DE4317104C2 - 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 containing germ-inhibiting organic substances an amount of at least about 0.5 g / kg of sanitary cleaner, on standard lime-dissolving water-soluble acids, on against the lime-dissolving water-soluble acid resistant germ-promoting organic substances in an amount of at least 10 mg / kg Sanitary cleaner and optionally other additives, wherein after dilution or rinsing the organic matter of the water-degrading germs in their Be promoted effect.

The above-described prior art is based on the international application PCT / EP 90/01718. He shows the advantage that, on the one hand, the desirable germ-inhibiting function in the first phase of action of a sanitary cleaner, so For example, in a toilet bowl, unfolded, on the other hand, the degradation performance the microflora of the wastewater (in the second phase of action) is not disturbed. In order to This state of the art, for example, a sanitary cleaner according to DE-OS 25 32nd 432 superior. This sanitary cleaner works only in the first phase of effect, for example, in a toilet bowl. He does not extend his effect to the second Action phase. It is in tablet form and is mainly used to remove Limescale residues, with citric acid being used as the limescale remover.

In the sanitary cleaner according to PCT / EP 90/01718, it has been found that it it is desirable to increase its effectiveness in the second phase of action.

The invention was therefore based on the object, the above-described prior To develop technology so that the desirable germ inhibiting function in the first phase of action, such as in a toilet bowl, continue to be maintained On the other hand, however, the degradation efficiency of the microflora of the wastewater (in the second phase of action) is not only disturbed, but further improved.  

According to the invention, this object is achieved in that the sanitary cleaner as germ-promoting organic substance containing urea.

The sanitary cleaner according to the invention can be used in a variety of applications in the entire sanitary cleaning sector, in particular in Toilet bowls, urine bowls, bathtubs, bidets, sinks and shower trays. This list of application areas is not exhaustive.

In the context of the invention, urea is used as a germ-promoting organic substance used. Also it is possible urea in the form of suitable compounds, such as in Form of a suitable salt. Basically, connections can also be considered come, which release urea only in the aqueous medium. The following Quantities always refer to the urea as such.

In addition to the urea, the germ-promoting organic substances that are derived from the international Application PCT / EP 90/01718 are known. The known germ-promoting and germ-inhibiting organic substances have certain similarities. So they are, like in the also urea, resistant to organic acids or their salts.

As germ-inhibiting organic substances are in particular acidic organic substances or their salts or suitable derivatives and essential oils in question. Prefers become such germ-inhibiting organic substances that occur in nature. The on spoken acidic organic substances are in particular aromatic, aliphatic, alicyclic and / or heterocyclic carboxylic acids or their salts, in particular in Form of alkali or alkaline earth salts, or also suitable derivatives thereof. Above In addition, the acidic organic substances should unfold the desirable Germ inhibition be water-soluble. In some cases, the carboxylic acid itself insoluble in water, but the suitable salt thereof is water-soluble and suitable. To  the particularly suitable aliphatic carboxylic acids include in particular lower Carboxylic acids having 1 to 7 carbon atoms, in particular formic acid, Acetic acid, propionic acid, caproic acid, malonic acid and oxalic acid, as well as various fatty acids having 8 to 12 carbon atoms, such as. B. undecenoic acid, provided they can be used in the form of suitable water-soluble salts. Fatty acids with more than 12 Carbon atoms are generally not suitable since they themselves are not water-soluble and, moreover, the majority of their salts are the requirement of Water solubility not met. The butyric acid, which is attributed to the lower fatty acids is not recommended in view of its unpleasant odor. suitable Derivatives of the above carboxylic acids are hydroxy acids, such as glycolic acid and Tartaric acid, and oxo acids, such as acetoacetic acid and pyruvic acid. Particularly suitable are water-soluble aromatic carboxylic acids, in particular in particular the benzoic acid, salicylic acid and also phenolcarboxylic acids.

The use of furan carboxylic acids and their derivatives is excluded.

Of particular advantage are also essential oils. As a microbiocidally effective essential Oils are particularly suitable: thyme oil, citrus peel oil, eucalyptus oils, Origanum oil, rosemary oil, cinnamon oil, almond oil, camphor oil, coniferous oils and fennel oils. The Thyme oil is particularly preferred. Can be used in their place, the active ingredients contained therein. Examples of germ-inhibiting acting Ingredients of essential oils are: thymol, carvacrol, therpineol, cineole, and fenchone. The essential oils are insoluble in water, but can as well as the water-insoluble Vitamins with suitable, especially environmentally friendly emulsifiers or Solubilizers can be used as germ-inhibiting substances in sanitary cleaners.

As a solubilizer for the above-mentioned substance group virtually all surfactants ("surfactants") serve. The selection of the most suitable Solubilizer for aqueous systems happens after the HLB system and must for every single essential oil can be determined experimentally. For essential oils in aqueous systems are particularly solubilizers with HLB values of 12 to 18 suitable. There are in particular those solubilizers in question, in Römpps Chemie-Lexikon, 8th ed., Vol. 3, p. 2399 are described. Basically are suitable the following grouped surfactants: anionic surfactants: fatty alcohol sulfonates, e.g. B. Na lauryl ether sulfate, soaps, e.g. K stearate; cationic surfactants: quaternary Ammonium compounds, eg. B. didecyl-dimethyl-ammonium chloride, betin derivatives, eg. B. Fatty acid-amidopropyl-dimethylamino-acetic acid betaine; nonionic emulsifiers or solubilizer: fruit acid esters of mono-di-glycerides, z. B. Citric acid esters, polyoxyethylene glycerol fatty acid esters, e.g. B. polyoxyethylene  Glycerol mono-laurate with 30 moles of EA.

Of particular advantage have proven to be germ-inhibiting organic acids 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. It can be seen that the lime-dissolving organic Acids, such as citric acid, and the germ-inhibiting organic acids in the general with respect to the different effects in a suitable sanitary cleaner stand out from each other. In individual cases, on the one hand, an organic acid can dissolve limescale Beyond that, they also have the germ-inhibiting effect. In general It is preferred, on the one hand, such an acid, which is a special Kallösösevermögen has, and on the other hand, such an acidic organic compound, which is a particular effective germ inhibition shows use.

The germ-inhibiting organic substances are in the sanitary cleaner according to the invention, regardless of whether it is in powdery, granulated or liquid form, at least in an amount of about 0.5 g / kg sanitary cleaner and preferably in one Amount of about 0.5 to 150 g / kg sanitary cleaner, especially in an amount of 1 to 80 g / kg sanitary cleaner and most preferably in an amount of about 2 to 7 g / kg sanitary cleaner before.

The concentration of germ-inhibiting organic substances in the first phase of action is preferably adjusted such that their concentration therein or in at least about the minimum to be treated to be treated Inhibitory concentration (MIC) and at most about 200 times the minimum Inhibitory concentration (MIC) is. It is particularly preferred that the concentration the germ-inhibiting organic substances in the phase of action at least about Double and at most about 50 times, especially about 30 times the minimal inhibitory concentration.

In the context of the invention, in addition to urea as germ-promoting organic substances additionally and preferably Amino acids and / or orotic acid or suitable salts or derivatives thereof and Vitamins are used. The mentioned derivatization must not go so far that the desired effect of germination is impaired. Particularly suitable Amino acids are: alanine, arginine, asparagine, aspartic acid, cysteine, cystine, glutamine, Glutamic acid, glycine, histidine, hydroxyproline, isoleucine, leucine, lysine, methionine, ornithine,  Phenylalanine, proline, serine, threonine, tryptophan, tyrosine and valine. To the particular suitable vitamins, including their provitamins, include: L-ascorbic acid, salts ascorbic acid, in particular the Ca salt, L-ascorbyl palmitate, (+) - biotin, b-carotene, Cholecalciferol, dehydroascorbic acid, ergocalciferol, folic acid, hydroxocobalamin, Niacinamide, nicotinic acid (niacin), D-panthenol, D-pantothenic acid, pyridoxal, pyridoxa-5 phosphate, pyridoxamine, pyridoxamine 5'-phosphate, pyridoxine, pyridoxine phosphate, Riboflavin, riboflavin 5'-phosphate, rutin, rutin salt, in particular the rutin sulfate, Thiamine, thiamine nitrate, thiamine phosphoric acid ester, thiamine pyrophosphate, alpha Tocopherol, delta tocopherol, alpha tocopheryl acetate, alpha tocopheryl quinone, alpha Tocopheryl phosphate, alpha tocopheryl succinate, vitamin A acetate, vitamin A aldehyde, Vitamin A alcohol, vitamin A acid, vitamin B₄ (adenine), vitamin K₁, vitamin K₄, vitamin P. and Vitamin U (methionine · S-methylsulfonium chloride). In the event that the vitamins are acidic Generally, it is also possible to use suitable salts thereof consulted.

With the invention it is possible to hygienic cleaning of sanitary facilities achieve without the microbial degradation of the organic substances of the wastewater to disturb. These seemingly contradictory characteristics could surprise be implemented in a manner by the described germ-inhibiting or Germicidal agents in such a concentration in the inventive Sanitärreiniger be introduced that their concentration when used in the intended for this phase of action, for example in the toilet bowl, above the minimal inhibitory concentration (MIC). The "minimum inhibitory concentration" is a common technical term. At the same time, the germ-promoting organic substances in such a concentration or amount introduced into the product that they after the usual dilution of the medium of the first phase of action when entering the Waste water there have a growth-promoting effect on the microorganisms.

In the application of the sanitary cleaner according to the invention, the z. In powdery, granulated form or may be in aqueous form, this z. B. in the Toilet bowl diluted with a little water. There, the hygiene agents germinate inhibiting or germicidal effect, while the germ-promoting substances first ineffective. After rinsing the toilet bowl following the The action of the sanitary cleaner will be the germ-inhibiting organic substances in their Concentration below the MIC value lowered and thus ineffective. The germ-promoting organic substances are in their concentration in the Sanitary cleaner according to the invention dimensioned so that it also after rinsing or  a strong diluting the activity of sewage germs containing the organic matter reduce, promote and thus accelerate biological wastewater treatment at least not disturb.

The amount of germ-promoting organic matter in the form of urea in the sanitary cleaner according to the invention is not critical. In individual cases, it must be tested, which minimum concentration in each case is used. The quantitative minimum is 10 mg / kg Sanitary cleaner, in particular the range from about 10 mg / kg to about 50 g / kg Sanitary cleaner, in particular about 1 g to 15 g / kg of sanitary cleaner on urea.

As a quantitative guideline for the further germ-promoting organic substances, the in addition to the urea or the appropriate urea compounds could be a minimum of 10 mg / kg and especially from about 10 to 1000 mg. As a germ-promoting further organic substances are the substances mentioned in question, preferably Amino acids, vitamins, orotic acid and p-aminobenzoic acid. 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 orotic acid, this being Mixture is preferably present in about 1 kg of sanitary cleaner. To optimize the The desired effects of the germ-promoting organic substances are these, if they are in the Mixture be used, qualitatively and quantitatively with regard to the respective milieu selected.

The sanitary cleaner according to the invention may incorporate other known additives such as fragrances, dyes, biological frothers. As a foamer has a particularly water-soluble protein with simultaneous germ-promoting Effect proved, such as water-soluble whey protein. Preferably omitted when used this water-soluble protein thereof, about 2 to 30 g, especially about 5 to 10 g to about 1 kg of powdered sanitary cleaner or about 1000 ml of liquid Sanitary cleaners. Of course, the invention does not exclude that more in the The prior art known substances are added, in the selection of the desired benefits of environmental friendliness, etc. should be preserved as possible.

The particular advantage of the method according to the invention thus shows that the  Breathability of microflora in urban wastewater, as the following Examples show that they can be increased to a surprising extent. Thus It leads to a noticeable reduction of environmental pollution, because its disinfecting Effect on degradable natural products is attributed, d. h., it can be the limesolvent water-soluble acid, the germ-inhibiting organic substances as well as the germ-promoting organic substances in the form of urea of natural origin. The sanitary cleaner according to the invention is thus particularly favorable for the environment and meets the requirements and comes with increasing environmental awareness the wishes of consumers very much opposite.

The invention will be explained in more detail with reference to three recipe examples become:

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 gum) 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 were 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 gum) 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 to reflect the amount of Urea was modified. It was 2 g in Example 3 and 5 g in Example 4.

Comparative tests

It should have the positive effect of sanitary cleaners according to the above examples 1 to 4 are examined for the microflora of the wastewater. It became the breathability measured the microflora in municipal wastewater to check if the said Sanitary cleaner promote the flora or are easily degradable. Fresh sewage was with the products of Examples 1 to 4 in three concentrations. After 24 hours the formed carbon dioxide was measured. Parallel became the pH of the products is determined.

test results pH of the products

product PH value 1 2.90 2 2.78 3 2.83 4 2.75

The products differ in terms of pH slightly. The change in the respiratory activity of the microflora is in shown in Table 1 below.  

Table 1

(Breathability of the waste water flora depending on the composition of the WC cleaners and their concentration in the waste water)

The above comparison values show that the breathability is enhanced by the addition of Urea is markedly increased compared to the comparative product (1). The addition increased by 5 g of the growth factor in the form of urea at No. 4 sanitary cleaner the respiration compared to the reference product (1) to an average of 135 (!)%. It shows thus that the addition of urea in the amounts indicated to a bemer significantly increase the efficacy of the wastewater flora.

Claims (9)

1. A process for sanitary cleaning with a sanitary cleaner in liquid or solid form containing at least about 0.5 g / kg of sanitary cleaner, on conventional lime-soluble water-soluble acids, against the lime-dissolving water-soluble acid resistant germ-promoting organic substances in a quantity of germ-inhibiting organic substances in an amount of at least 10 mg / kg sanitary cleaner and optionally other additives, wherein after dilution or rinsing the organic substance of the water-degrading germs are promoted in their effect and furan carboxylic acids and their derivatives are excluded, characterized that the sanitary cleaner contains urea as a germ-promoting organic substance. 2. The method according to claim 1, characterized in that the concentration of germ-promoting urea in the sanitary cleaner about 10 mg / kg to 50 g / kg Sanitary cleaner, in particular about 1 g to 15 g / kg sanitary cleaner amounts. 3. The method according to at least one of the preceding claims, characterized characterized in that the sanitary cleaner to optimize its effect more germ-promoting organic substances in the form of amino acids, orotic acid or salts thereof and / or vitamins are added. 4. The method according to at least one of the preceding claims, characterized characterized in that the sanitary cleaner germ-inhibiting organic substances in an amount from about 1 to 150 g / kg sanitary cleaner, in particular about 1 to 80 g / kg sanitary cleaner, and in particular against the lime-dissolving water-soluble acid resistant additional germ-promoting organic substances in an amount of at least 10 mg / kg sanitary cleaner, contains in particular 100 to 1000 mg / kg sanitary cleaner. 5. sanitary cleaner, in particular for carrying out the method after at least  one of the preceding claims, the usual lime-dissolving water-soluble acids, germ-inhibiting organic substances in one Concentration of at least about 0.5 g / kg, in particular in an amount of about 1 to 150 g / kg sanitary cleaner, and resistant to the lime-soluble water-soluble acid germ-promoting organics in the form of urea in an amount of at least about Contains 10 mg / kg, in particular up to 50 g / kg sanitary cleaner, wherein furan carboxylic acids and their derivatives are excluded. 6. Sanitary cleaner according to claim 5, characterized in that it additionally has a Contains germ-promoting water-soluble protein as a foam carrier. 7. Sanitary cleaner according to claim 6, characterized in that it contains about 2 to 30 g water-soluble protein / kg sanitary cleaner contains. 8. sanitary cleaner according to claim 6 or 7, characterized in that the water-soluble protein is water-soluble whey protein. 9. Sanitary cleaner according to at least one of claims 5 to 8, characterized characterized in that the lime-dissolving water-soluble acids, the germ-inhibiting naturally occurring organic substances and / or the germ-promoting organic matter.