, e.g. B. acetic acid, formic acid, sulfuric acid, nitric acid etc. should contain.

Solid products

Solid, mostly powdered cleaning mixtures contain aluminum, for example sulfate plus crystalline organic acids, e.g. B. citric acid, tartaric acid.  

Other possible mixtures can be amidosulfonic acid plus or citric acid Include aluminum sulfate plus citric acid plus amidosulfonic acid.

The anionic surfactants are added as powdered sodium salts.

In products containing Al ³⁺ or Fe ³⁺ , apart from alkylbenzenesulfonates, all of the other anionic surfactants mentioned can be used as a formulation component. For Al ³⁺ or Fe ³⁺ -free variants, there are no restrictions with regard to the surfactants.

In application and storage tests it has been shown that the hydrolysis-labile alkyl sulfates, e.g. B. the sodium lauryl sulfate, in solutions that serve as inorganic anions only Contain amidosulfonate, sulfate or hydrogen sulfate, especially against hydrolysis are stabilized, even over months and years.

The following generally formulated mixtures proved to be special in solution stable: e.g. B.

• - aluminum sulfate, citric acid and sodium lauryl sulfate.
• - H₂SO₄ or NaHSO₄, citric acid and Na lauryl sulfate.
• - Aluminum sulfate and H₂SO₄, citric acid and lauryl sulfate.
• - Amidosulfonic acid, aluminum sulfate and citric acid (and many more)

Alkylarylsulfonates are already quite stable in Al ³⁺ -free acid systems, e.g. B. in mixtures of inorganic acids and organic acids.

The concentrations of the product components reach in the product (mostly liquid or solid concentrate) the following values:

Acid system: total 5 - almost 100%, preferably total 10-50%

Anionic surfactant (as Na salt): 0.01 to 20%, preferably 0.05 to 5%

The following concentrations are used in the application:

Acid system: total 1-30%, preferably 5-15%

Anionic surfactant: 0.02-5.0%, preferably 0.025-1.0%

The application is practically always by dissolving or mixing the Concentrate in tap water instead. The recipes of all of the invention antimicrobial acid cleaners are characterized in that they are in the product and are available in the application as clear solutions.

In addition to the components already described, according to the prior art additional recipe components are installed, e.g. B.

• - non-ionic surfactants
• - thickener
• - dyes
• - flavorings
• - organic solvents, e.g. B. alcohols
• - corrosion inhibitors.

The possible forms of application according to the prior art include the following Preparations:

• - aqueous or aqueous-organic solutions or suspensions
• - gels, pastes
• - Solvent-free solid forms such as powder mixtures; or pressed forms like Tablets, granules, pellets, extrudates, agglomerates etc.
• - Multi-component products, where z. B. a component in liquid form, the others are in solid form.

Of course, liquid or solid cleaning systems are also conceivable realizable in which more than one acid system with more than one anionic Surfactant can be mixed if the individual components together are compatible.

3. Advantages of the agents and methods according to the invention

From the new formulation of the antimicrobial acid cleaners and their application compared to means and methods of the prior art A number of improvements and advantages:

• - The antimicrobial lime and crust or deposit dissolution creates particularly hygienic conditions.
• - The particle-free product and application solutions without undissolved components contribute to better cleaning without residues.
• - Preparations rich in sulfate enable greatly improved long-term stability of fatty alcohol or alkyl sulfates, including ethoxylated alkyl sulfates, in acidic Solution.  
• - In the case of the Al ³⁺ or Fe ³⁺ -containing variants, an action synergism is achieved by the interaction of the M³ + ions and the acidic solution containing anionic surfactants.
• - All recipes are characterized by functionally optimized mixing ratios of the individual components, especially the acid system.
• - The acid systems are in their composition for optimal dissolution of lime and other crusts optimized.
• - Product variants with sodium lauryl sulfate prove to be toxicologically harmless conceivable, residue-free and tasteless. They are therefore especially for Applications in the food and beverage sector and in the mouth and tooth predestined hygiene area.
• - With certain mixtures, even without a thickener, clear, viscous Solutions.
• - With optimized formulations, all dilution levels remain clear. B. at Rinsing guarantees residue-free cleaning.

4. Specific Examples of Antimicrobial Acid Cleaners According to the Invention Systems

A series of are representative of many other product formulations Recipes listed.

4.1. Al ³⁺ -containing cleaning solutions

1) Aluminum sulfate (18 H₂O) 5-20% and 0.02-15% Na lauryl sulfate give one clear aqueous solution.

2) aluminum sulfate (18 H₂O) and amidosulfonic acid (50:50), 5-20% and 0.025- 5.0% Na lauryl sulfate clearly dissolves in water.

3) aluminum sulfate (18 H₂O) and citric acid (H₂O) 35: 65, 10-50% dissolve 0.025 up to 10% Na lauryl sulfate to a clear solution.

4) Aluminum chloride (6 H₂O) and citric acid (H₂O), 50:50, concentration 10- 50%, dissolve 0.1 to 10% Na lauryl sulfate to form a viscous, clear Solution.

5) aluminum sulfate (18 H₂O) and citric acid (H₂O) in a weight ratio of 35:65 are mixed 1: 1 with amidosulfonic acid. 1.25-20% of this acid dissolve 1.0- 10% Na lauryl sulfate to a clear solution.  

4.2. A ³⁺ -free cleaning solutions

1) 1.25 to 20% sulfuric acid dissolve 0.025-10.0% Na lauryl sulfate to a clear Solution.

2) Dissolve 0.025-5.0% Na laurylbenzenesulfonate in 1.25 to 2.5% sulfuric acid clear on.

3) In 1.25 to 10.0% amidosulfonic acid 0.025-5.0% Na lauryl sulfate or 0.025-5.0% laurylbenzenesulfonate clearly dissolved.

4) Clearly in 1.25 to 20% mixtures of sulfuric acid plus citric acid (H₂O), 20:80, or citric acid (H₂O) and amidosulfonic acid 50:50:
0.025-10% Na lauryl sulfate or,
0.025-10% Na lauryl ether sulfate or,
0.025-10% Na laurylbenzenesulfonate.

5) 1-20% citric acid (H₂O) clear 0.025-10% Na lauryl ether sulfate.

6) 1.25-20% glycolic acid with 0.25-10% Na lauryl sulfate and / or 0.5-10% Na laurylbenzenesulfonate clear, partially thickened solutions.

4.3. Examples of solid detergent mixtures (the mixing ratios are adapted to the special case, as well as the dosage in the application solution)

1) Citric acid (H₂O), amidosulfonic acid and Na lauryl sulfate or Na Laurylbenzenesulfonate.

2) Citric acid (H₂O), NaHSO₄xH₂O and Na lauryl sulfate or Na laurylbenzenesulfonate.

3) Citric acid (H₂O) + NaHSO₄xH₂O + amidosulfonic acid and Na lauryl sulfate or Na laurylbenzenesulfonate or Na lauryl ether sulfate.

4) Citric acid (H₂O) + aluminum sulfate (18 H₂O) and Na lauryl sulfate or Na lauryl ether sulfate.

5) Citric acid (H₂O) + aluminum sulfate (18 H₂O) + amidosulfonic acid and Na lauryl sulfate or Na lauryl ether sulfate.

6) Mixtures 1-5, the citric acid being replaced by tartaric acid becomes.

Claims (21)

1. Antimicrobial, acidic cleaners, which, due to their composition, are suitable for the simultaneous removal of crusts, deposits and contamination by microorganisms, containing:

• a) An acid system consisting of Al ³⁺ , Fe ³⁺ salts, inorganic acids, organic acids, individually or in combination, and
• b) one or more anionic surfactants.

2. Antimicrobial, acidic cleaner according to claim 1, characterized in that the following Al ³⁺ , Fe ³⁺ salts are used individually or in combination:
AlX₃ yH₂O, FeX₃ yH₂O with X = chloride, nitrate, hydrogen sulfate, amidosulfonate and Al₂ (X) ₃ yH₂O, Fe₂ (X) ₃ yH₂O with X = sulfate. Y can take all values between 0 and 18. 3. Antimicrobial, acidic cleaner according to claim 1, characterized in that they contain the following inorganic acids alone or in combination:
Sulfuric acid, sodium hydrogen sulfate, amidosulfonic acid, phosphoric acid (H₃PO₄), phosphonic acid (H₃PO₃) and phosphinic acid (H₃PO₂). 4. Antimicrobial, acidic cleaner according to claim 1, characterized in that they contain the following organic acids, alone or in combination:
Citric acid, tartaric acid, formic acid, acetic acid, glycolic acid, lactic acid, malic acid, grape acid, oxalic acid, sugar acids (mono- and dicarboxylic acids from triosen, tetrosen, pentoses, hexoses), organic phosphonic acids (e.g. 2-phosphonobutane-1,2,4 Tricarboxylic acid; 1-hydroxyethane-1,1-dimethylenephosphonic acid etc.). 5. Antimicrobial, acidic cleaner according to claims 1 to 4, characterized in that the salts (with Na⁺ and other cations) or the free acids of the anionic surfactants

• - fatty alcohol sulfates
• - Ethoxylated fatty alcohol sulfates or fatty alcohol ether sulfates (with 1 to 100 ethylene oxide groups or oxyethylene groups and their C-substituted derivatives.
• - Fatty alcohol ether phosphates with 1 to 100 oxyethylene groups and their C-substituted derivatives.
• - fatty alcohol sulfosuccinates
• - Fatty acid methyl ester sulfonates
• - alkylbenzenesulfonates

can be used individually or in combination. 6. Antimicrobial, acidic cleaner, according to claims 1 to 5, characterized characterized in that in the anionic surfactants defined according to claim 5 Alkyl groups with 8 to 18 carbon atoms, mainly with 10 to 14 carbon atoms, in particular with 12 carbon atoms (lauryl radical). 7. Antimicrobial, acidic cleaner according to claims 1 to 7, characterized in that the following combinations of the acid types defined in claims 2 to 4 are contained as the acid system:

• - Al ³⁺ , Fe ³⁺ salts and inorganic acids,
• - Al ³⁺ , Fe ³⁺ salts and organic acids,
• - Al ³⁺ , Fe ³⁺ salts and inorganic and organic acids,
• - Inorganic and organic acids.

8. Antimicrobial, acidic cleaner according to claims 1 to 7, characterized in that in particular the following acid systems are included:

• - Aluminum sulfate and citric acid in a mixing ratio of 40:60 to 10:90
• - Sulfuric acid and citric acid in a mixing ratio of 40:60 to 5:95
• - Sodium hydrogen sulfate and citric acid in a mixing ratio of 40:60 to 10:90
• - Aluminum sulfate and amidosulfonic acid in a mixing ratio of 60:40 to 10:90
• - Amidosulfonic acid and aluminum sulfate and citric acid in the mixing ratio 10: 50: 40 to 10: 20: 70 up to 70: 15: 15 to 70: 7:23
• - Amidosulfonic acid and citric acid in a mixing ratio of 10:90 to 90:10
• - Amidosulfonic acid and sodium hydrogen sulfate and citric acid in the mixing ratio 10: 50: 40 to 10: 20: 70 up to 70: 15: 15 to 70: 7:23
• 9. Antimicrobial, acidic cleaner according to claims 1 to 8, characterized in that all anionic surfactants defined according to claim 5 can be used in Al ³⁺ , Fe ³⁺ -free acid systems.

10. Antimicrobial, acidic cleaner according to claims 1 to 8, characterized in that in Al ³⁺ , Fe ³⁺ -containing acid systems all anionic surfactants defined according to claim 5 can be contained except the alkylbenzenesulfonates. 11. Antimicrobial, acidic cleaner according to claims 1 to 10, characterized by a particularly pronounced storage stability if the inorganic anions Acid systems only amidosulfonate, sulfate, hydrogen sulfate individually or in combination are contained and as anionic surfactants only fatty alcohol sulfates and their ethoxylated derivatives are used. 12. Antimicrobial, acidic cleaning solutions according to claim 11, characterized in that that sodium lauryl sulfate is preferably used as the anionic surfactant. 13. Antimicrobial, acidic cleaner according to claims 1 to 12, characterized characterized in that they are present as clear liquid solutions or concentrates which result in clear application solutions after dilution. 14. Antimicrobial acid cleaner according to claims 1 to 12, characterized characterized in that they are in the form of solid preparations, preferably in the form Powdery mixtures are present that clear after their dissolution Application solutions result.   15. Antimicrobial, acidic cleaner according to claims 1 to 14, characterized characterized in that they are preferably 5-99% as liquid or solid preparations Contain 10-50% of the acid system and 0.01-20%, preferably 0.025-5.0% contain an anionic surfactant system. 16. Antimicrobial, acidic cleaner according to claims 1 to 15, characterized characterized that their practical application solutions 1-30%, preferably Contain 5-15% of the acid system and 0.02-5.0%, preferably 0.025-1.0% contain an anionic surfactant system. 17. Use of the antimicrobial, acidic cleaner according to claims 1 to 16, characterized in that these are in diluted form for permanent cleaning, Disinfection and storage of toothbrushes, interdental brushes, dental floss, but also removable dentures, partial dentures. 18. The method according to claim 17, characterized in that preferably antimicrobial, acidic cleaners according to claims 11 and 12 are used. 19. Use of the antimicrobial, acidic cleaner according to claims 1 to 16 for Cleaning of beverage and beer lines in the brewery and in the Gastronomy. 20. The method according to claim 19, characterized in that preferably antimicrobial Cleaners are used according to claims 11 and 12. 21. Use of the antimicrobial, acidic cleaner according to claims 1 to 16 for the following cleaning processes:

• - Microbicidal descaling of tea and coffee machines, washing machines and dishwashers in the private and commercial sector.
• - Microbicidal cleaning and limescale removal in kitchens, bathrooms, toilets in the private and commercial sector.
• - Microbicidal cleaning and removal of lime, crusts and deposits in buildings, plants and lines in the dairy industry, food and beverage industry as well as in dairies and slaughterhouses.
• - Antimicrobial limescale or water stone removal, dissolution from water pipes in private and commercial areas.
• - Antimicrobial, especially antifungal cleaning of lime residues and calcareous surface coverings in swimming pools.