EP0651780B1 - Process for sanitary cleaning and a sanitary cleaner - Google Patents

Abstract

The description relates to a process for sanitary cleaning with a sanitary cleaner in liquid or solid form containing germicidal organic substances in a quantity of at least some '.5 g/kg sanitary cleaner, conventional scale-removing water-soluble acids, germ-conveying organic materials resistant to the scale-removing water-soluble acids in a quantity of at least 10 mg/kg sanitary cleaner and possibly other additives. After dilution or washing, the action of the germs decomposing the organic substance in the water is promoted. As germ-conveying organic substance, the sanitary cleaner contains a compound of the formula (I): R1R2N-CO-NR3R4 in which R1 to R4 are mutually independently open-chained or cyclised and may be: hydrogen, a lower alkyl group with 1 to 4 carbon atoms, a cyclo-alkyl group with 3 to 6 carbon atoms, an aryl group in the form of a phenyl or naphthyl rest, an aralkyl group with 7 to 18 carbon atoms, an alkylaryl group with 7 to 18 carbon atoms or an O, S or N-containing heterocyclic group with 2 to 5 carbon atoms. This process and the sanitary cleaner used therein promote the respiratory activity of microflora in the communal waste water. This also results in the desirable germicidal function in the initial operating phase of a sanitary cleaner, e.g. in a toilet pan.

Description

The invention relates to a method for sanitary cleaning with a sanitary cleaner in liquid or solid form with a content of germ-inhibiting organic substances in an amount of at least about 0.5 g / kg sanitary cleaner, conventional lime-dissolving water-soluble acids, and germ-promoting resistant to the lime-dissolving water-soluble acid organic substances in an amount of at least 10 mg / kg of sanitary cleaner and, if appropriate, of other additives, the activity of which disintegrates the germs which break down the organic substance of the water after dilution or rinsing, and a sanitary cleaner for carrying out this process.

The prior art described above is evident from the international application PCT / EP 90/01718. It shows the advantage that, on the one hand, the desirable germ-inhibiting function is developed in the first action phase of a sanitary cleaner, for example in a toilet bowl, and on the other hand, the degradation performance of the microflora of the waste water (in the second action phase) is not disturbed. This prior art is thus superior to a sanitary cleaner according to DE-OS 25 32 432, for example. This sanitary cleaner only works in the first phase, for example in a toilet bowl. It does not extend to the second phase. It is in tablet form and is mainly used to remove lime residues, with citric acid serving as a descaling agent.

With the sanitary cleaner according to PCT / EP 90/01718, it has been shown that it is desirable to increase its effectiveness in the second phase of action. The state of the art according to US Pat. No. 4,013,579 and DD 241,747 do not provide any suggestions for this desirable improvement. US Pat. No. 4,013,579 describes acidic cleaning agents which necessarily contain furan carboxylic acids or their derivatives. This is to remove dirt adhering to objects. The US-PS 4 013 579 writes the furan carboxylic acids or their derivatives, the large Show toxicity, no double function, as it is achieved in the above-described process of the prior art according to PCT / EP 90/01718 with the simultaneous use of germ-inhibiting and germ-promoting substances. The connecting group of the furan carboxylic acids or their derivatives, which is referred to in US Pat. No. 4,013,579 as "FCA", is intended to replace the oxalic acid previously used in the prior art. In contrast, the FCA should be easier and safer to use because they have no comparable high toxicity. In any case, they are still very toxic. The invention described below is particularly based on the fact that such toxic agents do not have to be used in the sanitary cleaner. Their incorporation means that in the second phase of action already mentioned, the inhibition of germs is not eliminated, but because of the toxicity of the existing FCA, the growth of the microorganisms desired there is excluded or at least undesirably reduced. DD 241 747 relates to an agent for cleaning and disinfecting toilet cisterns and basins, which is intended to prevent the formation of limescale. The thought of improving the microbial degradation of organic substances in wastewater is not mentioned in any way. Comparatively complex compounds, such as fatty alcohols, ethylene propylene copolymers and alkylphenol polyglycol ethane, are used which additionally pollute the waste water.

The invention was based on the object of developing the prior art described at the outset in such a way that the desirable germ-inhibiting function is maintained in the first phase of action, for example in a toilet bowl, and on the other hand the degradation performance of the microflora of the waste water (in the second phase of action) is further improved .

According to the invention, this object is achieved in that the sanitary cleaner, as a germ-promoting organic substance, is an open-chain or cyclic compound of the formula (I) R ₁ R ₂ N-CO-NR ₃ R ₄ , in which R ₁ to R _{4 are} each independently open-chain or cyclized and can have the following meaning:
Hydrogen, a lower alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, an aryl group in the form of a phenyl or naphthyl radical, an aralkyl group with 7 to 18 carbon atoms, an alkylaryl group with 7 to 18 carbon atoms or an O- , S-, or N-containing heterocyclic group with 2 to 5 carbon atoms.

The following formula (I) should also include the following urea derivatives:

In the formula (I), the respective radicals R ₁ , R ₂ , R ₃ and R _{4 are} preferably hydrogen, since the corresponding starting compounds are commercially available or easier to prepare. Particularly suitable in the context of the invention are the substituents which are specified in the above definition of the invention. The lower alkyl group having 1 to 4 carbon atoms are the methyl, ethyl, n-propyl, i-propyl and the various isomers of the butyl group. The cycloalkyl group with 3 to 6 carbon atoms includes in particular the cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl radical, the aralkyl group with 7 to 18 carbon atoms in particular the benzyl and phenethyl group, the alkylaryl group with 7 to 18 carbon atoms in particular the tolyl group and also the heterocyclic group with 2 to 5 carbon atoms, in particular those in whose heterocyclic ring there is at least one oxygen, sulfur or N atom, suitable examples being the radicals of oxirane, tetrahydrofuran, dioxane and pyran. In principle, the compounds of the formula (I) can also be used in the form of their salts or other precursors, which can promote solubility. In individual cases, this can only lead to the desired solubility in the sanitary cleaner according to the invention. In principle, therefore, compounds can be considered which only release the compounds of the formula (I) in the aqueous medium or allow their activity to develop there. The following quantities always relate to the compounds of formula (I) as such or their proportion within the suitable derivatives or compounds.

In addition to the compounds of formula (I) mentioned, germ-promoting organic substances can be used, which are known from the international application PCT / EP 90/01718. The known germ-promoting and germ-inhibiting organic substances have certain things in common. Thus, like the rest of them in particular urea and the urea derivatives suitable for the purposes of the invention, they are sufficiently resistant to organic acids or their salts in the usual temperature and pH range.

Suitable germ-inhibiting organic substances are in particular acidic organic substances or their salts or suitable derivatives and essential oils. Those germ-inhibiting organic substances that occur in nature are preferred. The addressed Acidic organic substances are in particular aromatic, aliphatic, alicyclic and / or heterocyclic carboxylic acids or their salts, in particular in the form of the alkali or alkaline earth metal salts, or also suitable derivatives thereof. In addition, the acidic organic substances should be sufficiently water-soluble to develop the desirable inhibition of germs be. In individual cases, the carboxylic acid itself can be sparingly water-soluble, but the suitable salt thereof can be water-soluble and suitable. The particularly suitable aliphatic carboxylic acids include, in particular, lower carboxylic acids with 1 to 7 carbon atoms, such as in particular formic acid, acetic acid, propionic acid, caproic acid, malonic acid and oxalic acid, and also various fatty acids with 6 to 12 carbon atoms, such as sorbic acid or undecenoic acid, if they are in the form suitable water-soluble salts can be used. Fatty acids with more than 12 carbon atoms are generally not suitable because they are not themselves water-soluble and, moreover, the majority of their salts also do not meet the requirement for water solubility. The butyric acid, which is assigned to the lower fatty acids, is not recommended due to its unpleasant smell. Suitable derivatives of the above carboxylic acids are hydroxy acids, such as glycolic acid, tartaric acid and citric acid, and oxo acids, such as acetoacetic acid and pyruvic acid. Sufficiently water-soluble aromatic carboxylic acids are also particularly suitable, such as in particular benzoic acid, salicylic acid and also other phenol carboxylic acids.

Essential oils are also of particular advantage. Essential microbiocidally active essential oils are in particular: thyme oil, citrus peel oil, eucalyptus oils, clove oil, origanum oil, rosemary oil, cinnamon oil, alum oil, camphor oil, coniferous oils and fennel oils. The thyme oil is particularly preferred. The active ingredients contained therein can also be used instead. Examples of germ-inhibiting ingredients of essential oils are: Thymol, Carvacrol, Terpineol, Cineol, and Fenchon. The essential oils are water-insoluble, but just like the water-insoluble vitamins, they can be used with suitable, especially environmentally friendly emulsifiers or solubilizers as germ-inhibiting substances in sanitary cleaners.

Practically all surface-active substances ("surfactants") can serve as solubilizers for the group of substances described above. The most suitable solubilizers for aqueous systems are selected according to the HLB system and must be determined experimentally for each individual essential oil. Solubilizers with HLB values of 12 to 18 are particularly suitable for essential oils in aqueous systems. Solubilisers in particular that come into question in Römpps Chemistry Lexicon, 8th ed., Vol. 3, p. 2399. The following grouped surfactants are generally suitable: anionic surfactants: fatty alcohol sulfonates, for example Na lauryl ether sulfate; cationic surfactants: quaternary ammonium compounds, for example didecyl-dimethyl-ammonium chloride, betaine derivatives, for example fatty acid amidopropyl-dimethyl-amino-acetic acid betaine; Non-ionic emulsifiers or solubilizers: fruit acid esters of the mono-di-glycerides, for example citric acid esters, polyoxyethylene-glycerol-fatty acid esters, for example polyoxyethylene-glycerol-mono-laurate with 30 mol of ÄO.

Formic acid, acetic acid, propionic acid, benzoic acid or simple derivatives of benzoic acid, sorbic acid, also in the form of suitable water-soluble salts thereof, such as the sodium and potassium salts, have proven to be particularly advantageous as germ-inhibiting organic acids. It can be seen that the lime-dissolving organic acids, such as citric acid, and the germ-inhibiting organic acids generally stand out from one another in terms of the different effects in a suitable sanitary cleaner. In individual cases, an organic acid can be lime-dissolving on the one hand and also have a germ-inhibiting effect. In general, it is preferred on the one hand to use such an acid, which has a particular ability to dissolve limescale, and on the other hand to use such an acidic organic compound, which shows a particularly effective inhibition of germs. If benzoic acid is used as the germ-inhibiting organic substance, a different lime-dissolving water-soluble organic acid is used.

The germ-inhibiting organic substances in the sanitary cleaner according to the invention, regardless of whether it is in powder, granular or liquid form, are present in at least about 0.5 g / kg of sanitary cleaner and preferably in an amount of 0.5 to 150 g / kg of sanitary cleaner, in particular in an amount of 1 to 80 g / kg of sanitary cleaner and very particularly preferably in an amount of 2 to 7 g / kg of sanitary cleaner.

The concentration of the germ-inhibiting organic substances in the first phase of action will preferably be set such that their concentration in or in the pool to be cleaned is at least about the minimum inhibitory concentration (MIC) and at most about 200 times the minimum inhibitory concentration (MIC). It is particularly preferred that the concentration of the germ-inhibiting organic substances in the first phase of action is at least about twice and at most about 50 times, in particular about 30 times the minimum inhibitory concentration.

In the context of the invention, in addition to the designated compounds of the formula (I), additional and preferably amino acids and / or as germ-promoting organic substances Orotic acid or suitable salts or derivatives thereof and vitamins can be used. The derivatization mentioned must not go so far as to impair the desired effect of promoting germs. Particularly suitable amino acids are: alanine, arginine, asparagine, aspartic acid, citrulline, cysteine, cystine, glutamine, glutamic acid, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, ornithine, phenylalanine, proline, serine, threonine, trypt as well as valine. Particularly suitable vitamins, including their provitamins, include: L-ascorbic acid, salts of ascorbic acid, in particular the Ca salt, L-ascorbyl palmitate, (+) - biotin, b-carotene, cholecalciferol, cyanocobalamin, dihydrofolic acid, dehydroascorbic acid, ergocalciferol Folic acid, hydroxocobalamin, niacinamide, nicotinic acid (niacin), D-panthenol, D-pantothenic acid, pyridoxal, pyridoxal-5-phosphate, pyridoxamine, pyridoxamine-5'-phosphate, pyridoxine, pyridoxine phosphate, riboflavin, riboflavin-5'-phosphate, ruthenium , Rutin salt, in particular the rutin sulfate, tetrahydrofolic acid, thiamine, thiamine nitrate, thiamine phosphoric acid ester, thiamine pyrophosphate, alpha-tocopherol, delta-tocopherol, alpha-tocopheryl acetate, alpha-tocopherylquinone, alpha-tocopherylphosphate, alpha-tocophenate, alpha-tocophenate , Vitamin A aldehyde, vitamin A alcohol, vitamin A acid, vitamin B ₄ (adenine), vitamin K ₁ , vitamin K ₄ , vitamin P and vitamin U (methionine S-methylsulfonium · chloride). In the event that the vitamins have acidic or basic groups, suitable salts thereof can generally also be used.

With the invention it is possible to achieve hygienic cleaning of sanitary facilities without interfering with the microbial degradation of the organic substances in the waste water. These apparently contradictory properties could be achieved by introducing the described germ-inhibiting or germ-killing active ingredients into the sanitary cleaner according to the invention in such a concentration that their concentration above the minimum inhibitory concentration (MIC) when used in the first effective phase provided for this purpose, for example in the toilet bowl ) lies. The "minimal inhibitory concentration" is a common technical term. At the same time, the germ-promoting organic substances are introduced into the product in such a concentration or quantity that, after the usual dilution of the medium in the first phase of action, they exert a growth-promoting effect on the microorganisms when they enter the waste water.

When using the sanitary cleaner according to the invention, which can be, for example, in powdered, granulated form or in aqueous form, it is diluted with a little water, for example in the toilet bowl. There, the active hygiene substances have a germ-inhibiting or germicidal effect, while the germ-promoting substances initially are ineffective. After flushing the toilet bowl following the action of the sanitary cleaner, the concentration of the germ-inhibiting organic substances is reduced below the MIC value and are therefore ineffective. The concentration of the germ-promoting organic substances in the sanitary cleaner according to the invention is such that they promote the activity of the wastewater germs, which degrade the organic substance, even after rinsing or strong dilution and thus accelerate or at least do not interfere with the biological wastewater treatment.

The amount of germ-promoting organic substances in the form of the compounds of the formula (I) in the sanitary cleaner according to the invention is not critical. In individual cases it must be tested which minimum concentration is used in each case. The quantitative minimum framework is an amount of approximately 10 mg / kg of sanitary cleaner, in particular the framework of 10 mg / kg to 50 g / kg of sanitary cleaner, in particular 1 g to 15 g / kg of sanitary cleaner, on the compounds (I) and / or (II) .

A minimum quantity of 10 mg / kg and in particular of 10 to 1000 mg / kg could be mentioned as a quantitative guideline for the further germ-promoting organic substances which can be used in addition to the designated germ-promoting organic substances in the form of the compound of the formula (I). The substances mentioned, preferably amino acids, vitamins, orotic acid and p-aminobenzoic acid, are suitable as germ-promoting further organic substances. Of practical importance is a mixture of about 2 mg biotin, about 20 mg nicotinamide, about 10 mg thiamine, about 10 mg p-aminobenzoic acid, about 5 mg pantothenic acid, about 50 mg pyridoxamine, about 2 mg cyanocobalamin (vitamin B12) and about 10 mg of orotic acid, this mixture preferably being present in about 1 kg of sanitary cleaner. To optimize the desired effects of the germ-promoting organic substances, these are selected qualitatively and quantitatively with regard to the respective milieu when they are used in a mixture.

Further known additives can be incorporated into the sanitary cleaner according to the invention, for example fragrances, dyes, biological foaming agents. A water-soluble protein with a simultaneous germ-promoting effect, in particular water-soluble whey protein, has proven to be a foamer. When using a water-soluble protein substance, 2 to 30 g, in particular 5 to 10 g, are preferably used for about 1 kg of powdered sanitary cleaner or also for about 1000 ml of liquid sanitary cleaner. Of course, the invention does not exclude that other substances known in the prior art can also be added, the selection of which is intended to retain the desired advantages of environmental friendliness, etc., as far as possible.

The particular advantage of the invention is that the breathability of the microflora in municipal waste water, as the following examples show, can be increased to a surprising extent. Thus, the sanitary cleaner according to the invention leads to a noticeable reduction in the environmental impact because its disinfectant effect is attributed to degradable natural substances, ie the lime-dissolving water-soluble acid, the germ-inhibiting organic substances and also the germ-promoting organic substances in the form of the compounds of the formula (I), in particular in the form of urea, can be of natural origin. The sanitary cleaner according to the invention is therefore particularly favorable for the environment, fulfills the requirements and, with increasing environmental awareness, meets the wishes of the consumers very much. It can therefore be used in a wide range of applications, such as in the entire sanitary cleaning sector, such as in particular in toilet bowls, urine pools, bathtubs, bidets, sinks and shower trays. This list of areas of application is not exhaustive.

The invention will be explained in more detail below with the aid of three recipe examples:

Example 1 (aqueous product / comparative example according to PCT / EP 90/01718):

citric acid 175 g Sodium hydroxide 22 g Formic acid 10 ml Sodium benzoate 2 g Potassium sorbate 2 g Mixture of vitamins and amino acids (see below) 0.5 g Thickener (xanthan) 5 g soluble whey protein 10 g

The above mixture was made up to 1000 ml with water. The mixture of vitamins and amino acids was composed as follows: 2 mg biotin, 20 mg nicotinamide, 10 mg thiamine, 10 mg p-aminobenzoic acid, 5 mg pantothenic acid, 50 mg pyridoxamine, 2 mg cyanocobalamin (vitamin B12) and 10 mg orotic acid.

Example 2 (Invention)

citric acid 175 g Sodium hydroxide 22 g Formic acid 10 ml Sodium benzoate 2 g Potassium sorbate 2 g urea 1 g Thickener (xanthan) 5 g soluble whey protein 10 g

This mixture was made up to 1000 ml with water.

Examples 3 and 4 (invention):

The formulation of Example 2 was modified by modifying the amount of urea. It was 2g in Example 3 and 5g in Example 4.

Comparative tests:

The positive effect of the sanitary cleaners according to Examples 1 to 4 above on the microflora of the waste water should be investigated. The breathability of the microflora in municipal wastewater was measured to check whether the sanitary cleaners mentioned promote the flora or are easily degradable. Fresh wastewater was prepared with the products from Examples 1 to 4 in three concentrations. After 24 hours, the carbon dioxide formed was measured. The dry matter content and the pH of the products were determined in parallel.

Test results: pH and dry matter content of the products

product PH value Dry matter (%) 1 2.90 5.8 2nd 2.78 6.0 3rd 2.83 6.2 4th 2.75 6.4

The products differ slightly in terms of pH and dry matter content. The change in the breathability of the microflora is shown in Table 1 below. Table 1 (Breathability of the wastewater flora depending on the composition of the toilet cleaner and its concentration in the wastewater) product Conc. Of product in waste water (%) Microbial breathability (mg CO ₂ / 10ml deviation = 24 h) Control (untreated waste water) 0 3.18 1 0.1 4.06 0.5 7.61 1.0 8.31 2nd 0.1 4.09 0.5 8.09 1.0 9.23 3rd 0.1 5.16 0.5 8.35 1.0 10.36 4th 0.1 5.85 0.5 10.11 1.0 10.73

The above comparative values show that the breathability is markedly increased by the addition of urea compared to the comparative product (1). The addition of 5 g of the growth factor in the form of urea to the sanitary cleaner No. 4 increases breathing compared to the comparison product (1) to an average of 135 (!)%. Thus, the addition of urea in the indicated amounts leads to a remarkable increase in the effectiveness of the wastewater flora.

Claims (11)

1. Process for sanitary cleaning with a sanitary cleaner in liquid or solid form having a content of bactericidal, organic substances in a quantity of at least 0.5 g/kg of sanitary cleaner, of conventional scale-removing, water-soluble acids, of germ-conveying, organic substances resistant to the scale-removing, water-soluble acid in a quantity of at least 10 mg/kg of sanitary cleaner and optionally of further additives in which, following the dilution or washing, the action of the germs decomposing the organic substance of the water is promoted, characterized in that the sanitary cleaner, as a germ-conveying, organic substance, contains an open-chain or cyclic compound of formula
   
           R₁R₂N-CO-NR₃R₄     (I),
   
   in which R₁ to R₄, in each case independent of one another, are present in open-chain or cyclized form and can have the following meaning:
   hydrogen, a lower alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, an aryl group in the form of a phenyl or naphthyl residue, an aralkyl group with 7 to 18 carbon atoms, an alkylaryl group with 7 to 18 carbon atoms or an 0, S or N-containing, heterocyclic group with 2 to 5 carbon atoms,
   and when use is made of benzoic acid as the bactericidal organic substance use is made of a scale-removing, water-soluble, organic acid differing therefrom.
2. Process according to claim 1, characterized in that citric acid is used as the scale-removing, water-soluble, organic acid.
3. Process according to claim 1, characterized in that the radicals R₁, R₂, R₃ and R₄ are hydrogen and consequently the compound of formula (I) is urea.
4. Process according to at least one of the preceding claims, characterized in that the concentration of the bactericidal compound of formula (I) in the sanitary cleaner is 10 mg/kg to 50 g/kg.
5. Process according to at least one of the preceding claims, characterized in that for optimizing its action, addition takes place to the sanitary cleaner of further germ-conveying, organic substances in the form of amino acids, orotic acid or their salts and/or vitamins.
6. Process according to at least one of the preceding claims, characterized in that the sanitary cleaner contains one or more bactericidal, organic substances in a quantity of 0.5 to 150 g/kg of sanitary cleaner.
7. Sanitary cleaner containing one or more bactericidal, organic substances in a concentration of at least 0.5 g/kg of sanitary cleaner and a germ-conveying organic substance or substances resistant to the scale-removing, water-soluble acid in the form of a compound of formula (I) in a quantity of at least 10 mg/kg of sanitary cleaner and in the case where benzoic acid is used as the bactericidal, organic substance, use is made of a scale-removing, water-soluble, organic acid differing therefrom.
8. Sanitary cleaner according to claim 7, characterized in that it also contains a germ-conveying, water-soluble protein as a foam carrier.
9. Sanitary cleaner according to claim 8, characterized in that it contains 2 to 30 g of water-soluble protein/kg of sanitary cleaner.
10. Sanitary cleaner according to claim 8 or 9, characterized in that the water-soluble protein is water-soluble whey protein.
11. Sanitary cleaner according to at least one of the claims 7 to 10, characterized in that the scale-removing, water-soluble acid or acids, the bactericidal, organic substance or substances and/or the germ-conveying, organic substance or substances occur naturally.